EP1557457A1 - Use of transition metal complexes as bleach catalysts in washing and cleaning agents - Google Patents

Abstract

Use is claimed as a bleaching catalyst in detergents or cleansing compositions of transition metal complexes containing manganese or iron and tetraazacyclotetradecane or tetraazacyclotetraoctane ligands. Use is claimed as a bleaching catalyst in detergents or cleansing compositions of transition metal complexes containing manganese or iron and of formula [M(L)Y n]X m(I): M = manganese or iron; L = a 1,4,8,11-tetraazacyclotetradecane ligand of formula (II) or a 1,4,7,10-tetraazacyclotetraoctane ligand of formula (III); R 1>- R 4>= H, 1-6C alkyl or 6-12C alkaryl; X and Y = neutral or anionic ligands comprising CH 3CN, chloride, bromide, nitrate, perchlorate, sulfate, citrate, hexafluorophosphate, trifluoromethanesulfonate, tetrafluoroborate, tetraphenylborate or an anion of a 1-22C organic acid; and n and m = integer 0-4. [Image].

Description

The present invention relates to the use of certain macrocyclic, N-containing ligands, in particular unbound cycles or cyclam ligands and their transition metal complexes in bleaching colored Soiling on textiles as well as on hard surfaces, and washing Detergents 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 improved by the addition of so-called bleach activators become. For this purpose, numerous proposals have been worked out in the past all from the classes of N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylglycoluril, N-acylated Caprolactams such as benzoylcaprolactam, acetylcaprolactam or Nonanoyl-caprolactam, hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, Diketopiperazines, sulfurylamides and cyanurates, as well as carboxylic acid 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, like pentaacetylglucose. By adding these substances, the bleaching effect aqueous peroxide solutions are increased so much that even at temperatures at 60 ° C, substantially the same effects as with the peroxide solution alone at 95 ° C.

In the search for energy-saving washing and bleaching processes in recent years application temperatures well below 60 ° C, especially below 45 ° C down to the cold water temperature in importance.
At these low temperatures, the effect of the previously known activator compounds usually decreases noticeably. There has therefore been no lack of efforts to develop for this temperature range more effective bleaching systems, without that to date a convincing success would have been recorded.

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

A variety of macrocyclic N-containing ligand complexes have been reported in the literature as bleach catalysts in recent years. For example, EP 0 439 387 claims binuclear metal complexes with ligands obtained by reacting a dialdehyde with primary polyamines as an oxygen carrier.
EP 0 458 397 and '398 describe the use of manganese complexes of the general formula [L _n Mn _m X _p ] ^z Y _q , wherein L comprises macrocyclic, N-containing ligands. 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, suitable ligands being, in particular, TACN, Me ₃ TACN, 1,5,9-trimethyl-1,5,9-triazacyclodecane. 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 WO 1998/039 098 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. WO 2001/048 298 describes corresponding bridged ligands for bleaching with atmospheric oxygen. The problem with these ligands, however, is their complicated production, which results in particular from the introduction of the bridge into the molecule. As a result, the overall yields of the syntheses are not very high.

wobei die Gruppen R1-R4 Wasserstoff, Alkyl-, Aryl- oder Heteroarylgruppen bzw. über- bzw. verbrückende Gruppen darstellen können. Näher wird auf diese Verbindungsklasse weder in der Beschreibung noch in den Beispielen eingegangen.Similar metal complexes based on unbridged macrocyclic ligands are claimed in WO 2000/012 808 as "aerial bleaching systems" for use in detergents and cleaners. The multitude of listed potential ligands also includes cyclam ligands and cyclic ligands of the general formulas (I) and (II):

where the groups R 1 -R 4 can represent hydrogen, alkyl, aryl or heteroaryl groups or bridging or bridging groups. This class of compounds is not discussed in detail in the description or in the examples.

According to the information there these connections are expressly only in such detergents and cleaners used, which are free of Hydrogen peroxide and other peroxy compounds.

