EP2673349B1 - Use of transition metal complexes as bleach catalysts in washing and cleaning compositions - Google Patents

Description

The present invention relates to the use of transition metal complexes which, in addition to a tetraoxylene unit, contain two macrocyclic, N-containing ligands, in particular cyclic or cyclam ligands, for bleaching colored stains on textiles as well as on hard surfaces. The invention also relates to detergents and cleaners containing such complex compounds.

Inorganic peroxygen compounds, particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes. The oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H ₂ O ₂ or perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles.

At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators. For this purpose, numerous proposals have been worked out in the past, especially from the classes of N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylglycoluril, N-acylated caprolactams such as benzoylcaprolactam, acetylcaprolactam or Nonanoylcaprolactam, hydantoins, hydrazides, triazoles, hydrotriazines, urazoles , Diketopiperazines, sulfururamides and cyanurates, as well as carboxylic anhydrides, in particular phthalic anhydride and substituted maleic anhydrides, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate (NOBS), sodium isononanoyloxy-benzenesulfonate (ISONOBS) and acylated sugar derivatives, such as pentaacetylglucose. By adding these substances, the bleaching effect of aqueous peroxide solutions can be increased so far be that even at temperatures around 60 ° C substantially the same effects as with the peroxide solution alone at 95 ° C occur.

In the quest for environmentally friendly and energy-saving washing and bleaching processes in recent years, application temperatures well below 60 ° C, especially below 45 ° C, sometimes even up to the cold water temperature in importance.

At these low temperatures, the effect of the previously known activator compounds can usually be discerned. There has therefore been no lack of efforts to develop more effective bleaching systems for this temperature range without a truly convincing success to date.

One starting point for this is the use of transition metal salts and their complex compounds, as described, for example, in US Pat EP 0 237 111 . EP 0 272 030 . EP 0 306 089 . EP 0 392 592 or EP 0 443 651 are described. Continue to be in WO 97/07191 Complexes of manganese, iron, cobalt, ruthenium and malenbdenum with salen-type ligands have been proposed as catalysts for peroxygen compounds in hard surface cleaning solutions.

A variety of macrocyclic N-containing ligand complexes have been reported in the literature as bleach catalysts in recent years. So be in EP 0 439 387 Binuclear metal complexes with ligands obtained by reacting a dialdehyde with primary polyamines, claimed as Sauerstoffcarrier. EP 0 458 397 and EP 0 458 398 describe the use of manganese complexes of the general form [L _n Mn _m X _p] ^z Y _q, wherein L macrocyclic, N-containing ligands comprises. In particular, ligands based on 1,4,7-trimethyl-1,4,7-triazacyclononane (Me ₃ TACN) and their derivatives are described. Compounds of the type [LMn (OR) ₃ ] Y are described in EP 0 544 519 TACN, Me ₃ TACN, 1,5,9-trimethyl-1,5,9-triazacyclodecane are particularly suitable as ligands.

Transition-metal complexes with rigid ligands, in particular rigidly bridged N-containing macrocycles having at least 3 donor atoms, 2 of which form a bridgehead, are described in detail in US Pat WO 1998/039335 and WO 1998/039098 described as oxidation catalysts. Examples of the ligands are 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane (Bcyclam) and 5-N-octyl-12-methyl-1,5,8,12- tetraaza-bicyclo [6.6.2] hexadecane. In WO 2001/048298 corresponding bridged ligands for bleaching with atmospheric oxygen are described. Similar metal complexes based on unbridged macrocyclic ligands are proposed in WO 2000/012808 claimed as "aerial whitening systems" for use in detergents and cleaners.

Metal complexes containing one or more dioxolene or tetraoxolene units are interesting systems because the ligands are "non-innocent" ligands that can change their oxidation state in redox reactions. As a dioxole unit usually (substituted) catecholates or semichinones are used. Bioinorganic aspects of "non-innocent" ligands are e.g. In W. Kaim and B. Schwerderski, "Non-innocent ligands in bioinorganic chemistry", Coordination Chemistry Reviews, 254 (2010), 1580-1588 described. For a review of complexes with catecholate and semiquinone ligands, see CG Pierpont, "Studies on charge distribution and valence tautomerism in transition metal complexes of catecholate and semiquinone ligands", Coordination Chemistry Review, 216-217 (2001), 99-125 given.

Tetraoxolene complexes with a tetraoxolate unit between two transition metals and their redox chemistry are z. In JS Miller and KS Min "Oxidation Leads to Reduction - Redox-Induced Electron Transfer (RIET)," Angew. Chem. 121 (2009), 268-278 or Ch. Carbonera et al., "Thermally and Light-Induced Valence-Tautomeric Transition in Dinuclear Cobalt-Tetraoxolene Complex", Angew. Chem. Int. Ed., 43 (2004), 3136-3138 described.

Surprisingly, it has now been found that certain transition metal complexes containing catecholate, semiquinone or tetraoxolene ligands can be used in detergents and cleaning agents and have clear advantages in terms of bleaching ability on colored stains. They can be used either in detergents and cleaners which contain hydrogen peroxide and other peroxy compounds (eg peroxycarboxylic acids), but also in those which are free of oxidizing agents.

Object of the present invention was to improve the oxidation and bleaching action of detergents and cleaners at particularly low temperatures below 60 ° C, in particular in the temperature range of 20 ° C to 45 ° C to achieve.

