WO1997007191A1

WO1997007191A1 - Detergents with activator complexes for peroxy compounds

Info

Publication number: WO1997007191A1
Application number: PCT/EP1996/003465
Authority: WO
Inventors: Helmut Blum; Christian Nitsch; Peter Jeschke; Jürgen Härer; Ulrich Pegelow
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1995-08-15
Filing date: 1996-08-06
Publication date: 1997-02-27
Also published as: DE19529904A1; ES2174093T3; DE59608926D1; EP0846156B1; EP0846156A1

Abstract

Used as activators for peroxy compounds in cleaning solutions for hard surfaces, especially for dishes, are transition metal complexes of formula (I) wherein UM is manganese, iron, cobalt, ruthenium or molybdenum; R is an alkylene, alkenylene, phenylene or cycloalkylene radical, which in addition to substituent X can optionally be alkyl- and/or aryl-substituted, with a total of 1 to 12 C atoms, where within R the shortest distance between the N atoms complexing with UM is 1 to 5 atoms; X is -H, -OR3, -NO2, -F, -Cl, -Br or -J; R?1, R2 and R3¿, independently of one another, are hydrogen or an alkyl radical with 1 to 4 C atoms; Y?1 and Y2¿, independently of each other, are hydrogen or an electron-displacing substituent; Z?1 and Z2¿, independently of each other, are hydrogen, -CO¿2?M, -SO3M or -NO2; M is hydrogen or an alkali metal such as lithium, sodium or potassium, and A is a charge-balancing anionic ligand. Dishwashing detergents contain preferably 0.005 to 0.1 wt % of such activator complexes.

Description

"Detergent with activator complexes for peroxygen compounds"

The present invention relates to the use of certain transition metal complexes as catalytically active activators for in particular inorganic peroxygen compounds for bleaching colored stains on hard surfaces and cleaning agents for hard surfaces which contain such activators or catalysts.

Inorganic peroxygen compounds, in particular hydrogen peroxide and solid peroxygen compounds which dissolve in water with the liberation of hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfection and bleaching purposes. The oxidizing effect of these substances in dilute solutions depends strongly on the temperature; For example, with H ₂ O ₂ or perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 80 ° C. At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for which numerous suggestions, especially from the classes of the N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, moreover carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-acyl benzene sulfonate, benzyl sulfonate, benzyl sulfonate, have become known in the literature. By adding these substances, the bleaching effect of aqueous peroxide liquors can be increased to such an extent that even at temperatures around 60 ° C essentially the same effects occur as with the peroxide liquor alone at 95 ° C.

These temperatures, too, are still too high for manual cleaning of hard surfaces, for example of dishes, and are normally not always reached even in automatic dishwashing processes. In the past few years, application temperatures have increased in the effort for energy-saving processes for the mechanical cleaning of dishes from below 60 ° C, in particular below 50 ° C down to the cold water temperature.

At these low temperatures, the effect of the activator compounds known to date generally diminishes noticeably, particularly in the case of soils which are difficult to bleach, such as, for example, tea residues on porcelain or glass. There has therefore been no lack of efforts to develop more effective activators for this temperature range without convincing success to date. One starting point for this could be the use of transition metal salts and complexes, as proposed for example in European patent applications EP 392 592, EP 443 651, EP 458 397, EP 544 490 or EP 549 271 for detergents, as so-called bleach catalysts . From European patent application EP 630 964, certain manganese complexes are also known of the salen type, which, as stated there, have no pronounced effect with regard to bleaching enhancement of peroxygen compounds and only the bleaching of dirt present in washing liquors, that is to say already removed from the textile surface to be cleaned or Can cause dye.

Surprisingly, it has now been found that transition metal complexes, the ligands of which correspond to the Bis-Schiff bases available from salicylaldehyde or salicylaldehyde derivatives and bisamines, have a clear bleach-catalyzing effect on colored stains which are found on hard surfaces.

