EP2129762A1 - Siderophore-metal- complexes used as bleach catalysts - Google Patents

Abstract

The invention relates to siderophore-metal-complexes and to the uses thereof as bleach catalysts, in particular in washing and cleaning agents.

Description

 Siderophore-metal complexes as bleach catalysts

The present invention relates to siderophore-metal complexes and their use as bleach catalysts, especially in detergents and cleaners.

For effective bleaching with hydrogen peroxide, it must be converted to a more bleach-active species. One way to generate activated peroxy compounds is to use peracid precursors, so-called bleach activators such as, for example, TAED, which are converted by perhydrolysis into the active species.

Another possibility for generating activated species is the enzymatically catalyzed perhydrolysis of carboxylic acid esters or nitrile compounds using perhydrolases.

Finally, it is also known to use bleach catalysts to produce activated species, wherein a bleach catalyst is to be understood as meaning a substance which can improve the bleaching performance of hydrogen peroxide on a bleachable substance without itself being involved stoichiometrically in the reaction.

The use of bleach catalysts has the advantage over the other methods of bleach activation that sub-stoichiometric amounts of the compound are sufficient to achieve space and weight savings in the formulation of the bleach-containing product. Furthermore, the reduction in weight, in particular in washing and cleaning applications, also has the advantage that there is less introduction of substances into the environment, which is particularly advantageous for ecological reasons. In addition, this also transport and packaging costs can be saved.

Furthermore, it must be taken into account that premature hydrolysis may occur when using bleach activators such as nitriles or TAED in the presence of water, while this problem can be largely avoided when using bleach catalysts. In addition, the production of acids from non-catalytic bleach activation from the peracids causes a pH shift which may adversely affect bleaching performance. Furthermore, the bleaching performance of most bleach activators is often insufficient at low temperatures.

For the above reasons, the use of bleach catalysts is of particular interest over the other techniques of bleach activation, so that there is a general need for new bleach catalysts. As bleach catalysts in particular metal complexes of organic ligands such as salenes, Saldiminen, tris [salicylidenaminoethyl] annines, monocyclic polyazaalkanes, cross-bridged polycyclic polyazaalkanes, terpyridines and tetraamido ligands are described. A disadvantage of the metal complexes described, however, is that they either do not have sufficient bleaching performance, especially at low temperature, or that, with sufficient bleaching performance, undesired damage to paints and possibly also the 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. There is therefore a general need to produce complex ligands predominantly or preferably completely from renewable raw materials. This is e.g. carried out on a large scale for citric acid, which is produced biotechnologically by means of fungal cultures. Citric acid can chelate metal ions as a chelator, but such citric acid complexes are not particularly important for bleach catalysis, especially for washing and cleaning applications.

It is an object of the present invention to provide novel bleach catalysts, preferably those which can be prepared from renewable raw materials. Ideally, the ligands are natural products or are readily derivable from these derivatives. Furthermore, the new bleach catalysts should allow effective cleaning of hard surfaces and fabrics, preferably without unduly damaging the latter and / or the latter. Furthermore, the new bleach catalysts should, if possible, have sufficient storage stability in order to be used in detergents and cleaners.

This problem is solved by the use of siderophore metal complexes as bleach catalysts.

Siderophores are complex ligands which are released by organisms (especially microbes) to firmly bind iron (III) ions and then to transport the loaded complex into the cell, with the aim of accessing the important iron. 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 at least two, usually at least three, are usually present in the molecule. Because siderophores are natural products, they can be easily and inexpensively produced from renewable raw materials, for example, by culturing suitable microorganisms in appropriate media and separating the siderophores they have extracted. The fact that siderophores can be eagerly imported and recycled by countless microorganisms proves that they have good biodegradability, which is a particular advantage for bleach catalysts of this type, especially for detergents and cleaners which ultimately end up in the environment.

Because of their ability to complex iron ions, siderophores also have antibacterial properties, so that in the literature in particular applications of siderophores as preservatives and disinfectants for different applications are described (see, for example, DE19642127, DE4433376, EP641275 and EP682091). In addition, desferrioxamine B is also used in the medical field because of its ability to complex iron ions.

It is also known that siderophores can be used to bleach pulp in papermaking or are involved in the natural bleaching process of pulp. In this context, the hydroxamate siderophores desferrioxamine B, desferritriacetyl fusigen and nocardamine are mentioned in particular. A mediator function with respect to the degradation of lignin by laccases is discussed in the first place (Niku-Paavola et al. (2003) American Chemical Society Symp Ser 855, 176-190, Milagres et al (2002) Enzymes and Microbial Technology 30, 562-565). It is also generally stated that the iron siderophores could catalyze redox reactions and activate oxygen. However, the use of siderophores in detergents and cleaners is not described here.

Older publications have also described the preparation of an Mn-siderophore complex. Thus, Beyer et al. (1989, Archives of Biochemistry and Biophysics 271, 149-156) describe the preparation of manganese complexes of desferrioxamine B. They demonstrate that these complexes possess superoxide dismutase activity, ie the conversion of O ₂ ^" to H ₂ O ₂ and O ₂ catalyze. However, as applications of these complexes, only the use as antioxidants and pharmaceutical agents are mentioned, the use of siderophores in detergents and cleaners is not considered.

Faulkner et al. (1994, Archives of Biochemistry and Biophysics 310, 341-346) describe the preparation of the Mn (III) complexes of desferrioxamine B and E. Again, only the use as an antioxidant and especially in the medical field are discussed.

WO93 / 03045 discloses different metal complexes of desferrioxamine B and discusses their utility as contrast agents. EP0325559 discloses a process for the preparation of different metal complexes of desferrioxamines B and E and desferrithiocin in purer form.

Duckworth et al. (2006, Abstracts of Papers, 232nd ACS National Meeting, San Francisco, Calif., United States, Sept. 10-14, 2006, American Chemical Society) disclose theoretical studies on different metal complexes of desferrioxamine B.

Joshi et al. (1994, Proceedings - Indian Academy of Sciences, Chemical Sciences 106 (5), 1089-1108) disclose studies on the interaction of nucleic acids with complexes of desferrioxamine B with copper, cobalt and nickel ions.

Abergel et al. (2006, Abstracts of Papers, 232nd ACS National Meeting, San Francisco, Calif., United States, Sept. 10-14, 2006, American Chemical Society) disclose complexes of enterobactin with iron, gallium, aluminum, indium, and vanadium Ions to study the interaction of these complexes with the protein siderocalin.

Yoder et al. (2006, Journal of Environmental Science and Health, Part A: Toxic / Hazardous Substances & Environmental Engineering 41 (3), 369-380) disclose complexes of a pyoverdine with aluminum, calcium, copper, iron, manganese, magnesium - And zinc ions and studies on their fluorescence.

US5371234 discloses complexes of pyoverdine Pf244 with metal ions of iron, aluminum, chromium, gallium and actinides and the use of pyoverdine Pf244 for complexing these metal ions.

Choi et al. (2006, Journal of Inorganic Biochemistry 100 (12), 2150-2161) disclose various metal complexes of methanobactin and thermodynamic studies of these complexes.

The use of siderophore metal complexes as bleaching agents in detergents and / or their use for the cleaning of textiles or dishes is not yet described in the prior art and thus new. Furthermore, it was surprising that siderophore-metal complexes enable effective cleaning of fabrics without unduly damaging the fabrics and, at the same time, behaving very gently with respect to the colors of the textile fabrics.

A first subject of the present invention are therefore detergents and cleaners containing at least one siderophore, preferably at least one siderophore-metal complex. Due to their low fiber and color damage, this is preferably a particularly fiber and / or color gentle washing and / or Cleaning supplies. The siderophore as well as the siderophore-metal complex can be used in free form as well as in the form of any salt.

Another object of the present invention is therefore also the use of siderophores, in particular of siderophore-metal complexes, in detergents and cleaners, in particular in detergents and cleaners for cleaning hard surfaces and textile fabrics.

Another object of the present invention is therefore also the use of siderophores, in particular of siderophore metal complexes, as an aid for cleaning hard surfaces and as an aid for cleaning textile fabrics.

The present invention also relates in particular to the use of siderophores, in particular of siderophore-metal complexes, for the cleaning and / or removal of stains, in particular selected from soiling of tea, coffee, blood, soot, egg, milk, butter, ink, Makeup, lipstick, chocolate, chocolate cream, olive oil, blackcurrant, blueberry, apple juice, red wine, peanut oil, and mixtures thereof.

It is also possible to catalyze other redox reactions than only bleaching reactions with such new catalysts. Another object of the present invention is in particular the use of siderophores, in particular siderophore metal complexes, for bleaching pulp and / or raw cotton.

On account of the determination according to the invention of its germicidal properties, a further subject matter of the present invention is the use of siderophore-metal complexes, in particular in detergents and cleaning agents, for killing germs, in particular for killing bacteria and / or fungi.

The present invention further provides a process for the cleaning of textile fabrics or hard surfaces, characterized in that the cleaning is carried out using a siderophore-metal complex, wherein it is due to the particularly fiber and color-preserving properties of the siderophore metal Complex is preferably a fiber and / or color-sparing process.

The siderophores are used in a preferred embodiment according to the invention directly in the form of a catalytically active siderophore-metal complex. However, it is also possible to generate the catalytically active siderophore-metal complex first in situ. For this purpose, siderophore and metal ion - optionally in the form of any salt - can be presented spatially separated from each other and / or applied sequentially in time. The union of siderophore and metal ion and thus the formation of the bleach catalyst can then done directly at the application. The spatial separation of siderophore and metal ion can take place, for example, by using a multi-chamber system, the siderophore and the metal ion being contained in different chambers. By mixing the components of the various chambers of the multi-chamber system, the siderophore metal complex can then be generated in situ. Alternatively, the siderophore and the metal ion may also be contained in different compartments of a powdered detergent, such as in different granules or in different layers of a multilayered granule. Upon dissolution of the granules during application, the siderophore and metal ion can then combine to form the catalytically active complex.

A special subject of the present invention is therefore also a process for the cleaning of textile fabrics or hard surfaces, characterized in that the cleaning is carried out using a siderophore-metal complex, wherein the siderophore-metal complex is generated in situ.

Furthermore, in a preferred embodiment, the siderophore and siderophore metal complexes are used in conjunction with an oxygen source, such as a bleach (or bleach activator), which will be discussed further below. However, it has surprisingly been found that the siderophore metal complexes cause a relatively strong cleaning and bleaching effect even without the addition of an oxygen source.

A particular object of the present invention is therefore also a process for the cleaning of fabrics or hard surfaces, characterized in that the cleaning is carried out using a siderophore-metal complex, wherein no bleaching agent and / or bleach activator is added, so preferably Atmospheric oxygen is used as the sole source of oxygen.

By definition, siderophores are compounds that are produced by an organism only under conditions of iron deficiency. However, this limitation does not apply to the present invention, as even complex ligands produced with sufficient iron present can fulfill the purpose of the present invention. Therefore, in the context of the present invention, the term "naturally occurring siderophore" is to be understood as meaning any naturally occurring complexing ligand having similar complexing properties and a similar structure and function to a siderophore to understand that are similar to siderophores and also make metal ions available for bacteria. In a preferred embodiment, however, the naturally occurring siderophore is a siderophore in the strict sense according to the above-mentioned definition. According to the invention, a siderophore is furthermore to be understood in a broader sense as meaning in general any compound which contains at least two, preferably at least three, more preferably two or three, especially exactly three, radicals selected from the group consisting of hydroxamate, catecholate, and alpha-hydroxy. Carboxylate, alpha-keto-carboxylate, carboxamide, Citrathydroxamat and, optionally partially or fully hydrogenated, oxazole or thiazole, with those compounds are preferably at least three, more preferably exactly three, selected from catecholate, hydroxamate and, optionally partially or fully hydrogenated, oxazole or thiazole.

According to the invention, "catecholate" is to be understood as meaning the doubly deprotonated form of catechol, but the catecholate residues may also be fully or partially protonated, in particular in the presence of the uncomplexed free form of the corresponding siderophores.These protonated forms of the catecholate are according to the invention by the term "catecholate". Likewise, the other radicals mentioned, in particular in the uncomplexed form of the siderophores, can likewise be present in the protonated or deprotonated state. In this sense, hydroxamic acid radicals are included in particular by the term "hydroxamate" and by the term "carboxylate" carboxylic acid radicals with. In the complex with the metal cation, however, the radicals mentioned are preferably present in deprotonated form.

In a particularly preferred embodiment, the siderophore is a compound which has at least two, preferably exactly two, hydroxamate groups and at least one further, preferably exactly one further, complexing group, in particular selected from catecholate, carboxylate, alpha-hydroxy Carboxylate, alpha-keto-carboxylate, phenolate, carboxylic acid amide and, optionally partially or fully hydrogenated, imidazole, oxazole or thiazole contains, wherein the further complexing group is preferably selected from catecholate and, optionally partially or fully hydrogenated, oxazole or thiazole.

In a very particularly preferred embodiment according to the invention, the siderophore is a compound which contains at least three, preferably exactly three, hydroxamate groups.

In a further particularly preferred embodiment, the siderophore is a compound which has at least two, preferably exactly two, catecholate groups and at least one further, preferably exactly one further, complexing group, in particular selected from hydroxamate, carboxylate, alpha-hydroxy -Carboxylate, alpha-keto-carboxylate, phenolate, carboxylic acid amide and, optionally partially or fully hydrogenated, imidazole, oxazole or thiazole, wherein the further complexing group is preferably is selected from hydroxamate and, optionally partially or fully hydrogenated, oxazole or thiazole.

In a further particularly preferred embodiment, the siderophore is a compound containing at least three, preferably exactly three, catecholate groups.

In a further particularly preferred embodiment, the siderophore is a compound which has at least two, preferably exactly two, optionally partially or fully hydrogenated, oxazole groups and at least one further, preferably exactly one further, complexing group, in particular selected from hydroxamate , Catecholate, carboxylate, alpha-hydroxy-carboxylate, alpha-keto-carboxylate, phenolate, carboxamide and, optionally partially or fully hydrogenated, imidazole or thiazole, wherein the further complexing group is preferably selected from hydroxamate, catecholate and optionally partially or fully hydrogenated, thiazole.

In a further particularly preferred embodiment, the siderophore is a compound which contains at least three, preferably exactly three, optionally partially or completely hydrogenated, oxazole groups.

In a further particularly preferred embodiment, the siderophore is a compound which has at least two, preferably exactly two, optionally partially or fully hydrogenated, thiazole groups and at least one further, preferably exactly one further, complexing group, in particular selected from hydroxamate , Catecholate, carboxylate, alpha-hydroxy-carboxylate, alpha-keto-carboxylate, phenolate, carboxamide and, optionally partially or completely hydrogenated, imidazole or oxazole, wherein the further complexing group is preferably selected from hydroxamate, catecholate and optionally partially or fully hydrogenated, oxazole.

In a further particularly preferred embodiment, the siderophore is a compound which contains at least three, preferably exactly three, optionally partially or completely hydrogenated, thiazole groups.

In a further particularly preferred embodiment, the siderophore is a compound which has at least two, preferably exactly two, alpha-hydroxy carboxylate groups and at least one further, preferably exactly one further, complexing group, in particular selected from hydroxamate, Catecholate, carboxylate, alpha-keto-carboxylate, phenolate, carboxylic acid amide and, optionally partially or fully hydrogenated, imidazole, oxazole or thiazole, wherein the further complexing group is preferably selected from hydroxamate, catecholate and, optionally partially or fully hydrogenated, oxazole or thiazole. In a further particularly preferred embodiment, the siderophore is a compound which contains at least three, preferably exactly three, alpha-hydroxy carboxylate groups.

In the context of the present invention, a "siderophore" is therefore to be understood as meaning any naturally occurring or naturally occurring compound which has the abovementioned combination of functional groups, irrespective of how it was obtained.

In a preferred embodiment, however, the siderophore is a naturally occurring siderophore or a derivative thereof, a derivative of a naturally occurring siderophore being understood in particular to be a compound which, starting from a naturally occurring siderophore, is obtained, for example, by halogenation, alkylation, Acylation, sulfonation, nitration, hydroxylation, decarboxylation or similar modifying reactions, preferably without destroying the backbone of the naturally occurring siderophore. The modification may be biotechnical, e.g. during production in a microorganism, or chemically in vitro. In particular, the modification may serve to further improve the properties of the siderophore for use as bleach catalyst ligands, e.g. in terms of oxidation stability, solubility or color.

In a further preferred embodiment, the siderophore according to the invention is an optionally modified oligopeptide, which preferably comprises 2 to 8 optionally modified peptide bonds, in particular a cyclic oligopeptide, in particular a cyclic pentapeptide or a cyclic hexapeptide can. The abovementioned functional groups may in this case be part of the amino acid residues, but they may instead, in particular the hydroxamate groups, also be part of the optionally cyclic peptide chain and have arisen here in particular by modification of the peptide bonds.

In a particularly preferred embodiment, the siderophore is a naturally occurring siderophore.