M

ein Metallatom aus der Gruppe Mn und Fe,

L

ein Ligand der allgemeinen Formel (II) oder (III)

worin

R

ein Wasserstoff, Alkyl mit 1 bis 8 Kohlenstoffatomen,

R1, R2, R3 und R4

gleich oder verschieden sind und ein Wasserstoff, Alkyl mit 1 bis 8 Kohlenstoffatomen, eine Stickstoff-verbrückende Alkyleneinheit mit 2 bis 4 Kohlenstoffatomen oder Alkaryl mit 6 bis 16 Kohlenstoffatomen,

n

eine ganze Zahl von 0 bis 6,

Y

eine Gruppe der Formel (IV)

worin

R5

gleich oder verschieden sind und ein Wasserstoff, Alkyl mit 1 bis 4 Kohlenstoffatomen, Cl oder Br,

X

ein Neutral- oder Anionligand aus der Gruppe CH₃CN, Chlorid, Bromid, Nitrat, Perchlorat, Sulfat, Citrat, Hexafluorophosphat, Trifluormethansulfonat, Tetrafluoroborat, Tetraphenylborat, oder Anionen organischer Säuren mit C₁-C₂₂ Kohlenstoffatomen, oder H₂O, und

m

eine Zahl von 0 bis 4 bedeuten,

als Bleichkatalysator in Wasch- und Reinigungsmitteln.This object is achieved by the use of transition metal complexes of the formula (I)

[(L) M (Y) M (L)] X _m (I)

in which

M

a metal atom from the group Mn and Fe,

L

a ligand of the general formula (II) or (III)

wherein

R

a hydrogen, alkyl of 1 to 8 carbon atoms,

R1, R2, R3 and R4

are the same or different and are a hydrogen, alkyl having 1 to 8 carbon atoms, a nitrogen-bridging alkylene moiety having 2 to 4 carbon atoms or alkaryl having 6 to 16 carbon atoms,

n

an integer from 0 to 6,

Y

a group of the formula (IV)

wherein

R5

are the same or different and are hydrogen, alkyl of 1 to 4 carbon atoms, Cl or Br,

X

a neutral or anion ligand from the group CH ₃ CN, chloride, bromide, nitrate, perchlorate, sulfate, citrate, hexafluorophosphate, trifluoromethanesulfonate, tetrafluoroborate, tetraphenylborate, or anions of organic acids with C ₁ -C ₂₂ carbon atoms, or H ₂ O, and

m

a number from 0 to 4,

as a bleach catalyst in detergents and cleaners.

Preference is given to using complexes with transition metal central atoms in the oxidation states +2, +3 or +4, with complexes with manganese as the central atom being preferred according to the invention. The radicals R and R 1 to R 4 are preferably hydrogen or methyl groups, alkylaryl radicals containing 6 to 16 C atoms in the alkyl part, phenyl being preferred as aryl.

In the metal-bridging group of the formula (IV), the radicals R5 are preferably hydrogen or chlorine.

• 1,4,7,10-Tetraazacyclododecan (Cyclen); 1,7-Dimethyl-1,4,7,10-tetraazacyclododecan; 1,4,8,11-Tetraazacyclotetradecan (Cyclam);
• 1,4,8,11-Tetramethy-1,4,8,11-tetraazacyclotetradecan; 5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecan; 1,8-Dimethyl-1,4,8,11-Tetraazacyclotetradecan; 1,8-Diethyl-1,4,8,11-Tetraazacyclotetradecan (Diethylcyclam); 5,12-Dimethyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecan (Dimethyl-Bcyclam), 5,12-Diethyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecan (Diethyl-Bcyclam) und 5-N-Octyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecan.

Preferred ligands L are:

• 1,4,7,10-tetraazacyclododecane (Cyclen); 1,7-dimethyl-1,4,7,10-tetraazacyclododecane; 1,4,8,11-tetraazacyclotetradecane (cyclam);
• 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane; 1,8-dimethyl-1,4,8,11-tetraazacy-; 1,8-diethyl-1,4,8,11-tetraazacyclotetradecane (diethylcyclam); 5,12-Dimethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane (dimethyl-Bcyclam), 5,12-diethyl-1,5,8,12-tetraaza-bicyclo [6.6.2 ] hexadecane (diethyl-Bcyclam) and 5-N-octyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane.

wobei R4 und R4 unabhängig voneinander eine Methyl-, Ethyl-, Propyl-, Butyl- oder Benzylgruppe darstellen.In addition to the complexes according to the invention of the unsubstituted or tetrasubstituted cyclams or cyclenes of the formula (I), particular preference is given to complexes having 2 alkyl or alkaryl radicals on the tetraazacycle having the general structures (V), (VI) and the bridged cyclams (VII):

wherein R4 and R4 independently represent a methyl, ethyl, propyl, butyl or benzyl group.

Especially preferred according to the invention are complexes with the following ligands: 1,8-dimethylcyclam, 1,7-dimethylcycles, 1,8-diethylcyclam, 1,7-diethylcycles, 1,8-dibenzylcyclam and 1,7-dibenzylcycles.

The ligands (V) and (VI) can be prepared according to J. Kotter et al., Collect. Czech. Chem. Commun., 2000, 65, 243-266 , or R. Tripier et al., Chem. Commun., 2001, 2728-2729 , Syntheses of ligands of formula (VII) are z. In WO 1998/039335 and WO 1998/039098 described.