The invention accordingly relates to the use of transition metal (III) complexes of the formula (I),

X

in the

UM stands for manganese, iron, cobalt, ruthenium or molybdenum,

R represents an alkylene, alkenylene, phenylene or cycloalkylene radical which, in addition to the substituent X, can optionally be alkyl and / or aryl-substituted, with a total of 1 to 12 carbon atoms, R within being the shortest distance between the UM complexing N atoms is 1 to 5 C atoms,

X represents -H, -OR ³ , -NO ₂ , -F, -Cl, -Br or -J,

R ¹ , R ² and R independently of one another represent hydrogen or an alkyl radical having 1 to 4 carbon atoms,

Y ¹ and Y ² independently of one another represent hydrogen or an electron-shifting substituent,

Z 'and Z ² independently of one another represent hydrogen, -CO ₂ M, -SO ₃ M or -NO ₂ ,

M stands for hydrogen or an alkali metal such as lithium, sodium or potassium and A stands for a charge-balancing anion ligand, as activators for in particular inorganic peroxygen compounds in cleaning solutions for hard surfaces, in particular for dishes.

The preferred transition metal (UM in formula I) is manganese. The preferred compounds of the formula (I) include those in which R is a methylene group, 1,2-ethylene group, 1,3-propylene group, in position 2 hydroxyl- or nitro-substituted 1,3-propylene group, 1,2-cycloalkylene group with 4 is up to 6 carbon atoms, in particular a 1,2-cyclohexylene group, or an o-phenylene group.

The electron-shifting substituents Y ¹ and Y ² in formula (I) include the hydroxyl group, alkoxy groups with 1 to 4 carbon atoms, arylox groups, the nitro group, halogens such as fluorine, chlorine, bromine and iodine, the amino group, which are also mono- or may be dialkylated or -arylated, linear or branched chain alkyl groups having 1 to 4 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, linear or branched chain alkenyl groups having 2 to 5 carbon atoms, and aryl groups, which in turn have the aforementioned substituents can wear. The alkenyl groups, which may contain 1 or 2 CC double bonds, preferably have at least one double bond conjugated to the benzene ring. The preferred alkenyl substituents include the allyl and vinyl groups. The substituents Y ¹ and Y ² are preferably in the 5-position. The compounds of formula (I) used with preference include those in which Y ¹ and Y ^{2 are} identical.

The alkyl radicals having 1 to 4 carbon atoms, in particular R ¹ , R ² and R ³ , include in particular the methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl and tert-butyl group.

The charge-balancing anion ligand A in the compounds of the formula (I) can be mono- or polyvalent, in which case it can neutralize a plurality of transition metal atoms with the organic ligands mentioned. It is preferably a halide, in particular chloride, a hydroxide, hexafluorophosphate, perchlorate or the anion of a carboxylic acid, such as formate, acetate, benzoate or citrate.

The compounds of the formula (I) used according to the invention can be prepared by processes known in principle by the reaction of salicylaldehyde or corresponding ketones (if R ¹ and / or R ^{2 are} not hydrogen), which, if appropriate, define the above Substitutes Y ¹ , Y ² , Z ¹ and / or Z ² , be prepared with diamines H ₂ NR-NH ₂ and the reaction of the salen ligand thus obtainable with transition metal salts, as described for example in European patent application EP 630 694 or by BB De, BB Lohraj, S. Sivaram and PK Dhal in Macromolecules 27 (1994), 1291-1296.

Furthermore, the invention relates to cleaning agents for hard surfaces, in particular cleaning agents for dishes, and among these preferably those for use in mechanical cleaning processes which contain a bleaching catalyst of the formula (I) described above, and a process for cleaning hard surfaces, especially of dishes, using such a bleaching catalyst.

The use according to the invention essentially consists in creating, in the presence of a hard surface contaminated with colored soils, conditions under which a peroxidic oxidizing agent and the bleaching catalyst according to formula (I) can react with one another with the aim of obtaining secondary products having a more oxidizing effect . Such conditions exist in particular when both reactants meet in aqueous solution. This can be done by separately adding the peroxygen compound and the bleaching catalyst to an optionally detergent-containing solution. However, the process according to the invention is particularly advantageously carried out using a cleaning agent according to the invention for hard surfaces, which contains the bleaching catalyst and optionally an oxidizing agent containing peroxygen. The peroxygen compound can also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, if a peroxide-free cleaning agent is used.

