DE102012219405A1 - Use of metal complexes with nitrogen-acylated siderophore ligands e.g. for enhancing oxidizing power of inorganic peroxygen compounds in oxidizing-, washing-, cleaning- or disinfecting solutions - Google Patents

Abstract

Use of metal complexes with nitrogen-acylated siderophore ligands for enhancing oxidizing power of inorganic peroxygen compounds in oxidizing-, washing-, cleaning- or disinfecting solutions, is claimed. Independent claims are also included for: (1) a washing-, cleaning- or disinfecting agent comprising the metal complex with the nitrogen-acylated siderophore ligands; (2) washing textiles or cleaning hard surfaces in presence of a peroxygen bleaching agent and the metal complex with the nitrogen-acylated siderophore ligand; and (3) the complex of nitrogen-acylated siderophore with silver, aluminum, gold, boron, bismuth, cerium, cobalt, copper, gallium, mercury, manganese, molybdenum, nickel, lead, platinum, ruthenium, titanium, uranium, vanadium and/or zinc, preferably manganese, vanadium, copper, molybdenum, cerium and/or bismuth.

Description

The present invention relates to the use of complexes of acylated siderophores to enhance the oxidizing power of peroxygen compounds, in particular for bleaching paint stains when washing textiles, as well as detergents, cleaners and disinfectants containing such a complex or an acylated siderophore.

Inorganic peroxygen compounds, particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes. The oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H ₂ O ₂ or alkali perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles. At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by addition of so-called bleach activators which are able to provide peroxycarboxylic under the abovementioned perhydrolysis and for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example several times acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic anhydrides, in particular phthalic anhydride and alkylsuccinic anhydrides, carboxylic esters, in particular sodium nonanoyloxybenzenesulphonate, sodium isononanoyloxy Benzenesulfonate, O-acylated sugar derivatives, such as pentaacetyl glucose, and N-acylated lactams, such as N-benzoyl-caprolactam, have become known in the literature. By adding these substances, the bleaching action of aqueous peroxide liquors can be increased so much that even at temperatures around 60 ° C substantially the same effects as with the peroxide solution alone at 95 ° C occur.

In the search for energy-saving washing and bleaching processes in recent years application temperatures well below 60 ° C, especially below 45 ° C down to the cold water temperature in importance.

At low temperatures, the effect of the previously known activator compounds usually decreases noticeably.

As an alternative to the bleach activators, the use of metal complexes as bleach catalysts has been proposed on various occasions. As bleach catalysts in particular metal complexes of organic ligands such as salenes, Saldiminen, tris [salicylideneaminoethyl] amines, monocyclic polyazaalkanes, cross-bridged polycyclic polyazaalkanes, terpyridines and tetraamido ligands are described. However, a disadvantage of such metal complexes is that they either have only an unsatisfactory bleaching performance, in particular at low temperature, or, in the case of sufficient bleaching performance, undesired damage to paints and possibly even textile fibers occurs.

In addition, the production of complex ligands of an organic nature is conventionally based on non-renewable raw materials such as crude oil and coal. These production methods have the disadvantage of reducing irretrievable resources, so that they are no longer available for subsequent generations.

From the international patent application WO 2008/101909 A1 For example, the use of siderophore metal complexes as bleach catalysts and detergents and cleaners containing such siderophore metal complexes are known. These complexes have the advantage that their ligands can be generated entirely from renewable raw materials.

Siderophores are complex ligands which are released by microorganisms to firmly bind iron (III) ions and then to transport the loaded complex into the cell, with the aim of accessing the iron important for the metabolism. The complexation of the iron here serve different functional groups such as catecholate groups, salicylate groups, hydroxamate groups, oxazole rings, thiazole rings, citrate hydroxamate groups, alpha-keto-carboxylate groups, alpha-hydroxy carboxylate groups or carboxylic acid amide groups, of which two or more are usually present in the molecule. Because siderophores are naturally occurring products, they can be easily and inexpensively made from renewable resources, for example, by culturing suitable microorganisms in appropriate media and separating the siderophores they have removed. The fact that Siderophores can be eagerly imported and utilized by countless microorganisms, proving that they have good biodegradability, which is a particular advantage for corresponding bleach catalysts, which end up in the environment after completion of their application process as constituents of the wastewater. Siderophores and metal complexes containing siderophores, such as desferrioxamine B as ligands, can be used as in WO 2008/101909 A1 and the prior art cited therein.

Surprisingly, it has been found that complexes with certain siderophore derivative ligands have a stronger bleach catalyst activity than complexes with the siderophore ligand.

The invention relates to the use of metal complexes with N-acylated siderophore ligands for enhancing the oxidizing power of inorganic peroxygen compounds in particular in oxidation, washing, cleaning or disinfecting solutions.

The present invention achieves an improvement in the oxidation and bleaching action of peroxygen compounds, especially at low temperatures in the range of about 15 ° C to 45 ° C. Further objects of the invention are therefore the use of metal complexes with N-acylated siderophore ligands, in particular in combination with peroxygen compound, for enhancing the cleaning performance of detergents, cleaners or disinfectants in aqueous, especially surfactant-containing liquor, and a process for washing in particular cotton-containing textiles or for cleaning hard surfaces, especially those of dishes, in the presence of a pers oxygen-containing bleach which is carried out in the presence of a metal complex with an N-acylated siderophore ligand. The methods mentioned can be carried out manually or with the aid of conventional washing machines or dishwashers; they are essentially based on bringing the object to be washed or cleaned or at least the soiled part of its surface into contact with an aqueous, in particular surfactant-containing, liquor a detergent or cleaning agent, diluted with water or as such, applied to the object or at least the soiled part of its surface and then optionally washed off.