Syntheses of tetraoxylene transition metal complexes are described, inter alia, in A. The et al., "Tetraoxylenes Radical Stabilization by Interaction with Transition Metal Ion", Inorg. Chem., 30 (1991), 2590 , Compounds with non-cyclic Ligands in D. Guo et al., "Spin Exchange Effects on the Physicochemical Properties of Tetraoxolene-Bridged Bimetallic Complexes", Inorg. Chem., 46 (2007), 3257-3274 ,

The transition metal complexes of the formula (I) are used in detergents and cleaners, in particular in textile washing and in hard-surface cleaners, then especially for dishes, and in solutions for bleaching colored stains. This is done firstly in the presence of hydrogen peroxide, hydrogen peroxide-releasing compounds or a peroxygen compound. It was surprising that the complexes can also be used without a peroxo compound or z. B. be activated by the oxygen in the air.

To activate the complexes, peroxygen compounds or atmospheric oxygen come into question. The peroxygen compounds used are primarily hydrogen peroxide, alkali perborate mono- or tetrahydrate and / or alkali metal percarbonate, with sodium being the preferred alkali metal. In addition, however, alkali metal or ammonium peroxosulphates, such as. As potassium peroxomonosulfate (technically: Caroat ^® or Oxone ^® ) can be used. The concentration of the inorganic oxidizing agents on the total formulation of detergents and cleaners is 2 to 90%, preferably 3 to 60%, particularly preferably 5 to 25%.

Also suitable as peroxygen compounds are organic-based oxidants. These include all known peroxycarboxylic acids, eg. Monoperoxyphthalic acid, peracetic acid, dodecanediperoxyacid, phthalimidoperoxycarboxylic acids such as PAP and related systems or amido peracids.

The amounts of peroxygen compounds used are generally selected so that between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm active oxygen, are present in the solutions of the detergents and cleaners. Also the amount used Bleach-enhancing complex compound depends on the application. Depending on the desired degree of activation, it is used in an amount of 0.01 mmol to 25 mmol, preferably 0.1 mmol to 2 mmol complex per mole of peroxygen compound. However, these limits can also be exceeded or fallen short of in special cases.

In detergents and cleaners are preferably 0.0025 to 1 wt .-%, in particular 0.01 to 0.5 wt .-%, of the above-defined bleach-enhancing complex compound.

In addition to the iron or manganese complexes, hydrogen peroxide and persalts according to the invention, further bleach catalysts or bleach activators can advantageously be used in combination in order to widen the spectrum of action of the bleaching systems used according to the invention and to increase the efficiency, in particular with regard to the germicidal effect (disinfection).

In addition to the complex compounds used according to the invention, conventional bleach activators, that is to say compounds which release peroxycarboxylic acids under perhydrolysis conditions, can be used. Suitable are the usual bleach activators containing O- and / or N-acyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenedianim (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives-in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenylsulfonates , in particular nonanoyl, isononanoyl or lauroylbenzenesulfonate (NOBS, ISONOBS or LOBS) or their amido derivatives (eg NACAOBS), acylated hydroxycarboxylic acids such as acetylsalicylic acid or nonanoyloxybenzoic acid (NOBA) and decanoyloxybenzoic acid (DOBA), acylated polyhydric alcohols, in particular triacetin, Ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol, and acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and Gluconolactone. Furthermore, open-chain or cyclic nitrile quats are suitable for this purpose. Also from the DE-A 44 43 177 known combinations of conventional bleach activators can be used. Furthermore, benzoylcaprolactam or acetylcaprolactam can be used. In addition, combinations of the complexes according to the invention with other metal complexes can also be used. The concentration of bleach activators in the overall formulation of detergents and cleaners is 0.1 to 20 wt .-%, preferably 0.5 to 10 wt .-%, particularly preferably 1 to 6 wt .-%, each based on the total weight.

According to the application, the term bleaching encompasses both the bleaching of dirt located on the textile surface and the bleaching of dirt located in the wash liquor and detached from the textile surface. The same applies analogously to the bleaching of soiling on hard surfaces. Further potential applications can be found in the personal care field z. As in the bleaching of hair and to improve the effectiveness of denture cleaners, especially at low temperatures. Furthermore, the described metal complexes find use in commercial laundries, in wood and paper bleaching, bleaching of cotton and in disinfectants.

Furthermore, the invention relates to a process for the purification of textiles as well as hard surfaces, in particular crockery, using said complex compounds together with peroxygen compounds in aqueous, optionally further detergent or cleaning agent components containing solution. The invention also relates to detergents and hard surface cleaners, in particular to dishwashing detergents, such being preferred for use in machine processes containing such complex compounds.

The use according to the invention essentially consists of providing conditions for colored surfaces contaminated with colored soiling or, in the case of soiled textiles, among them peroxidic oxidizing agent and the complex compound can react with each other, with the aim of obtaining more oxidizing secondary products. Such conditions are especially present when the reactants meet in aqueous solution. This can be done by separately adding the peroxygen compound and the complex to the aqueous solution of the detergent and cleaner. However, the process according to the invention is particularly advantageously carried out using a detergent or hard surface cleaning agent which contains the complex compound and optionally a peroxygen-containing oxidizing agent. The peroxygen compound may also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, when a non-oxygen detergent or cleaner is used.

The washing and cleaning agents, which may be in the form of granules, powdery or tablet-like solids, other shaped bodies, homogeneous solutions or suspensions, may contain, in principle, all known ingredients customary in such agents, as well as the said bleach-enhancing metal complex. The compositions may contain, in particular, builder substances, surface-active surfactants, peroxygen compounds, additional peroxygen activators or organic peracids, water-miscible organic solvents, sequestering agents, enzymes, and special additives with color- or fiber-sparing action. Other auxiliaries such as electrolytes, pH regulators, silver corrosion inhibitors, foam regulators, as well as dyes and fragrances are possible.

