EP1996293A2

EP1996293A2 - Reductive colour removal

Info

Publication number: EP1996293A2
Application number: EP07723364A
Authority: EP
Inventors: Burkhard Müller; Inge Neubueser; Wibke Gross
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2006-03-21
Filing date: 2007-03-19
Publication date: 2008-12-03
Also published as: EP2277598B1; EP2277598A1; WO2007107308A2; WO2007107308A3

Abstract

The invention relates to agents which are contained in a carrier of a combination of special sulphinic acid derivatives of formula (I), wherein M represents a hydrogen atom or an equivalent of a mono or polyvalent cation, R is derived from a peptide or represents a group according to one of the formulae (II) to (VI), (for the meanings of the remaining substitutients see claim 1) and contains at least one non-ionic surfactant. Said agents enable a durable decolouration of the dyed substrates to take place without darkening the decoloured substrate. The substrate structure is not damaged during the decolouration process.

Description

"Reductive color print"

The invention relates to compositions for reductive color printing, which contain at least one nonionic surfactant in addition to organic sulfinic acid derivatives. These color proofing agents are suitable for the decolorization of colored substrates such as paper, textiles and, in particular, keratin-containing fibers, for example human hair. Likewise, a process for decolorization of colored substrates, as well as the use of said color proofing agent is the subject of the invention.

Colored or printed materials have always exerted a special charm on humans. This fascination still exists today. Either a coloring provides a fashionable component, for example in the form of dyed textiles or dyed hair. Or the coloring, for example in the form of a print, is used for the transmission of information or art. Dyeing promotes cultural and social identity and is also a craft that has become a lucrative and innovative industry over the years.

In dyeing, the dye is transferred to the substrate by adsorption to the surface, by diffusion, by formation on and / or in the substrate, or by chemical bonding. First, natural dyes such as purple or carmine were used. Through the rapid advances in science, tailor-made synthetic dyes have become available over the years for each application. For dyeing, for example, paper, textiles or keratin fibers, either direct dyes or oxidation dyes are generally suitable. Oxidative dyes are formed by oxidative coupling of one or more developer components with each other or with one or more coupler components. Coupler and developer components are also known as Oxidation dye precursors referred. The oxidative coupling preferably takes place during the dyeing process so that the dye precursors can diffuse into the substrate and the dye forms in the substrate. The size of the resulting dye molecule makes it difficult to wash out of the substrate.

The developer components are usually primary aromatic amines having a further free or substituted hydroxy or amino group in para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives thereof used.

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2, 4,5, 6-tetraminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2.5 - diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-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.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used. Suitable coupler substances are in particular 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.

Direct-acting dyes are generally understood to be dyes which are already preformed before the beginning of dyeing and are applied to the substrate. Important representatives of this class of dyes are, for example, triphenylmethane dyes, azo dyes, anthraquinone dyes or nitrobenzene dyes, which may each carry cationic or anionic groups. In addition to dyeing, an important technical field is the removal of dyes. This generally refers to the removal of dyeings or prints by washing, chemical modification or destruction of the dye. The oxidative or reductive discoloration of dyed materials finds particular application in the decolorization of textiles or hair.

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. For example, textiles or hair can become brittle or even break, especially if they are discolored several times. The visual impression, the feel as well as the durability of the substrate are negatively influenced.

Less influence on the substrate structure, in particular on the structure of keratin-containing fibers, take reductive decolorizing agents. The reductive decolorizing agents scarcely discolour the natural hair color but have a reductive effect only on the dyes applied by dyeing. There is thus hardly any whitening of the hair. However, the reductive decolorants require an improvement in decolorization performance.

Predominantly, one uses reductive sulfur compounds for decolorization. As is known, dithionites or derivatives of 1-hydroxymethylsulfinic acid or of 1-aminomethylsulfinic acid are suitable as reducing agents.

From the document US Pat. No. 3,892,845, the person skilled in the art is aware of reductive color stripping agents with the aid of which colored keratin-containing fibers can be decolorized. As the reducing agent, 1-hydroxymethylsulfinic acid or a salt thereof is contained in the decolorizing agents. According to DE-OS-1 617 829, the addition of 1-hydroxymethylsulfinic acid to oxidative decolorizing agents containing hydrogen peroxide and persulfates enhances their bleaching action. According to EP-A-1 079 018, aminoalkanesulfinates of the formula RY _Z N (CR ² R ³ -SO ₂ -M) _Z (R ² , R ³ = hydrogen or (C ₁ to C ₄ ) -alkyl) are suitable for 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 which carry a carboxy group, a sulfonic acid group, an acyl group, an aminocarbonyl group or an alkoxycarbonyl group are suitable for decolorization of colored substrates. Said derivatives have a comparable or better decolorization power as the 1-hydroxymethylsulfinic acid (vide supra), but do not cleave formaldehyde. W0-A1 -02 / 30369 describes the discovery that with the sulfinic acid derivatives of WO-A1 -99 / 18067 keratin-containing fibers, such as, for example, hair, can be decolorized. Further sulfinic acid derivatives which are suitable for decolorizing keratin-containing fibers can be found in the publications W0-A1 -03 / 026597 and WO-A1-03 / 41668.

Substrates which have been reductively decolorized with the sulfinic acid derivatives of the prior art experience some undesirable darkening some time after color removal.

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

Surprisingly, the object is achieved by means which comprise a combination of at least one of the organic sulfinic acid derivatives according to the invention with at least one nonionic surfactant. The discoloration of colored substrates, such as paper, textiles or keratin fibers, in particular human hair, without subsequent darkening to a high degree after the decolorization process, as is caused by the use of the sulfinic acid derivatives alone. The compositions according to the invention are particularly suitable for the fiber-sparing decolorization of keratin-containing fibers. By keratin fibers are, for example, wool, furs, feathers and especially human hair to understand.

A first subject of the invention are therefore agents which comprise in a carrier at least one sulfinic acid derivative of the formula (I)

O Il MO-S-R (I)

wherein

M represents a hydrogen atom or one equivalent of a mono- or polyvalent one

Kations, R is derived from a peptide or a radical according to one of the formulas (II) to (VI),

(IV)

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 (Ci -C ₆₎ hydroxyalkyl group, a (C ₂ -C ₆₎ -polyhydroxyalkyl group, an aryl group or an aryl (d to _C6) alkyl group are,

M 'independently of M the characteristics listed under M,

X is a direct bond or an organic radical with two free ones

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 ", in the M" 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 XrCOOM ¹ "with M ¹ " = hydrogen atom or one equivalent of a mono- or polyvalent cation and n is an integer O ₁ 1, 2 , 3, 4, 5 or 6, a (C ₁ to C ₆ ) alkyloxycarbonyl, an N ₁ N ₁ N-TnI (C ₁ to C ₆ ) alkyljammonium to C ₆ ) alkyl group, a carboxy (C ₂ to C ₆ ) alkenyl group, a CyBnO (C ₁ to C ₆ ) alkyl group or a (C ₁ to CeJ alkoxycarbonyl ^ d 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 Ca ^ oxy (C ₁ to C ₆₎ alkyl group is a Ca ^ oxy- (C ₁ -C ₆₎ alkoxy group or a group -N ⁺ R ¹ R ¹¹ R ¹ ", where R ¹ , R ¹¹ and R ¹ " independently of one another represent a (C ₁ to C ₆ ) -alkyl group, a (C ₂ to C ₆ ) -alkenyl group, an ArVl (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 (Ci 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 represents a hydrogen atom, a (C ₁ to C ₆₎ alkyl group, a (C ₂ to C ₆₎ alkenyl group, a perfluoro (Ci to _C6) alkyl group ¹² and R ¹³ independently of one another, 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 Al yl (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 (M) R ¹ and R ^{2 are} not simultaneously a hydrogen atom, in combination with at least one nonionic surfactant.