Surprisingly, it has now been found that certain compounds are within the groups of Cyclame and Cyclene (I) and (II) also in hydrogen peroxide and used other washing and cleaning agents containing peroxy compounds can be and have significant advantages in terms of bleaching ability.

The present invention has the improvement of the oxidation and bleaching action of detergents and cleaners at low temperatures below 80 ° C, especially in the temperature range of about 20 ° C to 45 ° C, to the destination.

M

ein Metallatom aus der Gruppe Mn und Fe,

L

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

worin R1, R2, R3 und R4 gleich oder verschieden sind und ein Wasserstoff, Alkyl mit 1 bis 8 Kohlenstoffatomen oder Alkaryl mit 6 bis 16 Kohlenstoffatomen,
X und Y 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,
n und m eine Zahl von 0 bis 4 bedeuten, als Bleichkatalysator in Wasch- und Reinigungsmitteln.The invention relates to the use of transition metal complexes of the formula (I) [M (L) Y _n ] X _m in which

M

a metal atom from the group Mn and Fe,

L

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

wherein R 1, R 2, R 3 and R 4 are the same or different and are a hydrogen, alkyl having 1 to 8 carbon atoms or alkaryl having 6 to 16 carbon atoms,
X and Y are 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,
n and m represent a number from 0 to 4, as a bleach catalyst in detergents and cleaners.

Preference is given to complexes with transition metal central atoms in the Oxidation levels +2, +3 or +4 are used, with complexes containing manganese or iron are preferred as the central atom. The alkylaryl radicals contain 6 to 16 carbon atoms in the Alkyl part, as aryl phenyl is preferred.

These transition metal complexes of the formula (I) are used in washing and Detergents, in particular in textile washing and in cleaning preparations for Hard surfaces, especially for dishes, and in solutions for bleaching used colored stains. This happens on the one hand in the presence of Hydrogen peroxide, hydrogen peroxide-releasing compounds or a Peroxygen compound. On the other hand, the complexes can also by the Oxygen in the air can be activated without the addition of a peroxo compound necessary is.

Iron or manganese complexes of cyclam or tetraalkylcyclam according to the invention have already been described in the literature. Thus, cis- (1,4,8,11-tetraazacyclotetradecane) dichloro-iron (III) chloride and trans- (1,4,8,11-tetraazacyclotetradecane) dichloro-iron (III) chloride are disclosed in J. Chem. Soc. Dalton Trans., 1997, 3459-3463. Manganese derivatives of tetramethylcyclam (tmc) are described, for example, in Inorg. Chem. 2001, 40, 5722-5726. Fe (tcm) (OTf) 2 is used in Science, 2003, 299, 1037-1039 as a precursor to [FeO (tmc) (NCCH ₃ )] (OTf) ₂ . The synthesis of cyclam is described inter alia in WO 1997/049691. None of these references gives hints on the use of these compounds as bleaching agents in detergents and cleaners.

wobei R1 und R3 eine Methyl-, Ethyl-, Propyl-, Butyl- oder Benzylgruppe darstellen.In addition to the inventive complexes 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 (IV) and (V):

wherein R1 and R3 represent a methyl, ethyl, propyl, butyl or benzyl group.

Particular preference is given to complexes with the following ligands: 1,8-dimethylcyclam, 1,7-dimethylcycles, 1,8-diethylcyclam, 1,7-diethylcycles, 1,8-dibenzylcyclam and 1.7 Dibenzylcyclen.

The ligands (IV) and (V) 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.

To activate the complexes come peroxygen compounds or Atmospheric oxygen in question. As peroxygen compound come in the first place Hydrogen peroxide, alkali perborate mono or tetrahydrate and / or Alkali percarbonates, with sodium being the preferred alkali metal, into consideration. In addition, however, alkali metal or ammonium peroxosulphates, such as e.g. Potassium peroxomonosulfate (technically: Caroat® or Oxone®) can be used. The Concentration of the inorganic oxidizing agent on the overall formulation of the Washing and cleaning agent is 2 - 90%, preferably 5 - 60%.