The conditions can be varied widely depending on the intended use. In addition to purely aqueous solutions, mixtures of water and suitable organic solvents are also suitable as the reaction medium. The amounts of peroxygen compounds used are generally chosen so that the solutions contain between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5,000 ppm active oxygen. The amount of bleach catalyst used also depends on Application purpose. Depending on the desired degree of activation, 0.00001 mol to 0.025 mol, preferably 0.0001 mol to 0.02 mol, of activator per mol of peroxygen compound are used, but in special cases these limits can also be exceeded or fallen short of. In the context of the method and the use according to the invention, it is also possible to use a precursor of the complex compound of the formula (I) in the form of a corresponding complex which lacks the ligand A and in which the transition metal has a lower oxidation state, for example +2 , from which the complex of formula (I) forms under the action of the peroxygen compound.

The invention further relates to a cleaning agent for hard surfaces, in particular for dishes, which contains 0.001% by weight to 1% by weight, in particular 0.005% by weight to 0.1% by weight, of a bleaching catalyst of the formula ( I) in addition to conventional ingredients compatible with the bleaching catalyst. The bleaching catalyst can be adsorbed onto carriers and / or embedded in coating substances in a manner known in principle.

In addition to the bleaching catalyst used according to the invention, the cleaning agents according to the invention, which can be in the form of solids in powder or tablet form, homogeneous solutions or suspensions, can in principle contain all the known ingredients which are customary in such agents. In particular, the agents according to the invention can contain builder substances, surface-active surfactants, peroxygen compounds, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as silver corrosion inhibitors, foam regulators, additional peroxygen activators, and colorants and fragrances.

A cleaning agent for hard surfaces according to the invention can moreover have abrasive components, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and micro-glass balls and mixtures thereof, contain. Abrasives are preferably not contained in the cleaning agents according to the invention in excess of 20% by weight, in particular from 5% by weight to 15% by weight.

Another subject matter of the invention is a low-alkaline agent for the mechanical cleaning of dishes, the 1% by weight solution of which has a pH of 8 to 11.5, preferably 9 to 10.5, containing 15% by weight to 60% by weight. %, in particular 30% by weight to 50% by weight of water-soluble builder component, 5% by weight to 25% by weight, in particular 10% by weight to 15% by weight, oxygen-based bleaching agent, in each case based on the total Agent which contains a bleaching catalyst according to formula (I), in particular in amounts of 0.005% by weight to 0.1% by weight.

In principle, all builders customarily used in machine dishwashing detergents are suitable as water-soluble builder components, in particular in such low-alkaline cleaning agents, for example polymeric alkali metal phosphates which may be present in the form of their alkaline neutral or acidic sodium or potassium salts. Examples include tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. Their amounts can range up to about 35% by weight, based on the total agent; however, the agents according to the invention are preferably free of such phosphates. Other possible water-soluble builder components are, for example, organic polymers of native or synthetic origin, especially polycarboxylates, which act as co-builders, particularly in hard water regions. Examples include polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids. Commercial products are, for example, Sokalan® CP 5 and PA 30 from BASF. Polymers of native origin that can be used as co-builders include, for example, oxidized starch, as known, for example, from international patent application WO 94/05762, and polyamino acids such as polyglutamic acid or polyaspartic acid. Other possible builder components are naturally occurring hydroxycarboxylic acids such as mono-, di-hydroxy succinic acid, α-hydroxypropionic acid and gluconic acid. The preferred builder components include the salts of citric acid, especially sodium citrate. As Sodium citrate can be anhydrous trisodium citrate and preferably trisodium citrate dihydrate. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder. Depending on the pH ultimately set in the agents according to the invention, the acids corresponding to the co-builder salts mentioned can also be present.

Suitable oxygen-based bleaches are primarily alkali perborate mono- or tetrahydrate and / or alkali percarbonate, with sodium being the preferred alkali metal. The use of sodium in particular in Reini¬ supply medium for dishes advantages because it has a particularly favorable effect on ^'the corrosion behavior of glasses. The oxygen-based bleach is therefore preferably an alkali percarbonate, especially sodium percarbonate. In addition or in particular as an alternative, known peroxycarboxylic acids, for example dodecanediperic acid or phthalimidopercarboxylic acids, which can optionally be substituted on the aromatic, can also be present. In addition, the addition of small amounts of known bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates as well as magnesium salts such as magnesium sulfate can also be useful.