The naturally occurring siderophores may according to the invention in particular be sideromycins, siderochromes or sideramines. However, due to their structural structure, as stated above, in a broader sense, especially chalcophores such as methanobactin, which are not actually referred to as siderophores, according to the invention are attributable to the siderophores. The naturally non-occurring siderophores in a preferred embodiment are the abovementioned derivatives of naturally occurring siderophores. In addition, however, it may be any other compound, provided that the above combination is found in functional groups. In this case, as with many naturally occurring siderophores, it may in particular also be an oligopeptide, in particular a cyclic oligopeptide such as a cyclic hexapeptide.

In the following, some siderophores which can be used according to the invention are mentioned. It is accordingly - even if the term "Desferri" is not prefixed - always meant the iron-free forms of siderophores.

Naturally occurring siderophores with three hydroxamate groups can be used according to the invention in particular desferrichromes, in particular desferrichrome, desferrichrome A or desferrichrome C, tetraglycyldesferrichromes, desferricrocin, desferrichrysin, desferrirhodin, hexahydrodesferrirhodin, desferrirubin, desferricoprogen, desferrineocoprogen I, desferrineocoprogen II, exochelin MS, fusigen ( Fusarinine C), nocardamine, desferrisalmycin, desferrialbomycins, in particular desferrialbomycin O ₁ , δ ₂ or ε, desferrioxamine, in particular desferrioxamine A, A1, A2, B, C, D 1, D 2, E, EtI, Et 2, Et 3, Fm, G, H, I, X1, X2, X3, X4, Tel, Te2 or Te3, and desferrimycins, in particular desferrimycin A ₁ . Preferably, the siderophore with three hydroxamate groups is desferrioxamine E.

As naturally occurring siderophores with two hydroxamate groups and one catecholate group it is possible according to the invention in particular to use pyoverdins, in particular the pyoverdines C, D, E or Pa.

As naturally occurring siderophores with two hydroxamate groups and one dihydrooxazole ring, in particular mycobactins can be used according to the invention, in particular mycobactin J, P, S or T.

As a naturally occurring siderophore with two hydroxamate groups and one alpha-hydroxy carboxylate group, according to the invention, in particular aerobactin, arthrobactin, acinetoferrin, an aquaquinin, in particular aqua alein A, B, C or D, an ornibactin, in particular ornibactin C4, C6 or C8 , a nannochelin, especially nannochelin B or C, or schizokines.

As a naturally occurring siderophore with two hydroxamate groups and one imidazole group, it is possible according to the invention in particular to use exochelin MN. As a naturally occurring siderophore with two hydroxamate groups and several carboxamide groups, it is possible according to the invention in particular to use the rhodotorulic acid or a marinobactin, in particular marinobactin A, B, C, D 1, D 2 or E.

As a naturally occurring siderophore with a hydroxamate group, a catecholate group and an alpha-keto-carboxylate group, in particular azotobactin D can be used according to the invention.

As a naturally occurring siderophore with a hydroxamate group, a catecholate group and an alpha-hydroxy carboxylate group, a pseudobactin can be used according to the invention, in particular pseudobactin, pseudobactin 7NSK2, 7SR1, A, A214, M1 14 or St3.

As a naturally occurring siderophore with a hydroxamate group, a catecholate group and a partially hydrogenated oxazole ring, in particular aceticobactin can be used according to the invention.

As a naturally occurring siderophore with a hydroxamate group, an alhpa- hydroxy-carboxylate group and several carboxylic acid amide groups, pseudobactin can be used according to the invention in particular.

As a naturally occurring siderophore with a hydroxamate group and several carboxylic acid amide groups, in particular, putrebactin can be used according to the invention.

As a naturally occurring siderophore with three alpha-hydroxy carboxylate groups, in particular achromobactin can be used according to the invention.

As a naturally occurring siderophore with two alpha-hydroxy carboxylate groups, two carboxylic acid amide groups and two further carboxylate groups, rhizoferrin can be used according to the invention in particular.

As a naturally occurring siderophore with two alpha-hydroxy carboxylate groups and one catecholate group, particular preference may be given according to the invention to alterobactins, in particular alterobactin A or B.

As a naturally occurring siderophore with three catecholate groups, it is possible according to the invention in particular to use agrobactin, enterobactin (enterochelin), fluvibactin, homofluvibactin or bacillibactin (corynebactin). As naturally occurring siderophore with two catecholate groups and one alpha-hydroxy-carboxylate group, in particular petrobactin can be used according to the invention.

Salmochelin, azotochelin or a myxochelin, in particular myxochelin A or B, can be used according to the invention as a naturally occurring siderophore with two catecholate groups and several carboxamide groups.

As a naturally occurring siderophore with a catecholate group and two carboxylic acid amide groups, in particular chrysobactin can be used according to the invention.

As a naturally occurring siderophore with three partially hydrogenated thiazole rings, Yersiniabactin can be used according to the invention in particular.

As a naturally occurring siderophore with two partially hydrogenated thiazole rings, in particular ferrrithiocin or pyochelin A can be used according to the invention.

As a naturally occurring siderophore with two partially hydrogenated oxazole groups and one catecholate group, in particular the vulnibactin can be used according to the invention.

Further naturally occurring siderophores which can be used according to the invention are daunorubicin, succinimycin, rifamycin, trencam, pseudomonin, corugatin, gallichrom, fusigen, desferristaphyloferrin, in particular desferristaphyloferrin A or B, desferrivibrioferrin, desferrimaduraferrin, a fusarin, in particular fusarin C, PM, X or Z or triacetylfusarinine C, dimerumic acid, mugineic acid, coelichelin, WCS, methanobactin, gonobactin, amonabactin, in particular amonabactin P or T, an amphibactin, in particular amphibactin G, a rhizobactin, in particular rhizobactin 1021 or DM4, rutuckactin, anguibactin, brucebactin, carboxymycobactin, erythrobactin, Cepabactin, meningobactin, chrysobactin, quinolobactin, thioquinolobactin, vibriobactin, vanchrobactin, parabactin and ballibactin.

According to the invention, the siderophore which can be used according to the invention preferably has a complexing constant with respect to iron (III) of less than 10 ³ M ^-1 , particularly preferably less than 10 ^-7 , in particular less than 10 ^-20 M ^-1 .

Naturally occurring siderophores are mainly produced by microorganisms, especially bacteria. In addition, siderophores are also produced by other organisms, in particular by certain plants that form a community with Wurzelymbionten. According to the invention, all naturally occurring siderophores are suitable for the formation of siderophore-metal complexes according to the invention. The naturally occurring siderophores to be used according to the invention are preferably derived from microorganisms, more preferably from bacteria, in particular from Acinetobacter, Actinomyces, Alcaligenes, Bordetella, Alteromonas, Agrobacterium, Aeromonas, Arthrobacter, Azotobacter, Bacillus, Corynebacterium, Brucella, Burkholderia, Erwinia, Penicillium, Aspergillus , Neurospora, Ustillago, Escherichia, Klebsiella, Aerobacter, Saccharopolyspora, Mycobacterium, Penicillium, Fusarium, Neisseria, Pseudomonas, Shewanella, Shigella, Rhizobioma, Rhodotorula, Ralstonia, Salmonella, Staphylococcus, Streptomyces, Vibrio or Yersinia.

The naturally occurring siderophores, on the one hand, can be obtained from their natural producers, but alternatively can also be produced heterologously in another organism by genetically modifying these oranges by incorporating the DNA coding for one or more enzymes involved in the siderophore synthesis. Furthermore, the chemical synthesis of siderophores as another alternative into consideration.

As production organisms for heterologous production are preferably also microorganisms in question, preferably fungi, yeasts and bacteria, in particular the genera Aspergillus, Bacillus, Brevibacillus, Actinomyces, Escherichia, Streptomyces, Corynebacterium, Pseudomonas, Saccharomyces, Hansenula, Pichia and Lactobacillus.

The genetic modification of the producing organisms is relatively simple, with a variety of genetic engineering changes being possible to produce a siderophore in an adapted structure, purity, yield or process time. As a result, a siderophore-based catalyst can be adapted to the requirements in a particularly versatile manner compared to a non-biotechnologically produced catalyst. It is also possible, by means of appropriately engineered production organisms, to produce further biomolecules which are of advantage for the use or purification of the product, e.g. the co-expression of a hydrogen peroxide producing enzyme such as an oxidase or catalase, superoxide dismutase, and other enzymes that reduce oxidative stress. This is only possible with biotechnical methods.

With regard to naturally occurring siderophores it is advantageous to emphasize that the biotechnical producibility of the complex ligands from renewable raw materials is particularly sustainable and enables particularly cost-effective process paths which are not accessible with conventional chemical synthesis.

Another advantage of naturally occurring siderophores is that they are readily biodegradable, since they are absorbed by numerous microorganisms and are natural substances. This is of particular advantage if the complexes are as intended or get into the environment through unwanted processes. Derivatives of naturally occurring siderophores should also be readily degradable.

As a central atom for the metal-siderophore complex, basically any metal atom in any oxidation state comes into question. Preferably, the central atom of the metal siderophore complex is an element selected from Ag, Al, Au, B, Bi, Ce, Co, Cr, Cu, Eu, Fe, Ga, Hg, Mn, Mo. , Ni, Pb, Pt, Ru, Ti, U, V, W, Zn and Zr in any oxidation states, in particular around Ag (I), Al (III), Au (III), B (III), Bi (III) , Ce (III), Ce (IV), Co (II), Co (III), Cr (III), Cu (I), Cu (II), Eu (II), Eu (III), Fe (II) Fe (III) Ga (III) Hg (II) Mn (II) Mn (III) Mo (IV) Mo (VI) Ni (II) Pb (II) Pt (II) , Ru (II), Ru (III), Ru (IV), U (IV), V (IV), V (V), W (VI) or Zn (II). Most preferably, the central atom of the metal siderophore complex is a transition metal atom, preferably selected from the group consisting of Mn, Fe, W, Co, Cr, Zn, Bi, Mo, V, Ce, and Cu all from the group Co, Mn, Ce, Zn, Bi or Fe, in any oxidation state. In a particularly preferred embodiment, the central atom is selected from Fe (III), Co (II), Co (III), Mn (II), Mn (III), Ce (III), Ce (IV), Zn (II) and Bi (III).

Particularly noteworthy in accordance with the invention are the complexes of siderophores with at least three hydroxamate groups, in particular desferrioxamines, desferrichromes and coprogens, in particular desferrioxamine E, with metal ions of Mn, Fe, Co, Ce, Cr, Zn, Cu, Mo, V, W and Bi ; Complexes of siderophores having at least two hydroxamate groups and at least one catecholate group, in particular pyoverdine Pa, with metal ions of Mn, Fe, Co, Ce, Zn, Cu, Mo, V, and Bi; Complexes of siderophores having at least two hydroxamate groups and at least one alpha-hydroxy carboxylate group, especially ornibactin, arthrobactin and schizokinene, with metal ions of Mn, Fe, Co, Ce, Cr, Zn, Cu, Mo, V , W and Bi; Complexes of siderophores having at least two hydroxamate groups and at least one carboxylic acid amide group, in particular rhodotorulic acid, with metal ions of Mn, Fe, Co, Ce, Cr, Zn, Cu, Mo, V, W and Bi; Complexes of siderophores with at least three partially hydrogenated thiazole rings, in particular yersinabactin, with metal ions of Mn, Fe, Co, Ce, Cr, Zn, Cu, Mo, V and Bi; Complexes of siderophores with at least two alpha-hydroxy-carboxylate groups, at least two carboxamide groups and at least two further carboxylate groups, in particular of rhizoferrin, with metal ions of Mn, Fe, Co, Ce, Zn, Cu, Mo, V, W and Bi; Complexes of siderophores with at least three catecholate groups, in particular of enterobactin, with metal ions of Mn, Fe, Co, Ce, Cu, V and Bi.

The metal siderophore complex may be in the form of any salt, and optionally also other ligands and / or coligands. Suitable ligands and / or coligands are in particular any desired salt anions, phosphonates, amines, polymers, polyols and co-builders and surfactants, in particular the cobuilders and surfactants listed below by way of example. Depending on the charge of the metal siderophore complex, counterion ions are cationic counterions, in particular alkali metal and potassium Alkaline earth metal ions or anionic counterions such as in particular halide ions or the anions of organic acids into consideration.

The preparation of the metal siderophore complex can generally be carried out in a simple manner by mixing a metal salt of the corresponding metal with the corresponding siderophore or a salt of the corresponding siderophore in an aqueous environment. By setting a suitable redox potential, the formation of a desired oxidation state can be promoted.

Another object of the present invention are siderophore metal complexes, characterized in that the central atom is selected from Ag, Al, Au, B, Bi, Ce, Co, Cr, Cu, Eu, Ga, Hg, Mn, Mo, Ni, Pb, Pt, Ru, Ti, U, V, W, Zn and Zr in any oxidation states, in particular of Ag (I), Al (III), Au (III), B (III), Bi (III), Ce (III), Ce (IV), Co (II), Co (III), Cr (III), Cu (I), Cu (II), Eu (II), Eu (III), Fe (II) Fe (III), Ga (III), Hg (II), Mn (II), Mn (III), Mo (IV), Mo (VI), Ni (II), Pb (II), Pt (II) Ru (II), Ru (III), Ru (IV), U (IV), V (IV), V (V), W (VI) or Zn (II), with the exception of the metal complexes of Desferrioxamine B and E, preferably with the exception of the metal complexes of all desferrioxamines, and with the exception of the metal complexes of desferrithiocine, methanobactin, Al and Cr complexes, preferably all metal complexes, pyoverdine Pf244 and Al, Cu, Mn and Zn complexes, preferably all metal complexes of Pyoverdins from Pseudomonas aeruginosa, particularly preferably with Au the metal complexes of all pyoverdines. Otherwise, the siderophore may be any of the siderophores listed above.

The central atom of the metal-siderophore complex is particularly preferably a transition metal atom which is selected from the group consisting of Mn, W, Co, Cr, Zn, Bi, Mo, V, Ce and Cu, especially from Group Co, Mn, Ce, Zn or Bi, in any oxidation state. In a particularly preferred embodiment, the central atom is selected from Co (II), Co (III), Mn (II), Mn (III), Ce (III), Ce (IV), Zn (II) and Bi (III).

In a most preferred embodiment, the metal siderophore complexes are selected from complexes of the coprogen with metal ions of Mn, Co, Ce, Cr, Zn, Cu, Mo, V, W and Bi; Complexes of siderophores having at least two hydroxamate groups and at least one alpha-hydroxy carboxylate group, in particular ornibactin, arthrobactin and schizokinene, with metal ions of Mn, Co, Ce, Cr, Zn, Cu, Mo, V, W and Bi; Complexes of siderophores having at least two hydroxamate groups and at least one carboxylic acid amide group, in particular the rhodotorulic acid, with metal ions of Mn, Co, Ce, Cr, Zn, Cu, Mo, V, W and Bi; Complexes of siderophores having at least three partially hydrogenated thiazole rings, in particular yersinabactin, with metal ions of Mn, Co, Ce, Cr, Zn, Cu, Mo, V and Bi; Complexes of siderophores having at least two alpha-hydroxy carboxylate groups, at least two carboxylic acid amide groups and at least two further carboxylate groups, in particular rhizoferrin, with metal ions of Mn, Co, Ce, Zn, Cu, Mo, V, W and Bi; Complexes of siderophores with at least three catecholate groups, in particular of enterobactin, with metal ions of Mn, Co, Ce, Cu, V and Bi.

A particular object of the present invention is the use in particular of the abovementioned siderophore metal complexes having the stated central atoms in detergents or cleaners, in particular for cleaning textile fabrics or for cleaning hard surfaces.

Another particular subject of the present invention is the use in particular of the abovementioned siderophore-metal complexes having the stated central atoms as aids for the cleaning of textile fabrics and as aids for the cleaning of hard surfaces.

Another particular object of the present invention is also the use in particular of the aforementioned siderophore metal complexes having the indicated central atoms for bleaching pulp and / or raw cotton.

Another object of the present invention are detergents and cleaning agents, in particular surfactant-containing, containing a siderophore-metal complex according to the invention.

The detergents and cleaning agents according to the invention may be any conceivable type of cleaning agent, both concentrates and agents to be used undiluted, for use on a commercial scale, in the washing machine or in hand washing or cleaning. These include, for example, detergents for textiles, carpets, or natural fibers, for which according to the present invention the term laundry detergent is used. These include, for example, dishwashing detergents for dishwashers or manual dishwashing detergents or cleaners for hard surfaces such as metal, glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather; for such according to the present invention, the term cleaning agent is used. In a broader sense sterilizing and disinfecting agents are to be regarded as detergents and cleaners in the sense of the invention.

Embodiments of the present invention include all of the prior art and / or all suitable administration forms of the washing or cleaning agents according to the invention. These include, for example, solid, powdery, liquid, gelatinous or pasty agents, optionally also of several phases, compressed or uncompressed; further include, for example: extrudates, granules, tablets or pouches, packed both in large containers and in portions. In a preferred embodiment, the detergents or cleaners according to the invention comprise the above-described inventive siderophore-metal complexes in an amount of up to 5% by weight, in particular from 0.001% by weight to 1% by weight and more preferably of 0 , 01 wt .-% to 0.5 wt .-%, especially from 0.01 to 0.25 wt .-%, each based on the total weight of the detergent or cleaning agent.