As peroxygen compounds also come oxidizing agents on an organic basis in question. These include all known peroxycarboxylic acids, e.g. Monoperoxyphthalic acid, peracetic acid, dodecanediperoxyacid, phthalimidoperoxycarboxylic acids like PAP and related systems or amido peracids.

The amounts of peroxygen compounds are generally so chosen that in the solutions of detergents and cleaners between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm Active oxygen are present. Also the amount of bleach-enhancing Complex connection depends on the purpose of use. Depending on the desired Activation level is in an amount of 0.01 mmol to 25 mmol, preferably 0.1 mmol to 2 mmol complex per mole of peroxygen compound used, however In special cases, these limits may also be exceeded or fallen short of. 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 included.

In addition to the iron or manganese complexes, hydrogen peroxide and persalts according to the invention, further bleach catalysts or bleach activators can be used in order to widen the spectrum of action of the bleaching systems 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 or Isononanoyloxybenzolsulfonat (NOBS or ISONOBS) or their amido derivatives, 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 pentaacetylglucose (PAG ), Pentaacetyl-fructose, tetraacetyl-xylose and octa-acetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone. Furthermore, open-chain or cyclic nitrile quats are suitable for this purpose. The combinations of conventional bleach activators known from German patent application DE 44 43 177 can also 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 term bleaching here includes both the bleaching of on the textile surface dirt as well as the bleaching of the wash liquor, dirt removed from the textile surface. For the bleaching of Soiling on hard surfaces applies mutatis mutandis to the same. Further potential applications are in the personal care field, e.g. at the bleaching of hair and improve the effectiveness of denture cleaners. Of others find the metal complexes described use in commercial Laundries, in the bleaching of wood and paper, the bleaching of cotton and in Disinfectants.

Furthermore, the invention relates to a method for cleaning textiles as well hard surfaces, in particular dishes, using said Complex compounds together with peroxygen compounds in aqueous, optionally further detergent or cleaning agent components containing solution, as well as detergents and cleaners for hard surfaces, especially dishwashing detergents, such being for use in are preferred by mechanical methods, such complex compounds contain.

The use of the invention consists essentially in, with colored Stains contaminated hard surfaces or at polluted textiles to create conditions under which a peroxidic Oxidizing agent and the complex compound can react with each other Aim to obtain more strongly oxidizing secondary products. Such conditions are particularly present when the reactants in aqueous solution meet each other. This can be done by separately adding the peroxygen compound and the complex to the aqueous solution of the washing and cleaning agent happen. However, the method according to the invention is particularly advantageous using a detergent or cleaning agent for hard Surfaces containing the complex compound and optionally one pers oxygen-containing oxidant. The Peroxygen compound may also be used separately in substance or as preferred aqueous solution or suspension are added to the solution when a non-oxygen detergent or cleaning agent is used.

The detergents and cleaners, which are in the form of granules, powdered or tablet-shaped Solids, as other shaped bodies, homogeneous solutions or suspensions may be present except the said bleach-enhancing metal complex contain in principle all known and customary in such agents ingredients. The agents may in particular be builders, surface-active surfactants, Peroxygen compounds, additional peroxygen activators or organic Peracids, water-miscible organic solvents, sequestering agents, Enzymes, as well as special additives with color or fiber-sparing effect included.

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 cleaner according to the present invention may be used Abrasive constituents, in particular quartz flours, wood flours, Plastic flours, chalks and glass microspheres and mixtures thereof. Abrasives are preferably not more than 20% by weight in the cleaning agents, in particular from 5 to 15% by weight.

The detergents and cleaning agents may contain one or more surfactants, wherein in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants come into question. 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 Shares, that is amounts up to 20 wt .-%, in particular up to 10 wt .-% and preferably in the range of 0.5 to 5 wt .-% are included. In detergents for use in automatic dishwashing are usually low-foam connections used.