In addition, a hard surface cleaning agent according to the invention may contain abrasive constituents, in particular quartz flours, wood flours, plastic flours, chalks and glass microspheres, and mixtures thereof. Abrasives are preferably not more than 20 wt .-%, in particular from 5 to 15 wt .-%, contained in the cleaning agents.

The detergents and cleaners may comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants. Such surfactants are present in detergent compositions according to the invention in proportions of preferably from 1 to 50% by weight, in particular from 3 to 30% by weight, whereas in hard-surface cleaners normally lower proportions, ie. H. Amounts up to 20 wt .-%, in particular up to 10 wt .-% and preferably in the range of 0.5 to 5 wt .-%, are included. Dishwashing detergents typically use low-foam compounds.

Anionic surfactants which are suitable according to the invention are in particular soaps and those which contain sulfate or sulfonate groups. As surfactants of the sulfonate type are preferably C ₉ -C ₁₃ alkylbenzenesulfonates, olefinsulfonates, that is mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those of monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C ₁₂ -C ₁₈ -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also 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 obtained by sulfonating the methyl esters of fatty acids of vegetable and / or animal origin having 8 to 20 carbon atoms be prepared in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts.

Further anionic surfactants which are suitable according to the invention are sulfated fatty acid glycerol esters which are mono-, di- and triesters and mixtures thereof. Examples of alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₈ -C ₂₀ -oxo alcohols and those half esters of secondary alcohols this chain length is preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis. 2,3-alkyl sulfates are also suitable anionic surfactants. Also suitable are the sulfuric acid monoesters of straight-chain or branched alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ -alcohols containing on average 3.5 mol of ethylene oxide (EO) or C ₁₂ -C ₁₈ -fatty alcohols with 1 up to 4 EO.

The preferred anionic surfactants also include 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 with fatty alcohols and in particular with ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ -C ₁₈ fatty alcohol residues or mixtures of these. Suitable further anionic surfactants according to the invention are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosinate). As further anionic surfactants are in particular soaps, for example in amounts of 0.2 to 5 wt .-%, into consideration. Particularly suitable in the context 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 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. Anionic surfactants are preferably present in detergents according to the invention in amounts of from 0.5 to 10% by weight and in particular in amounts of from 5 to 25% by weight.

The nonionic surfactants used are preferably alkoxylated, preferably ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for. From coconut, palm, tallow fat or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ -alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ -alcohols with 7 EO, C ₁₃ -C ₁₅ -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ -C ₁₄ -alcohol with 3 EO and C ₁₂ -C ₁₈ -alcohol with 7 EO. The degrees of ethoxylation given above represent statistical averages which may be an integer or a fractional number for a particular product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

in der Rest R¹ CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Vorzugsweise leiten sich die Polyhydroxyfettsäureamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab.The nonionic surfactants also include 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 represents 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 which, as the size to be determined analytically, can also be fractions, between 1 and 10; preferably x is 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula (VIII)

in the radical R ¹ CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{2 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 preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.

in der R³ einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 21 Kohlenstoffatomen, R⁴ einen linearen, verzweigten oder cyclischen Alkylenrest oder einen Arylenrest mit 6 bis 8 Kohlenstoffatomen und R⁵ einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen bedeutet, wobei C₁-C₄-Alkyl- oder Phenylreste bevorzugt sind, und Z für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes. Z wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Alyloxy-substituierten Verbindungen können dann beispielsweise durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.The group of polyhydroxy fatty acid amides also includes compounds of the formula (IX)

in R ^{3 is} a linear or branched alkyl or alkenyl radical having 7 to 21 carbon atoms, R ^{4 is} a linear, branched or cyclic alkylene radical or an arylene radical having 6 to 8 carbon atoms and R ^{5 is} a linear, branched or cyclic alkyl radical or an aryl radical or a Oxy-alkyl radical having 1 to 8 carbon atoms, wherein C ₁ -C 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 also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-allyloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Another class in the context of the present invention preferably used nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide and of the fatty acid alkanolamide type may also be suitable according to the invention.

mit den Resten R1, R2, R3 = C₁-C₂₂ Alkyl, und n = 1 bis 5.Of the large group of cationic surfactants, in particular hydroxyalkyl quats of the general structures (X) and (XI) are preferred.

with the radicals R _1, R _2, R ₃ = C ₁ -C ₂₂ alkyl, and n = 1 to 5.

Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides. Other surfactant types may have dendrimeric structures.

A detergent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.

Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates and polymeric alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. The water-insoluble, water-dispersible inorganic builder materials used are, in particular, crystalline or amorphous alkali aluminosilicates, in amounts of up to 50% by weight. Among these, preferred are the detergent grade crystalline sodium aluminosilicates, especially zeolite A, P and optionally X, alone or in mixtures, for example in the form of a cocrystal of zeolites A and X. Their calcium binding capacity, according to the information of the German Patent DE 24 12 837 can be determined, is usually in the range of 100 to 200 mg CaO per gram. Suitable builder substances are also crystalline alkali metal silicates, which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders preferably have a molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates with a molar ratio of Na ₂ O: SiO, of 1: 2 to 1: 2.8. Such silicates can be prepared by the process of European patent application EP 0 425 427 getting produced. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na ₂ Si _x O used _{2x + 1} · y H ₂ O in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in the European patent application EP 0 164 514 described. preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both δ- and β-sodium disilicates (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred, whereby β-sodium disilicate can be obtained, for example, by the process described in US Pat WO 91/08171 is described. β-Sodium silicates with a modulus between 1.9 and 3.2 can according to Japanese Patent Applications JP 04/238 809 or JP 04/260 610 getting produced. Also prepared from amorphous silicates, practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used. In a further preferred embodiment of such agents, a crystalline sodium layer silicate with a modulus of 2 to 3 is used. Crystalline sodium silicates with a modulus in the range 1.9 to 3.5 are used in another preferred embodiment. In a preferred embodiment is a granular compound of alkali metal silicate and alkali metal as it is available, for example under the name Nabion ^® commercially. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10: 1. In compositions containing both amorphous and crystalline alkali silicates, the weight ratio is from amorphous alkali metal silicate to crystalline alkali metal silicate, preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.

Such builder substances are preferably present in detergents and cleaners according to the invention in amounts of up to a maximum of 60% by weight, preferably in the range of from 5 to 40% by weight, based on the total weight of the washing and cleaning agent.

The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid. Polyphosphonic acids, especially aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid can also be used. Also preferred are polymeric (poly) carboxylic acids, in particular the polycarboxylates of the international patent application which are obtainable by oxidation of polysaccharides or dextrins WO 93/16110 or the international patent application WO 92/18542 or the European patent specification EP 0 232 202 , polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small amounts of polymerizable substances copolymerized without carboxylic acid functionality. According to the manufacturer, the average molecular weight of the homopolymers of unsaturated carboxylic acids, expressed as M _w , is generally between 5000 and 200 000, that of the copolymers between 2000 and 200 000, preferably between 50 000 to 120 000, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has an average molecular weight of 50,000 to 100,000. Commercial products are, for example Sokalan ^® CP 5, CP 10 and PA 30 from BASF. Also suitable are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. It is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ -carboxylic acid, preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (meth) acrylic acid, wherein the second acidic monomer or its salt Derivative of a C ₄ -C ₈ dicarboxylic acid, maleic acid is particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position with an alkyl or aryl radical. Such polymers can be prepared in particular by methods described in the German patents DE 42 21 381 and DE 43 00 772 are generally described, and generally have a molecular weight between 1000 and 200,000. Further preferred Copolymers are those described in German patent applications DE 43 03 320 and DE 44 17 734 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or vinyl acetate.

The organic builder substances can, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 wt .-% aqueous solutions are used. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

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

Suitable water-soluble builder components in hard surface cleaners according to the invention are in principle all builders customarily used in detergents for dishwashing, for example the abovementioned alkali metal phosphates. Their amounts may be in the range of up to about 60 wt .-%, in particular 5 to 20 wt .-%, based on the total mean. Other possible water-soluble builder components, in addition to polyphosphonates and phosphonate alkyl carboxylates, are, for example, organic polymers of the above-mentioned type of polycarboxylates, which act as co-builders, especially in hard water regions, and naturally occurring hydroxycarboxylic acids, such as mono-, dihydroxysuccinic acid, alpha- Hydroxypropionic acid and gluconic acid. Preferred organic builder components include the salts of citric acid, especially sodium citrate. As sodium citrate, anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder. Depending on the ultimate in the invention Detergents adjusted pH value can also be present corresponding to the said co-builder salts acids.

Among the optionally present in the inventive compositions enzymes include proteases, amylases, pullulanases, cellulases, cutinases and / or lipases, for example proteases such as BLAP ^®, Optimase ^®, Opticlean ^®, Maxacal ^®, Maxapem ^®, Durazym ^®, Purafect ^® OxP, Esperase ^® and / or Savinase ^®, amylases as Termamy ^®, amylase LT, Maxamyl ^®, Duramyl ^®, Purafectel OxAm, cellulases as Celluzyme ^®, Carezyme ^®, K-AC ^® and / or from the international patent applications WO 96/34108 and WO 96/34092 known cellulases and / or lipases such as Lipolase ^®, Lipomax ^®, Lumafast ^® and / or Lipozym ^®. The enzymes used can, for example, in the international patent applications WO 92/111347 or WO 94/23005 be adsorbed to carriers and / or embedded in encapsulating substances to protect against premature inactivation. They are preferably present in detergents and cleaners according to the invention in amounts of up to 10% by weight, in particular from 0.05 to 5% by weight, enzymes which are particularly preferably stabilized against oxidative degradation being used.

Machine dishwashing detergents according to the invention preferably comprise the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali hydrogen carbonates. The alkali carriers used conventionally include carbonates, bicarbonates and alkali silicates having a molar ratio SiO ₂ / M ₂ (M = alkali metal) of from 1: 1 to 2.5: 1. Alkali silicates may be present in amounts of up to 40% by weight, in particular 3 to 30 wt .-%, based on the total agent to be included. The alkali carrier system used most preferably in cleaning agents according to the invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which may be present in an amount of up to 50% by weight, preferably 5 to 40% by weight.

A further subject of the invention is a means for mechanically cleaning dishes containing 15 to 65% by weight, in particular 20 to 60% by weight. water-soluble Builderkompenente, 5 to 25 wt .-%, in particular 8 to 17 wt .-%. Oxygen-based bleaching agent, in each case based on the total agent, and 0.1 to 1 wt .-% of one or more of the metal complexes defined above. Such an agent is preferably lower alkyl, ie its solution has a pH of 8 to 11.5, especially 9 to 11.