In addition to the siderophore-metal complexes according to the invention, other bleach catalysts may optionally additionally be present in the agents according to the invention. These substances may generally be any bleach-enhancing transition metal salt or transition metal complex. Suitable transition metals here are in particular Mn, Fe, Co, Ru, Mo, Ti, V or Cu in different oxidation states. As possible complexing ligands are, in particular, as described in the literature, guanidines, aminophenols, amine oxides, salene, Saldimine, lactams, monocyclic and cross-bridged polycyclic polyazaalkanes, terpyridines, dendrimers, tetraamido ligands, bis- and tetrakis (pyridylmethyl) alkylamines, secondary amines and polyoxometalates.

In a preferred embodiment, as an additional bleach catalyst, a complex of manganese in the oxidation state II, III, IV or V is used which preferably contains one or more macrocyclic ligands having the donor functions N, NR, PR, O and / or S. Preferably, in this case ligands are used which have nitrogen donor functions. It is particularly preferred to additionally use a bleach catalyst in the compositions according to the invention, which is used as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me-TACN), 1, 4,7-triazacyclononane (TACN). , 1, 5,9-Trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1, 4,7-triazacyclononane (Me / TACN). Examples of suitable manganese complexes are [Mn '" ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (CIO ₄ ) ₂ , [Mn ¹ " Mn ^lv (μ-O) ₂ (μ-OAc) ₁ (TACN) ₂ ] (BPh ₄ ) ₂ , [Mn ^ιv ₄ (μ-O) ₆ (TACN) ₄ ] (CIO ₄ ) ₄ , [Mn ^I " ₂ (μ-O) ₁ (μ-OAc) ₂ ( Me-TACN) ₂ ] (CIO ₄ ) ₂ , [Mn '"Mn ^lv (μ-O) ₁ (μ-OAc) ₂ (Me-TACN) ₂ ] (CIO ₄ ) ₃ , [Mn' ^v ₂ (μ -O) ₃ (Me-TACN) _2] (PF _{6) 2} and [Mn ^'v ₂ (μ-O) ₃ (Me / Me-TACN) _2] (PF _{6) 2} (OAc = OC (O) CH ₃ ).

The additional bleach catalyst, if used, in the inventive compositions preferably in an amount of up to 5 wt .-%, in particular from 0.0025 wt .-% to 1 wt .-% and particularly preferably from 0.01 wt. % to 0.25% by weight, in each case based on the total weight of the washing or cleaning agent.

Furthermore, bleaches are preferably present in the detergents and cleaners of the invention in a preferred embodiment, which are preferably the substrate for the bleach catalysts according to the invention and / or deliver, albeit, as already mentioned, catalysis can also be carried out without the addition of bleaching agents. Under a bleach according to the invention, on the one hand, hydrogen peroxide itself and, on the other hand, any compound which produces hydrogen peroxide in an aqueous medium. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxopyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as persulfates or persulfuric acid. Also useful is the urea peroxohyd rat percarbamide, which can be described by the formula H ₂ N-CO- NH ₂ H ₂ O ₂ . In particular, when using the means for cleaning hard surfaces, for example in automatic dishwashing, they may, if desired, also contain bleaching agents from the group of organic bleaches, although their use is also possible in principle for laundry detergents. Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid (phthalimidoperoxyhexanoic acid , PAP), o-Carboxybenzamidoperoxycaproic acid, N-Nonenylamidoperadipinsäure and N-Nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-Diperoxyazelainsäure, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic, 2-decyldiperoxybutane -1, 4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid).

As a bleaching agent and chlorine or bromine releasing substances can be used. Among the suitable chlorine or bromine releasing materials are for example heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

According to the invention, washing or cleaning agents, in particular automatic dishwashing agents, are preferred which contain up to 45% by weight, in particular 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably 3.5 to 20% by weight .-% and in particular 5 to 15 wt .-% bleach, preferably sodium percarbonate.

The active oxygen content of the washing or cleaning agents, in particular the automatic dishwashing detergents, in each case based on the total weight of the composition, preferably between 0.4 and 10 wt .-%, particularly preferably between 0.5 and 8 wt .-% and in particular between 0.6 and 5 wt .-%. Particularly preferred compositions have an active oxygen content above 0.3 wt .-%, preferably above 0.7 wt .-%, more preferably above 0.8 wt .-% and in particular above 1, 0 wt .-% to.

As an alternative to and simultaneously with the bleaching agents, to provide the hydrogen peroxide, it is also possible to use enzymes which, starting from other substrates, are capable of generating hydrogen peroxide in situ. These are oxidoreductases, which can transfer electrons from - as a rule - an organic substrate, such as glucose, to oxygen as an electron acceptor and thus allow the formation of the desired hydrogen peroxide in situ. The oxidoreductase can be used here together with the corresponding organic substrate. However, since the soils to be treated can already contain the required substrate, the use of the oxidoreductases can optionally also be carried out without addition of the corresponding substrate.

The hydrogen peroxide-producing oxidoreductase is preferably an oxidoreductase which produces hydrogen peroxide by using oxygen as the electron acceptor. In particular, oxidoreductases of EC classes EC 1.1.3 (CH-OH as electron donor), EC 1.2.3 (aldehyde or oxo group as electron donor), EC 1.4.3 (CH-NH ₂ as donor), EC 1.7 are used. 3 (N-containing group as donor) and EC 1.8.3 (S-containing group as donor) into consideration, preference being given to enzymes of the EC class EC 1.1.3.

Preferred enzymes are in particular selected from the group consisting of malate oxidase (EC 1.1.3.3), glucose oxidase (EC 1.1.3.4), hexose oxidase (EC 1.1.3.5), cholesterol oxidase (EC 1.1.3.6), Galactose oxidase (EC 1.1.3.9), pyranose oxidase (EC 1.1.3.10), alcohol oxidase (EC 1.1.3.13), choline oxidase (EC 1.1.3.17, see in particular WO 04/58955), oxidases for long-chain Alcohols (EC 1.1.3.20), glycerol-3-phosphate oxidase (EC 1.1.3.21), cellobiose oxidase (EC 1.1.3.25), nucleoside oxidase (EC 1.1.3.39), D-mannitol oxidase (EC 1.1 3.40), xylitol oxidase (EC 1.1.3.41), aldehyde oxidase (EC 1.2.3.1), pyruvate oxidase (EC 1.2.3.3), oxalate oxidase (EC 1.2.3.4), glyoxylate oxidase (EC 1.2 .3.5), indole-3-acetaldehyde oxidase (EC 1.2.3.7), pyridoxal oxidase (EC 1.2.3.8), aryl aldehyde oxidase (EC 1.2.3.9), retinal oxidase (EC 1.2.3.11), L- Amino acid oxidase (EC 1.4.3.2), amine oxidase (EC 1.4.3.4, EC 1.4.3.6), L-glutamate oxidase (EC 1.4.3.1 1), L-lysine oxidase (EC 1.4.3.14), L-aspartate-O xidase (EC 1.4.3.16), tryptophan-alpha, beta-oxidase (EC 1.4.3.17), glycine oxidase EC 1.4.3.19), urea oxidase (EC 1.7.3.3), thiol oxidase (EC 1.8.3.2) , Glutathione oxidase (EC 1.8.3.3), sorbitol oxidase and enzymes such as described in DE102005053529.

The hydrogen peroxide-producing oxidoreductase, in a preferred embodiment, is one which uses a sugar as an electron donor. The hydrogen peroxide producing and sugar oxidizing oxidoreductase is according to the invention preferably selected from glucose oxidase (EC 1.1.3.4), hexose oxidase (EC 1.1.3.5), galactose oxidase (EC 1.1.3.9) and pyranose oxidase (EC 1.1.3.10). Particularly preferred according to the invention is the glucose oxidase (EC 1.1.3.4).

Advantageously, when using a hydrogen peroxide-producing oxidoreductase additionally preferably organic, more preferably aromatic, interacting with the enzymes compounds added to enhance the activity of the respective oxidoreductases (enhancer) or to the electron flow at greatly different redox potentials between the oxidizing enzymes and the stains ensure (mediators).

The hydrogen peroxide-producing oxidoreductase is preferably used in the detergents and cleaning agents according to the invention, if used, in an amount such that the total composition has an oxidoreductase-related enzyme activity of from 30 U / g to 20,000 U / g, in particular of 60 U / g to 15,000 U / g. The unit 1 U (unit) corresponds to the activity of that amount of enzyme which converts 1 μmol of its substrate at pH 7 and 25 ⁰ C in one minute.

The substrate optionally to be used when using such a hydrogen peroxide-producing oxidoreductase is generally obtained directly from the name of the particular oxidoreductase.

In order to achieve an improved bleaching effect during washing at temperatures of 60 ^° C. and below, and in particular during the laundry pretreatment, the means may optionally also contain bleach activators in addition to the inventive siderophore-metal complexes and the optional further bleach catalysts as additional bleaching aid. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylene diamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5- Diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA) and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used.

Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula

Ri

R2-N- (CH ₂₎ -cnx ^"

R3

in which R ¹ is -H, -CH _3, a C ₂ - ₂₄ alkyl or alkenyl group, a substituted C _2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH _2, -CN, an alkyl or alkenylaryl radical with a CI_ ₂₄ alkyl group, or a substituted alkyl- or alkenylaryl radical with a CI_ ₂₄ alkyl group and at least one further substituent 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 and X is an anion.

Particularly preferred is a cationic nitrile of the formula

in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ - CH ₃ , -CH (CH ₃ ) -CH ₃ , wherein R ⁴ additionally also -H may be and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ( CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{" are} particularly preferred, wherein from the group of these substances turn the cationic Nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^' in which X ^{' is} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is particularly preferred. Bleach activators according to the invention preferably in amounts of up to 15 wt .-%, preferably up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, especially 2 to 8 wt .-% and particularly preferably 2 to 6 % By weight, based in each case on the total weight of the bleach activator-containing agents.

In addition to at least one siderophore and / or at least one siderophore metal complex and the aforementioned bleaching agents and optional further bleaching aids, a washing or cleaning agent according to the invention optionally contains further ingredients such as further enzymes, enzyme stabilizers, surfactants and / or builders, and optionally other common ingredients that are listed below.

The compositions according to the invention preferably contain surfactants, in particular selected from nonionic, anionic, cationic and amphoteric surfactants. Surfactants used according to the invention are preferably nonionic, anionic and / or amphoteric surfactants.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; preferably x is 1, 2 to 1, 4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula

R-CO- ΨN- [Z] wherein R is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula

R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, wherein Ci_ ₄ alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, washing or cleaning agents, in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred. Preferred ethoxylated alcohols include, for example, _C12 - ₁₄ - alcohols with 3 EO or 4 EO, C ₉ n-alcohol with 7 EO, C-ms alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Ci ₂ - ₁₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ -i ₄ -alcohol with 3 EO and C ₁₂ -i ₈ -alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

With particular preference, therefore, ethoxylated nonionic surfactant selected from C ₆ - o- ₂ monohydroxy alkanols or C ₆ - ₂ o-alkyl phenols or C ₆ - ₂ o-fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol Ethylene oxide per mole of alcohol were used. A particularly preferred nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C-ι ₆ - ₂ o alcohol), preferably obtained a d ₈ alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide. Of these, the so-called "narrow ranks ethoxylates" are particularly preferred.

With particular preference further combinations of one or more Taigfettalkoholen be used with 20 to 30 EO and silicone defoamers.

Especially preferred is the addition of ethoxylated and propoxylated alcohols as nonionic surfactants. Machine dishwashing detergent, characterized in that it contains nonionic surfactant (s) of the general formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH ₂ CH ₂ OI _y H, in which R ^{1 is} linear or branched , saturated or unsaturated, aliphatic hydrocarbon radicals having 6 to 30 carbon atoms, x are values between 15 and 120, preferably for values between 40 and 120, particularly preferably for values between 45 and 120 and y stands for values between 2 and 80 are used with particular advantage, since the addition of these surfactants to the compositions of the invention a further unexpected increase in cleaning and rinsing performance could be achieved.

Particular preference is given to nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) (e) with a melting point above 2O ⁰ C, preferably above 25 ⁰ C, more preferably between 25 and 6O ⁰ C and in particular from 26.6 to 43.3 ⁰ C, is / are particularly preferred ,

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Also Nonionic surfactants having waxy consistency at room temperature are preferred depending on their purpose.

Nonionic surfactants from the group of alkoxylated alcohols, more preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-Niotenside, are also used with particular preference.

The nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol content of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight, of the total molecular weight of such nonionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.

Preferably used surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

Further particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nichionic surfactants of the general formula Ri-O- (CH ₂ -CH ₂ -O) - (CH ₂ -CHO) - (CH ₂ -CH ₂ -O) - (CH ₂ -CHO) -H

R2 R3

preferably, R ¹ is a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl; each group R ² or R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently stand for integers from 1 to 6.

The preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions, preference is given to nonionic surfactants in which R ¹ in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or -CH (CH ₃ ) ₂ are suitable. Preference is given to using nonionic surfactants of the above formula in which R ² or R ^{3 is} a radical -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another are values of 1 or 2.

Nonionic surfactants are particularly preferred In summary, the ₉ have a C .i ₅ alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

Surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² , in which R ¹ and R ² independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C ₂ . ₄₀ alkyl or alkenyl; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ - CH ₂ -CH ₂ , -CH ₂ -CH (CHs) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

Particular preference is given to surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² in which R ¹ denotes a linear or branched aliphatic hydrocarbon radical 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1, 5 and y for a value of at least 15.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are most preferred.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ P] _x [CH ₂ J _k CH (OH) [CH ₂ ] _J OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl - or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x> 2, each R ³ in the The above formula R ¹ O [CH ₂ CH (R ³ P] _x [CH _{2 Ik} CH (OH) [CH ₂ ] PR ^{2 may be} different R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred, and for the radical R ³ are particularly H, -CH ₃ or -CH ₂ CH ₃ prefers. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15. As described above, each R ³ in the above formula may be different if x> 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is R ¹ O [CH ₂ CH (R ³ P] _X CH ₂ CH (OH) CH ₂ OR ^2. In the latter formula, R ^1, R ² and R ^{3 are} as defined above and x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. particularly preferred are surfactants wherein where the radicals R ¹ and R ^{2 have} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.

Of course, the aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants. Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,

As anionic surfactants, for example, those of the sulfonate type and sulfates can be used. As surfactants of the sulfonate type are preferably C ₉ .i ₃ - alkylbenzenesulfonates, olefinsulfonates, that is, mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those from Ci ₂ _i ₈ monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained. Suitable are also alkanesulfonates, which are from C | ₂ - ₁₈ alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.

Likewise suitable are the esters of .alpha.-sulfo fatty acids (ester sulfonates), for example the .alpha.-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol Glycerol can be obtained. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and especially the sodium salts of the Schwefelsäurehalbester C ₂ -C ₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or d ₀ -C ₂ o Oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. From the washing the C ₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₅ alkyl sulfates and C ₁₄ -C preferably ₅ alkyl sulfates. Also 2,3-alkyl sulfates are suitable anionic surfactants.

Also, the sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 moles of ethylene oxide. ₂ i-alcohols, such as 2-methyl-branched C ₉ .n-alcohols having on average 3.5 moles of ethylene oxide (EO) or Ci ₂ -i ₈ -fatty alcohols having 1 to 4 EO, are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of up to 5% by weight, usually from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ -i ₈ -fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol radical which is derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (description see above). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.

The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

If anionic surfactants are used as constituents of automatic dishwasher detergents, their content, based on the total weight of the compositions, is preferably less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight. Machine dishwashing detergents which do not contain anionic surfactants are particularly preferred.

Instead of the surfactants mentioned or in conjunction with them, it is also possible to use cationic and / or amphoteric surfactants.

As cationic active substances, for example, cationic compounds of the following formulas can be used:

Ri

Ri-N- (CH _{2) n} -T-R 2 (CH _{2) n} -T-R2

wherein each R ¹ group is independently selected from CI_ ₆ alkyl, alkenyl or hydroxyalkyl groups; each group R ² is independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

In automatic dishwashing detergents, the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. %. Automatic dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred.

The surfactants are contained in the cleaning or washing agents according to the invention in an amount of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%, based on the finished composition.

Detergents or cleaners according to the invention generally contain one or more builders, in particular zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological reasons against their use, the phosphates. The latter are particularly preferred builders to be used in automatic dishwashing detergents.

With preferred crystalline layered silicates of general formula NaMSi _x O are used _{2x + 1} ^■ y H ₂ O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, wherein particularly preferred Values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layered silicates of the formula NaMSi _x O _{2x + 1} ^■ y H ₂ O are sold for example by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ ^.xH ₂ O, kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ ^.xH ₂ O, magadiite), Na-SKS -3 (Na ₂ Si ₈ O ₁₇ ^.xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ ^.xH ₂ O, Makatite).