Another object of the present invention is a washing, cleaning or disinfecting agent containing a metal complex with an N-acylated siderophore ligand. If appropriate, said complex can also be generated only during the use of the agent in aqueous systems, so to speak in situ, from the ligand and the central atom to be complexed. Another object of the present invention is therefore a washing or cleaning agent containing a metal salt and an N-acylated siderophore. If the water intended for the use of the washing or cleaning agent contains metal ions or if the hard surfaces or textile fabrics to be cleaned have metal-containing soiling, the washing or cleaning agent may also lack the metal salt. Another object of the invention is therefore a washing or cleaning agent containing an N-acylated siderophore. Further objects of the invention are complexes of the N-acylated siderophores with Ag, Al, Au, B, Bi, Ce, Co, Cu, Ga, Hg, Mn, Mo, Ni, Pb, Pt, Ru, Ti, U, V and Zn and mixtures thereof, in particular with Mn, V, Cu, Mo, Ce and Bi and mixtures thereof.

Pyoverdin, Ornibactin, Chrysobactin, Exochelin MN, Tenacibactin D, Desferribactin, Fusarinin C, Myxochelin B, Desferrimycin A, sowie auch die sekundäre Aminogruppen enthaltenden Siderophore Yersiniabactin, Salmycin B und Petrobactin und Mischungen aus diesen. Unabhängig davon, ob im voranstehenden oder nachfolgenden Text zur Bezeichnung des Liganden das Desferrisiderophor oder das Siderophor genannt ist, soll damit die eisenfreie Siderophorform gemeint sein. Das bevorzugt für die N-Acylierung eingesetzte Desferrioxamin B ist ein offenkettiger Verwandter des makrocyclischen Lactams Desferrioxamin E, es weist die nachstehend wiedergegebene Formel auf:

Bevorzugte Ausführungsformen aller Aspekte der vorliegenden Erfindung betreffen den Einsatz von N-acyliertem Desferrioxamin B. The N-acylated siderophore ligands are accessible by acylation of naturally occurring or synthetically produced siderophores. A corresponding Aylierungsverfahren is known from the patent BE 616 139 known. In order for the siderophore to be N-acylated, it has a primary or optionally a secondary amino group which is not part of an amide bond. Examples of such siderophores are Desferrioxamine A ₁ , A ₂ , G and B, which in their biosynthesis sometimes occurring and partially secreted intermediates such

Pyoverdin, ornibactin, chrysobactin, exochelin MN, tenacibactin D, desferribactin, fusarinine C, myxochelin B, desferrimycin A, as well as the secondary amino group-containing siderophores yersiniabactin, salmycin B and petrobactin and mixtures thereof. Irrespective of whether the desferrisiderophore or the siderophore is mentioned in the preceding or following text to designate the ligand, this is intended to mean the iron-free siderophore form. The preferred desferrioxamine B used for the N-acylation is an open-chain relative of the macrocyclic lactam desferrioxamine E, having the formula given below:

Preferred embodiments of all aspects of the present invention relate to the use of N-acylated desferrioxamine B.

When the siderophores contain hydroxamate groups, acylation with reagents common for this reaction, such as acid chlorides, also leads to O-acylations in addition to the desired N-acylation. This can lead to deterioration of the complexing properties. By reaction with primary alkylamines or preferably ammonia, the O-acyl radicals can be removed. From desferrioxamine B is obtained by reaction with an excess of acyl chloride (RC (O) Cl) and subsequent ammonolysis of per- or at least multiacylated intermediates at the terminal N-atom acylated compounds of the formula RC (O) -NH (CH ₂ ) ₅ - (N (OH) -C (O) -CH ₂ CH ₂ -C (O) -NH- (CH ₂ ) ₅ ) ₂ -N (OH) -C (O) CH ₃ .

The acyl groups are selected from the radicals RC (O) -, in which R is preferably a linear, branched or cyclic alkyl or alkenyl group having up to 20, in particular 1 to 12 C atoms or an aryl, aralkyl or alkaryl group with 3 to 20, in particular 5 to 15 C atoms, where the alkyl or alkenyl groups may be interrupted by 1 or more heteroatoms, in particular by -O- or -NH-, and the aryl groups may have 1 to 3 heteroatoms, in particular N atoms , may contain. Most preferably, the acyl group is selected from the group consisting of benzoyl, C _1-12 alkyl-substituted benzoyl, such as 4-octylbenzoyl, octanoyl, nonanoyl, decanoyl, decenoyl, undecanoyl, undecenoyl, and mixtures thereof.