In a further embodiment of inventive means for the automatic cleaning of dishes are 20 to 60 wt .-% of water-soluble organic builder, in particular alkali citrate, 3 to 20 wt .-% alkali carbonate and 3 to 40 wt .-% Alkalidisilikat included.

To effect silver corrosion protection, silver corrosion inhibitors can be used in dishwashing detergents according to the invention. Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, hafnium, molybdenum, vanadium or cerium salts and / or complexes, as well as Salts and / or complexes of the metals present in the complexes suitable according to the invention with other than in formula (I) predetermined ligands.

If the agents foam too much during use, they may still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-regulating compound, preferably from the group consisting of silicones, paraffins, paraffin-alcohol combinations , Hydrophobicized silicic acids, Bisfettsäureamide and mixtures thereof and other other known commercially available foam inhibitors are added. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred. Further optional ingredients in the compositions according to the invention are, for example, perfume oils.

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

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

The compositions according to the invention are present as pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roll compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and the like Bleaching catalyst are expected to be produced. Solutions according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

For the production of particulate agents having an increased bulk density, in particular in the range of 650 g / l to 950 g / l, is one of the European Patent EP 0 486 592 known method comprising an extrusion step is preferred. Another preferred preparation by means of a granulation process is in the European patent specification EP 0 642 576 described. The preparation of compositions according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range from 800 to 1000 g / l can also be achieved by using the builder components with at least a proportion of liquid mixture components in a first process stage while increasing the bulk density of this premix and subsequently - if desired after an intermediate drying - the other constituents of the agent, including the bleach catalyst, combined with the thus obtained premix.

For the preparation of compositions according to the invention in tablet form, the procedure is preferably such that all constituents are mixed together in a mixer and the mixture is compressed by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressing pressures in the range from 20 to 150 MPa. This gives unbreakable, yet sufficiently rapidly soluble tablets under application conditions with flexural strengths of normally over 150 N. Preferably, a tablet thus produced has a weight of 1 to 40 g, in particular from 5 to 30 g, with a diameter of 3 to 40 mm, preferably from 5 to 35 mm.

In liquid or pasty applications, the complexes according to the invention are preferably used as aqueous solution or in microencapsulated form. If they are used for the purpose of using atmospheric oxygen (aerial bleaching), the use of peroxo compounds can be dispensed with. become. However, if they are to be used in combination with a peroxo compound, e.g. B. hydrogen peroxide are used, the use of a multi-chamber container is recommended.

embodiments example 1 Catalyst 1: (diethyl-cyclam) ₂ Mn ₂ (DHBQ) (PF ₆ ) ₂ a.) Synthesis of 1,8-diethyl-1,4,8,11-tetraazacyclotetradecane manganese (II) dichloride

12.6 g (0.1 mol) of manganese (II) chloride were dissolved in 100 ml of DMAC. The solution was treated with 25.6 g (0.1 mol) of 1,8-diethyl-1,4,8,11-tetraazacyclotetradecane. The reaction mixture was heated to 100 ° C for 5 hours. The suspension obtained was then cooled to room temperature, the resulting solid was filtered off, washed with 50 ml of DMAC and then dried at a temperature of 80 ° C in vacuo. There were obtained 37.1 g of the light gray complex, which corresponds to a yield of 97.0%.

Analytical data:

Elemental analysis for C ₁₄ H ₃₂ N ₄ Cl ₂ Mn (382.2 g / mol): calculated: C 43.9%, H 8.4%, N 14.6%, Cl 18.6%, Mn 14.6% found: C 44.1%, H 8.8%, N 14.6%, Cl 18.7%, Mn 13.7%

b.) Reaction of 1,8-diethyl-1,4,8,11-tetraazacyclotetradecane manganese (II) chloride with 2,5-dihydroxy-1,4-benzoquinone to give (diethylcyclam) ₂ Mn ₂ (DHBQ) (PF ₆ ) ₂

38.2 g (= 100 mmol) of 1,8-diethyl-1,4,8,11-tetraazacyclotetradecan manganese (II) dichloride were suspended in 2000 ml of methanol, 7 g (= 50 mmol) 2,5-dihydroxy-1,4-benzoquinone (DHBQ) was added followed by the addition of 4 g (= 100 mmol) of NaOH prills. The dark brown solution was boiled for a period of 30 minutes and then a solution of 60 g of KPF ₆ in 1000 ml of water was added for the precipitation. The solution was stored in the refrigerator for several days for crystallization. The mixture was filtered off with suction and washed with water.
Yield: 38.2 g.

The product was dissolved in 1400 ml of methylene chloride, filtered off the manganese dioxide and the filtrate was rotary evaporated and then recrystallized from 500 ml of MeOH.
Yield: 28.1 g (corresponding to 54% of theory) of dark violet crystals.

Elemental analysis:

calculated: C 38.9%, H 6.3%, N 10.7%, Mn 10.5% found: C 38.8%, H 6.6%, N 10.3%, Mn 10.7%

IR (KBr): 1537, 825 cm ^-1
UV (methanol): 326, 498 nm

Example 2 Catalyst 2: (dimethyl cyclam) ₂ Mn ₂ (DHBQ) (PF ₆ ) ₂

The procedure is analogous to Example 1 and initially prepared from 1,8-dimethyl-1,4,8,11-tetraazacyclotetradecane and manganese dichloride 1,8-dimethyl-1,4,8,11-tetraazacyclotetradecan manganese (II) dichloride. This is then mixed with 2,5-dihydroxy-1,4-benzoquinone (DHBQ) and sodium hydroxide solution and precipitated with KPF ₆ . It is taken up in methyl chloride, filtered off formed brownstone and the concentrate recrystallized from methanol. Yield: 62% blue-violet fine crystals.