If the compounds of the formula (I) contain at least one chiral center, it is to be understood that all stereoisomers alone and mixtures thereof, in particular their racemates, are according to the invention.

The compounds of the formula (I) can be present in the form of the free acid or salt thereof as the inner salt, especially if, in addition to the sulfinate group of the formula (I), a cationic substituent (see definition R ² and R ⁷ ) is contained in the molecule.

When the compound of the formula (I) is present as an acid, the radicals M, M ', M "and / or M ¹ " represent a hydrogen atom. The fragments MO- of the formula (I), M ¹ O- of the formula (III) and M ¹¹ O- or M ¹¹¹ O- according to R ¹ or R ² from formula (M) in this case form 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 "or M ¹ " represents one equivalent of a monovalent or polyvalent one Cation. The monovalent or polyvalent cation M ^{z +} with a charge number z of one or higher is only used for reasons of electroneutrality to compensate for the single negative charge of salt formation

O

Il OSR present sulfinate fragment of formula (I) or mutatis mutandis from formula (Ml) ₁ or the carboxylate fragments of the radicals of R ¹ or R ^{2 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 ¹ 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 "and M ¹ ".

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 the groups Ia ₁ Ib, IIa, IIb, IMb, 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 formed for example by protonation of primary, secondary or tertiary organic amines with an acid, such as 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 "and M ¹ " 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, a potassium ion, Vz calcium ion, Vz magnesium ion or Vz 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. By definition, the anions are symbolized as ^" anols." They are preferably selected from halide, / 2 Suifat, hydrogen sulfate, Vz carbonate, hydrogen carbonate, 1/3 phosphate, ^Λ A hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate. The anion is particularly preferably chloride, bromide, p-toluenesulfonate or hydrogen sulfate.

In accordance with the invention, preference is furthermore given to those sulfinic acid derivatives of the formula (I) in which the radicals Y and Y 'independently of one another have a hydroxy group or a

group

Mean -NH ₂ .

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

The radical R according to formula (I) must be for solving the technical problem for one of the radicals described above, wherein it is preferred that R is a radical of the above formulas (II) to (VI).

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 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 above-mentioned selected aliphatic or aromatic heterocycles of this embodiment are substituted, then these are preferably at least one Radical from (Ci to _C6) alkyl, (C ₂ to C ₆₎ alkenyl, (C, to C ₆₎ hydroxyalkyl, aryl (Ci to _C6) - alkyl, hydroxy, (C ₁ to C ₆ ) Alkoxy, amino, di (C ₁ to C ₆ ) alkylamino, nitro, halo, carbamoyl, sulfonamido, cyano or carboxamido.

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.

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 ¹ , in which R ^{1 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 AIyI (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 ) 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 ¹ from residue Z ¹ forms an azandiyl group in the ring of the heterocycle.

NR ■ _> ιv-. The group CH of the radicals Z and Z forms in the ring of the heterocycle one

M Meetthhaannyyllyylliiddeennggrruuppppee = CH-, which of course may also be substituted by one of the radicals R ⁵ or R.

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 hydroxyl group, then it is preferred according to the invention in the formulas (Ia-1) or (la-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, ArVl- (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 are of the formulas (la-1) to (la-4) are particularly preferably a hydrogen atom, a hydroxy group, a (C ₁ to C ₆₎ alkyl group, a (C ₁ -C ₆₎ - alkoxy group, a (C ₁ to C ₆ ) hydroxyalkyl group, halogen atom or notro group. When the radicals R ¹ and R ^ form according to formula (II) membered 7 in the context of the first embodiment together with the remainder of the molecule is an aliphatic 5-, 6-, or ring which contains at least one cationic, quaternized nitrogen atom as a hetero atom wherein the cationic Charge is optionally compensated by the one equivalent of a monovalent or polyvalent anion, the following compounds according to formulas (la-5) and (la-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 is an azonium diyl group N ⁺ R ^V R ^VI with R ^v and R ^vι independently of one another represent a (C ₁ to C ₆ ) ^-alkyl group, a (C ₂ to C ₆ ) Alkenyl group, a (Ci to C ₆ ) - hydroxyalkyl group or an ArVl (C ₁ to C ₆ ) alkyl group, and the remaining of these radicals are a CH ₂ group,

R ¹⁷ and R ¹⁸ independently represent a hydrogen atom, a (C ₁ to C ₆ ) alkyl group, a hydroxy group, a halogen atom or a carboxy group, provided that one equivalent of a mono- or polyvalent anion is present when M is none means 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 aforementioned preferred definitions of the radicals M and Y also apply here, alone or together, to formulas (Ia-5) and (Ia-6), as being preferred. The condition described under the proviso describes the formation of an internal salt, which is also a preferred embodiment. 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).

Those compounds of the 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 ¹ R ¹¹ R " ¹ , with R ¹ _, R" and R ¹ "independently of one another represent a (C ₁ to C ₆ ) -alkyl group, one

(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.

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 ¹ "have the meanings given under formula (I) and (II).

Preferred compounds of the formula (Ia-8) according to the invention are those in which Y is a hydroxy or amino group.

Preferably, n in formula (Ia-8) is a number 0, 1 or 2. 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. Suitable radicals according to the invention are in principle all organodiyl radicals, such as, for example, 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 arenediyl, heteroarendiyl, alkanediyl, alkenediyl, cycloalkanediyl, cycloalkendiyl and D 1 ( 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, Ar ^ - (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.

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 (Xl) is selected,

in which mean

R ¹⁵ and R ^{16 are} independently of one another 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 is} a group CH ₂ , an oxygen atom, a sulfur atom or a

Group NR ', with R' = hydrogen, an (Ci to _C6) 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 from the formulas (VII) to (XI) within the definition of the formula concerned.

If the organic radical having two free valencies X is selected 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.

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,

(IC) wherein M ₁ R ⁷ , R ^ö and R ^{9 have} the meaning defined under the formulas (I) and (IV). The aforementioned preferred definitions of the radicals M ₁ R ⁷ , R ⁸ and R ^{9 also} apply here, applied alone or together to formula (Ic), as being preferred.

Particularly preferred radicals R according to formula (IV) ₁ are selected from 4-cyanophenyl, 4-carboxyphenyl, 4-carboxymethyloxy and 4-trimethylammoniophenyl.

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 of the formula (Id) ₁ according to the invention

OO MO-SCNR ¹⁰ (Id)

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.

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, where linear or branched (C ₁ to C ₆ ) alkyl groups are preferred. In particular, the groups

Methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl and n-hexyl 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 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-butyl

Butoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 3

Propoxycarbonylpropyl, 3-isopropoxycarbonylpropyl, 3-butoxycarbonylpropyl, 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 the

Methoxyhexylgruppe are examples of inventive (C ₁ to C ₆ J-AIkOXy- (C ₁ to C ₆ ) - alkyl groups.