The central atom of the N-acylated siderophore ligand complex used according to the invention is preferably selected from Ag, Al, Au, B, Ce, Co, Cu, Fe, Ga, Hg, Mn, Mo, Ni, Pb, Pt, Ru, Ti , U, V and Zn and mixtures thereof, wherein the metal can be present in any desired oxidation states, in particular of Ag (I), Al (III), Au (III), B (III), Co (II), Co (III) , Cu (I), Cu (II), Ga (III), Hg (II), Mn (II), Mn (III), Ni (II), V (IV), V (V), Fe (II) , Fe (III), Ce (III), Bi (III), Pb (II), Pt (II), U (IV) and Zn (II) and mixtures thereof. More preferably, it is a metal atom selected from the group consisting of Mn, Co, Bi, Mo, Ce, Ti, V and Cu, especially of Co and Mn, in any oxidation states. In a particularly preferred embodiment, the central atom of the N-acylated siderophore ligand complex is selected from Co (II), Co (III), Mn (II) and Mn (III).

If the coordination sites of the metal atom are not completely occupied by the presence of 1 or more N-acylated siderophore ligands, the complex used according to the invention may contain further co-ligands. In question, both inorganic and organic compounds are suitable, in addition to carboxylates in particular compounds having primary, secondary and / or tertiary amine and / or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, triazole, 2,2'-bispyridylamine, tris (2-pyridylmethyl) amine, 1,4,7-triazacyclononane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-trimethyl-1, 5,9-triazacyclododecane, (bis ((1-methylimidazol-2-yl) -methyl)) - (2-pyridylmethyl) -amine, N, N'- (bis (1-methylimidazol-2-yl) - methyl) ethylenediamine, N-bis (2-benzimidazolylmethyl) aminoethanol, 2,6-bis (bis (2-benzimidazolylmethyl) aminomethyl) -4-methylphenol, N, N, N', N'-tetrakis (2-benzimidazolylmethyl) -2-hydroxy-1,3-diaminopropane, 2,6-bis (bis (2-pyridylmethyl) aminomethyl) -4-methylphenol, 1,3-bis (bis (2-benzimidazolylmethyl) ) aminomethyl) benzene, sorbitol, mannitol, erythritol, adonitol, inositol, lactose, and optionally substituted salene, porphins and porphyrins n. The inorganic neutral ligands include in particular ammonia and water. If not all coordination sites of the transition metal central atom are occupied by neutral ligands, the complex contains further, preferably anionic and among these in particular mono- or bidentate ligands. These include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO ₂ ) ^- group, that is, a nitro ligand or a nitrito ligand. The (NO ₂ ) ^- group may also be chelated to the metal or it may asymmetrically bridge two transition metal atoms or η ¹ -O-bridge. In addition to the ligands mentioned, the metal complexes may carry further, generally simpler ligands, in particular mono- or polyvalent anion ligands. In question, for example, nitrate, actetate, trifluoroacetate, formate, carbonate, citrate, oxalate, perchlorate and complex anions such as hexafluorophosphate. The anion ligands should provide charge balance between the transition metal central atom and the ligand system. The presence of oxo ligands, peroxo ligands and imino ligands is also possible. In particular, such ligands can also act bridging, so that polynuclear complexes arise. In the case of bridged, polynuclear or polynuclear complexes, not all or all of the metal atoms in the complex must be the same. The use of bi- or polynuclear complexes in which the metal central atoms have different oxidation numbers is also possible. If anion ligands are missing or the presence of anionic ligands does not result in charge balance in the complex, anionic counterions which neutralize the cationic transition metal complex are present in the metal complex compounds. These anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, oxalate, benzoate or citrate.

A metal complex with N-acylated siderophore ligands, especially in combination with a peroxygen compound, is preferably used for bleaching paint stains during the washing of textiles, in particular in aqueous, surfactant-containing liquor. The phrase "bleaching of color stains" is to be understood in its broadest sense and includes both the bleaching of dirt present on the textile, the bleaching of debris located in the wash liquor, and the deoxidation of the wash liquor in the wash liquor Textile dyes that detach under the washing conditions of textiles before they can be applied to different colored textiles.

Another preferred embodiment of the invention is the use of a metal complex with N-acylated siderophore ligand, especially in combination with a peroxygen compound, in hard surface cleaning solutions, especially for dishes, for bleaching stained stains, for example tea. Here too, the term bleaching is understood as meaning both the bleaching of dirt on the hard surface, in particular tea, and the bleaching of dirt removed from the hard surface in the dishwashing liquor.

Further objects of the invention are detergents, cleaners and disinfectants containing a metal complex with N-acylated siderophore ligands.

Within the context of a use according to the invention, the metal complex with N-acylated siderophore ligand can be used wherever a particular increase in the oxidation effect of the peroxygen compounds at low temperatures is required, for example in the bleaching of textiles or hair, in the oxidation of organic or inorganic Intermediates, in the production of pulp and in disinfection.

Essentially, the use of the present invention is to provide conditions under which the peroxygen compound and the complex can react with one another, with the aim of obtaining more strongly oxidizing secondary products. Such conditions are especially present when the reactants meet in aqueous solution. This can be done by separately adding the peroxygen compound and the metal complex with N-acylated siderophore ligand to an optionally washing or detergent-containing solution. However, the process according to the invention is particularly advantageously carried out using a washing, cleaning or disinfecting agent which comprises said metal complex with N-acylated siderophore ligand and optionally a peroxidic oxidizing agent. The peroxygen compound may also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, when a peroxygen-free agent is used. In agents according to the invention are preferably 0.001 wt .-% to 5 wt .-%, in particular 0.01 wt .-% to 1 wt .-% and particularly preferably 0.05 wt .-% to 0.5 wt .-% metal complex containing N-acylated siderophore ligand.