Particularly suitable for the purposes of the present invention are crystalline layer silicates with the formula NaMSi _x O _{2x + 1} ^■ y H ₂ O, in which x stands for 2 h. In particular, both .beta.- and δ-sodium Na ₂ Si ₂ O ₅ ^■ y H ₂ O, and further in particular Na-SKS-5 (Oc-Na ₂ Si ₂ O _5), Na-SKS-7 (.beta.-Na ₂ Si ₂ 0 _5, natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ ^■ H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ ^■ 3 H ₂ O, kanemite), Na-SKS-11 ( t-Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (5-Na ₂ Si ₂ O ₅ ) are preferred.

Washing or cleaning composition preferably contain a weight proportion of crystalline layered silicate of the formula NaMSi _x O _{2x + 1} ^■ y H ₂ O from 0.1 to 20 wt .-%, preferably from 0.2 to 15 wt .-% and in particular of 0.4 to 10 wt .-%, each based on the total weight of these agents. It may also be advantageous to use chemical modifications of these phyllosilicates. For example, the alkalinity of the layered silicates can be suitably influenced. Phyllosilicates doped with phosphate or carbonate have, compared to the δ-sodium disilicate, altered crystal morphologies, dissolve more rapidly and show an increased calcium binding capacity in comparison to δ-sodium disilicate. Thus, phyllosilicates of the general empirical formula x Na ₂ O • y SiO ₂ • z P ₂ O ₅ , in which the ratio x to y is a number 0.35 to 0.6, the ratio x to z a number from 1, 75 to 1200 and the ratio y to z correspond to a number from 4 to 2800, described in the patent application DE 196 01 063. The solubility of the layered silicates can also be increased by using particularly finely divided layered silicates. Also compounds from the crystalline layer silicates with other ingredients can be used. In particular, compounds with cellulose derivatives which have advantages in the disintegrating effect and are used in particular in detergent tablets, and compounds with polycarboxylates, for example citric acid, or polymeric polycarboxylates, for example copolymers of acrylic acid, may be mentioned.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle , cause.

Alternatively or in combination with the abovementioned amorphous sodium silicates, X-ray-amorphous silicates are used whose silicate particles give washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such X-ray amorphous silicates also have a dissolution delay compared to conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

An optionally usable, finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. As zeolite P zeolite MAP ^® (commercial product from Crosfield) is particularly preferred. However, zeolite X is also suitable and mixtures of A, X and / or P. Commercially available and preferably used in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80 wt .-% zeolite X), available from the company CONDEA Augusta SpA is marketed under the brand name VEGOBOND AX ^® and represented by the formula

n Na ₂ O ^■ (1-1I) ^■ K ₂ O Al ₂ O ₃ ^■ (2 to 2.5) SiO ₂ ^■ (3.5 to 5.5) H ₂ O

can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

In the context of the present invention, it is preferred that the said silicates, preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, in detergents or cleaners, in particular in automatic dishwashing agents, in amounts of 3 to 60 wt .-%, preferably from 8 to 50 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the washing or cleaning agent, are included.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with particular preference of pentasodium or pentakalium triphosphate (sodium or potassium tripolyphosphate) in the washing and cleaning industry have the greatest importance.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1, 91 like ^'3 , melting point 60 °) and monohydrate (density 2.04 like ^{' 3} ). Both salts are white powders which are very slightly soluble in water and which lose the water of crystallization when heated and at 200 ^° C. into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium, potassium phosphate, KDP), KH ₂ PO ₄ , is a white salt of density 2.33 " ³ " a melting point of 253 ⁰ C [decomposition to form potassium polyphosphate (KPO ₃ ) J and is readily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 like ^"3 , water loss at 95 °), 7 mol. (Density 1, 68 like ^'3 , melting point 48 ⁰ C with loss of 5 H ₂ O) and 12 mol (Density 1, 52 like ^'3 , melting point 35 ⁰ C with loss of 5 H ₂ O), becomes anhydrous at 100 ⁰ C and on more intense heating in the diphosphate Na ₄ P ₂ O ₇ disodium hydrogen phosphate is by neutralization of phosphoric acid prepared with soda solution using phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals containing as dodecahydrate a density of 1, 62 like ^'3 and a melting point of 73-76 ⁰ C (decomposition), as decahydrate (corresponding 19-20% P ₂ O ₅₎ like to have a melting point of 100 ⁰ C and (in anhydrous form, corresponding to 39-40% P ₂ O ₅₎ a density of 2.536 ^"3. trisodium phosphate is readily soluble in water with an alkaline reaction and is prepared by evaporating a solution of exactly 1 Triphosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 ^"3 , has a melting point of 1340 ° and is in water with alkaline Reaction slightly soluble. It is produced, for example, by heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 ^"3 , melting point 988 ⁰ C, also indicated 88O ⁰ C) and as decahydrate (density 1, 815- 1, 836 like ^'3 , melting point 94 ⁰ C with loss of water). Both substances are colorless crystals which dissolve in water with an alkaline reaction, crystals. Na ₄ P ₂ O ₇ is formed when disodium phosphate is heated to> 200 ° C, or by reacting phosphoric acid with soda in a stoichiometric ratio and the solution The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.Kali diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and produces a colorless, hygroscopic powder with a density of 2.33 like ^"3 , which is soluble in water, wherein the pH of the 1% solution at 25 ⁰ C is 10.4.

Condensation of the NaH ₂ PO ₄ or of the KH ₂ PO ₄ gives rise to relatively high molecular weight sodium and potassium phosphates in which cyclic representatives, the sodium or potassium metaphosphates and chain-type, the sodium or potassium Potassium polyphosphates, may differ. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The industrially important pentasodium triphosphate (Na ₅ P ₃ O ₁₀ ; sodium tripolyphosphate) is an anhydrous or water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _{n which} crystallizes with 6 H ₂ O and which is non-hygroscopic. Na with n = 3. In 100 g of water at room temperature dissolve about 17 g, at 6O ⁰ C about 20 g, at 100 ⁰ C, about 32 g of the salt water-free salt; after two hours of heating the solution to 100 ⁰ C caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ Oi ₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH ^■ * Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

If phosphates are used as detergents or cleaning agents in the context of the present application, preferred agents comprise these phosphate (s), preferably alkali metal phosphate (s), more preferably pentasodium or pentapotassium triphosphate (sodium or pentasodium) Potassium tripolyphosphate), in amounts of 5 to 80 wt .-%, preferably from 15 to 75 wt .-% and in particular from 20 to 70 wt .-%, each based on the weight of the detergent or cleaning agent.

Further builders are the alkali carriers. Examples of alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the alkali silicates mentioned, alkali metal silicates, and mixtures of the abovementioned substances, preference being given to the alkali metal carbonates, in particular Sodium carbonate, sodium bicarbonate or sodium sesquicarbonate can be used. Particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate. Also particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate. Because of their low chemical compatibility with the other ingredients of detergents or cleaners compared with other builders, the alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 wt .-% and in particular below 2 wt .-%, each based on the total weight of the detergent or cleaning agent used. Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.

Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 2 to 50 wt .-%, preferably from 5 to 40 wt .-% and in particular from 7.5 to 30 wt .-%, each based on the weight of the washing or cleaning agent. Particular preference is given to compositions which, based on the weight of the washing or cleaning agent, contain less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and in particular less than 9% by weight of carbonate ( e) and / or bicarbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals, optionally oxidized dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use can not be avoided for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder effect, they also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners, unless the pH resulting from the mixture of the other components is desired. In particular, systemic and environmentally friendly acids such as citric acid, acetic acid, Tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof. But also mineral acids, in particular sulfuric acid or bases, in particular ammonium or alkali hydroxides can serve as pH regulators. Such regulators are contained in the agents according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.

The use of citric acid and / or citrates in these compositions has proven particularly advantageous for the cleaning and rinsing performance of dishwashing compositions according to the invention. Therefore, according to the invention, preference is given to automatic dishwasher detergents, characterized in that the automatic dishwashing agent contains citric acid or a salt of citric acid and the weight proportion of citric acid or of the salt of citric acid is preferably more than 10% by weight, preferably more than 15% by weight and in particular between 20 and 40 wt .-% is.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol. The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of detergents or cleaning agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,

Further preferred copolymers are those which have as their monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference in automatic dishwashing detergents.

Particularly preferred as sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.

In the context of the present invention are as unsaturated monomer carboxylic acids of the formula

R ¹ (R ² ) C = C (R ³ ) COOH

in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the above formula are in particular acrylic acid (R = R = R = H), methacrylic acid (R = R = H, R = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) is preferred.

In the sulfonic acid-containing monomers are those of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H in which R ⁵ to R ⁷ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) -, where n = 0 to 4, -C00- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

HO ₃ SX (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = O to 4, -C00- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids.

Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds. The content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers to be used consist only of monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH and monomers of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -

X-SO ₃ H.

In summary, copolymers of i) unsaturated carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH in the R ¹ to R ^{3 are} independently of one another -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, ii) sulfonic acid group-containing monomers of Formula R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H in the R ⁵ to R ⁷ independently of one another is -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or for -COOH or -COO R ⁴ is where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - where n = 0 to 4, -C00- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) - iii) optionally further ionogenic or nonionic monomers are particularly preferred.

Further particularly preferred copolymers consist of i) one or more unsaturated carboxylic acids from the group of acrylic acid,

Methacrylic acid and / or maleic acid ii) one or more sulfonic acid group-containing monomers of the formulas:

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

HO ₃ SX (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ), - - with n = O to 4, -C00- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₂ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) - iii) optionally further ionogenic or non-ionogenic monomers.

The copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii). Particularly preferred polymers have certain structural units, which are described below.

For example, copolymers which are structural units of the formula are preferred - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CHs) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. When the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred. The corresponding copolymers contain the structural units of the formula

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein O- (CH ₂ ) _n - where n = 0 to 4, -O- (C ₆ H ₄ ) -, -NH-C (CHs) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, copolymers which are structural units of the formula

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) -, are particularly preferred, just as preferred as copolymers, the structural units of the formula

- [CH ₂ -C (CH ₃ ) COOH] ^ [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _P -

in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y is -O- (CH ₂ ) _n - where n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH- C (CHs) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are preferred.

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred. Also preferred according to the invention are copolymers which contain structural units of the formula

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CHs) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In summary, such copolymers are preferred according to the invention, the structural units of the formulas

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p -

- [CH ₂ -C (CH ₃ ) COOH] ^ [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _P -

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CHs) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred. In the polymers, the sulfonic acid groups may be wholly or partly in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.

The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.

In the case of terpolymers, particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol ^"1 , preferably from 4000 to 25,000 gmol ^{" 1} and in particular from 5000 to 15,000 gmol ^"1 .

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrups having a DE of between 20 and 37, and so-called yellow dextrins and white dextrins having higher molecular weights in the range of 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. Ethylenediamine-N, N ^'- disuccinate (EDDS) is preferably used in form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are from 3 to 15 wt .-%.

With particular preference, the inventive machine dishwashing detergents contain methylglycinediacetic acid or a salt of methylglycinediacetic acid, wherein the weight fraction of methylglycinediacetic acid or of the salt of methylglycinediacetic acid is preferably between 0.5 and 15% by weight, preferably between 0.5 and 10% by weight and in particular between 0.5 and 6 wt .-% is.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

Another substance class with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned. Moreover, all compounds capable of forming complexes with alkaline earth ions can be used as co-builders.

Builder substances may optionally be present in the detergents or cleaners according to the invention in amounts of up to 90% by weight. They are preferably contained in amounts of up to 75% by weight. Detergents according to the invention have builder contents of, in particular, from 5% by weight to 50% by weight. In agents according to the invention for the cleaning of hard surfaces, in particular for the automated cleaning of dishes, the content of builder substances is in particular from 5% by weight to 88% by weight, wherein preferably no water-insoluble builder materials are used in such agents. In a preferred embodiment of the invention means for the particular automatic cleaning of dishes are 20 wt .-% to 40 wt .-% of water-soluble organic builder, in particular alkali, 5 wt .-% to 15 wt .-% alkali carbonate and 20 wt .-% bis 40 wt .-% Alkalidisilikat included.

The group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.

"Cationic polymers" for the purposes of the present invention are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride Copolymers, the quaternized polyvinyl alcohols or the polymers listed under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

For the purposes of the present invention, "amphoteric polymers" also have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may, for example, be carboxylic acids, sulfonic acids or phosphonic acids.

Preferred washing or cleaning agents, in particular preferred automatic dishwashing agents, are characterized in that they contain a polymer a) which has monomer units of the formula R ¹ R ² C =CR ³ R ⁴ in which each R ¹ , R ² , R ⁴ radical ³ , R ^{4 is} independently selected from hydrogen, derivatized hydroxy group, Ci- ₃₀ linear or branched alkyl groups, aryl, aryl substituted Ci _-30 linear or branched alkyl groups, polyalkoyxylierte alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen, at least one quaternized nitrogen atom or at least one amino group having a positive charge in the partial region of the pH range from 2 to 11, or salts thereof, with the proviso that at least one radical R ¹ , R ² , R ³ , R ^{4 is} a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one Amino group with a positive charge.

In the context of the present application, particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula

in which R ¹ and R ⁴ are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ^{3 are} independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X represents a counterion, preferably a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula are selected from -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 , and - (CH ₂ CH ₂ -O) _n H.

Very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ¹ and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer unit of the formula

H ₂ C = C H- (CH ₂ ) -N ⁺ (CH ₃ ) ₂ - (CH ₂ ) -CH = CH ₂ X ^"

in the case of X = chloride, they are also referred to as DADMAC (diallyldimethylammonium chloride). Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula

R1 HC = CR2-C (O) -NH- (CH ₂₎ -N ⁺ R3R4R5

X ^" in the R ¹ , R ² , R ³ , R ⁴ and R ^{5 are} independently of one another a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from 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 , and - (CH ₂ CH ₂ -O) _{n is} H and x is an integer between 1 and 6.

For the purposes of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ^{1 is} H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula

H ₂ C = C (CHS) -C (O) -NH- (CH ₂ ) X-N ⁺ (C HS) ₃

X ^"

in the case of X = chloride also referred to as MAPTAC (Methyacrylamidopropyl trimethylammonium chloride).

According to the invention, preference is given to using polymers which contain diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.

The aforementioned amphoteric polymers have not only cationic groups but also anionic groups or monomer units. Such anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids. Preferred usable amphoteric polymers are selected from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the

Alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.

Also preferred are amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride.

Particularly preferred amphoteric polymers are selected from the group of the methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyl trialkyl ammonium chloride / dimethy1 diallyl ammonium chloride / alkyl ( meth) acrylic acid copolymers and their alkali metal and ammonium salts. Particular preference is given to amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyldiallylammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers as well as their alkali and ammonium salts.

In a particularly preferred embodiment of the present invention, the polymers are present in prefabricated form. For the preparation of the polymers, inter alia, the encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers; the encapsulation of the polymers by means of water-insoluble, meltable coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ⁰ C; the co-granulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing- or cleaning-active substances, more preferably from the group of builders or cobuilders.

Detergents or cleaning agents contain the aforementioned cationic and / or amphoteric polymers preferably in amounts of between 0.01 and 10 wt .-%, each based on the total weight of the detergent or cleaning agent. In the context of the present application, however, preference is given to those detergents or cleaners in which the weight fraction of the cationic and / or amphoteric polymers is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4 wt .-%, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing agent is.

Solvents that can be used in the liquid to gelatinous compositions of detergents and cleaners, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible in the specified concentration range with water. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, -ethyl or -propyl ether, dipropylene glycol monomethyl, or -ethyl ether, di-isopropylene glycol monomethyl, or -ethyl ether, methoxy, ethoxy or Butoxytriglykol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents.

Solvents may be used in the liquid to gelled detergents and cleaners according to the invention in amounts of between 0.1 and 20% by weight, but preferably below 15% by weight and in particular below 10% by weight.

To adjust the viscosity, one or more thickeners or thickening systems can be added to the composition according to the invention. These high-molecular substances, which are also called swelling agents, usually absorb the liquids and swell up to finally pass into viscous true or colloidal solutions.

Suitable thickeners are inorganic or polymeric organic compounds. The inorganic thickeners include, for example, polysilicic acids, clay minerals such as montmorillonites, zeolites, silicas and bentonites. The organic thickeners are derived from the groups of natural polymers, modified natural polymers and fully synthetic polymers. Such naturally derived polymers are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, Locust bean gum, starch, dextrins, gelatin and casein. Modified natural products, which are used as thickeners, come mainly from the group of modified starches and celluloses. By way of example, carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose and core flour ethers may be mentioned here. Fully synthetic thickeners are polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.

The thickeners may be present in an amount of up to 5% by weight, preferably from 0.05 to 2% by weight, and more preferably from 0.1 to 1.5% by weight, based on the finished composition ,

The washing and cleaning agent according to the invention may optionally contain further conventional ingredients sequestrants, electrolytes and other auxiliaries, such as optical brighteners, grayness inhibitors, glass corrosion inhibitors, corrosion inhibitors, Farbü transmission inhibitors, foam inhibitors, Disintegrationshilfsstoffe, abrasives, dyes and / or fragrances, and microbial Active ingredients, UV absorbents and / or enzyme stabilizers.

Detergents according to the invention may contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which are used instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Further, brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned optical brightener can be used.

Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions ,

Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. preferred Glass corrosion inhibitors come from the group of magnesium and zinc salts as well as magnesium and zinc complexes.