A preferred hydroxy ^ 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 PePfIuOr (C ₁ to C ₆ ) alkyl groups.

Examples of halogen atoms are F, Cl, Br or I atoms, with Cl and Br atoms being very particularly preferred.

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

The trimethylammonium and diethylmethylammonium are examples of a group

N ⁺ R ¹ R ¹¹ R " ¹ .

The 2-trimethylammoniumethyl- is an example of a N ₁ N, N-TnI (C ₁ to C ₆ ) -alkylammonium C _! to C ₆ ) alkyl group.

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

The other terms used are according to the invention of the given here

Definitions off.

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:

Name: corresponding structure:

2-furyl (amino) methanesulfinic acid,

Amino (thien-2-yl) methanesulfinic acid,

Amino (1 / - / - imidazol-2-yl) methanesulfinic acid,

Amino (1, 3-thiazol-2-yl) methanesulfinic acid, OSX ^> L ^ l ^'S "OH Äminoό .S-oxazole ^ -yOmethanesulfinic acid, OL 1 ^* OH

NH ₂

Amino (1H-pyrrol-2-yl) methanesulfinic acid,

Amino (hydroxyl-2-yl) methanesulfinic acid,

Amino (hydroxyl-4-yl) methanesulfinic acid, N ^ I

Oy ^* Oh

NH,

Amino [3-hydroxy-5- (hydroxymethyl) -2-methyl-pyridin-4-yl-methanesulfinic acid,

Amino (quinolin-2-yl) methanesulfinic acid,

Amino (quinolin-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 (thien-2-yl) methanesulfinic acid,

Hydroxy (thien-3-yl) methanesulfinic

(3-bromothien-2-yl) (hydroxy) methanesulfinic acid,

Hydroxy (1H-imidazol-2-yl) methanesulfinic acid,

Hydroxy (1H-imidazol-5-yl) methanesulfinic acid, ff S-, OH

OH

Hydroxy (1-metyl-b-nιtro-1 / - / - ιmιdazol ---- 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 (hydroxyl-2-yl) methanesulfinic acid,

Hydroxy (hydroxyl-4-yl) methanesulfinic acid,

Hydroxy [3-hydroxy-5- (hydroxymethyl) -2-methylpyridin-4-yl] methanesulfinic acid,

HydroxyCchinolin ^ -yOmethansulfinsäure,

Hydroxy (quinolin-4-yl) methanesulfinic acid,

1 / - / - benzimidazol-2-yl (hydroxy) methanesulfinic acid,

1, 3-benzothiazol-2-yl (hydroxyl) methanesulfinic acid,

1, 3-benzoxazol-2-yl (hydroxy) methanesulfinic acid,

1, 2-Dihydroxyethane-1, 2-disulfinic acid, HO OH

) ~~ Λ

HO-S _4, S-OH oo ^v ^{/ 7} 1, 3-dihydroxypropane-i, 3-disulfinic acid,

Hydroxy {4- [hydroxy (sulfino) methyl] phenyl} methanesulfinic acid,

{2-chloro-3- [hydroxy (sulfino) methyl] cyclohexyl} - (hydroxy) methanesulfinic acid,

{2-chloro-3- [hydroxyl (sulfino) methyl] cyclopentyl} - (hydroxyl) 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,

HO, JCJC, OH

4-hydroxy-4-sulfinobutansäure,

1-hydroxy-4-methoxy-4-oxobutane-1-sulfinic acid,

-Hydroxy-4-ethoxy-4-oxobutane-1-sulfinic acid,

-Hydroxy-4-sulfinopentansäure,

-Hydroxy-5-methoxy-5-oxopentan-2-sulfinic acid,

-Hydroxy-5-ethoxy-5-oxopentan-2-sulfinic acid,

-Hydroxy-4-sulfinobut-2-enoic acid,

Hydroxy-4-methoxy-4-oxobut-2-en-1-sulfinic acid, op

OH -hydroxy-4-ethoxy-4-oxobut-2-en-1-sulfinic acid,

-Hydroxy-4-sulfinopent-2-enoic acid,

-Hydroxy-5-methoxy-5-oxopent-3-en-2-sulfinic acid,

-Hydroxy-5-ethoxy-5-oxopent-3-en-2-sulfinic acid,

Hydroxy-5-sulfinopentansäure,

-Hydroxy-5-methoxy-5-oxopentan-1-sulfinic acid,

1-hydroxy-5-ethoxy-5-oxopentan-1-sulfinic acid,

5-hydroxy-5-sulfinohexansäure,

2-hydroxy-6-methoxy-6-oxo-hexane-2-sulfinic acid,

2-hydroxy-6-ethoxy-6-oxo-hexane-2-sulfinic acid,

4- [hydroxy (sulfino) methyl] benzoic acid,

4- [amino (sulfino) methyl] benzoic acid,

{4- [hydroxy (sulfino) 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) -methansulfinsäure,

(4-cyanophenyl) (amino) -methansulfinsäure,

(4-nitrophenyl) (hydroxy) -methansulfinsäure,

(4-nitrophenyl) (amino) -methansulfinsäure,

Salt of 4-hydroxy-1,1-dimethyl-4-sulfinopiperidinium with An ^" as the equivalent of a mono- or polyvalent anion,

Salt of 1-allyl-4-hydroxy-1-methyl-4-sulfinopiperidinium with An ^" as the equivalent of a mono- or polyvalent anion,

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,

[(Phenylsulfonyl) amino] methanesulfinic

1-hydroxy-2- (trimethylammonio) ethansulfinat,

Hydroxy [4- (trimethylammonio) phenyl] methanesulfinate,

4- [hydroxy (sulfino) methyl] benzenesulfonic acid and

2- [hydroxy (sulfino) methyl] benzenesulfonic acid

2-hydroxy-2-sulfino-acetic acid

2-amino-2-sulfino-acetic acid

2-hydroxy-2-sulfino-propionic acid

2-amino-2-sulfino-propionic 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-oxoethansulfinsäure

2-amino-1-hydroxy-2-oxoethansulfinsäure

2- (dimethylamino) -1-hydroxy-2-oxoethansulfinsäure

Hydroxy (sulfino) methanesulfonic acid

Hydroxy (phenyl) methanesulfinic

Hydroxy (4-hydroxyphenyl) methanesulfinic

Hydroxy (4-methoxyphenyl) methanesulfinic

For the preferred mono- or polyvalent cations of all salts of the aforementioned compounds, what has been stated above applies.

Preferably, the agent according to the invention contains at least one sulfinic acid derivative of the formula (I) in an amount of 0.01 to 20 wt .-%, particularly preferably from 1 to 20 wt .-%, each based on the weight of the composition.

Nonionic surfactants are surfactants with an uncharged, polar, hydrophilic headgroup carrying no ionic charge at neutral pH, which adsorb at interfaces and aggregate above the critical micelle concentration to neutral micelles.