In addition to the bleaching catalysts according to formula (I), other transition metal salts or complexes known as bleach-activating agents and / or conventional bleach activators, ie compounds which contain perbenzoic acid and / or peroxocarboxylic acids with 1 to 10 carbon atoms which are optionally substituted under perhydrolysis conditions , especially 2 to 4 carbon atoms, are used. Suitable are the conventional bleach activators cited at the outset which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated 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 phenyls are preferred , in particular nonanoyloxy or isononanoyloxybenzenesulfonate, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-di-acetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol, and acylated sugar deri- vate, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone. The combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used.

The lower alkaline machine dishwashing agents according to the invention preferably contain the usual alkali carriers such as, for example, alkali silicates, alkali metal carbonates and / or alkali metal hydrogen carbonates. The alkali carriers commonly used include carbonates, hydrogen carbonates and alkali silicates with a molar ratio SiÜ2 / M2O (M.

= Alkali atom) from 1.5: 1 to 2.5: 1. Alkali silicates can be present in amounts of up to 30% by weight, based on the total agent. The use of the highly alkaline metasilicates as alkali carriers is preferably omitted entirely. The alkali carrier system preferably used in the agents according to the invention is a mixture of carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, in an amount of up to 60% by weight, preferably 10% by weight to 40% by weight , is included. Depending on which pH is ultimately desired, the ratio of carbonate and hydrogen carbonate used varies, but an excess of sodium hydrogen carbonate is usually used, so that the weight ratio between hydrogen carbonate and carbonate is generally 1: 1 to 15: 1.

In a further preferred embodiment of agents according to the invention, 20% by weight to 40% by weight of water-soluble organic builders, in particular alkali citrate, 5% by weight to 15% by weight of alkali carbonate and 20% by weight to 40% by weight Contain alkali disilicate.

If appropriate, surfactants, in particular weakly foaming nonionic surfactants, can also be added to the agents according to the invention, which serve to better detach fatty soils, as wetting agents and, if appropriate, as granulating aids in the course of the preparation of the cleaning agents. Their amount can be up to 10% by weight, in particular up to 5% by weight, and is preferably in the range from 0.5% by weight to 3% by weight. Extremely low-foaming compounds are usually used, in particular, in cleaning agents for use in machine dishwashing processes. These preferably include C ₂ -C ₈ -alkyl polyethylene glycol polypropylene glycol ether each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule. But you can also use other known low-foaming nonionic surfactants, such as Cι ₂ - Cig-Alkylpolyethylenglycol-polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, end-capped alkyl polyalkylene glycol mixed ether and the foaming, but ecologically attractive Cg-Cι ₄ - alkyl polyglucosides with a degree of polymerization of about 1 to 4 (e.g. APG® 225 and APG® from Henkel) and / or Cπ-Cπ-alkyl polyethylene glycols with 3 to 8 ethylene oxide units in the molecule. Also suitable are surfactants from the family of glucamides, such as, for example, alkyl-N-methyl-glucamides, in which the alkyl part preferably comes from a fatty alcohol with the C chain length Cβ-Cι ₄ . It is sometimes advantageous if the surfactants described are used as mixtures, for example the combination of alkyl polyglycoside with fatty alkiol ethoxylates or glucamide with alkyl polyglycosides.

Although transition metal complexes, in particular manganese complexes, are known to counteract the corrosion of silver, the compounds of the formula (I) are generally used in amounts which are too small to provide protection against silver corrosion, so that silver corrosion inhibitors are still present in dishwashing detergents according to the invention can also be used, the effect of which can be enhanced by the compounds of the formula (I). Preferred silver corrosion inhibitors are organic disulfides, dihydric phenols, trihydric phenols, optionally substituted benzotriazole, manganese, titanium, zirconium, hafnium, vanadium, cobalt or cerium salts and / or complexes, in which the metals mentioned exist in one of the oxidation states π, HI, IV, V or VI.