Depending on the intended use, the conditions of use can be varied widely. Thus, in addition to purely aqueous solutions and mixtures of water and suitable organic solvents as the reaction medium in question. The amounts of peroxygen compounds are generally chosen so that in the solutions between 10 ppm and 10% active oxygen, preferably between 50 and 5000 ppm of active oxygen are present.

The detergents, cleaners and disinfectants according to the invention, which may be present as particularly pulverulent solids, in densified particle form, as homogeneous solutions or as suspensions or dispersions, may in principle contain all known ingredients customary in such agents, apart from the bleach-intensifying compound used according to the invention. The detergents and cleaners according to the invention may in particular be builders, surface-active surfactants, organic and / or inorganic peroxygen compounds, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, grayness inhibitors, dye transfer inhibitors, foam regulators, additional peroxygen Activators and dyes and fragrances included.

A disinfectant according to the invention may contain conventional antimicrobial active ingredients in addition to the previously mentioned ingredients to enhance the disinfecting action against special germs. Such antimicrobial additives are preferably not more than 10% by weight, particularly preferably from 0.1% by weight to 5% by weight, in the disinfectants according to the invention.

Suitable peroxygen compounds are organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid, monoperoxyphthalic acid, and diperdodecanedioic acid and salts thereof, such as magnesium monoperoxyphthalate, hydrogen peroxide and inorganic salts releasing hydrogen peroxide under the conditions of purification, such as perborate, percarbonate and / or persilicate, and hydrogen peroxide inclusion compounds , such as H ₂ O ₂ -urea adducts, into consideration. Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. The peroxygen compounds can be added to the washing or cleaning liquor as such or in the form of these containing agents, which may in principle contain all conventional detergents, cleaners or disinfectant ingredients. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate or hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide. If a washing or cleaning agent according to the invention contains peroxygen compounds, these are present in amounts of preferably up to 35% by weight, in particular from 1% by weight to 30% by weight and more preferably from 7% by weight to 20% by weight. % present, while in disinfectants according to the invention preferably from 0.5 wt .-% to 40 wt .-%, in particular from 5 wt .-% to 20 wt .-%, of peroxygen compounds are included.

If desired, in the context of the invention, in addition to the metal complex with N-acylated siderophore ligands, peroxocarboxylic acid-yielding compounds can also be used under perhydrolysis conditions, although the bleach-improving action of the metal complex with N-acylated siderophore ligand also occurs in their absence. Compounds which give peroxocarboxylic acid under perhydrolysis conditions can in particular be compounds which give perbenzoic acid which is optionally substituted under perhydrolysis conditions and / or aliphatic peroxycarboxylic acids having 1 to 12 C atoms, in particular 2 to 4 C atoms, alone or in mixtures. Suitable are the bleach activators cited at the beginning, which carry O- and / or N-acyl groups, in particular of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids of these, especially nonanoyl or Isononanoyl- or Lauroyloxybenzolsulfonat (NOBS or iso-NOBS or LOBS) or Decanoyloxybenzoat (DOBA), their formal carbonic ester derivatives such as 4- (2-decanoyloxyethoxycarbonyloxy) benzenesulfonate (DECOBS), acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, and acetylated sorbitol and mannitol and mixtures thereof (SORMAN), acylated sugar derivatives, in particular Pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose, acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam. A washing, cleaning or disinfecting agent according to the invention preferably contains from 0.01% by weight to 10% by weight, in particular from 1% by weight to 8% by weight, of peroxycarboxylic acid-yielding compound under perhydrolysis conditions.

The metal complex with N-acylated siderophore ligand, as well as, if desired, the peroxygen compound, can be adsorbed to carriers in a manner known in principle and / or embedded in encapsulating substances. In particular, by wrapping can be achieved in addition to a generally improved storage stability that the formation of bleaching active species takes place, but the formation only after Release from the wrapping material, so that other detergent ingredients, such as enzymes, can exert their effect without being affected by bleach-active species can.

The compositions of the invention may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof come into question. Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form. Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation. Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkane sulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from the sulfonation of fatty acid methyl or ethyl esters.

Such surfactants are in the cleaning or washing agents according to the invention in proportions of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%, while the inventive disinfectants as well as inventive compositions for cleaning dishes preferably 0.1 wt .-% to 20 wt .-%, in particular 0.2 wt .-% to 5 wt .-% surfactants containing.

An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), Ethylenediaminetetrakis (methylenephosphonic acid), lysine tetra (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, especially by oxidation of polysaccharides accessible polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. The relative average molecular weight (here and hereinafter: weight average) of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50 000 g / mol to 120 000 g / mol, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 to 100,000. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight.

As water-soluble organic builders, it is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ -carboxylic acid and preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ -dicarboxylic acid, with maleic acid being particularly preferred. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, preferred are vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example C ₁ -C ₄ carboxylic acids, with vinyl alcohol. Preferred polymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate. All Polymers in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2, are particularly preferred. 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted. Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate. This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Particularly preferred is sucrose. The use of the third monomer presumably incorporates predetermined breaking points into the polymer which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol. Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. The organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

If desired, such organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in paste-form or liquid, in particular water-containing, agents according to the invention.