Example 3 Catalyst 3: (CHT) ₂ Mn ₂ (DHBQ) Cl ₂ .H ₂ O

Catalyst 3 was analog A. The et al., "Tetraoxylenes Radical Stabilization by Interaction with Transition Metal Ion", Inorg. Chem., 30 (1991), 2590 from d, l-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (CHT), manganese dichloride, 2,5-dihydroxy-1,4-benzoquinone (DHBQ) and KPF ₆ produced. Yield after primary crystallization 65%.

Example 4 Catalyst 4: (diethyl-Bcyclam) ₂ Mn ₂ (DHBQ) (PF ₆ ) ₂

For the preparation of 5,12-diethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane (diethyl-Bcyclam) was prepared according to WO 1998/039 098 method, however, carried out the quaternization with diethyl sulfate instead of methyl iodide. The ligand was then reacted with managandichloride in dimethylactetamide to (diethyl-Bcyclam) MnCl ₂ . In a further synthesis step, as in Example 1b.) 2 molecules (diethyl-Bcyclam) MnCl ₂ implemented by reaction with 2,5-dihydroxybenzoquinone in the presence of sodium hydroxide to Tetraoxolenkomplex, which is precipitated by the addition of KPF ₆ .

Starting from 20.4 g (= 50 mmol) of (diethyl-Bcyclam) MnCl ₂ , 24.5 g (corresponding to 89%) of crude product are obtained, which is purified by means of methylene chloride and methanol / acetone.
Yield: 22.8 g (corresponding to 83% of theory) of deep violet microcrystals.

Elemental analysis:

calculated: C 41.4%, H 6.4%, N 10.2%, Mn 9.9% found: C 44.1%, H 6.9%, N 9.2%, Mn 9.4% IR (KBr): 1536, 830 cm ^-1
UV (methanol): 330, 498 nm

Example 5 Bleaching performance of Catalyst 1 (Cat 1) and Catalyst 4 (Cat 4) in the presence of peroxides

The bleach-increasing performance of the compounds of the invention Cat 1 and Cat 4 was tested in comparison to sodium percarbonate. For this purpose, 10 mg / l Cat 1 or Cat 4 were dissolved in a wash liquor prepared by dissolving 2 g / l of a bleach-free basic detergent (IEC-A, WFK, Krefeld). After addition of 0.5 g / l of sodium percarbonate SPC (Degussa), the washing tests were carried out in a Linitest apparatus (Heraeus) at a temperature of 40.degree. The washing time was 30 min, water hardness 18 ° dH. Tea bleach on cotton (BC-1, WFK, Krefeld), grass on cotton (CS-8, CFT) and curry on cotton (BC-34, CFT) were used as bleaching test cloth. As a bleaching result, the remission difference, measured with an Elrepho apparatus, after washing compared to the unwashed fabric was evaluated. As a comparative experiment (V1), the bleaching performance of SPC without addition of catalyst was determined.
Results of the wash at 40 ° C Remission difference (delta R%) connection BC-1 CS-8 BC-34 Cat 1 6.9 18.8 29.7 Cat 4 6.1 19.6 29.6 SPC (V1) 4.5 16.7 16.6

It can be seen that a significantly better bleaching effect can be achieved by the compounds according to the invention (Cat 1 and Cat 4). Substantially similar results were obtained when replacing sodium percarbonate with sodium perborate.

Example 6 Bleaching in the presence of atmospheric oxygen

The bleaching performance of the compounds of the invention Cat 1 and Cat 4 was tested without the addition of peroxides. For this purpose, 10 mg / l Cat 1 or Cat 4 were dissolved in a wash liquor prepared by dissolving 2 g / l of a bleach-free basic detergent (IEC-A, WFK, Krefeld). The washing tests were carried out in a Linitest apparatus (Heraeus) at a temperature of 40 ° C. The washing time was 30 min, water hardness 18 ° dH. After washing, the fabric was dried and ironed. Curry on cotton (BC-34, CFT), ketchup on cotton (10-T, WFK, Krefeld), tomato on cotton (CS-20, CFT) served as bleaching test cloth. As a bleaching result, the remission difference, measured with an Elrepho apparatus, after washing compared to the unwashed fabric was evaluated. As a comparative experiment (V1), the detergent without complex addition was used.
Results of the wash at 40 ° C Remission diference (delta R%) connection BC-34 10-T CS-20 Cat 1 20.3 23.9 18.5 cat4 19.7 23.5 29.9 IEC-A (V1) 16.8 19.0 18.3

It can also be seen from the higher values that the compounds of the invention Cat 1 and Cat 4, allow a significantly better bleaching effect even without the addition of peroxides.