The spectrum of the invention preferred zinc salts, preferably organic acids, particularly preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 have mg / l, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubilities at 2O ⁰ C. water temperature). The first group of zinc salts includes, for example, the zinc nitrate, the zinc oleate and the zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

With particular preference is used as the glass corrosion inhibitor at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and Zinkeitrat used. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

In the context of the present invention, the content of zinc salt in detergents or cleaners is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight. , or the content of zinc in oxidized form (calculated as Zn ²⁺ ) between 0.01 to 1 wt .-%, preferably between 0.02 to 0.5 wt .-% and in particular between 0.04 to 0, 2 wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.

Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. According to the invention, preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts, these substances being particularly preferably present in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2 Wt .-%, particularly preferably 0.01 to 0.04 wt .-% are used. Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric and succinic acid. Especially effective are 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-versatic-10-alkyl-3-amino-1, 2,4-triazoles and mixtures of these substances.

In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds used. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

Instead of or in addition to the silver protectants described above, for example the benzotriazoles, redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, wherein the metals preferably in one of the oxidation states II, III, IV, V or VI are present.

The metal salts or metal complexes used should be at least partially soluble in water. The counterions suitable for salt formation comprise all customary mono-, di- or tri-positively negatively charged inorganic anions, for example oxide, sulfate, nitrate, fluoride, but also organic anions such as stearate. Particularly preferred metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ , and mixtures thereof, such that the metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) _{3 are used} with particular preference ,

The inorganic redox-active substances, in particular metal salts or metal complexes are preferably coated, i. completely coated with a waterproof, but easily soluble in the cleaning temperatures material to prevent their premature decomposition or oxidation during storage. Preferred coating materials, which are applied by known methods, such as Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids.

The metal salts and / or metal complexes mentioned are in mechanical

Dishwashing detergents preferably in an amount of 0.05 to 6 wt .-%, in particular from 0.2 to 2.5 wt .-%, each based on the total agent.

"Soil-release" or "soil repellents" are mostly polymers which impart soil repellency when used in a laundry detergent detergent and / or aid in the soil release performance of the other detergent ingredients. A similar effect can also be observed in their use in hard surface cleaners.

Particularly effective and long-known soil release agents are copolyesters with dicarboxylic acid, alkylene glycol and polyalkylene glycol units. Examples thereof are copolymers or copolymers of polyethylene terephthalate and polyoxyethylene glycol, copolymers of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol, polymers of ethylene terephthalate and polyethylene terephthalate, copolyesters of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid, methyl or ethyl group end-capped Polyesters containing ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units, polyesters which, in addition to oxyethylene groups and terephthalic acid units, also contain substituted ethylene units and also glycerol units, polyesters which, in addition to oxyethylene groups and terephthalic acid units, contain 1, 2-propylene, Contain 1, 2-butylene and / or 3-methoxy-1, 2-propylene groups and glycerol units and end-capped with C ₁ - to C ₄ alkyl groups, at least partially by d. _4- alkyl or acyl groups end-capped polyesters with polypropylene terephthalate and polyoxyethylene terephthalate units, sulfoethyl- end-capped terephthalate-containing soil release polyester. According to the European patent application EP 0 357 280, by sulfonation of unsaturated terminal groups soil-release polyesters containing terephthalate, alkylene glycol and poly-C ₂ - ₄ prepared glycol units. International Patent Application WO 95/32232 relates to acidic, aromatic soil release polymers. International Patent Application WO 97/31085 discloses non-polymeric soil repellent active ingredients for multi-functional cotton materials: a first entity, which may be cationic, for example, is capable of adsorption to the cotton surface by electrostatic interaction, and a second Unit that is hydrophobic is responsible for the retention of the drug at the water / cotton interface.

The color transfer inhibitors which are suitable for use in textile detergents according to the invention include in particular polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole.

When used in automated cleaning processes, it may be advantageous to add foam inhibitors to the agents concerned. As foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally signed silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with signed silica or bistearylethylenediamide. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes. Preferably, the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble, or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamides are preferred.

In addition, a hard surface cleaning agent according to the invention may contain abrasive constituents, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and glass microspheres and mixtures thereof. Abrasives are preferably present in the detergents according to the invention in an amount of not more than 20% by weight, in particular in an amount of from 5 to 15% by weight.

In order to facilitate the disintegration of preformed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these compositions in order to shorten the disintegration times. By tablet disintegrants or disintegrants are meant excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients. These substances, which are also referred to as "explosives" due to their effect, increase their volume upon ingress of water, on the one hand increasing the intrinsic volume (swelling), and on the other hand creating a pressure via the release of gases which can break the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.

Preferred disintegrating agents are cellulosic disintegrating agents, so that preferred washing or cleaning agents comprise such cellulose-based disintegrants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. % contain. Pure cellulose has the formal gross composition (C ₆ H ₁₀ Os) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.

The cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns. As a further disintegrating agent based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact. Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 μm and can be compacted, for example, into granules having an average particle size of 200 μm.

Preferred disintegration aids, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are present in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 wt .-%, each based on the total weight of the disintegrating agent-containing agent.

Furthermore, according to the invention, gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries. The gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water. Among these compounds, mention should be made in particular of magnesium peroxide, which liberates oxygen on contact with water. Usually, however, the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas. While a variety of systems are conceivable and executable here, which release, for example, nitrogen, oxygen or hydrogen, the bubble system used in detergents and cleaners can be selected both on the basis of economic and environmental considerations. Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.

As Acidifizierungsmittel which release carbon dioxide from the alkali metal salts in aqueous solution, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred.

Dyes and fragrances are added to detergents and cleaners in order to improve the aesthetic appearance of the products and to provide the consumer with a visually and sensory "typical and unmistakable" product in addition to the washing and cleaning performance. As perfume oils or fragrances can individual Fragrance compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, LiNaI and Bourgeonal, to the ketones, for example, the Jonone, α-lsomethylionon and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons include mainly the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, for example, pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood. Usually, the content of detergents and cleaners to dyes is less than 0.01 wt .-%, while perfumes can account for up to 2 wt .-% of the total formulation.

The fragrances can be incorporated directly into the detergents or cleaners, but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the items to be cleaned and provide a slower release of fragrance for long-lasting fragrance, especially of treated textiles. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients. A further preferred carrier for fragrances is the described zeolite X, which can also absorb fragrances instead of or in mixture with surfactants. Preference is therefore given to washing and cleaning agents containing the described zeolite X and fragrances, which are preferably at least partially absorbed on the zeolite.

Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents such as textiles, glass, ceramics or plastic dishes do not stain them. When choosing the colorant, it must be taken into account that the colorants have a high storage stability and insensitivity to light. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, colorant concentrations in the range of a few 10 ^-2 to 10 ³ % by weight are typically selected. By contrast, in the case of the pigment dyes preferred in particular but less readily water-soluble on account of their brilliance, the suitable concentration of the colorant in detergents or cleaners is typically about 10 ³ to 10 ^-4 % by weight.

Colorants are preferred which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable are, for example, anionic colorants, e.g. anionic nitrosofarads.

Detergents or cleaners may contain antimicrobial agents to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate. The terms antimicrobial action and antimicrobial active substance have the usual meaning within the scope of the teaching according to the invention, which is described, for example, by KH Wallhäußer in "Praxis der Sterilisation, Disinfection - Conservation: Germ Identification - Company Hygiene" (5th edition - Stuttgart, New York: Thieme, 1995 Suitable antimicrobial agents are preferably selected from the groups of the alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, Urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propyl butyl carbamate, iodine, iodophores, peroxo compounds, halogen compounds and any mixtures of the foregoing.

The antimicrobial agent may be selected from ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholine. acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 4,4'-dichloro-2'-hydroxydiphenyl ether (Dichlosan), 2,4,4'-trichloro-2'-hydroxydiphenyl ether (trichlosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) -urea, N, N '- (1 , 10-decanediyldi-1-pyridinyl-4-ylidene) bis- (1-octanamine) dihydrochloride, N, N'-bis (4-chlorophenyl) -3,12-diimino-2,4,11 , 13-tetraaza-tetradecandiinnidanide, glucoprotamines, antimicrobial surface-active quaternary compounds, guanidines including the bi- and polyguanidines, such as, for example, 1,6-bis- (2-ethylhexyl-biguanido-hexane) -dihydrochloride, 1,6-di- ( ₁ N, N-ι'-phenyldiguanido-N _5, N ₅ ') -hexane-tetrahydochlorid, 1, 6-di- (N _{1 11} N' - phenyl-N ^ N ^ N ^ Ns ^ methyldiguanido--hexan- dihydrochloride, 1,6-di- (N ₁ , N ₁ '-o-chloro-phenyldiguanido-N ₅ , N ₅ ') -hexane-dihydrochloride, i-thi-di-Ni, N-i'-thio-dichlorophenyl-diguanido- N ₅ , N ₅ ') hexane dihydrochloride, 1,6-di- [N ₁ , N-i'-beta- (p-nethoxyphenyl) diguanido-N ₅ , N ₅ '] -hexane dihydrochloride, 1, 6 Di- (N ₁ , N ₁ '-alpha-methyl-.beta.-phenyldiguanido-N ₅ , N ₅ ') -hexane dihydrochloride, 1,6-D i- (N ₁ , N-1'-p-nitrophenyldiguanido-N ₅ , N ₅ ') hexane dihydrochloride, omega: onnega-di (N ₁₁ N ₁ ' - phenyldiguanido-N ₅ , N ₅ ') -di n-propyl ether dihydrochloride, omega: onnega'-di- (N ₁ , N ₁ '-p-chlorophenyldiguanido-N ₅ , N ₅ ') di-n-propyl ether tetrahydrochloride, 1,6-di- (N ₁ , N ₁ '-2,4-dichlorophenyldiguanido-N ₅ , N ₅ ') hexane-tetrahydrochloride, 1,6-di- (N ₁ , N ₁ '-p-methylphenyl-diguanido- N ₅ , N ₅ ') hexane dihydrochloride, 1,6-di (N ₁ , N ₁ '-2,4, 5-trichlorophenyldiguanido-N ₅ , N ₅ ') hexanetrahydrochloride, 1,6-di- [N ₁ , N-1'- alpha- (p -chlorophenyl) ethyldiguanido-N ₅ , N ₅ '] hexanedihydrochloride, omega-omega-di-N, N 1 -p-chlorophenyldiguanido-N, N, n-xylenedihydrochloride, 1, 12-di- ( N ₁ , N-1'-p-chlorophenyldiguanido-N ₅ , N ₅ ') dodecane dihydrochloride, 1, 10-di- (N ₁₁ N ₁ ' - phenyldiguanido- N ₅ , N ₅ ') -decane tetrahydrochloride, 1, 12-di- (N ₁ , N-i'-phenyl-diguanido- N ₅ , N ₅ ') dodecane-tetrahydrochloride, 1, 6-di- (N ₁ , N-i'-o-chlorophenyldiguanido- N ₅ , N ₅ ') hexane-dihyd ochloride, 1,6-di- (N ₁ , N-i'-o-chlorophenyldiguanido- N ₅ , N ₅ ') hexane-tetrahydrochloride, ethylene-bis- (1-tolyl biguanide), ethylene-bis- (p-) tolyl biguanide), ethylene bis (3,5-dimethylphenylbiguanide), ethylene bis (p-tert-amylphenyl biguanide), ethylene bis (nonylphenyl biguanide), ethylene bis (phenylbiguanide), ethylene bis (N butylphenylbiguanide), ethylene bis (2,5-diethoxyphenylbiguanide), ethylene bis (2,4-dimethylphenyl biguanide), ethylene bis (o-diphenylbiguanide), ethylene bis (mixed amyl naphthyl biguanide), N-butyl ethylene -bis (phenylbiguanide), trimethylene bis (o-tolylbiguanide), N-butyl-trimethyl-bis (phenyl biguanide) and the corresponding salts such as acetates, gluconates, hydrochlorides, hydrobromides, citrates, bisulfites, fluorides, polymaleates, N- Cocoalkyl sarcosinates, phosphites, hypophosphites, perfluorooctanoates, silicates, sorbates, salicylates, maleates, tartrates, fumarates, ethylenediaminetetraacetates, iminodiacetates, cinnamates, thiocyanates, arginates, pyromellitates, tetracarboxybutyrates, Ben zoates, glutarates, monofluorophosphates, perfluoropropionates and any mixtures thereof. Also suitable are halogenated xylene and cresol derivatives, such as p-chlorometacresol or p-chloro-meta-xylene, and natural antimicrobial agents of plant origin (for example, from spices or herbs), animal and microbial origin. Preferably, antimicrobial surface-active quaternary compounds, a natural antimicrobial agent of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent of plant origin from the group comprising caffeine, theobromine and theophylline and essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial agent of animal origin from the group comprising Enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound having an ammonium, sulfonium, phosphonium, iodonium or Arsoniumgruppe, peroxo compounds and chlorine compounds are used. Also substances of microbial origin, so-called bacteriocins, can be used.

The quaternary ammonium compounds (QAV) suitable as antimicrobial agents have the general formula (R ¹ ) (R ² ) (R ³ ) (R ⁴ ) N ⁺ X ^- , in which R ¹ to R ^{4 are the} same or different C ₁ - C ₂₂ -alkyl radicals, C ₇ -C ₂₈ -aralkyl radicals, or heterocyclic radicals, or in the case of an aromatic compound such as pyridine-even three groups together with the nitrogen atom forming the heterocycle, for example a pyridinium or imidazolinium compound, and X ^" For optimal antimicrobial activity, at least one of the radicals preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.

QACs can be prepared by reacting tertiary amines with alkylating agents, such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide. The alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly easy, the quaternization of tertiary amines with two long radicals and one methyl group can be carried out with the aid of methyl chloride under mild conditions. Amines having three long alkyl radicals or hydroxy-substituted alkyl radicals are less reactive and are preferably quaternized with dimethyl sulfate.

Suitable QACs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (m, p-dichlorobenzyldimethyl-C 12 -alkylammonium chloride, CAS No. 58390-78-6), benzoxonium chloride (benzyldodecylbis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethylammonium bromide, CAS No. 57 -09-0), Benzetonium chloride (N, N-dimethyl-N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzyl ammonium chloride, CAS No 121-54-0), dialkyldimethylammonium chlorides such as di-n-decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyl- dimethyl ammonium chloride, 1-cetylpyridinium chloride (CAS No. 123-03-5) and thiazoline iodide (CAS No. 15764-48-1) and mixtures thereof. Particularly preferred QUATS are the benzalkonium chlorides having C ₈ -C ₁₈ alkyl radicals, in particular C ^ -C _M -Aklyl-benzyl-dimethyl-ammonium chloride.

Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ^® ex Lonza, Marquat® ^® ex Mason, Variquat ^® ex Witco / Sherex and Hyamine ^® ex Lonza and as Bardac ^® ex Lonza. Other commercially obtainable antimicrobial agents are hexaminium N- (3-chloroallyl) as Dowicide and Dowicil ^{® ®} ex Dow, Benzethonium as Hyamine ^® 1622 ex Rohm & Haas, methylbenzethonium as Hyamine ^® 10X ex Rohm & Haas, cetylpyridinium chloride such Cepacol ex Merrell Labs.

The antimicrobial agents are used in amounts of 0.0001 wt .-% to 1 wt .-%, preferably from 0.001 wt .-% to 0.8 wt .-%, particularly preferably from 0.005 wt .-% to 0.3 wt .-% and in particular from 0.01 to 0.2 wt .-% used.

The detergents or cleaners according to the invention may contain UV absorbents (UV absorbers) which are applied to the treated textiles and improve the lightfastness of the fibers and / or the lightfastness of other formulation constituents. Under UV absorber are organic substances (sunscreen) to understand, which are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, for example, to give off heat.

Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Furthermore, substituted benzotriazoles, in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives, optionally with cyano groups in the 2-position), salicylates, organic Ni complexes and natural products such as umbelliferone and the body's own urocanic acid are suitable. The biphenyl and, above all, stilbene derivatives as described for example in EP 0728749 A are described and commercially available as Tinosorb FD ^{® ®} or Tinosorb FR ex Ciba. As UV-B absorbers may be mentioned: 3-Benzylidencampher or 3-Benzylidennorcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor, as described in EP 0693471 B1; A-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl A- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives such as 2,4,6-trianilino (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyl triazone as described in EP 0818450 A1 or dioctyl butamido Triazone (Uvasorb® HEB); Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives, as described in EP 0694521 B1. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5- sulfonic acid and its salts; Sulfonic acid derivatives of 3-Benzylidencamphers, such as A- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.

As a typical UV-A filter, in particular derivatives of benzoylmethane come into question, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1, 3-dione and also enamine compounds, as described in DE 19712033 A1 (BASF). Of course, the UV-A and UV-B filters can also be used in mixtures. In addition to the soluble substances mentioned, insoluble photoprotective pigments, namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. As salts silicates (talc), barium sulfate or zinc stearate can be used. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape. The pigments may also be surface-treated, that is to say hydrophilized or hydrophobicized. Typical examples are coated titanium dioxides, such as, for example, titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck; preferred hydrophilic coating agents are silicones and particularly preferably trialkoxyoctylsilanes or simethicones.) Micronized zinc oxide is preferably used in the review by P. Finkel in SÖFW-Journal XΣλ (1996), p. 543.