Suitable water-soluble inorganic builder materials are, in particular, polyphosphates, preferably sodium triphosphate. As water-insoluble inorganic builder materials are in particular crystalline or amorphous, water-dispersible alkali metal aluminosilicates, in amounts not exceeding 25 wt .-%, preferably from 3 wt .-% to 20 wt .-% and in particular in amounts of 5 wt .-% to 15 wt. -% used. Among these, the detergent-grade crystalline sodium aluminosilicates, particularly zeolite A, zeolite P, and zeolite MAP, and optionally zeolite X, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Their calcium binding capacity is generally in the range of 100 to 200 mg CaO per gram.

In addition to or as an alternative to said water-insoluble aluminosilicate and alkali carbonate, further water-soluble inorganic builder materials may be included. In addition to the polyphosphates, such as sodium triphosphate, these include in particular the water-soluble crystalline and / or amorphous alkali metal silicate builders. Such water-soluble inorganic builder materials are preferably present in agents according to the invention in amounts of from 1% by weight to 20% by weight, in particular from 5% by weight to 15% by weight. The alkali silicates useful as builder materials preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be amorphous or crystalline. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na ₂ Si _x O used _{2x + 1} · y H ₂ O in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred. Also prepared from amorphous alkali silicates, practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used in inventive compositions. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further embodiment of inventive agents. In a preferred embodiment of inventive compositions, a granular compound of alkali metal silicate and alkali, such as is available, for example under the name Nabion ^® 15 commercially.

Machine dishwashing detergents according to the invention are preferably of low alkalinity and contain the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali hydrogen carbonates. The alkali carriers used conventionally include carbonates, bicarbonates and alkali metal silicates having a molar ratio of SiO ₂ / M ₂ O (M = alkali atom) of from 1.5: 1 to 2.5: 1. Alkali silicates may be present in amounts of up to 30% by weight, based on the total agent. The use of the highly alkaline metasilicates as alkali carriers is preferably completely dispensed with. The alkali carrier system preferably used in the inventive compositions is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which is present in an amount of up to 60 wt .-%, preferably 10 wt .-% to 40 wt .-% , Depending on which pH is ultimately desired, the ratio of carbonate used and bicarbonate used varies, but usually an excess of sodium bicarbonate is used, so that the weight ratio of bicarbonate to carbonate is generally from 1: 1 to 15: 1.

In a further embodiment of dishwashing compositions according to the invention, 20 wt.% To 40 wt.% Of water-soluble organic builders, in particular alkali citrate, 5 wt.% To 15 wt.% Alkali carbonate and 20 wt 40 wt .-% Alkalidisilikat included.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_1-24-Alkyl- oder C_2-24-Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN und -N⁽⁺⁾-CH₂-CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit mindestens einer, vorzugsweise zwei, gegebenenfalls substituierten C_1-24-Alkylgruppe(n) und gegebenenfalls weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6, R⁴ und R⁵ unabhängig voneinander eine voranstehend für R¹, R² oder R³ angegebene Bedeutung haben, wobei mindestens 2 der genannten Reste, insbesondere R² und R³, auch unter Einschluß des Stickstoffatoms und gegebenenfalls weiterer Heteroatome ringschließend miteinander verknüpft sein können und dann vorzugsweise einen Morpholino-Ring ausbilden, und X(^–) ein ladungsausgleichendes Anion, vorzugsweise ausgewählt aus Benzolsulfonat, Toluolsulfonat, Cumolsulfonat, den C_9-15-Alkylbenzolsulfonaten, den C_1-20-Alkylsulfaten, den C_8-22-Carbonsäuremethylestersulfonaten, Sulfat, Hydrogensulfat und deren Gemischen, ist, können eingesetzt werden. In addition to the compounds that form peroxycarboxylic acids under perhydrolysis conditions, other bleach-activating compounds, such as nitriles, from which perimic acids are formed may be present. These include in particular aminoacetonitrile derivatives with quaternized nitrogen atom according to the formula

in the R ^{1 is} -H, -CH ₃ , a C _2-24 -alkyl or alkenyl radical, a substituted C _1-24 -alkyl or C _2-24 -alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN and -N ⁽⁺⁾ -CH ₂ -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or a substituted alkyl- or alkenylaryl radical having at least one, preferably two, optionally substituted C _1-24 -alkyl group (s) and optionally further substituents on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6, R ⁴ and R ⁵ independently of one another have the meaning given above for R ¹ , R ² or R ³ , where at least 2 of the radicals mentioned, in particular R ² and R ³ , also include the Nitrogen atom and optionally further heteroatoms ring-closing linked together and then preferably form a morpholino ring, and X ( ^- ) a charge-balancing anion, preferably selected from benzenesulfonate, toluenesulfonate, cumenesulfonate, the C _9-15 -alkylbenzenesulfonates, the C _1-20 Alkyl sulfates, the C _8-22 -Carbonsäuremethylestersulfonaten, sulfate, hydrogen sulfate and mixtures thereof, can be used.