The selection of nonionic surfactants is initially no limit. Nonionic surfactants having an HLB value of from 0.5 to 20 are preferably suitable according to the invention. It has proven particularly advantageous for the compositions according to the invention to comprise as nonionic surfactant at least one member from the group which is formed :

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 mol

Propylene oxide to:

- linear fatty alcohols containing 8 to 22 carbon atoms,

Fatty acids with 12 to 22 C atoms and

Alkylphenols having 8 to 15 carbon atoms in the alkyl group, C ₁₂ -C ₂₂ -fatty acid mono- and di-esters of addition products of 1 to 30 mol of ethylene oxide onto polyols having 3 to 6 carbon atoms, in particular to glycerol,

C ₆ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs, ethylene oxide and polyglycerol addition products

- methyl glucoside fatty acid ester,

- fatty acid alkanolamides and - fatty acid glucamides,

C ₈ -C ₂₂ -alkylmono- and -oligoglycosides and their ethoxylated analogues, with degrees of oligomerization of 1, 1 to 5, in particular 1, 2 to 2.0, and glucose being preferred as the sugar component,

Mixtures of alkyl (oligo) glucosides and fatty alcohols (for example, the commercially available product ^® Montanov 68)

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

Partial esters of polyols having 3 to 6 carbon atoms with fatty acids having 8 to 22 C atoms, sterols,

Fettsäureestern of sugars and sugar alcohols (such as sorbitol), polyglycerols and polyglycerol derivatives (such as polyglycerol poly-12-hydroxystearate (commercial product Dehymuls ^® PGPH)),

Phosphoric acid esters with (C ₈ to C ₂₂ ) fatty alcohols, with their ethoxylates / propoxylates, with (C ₈ to C ₂₂ ) -alkylphenol ethoxylates, with (C ₈ to C ₂₂ ) -alkylphenol propoxylates, (C ₈ to C ₂₂ ) -fatty acid Protein condensates, nonionic silicone surfactants.

In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. By "normal" homolog distribution are meant mixtures of homologues which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alkoxides are used as catalysts.

The addition products which contain only a small amount of free fatty alcohol and have a narrow homolog distribution (so-called "narrow-ranked ethoxylates"), as are obtainable, for example, by the process described in DE 38 43 713 A1, may have advantages in the inventive compositions.

Preferred alkyl polyglycosides obey the general formula (T1),

R ¹ O- (Z) _x (T1).

These connections are identified by the following parameters:

The alkyl radical R ¹ according to formula (T1) contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. When using so-called "oxo-alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides of the formula (T1) which can be used according to the invention can contain, for example, only one particular alkyl radical R ¹ . Usually, however, these compounds are prepared starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R ^{1 are} mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds.

And C ₁₀ alkyl groups, mainly of C ₁₂ - - and C ₄ alkyl groups, essentially of C ₈ - to C ₁₆ -alkyl groups such alkyl polyglycosides of formula (T1), in which R ¹ consists essentially of C ₈ are particularly preferred or consists essentially of Ci ₂ - to C ₁₆ alkyl groups.

As sugar unit Z according to formula (T1) any mono- or oligosaccharides can be used. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, Mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x is 1: 1 to 1, 4.

The alkoxylated homologs of said alkyl polyglycosides can also be used according to the invention. These homologs may contain on average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Preferably used partial esters of polyols having 3 to 6 carbon atoms are partial glycerides. Partial glycerides, ie monoglycerides, diglycerides and their technical mixtures may contain small quantities of triglycerides due to their production. The preferred partial glycerides preferably follow the formula (T2),

in which the group COR ^{1 is} a linear or branched, saturated or unsaturated acyl radical having 6 to 22, preferably 12 to 18, carbon atoms,

R ² and R ³ independently of one another represent a linear or branched, saturated or unsaturated acyl radical having 6 to 22, preferably 12 to 18 carbon atoms or a hydrogen atom and the sum (m + n + p) for 0 or numbers from 1 to 100, preferably 5 to 25, with the proviso that at least one of the two radicals R ² or R ³ a

Means hydrogen.

Typical examples are mono- and / or diglycerides based on caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myrotic acid, ristinic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid, and technical mixtures thereof. Preferably, technical lauric acid glycerides, palmitic acid glycerides, stearic acid glycerides, isostearic acid glycerides,

Oleic acid glycerides, behenic acid glycerides and / or erucic acid glycerides used which have a Monoglyceridanteil in the range of 50 to 95, preferably 60 to 90 wt .-%.

Sterols are understood to mean a group of steroids which carry a hydroxyl group on C-atom 3 of the steroid skeleton and are isolated both from animal tissue (zoosterines) and from vegetable fats (phytosterols). Examples of zoosterols are cholesterol and lanosterol. Examples of suitable phytosterols are ergosterol, stigmasterol and sitosterol. Mushrooms and yeasts are also used to isolate sterols, the so-called mycosterols.

The nonionic silicone surfactants are again preferably selected from the group of polyoxyalkylene-modified dimethylpolysiloxanes (INCI name: dimethicone copolyol). The polyoxyalkylene-modified dimethylpolysiloxanes which are particularly preferred according to the invention include in particular the compounds of the general formulas (Si-1) or (Si-2):

R ¹ -Si - [[OSi (CH 3) ₂ ] _x - (OC ₂ H ₄ ) _a - (OC ₃ H ₆ ) _b -OR ¹ ].

(Si-2) wherein

the radical R can be a hydrogen atom, an alkyl group having 1 to 12 C atoms, an alkoxy group having 1 to 12 C atoms or a hydroxyl group,

the radicals R 'and R "represent alkyl groups having 1 to 12 C atoms,

x is an integer from 1 to 100, preferably from 20 to 30,

Y is an integer from 1 to 20, preferably from 2 to 10, and

a and b are integers from 0 to 50, preferably from 10 to 30.

Compounds falling within the above formulas are disclosed in the following patent applications, which are incorporated herein by reference: US-A-4,122,029; US-A-4,265,878; US-A-4,421,769 and GB-A-2,066,659.

Particularly preferred dimethicone copolyols according to the invention are, for example, the products sold commercially under the trade name SILWET (Union Carbide Corporation) and DOW CORNING (Dow).

Particularly preferred dimethicone copolyols according to the invention are Dow Corning 190 and Dow Corning 193.

The compositions according to the invention preferably contain the nonionic surfactants in amounts of from 0.1 to 25% by weight, in particular from 0.5 to 15% by weight, in each case based on the total composition. It is furthermore preferred if, in the composition according to the invention, the weight ratio of the sulfinic acid derivatives of the formula (I) to the nonionic surfactants is from 1: 2000 to 10: 1, more preferably from 1: 200 to 2.5: 1, very particularly preferably from 1 to 50 to 1 to 1, is.

In addition, the agents according to the invention may contain at least one compound selected from the aldehydes or the ketones. Preferred compounds of the aldehydes or the ketones are selected from at least one member of 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 aldehydes and

- alicyclic, aromatic or heterocyclic ketones.

In general, in the abovementioned compounds of the cyclic, alicyclic or heterocyclic ketones according to the invention, the keto group (s) may be (endocyclically) bonded (and / or) or exocyclically.

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,

RC- (CHz) _n -C -OH

Il

O O (XII)

in which mean R is a hydrogen atom, a (Ci to C ₆ ) alkyl group, a (Ci 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 (Ci to C ₆ alkyl group), n is a number 0, 1, 2 or 3rd

The oxocarboxylic acids are particularly preferably selected from at least one member from the group consisting of glyoxylic acid, acetoacetic acid, 3-oxoglutaric acid, 4-oxovaleric acid and pyruvic acid or the salts of the abovementioned acids.

