EP1996293A2 - Décoloration réductive - Google Patents

Décoloration réductive

Info

Publication number
EP1996293A2
EP1996293A2 EP07723364A EP07723364A EP1996293A2 EP 1996293 A2 EP1996293 A2 EP 1996293A2 EP 07723364 A EP07723364 A EP 07723364A EP 07723364 A EP07723364 A EP 07723364A EP 1996293 A2 EP1996293 A2 EP 1996293A2
Authority
EP
European Patent Office
Prior art keywords
hydroxy
acid
group
amino
methanesulfinic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07723364A
Other languages
German (de)
English (en)
Inventor
Burkhard Müller
Inge Neubueser
Wibke Gross
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=38522781&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1996293(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from DE102006013260A external-priority patent/DE102006013260A1/de
Priority claimed from DE200610022214 external-priority patent/DE102006022214A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP10177134.3A priority Critical patent/EP2277598B1/fr
Publication of EP1996293A2 publication Critical patent/EP1996293A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4986—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with sulfur as the only hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4933—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having sulfur as an exocyclic substituent, e.g. pyridinethione
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/08—Preparations for bleaching the hair
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/30—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using reducing agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/62—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
    • D06P1/621—Compounds without nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/62—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
    • D06P1/621—Compounds without nitrogen
    • D06P1/622—Sulfonic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/62—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
    • D06P1/628—Compounds containing nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/13—Fugitive dyeing or stripping dyes
    • D06P5/134—Fugitive dyeing or stripping dyes with reductants
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/15—Locally discharging the dyes
    • D06P5/155—Locally discharging the dyes with reductants
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/32—Bleaching agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/09—Sulfur-containing compounds