Oxygen-carrying sulfonimines and / or acylhydrazones can also be used. The additional presence of further bleach-catalyzing transition metal complexes is possible. These are preferably selected from the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes. Suitable ligands in these additional transition metal complexes are the co-ligands mentioned above in connection with the complexes used according to the invention. Examples of such optionally additionally present transition metal complex compounds are Mn (IV) ₂ (μ-O) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) di-hexafluorophosphate, [N, N'-bis [(2-hydroxy-5-vinylphenyl) methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-nitrophenyl) methylene] - 1,2-diaminocyclohexane] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-phenylenediamine] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2- diaminoethane] manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-sulfonatophenyl) methylene] -1,2-diaminoethane] manganese (III) chloride, manganese oxalato complexes, nitropentammine cobalt (III) chloride, nitritopentammine cobalt (III) chloride, hexammine cobalt (III) chloride, chloropentammine cobalt (III) chloride and the peroxo complex [(NH ₃ ) ₅ Co-OO-Co (NH ₃ ) ₅ ] Cl ₄ .

Suitable enzymes which may be present in the compositions according to the invention are, in particular, those from the class of proteases, lipases, cutinases, amylases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of Protease, amylase, lipase and / or cellulase is particularly preferred. The proportion is preferably 0.2 wt .-% to 1.5 wt .-%, in particular 0.5 wt .-% to 1 wt .-%. The enzymes can be adsorbed in a customary manner on carriers and / or embedded in coating substances or incorporated as concentrated, as anhydrous liquid formulations.

Suitable gravel inhibitors or soil release agents are cellulose ethers, such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose. Preferably, sodium carboxymethylcellulose and mixtures thereof with methylcellulose are used. Commonly used soil release agents include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. The proportion of grayness inhibitors and / or soil-release active ingredients in compositions according to the invention is generally not more than 2% by weight and is preferably from 0.5% by weight to 1.5% by weight.

As an optical brightener for particular textiles made of cellulose fibers (for example, cotton), for example, derivatives of diaminostilbene disulfonic acid or their alkali metal salts may be included. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulphonic acid or similarly constructed compounds which are suitable instead of the morpholino group, carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group. Further, brighteners of the substituted 4,4'-distyryl-diphenyl type may be present, for example, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl. Also, mixtures of brighteners can be used. Brighteners of the 1,3-diaryl-2-pyrazolines type, for example 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, and compounds of similar construction are particularly suitable for polyamide fibers. The content of the composition in optical brighteners or brightener mixtures is generally not more than 1 wt .-%, preferably 0.05 wt .-% to 0.5 wt .-%. In a preferred embodiment of the invention, the agent is free of such agents.

The usual foam regulators which can be used in the compositions according to the invention include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein preferably being silanated or otherwise rendered hydrophobic. The polysiloxanes can consist of both linear compounds as well as crosslinked polysiloxane resins and mixtures thereof. Further antifoams are paraffin hydrocarbons, in particular microparaffins and paraffin waxes whose melting point is above 40 ° C., saturated fatty acids or soaps having in particular 20 to 22 carbon atoms, for example sodium behenate, and alkali metal salts of phosphoric mono- and / or dialkyl esters in which the alkyl chains each having 12 to 22 carbon atoms. Among these, preference is given to using sodium monoalkyl phosphate and / or dialkyl phosphate having C ₁₆ - to C ₁₈ -alkyl groups. The proportion of foam regulators may preferably be from 0.2% by weight to 2% by weight.

Among the organic solvents which can be used in the compositions according to the invention, especially if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms , in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compound ethers. Such water-miscible solvents are present in compositions according to the invention in amounts of preferably not more than 20% by weight, in particular from 1% by weight to 15% by weight. Preferably, instead of the organic solvent or together with this water is present as a solvent.

In order to establish a desired pH, which does not result from the mixture of the other components, the compositions according to the invention can contain system- and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid. but also mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not more than 10 wt .-%, in particular from 0.5 wt .-% to 6 wt .-%, contained in the inventive compositions.

The preparation of solid agents according to the invention presents no difficulties and can be carried out in a manner known in the art, for example by spray-drying or granulation, wherein peroxygen compound and bleach catalyst are optionally added separately later.

Compositions according to the invention in the form of solutions containing aqueous or other conventional solvents are produced particularly advantageously by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

The compositions according to the invention are preferably in the form of pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roll compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and the bleach-activating system can be expected to be prepared. For the preparation of inventive compositions having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.

For the preparation of detergents according to the invention in tablet form, the procedure is preferably such that all ingredients are mixed together in a mixer and the mixture by means of conventional tablet presses, such as eccentric or rotary presses with pressing pressures in the range of 200 · 10 ⁵ Pa to 1 500 · 10 ⁵ Pa pressed. This gives unbreakable, yet sufficiently rapidly soluble tablets under application conditions with flexural strength of usually over 150 N. Preferably, a tablet thus produced has a weight of 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of 35 mm to 40 mm.

The preparation of compositions according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range from 800 to 1000 g / l can also be effected by using the builder components with at least a proportion of liquid mixture components in a first process substep while increasing the bulk density of this premix and subsequently - if desired after intermediate drying - the other constituents of the agent, including the bleach-activating system, combined with the thus obtained premix.