In addition, the agents according to the invention can contain enzymes such as proteases, amylases, pullulanases, cutinases and lipases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Esperase® and / or Savinase®, amylases such as Termamyl® , Amylase-LT®, Maxamyl® and / or Duramyl®, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®. The optionally used enzymes can, as described for example in the international patent applications WO 92/11347 or WO 94/23005, adsorbed on carriers and / or in Envelope substances are embedded to protect them against premature inactivation. They are preferably contained in the cleaning agents according to the invention not more than 2% by weight, in particular from 0.1% by weight to 0.7% by weight.

If the cleaning agents foam too much during use, they can still contain up to 6% by weight, preferably about 0.5% by weight to 4% by weight, of a foam-suppressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffins, paraffin-alcohol combinations, hydrophobicized silica, the bisfatty acid amides, and other other known commercially available defoamers. Other optional ingredients in the agents according to the invention are, for example, perfume oils.

The organic solvents which can be used in the agents according to the invention, in particular if they are in liquid or pasty form, include alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert. -Butanol, diols with 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol, as well as their mixtures and the ethers derived from the compound classes mentioned. Such water-miscible solvents are preferably not present in the cleaning agents according to the invention in excess of 20% by weight, in particular from 1% by weight to 15% by weight.

To set a desired pH value which does not result from the mixture of the other components, the agents according to the invention can contain system and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or Adipic acid, but also mineral acids, especially sulfuric acid or alkali hydrogen sulfates, or bases, especially ammonium or alkali hydroxides. Such pH regulators are preferably contained in the agents according to the invention not more than 10% by weight, in particular from 0.5% by weight to 6% by weight.

The preparation of the solid compositions according to the invention is not difficult and can be carried out in a manner known in principle, for example by spray drying or granulation. take place, the peroxygen compound and bleaching catalyst optionally being added separately later.

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

The agents according to the invention are preferably in the form of powdery, granular or tablet-like preparations which are known in a manner known per se, for example by mixing, granulating, roller compacting and / or by spray drying the thermally loadable components and admixing the more sensitive components, in particular enzymes, bleaches and the bleaching catalyst can be expected to be produced.

For the preparation of cleaning agents according to the invention in tablet form, the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200 10 ⁵ Pa to 1 500 10 ⁵ Pa veφresst. In this way, unbreakable tablets are obtained with a flexural strength of normally more than 150 N that are sufficiently quickly soluble under conditions of use. A tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm to 40 mm.

Agents according to the invention can be produced 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 / 1 in that the builder components are at least partially liquid in a first process stage Mixing components are mixed while increasing the bulk density of this premix and then, if desired after an intermediate drying, the further constituents of the composition, including the bleaching catalyst, are combined with the premix obtained in this way. Agents for cleaning dishes according to the invention can be used both in household dishwashers and in commercial dishwashers. It is added by hand or using suitable dosing devices. The application concentrations in the cleaning liquor are generally about 1 to 8 g / 1, preferably 2 to 5 g / 1.

A machine wash program is generally supplemented and ended by a few intermediate rinse cycles with clear water following the cleaning cycle and a rinse cycle with a customary rinse aid. After drying, when using agents according to the invention, completely clean dishes which are impeccable in terms of hygiene are obtained.

Examples

example 1

98 mg of sodium perborate monohydrate were dissolved in a solution containing 2.5 mg of morin in 99.5 ml of fully demineralized water. The pH was adjusted to 9.5 and kept at this value with the aid of a pH stat device during the entire subsequent measurement period. The temperature was also kept constant at 20 ° C. 0.5 ml of a solution containing the bleaching catalyst to be tested in a concentration of 50 ppm based on transition metal (Mn) was added. The absorbance E of the solution at 400 nm was measured every minute over a period of 30 minutes. The table below shows the values for the percent decolorization D (t), calculated according to D (t) = [E (0) - E (t)] / E (0) * 100.