Suitable anionic surfactants 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.

Other suitable anionic surfactants 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 of this chain length are 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 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 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 present. Preferably, the anionic Surfactants in the form of their sodium or potassium salts, in particular in the form of Sodium salts. Anionic surfactants are in detergents according to the invention preferably in amounts of from 0.5 to 10% by weight and in particular in amounts of 5 contain up to 25 wt .-%.

The nonionic surfactants used are preferably alkoxylated, advantageously 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 can be linear or preferably methyl-branched in the 2-position , or may contain 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 represent statistical means which, for a particular product, may be an integer or a fractional number. 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.
Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel (II)

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, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [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-Alyloxysubstituierten Verbindungen können dann beispielsweise durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden. 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 is a Glykoseeinheit with 5 or 6 C-atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula (I)

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.
The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

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 this rest stands. [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-alyloxy-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 of preferred nonionic surfactants used either as sole nonionic surfactant or in combination with other nonionic surfactants Surfactants, especially together with alkoxylated fatty alcohols and / or Alkyl glycosides used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 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 the Fatty acid alkanolamides may be suitable.

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 (III) and (IV) 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. this includes In general, compounds which are two hydrophilic Own groups per molecule. These groups are usually by one so-called "spacer" separated from each other. This spacer is usually one Carbon chain, which should be long enough that the hydrophilic groups have a have enough distance to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to control the surface tension of the To greatly reduce water out. However, gemini polyhydroxy fatty acid amides can also be used or poly-polyhydroxy fatty acid amides. Further 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 present 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, particularly 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, which can be determined according to the specifications of the German patent DE 24 12 837, is generally 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 metal silicates are the sodium silicates, in particular the amorphous sodium silicates with a molar ratio Na 2 O: SiO 2, of 1: 2 to 1: 2.8. Such silicates can be prepared by the process of European Patent Application EP 0 425 427. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na ₂ Si _x O _{2x + 1} · YH be used ₂ O, in which x, the so-called module, a number from 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 European Patent Application EP 0 164 514. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both α- and ß-sodium (Na ₂ Si ₂ O ₅ · yH ₂ O) are preferred, with .beta.-sodium disilicate being obtainable, for example, by the process described in WO 91/08171. β-Sodium silicates with a modulus between 1.9 and 3.2 can be prepared according to Japanese patent applications JP 04/238 809 or JP 04/260 6 10. 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, a granular compound of alkali silicate and alkali carbonate is used, as it is commercially available, for example, under the name Nabion®. 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 contained in agents according to the invention in amounts of up to 60% by weight, in particular from 5 to 40% by weight.

The water-soluble organic builders include polycarboxylic acids, especially 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 obtainable by oxidation of polysaccharides or dextrins of international patent application WO 93/161 10 or international patent application WO 92/18542 or European patent EP 0 232 202, polymeric acrylic acids, methacrylic acids, Maleic acids and copolymers of these, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. Commercially available 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 and preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (meth) -acrylic acid.
The second acidic monomer or its salt may be a derivative of a C ₄ -C ₈ -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical. Such polymers can be prepared in particular by processes which are described in German patents DE 42 21 381 and DE 43 00 772, and generally have a molecular weight between 1000 and 200,000. Further preferred copolymers are those which are described in the German patent applications DE 43 03 320 and DE 44 17 734 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.

The organic builders can, in particular for the production of liquid Agent, in the form of aqueous solutions, preferably in the form of 30 to 50 wt .-% iger aqueous solutions are used. All the acids mentioned are usually in the form of their water-soluble salts, in particular their alkali metal salts used.

If desired, such organic builders may be used in amounts up to 40 wt .-%, in particular up to 25 wt .-% and preferably from 1 to 8 wt .-% be included. Quantities near the upper limit mentioned are preferably used in pasty or liquid, in particular water-containing agents used.