Examples

Example 1: Preparation of N-acylated desferrioxamine B derivatives

1st stage

• a: Ausbeute 1,58 g
• b: Ausbeute 0,68 g; MS m/e 977,1 (4 fach acyliert); 873,22 (3 fach acyliert); 855,26; 769,34; 733,35; 651,09; 511,36
• c: Ausbeute 1,32 g

To a solution of 1.3 g (2 mmol) of desferrioxamine B mesylate in 20 ml of water was added 1 g (about 5 eq) of NaHCO ₃ . At room temperature, 4 equivalents of acid chloride dissolved in a little diethyl ether (a: 2 g of 4-octylbenzoyl chloride, b: 1.3 g of octanoyl chloride, c: 1.2 g of benzoyl chloride) were slowly added dropwise via a syringe passed through a septum. The reaction mixture was stirred for about 2 hours at room temperature; A white precipitate formed. After extraction with dichloromethane, the organic phase was washed with 0.5 M aqueous hydrochloric acid, dried over MgSO ₄ and filtered. After removal of the solvent, N, O-acylated products were obtained as white solids.

• a: yield 1.58 g
• b: yield 0.68 g; MS m / e 977.1 (4 times acylated); 873.22 (3 times acylated); 855.26; 769.34; 733.35; 651.09; 511.36
• c: Yield 1.32 g

2nd stage

• a: Ausbeute 1 g
• b: Ausbeute 120 mg
• c: Ausbeute 1 g

The acylation product obtained in the 1st stage was taken up in 15 ml of methanol, then admixed with 4 equivalents of ammonia dissolved in methanol and stirred for 24 hours at room temperature. The precipitate was filtered off and washed with methanol. The solvent of the filtrate was removed in vacuo, the residue was washed several times with diethyl ether, combined with the previously isolated precipitate and dried in air.

• a: Yield 1 g
• b: yield 120 mg
• c: yield 1 g

Example 2: Preparation of Metal Complex Solutions

• A1: N-4-octylbenzoyl-desferrioxamine B (Example 1, a) was suspended in anhydrous ethanol (concentration 0.780 g / l) and mixed with 0.2 volumes of a solution of MnCl ₂ .4H ₂ O in anhydrous ethanol (concentration 0 , 9895 g / l) for several days at room temperature in a closed plastic container.
• A2: N-4-octylbenzoyl-desferrioxamine B (Example 1, a) was suspended in anhydrous ethanol (concentration 0.780 g / l) and mixed with 0.2 volumes of a solution of manganese (III) acetate dihydrate in anhydrous ethanol (concentration 1 , 38 g / l) for several days at room temperature in a closed plastic vessel.
• B: N-Octanoyl-desferrioxamine B (Example 1, b) was suspended in anhydrous ethanol (concentration 0.687 g / l) and treated with 0.2 volumes of a solution of MnCl ₂ .4H ₂ O in anhydrous ethanol (concentration 0.9895 g / l) for several days at room temperature in a closed plastic vessel.
• C1: N-benzoyl-desferrioxamine B (Example 1, c) was suspended in anhydrous ethanol (concentration 0.665 g / l) and mixed with 0.2 volumes of a solution of manganese (III) acetylacetonate in anhydrous ethanol (concentration 1.76 g / l) for several days at room temperature in a closed plastic vessel pivoted.
• C2: N-Benzoyl-desferrioxamine B (Example 1, c) was suspended in anhydrous ethanol (concentration 0.665 g / l) and mixed with 0.2 volumes of a solution of manganese (III) acetate dihydrate in anhydrous ethanol (concentration 1.38 g / l) for several days at room temperature in a closed plastic vessel.

Example 3: Bleaching experiments

Miniaturized washing tests at 40 ° C. with the standardized stains on cotton indicated in the table below using a wash liquor which contained 3.84 g / l of a powdery bleach-and-bleach activator-free detergent and 4 mmol / l H ₂ O ₂ (V1 ), an otherwise identical wash liquor (with a water hardness of 16 ° dH), each containing one of the complex solution prepared in Example 2 in an amount of 5.88 mg / l, based on Mn (E1 = V1 + A1, E2 = V1 + A2, E3 = V1 + B, E4 = V1 + C1, E5 = V1 + C2), and an otherwise similar wash liquor containing Mn (II) or Mn (III) in an amount of 5.88 mg / 1, based on Mn, (V2, V3), and an otherwise similar wash liquor containing Mn (III) desferrioxamine B (also present in an amount of 5.88 mg / L based on Mn) (V4) , The stain removal line was evaluated by drying over a brightness measurement (L value). The following table shows the dL values which resulted from the difference L (metal-containing wash liquor) -L (wash liquor V1) after washing (in each case the mean value from triple determination). tea blueberry E1 14.93 8.97 E2 14.56 8.67 E3 15.02 8.89 E4 14.51 9.04 E5 14,26 nb V2 14.52 8.33 V3 13.46 8.39 V4 nb 8.63 nb: not determined