Claims (15)

1. The use of transition metal complexes which, besides a tetraoxolene unit, contain two macrocyclic, N-containing ligands, in particular cyclen or cyclam ligands, as bleach catalysts in washing and cleaning compositions for textiles or for hard surfaces, wherein transition metal complexes with the chemical formula (I) are used
   
           [(L)M(Y)M(L)]X_m     (I)
   
   where

   M is a metal atom from the group Mn and Fe,

   L is a ligand of the formula (II) or (III)

   

   in which

   R is a hydrogen or alkyl having 1 to 8 carbon atoms,

   R1, R2, R3 and R4 are identical or different and are a hydrogen, alkyl having 1 to 8 carbon atoms, a nitrogen-bridging alkylene unit having 2 to 4 carbon atoms or alkaryl having 6 to 16 carbon atoms,

   n is an integer from 0 to 6,

   Y is a group of the formula (IV)

   

   in which

   R5 are identical or different and are a hydrogen, alkyl having 1 to 4 carbon atoms, Cl or Br,

   X is a neutral or anion ligand from the group CH₃CN, chloride, bromide, nitrate, perchlorate, sulfate, citrate, hexafluorophosphate, trifluoromethanesulfonate, tetrafluoroborate, tetraphenylborate, or anions of organic acids with C₁-C₂₂ carbon atoms, or H₂O, and

   m is a number from 0 to 4.
2. The use as claimed in claim 1, wherein complexes with transition metal central atoms in oxidation states +2, +3, or +4 are used, with preference being given to complexes with manganese as the central atom, and wherein the radicals R and R1 to R4 are preferably hydrogen or methyl groups or alkylaryl radicals containing 6 to 16 carbon atoms in the alkyl moiety, with phenyl being preferred as aryl.
3. The use as claimed in claim 1 or 2, wherein the radicals R5 in the metal-bridging group of the formula (IV) are hydrogen or chlorine.
4. The use as claimed in any one of claims 1 to 3, wherein the ligands L are selected from the group consisting of: 1,4,7,10-tetraazacyclododecane (cyclen); 1,7-dimethyl-1,4,7,10-tetraazacyclododecane; 1,4,8,11-tetraazacyclotetradecane (cyclam); 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane; 1,8-dimethyl-1,4,8,11-tetraazacyclotetradecane; 1,8-diethyl-1,4,8,11-tetraazacyclotetradecane (diethylcyclam); 5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane (dimethyl-Bcyclam), 5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane (diethyl-Bcyclam) and 5-N-octyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane.
5. The use as claimed in any one of claims 1 to 4, wherein, besides the complexes of the unsubstituted or tetrasubstituted cylams or cyclens of the formula (I), complexes with 2 alkyl or alkaryl radicals on the tetraazacycle with the general structures (V), (VI) and the bridged cyclams (VII) having the following chemical formulae are used:

   

   where R4 and R4, independently of one another, are a methyl, ethyl, propyl, butyl or benzyl group.
6. The use as claimed in any one of claims 1 to 5, wherein complexes are used having one or more of the ligands selected from the group consisting of: 1,8-dimethylcyclam, 1,7-dimethylcyclen, 1,8-diethylcyclam, 1,7-diethylcyclen, 1,8-dibenzylcyclam and 1,7-dibenzylcyclen.
7. A washing or cleaning composition for the washing of textiles or for hard surfaces, preferably for dishes, and for solutions for bleaching colored soilings, wherein it comprises transition metal complexes as claimed in any one of claims 1 to 6 as bleach catalysts.
8. The washing or cleaning composition as claimed in claim 7, wherein it comprises the transition metal complexes in an amount of from 0.0025 to 1% by weight, preferably from 0.01 to 0.5% by weight.
9. The washing or cleaning composition as claimed in claim 7 or 8, wherein it additionally comprises further bleach activators which release peroxocarboxylic acids under perhydrolysis conditions, preferably bleach activators which contain O- and/or N-acyl groups and which are selected from the group consisting of: polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenylsulfonates, in particular nonanoyl, isononanoyl or lauroyloxybenzenesulfonate (NOBS, ISONOBS and LOBS) or amido derivatives thereof, acylated hydroxycarboxylic acids such as acetylsalicylic acid or nonanoyloxybenzoic acid (NOBA) and decanoyloxybenzoic acid (DOBA), acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, and acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, and acetylated optionally N-alkylated glucamine and gluconolactone.
10. The washing or cleaning composition as claimed in claim 9, wherein it additionally comprises further bleach activators in an amount of from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, particularly preferably from 1 to 6% by weight, based on the total weight of the washing or cleaning composition.
11. The washing or cleaning composition as claimed in any one of claims 7 to 10, wherein it additionally comprises further open-chain or cyclic nitrile quats or benzoylcaprolactam or acetylcaprolactam.
12. The washing or cleaning composition as claimed in any one of claims 7 to 11, wherein it is present in the form of granules or in the form of a pulverulent or tablet-shaped solid or as a homogeneous solution or as a suspension.
13. The washing or cleaning composition as claimed in any one of claims 7 to 12, wherein it additionally comprises builder substances, surface-active surfactants, peroxygen compounds, additional peroxygen activators or organic peracids, water-miscible organic solvents, sequestrants, enzymes, or special additives having a color- or fiber-preserving effect and/or further auxiliaries such as electrolytes, pH regulators, silver corrosion inhibitors, foam regulators, and dyes and fragrances, or combinations of these additives.
14. The washing or cleaning composition as claimed in claim 13, wherein it comprises peroxygen compounds, preferably inorganic peroxides or hydrogen peroxide, in a preferred amount of from 5 to 25% by weight, based on the total weight of the washing or cleaning composition.
15. The use of a washing or cleaning composition as claimed in any one of claims 7 to 14 as a washing composition for textiles or as a cleaning composition for hard surfaces, in particular as a cleaning composition for dishes, with them being preferred for use in machine processes, or in the personal care sector, preferably for the bleaching of hair and for improving the effectiveness of denture cleaners, in particular at low temperatures, or in commercial laundries, in the bleaching of wood and paper, the bleaching of cotton or in disinfectants.