The complexes prepared by known processes [N, N'-bis [(2-hydroxy-5-vinylphenyl) methylene] -1, 2-diaminocyclohexane] manganese (III) chloride (El; formula ( I) with UM = Mn, R = 1,2-cyclohexylene, Y ¹ = Y ² = vinyl, R ¹ = R ² = X = Z ¹ = Z ² = H, A = Cl), [N, N'- Bis [(2-hydroxy-5-nitrophenyl) methylene] - 1,2-diaminocyclohexane] manganese (IΙI) acetate (E2; formula (I) with UM = Mn, R = 1,2-cyclohexylene, Y ¹ = Y ² = NO ₂ , R ^! = R ² = X = Z ¹ = Z ² = H, A = acetate), [N, N'-bis [(2-hydroxy-3-methoxyphenyl) methylene] - 1,2-diaminocyclohexane] manganese (III) chloride (E3; formula (I) with UM = Mn, R = 1,2-cyclohexylene, Y ¹ = Y ² = methoxy, R ¹ = R ² = X = Z ¹ = Z ² = H, A = Cl), [N, N-bis [(2-hydroxy-3-methoxyphenyl) methylene] - 1, 2-diaminocyclohexane] -manganese (III) - acetate (E4; formula (I) with UM = Mn, R = 1,2-cyclohexylene, Y ¹ = Y ² = methoxy, R ¹ = R ² = X = Z ¹ = Z ² = H, A = acetate ), [N, N-Bis [(2-hydroxy-3-ethoxyphenyl) methylene] -1, 2-diamino-cyclohexane] -manganese (ILI) chloride (E5; F ormel (I) with UM = Mn, R = 1,2-cyclohexylene, Y ¹ = Y ² = ethoxy, R ¹ = R ² = X = Z ¹ = Z ² = H, A = Cl), [N, N - bis [(2-hydroxy-3-ethoxyphenyl) methylene] -1, 2-diaminocyclohexane] manganese (ILI) acetate (E6; Formula (I) with UM = Mn, R = 1,2-cyclohexylene, Y ¹ = Y ² = ethoxy, R ¹ = R ² = X = Z ¹ = Z ² = H, A = acetate) and [N, N - bis [(2-hydroxyphenyl) methylene] - 1, 2-phenylenediamine] -manganese (III) acetate (E7; formula (I) with UM = Mn, R = 1,2-phenylene, Y ¹ = Y ² = R ¹ = R ² = X = Z ¹ = Z ² = H, A = acetate) in the sense of the invention. In addition, the conventional bleach activator N, N, N ', N ^, -Tetraacetyl-ethylenediamine (TAED) under otherwise identical conditions, but in a concentration of 6% by weight, also tested (VI).

Table 1: Decolorization as a function of time

^a) Value after 8 minutes ^b) Value after 30 minutes

It can be seen that a significantly better bleaching effect can be achieved by the uses according to the invention (E1 to E7) than by the conventional bleach activator TAED in a substantially higher concentration (VI).

Example 2

A cleaning agent (Ml) for the mechanical cleaning of dishes, containing 45 parts by weight of sodium citrate, 5 parts by weight of sodium carbonate, 31 parts by weight of sodium hydrogen carbonate, 1 part by weight of protease and amylase granules, 2 Parts by weight of nonionic surfactant and 12 parts by weight of sodium percarbonate and 2 parts by weight of N, N, NW tetraacetylethylene diamine (TAED), an agent according to the invention (M2), which was otherwise composed like MI, but instead of the TAED 0.05 part by weight [NN ¹ - Bis [(2-hydroxy-5-sulfonatophenyl) methylene] - 1, 2-diaminoethane] -manganese (III) chloride ent ent, and another agent according to the invention (M3), which instead 0.05 wt Parts. [N, N'-bis [(2-hydroxy-5-methylphenyl) methylene] -1, 2-diammocyclohexane] manganese (III) chloride was tested as follows:

To produce standardized tea coverings, tea cups were immersed 25 times in a 70 ° C tea solution. Then some of the tea solution was added to each tea cup and the cup dried in the drying cabinet. In a Bosch® S 710 dishwashing machine (doses of 20 g each in the economy program, soft water, operating temperature 40 ° C), 8 of the cups provided with tea toppings were washed and the deposit removal was then visually changed on a scale of 0 (= unchanged) very thick base) to 10 (= no base) graded. The grades of the agents according to the invention (M2 and M3) given in Table 2 below are significantly better than the value for the comparative product M1.