The UV absorbents are usually used in amounts of from 0.01% by weight to 5% by weight, preferably from 0.03% by weight to 1% by weight.

Compositions according to the invention may contain, in addition to the abovementioned, optionally contained hydrogen peroxide-producing oxidoreductases, also other enzymes for increasing the washing or cleaning performance, it being possible in principle to use all enzymes established for this purpose in the prior art. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, amadoriases or other oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Compositions according to the invention preferably contain these further enzymes in total amounts of 1 × 10 ^-6 to 5 percent by weight, based on active protein. Among the proteases, those of the subtilisin type are preferable. Examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg in a developed form under the trade names Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. Listed under the name BLAP ^® variants of the protease from Bacillus lentus DSM 5483 (WO 91/02792 A1) to derive, in particular, in WO 92/21760 A1, WO 95/23221 A1, WO 02/088340 A2 and WO 03 / 038082 A2. Other useful proteases from various Bacillus sp.- and ß. g / oson / V strains are evident from the patent applications WO 03/054185, WO 03/056017, WO 03/055974, WO 03/054184, DE 102006022216 and DE 102006022224.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, the ^® under the trade names Purafect ^®, Purafect ^® OxP, Purafect Prime and Properase.RTM ^® from Genencor, that under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, the P under the trade names Proleather® ^® and protease ^® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme under the name proteinase K-16 from Kao Corp., Tokyo, Japan, available.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from β. amyloliquefaciens or from ß. stearothermophilus and their improved for use in detergents and cleaners further developments. The enzyme from ß. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α- amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase of β. amyloliquefaciens is sold by Novozymes under the name BAN ^®, and variants derived from the α-amylase from B.. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes. Further usable commercial products are, for example, the amylase LT® and Stainzyme®, the latter also from Novozymes.

Furthermore, the α-amylase from Bacillus sp. Disclosed in the application WO 02/10356 A2 for this purpose. A 7-7 (DSM 12368) and described in the application WO 02/44350 A2 Cyclodextrin glucanotransferase (CGTase) from ß. agaradherens (DSM 9948). Furthermore, the amylolytic enzymes which belong to the sequence space of α-amylases, which is defined in the application WO 03/002711 A2, and those which are described in the application WO 03/054177 A2 can be used. Likewise, fusion products of the molecules mentioned can be used, for example those from application DE 10138753 A1.

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae, which are. Another commercial product is, for example, the amylase ^LT® .

Compositions according to the invention may contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^®, Lipolase Ultra ^®, LipoPrime® ^®, Lipozyme® ^® and Lipex ^®. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusahum solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. ^Lipase® , Lipase ^AP® , Lipase M- ^AP® and Lipase ^{AML® are} available. From the company Genencor, for example, the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products are the originally marketed by Gist-Brocades preparations M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention also the product Lumafast® ^® from Genencor.

Detergents according to the invention, especially if they are intended for the treatment of textiles, may contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously supplement each other in terms of their various performance aspects. These performance aspects include in particular contributions to the primary washing performance, to the secondary washing performance of the agent

(Anti-redeposition effect or graying inhibition) and softening (fabric effect), up to the exercise of a "stone washed" effect.

A useful fungal, endoglucanase (EG) -rich cellulase preparation, or its further developments are offered by Novozymes under the trade name Celluzyme ^®. The products also available from the company Novozymes Endolase ^® and Carezyme ^® based on the 50 kD EG and 43 kD EG from H. insolens DSM 1800. Further commercial products of this company are Cellusoft® ^® and Renozyme ^®. The latter is based on the application WO 96/29397 A1. Performance-enhanced cellulase variants are disclosed, for example, in the application WO 98/12307 A1. Likewise, the cellulases disclosed in the application WO 97/14804 A1 can be used; For example, it revealed 20 kD EG Melanocarpus, available from AB Enzymes, Finland, under the trade names Ecostone® ^® and Biotouch ^®. Further commercial products from AB Enzymes are Econase® ^® and ECOPULP ^®. Other suitable cellulases from Bacillus sp. CBS 670.93 and CBS 669.93 are disclosed in WO 96/34092 A2, wherein those derived from Bacillus sp. CBS 670.93 from the company Genencor under the trade name Puradax ^{® is} available. Further commercial products of the company Genencor are "Genencor detergent cellulase L" and lndiAge ^® Neutra.

Compositions according to the invention may contain, in particular for the removal of certain problem soiling, further enzymes which are combined under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 L from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, USA , A suitable ß-glucanase from a ß. alcalophilus, for example, results from the application WO 99/06573 A1. The from ß. subtilis derived beta-glucanase is available under the name Cereflo ^® from Novozymes.

In addition to the abovementioned hydrogen peroxide-producing oxidoreductase, further oxidoreductases may also be present in the compositions according to the invention, in particular oxidases, oxygenases, laccases (phenol oxidase, polyphenol oxidases) and / or dioxygenases. Suitable commercial products for laccases may be mentioned Denilite® ^® 1 and 2 from Novozymes. In a preferred embodiment, the optionally contained further oxidoreductase is selected from enzymes which use peroxides as electron acceptors (EC class 1.11 or 1.11.1), in particular from catalases (EC 1.11.1.6), peroxidases (EC 1.11.1.7), glutathione peroxidases (EC 1.11.1.9), chloride peroxidases (EC 1.11.1.10), manganese peroxidases (EC 1.1 1.1.13) and / or lignin peroxidases (EC 1.11.1.14), which are generally also summarized under the term peroxidases. Instead of or in addition to these peroxidases, perhydrolases can also be used. Perhydrolases, formerly also called metal-free haloperoxidases, usually contain the catalytic triad Ser-His-Asp in the reaction center and catalyze the reversible formation of peracids starting from carboxylic acids and hydrogen peroxide. With regard to perhydrolases which can be used according to the invention, reference may be made in particular to the applications WO 98/45398, WO 04/58961, WO 05/56782 and PCT / EP05 / 06178. When using perhydrolases are accordingly preferably also carboxylic acids whose

Salts and / or their esters and / or derivatives thereof in the inventive

Contain compositions. As examples, in general, compounds of the formula R ¹ - (R ² ) _m -

OR ³ called, where

R ^{1 is} R ⁴ C (O) - or R ⁴ C (NR ⁵ ) -,

R ^{3 is} hydrogen or optionally substituted, in particular substituted by optionally substituted amino groups, alkyl, alkenyl, alkynyl, aryl, alkylaryl, heteroaryl or

Alkylheteroaryl or a group -XO- (R ^2b ) _n -R ^1b ,

R ^{4 is} hydrogen or optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl,

Heteroaryl or alkylheteroaryl or a group -YR ^1a - (R ^2a ) _o -OR ^3a ,

X and Y are optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl, heteroaryl or

Are alkylheteroaryl,

R ² , R ^2a and R ^{2b represent} an alkoxy group,

R ^{1a represents} -C (O) - or -C (NR ⁵ ) -,

R ^{1b is} R ⁶ C (O) - or R ⁶ C (NR ⁵ ) -,

R ^3a and R ^{6 are} hydrogen or optionally substituted alkyl, alkenyl, alkynyl, aryl,

Alkylaryl, heteroaryl or alkylheteroaryl,

R ^{5 is} hydrogen or alkyl, m, n and o independently of one another assume a value of 0 to 12.

Examples of carboxylic acids which may optionally be used in the form of their esters and / or salts according to the invention include acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, decanoic acid, maleic acid, oxalic acid, benzoic acid, citric acid, lactic acid, fruit acids and phthalic acid. The carboxylic acids, their salts and / or their esters, if perhydrolases are used, preferably in an amount of 0.1 to 20 wt .-%, particularly preferably in an amount of 0.5 to 10 wt .-% in the inventive Contain compositions.

The enzymes used in agents according to the invention are preferably either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or filamentous fungi.

The purification of the relevant enzymes is conveniently carried out by conventional methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps. The enzymes are preferably employed in an amount of from 40 μg to 4 g, in particular from 50 μg to 3 g, more preferably from 100 μg to 2 g and most preferably from 200 μg to 1 g per application. Included are all integer and non-integer values lying between these numbers.

The agents of the invention may be added to the enzymes in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers. Alternatively, these proteins can be adsorbed and / or encapsulated on a solid support for both the solid and liquid dosage forms.

Encapsulation can be carried out, for example, by spray-drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core a water, air and / or chemical impermeable protective layer is coated. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

The encapsulated form lends itself to protecting the enzymes or other ingredients from other ingredients, such as bleaches, or to allow for controlled release. Depending on the size of these capsules, a distinction is made to MiIIi-, micro- and nanocapsules, with microcapsules for enzymes being particularly preferred. Such capsules are disclosed, for example, in patent applications WO 97/24177 and DE 19918267. Another possible encapsulation method is that the proteins are encapsulated in this substance, starting from a mixture of the protein solution with a solution or suspension of starch or a starch derivative. Such an encapsulation process is described in the application WO 01/38471.

In a particular embodiment, granulation of the enzymes can also be carried out as described in the application DE 102006018780. In addition to the enzymes, it is also possible to granulate further detergent or cleaning agent ingredients, in particular sensitive substances, such as, for example, fragrances or optical brighteners, and bleach activators and the siderophore metal complexes to be used according to the invention, in front of other components, in particular bleaching agents to protect, and / or to keep them in proper concentration provide. Furthermore, it is possible to combine two or more ingredients, in particular enzymes together, so that a single granulate contains several enzyme activities.

As particularly advantageous bleach catalyst granules have been found, based on the total weight of the granules a) 0.1 to 30 wt .-% of the metal siderophore complex and optionally further bleach catalyst, b) 10 to 99 wt .-% of a support material, and c) 0.1 to 5 wt .-% of a binder from the group of organic polymers.

The optionally used further bleach catalyst according to a) here is preferably selected from the further bleach catalysts mentioned above.

Suitable support materials b) are in principle all substances or mixtures of substances which can be used in detergents and cleaners and compatible with the other ingredients, in particular the builders enumerated above, especially the carbonates, including the hydrogencarbonates, the sulfates, the chlorides, the silicates and the phosphates , Particularly suitable carrier materials here are alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, alkali metal silicates, alkali metal silicates, alkali metal phosphates and mixtures of these substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, and / or alkali metal phosphates for the purposes of this invention. In a particularly preferred embodiment, the carrier used is the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) or the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate).

The proportion by weight of the support material b) on the total weight of the bleach catalyst granules can be varied within the limits given above, with particular weight percentages above 20 wt .-%, preferably above 40 wt. Regarding the processability and the actual bleaching performance after assembly with other washing and cleaning active ingredients .-% and in particular above 60 wt .-% have proven to be advantageous. Consequently, in the context of the present application, bleach catalyst granules are preferred in which the weight fraction of the carrier material b) in the total weight of the granules is from 20 to 99% by weight, preferably between 40 and 95% by weight and in particular between 60 and 90% by weight ,

As a third ingredient, the bleach activator granules of the invention contain a binder c) from the group of organic polymers. The polymers may be nonionic, anionic, cationic or amphoteric in nature. Natural polymers and modified polymers of natural origin are usable as well as synthetic polymers. The group of nonionic polymers used with particular preference as a binder c) include polyvinyl alcohols, acetalated polyvinyl alcohols, polyvinylpyrrolidones and polyalkylene glycols, especially polyethylene oxides. Preferred polyvinyl alcohols and acetalized polyvinyl alcohols have molecular weight in the range of 10,000 to 100,000 gmol ^1, preferably 11,000 to 90,000 gmol ^"1, more preferably from 12,000 to 80,000 ^{gmol" 1} and in particular from 13000 to 70,000 gmol ^"-1. Preferred polyethylene oxides have molecular weights Range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000.

The group of anionic polymers used with particular preference as a binder c) include, in particular, homo- or copolymeric polycarboxylates, polyacrylic acids and polymethacrylic acids, in particular those which have been mentioned previously as organic builders useful for detergents and cleaners, and polymers containing sulfonic acid groups, in particular those which have been previously mentioned as useful softeners.

With regard to the group of cationic and amphoteric polymers used with particular preference as binders c), reference is made to the polymers already listed above as washing and cleaning-active polymers.

In preferred bleach catalyst granules according to the invention, the weight fraction of the binder c) in the total weight of the granulate is between 0.2 and 4.5% by weight, preferably between 0.5 and 4.0% by weight and in particular between 1, 0 and 4, 0% by weight.

The bleach catalyst granules preferably have an average particle size of between 0.1 and 1.0 mm, more preferably between 0.2 and 0.8 mm and in particular between 0.3 and 0.7 mm, the proportion by weight of the particles having a particle size below 0 , 1 mm preferably at least 4 wt .-%, particularly preferably at least 6 wt .-% and in particular at least 8 wt .-%, but at the same time preferably at most 80 wt .-%, particularly preferably at most 60 wt .-% and in particular at most 40 Wt .-%, and the weight fraction of the particles having a particle size between 0.2 and 0.8 mm, preferably between 30 and 70 wt .-%, particularly preferably between 45 and 65 wt .-% and in particular between 40 and 60 wt .-% is

In addition to the bleach catalyst, enzymes or other ingredients, in particular sensitive, can also be formulated in the manner described above.

A protein contained in an agent according to the invention can be protected especially during storage against damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes is an inhibition of proteolysis particularly preferred, especially if the agents also contain proteases. Preferred agents according to the invention contain stabilizers for this purpose.

One group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of the compounds mentioned. Also, peptide aldehydes, that is oligopeptides with a reduced C-terminus, especially those of 2 to 50 monomers are used for this purpose. The peptidic reversible protease inhibitors include, among others, ovomucoid and leupeptin. Also, specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.

Other enzyme stabilizers are aminoalcohols, such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to Ci _2, such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Certain organic acids used as builders are additionally capable of stabilizing a contained enzyme.

Lower aliphatic alcohols, but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers. Di-glycerol phosphate also protects against denaturation due to physical influences. Likewise, calcium and / or magnesium salts are used, such as calcium acetate or calcium formate.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polyamine N-oxide containing polymers act simultaneously as enzyme stabilizers and as dye transfer inhibitors. Other polymeric stabilizers are linear C ₈ -C ₈ polyoxyalkylenes. Also, alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and are able, preferably, to additionally increase their performance. Crosslinked N-containing compounds preferably perform a dual function as soil release agents and as enzyme stabilizers. Hydrophobic, nonionic polymer stabilizes in particular an optionally contained cellulase.

Reducing agents and antioxidants increase the stability of the enzymes to oxidative degradation; For example, sulfur-containing reducing agents are familiar. Other examples are sodium sulfite and reducing sugars. Particular preference is given to using combinations of stabilizers, for example of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The effect of peptide-aldehyde stabilizers is favorably enhanced by the combination with boric acid and / or boric acid derivatives and polyols, and still further by the additional action of divalent cations, such as calcium ions.

In the case of solid agents, the proteins can be used, for example, in dried, granulated and / or encapsulated form. They may be added separately, ie as a separate phase, or with other ingredients together in the same phase, with or without compaction. If microencapsulated enzymes are to be processed in solid form, the water can be removed by methods known from the prior art from the aqueous solutions resulting from the workup, such as spray drying, centrifuging or by solubilization. The particles obtained in this way usually have a particle size between 50 and 200 microns.

The proteins may be added to liquid, gelatinous or pasty agents according to the invention in a concentrated aqueous or non-aqueous solution, suspension or emulsion starting from a protein recovery and preparation carried out in the prior art, but also in gel form or encapsulated or as a dried powder. Such detergents or cleaners according to the invention are generally prepared by simple mixing of the ingredients which can be added in bulk or as a solution in an automatic mixer.

The proportion of the enzymes, the enzyme liquid formulation (s) or the enzyme granules in a washing or cleaning agent may, for example, be about 0.01 to 5% by weight, preferably 0.12 to about 2.5% by weight.

A cleaning agent according to the invention, in particular a hard surface cleaner according to the invention, may also contain one or more propellants (INCI propellants), usually in an amount of 1 to 80% by weight, preferably 1 to 5 to 30% by weight, in particular 2 to 10 wt .-%, particularly preferably 2.5 to 8 wt .-%, most preferably 3 to 6 wt .-%, contained.

Propellants are inventively usually propellants, especially liquefied or compressed gases. The choice depends on the product to be sprayed and the field of application. When using compressed gases such as nitrogen, carbon dioxide or nitrous oxide, which are generally insoluble in the liquid detergent, the operating pressure decreases with each valve actuation. In the detergent soluble or even as a solvent Acting liquefied gases (liquefied gases) as propellants offer the advantage of constant operating pressure and uniform distribution, because in the air the propellant evaporates and takes up a volume of several hundred times.