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

According to the invention, cyclic, linear or branched aliphatic aldehydes are aliphatic aldehydes whose formyl group (s) are not in conjugation with an aromatic π-electron system. The corresponding aldehydes may carry aromatic radicals as long as the π-electrons of the formyl group (s) can not be delocalized via such an aromatic system. Preferred cyclic, linear or branched aliphatic aldehydes are saturated or unsaturated and are more preferably selected from at least one of 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.

According to the invention, cyclic, linear or branched aliphatic ketones are aliphatic ketones whose keto group (s) are not in conjugation with an aromatic π-electron system. However, the corresponding ketones may carry aromatic radicals as long as the π-electrons of the Keto group (s) can not be delocalized via such an aromatic system. Preferred cyclic, linear or branched aliphatic ketones are saturated or unsaturated and selected from at least one member selected from 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) benzoic acid methyl ester and 4- (3-

Oxopropyl) benzoate.

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

According to the invention, polyhydroxy-functionalized aldehydes are preferably the so-called aldoses and are more preferably selected from at least one of 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.

Monohydroxy-functionalized ketones which are particularly suitable according to the invention are preferably selected from at least one member selected from the group consisting of 1-hydroxy-2-propanone, 1-hydroxy-2-butanone, 3-hydroxy-2-butanone and benzoin.

Polyhydroxy-functionalized ketones according to the invention are preferably the so-called ketoses and are more preferably selected from at least one member of group 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. Preferred alicyclic, aromatic or heterocyclic ketones are preferably selected from at least one member of the group

- Benzylidenketone, in particular the Benzylidenketonen from the patent application

DE-A1-19717281 (see DE-A1-19717281: formula (I) of claim 1 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.

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 the group of benzaldehyde, naphthaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4 -hydroxybenzaldehyde, 4-hydroxy-1-naphthaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 3-bromo 4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino-2 -methoxybenzaldehyde, 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-dimet 4-hydroxy-2,6-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-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- Dimethoxybenzaldehyde, 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-methylbenzaldehyde, 2,4-dihydroxy-6-methylbenzaldehyde, 2,4-dihydroxy-3-methoxybenzaldehyde, 2,4-dihydroxy-5-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde 6-methoxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-methylbenzaldehyde, 3,4-dihydroxy-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-trihydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-pipe 3-chloro-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-hydroxy-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-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4- Diethylaminocinnamaldehyde, 4-dibutylaminobenzaldehyde, 3-allyl-4-hydroxybenzaldehyde, 3-allyl-4-hydroxy-5-methoxybenzaldehyde, 3-allyl-4-hydroxy-5-methylbenzaldehyde, 3-allyl-5-bromo 4-hydroxybenzaldehyde, 3,5-diallyl-4-hydroxybenzaldehyde, 3-allyl-4-hydroxy-5-formylbenzaldehyde (5-allyl-4-hydroxyisophthalaldeh yd) and piperonal.

All aldehyde or keto compounds should be selected from physiologically acceptable or non-toxic compounds if the agent according to the invention is to be used as a cosmetic agent. The compounds selected from aldehydes or ketones are according to the invention preferably in an amount of 0.1 wt .-% to 20 wt .-%, in particular from 0.5 wt .-% to 10 wt .-%, each based on the Weight of ready-to-use decolorizing agent containing decolorizing agent.

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

The reductones are inventively preferably in an amount of 0.1 wt .-% to 20 wt .-%, in particular from 0.5 wt .-% to 10 wt .-%, each based on the weight of the ready-to-use agent, in the contain agents according to the invention.

Suitable carriers for the agent according to the invention are preferably liquid media in which the sulfinic acid derivative according to the invention is preferably soluble, for example water or organic solvents. It is preferred according to the invention if the carrier is a cosmetic carrier.

As cosmetic carriers are particularly suitable creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are particularly suitable for use on the hair. But it is also conceivable to integrate the ingredients in a powdered or tablet-like formulation, which is dissolved in water before use. The cosmetic carriers may in particular be aqueous or aqueous-alcoholic.

An 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 -alkyl alcohol, in particular ethanol or isopropanol. Further 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 agent according to the invention preferably has a pH of from pH 1 to pH 9, in particular from pH 1.5 to pH 6.

Furthermore, the agents according to the invention may contain further active ingredients, auxiliaries and additives, such as

nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, with diethyl sulfate quaternized dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,

zwitterionic and amphoteric polymers, for example acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methylmethacrylate / tert-butylaminoethylmethacrylamide hydroxypropyl methacrylate copolymers, anionic polymers, for example polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone Vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers,

Structurants such as pantholactone, maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example soya lecithin,

Egg lecithin and cephalins, Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates, perfume oils, dimethyl isosorbide and cyclodextrins, fiber-structure-improving agents, especially mono-, di- and oligosaccharides such as glucose, galactose , Fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate defoamers such as silicones, colorants for staining the agent,

Antidandruff active ingredients such as Piroctone Olamine, zinc Omadine and Climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,

Substances for adjusting the pH, for example customary acids, in particular edible acids and bases, for example ammonia or 2-aminoethanol, active compounds such as pyrrolidonecarboxylic acids and salts thereof and bisabolol, vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,

Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi , Melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root ,.

Fats and waxes such as spermaceti, beeswax, montan wax and paraffins, fatty acid alkanolamides,

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids, swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers, pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate, pigments, Blowing agents such as propane-butane mixtures, N ₂ O ₁ dimethyl ether, CO ₂ and air,

Antioxidants, included.

With regard to further optional components as well as the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced.

A second object of the invention is the use of the composition according to the first subject of the invention for the decolorization of substrates which are colored with natural and / or synthetic dyes.

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

The natural fibers are preferably selected from cellulose-containing fibers, in particular cotton, and keratin-containing fibers, in particular wool or animal or human hair, very particularly preferably from human hair.

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

The substrates to be decolorized are preferably dyed with oxidation dyes and / or substantive dyes as representatives of the synthetic dyes.

In principle, developer components used to color the substrate can serve as downstream developer components.

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

G ¹ represents a hydrogen 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 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 - 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 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 one another, they may together form a bridging α, ω-alkylenedioxy group, for example an ethylenedioxy group ,

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino 3-methyl- (N, N-diethyl) -aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) -amino-2- methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (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 salts.

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

According to the invention, it may further be preferred for the dyeing of the substrate to use as developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.

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

in which:

Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ -ReSt which is optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ -hydroxyalkyl radical and / or is substituted by a bridge Y or which may be 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, of one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be interrupted or terminated and may be substituted by one or more hydroxyl or C ₁ - to C ₈ -alkoxy radicals, or a direct bond,

G ⁵ and G ⁶ are each independently a hydrogen or halogen atom, a C _r to C ₄ alkyl radical, a C _r -C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ - polyhydroxyalkyl radical, a Ci 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 independently of one another represent 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 bridging Y per molecule.