As water-soluble builder components in cleaning agents according to the invention for hard surfaces come in principle all in means for the machine cleaning crockery commonly used builders, for example the above-mentioned alkali metal phosphates. Their amounts can range up to about 60 Wt .-%, in particular 5 to 20 wt .-%, based on the total mean. Other possible water-soluble builder components are in addition Polyphosphonates and Phosphonatalkylcarboxylaten for example, organic Polymers of native or synthetic origin of the type listed above Polycarboxylates, which act in particular in hard water regions as a co-builder, and naturally occurring hydroxycarboxylic acids such as mono-, Dihydroxysuccinic acid, alpha-hydroxypropionic acid and gluconic acid. To the preferred organic builder components include the salts of Citric acid, especially sodium citrate. As sodium citrate come anhydrous Triatrium citrate and preferably trisodium citrate dihydrate. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder. Depending on the final cleaning agents in the invention Adjusted pH can also be added to the mentioned co-builder salts corresponding acids are present.

The enzymes optionally present in the compositions of the invention 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 such as Termamy®, amylase-LT, Maxamyl®, Duramyl®, Purafectel OxAm, cellulases such as Celluzyme®, Carezyme®, K-AC® and / or those 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 used enzymes, such as in the international Patent Applications WO 92/111347 or WO 94/23005 Carriers may be adsorbed and / or embedded in enveloping substances, against them Protect premature inactivation. They are in inventive washing and Detergents preferably in amounts up to 10 wt .-%, in particular of 0.05 to 5 wt .-%, with particular preference against oxidative degradation stabilized enzymes are 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 of SiO ₂ / M ₂ O (M = alkali metal) of 1: 1 to 2.5: 1. Alkali silicates may be present in amounts of up to 40% by weight. in particular from 3 to 30% by weight, based on the total agent. The alkali carrier system preferably used 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.

Another object of the invention is a means for machine cleaning of Tableware 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 bleach, based in each case on the total agent, and 0.1 to 1 wt .-% of one or more of the metal complexes defined above. Such a thing Agent is preferably lower alkyl, i. its solution has a pH of 8 to 11.5, especially 9 to 11 on.

In a further embodiment of the invention means for automatic Cleaning of dishes are 20 to 60% by weight of water-soluble organic builders, in particular alkali citrate, 3 to 20% by weight alkali carbonate and 3 to 40% by weight Alkalidisilicate included.

In order to effect silver corrosion protection, in inventive Detergents for tableware silver corrosion inhibitors are used. 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 in the present invention suitable complexes contained metals with other than in formula (I) predetermined ligands.

If the agents foam too much during use, they can still be used up to 6 wt .-%, preferably about 0.5 to 4 wt .-% of a foam-regulating Compound, preferably from the group comprising silicones, paraffins, paraffin-alcohol combinations, hydrophobized silicas, bis-fatty acid amides and their Mixtures and other known commercially available foam inhibitors added become. Preferably, the foam inhibitors, in particular silicone and / or paraffinic foam inhibitors, to a granular, water-soluble or dispersible carrier substance bound. In particular, there are Blends of paraffins and bistearylethylenediamide are preferred. Further optional Ingredients in the compositions according to the invention are, for example, perfume oils.

To those in the inventive compositions, especially when in liquid or pasty form, usable organic solvents include Alcohols having 1 to 4 carbon atoms, in particular -methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 carbon atoms, in particular ethylene glycol and Propylene glycol, and mixtures thereof and those mentioned Classes of derivable ether. Such water-miscible solvents are preferably not present in the cleaning agents according to the invention 20 wt .-%, in particular from 1 to 15 wt .-%, present.

To set a desired one, by mixing the rest Non-self-inflicting pH components can be used agents according to the invention system and environmentally friendly 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 metal hydrogensulfates, or bases, in particular Ammonium or alkali hydroxides. Such pH regulators are in the agents according to the invention preferably not more than 10% by weight, in particular of 0.5 to 6 wt .-%, contained.