Definitions

  • 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.
  • a process for decolorization of colored substrates, as well as the use of said color proofing agent is the subject of the invention.
  • the dye 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.
  • natural dyes such as purple or carmine were used.
  • oxidation dyes are generally suitable for dyeing, for example, paper, textiles or keratin fibers.
  • 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.
  • m-phenylenediamine derivatives naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used.
  • Suitable coupler substances are in particular ⁇ -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-dimeth
  • 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.
  • 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.
  • 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.
  • 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.
  • the reductive decolorants require an improvement in decolorization performance.
  • reductive sulfur compounds for decolorization.
  • dithionites or derivatives of 1-hydroxymethylsulfinic acid or of 1-aminomethylsulfinic acid are suitable as reducing agents.
  • 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.
  • 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.
  • the reducing agents used in the decolorizing agents for a cosmetic use should be physiologically acceptable and toxicologically harmless.
  • 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 compositions according to the invention are particularly suitable for the fiber-sparing decolorization of keratin-containing fibers.
  • 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)
  • M represents a hydrogen atom or one equivalent of a mono- or polyvalent one
  • R is derived from a peptide or a radical according to one of the formulas (II) to (VI),
  • 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,
  • X is a direct bond or an organic radical with two free ones
  • 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 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 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 sur
  • 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.
  • the radicals M, M ', M "and / or M 1 " represent a hydrogen atom.
  • 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
  • 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.
  • M ' z + the group: 1 / z (M ' z + ) O-.
  • 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.
  • 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.
  • the anions are symbolized as " anols.” They are preferably selected from halide, / 2 Suifat, hydrogen sulfate, Vz carbonate, hydrogen carbonate, 1/3 phosphate, ⁇ A hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate.
  • the anion is particularly preferably chloride, bromide, p-toluenesulfonate or hydrogen sulfate.
  • R is a radical of the above formulas (II) to (VI).
  • radical R of the formula (I) is a radical of the abovementioned formula (II)
  • the preferred sulfinic acid derivative of the formula (Ia) according to the invention results from the formula (I) as the preferred first embodiment
  • 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.
  • the radical R 2 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)
  • 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.
  • Z 1 is an oxygen atom
  • Z 2 is a group CH
  • Y is a hydroxyl group
  • 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.
  • 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,
  • 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 v ⁇ 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 .
  • 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,
  • radical R 7 is a carboxy group, a sulfonic acid group or a group.
  • 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
  • Hydroxyalkyl group and the radicals R 8 and R 9 represent a hydrogen atom.
  • Preferred compounds of the formula (Ia-8) according to the invention are those in which Y is a hydroxy or amino group.
  • 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,
  • 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.
  • 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.
  • 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,
  • 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 ' 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 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.
  • 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
  • radicals R according to formula (IV) 1 are selected from 4-cyanophenyl, 4-carboxyphenyl, 4-carboxymethyloxy and 4-trimethylammoniophenyl.
  • 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
  • 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
  • (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.
  • the groups or radicals mentioned as substituents in the context of this application are mentioned.
  • (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.
  • the groups or radicals mentioned as substituents in the context of this application are mentioned.
  • (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.
  • the groups or radicals mentioned as substituents in the context of this application are mentioned.
  • 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.
  • Butoxycarbonylpropyl and 3-tert-butoxycarbonylpropyl groups are examples of (C 1 to
  • cyano (C 1 to C 6 ) alkyl groups are cyanomethyl, 2
  • 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-
  • Methoxyhexyl distr 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,
  • Benzothiazolyl benzoxazolyl, indolyl, quinolinyl, quinoxalinyl and quinazolinyl.
  • the trifluoromethyl and pentafluoroethyl groups are preferred PePfIuOr (C 1 to C 6 ) alkyl groups.
  • 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
  • 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.
  • 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:
  • 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.
  • 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 :
  • alkyl (oligo) glucosides for example, the commercially available product ® Montanov 68
  • Fettkladreestern of sugars and sugar alcohols such as sorbitol
  • polyglycerols and polyglycerol derivatives such as polyglycerol poly-12-hydroxystearate (commercial product Dehymuls ® PGPH)
  • polyglycerol poly-12-hydroxystearate commercial product Dehymuls ® PGPH
  • both products with a "normal” homolog distribution and those with a narrow homolog distribution can be used.
  • "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.
  • Preferred alkyl polyglycosides obey the general formula (T1),
  • 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.
  • 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 .
  • these compounds are prepared starting from natural fats and oils or mineral oils.
  • the alkyl radicals R 1 are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds.
  • 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.
  • sugar unit Z according to formula (T1) any mono- or oligosaccharides can be used.
  • 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.
  • 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.
  • 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.
  • 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),
  • 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
  • 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.
  • 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):
  • 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,
  • 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.
  • 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).
  • dimethicone copolyols according to the invention are Dow Corning 190 and Dow Corning 193.
  • 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.
  • 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
  • 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 ⁇ -oxocarboxylic acids, ⁇ -oxocarboxylic acids, ⁇ -oxocarboxylic acids and ⁇ -oxocarboxylic acids of the formula (XII) or salts thereof,
  • 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.
  • cyclic, linear or branched aliphatic aldehydes are aliphatic aldehydes whose formyl group (s) are not in conjugation with an aromatic ⁇ -electron system.
  • the corresponding aldehydes may carry aromatic radicals as long as the ⁇ -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-
  • cyclic, linear or branched aliphatic ketones are aliphatic ketones whose keto group (s) are not in conjugation with an aromatic ⁇ -electron system.
  • the corresponding ketones may carry aromatic radicals as long as the ⁇ -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-
  • 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.
  • 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
  • Preferred alicyclic, aromatic or heterocyclic aldehydes are preferably selected from at least one member of the group
  • 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-dieth
  • 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.
  • 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 ⁇ 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.
  • 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.
  • aqueous cosmetic carrier contains at least 50% by weight of water.
  • 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.
  • 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.
  • 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,
  • anionic polymers for example polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone
  • Structurants such as pantholactone, maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example soya lecithin,
  • 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, ⁇ -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.
  • 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.
  • developer components used to color the substrate can serve as downstream developer components.
  • 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;
  • a halogen atom such as a chlorine, bromine, iodine or fluorine atom
  • a C 1 - to C 4 -alkyl radical such as a chlorine, bromine, iodine or fluorine atom
  • a C 1 - to C 4 -alkyl radical such as a chlorine, bromine, iodine or fluorine atom
  • 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 ⁇ , ⁇ -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- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- ( ⁇ -hydroxyethyl) -amino-2- methylaniline, 4-N
  • Very particularly preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 2- ( ⁇ , ⁇ -dihydroxyethyl) -p-phenylenediamine and N, N bis (.beta.-hydroxyethyl) -p-phenylenediamine.
  • the dyeing of the substrate 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.
  • 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:
  • 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
  • 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
  • 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.
  • Preferred binuclear developer components of the formula (E2) are, in particular: N, N'-bis- ⁇ -hydroxyethyl-N, N'-bis-C'-aminophenyl J-IS-diamino-propane, -ol, N, N'-bis- ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis ( ⁇ -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,
  • 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.
  • p-aminophenol derivatives of the formula (E3) 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)
  • 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.
  • 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- ( ⁇ -hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino 2-aminomethylphenol, 4-amino-2- ( ⁇ -hydroxyethyl-aminomethyl) phenol, 4-amino-2- ( ⁇ , ⁇ -dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2-fluorophenol, 4-amino-2 chlorophenol, 4-amino-2,6-
  • Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- ( ⁇ , ⁇ -dihydroxyethyl) phenol and 4-amino 2- (diethylaminomethyl) -phenol.
  • 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.
  • 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- ( ⁇ -
  • 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-ter
  • 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
  • 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.
  • 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.
  • an oxidative dye which additionally contains at least one coupler component in addition to at least one developer component.
  • 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
  • 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,
  • 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.
  • 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.
  • 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,
  • 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
  • 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.
  • 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.
  • 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
  • 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.
  • 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- ( ⁇ -hydroxyethyl) -amino-2-nitrobenzene, 3-nitro-4- ( ⁇ -hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'--
  • the substrates to be decolored may preferably be colored with a cationic substantive dye. Particularly preferred are
  • Preferred cationic substantive dyes of group (c) are in particular the following compounds:
  • the compounds of the formulas (DZ1), (DZ3) and (DZ5) are very particularly preferred cationic substantive dyes of group (c).
  • the cationic direct dyes which are sold under the trademark Arianor ® are, according to the invention particularly preferred substantive dyes.
  • 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.
  • the hair is rinsed out, wherein preferably a surfactant-containing agent, such as a cleaning agent or a shampoo, applies.
  • a surfactant-containing agent such as a cleaning agent or a shampoo
  • 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.
  • anionic group such as.
  • glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule.
  • 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),
  • 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
  • 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 s
  • Nonionic surfactants contain as hydrophilic group z.
  • a polyol group for example, a polyalkylene glycol ether or a combination of polyol and polyglycol ether group.
  • Such compounds are, for example
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • those dyes were preferably used, as we defined them in the second subject of the invention.
  • the decolorizing agents according to the invention according to Table 1 were provided. The following raw materials were used:
  • 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 .-%.
  • 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 ,
  • Oxigenta ® (6 wt .-% hydrogen peroxide, Schwarzkopf
  • a hair tress dyed with the oxidative hair color according to Experiment 1 was immersed in 30 mL of one of the decolorizing agents of Table 1 over an exposure time of 30 minutes at room temperature.
  • 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