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

Preferred binuclear developer components of the formula (E2) are, in particular: N, N'-bis-φ-hydroxyethyl-N, N'-bis-C'-aminophenyl J-IS-diamino-propane, -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-methyl-aminophenyl) tetramethylenediamine, N ₁ 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- ^l , 5'-diaminophenyl) -1,4,7,10- tetraoxadecane and its physiologically acceptable salts.

Very particularly preferred double bases of formula (E2) are N, N'-bis (.beta.-hydroxyethyl) -N, N ^l -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 of its physiologically acceptable salts.

Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts 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 radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ ) - Alkoxy (C _r to C ₄ ) alkyl, a C ₁ - to C ₄ -Aminoalkylrest, a hydroxy (d- to C ₄ ) alkylamino, a C ₁ - to C ₄ -hydroxyalkoxy, a C ₁ - C ₄ - hydroxyalkyKC _T to C ₄ ) -aminoalkyl or a (di-C ₁ - to C ^ alkylaminoHCr to C ₄ ) alkyl, and

G ¹⁴ is 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 -j- AIkOXy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a C ₁ - to C ₄ - cyanoalkyl radical,

G ¹⁵ is hydrogen, C ₁ - to C ₄ alkyl, 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 substituents used in formula (E3) are defined according to the invention analogously to the above statements. 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 and their physiologically acceptable salts.

Very 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, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Further, the developer component may be selected from heterocyclic developer components such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts.

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 German patent DE 2 359 399, Japanese laid-open specification JP 02019576 A2 or in published patent application 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 patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 4,5 diamino-1-methylpyrazole, 4,5-diamino-1 - (beta-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1 - (4 ¹ - chlorobenzyl) pyrazole, 4,5- Diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-Benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4, 5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-i-ethyl-3- (4'-methoxyphenyl) pyrazole , 4,5-diamino-i-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-dimethylpyr azole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) - amino-1-methylpyrazole.

Preferred 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:

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 polyhydroxyalkyl a (C ₁ - to C ₄₎ alkoxy, alkyl (C _r to C ₄₎ a C ₁ - to C ₄ -aminoalkyl radical, which may be optionally protected by an acetyl ureide or a sulfonyl radical , a (C ₁ - to to C ₄₎ alkyl group a DK (C ₁ - aminoalkyl to C _4), wherein the dialkyl residues optionally form a carbocycle or a heterocycle with 5 or 6 chain links - to C ₄₎ alkyl] - (C ₁ a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C _r to C ₄ ) -aminoalkyl, 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 radical, a (C ₁ - to C ₄ ) -alkylamino - (C ₁ - to C ₄ ) -alkyl radical, a DK (C ₁ - to C ₄ ) alkyl] - (C ₁ - to C ₄ ) -aminoalkyl radical, where the dialkyl radicals optionally have a carbon cycle or a heterocycle with 5 or Form 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ - hydroxyalkyl) aminoalkyl, an amino, a C ₁ - to C ₄ alkyl or di- (C ₁ - to C ₄ -hydroxyalkyl) -amino, 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 when p + q is 2, n is 0, and groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7); when p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

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

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:

Among the pyrazolo [1, 5-a] pyrimidines of the above formula (E4) may be mentioned in particular:

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-dimethyl-pyrazolo [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 pyrazolol, 5-a] pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization from an aminopyrazole or hydrazine.

In a further preferred embodiment, the substrates to be decolored were dyed with an oxidative dye which additionally contains at least one coupler component in addition to at least one developer component. As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used. Suitable coupler substances are in particular 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomonomethylether, m-phenylenediamine, 1-phenyl 3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1 _liter 3-bis- (2 ', 4'-diaminophenoxy) -propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2 Chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Preferred coupler components according to the invention are m-aminophenol and its derivatives, such as, for example, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2 6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'- Hydroxyethyl) -amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol and 2,4 dichloro-3-aminophenol,

o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as, for example, 2,4-diaminophenoxyethanol, 1,3-bis- (2 ', 4'-diaminophenoxy) -propane, 1-methoxy-2-amino- 4- (2'-hydroxyethylamino) benzene, 1,3-bis (2 ', 4'-diaminophenyl) -propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene, 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-yl-phenyl) -amino] -ethanol, 3-amino-4- (2-methoxy-ethoxy) -5-methyl-phenylamine and 1-amino-3-bis- (2'-hydroxyethyl) -aminobenzene, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene, pyridine derivatives such as 2,6-dihydroxypyridine , 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6- Dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine, naphthalene derivatives such as 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 preferred coupler components according to the invention 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-methyl resorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

In addition, the substrates to be decolorized with precursors of naturally-analogous dyes may preferably be dyed with the aid of such indoles and indolines, which preferably have at least two hydroxyl or amino groups, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. In the form of etherification or esterification of the hydroxyl group or alkylation of the amino group. Particularly suitable as precursors of natural-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula XIIIa,

(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 present as 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 represents one of the groups mentioned under G ²⁴ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 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.

Particularly noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5, 6-Dihydroxyindolin.

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

(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 CVCV 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 under G ³⁰ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-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.

Emphasized within 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 -Dihydroxyindol.

The substrate to be decolorized may also have been dyed with substantive dyes. Suitable direct dyes include, in particular, nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Acid Yellow 1, Acid Yellow 36, 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 known compounds as well as 1, 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1, 4- Bis- (β-hydroxyethyl) -amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-

Hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl ) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2 -Amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

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:

CH ₃ SO ₄ ^'

(DZ1) (Basic Yellow 87)

(DZ3) (Basic Orange 31)

(DZ5) (Basic Red 51)

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. Furthermore, the substrates to be decolorized with naturally occurring, natural dyes such as henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root are, be colored.

A third object of the invention is a process for the reductive decolorization of substrates dyed with natural and / or synthetic dyes, in which an agent of the first subject of the invention is applied to the dyed substrate and rinsed off again after a contact time.

The reaction time is preferably 1 to 60 minutes, preferably 5 to 30 minutes. The action of the agent according to the invention can be carried out not only at room temperature, but preferably in a temperature range from 15 to 60 ^° C., in particular from 25 to 60 ^° C.

After the exposure time, the hair is rinsed out, wherein preferably a surfactant-containing agent, such as a cleaning agent or a shampoo, applies. Optionally, the substrate can be rinsed out several times, or treated several times with the surfactant-containing agent.

The surface-active agent for rinsing or aftertreatment preferably contains in a carrier at least one surfactant selected from anionic, zwitterionic, ampholytic, nonionic or cationic surfactants, in particular from nonionic surfactants.

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. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 C atoms (soaps),

Ethercarbonsäuren the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 10 to 22 carbon atoms and x = O or 1 to 16, acylsarcosides having 10 to 18 C Atoms in the acyl group, acyltaurides having 10 to 18 C atoms in the acyl group, acyl isethionates having 10 to 18 C atoms in the acyl group,

Sulfobernsteinsäuremono- and dialkyl esters having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylester with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 12 to 18 carbon atoms, linear alpha-olefinsulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids having 12 to 18 carbon atoms, alkyl sulfates and Alkylpolyglykolethersulfate the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in the R is a preferably linear alkyl group with 10 bis 18 C atoms and x = 0 or 1 to 12,

Blends 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 C 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 ^H group.) Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinates, for example the cocoalkyl dimethyl-ammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines having in each case 8 to 18 C atoms in the alkyl A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in the ₃ H-group in addition to a C _8- i ₈ alkyl or acyl group in the molecule at least one free amino group and at least one -COOH or -SO and which are capable of forming inner 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, cocoacylaminoethyl aminopropionate and C ₂ i ₈ acyl sarcosine.