The compositions according to the invention are in the form of powdery, granular or tablet-shaped preparations which in a conventional manner, for example by Mixing, granulating, roll compacting and / or by spray-drying the thermally stable components and admixing the more sensitive Components, in particular enzymes, bleach and the Bleaching catalyst are expected to be produced. invention Composition in the form of aqueous or other conventional solvent-containing solutions be particularly advantageous by simply mixing the ingredients in Substance or as a solution in an automatic mixer, produced.

For the production of particulate agents with increased bulk density, in particular in the range of 650 g / l to 950 g / l, is one from the European Patent EP 0 486 592 known, having an extrusion step Preferred method. Another preferred preparation using a Granulation process is described in European Patent EP 0 642 576 described. The preparation of inventive agents in the form of not dusty, storage stable free-flowing powders and / or granules with high Bulk densities in the range of 800 to 1000 g / l can also take place in that in a first process stage, the builder components with at least one Proportion of liquid mixture components increasing the bulk density of this Premix mixed and subsequently - if desired after a Intermediate drying - the other ingredients of the product, including the Bleaching 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 ingredients are mixed together in a mixer and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, with pressing pressures in the range of 200. 10 ⁵ Pa to 1500 10 ⁵ Pa pressed. 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 1-5 g to 40 g, in particular from 20 g to 30 g, with a diameter from 3-5 mm to 40 mm.

In liquid or pasty applications, the invention Complexes preferably as an aqueous solution or in microencapsulated form for Commitment. Are they used for the purpose of using atmospheric oxygen (aerial bleaching) can be dispensed with the use of peroxo compounds. Should however, in combination with a peroxo compound, e.g. Hydrogen peroxide for Use, we recommend the use of a multi-chamber container.

Examples example 1 Synthesis of 1,8-diethyl-1,4,8,11-tetraazacyclotetradecane manganese (II) chloride (Cat 1)

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 resulting suspension was cooled to room temperature, the resulting solid was filtered off, washed with 50 ml of DMAC and then dried at 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%

Example 2 Synthesis of 1,8-diethyl-1,4,8,11-tetraazacyclotetradecane-iron (II) chloride (Cat 2)

12.7 g (0.1 mol) of iron (II) chloride were initially charged in 100 ml of DMAC and then admixed 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 resulting suspension was cooled to room temperature, the resulting solid was filtered off, washed with 50 ml of DMAC and then dried at 80 ° C in vacuo. There were obtained 34.9 g of the beige-light brown complex, which corresponds to a yield of 91.0%. Analytical data: Elemental analysis for C ₁₄ H ₃₂ N ₄ Cl ₂ Fe (383.1 g / mol): calculated C 43.8%, H 8.4%, N 14.6%, Cl 18.5%, Fe 14.7% found C 43.9%, H 8.8%, N 14.5%, Cl 18.6%, Fe 14.4%

Example 3 Synthesis of 1,4,8,11-tetraazacyclotetradecane manganese (II) chloride (Cat 3)

Under nitrogen, 9.0 g (0.072 mol) of manganese (II) chloride were dissolved in 100 ml of DMAC. The solution was added with 14.4 g (0.072 mol) of 1,4,8,11-tetraaza-cyclotetradecane. The reaction mixture was heated to 100 ° C for 5 hours, then cooled to room temperature. The resulting precipitate was filtered off, washed with 50 ml of DMAC and then dried at 80 ° C in vacuo. There were obtained 22.9 g of the light gray complex, which corresponds to a yield of 97.5%. Analytical data: ^{Elemental analysis for C ₁₀ H ₂₄ N ₄ MnCl ₂ (326.0 g / mol):} calculated C 36,8%, H 7.4%, 17.2%, Cl 21.8%, Mn 16.8% found C 37.1%, H 7.4%, N 16.5%, Cl 20.7%, Mn 16.1%