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Abstract

La présente invention concerne des agents qui contiennent dans un excipient une combinaison de dérivés spéciaux d'acide sulfinique de formule (I), dans laquelle M représente un atome d'hydrogène ou un équivalent d'un cation monovalent ou multivalent et R est dérivé d'un peptide ou représente un radical selon une des formules (II) à (VI) (Pour la signification des constituants restants, voir la revendication 1), et au moins un tensioactif non ionique. Ces agents permettent une décoloration durable de substrats teints, sans que lesdits substrats décolorés foncent ultérieurement. Pendant le processus de décoloration, la structure du substrat est épargnée.
EP07723364A 2006-03-21 2007-03-19 Décoloration réductive Withdrawn EP1996293A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10177134.3A EP2277598B1 (fr) 2006-03-21 2007-03-19 Décoloration réductive

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102006013260A DE102006013260A1 (de) 2006-03-21 2006-03-21 Organische Sulfinsäurederivate
DE200610022214 DE102006022214A1 (de) 2006-05-11 2006-05-11 Reduktiver Farbabzug
PCT/EP2007/002396 WO2007107308A2 (fr) 2006-03-21 2007-03-19 Décoloration réductive

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP10177134.3A Division EP2277598B1 (fr) 2006-03-21 2007-03-19 Décoloration réductive

Publications (1)

Publication Number Publication Date
EP1996293A2 true EP1996293A2 (fr) 2008-12-03

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Family Applications (2)

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EP10177134.3A Not-in-force EP2277598B1 (fr) 2006-03-21 2007-03-19 Décoloration réductive
EP07723364A Withdrawn EP1996293A2 (fr) 2006-03-21 2007-03-19 Décoloration réductive

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EP10177134.3A Not-in-force EP2277598B1 (fr) 2006-03-21 2007-03-19 Décoloration réductive

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EP (2) EP2277598B1 (fr)
WO (1) WO2007107308A2 (fr)

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Also Published As

Publication number Publication date
EP2277598B1 (fr) 2017-08-02
WO2007107308A2 (fr) 2007-09-27
WO2007107308A3 (fr) 2008-05-15
EP2277598A1 (fr) 2011-01-26

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