The dL values when using the active substances essential to the invention are greater than those which resulted when using only the metal salt or the non-derivatized desferrioxamine, which corresponds to a higher degree of whiteness and thus improved stain removal. Example 4: Detergent compositions (% by weight) Na C _12/12 alkyl benzene sulphonate 8th 7.1 7 6.5 Na C _12-15 alkyl ether sulfate (3 EO) 0 4.8 0 5.2 Na C _12-14 alkyl sulfate 1 0 1 0 C _12-15 -alcohol 7-ethoxylated 2.2 0 3.2 0 C _10-12 dimethylhydroxyethylammonium chloride 0.75 0.94 0.98 0.98 Crystalline layered silicate (δ-Na ₂ Si ₂ O ₅ ) 4.1 0 4.8 0 Zeolite Na-A 20 0 17 0 citric acid 3 5 3 4 sodium 15 20 14 20 Na silicate (SiO ₂ : Na ₂ O 2: 1) 0.08 0 0.11 0 Repel-O- ^Tex® PF 0.75 0.72 0.71 0.72 Acrylic acid-maleic acid copolymer 1.1 3.7 1.0 3.7 Na-carboxymethylcellulose 0.15 1.4 0.2 1.4 Protease (56 mg active substance / g) 0.37 0.4 0.4 0.4 Amylase Termamyl ^® (21.55 mg of active ingredient / g) 0.3 0.3 0.3 0.3 Lipase Lipex ^® (18 mg active substance / g) 0.05 0.15 0.1 0.5 Na Percarbonate 13 13.2 13 13.2 Na (S, S) ethylenediamine-N, N'-disuccinate 0.2 0.2 0.2 0.2 Na-hydroxy ethane diphosphonate 0.2 0.2 0.2 0.2 _MgSO4 0.42 0.42 0.42 0.42 Dufstoffe 0.5 0.6 0.5 0.6 Foam regulator granulate 0.05 0.1 0.05 0.1 Soap 0.45 0.45 0.45 0.45 Na sulphate 22 33 24 30 Invention-essential complex 0.1 to 0.3 Minor components, water on 100

The pH of the detergents is typically from 10 to 10.5. Example 5: Dishwashing detergent compositions (% by weight) phosphate 40.0 sodium 13.5 phosphonate 2.5 Sulfonic acid group-containing polymer 5.5 polyacrylate 8.5 Nonionic surfactants 6.5 percarbonate 15.5 TAED 2.5 Invention-essential complex 0.1 to 0.3 amylase 0.8 protease 2.4 zinc acetate 0.2 less components on 100

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2008/101909 A1 [0007, 0008]
• BE 616139 [0013]

Claims (10)

 Use of metal complexes with N-acylated siderophore ligands to enhance the oxidizing power of, in particular, inorganic peroxygen compounds in oxidation, washing, cleaning or disinfecting solutions.  Use of to enhance the cleaning performance of detergents, cleaners or disinfectants in aqueous, especially surfactant-containing liquor.  Use of metal complexes with N-acylated siderophore ligands, in particular in combination with a peroxygen compound, for bleaching color stains during the washing of textiles, in particular in aqueous, surfactant-containing liquors, or in hard-surface cleaning solutions, in particular for crockery, for bleaching colored stains , especially tea. Detergents, cleaners or disinfectants, characterized in that it contains a metal complex with an N-acylated siderophore ligand Composition according to claim 4, characterized in that it contains 0.001 wt .-% to 5 wt .-%, in particular 0.01 wt .-% to 1 wt .-% metal complex with an N-acylated siderophore ligand. Composition according to claim 4 or 5, characterized in that it contains up to 35 wt .-%, in particular 1 wt .-% to 30 wt .-% peroxygen compound. A process for washing textiles or for cleaning hard surfaces in the presence of a persoxy-containing bleaching agent, characterized in that it is carried out in the presence of a metal complex with an N-acylated siderophore ligand. Use according to one of claims 1 or 3, agent according to claim 6 or process according to claim 7, characterized in that it is an inorganic peroxygen compound. Use, means or method according to one of the preceding claims, characterized in that in the N-acylated siderophore ligands, the siderophore is selected from the Desferrioxaminen A ₁ , A ₂ , G and B, which in their biosynthesis sometimes occurring and partially secreted Intermediates like

Pyoverdin, ornibactin, chrysobactin, exochelin MN, tenacibactin D, desferribactin, fusarinin C, myxochelin B, desferrimycin A, yersiniabactin, salmycin B and petrobactin and mixtures thereof, and / or the acyl groups are selected from the radicals RC (O) - in which R is a linear, branched or cyclic alkyl or alkenyl group having up to 20, in particular 1 to 12, C atoms or an aryl, aralkyl or alkaryl group having 3 to 20, in particular 5 to 15, C atoms, where the alkyl or alkenyl groups can be interrupted by 1 or more heteroatoms, in particular by -O- or -NH-, and the aryl groups can contain 1 to 3 heteroatoms, in particular N atoms, and / or the metal is selected from Ag, Al, Au, B, Ce, Co, Cu, Fe, Ga, Hg, Mn, Mo, Ni, Pb, Pt, Ru, Ti, U, V and Zn and mixtures thereof, wherein the metal is present in any desired oxidation states can, in particular from Ag (I), Al (III), Au (III), B (III), Co (II), Co (III), Cu (I), Cu (II), Ga (III), Hg (II), Mn (II), Mn (III), Ni (II), V (IV), V (V), Fe (II), Fe (III), Ce (III), Bi (III), Pb (II), Pt (II), U (IV) and Zn (II) and mixtures thereof.  Complexes of the N-acylated siderophores with Ag, Al, Au, B, Bi, Ce, Co, Cu, Ga, Hg, Mn, Mo, Ni, Pb, Pt, Ru, Ti, U, V and Zn and mixtures thereof, in particular with Mn, V, Cu, Mo, Ce and Bi and mixtures thereof.