Nonionic surfactants contain as hydrophilic group z. For example, a polyol group, a polyalkylene glycol ether 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 to linear fatty alcohols having 8 to 22 C-atoms, to fatty acids having 12 to

22 C atoms and alkylphenols having 8 to 15 C atoms in the alkyl group,

C _2-22 fatty acid mono- and diesters of addition products of 1 to 30 mol

Ethylene oxide with glycerine,

Cβ- ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs,

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

Castor oil,

Addition products of ethylene oxide to sorbitan fatty acid esters Addition products of ethylene oxide to fatty acid alkanolamides.

Examples of the cationic surfactants which can be used in the surface-active compositions according to the invention for rinsing or after-treatment are, in particular, quaternary ammonium compounds. Preference is given to ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

Also suitable in the present invention are cationic silicone oils such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamide dimethicone), 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 Quatemium- 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 such as those sold under the trademark Stepantex ^® methyl.

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".

The compounds containing alkyl groups used as surfactants may each be uniform substances. However, it is usually preferred at the Producing these substances from native plant or animal raw materials, so as to obtain substance mixtures with different, depending on the particular raw material alkyl chain lengths.

The surfactants are preferably used in concentrations of 0.5 to 30 wt .-%, based on the weight of the composition, in the surfactant-containing agent for rinsing or aftertreatment.

In addition, the surfactant-containing agent for rinsing or aftertreatment 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 / HCI buffer or monophthalate / NaOH buffer.

It may be advantageous to subsequently post-treat the substrate with an oxidant-containing composition. Hydrogen peroxide is preferably used as the oxidizing agent, preferably in concentrations of from 0.5 to 6% by weight. The reaction time is preferably 1 to 30 minutes, more preferably 1 to 10 minutes. After expiry of the contact time, the oxidant-containing composition is rinsed out.

Preferred colored substrates are those defined in the second subject of the invention.

As preferred natural or synthetic dyes, those dyes were preferably used, as we defined them in the second subject of the invention.

The subject of the invention will be explained by way of example with reference to the following statements. Examples

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

Raw material: Content Manufacturer:

Brif 30 polyethylene glycol monolauryl ether, Uniqema

Dodecanol ethoxylated with approx. 4

Molar equivalent of ethylene oxide (INCI)

Designation: Laureth-4)

Eumulgin ^® B 2 Ceteareth-20 Cognis Eumulgin ^® B 3 Ceteareth-30 Cognis Genapol ^® UD 088 Cn-alcohol ethoxylated with about 8 Clariant

Molar equivalent of ethylene oxide

Brüggolit ^® FF7 contains about 65% 2-hydroxy-2-sulfinoessig- Brüggemann acid sodium salt

The raw materials were gradually mixed in 75 wt% water with stirring. Subsequently, the pH was adjusted and optionally filled with water to 100 wt .-%.

Table 1: Decolorizing agent

Raw material E1 E2 E3 E4 E5

[% By weight] [weight%] [weight%] [weight%] [weight%]

Brüggolit ^® FF7 10.0 10.0 10.0 10.0 10.0

Brij ^® 30 3.0 10.0 - - -

Eumulgin ⁴ ^D B2 - - 3.0 - -

Eumulgin ¹¹ ^Ö B3 - - - 3.0 -

Genapol ^® UD 088 - - - - 3.0

H ₃ PO ₄ ad pH 1, 5 ad pH 1, 5 ad pH 1, 5 ad pH 1, 5 ad pH 1, 5

Water ad 100 ad 100 ad 100 ad 100 ad 100 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 dyed, rinsed and stored for 24 hours at room temperature, after which the tress was immersed in 30 mL of a decolorizer of Table 1 for 30 minutes at room temperature, then thoroughly rinsed under running water for 3 minutes and air-dried ,

All hair strands showed after the decolorization procedure an excellent lightening and a small hair damage. The strands of hair 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. Tabeiie 2: surfactant-containing rinsing agent

Raw material BI B2 B3 B4

[Wt%] [wt%] [wt%] [wt%]

KH ₂ PO ₄ 5.0 5.0 5.0 5.0

EumulgirV ^S B2 - 10.0 - -

Eumulgin * ^δ B3 - - 10,0 -

Genapol ^® UD 088 - - - 10.0

H ₃ PO ₄ ad pH 2 ad pH 2 ad pH 2 ad pH 2

Water ad 100 ad 100 ad 100 ad 100

All strands of hair exhibited improved lightening compared to a strand of hair from Procedure 1 which was rinsed with water only. The hair damage is low. The strands of hair experienced no darkening even after 2 weeks of storage.

Claims

Patent claims

1. A color reductant comprising at least one sulfinic acid derivative of the formula (I) in a carrier

O Il MO-S-R (I)

wherein

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

(II) to (VI),

(IV)

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 (Ci 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 with two free ones

valences,

R ¹ and R ¹⁴ independently of one another represent a hydrogen atom, a (C ₁ to C ₆ ) -alkyl group or a carboxyalkyl group - (CH ₂ ) _m -COOM ", in M ^{11 is} 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 ) _O -COOM ¹ "with M ¹ " = 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 radical, an NNN-Tri ^ C _! ₆₎ to C - alkyl] ammonium (Ci to _C6) alkyl, carboxy (C ₂ alkenyl group to C _6), cyano (C ₆₎ alkyl to C or a (C ₁ to _CeJ-! AlkoxycarbonyKC _T to C ₆ ) alkyl group, an aliphatic or aromatic heterocycle which may be substituted, or a radical according to formula (IV) or

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 (d ₆ to C) - alkyl group, a Ca ^ oxy- (C ₁ -C ₆₎ alkoxy group or a group -N ⁺ R ¹ R ¹¹ R ¹ " with R ¹ _, R ¹¹ and R ¹ "are each independently a (C ₁ to C ₆ ) alkyl group, a (C ₂ to C ₆ ) alkenyl group, an ArVl (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, a (C ₁ to C ₆ ) alkoxy group, a hydroxy group, a Amino group, a carboxy group, a nitro group, a cyano group or a halogen atom,

R ^{10 is} a (C ₁ to C ₆ ) alkyl group, an optionally substituted

Aryl group, an optionally substituted heteroaryl group, a Ca ^ OXy- (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 CeJ-alkoxycarbonyKC _T to C ₆ ) -alkyl group,

R ^11, R represents a hydrogen atom, a (C ₁ to C ₆₎ alkyl group, a (C ₂ to C ₆₎ alkenyl group, a perfluoro (Ci to _C6) alkyl group ¹² and R ¹³ independently of one another, 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 Al yl (C ₁ to C ₆ ) alkyl group, a Ca ^ oxy (C ₁ to C ₆₎ alkyl group, a carboxy alkenyl (C ₂ to C ₆₎ or a (C ₁ -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 nonionic surfactant.