Example 4 Synthesis of 1,8-dimethyl-1,4,8,11-tetraazacyclotetradecane manganese (II) chloride tetraphenylborate (Cat 4)

Under nitrogen, 2.5 g (0.02 mol) of manganese (II) chloride were dissolved in 100 ml of methanol. The solution was treated with 4.5 g (0.02 mol) of 1,8-dimethyl-1,4,8,11-tetraazacyclotetradecane added. The reaction mixture was allowed to stand at room temperature for 2 hours stirred and then mixed with 16.4 g (0.048 mol) of sodium tetraphenylborate. After the reaction was stirred for a further 30 minutes at room temperature, the filtered precipitate, washed several times with methanol and dried. There were obtained 11.3 g of the light gray complex, which was a Yield of 88.6% corresponds.

Example 5 Synthesis of 1,8-diethyl-1,4,8,11-tetraazacyclotetradecane manganese (II) chloride tetraphenylborate (Cat 5)

Under nitrogen, 2.5 g (0.02 mol) of manganese (II) chloride were dissolved in 100 ml of methanol. The solution was treated with 5.1 g (0.02 mol) of 1,8-diethyl-1,4,8,11-tetraazacyclotetradecane added. The reaction mixture was stirred for 2 hours at room temperature and then mixed with 16.4 g (0.048 mol) of sodium tetraphenylborate. after the Reaction was stirred for a further 30 min at room temperature, the resulting Precipitate filtered off, washed several times with methanol and dried. It 6.4 g of the light beige complex were obtained, resulting in a yield of 48.0%. equivalent.

Example 6 Bleaching performance of Cat 1, Cat 2 and Cat 3 in the presence of peroxides

The bleaching performance of the compounds of the invention Cat 1 and Cat 2 was tested in comparison to the bleach activator TAED. For this purpose, 10 mg / l Cat 1, Cat 2 or Cat 3 were dissolved in a wash liquor prepared by dissolving 2 g / l of a bleach-free basic detergent (WMP, WFK, Krefeld). After addition of 1 g / l of sodium percarbonate (Degussa), the washing experiments were carried out in a Linitest apparatus (Fa. The washing time was 30 min, water hardness 18 ° dH. As a bleaching test fabric served two tea stains on cotton (BC-1 and BC3, WFK, Krefeld). 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), instead of the 10 mg / l of the compounds according to the invention (Cat 1 to Cat 3), 250 mg / l of TAED were used. Remission difference (ddR%) connection BC1 BC3 Cat 1 7.1 10.6 Cat 2 1.6 2.0 Cat 3 7.2 8.1 TAED (V1) 3.1 3.2

It can be seen that a significant bleaching effect can be achieved by the compounds according to the invention (Cat 1 to Cat 3). In particular, Cat 1 also shows significant advantages over the conventional bleach activator TAED, which was used in much higher concentrations (V1).
Substantially similar results were obtained when replacing sodium percarbonate with sodium perborate.

Example 7 Bleaching performance in combination with an activator

The bleaching performance of the compound of the invention Cat 1 was tested in combination with the bleach activator TAED. For this purpose, 10 mg / l Cat 1 and 200 mg / l TAED were dissolved in a wash liquor prepared by dissolving 2 g / l of a bleach-free basic detergent (WMP, WFK, Krefeld). After addition of 1 g / l of sodium percarbonate (Degussa), the washing experiments were carried out in a Linitest apparatus (Fa. The washing time was 30 min, water hardness 18 ° dH. As a bleaching test fabric served two tea stains on cotton (BC-1 and BC3, WFK, Krefeld). 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 (V2) 250 mg / l TAED were used. Remission difference (ddR%) connection BC1 BC3 Cat 1 + TAED 8.8 10.2 TAED (V2) 3.0 3.1

It can be seen that by means of the compound Cat 1 according to the invention a significant Bleaching effect can be achieved. Substantially similar results were obtained obtained by replacing the sodium percarbonate with sodium perborate.