According to INCI suitable blowing agents are accordingly: butanes, carbon dioxides, dimethyl carbonates, dimethyl ether, ethanes, Hydrochlorofluorocarbon 22, hydrochlorchlorofluorocarbon 142b, hydrofluorocarbon 152a, hydrofluorocarbon 134a, hydrofluorocarbon 227ea, isobutanes, isopentanes, nitrogen, nitrous oxides, pentanes, Propane. Chlorofluorocarbons (chlorofluorocarbons, CFCs) as propellant are, however, preferably largely and in particular completely dispensed with because of their harmful effect on the ozone shield of the atmosphere, which protects against hard UV radiation, the so-called ozone layer.

Preferred blowing agents are liquefied gases. Liquid gases are gases that can be performed at mostly already low pressures and 2O ⁰ C from the gaseous to the liquid state. In particular, under liquefied gases, however, are the hydrocarbons propane, propene, butane, butene, isobutane (2-methylpropane), isobutene (2-methylpropene), which are obtained in oil refineries as by-products from distillation and cracking of petroleum and in natural gas treatment during gasoline separation. Isobutylene) and mixtures thereof.

The cleaning agent particularly preferably contains propane, butane and / or isobutane, in particular propane and butane, as one or more propellants, more preferably propane, butane and isobutane.

A separate subject of the invention are processes for the automated cleaning of textiles or of hard surfaces, in which at least in one of the process steps an inventive siderophore-metal complex is used.

This includes both manual and mechanical processes, with mechanical processes being preferred on account of their more precise controllability, for example with regard to the quantities and reaction times used.

Methods for cleaning textiles are generally distinguished by the fact that various cleaning-active substances are applied to the items to be cleaned in a plurality of process steps and washed off after the action time, or that the items to be cleaned are otherwise treated with a detergent or a solution of this agent. The same applies to processes for the purification of all materials other than textiles, which are summarized under the term "hard surfaces." All conceivable washing or cleaning processes can be used in at least one of the process steps in accordance with the invention Siderophore metal complexes are enriched, and then represent embodiments of the present invention.

A separate subject of the invention is the use of siderophore-metal complexes according to the invention for the purification of textiles or of hard surfaces. Accordingly, the above-mentioned concentration ranges apply correspondingly for these uses.

For inventive siderophore-metal complexes can, in particular according to the properties described above and the methods described above, be used to oxidatively remove impurities from textiles or hard surfaces. Embodiments include, for example, hand washing, manual removal of stains from fabrics or hard surfaces, or use in conjunction with a machine process.

In a preferred embodiment of this use, the siderophore-metal complexes according to the invention are in this case provided in the context of one of the above formulations for agents according to the invention, preferably detergents or cleaners.

A powdery heavy duty detergent according to the invention may preferably be e.g. Contain components that are selected from the following:

Anionic surfactants, e.g. Alkylbenzenesulfonate, alkyl sulfate, in amounts of advantageously 5-30 wt .-%, preferably 8-15 wt .-%, in particular 15-20 wt .-%,

Nonionic surfactants, e.g. Fatty alcohol polyglycol ethers, alkyl polyglucoside, fatty acid glucamide, advantageously 0.1-20% by weight, preferably 2-15% by weight, in particular 6-11% by weight,

Builders, e.g. Zeolite, polycarboxylate, sodium citrate, 5-60% by weight, preferably 10-55% by weight, in particular 15-40% by weight,

Alkalis, e.g. Sodium carbonate, advantageously 1-30% by weight, preferably 2-25% by weight, in particular 5-20% by weight,

Bleaching agents, e.g. Sodium perborate, sodium percarbonate, advantageously 5-25% by weight, preferably 10-20% by weight,

- corrosion inhibitors, e.g. Sodium silicate, advantageously 1-6% by weight, preferably 2-5% by weight, in particular 3-4% by weight,

Stabilizers, e.g. Phosphonates advantageously 0-1% by weight,

Foam inhibitor, e.g. Soap, silicone oils, paraffins advantageously 0.1-4% by weight, preferably 0.2-2% by weight, in particular 1-3% by weight,

Enzymes, e.g. Proteases, amylases, cellulases, lipases, advantageously 0.1-2% by weight, preferably 0.2-1% by weight, in particular 0.3-0.8% by weight,

Graying inhibitor, eg carboxymethylcellulose, advantageously 0-1% by weight, Discoloration inhibitor, for example polyvinylpyrrolidone derivatives, advantageously 0-2% by weight,

- Adjustment means, e.g. Sodium sulfate, advantageously 0-20% by weight,

Optical brighteners, e.g. Stilbene derivative, biphenyl derivative, advantageously 0.1-0.3 wt .-%, in particular 0.1-0.4 wt .-%,

- fragrances,

- Water,

- Soap,

- bleach activators

- Cellulosic derivatives

- dirt deflector,

0.01 to 5% by weight, preferably 0.02 to 4% by weight and in particular 0.05 to 3% by weight of siderophores and / or siderophore-metal complexes as bleach catalysts.

A liquid heavy duty detergent according to the invention may preferably be e.g. contain the following components that are selected from the following:

Anionic surfactants, e.g. Alkylbenzenesulfonate, alkyl sulfate, in amounts of advantageously 5-40 wt .-%, preferably 8-30 wt .-%, in particular 15-25 wt .-%,

Nonionic surfactants, e.g. Fatty alcohol polyglycol ethers, alkyl polyglucoside, fatty acid glucamide, advantageously 0.1-25% by weight, preferably 5-20% by weight, in particular 10-15% by weight,

Builders, e.g. Zeolite, polycarboxylate, sodium citrate, advantageously 0-15% by weight, preferably 0.01-10% by weight, in particular 0.1-5% by weight,

Foam inhibitor, e.g. Soap, silicone oils, paraffins, advantageously 0.1-4% by weight, preferably 0.2-2% by weight, in particular 1-3% by weight,

Enzymes, e.g. Proteases, amylases, cellulases, lipases, advantageously 0.1-2% by weight, preferably 0.2-1% by weight, in particular 0.3-0.8% by weight,

Optical brighteners, e.g. Stilbene derivative, biphenyl derivative, advantageously 0.1-0.3 wt .-%, in particular 0.1-0.4 wt .-%,

- perfumes

- stabilizers,

- Water,

Soap, advantageously 1-20% by weight, preferably 2-15% by weight, in particular 5-10% by weight,

Alcohols / solvents, advantageously 0-25% by weight, preferably 1-20% by weight, in particular 2-15% by weight,

From 2 to 20% by weight, preferably from 4 to 15% by weight and in particular from 6 to 12% by weight of bleaching agent; such as

0.01 to 5% by weight, preferably 0.02 to 4% by weight and in particular 0.05 to 3% by weight, of siderophores and / or siderophore-metal complexes as bleach catalysts. Another object of the present invention is also a product comprising a composition according to the invention or a detergent or cleaning agent according to the invention, in particular a hard surface cleaner according to the invention, and a spray dispenser. The product may be both a single-chamber and a multi-chamber container, in particular a two-chamber container. The spray dispenser is preferably a manually activated spray dispenser, in particular selected from the group consisting of aerosol spray dispensers (pressurized gas containers, also known as spray can), pressure-building spray dispensers, pump spray dispensers and trigger spray dispensers, in particular pump spray dispensers and trigger spray dispensers with a transparent polyethylene or polyethylene terephthalate container. Spray dispensers are described in more detail in WO 96/04940 (Procter & Gamble) and the US patents cited therein about spray dispensers, to which reference is made in this regard and the contents of which are hereby incorporated by reference. Triggersprühspender and pump sprayer have over compressed gas tanks the advantage that no propellant must be used. By means of suitable particles-passing attachments, nozzles, etc. (so-called "nozzle valves") on the spray dispenser, optionally contained enzyme in this embodiment can optionally also be added to the composition in a form immobilized on particles and thus metered in as a cleaning foam.

Machine dishwashing agents which are particularly preferred according to the invention comprise

From 5 to 70% by weight, preferably from 10 to 60% by weight and in particular from 20 to 50% by weight

Scaffold (s), with the exception of washing and cleaning-active polymers;

2 to 28 wt .-%, preferably 4 to 20 wt .-% and in particular 6 to 15 wt .-% washing and cleaning-active polymers;

0.5 to 10 wt .-%, preferably 1 to 8 wt .-% and in particular 2 to 6 wt .-% of surfactant (s), preferably nonionic (s) and / or amphoteric (s) surfactant (s);

0.5 to 8 wt .-%, preferably 1 to 7 wt .-% and in particular 2 to 6 wt .-% enzyme (s);

2 to 20% by weight, preferably 4 to 15% by weight and in particular 6 to 12% by weight

Bleach; such as

0.01 to 5 wt .-%, preferably 0.02 to 4 wt .-% and in particular 0.05 to 3 wt .-%

Siderophores and / or siderophore metal complexes as bleach catalysts.

The preparation of automatic dishwashing agents according to the invention can take place in different ways. The compositions according to the invention can be present in solid or liquid form as well as a combination of solid and liquid forms.

Powder, granules, extrudates or compactates, in particular tablets, are particularly suitable as firm supply forms. The liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels. Inventive agents can be formulated in the form of single-phase or multi-phase products. In particular, automatic dishwashing detergents with one, two, three or four phases are preferred. Machine dishwashing detergent, characterized in that it is in the form of a prefabricated dosing unit with two or more phases, are particularly preferred.

The individual phases of multiphase agents may have the same or different states of aggregation. Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one solid phase are preferred.

Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g.

The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.

The automatic dishwasher detergents according to the invention, in particular the prefabricated metering units, have a water-soluble coating, with particular preference.

The following examples further illustrate the invention without being limited thereto.

embodiments

Example 1: Preparation of Desferrioxamine E Metal Complexes and Examination of Their Bleaching Effect on Tea

a) Preparation of the tea solution

1, 6 g of black unscented tea is poured boiling with one liter of distilled water and allowed to soak for 5 minutes. Subsequently, the insoluble constituents are filtered through a pleated filter and after cooling to room temperature, the pH is adjusted to 10.0 with sodium hydroxide solution. The solution can be used for 1-2 days. b) Preparation of Siderophore Metal Complexes

0.025 mmol (based on the metal atom) of the metal salt to be tested is stirred in 25 ml of deionized water with 0.050 mmol desferrioxamine E (DFE) for up to 24 hours at room temperature in an open vessel. Subsequently, the pH is adjusted to 10 and allowed to stand for 48 hours at room temperature and then freed of insoluble matter by sterile filtration through a syringe attachment filter. A metal-free solution of desferrioxamine E is prepared in the same way, but not mixed with metal salt.

c) Measurement of the bleaching performance

A hydrogen peroxide solution of 1050 μl of 30% perhydrol in 100 ml of borate buffer is freshly prepared. The metal complexes are diluted with 50 mM borate buffer, pH 10.0 to 5.88 mg of the metal per liter. For comparison, the bleaching performance of a commercially available bleach catalyst is determined. For this purpose, an Mn-TACN solution (complex of manganese ions and triazacyclononane) with 5.88 mg Mn per liter is used.

Table 1: Pipetting scheme:

The hydrogen peroxide solution is added as the last before lugs sealed and incubated at 4O ⁰ C for one hour. Subsequently, the Extinktiosmessung takes place at 400 nm in the spectrophotometer against water. The decrease in absorbance ΔE minus that of the uncatalyzed bleach is a measure of the bleaching performance and indicates how much the tested metal complex can favor hydrogen peroxide bleaching.

Table 2: Bleaching performance of DFE metal complexes compared to Mn-TACN

It can be seen that the siderophore metal complexes of manganese and cobalt improved the bleaching performance of hydrogen peroxide. In addition, the bleaching performance of the cobalt complex has been improved compared to Mn-TACN, which has been used as an example of the prior art.

Example 2: Preparation of Further Siderophore Metal Complexes and Examination of Their Bleaching Effect on Tea

The preparation of the siderophore-metal complexes and the rest of the experiment was carried out as described in Example 1. However, the washing tests were not carried out in water, but in the formulation of a commercial liquid detergent as a matrix.

Various metal complexes of the following siderophores were prepared and tested for bleaching performance: a) siderophores with three hydroxamate groups: ferrichrome, coprogen b) siderophore with two hydroxamate groups and one catecholate group: pyoverdin Pa c) siderophore with two hydroxamate groups and one alpha-hydroxy carboxylate Group: ornibactin, arthrobactin, schizokines d) siderophores with two hydroxamate groups and several carboxylic acid amide groups: rhodotorulic acid e) siderophores with three partially hydrogenated thiazole rings: yersiniabactin f) siderophores with two alpha-hydroxy carboxylate groups, two carboxylic acid amide groups and two other carboxylate groups: rhizoferrin g) siderophore with three catecholate groups: enterobactin

To evaluate the bleaching performance, the bleaching performance of the solution with hydrogen peroxide without catalyst was set to 100%, meaning that values above 100 indicate better bleaching performance and values below 100 indicate poorer bleaching performance than the detergent with hydrogen peroxide without catalyst.

Table 3: Bleaching performance of various siderophore-metal complexes

Table 4: Bleaching performance of various siderophore-metal complexes

As can be seen from the table, a significant improvement in the bleaching performance can be achieved by numerous different siderophore-metal complexes. Particularly noteworthy is the consistently high increase in bleaching performance by complexes of siderophores with cerium, vanadium, manganese and cobalt ions. Furthermore, the consistently high bleaching performance of schizokinin, rhodotrulsic acid and ornibactin metal complexes is striking.

Example 3: Bleaching of tea and blueberry stains on fabrics by Mn-DFE and Mn-schizokines

With the Mn-desferrioxamine complex according to Example 1, the bleaching effect on tea and blueberry stains on cotton fabric was examined and compared with a Mn-schizokine complex. For this purpose, mini-wash tests were carried out and then performed a quantitative digital optical evaluation.

Solutions:

- Hydrogen peroxide solution from 1050 ul_ 30% perhydrol in 100 ml_ borate buffer (see Example 1) set.

Mn-desferrioxamine complex (see Example 1) is treated with borate buffer 50 mM; pH 10 to 5.88 mg of the metal per liter.

- Mn-schizokine complex, prepared analogously to desferrioxamine complex.

Synthetic tap water consisting of deionized water with subsequently defined hardness. Glycine / NaOH buffer 150 mM, pH 10.

Table 5: Pipetting scheme

Tea and blueberry stains on cotton fabric were punched with 1 cm diameter and covered with 3 mL each wash liquor according to the pipetting scheme and pivoted at temperatures of 3O ⁰ C 40 30 minutes times per minute 180 ° to the horizontal. The fabrics were then rinsed under running tap water and air dried overnight. The lobes were then fixed on a standardized surface to measure the light reflection: For this, the whiteness L * of the washed fabrics was normalized compared to a white standard (d / 8, 8mm, SCI / SCE) normalized to L * = 100 was, measured. The measurement was carried out on a colorimeter (Minolta Cm508d) with an illumination setting of 107D65. The L * value, minus that of the uncatalyzed bleach, is a measure of the bleaching performance and indicates how much the tested metal complex promotes hydrogen peroxide bleaching. The results are shown below.

Table 6: Results of the mini-wash test for the blueberry stains

Table 7: Results of the mini-wash test for the tea stains

It can be seen that the schizokinen-manganese complex as well as the desferrioxamine-E-manganese complex significantly improves the bleaching performance of hydrogen peroxide in terms of blueberry soiling as well as tea soiling, although with 3O ⁰ C a rather low washing temperature was chosen.

While desferrioxamine E is a tris-hydroxamate siderophore, schizokinen is a bis-hydroxamate-alpha-hydroxycarboxylate siderophore.

Example 4: Checking the Washing Performance of Mn-DFE Compared to TAED To compare the washing performance of the Mn-DFE compared to that of the TAED, the catalyst was incorporated into a commercially available powdered detergent with soluble builder (sodium percarbonate). In each case 2.7% by weight of TAED were used as catalyst in comparison with Mn-DFE complexes each containing 5 mg, 10 mg or 20 mg of Mn ions. The washing experiments were carried out in a washing machine Miele W 918 at 2O ⁰ C and 3O ⁰ C, 16 ° dH (German hardness), pH 10.5. It was washed for 60 minutes in the main wash and the washing was repeated five times each.

As fabric cotton fabric (Co) and blended fabric of 35% cotton and 65% polyester (PE / Co) were used. The following stains were used: C-02 (olive oil / soot on cotton), C-10 (pigment / peanut oil / high milk concentration on cotton), BC-2 (coffee on cotton), BC-3 (tea on cotton), CS- 1 (aged blood on cotton), CS-3 (aged red wine on cotton), CS-10 (butterfat with dye on cotton), CS-12 (blackcurrant on cotton), CS-13 (apple juice on cotton), CS- 44 (chocolate drink on cotton), CS-103 (non-aged red wine on cotton), E-117 (blood / milk / ink on polyester / cotton blend), E-160 (chocolate cream on cotton), PCS-17 (Makeup on polyester / cotton blend).