Table 2: Sheet removal marks

Claims

claims

1. Use of transition metal (IH) complexes of the formula (I),

X

in the

UM stands for manganese, iron, cobalt, ruthenium or molybdenum,

X represents -H, -OR ³ , -NO ₂ , -F, -Cl, -Br or -J,

R, R ² and R ³ independently of one another represent hydrogen or an alkyl radical having 1 to 4 carbon atoms,

Z ¹ and Z ² independently of one another represent hydrogen, -CO ₂ M, -SO ₃ M or -NO ₂ ,

M represents hydrogen or an alkali metal such as lithium, sodium or potassium and

A stands for a charge-balancing anion ligand, as activators for peroxygen compounds in cleaning solutions for hard surfaces.

2. Use of complexes of the formula (I) as activators for peroxygen compounds in cleaning solutions for dishes.

3. Use according to claim 1 or 2, characterized in that the transition metal UM in the compound of formula (I) is manganese.

4. Use according to one of claims 1 to 3, characterized in that in formula (I) R a methylene group, 1,2-ethylene group, 1,3-propylene group, in position 2 hydroxy or nitro-substituted 1,3-propylene group , 1,2-cycloalkylene group having 4 to 6 carbon atoms, in particular a 1,2-cyclohexylene group, or an o-phenylene group.

5. Use according to one of claims 1 to 4, characterized in that Y * and

Y ² in formula (I) under the hydroxy group, alkoxy groups with 1 to 4 carbon atoms, arylox groups, the nitro group, the halogens, the amino group, which can also be mono- or dialkylated or -arylated, the linear or branched-chain alkyl groups with 1 up to 4 carbon atoms, cycloalkyl groups with 3 to 6 carbon atoms, linear or branched chain alkenyl groups with 2 to 5 carbon atoms, and aryl groups, which in turn can carry the aforementioned substituents.

6. Use according to one of claims 1 to 5, characterized in that γi and

Y2 in formula (I) is selected from the alkenyl groups which contain 1 or 2 CC double bonds, at least one double bond being conjugated to the benzene ring.

7. Use according to claim 6, characterized in that the alkenyl group is the allyl or vinyl group.

8. Use according to one of claims 1 to 7, characterized in that in the

Compounds of formula (I) the substituents Y * and Y ^{2 are} in the 5-position and / or are identical.

9. Use according to any one of claims 1 to 8, characterized in that the charge-balancing anion ligand A in the compounds of formula (I) is mono- or polyvalent, in the latter case it neutralizes several transition metal atoms with the salen ligands and in particular one Halide, a hydroxide, hexafluorophosphate, perchlorate or the anion of a carboxylic acid.

10. Use according to one of claims 1 to 9, characterized in that R ^, R ² and R ³ independently of one another from the methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec- Butyl, iso-butyl and tert-butyl groups can be selected

11. Use according to one of claims 1 to 10, characterized in that the peroxygen compound to be activated is selected from the group comprising organic peracids, hydrogen peroxide, perborate and percarbonate and mixtures thereof.

12. Process for cleaning hard surfaces, in particular dishes, using a compound of the formula (I).

13. Cleaning agent for hard surfaces, in particular for dishes, characterized in that it contains 0.001% by weight to 1% by weight, in particular 0.005% by weight to 0.1% by weight, of a bleaching catalyst of the formula (I) Contains usual ingredients compatible with the bleaching catalyst.

14. Low-alkaline agent for machine cleaning of dishes, the 1% by weight solution of which has a pH of 8 to 11.5, containing 15% by weight to 60% by weight, in particular 30% by weight to 50% by weight. -% water-soluble builder component, 5 wt .-% to 25 wt .-%, in particular 10 wt .-% to 15 wt .-% oxygen-based bleach, in each case based on the total agent, characterized in that it contains bleaching catalyst according to formula (I ), in particular in amounts of 0.005% by weight to 0.1% by weight.

15. A composition according to claim 13 or 14, characterized in that it contains alkali perborate monohydrate, alkali perborate tetrahydrate, alkali percarbonate and / or peroxycarboxylic acid as bleaching agent.