Example 8 Bleaching in the presence of atmospheric oxygen

The bleaching performance of the compounds of the invention Cat 1 and Cat 2 was tested without the addition of peroxides. For this purpose, 10 mg / l Cat 1 or Cat 2 in a wash liquor prepared by dissolving 2 g / L of a bleach-free Basic detergent (WMP, WFK, Krefeld), solved. The washing tests were in a Linitest device (Heraeus) at 20 and 40 ° C performed. The washing time was 30 min, water hardness 18 ° dH. After washing, the fabric was dried and ironed. As a bleaching test fabric served two self-made oily Stains on cotton (ketchup / oil and curry / oil, made by boil ketchup or curry powder with sunflower oil). As a bleaching result the remission difference, measured with an Elrepho device, after the Laundry compared to unwashed fabric. As a comparative experiment (V1) the detergent without complex addition was used.

Results of the wash at 20 ° C

Remission difference (dR%) connection Ketchup / oil Curry / Oil Cat 1 66.5 38.1 Cat 2 59.9 36.2 Cat 3 48.4 30.8 WMP 43.9 25.9

Results of the wash at 40 ° C

Remission difference (dR%) connection Ketchup / oil Curry / Oil Cat 1 75.6 57.8 Cat 2 67.0 54.2 WMP 42.8 35.2

It can be seen that the compounds according to the invention, in particular Cat 1 and 2, which cause a significant bleaching effect.

Example 9 Bleaching performance of Cat 4 and Cat 5 in the presence of peroxides

The experiments were carried out analogously to Example 6. The washing temperatures selected were 20 and 40 ° C. Remission difference (ddR%) 20 ° C 40 ° C connection BC1 BC3 BC1 BC3 Cat 4 0.7 0.4 1.5 3.2 Cat 5 1.4 1.3 5.9 9.0 TAED (V1) 1.3 1.3 3.0 3.1

Example 10 Bleaching performance of catalysts Cat 4 and Cat 5 in the presence of atmospheric oxygen

The experiments were carried out analogously to Example 8 at 20 ° C to curry / Ölanschmutzung carried out.

Results

Remission difference (dR%) connection Curry / Oil Cat 4 24.9 Cat 5 30.5 WMP 21.0

Claims (7)

Use of transition metal complexes of the formula (I) [M (L) Y _n ] X _m in which

M

a metal atom from the group Mn and Fe,

L

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

wherein R _1, R 2, R 3 and R 4 are the same or different and are H, C ₁ -C ₈ alkyl or C ₆ -C ₁₂ alkaryl
X and Y are a neutral or anion ligand selected from the group consisting of CH ₃ CN, chloride, bromide, nitrate, perchlorate, sulfate, citrate, hexafluorophosphate, trifluoromethanesulfonate, tetrafluoroborate, tetraphenylborate or an organic acid anion having C ₁ -C ₂₂ carbon atoms,
n and m represent a number from 0 to 4, as a bleach catalyst in detergents and cleaners. Use according to claim 1, characterized in that the transition metal complexes of the formula I are used with peroxygen compounds and / or in combination with atmospheric oxygen. Use according to claim 1, characterized in that the ligand L in the formula I has the general structure (IV) or (V)

wherein R4 represents a methyl, ethyl, propyl, butyl or benzyl group. Use according to claim 1 in aqueous solutions for textile washing, in aqueous cleaning solutions for hard surfaces and for bleaching colored Soils. Use according to claim 1, characterized in that the transition metal complexes of the formula I are used with a compound releasing peroxycarboxylic acid under perhydrolysis conditions. Solid, liquid or pasty washing, bleaching and cleaning agents containing a transition metal complex of the formula I according to claim 1. Composition according to claim 6, characterized in that it contains 0.0025 wt .-% to 1 wt .-%, in particular 0.01 wt .-% to 0.1 wt .-% of the transition metal complex compound.