Table 8: washing results at 3O ⁰ C

Soil Tissue TAED Mn-DFE Mn-DFE Mn-DFE LSD (5mg (10mg (20mg Mn) Mn) Mn)

CS-10 butterfat with Co 72.7 72.6 73.3 74.8 0.7 dye

BC-2 Coffee Co 62.1 63.1 63.0 63.7 1, 4

BC-3 Tea Co 59.7 60.6 61, 2 63.4 2.6

CS-12 black Johannisb. Co 66.4 68.5 69.6 70.9 2.9

CS-13 apple juice Co 83.7 84.8 85.4 85.4 1, 1

CS-44 Chocolate Drink Co 47.3 48.7 50.1 52.3 2.5

CS-3 red wine, aged Co 61, 5 62.9 64.0 65.6 2.0

E-117 Blood / Milk / Ink PE / Co 16.9 17.9 17.2 17.5 1, 1

E-160 chocolate cream Co 60.7 61, 8 63.1 64.0 2.6

PCS Makeup PE / Co 77.6 77.0 78.0 78.8 1, 4 17

It can be seen that the Mn-DFE on all soils tested at both 2O ⁰ C as well as at 3O ⁰ C at least slightly better, on some soils even significantly better cleaning performance than the TAED, which causes a similar low fiber damage as the Mn-DFE. The cleaning performance is as expected at 2O ⁰ C lower than at 3O ⁰ C, the decrease in cleaning performance is relatively low.

Example 5: Bleaching with atmospheric oxygen

To test the bleaching performance without the addition of oxidizing agents, ie with atmospheric oxygen as the sole oxidizing agent, experiments were performed with Mn-desferrioxamine and for comparison with Mn complexes of triazacyclononane (TACN) and tetraazacyclododecane, the Mn complex of a terpyridine and cobalt pentamine on cotton lobules carried out. The experiment was carried out as described in Example 3 with the difference that no hydrogen peroxide was added and the pH was adjusted to 11, 0. In addition, incubation was for 60 minutes instead of 30 minutes. As in Example 3, the recipe was the matrix a commercial liquid detergent used as a buffer 150 mM glycine / NaOH solution was used. The soils used were tea (EMPA167-13-07) and blueberry (CFT CS-15 025 0). The mean value was then calculated from the values obtained.

Table 10: Results of atmospheric oxygen bleaching

It can be seen that Mn-DFE also causes a significant bleaching effect with atmospheric oxygen as the sole source of oxygen, in contrast to the prior art Mn-containing catalysts used for comparison.

Example 6: Determination of color damage

To determine the color damage tests were carried out on different and differently colored fabrics as described by Luijkx et al. (Surfactants Surf., Det. 41 (2004) 4). It was washed 20 times in each case for this purpose at 4O ⁰ C with a detergent containing Mn-DFE (10 mg Mn). For comparison, the same stoichiometric amount of Mn-TACN was used in each case. It turned out that the Mn-DFE on many dyed fabrics causes a much weaker color damage than the Mn-TACN. Thus, when using Mn-DFE, especially on Direct Yellow on cotton and on Reactive Blue B3 on cotton, a roughly 10 times weaker color damage was observed than when using Mn-TACN.

Example 7 Determination of Bactericidal Activity

A commercial pulverulent detergent formulation containing percarbonate as a bleaching agent and Mn-DFE as a bleach catalyst was tested for bactericidal activity in the quantitative suspension test. To this end, 5.88 g of the detergent formulation with 7 mg of Mn-DFE were dissolved in 900 ml of distilled water and 9 mL of the solution thus obtained were used in the test and admixed with a test microbial suspension (see below). After 40 minutes of exposure at 3O ⁰ C For example, the remaining bleach was just completely deactivated with sodium thiosulfate solution and then the live germ count was determined. The suspension test was carried out in accordance with DIN EN 1040 (dilution neutralization method). The efficacy statement regarding the reduction of living bacteria is given as the reduction rate in orders of magnitude.

For Staphylococcus aureus DSM 799 was so at an initial bacterial count N = 4.75 * 10 ^Λ 8 / ml, a reduction factor of 2.12 * 10 ^Λ 2 and Pseudomonas aeruginosa DSM 939 at an initial bacterial count N = 4.2 * 10 ^Λ 8 / ml_ a reduction factor <2.8 * 10 ^Λ 5 can be detected. The formulation thus has a detectable bactericidal action.

Claims

claims

1. washing or cleaning agent, characterized in that it contains a siderophores.

2. washing or cleaning agent according to claim 1, characterized in that the siderophore is in the form of a siderophore-metal complex.

3. washing or cleaning agent according to claim 1 or 2, characterized in that it is the siderophore is a compound which has at least two radicals selected from the group consisting of hydroxamate, catecholate, alpha-hydroxy carboxylate, alpha-keto Carboxylate, phenolate, carboxamide, Citrathydroxamat and, optionally partially or fully hydrogenated, oxazole or thiazole.

4. washing or cleaning agent according to claim 3, characterized in that it is the siderophore is a compound containing at least three radicals selected from catecholate, hydroxamate and, optionally partially or fully hydrogenated, oxazole or thiazole.

5. washing or cleaning agent according to claim 3 or 4, characterized in that it is the siderophore is a compound containing at least two hydroxamate groups and at least one further complexing group selected from catecholate, carboxylate, alpha-hydroxy carboxylate, alpha-keto-carboxylate, phenolate, carboxylic acid amide and, optionally partially or fully hydrogenated, imidazole, oxazole or thiazole.

6. washing or cleaning agent according to claim 3 or 4, characterized in that it is the siderophore is a compound containing at least three hydroxamate groups.

7. washing or cleaning agent according to claim 3 or 4, characterized in that it is the siderophore is a compound containing at least two catecholate groups and at least one further complexing group selected from hydroxamate, carboxylate, alpha-hydroxy carboxylate, alpha-keto-carboxylate, phenolate, carboxylic acid amide and, optionally partially or fully hydrogenated, imidazole, oxazole or thiazole.

8. washing or cleaning agent according to claim 3 or 4, characterized in that it is the siderophore is a compound containing at least three catecholate groups.

9. washing or cleaning agent according to claim 3 or 4, characterized in that it is the siderophore is a compound containing at least two oxazole groups and at least one further complexing group selected from hydroxamate, catecholate, carboxylate, alpha-hydroxy Carboxylate, alpha-keto-carboxylate, phenolate, carboxylic acid amide and, optionally partially or fully hydrogenated, imidazole or thiazole.

10. washing or cleaning agent according to claim 3 or 4, characterized in that it is the siderophore is a compound containing at least three oxazole groups.

11. Washing or cleaning agent according to claim 3 or 4, characterized in that it is the siderophore is a compound containing at least two thiazole groups and at least one further complexing group selected from hydroxamate, catecholate, carboxylate, alpha-hydroxy Carboxylate, alpha-keto-carboxylate, phenolate, carboxylic acid amide and, optionally partially or fully hydrogenated, imidazole or oxazole.

12. Washing or cleaning agent according to claim 3 or 4, characterized in that it is the siderophore is a compound containing at least three thiazole groups.

13. washing or cleaning agent according to claim 3 or 4, characterized in that it is the siderophore is a compound containing at least two alpha-hydroxy carboxylate groups and at least one further complexing group selected from hydroxamate, catecholate, carboxylate, alpha-keto-carboxylate, phenolate, carboxylic acid amide and, optionally partially or fully hydrogenated, imidazole, oxazole or thiazole.

14. washing or cleaning agent according to claim 3 or 4, characterized in that it is the siderophore is a compound containing at least three alpha-hydroxy carboxylate groups.

15. Washing or cleaning agent according to one of claims 1 to 14, characterized in that it is the siderophore to a naturally occurring siderophore or a derivative thereof.

16. Washing or cleaning agent according to claim 15, characterized in that the naturally occurring siderophore is selected from the group consisting of sideromycins, siderochromes and sideramines.

17. Washing or cleaning agent according to claim 16, characterized in that the naturally occurring siderophore is selected from the group consisting of Desferrichromen, Tetraglycyldesferrichromen, Desferricrocin, Desferrichrysin, Desferrirhodin, Hexahydrodesferrirhodin, Desferrirubin, Desferrioroprogen, Desferrineocoprogen I, Desferrineocoprogen II, exochelins, Fusigen (Fusarinine C), nocardamine, desferrisalmycin, desferrialbomycins, desferrioxamines, desferrimycins, pyoverdines, mycobactins, aerobactin, arthrobactin, acinetoferrin, aqua achenes, ornibactins, nannochelins, schizokines, rhodotorulic acid, marinobactins, azotobactin D, pseudobactins, acinetobactin, pseudobactin, putrebactin, achromobactin, Rhizoferrin, alterobactins, agrobactin, enterobactin (enterochelin), fluvibactin, homofluvibactin, bacillibactin (corynebactin), petrobactin, salmochelin, azotochelin, myxochelins, chrysobactin, yersinibactin, ferrithiocin, pyochelin A, vulnibactin, daunorubici n, Succinimycin, Rifamycin, Trencam, Pseudomonin, Corrugatin, Gallichrom, Fusigen, Desferristaphyloferrine, Desferrivibrioferrin, Desferrimaduraferrin, Fusarinen, Dimerum Acid, Mugineic Acid, Coelichelin, WCS, Methanobactin, Gonobactin, Amonabactins, Amphibactins, Rhizobactins, Ruckerbactin, Anguibactin, Brucebactin, Carboxymycobactin, Erythrobactin, cepabactin, meningobactin, chrysobactin, quinolobactin, thioquinolobactin, vibriobactin, vanchrobactin, parabactin and ballibactin.

18. washing or cleaning agent according to one of claims 1 to 17, characterized in that it is the metal of the siderophore-metal complexes to an element selected from Ag, Al, Au, B, Bi, Ce, Co, Cr, Cu, Eu, Fe, Ga, Hg, Mn, Mo, Ni, Pb, Pt, Ru, Ti, U, V, W, Zn and Zr are in any oxidation state.

19. Washing or cleaning agent according to one of claims 1 to 18, characterized in that it is the metal of the siderophore-metal complexes is a transition metal.

20. Washing or cleaning agent according to claim 19, characterized in that the metal of the siderophore-metal complexes is selected from Fe (III), Co (II), Co (III), Mn (II), Mn (III), Ce (III), Ce (IV), Zn (II) and Bi (III).

21. Washing or cleaning agent according to one of claims 18 to 20, characterized in that the siderophore-metal complex is selected from complexes of siderophores with at least three hydroxamate groups, in particular of Desferrioxaminen, Desferrichromen and Coprogen, in particular desferrioxamine E, with metal ions of Mn, Fe, Co, Ce, Cr, Zn, Cu, Mo, V, W and Bi; Complexes of siderophores having at least two hydroxamate groups and at least one catecholate group, in particular pyoverdine Pa, with metal ions of Mn, Fe, Co, Ce, Zn, Cu, Mo, V, and Bi; Complexes of siderophores having at least two hydroxamate groups and at least one alpha-hydroxy carboxylate group, in particular ornibactin, arthrobactin and schizokinene, with metal ions of Mn, Fe, Co, Ce, Cr, Zn, Cu, Mo, V , W and Bi; Complexes of siderophores having at least two hydroxamate groups and at least one carboxylic acid amide group, in particular rhodotorulic acid, with metal ions of Mn, Fe, Co, Ce, Cr, Zn, Cu, Mo, V, W and Bi; Complexes of siderophores with at least three partially hydrogenated thiazole rings, in particular yersinabactin, with metal ions of Mn, Fe, Co, Ce, Cr, Zn, Cu, Mo, V and Bi; Complexes of siderophores having at least two alpha-hydroxy carboxylate groups, at least two carboxylic acid amide groups and at least two further carboxylate groups, in particular of rhizoferrin, with metal ions of Mn, Fe, Co, Ce, Zn, Cu, Mo, V, W and Bi; Complexes of siderophores with at least three catecholate groups, in particular of enterobactin, with metal ions of Mn, Fe, Co, Ce, Cu, V and Bi.

22. Washing or cleaning agent according to one of claims 1 to 21, characterized in that it contains at least one surfactant.

23. Washing or cleaning agent according to one of claims 1 to 22, characterized in that it contains at least one bleaching agent.

24. Washing or cleaning agent according to one of claims 1 to 22, characterized in that it contains no bleach.

25. Washing or cleaning agent according to one of claims 1 to 24, characterized in that it contains at least one hydrogen peroxide-producing oxidoreductase.

26. Washing or cleaning agent according to one of claims 1 to 25, characterized in that it is a fiber and / or color-protecting agent.

27. Use of detergents or cleaners according to one of claims 1 to 26 for the cleaning of textile fabrics.

28. Use of detergents or cleaners according to one of claims 1 to 26 for cleaning hard surfaces.

29. Use of siderophores in detergents or cleaners.

30. Use according to claim 29, characterized in that the siderophore is in the form of a siderophore-metal complex.

31. Use according to claim 29 or 30 for cleaning textile fabrics.

32. Use according to claim 29 or 30 for cleaning hard surfaces.

33. Use of siderophore-metal complexes as auxiliaries for cleaning textile fabrics.

34. Use of Siderophore Metal Complexes as a Hard Surface Cleaning Aid.

35. Use according to any one of claims 26 to 34 for cleaning and / or removal of stains selected from stains of tea, coffee, blood, soot, egg, milk, butter, ink, makeup, lipstick, chocolate, chocolate cream, olive oil, blackcurrant , Blueberry, apple juice, red wine, peanut oil and mixtures thereof.

36. Use of siderophore-metal complexes for bleaching pulp and / or virgin cotton.

37. Use of siderophore-metal complexes to kill germs.

38. Use according to any one of claims 30 to 37, characterized in that the siderophore-metal complex is generated in situ.

39. Use according to one of claims 26 to 38, characterized in that atmospheric oxygen is used as the sole source of oxygen.

40. siderophore metal complex, characterized in that the central atom is selected from Ag, Al, Au, B, Bi, Ce, Co, Cr, Cu, Eu, Ga, Hg, Mn, Mo, Ni, Pb, Pt , Ru, Ti, U, V, W, Zn and Zr in any oxidation state, except for the metal complexes of desferrioxamines B and E, desferrithiocin, methanobactin, the AI and Cr complexes of pyoverdine Pf244 and the AI- , Cu, Mn and Zn complexes of pyoverdin from Pseudomonas aeruginosa.

41. siderophore-metal complexes according to claim 40, characterized in that the central atom is selected from Co (II), Co (III), Mn (II), Mn (III), Ce (III), Ce (IV), Zn (II) and Bi (III).

42. siderophore-metal complex according to claim 40 or 41, characterized in that it is the siderophore of the siderophore-metal complex is a compound having at least two radicals selected from the group consisting of hydroxamate, catecholate, alpha-hydroxy Carboxylate, alpha-keto-carboxylate, carboxylic acid amide, citrate hydroxamate and, optionally partially or fully hydrogenated, oxazole or thiazole.

43. siderophore-metal complex according to claim 42, characterized in that it is the siderophore is a compound containing at least three radicals selected from catecholate, hydroxamate and, optionally partially or fully hydrogenated, oxazole or thiazole.

44. siderophore-metal complexes according to claim 43, characterized in that it is the siderophore is a compound comprising at least three hydroxamate groups.

45. siderophore-metal complex according to one of claims 40 to 44, characterized in that it is the siderophore is a naturally occurring siderophore.

46. siderophore-metal complex according to claim 44 or 45, characterized in that the siderophore is selected from desferrichromes, Tetraglycyldesferrichromen, desferricrocin, desferrichrysin, desferrirhodin, hexahydrodesferrirhodin, desferrirubin, desferricoprogen, desferrineocoprogen I, desferrineocoprogen II, exochelin MS, fusigen (fusarinin C), nocardamine, desferrisalmycin, desferrialbomycins, desferrioxamines and desferrimycins.

47. siderophore-metal complex according to at least one of claims 40 to 46, characterized in that the siderophore metal complex is selected from complexes of Coprogens with metal ions of Mn, Co, Ce, Cr, Zn, Cu, Mo, V , W and Bi; Complexes of siderophores having at least two hydroxamate groups and at least one alpha-hydroxy carboxylate group, in particular ornibactin, arthrobactin and schizokinene, with metal ions of Mn, Co, Ce, Cr, Zn, Cu, Mo, V, W and Bi; Complexes of siderophores having at least two hydroxamate groups and at least one carboxylic acid amide group, in particular the rhodotorulic acid, with metal ions of Mn, Co, Ce, Cr, Zn, Cu, Mo, V, W and Bi; Complexes of siderophores having at least three partially hydrogenated thiazole rings, in particular yersinabactin, with metal ions of Mn, Co, Ce, Cr, Zn, Cu, Mo, V and Bi; Complexes of siderophores with at least two alpha-hydroxy carboxylate groups, at least two carboxylic acid amide Groups and at least two other carboxylate groups, especially rhizoferrin, with metal ions of Mn, Co, Ce, Zn, Cu, Mo, V, W and Bi; Complexes of siderophores with at least three catecholate groups, in particular of enterobactin, with metal ions of Mn, Co, Ce, Cu, V and Bi.

48. A method for cleaning textile fabrics or hard surfaces, characterized in that the cleaning is carried out using a siderophore-metal complex.

49. The method according to claim 48, characterized in that the siderophore-metal complex is generated in situ.

50. The method according to claim 49, characterized in that a washing or cleaning agent is used which has siderophore-containing phases and metal salt-containing phases.

51. The method according to any one of claims 48 to 50, characterized in that atmospheric oxygen is used as the sole oxidant.

52. The method according to any one of claims 48 to 52, characterized in that it is a fiber and / or color gentle process.