2. Composition according to claim 1, characterized in that in formula (I) M, M ', M "and M ¹ " independently represent a hydrogen atom, an ammonium ion, an alkali metal ion, for half an equivalent of an alkaline earth metal ion or half an equivalent a zinc ion, in particular a hydrogen atom, an ammonium ion, a sodium ion, a potassium ion, ^Λ a calcium ion, magnesium ion, or 14! 4 zinc ion.

3. Composition according to one of claims 1 or 2, characterized in that the radicals Y and Y 'of the formula (I) independently of one another represent a hydroxy group or a group -NH ₂ .

4. Composition according to one of claims 1 to 3, characterized in that the radical R is a group of formula (II).

5. Composition 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-yl) methanesulfinic acid, amino (1,3-thiazol-2-yl) methanesulfinic acid, amino (1,3-oxazol-2-yl) methanesulfinic acid, amino (1H-pyrrol-2-yl) methanesulfinic acid, amino (pyridine) 2-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 (quinolin-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 (thien-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-nitro-1 / - / - 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-methyl-pyridin-4-yl] -methanesulfinic acid, hydroxy (quinolin-2-yl) -methanesulfinic acid, hydroxy-quinoline-cyano-methanesulfinic acid, 1 / - / - 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-i, 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-sulfinobutansäure,

1-hydroxy-4-methoxy-4-oxobutan-1-sulfinic acid,

1-hydroxy-4-ethoxy-4-oxobutane-1-sulfinic acid,

4-hydroxy-4-sulfinopentansäure,

2-hydroxy-5-methoxy-5-oxopentan-2-sulfinic acid,

2-hydroxy-5-ethoxy-5-oxopentan-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-en-2-sulfinic acid,

2-hydroxy-5-ethoxy-5-oxopent-3-en-2-sulfinic acid,

5-hydroxy-5-sulfinopentansäure,

1-hydroxy-5-methoxy-5-oxopentan-1-sulfinic acid,

1-hydroxy-5-ethoxy-5-oxopentan-1-sulfinic acid,

5-hydroxy-5-sulfinohexansäure,

2-hydroxy-6-methoxy-6-oxo-hexane-2-sulfinic acid,

2-hydroxy-6-ethoxy-6-oxo-hexane-2-sulfinic acid,

4- [hydroxy (sulfino) methyl] benzoic acid,

4- [amino (sulfino) methyl] benzoic acid,

{4- [hydroxy (sulfino) 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) -methansulfinsäure,

(4-cyanophenyl) (amino) -methansulfinsäure,

(4-nitrophenyl) (hydroxy) -methansulfinsäure,

(4-nitrophenyl) (amino) -methansulfinsäure,

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) ethansulfinat,

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-sulfino-propionic acid,

2-amino-2-sulfino-propionic 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, -hydroxy-2-methoxy-2-oxoethanesulfinic acid, -hydroxy-2-ethoxy-2-oxoethanesulfinic acid, -amino-1-hydroxy-2-oxoethanesulfinic acid,

2- (dimethylamino) -1-hydroxy-2-oxoethansulfinsäure,

Hydroxy (sulfino) methanesulfonic acid,

Hydroxy (phenyl) methanesulfinic acid,

Hydroxy (4-hydroxyphenyl) methanesulfinic acid and Hydroxy (4-methoxyphenyl) methanesulfinic.

6. Composition according to one of claims 1 to 5, characterized in that it contains the sulfinic acid derivative in an amount of 0.01 to 20 wt .-%, particularly preferably from 1 to 20 wt .-%, each based on the weight of the composition , contains.

7. Composition according to one of claims 1 to 6, characterized in that the nonionic surfactant is selected from at least one member of the group which is formed from

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide:

- linear fatty alcohols containing 8 to 22 carbon atoms,

Fatty acids with 12 to 22 C atoms and

Alkylphenols having 8 to 15 C atoms in the alkyl group, C ₂ -C ₂₂ -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide onto polyols having 3 to 6 carbon atoms, in particular to glycerol,

- methyl glucoside fatty acid ester,

- fatty acid alkanolamides and

- fatty acid glucamides,

Partial esters of polyols having 3 to 6 carbon atoms with fatty acids having 8 to 22 carbon atoms, sterols, fatty acid esters of sugars and sugar alcohols (such as sorbitol), Polyglycerols and polyglycerol derivatives (such as

Polyglycerol poly-12-hydroxystearate (commercial product Dehymuls ^® PGPH)),

Phosphoric acid esters with (C ₈ to C ₂₂ ) fatty alcohols, with their

Ethoxylates / propoxylates, with (C ₈ to C ₂₂ ) alkylphenolethoxylates, with (C ₈ to

C ₂₂ ) alkylphenol propoxylates,

(C ₈ to C ₂₂ ) fatty acid-protein condensates, nonionic silicone surfactants.

8. Composition according to one of claims 1 to 7, characterized in that it contains the nonionic surfactants in an amount of 0.1 to 25 wt .-%, in particular 0.5 to 15 wt .-%, each based on the total agent , contains.

9. Composition according to one of claims 1 to 8, characterized in that the weight ratio of the sulfinic acid derivatives of the formula (I) to the nonionic surfactants of 1 to 2000 to 10 to 1, particularly preferably from 1 to 200 to 2.5 to 1, most preferably from 1 to 50 to 1 to 1.

10. Composition according to one of claims 1 to 9, characterized in that it additionally contains at least one compound selected from the aldehydes or the ketones.

11. Composition according to claim 10, characterized in that the compounds selected from the aldehydes or ketones in an amount of 0.1% by weight to 20 wt .-%, in particular from 0.5 wt .-% to 10 % By weight, based in each case on the weight of the ready-to-use agent.

12. Composition according to one of claims 1 to 11, characterized in that it has a pH of pH 1 to pH 9, in particular from pH 1, 5 to pH 6, has.

13. Composition according to one of claims 1 to 12, characterized in that it additionally contains at least one reductone.

14. Composition 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.

15. Use of a composition according to any one of claims 1 to 14 for the decolorization of substrates which are colored with natural and / or synthetic dyes.

16. Use according to claim 15, characterized in that the substrate contains synthetic fibers and / or natural fibers.

17. Use according to one of claims 15 or 16, characterized in that the natural fibers are selected from cellulose-containing fibers, in particular cotton, and keratin-containing fibers, in particular animal or human hair.

18. Use according to any one of claims 15 to 17, characterized in that the synthetic fibers are selected from polyester, polyamide, elastane, viscose or polyacrylic.

19. Use according to any one of claims 15 to 19, characterized in that the substrates to be decolored are dyed with oxidation dyes and / or substantive dyes.

20. A process for the reductive decolorization of natural and / or synthetic dyes colored substrates, characterized in that an agent according to any one of claims 1 to 14 is applied to the dyed substrate and rinsed again after a contact time.

21. The method according to claim 20, characterized in that the substrate contains synthetic fibers and / or natural fibers.

22. The method according to claim 21, characterized in that the natural fibers are selected from cellulosic fibers, in particular cotton, and keratin fibers, in particular animal or human hair.

23. The method according to any one of claims 20 to 22, characterized in that the synthetic fibers are selected from polyester, polyamide, elastane, viscose or polyacrylic.

24. The method according to any one of claims 20 to 23, characterized in that the substrates to be decolored with oxidation dyes and / or substantive dyes are colored.