EP1105454A1

EP1105454A1 - Manganese complexes as catalysts for peroxygenated compounds to clean hard surfaces, especially dishes

Info

Publication number: EP1105454A1
Application number: EP99941530A
Authority: EP
Inventors: Menno Hazenkamp; Marie-Josée DUBS; Frank Bachmann; Gunther Schlingloff; Rachel Allemann; Josef Dannacher
Original assignee: Ciba Spezialitaetenchemie Holding AG; Ciba SC Holding AG
Current assignee: BASF Schweiz AG; Ciba SC Holding AG
Priority date: 1998-08-19
Filing date: 1999-08-06
Publication date: 2001-06-13
Also published as: AU5511099A; WO2000011129A1; NO20010766D0; KR20010072730A; NO20010766L; US20020058599A1; US6306808B1; JP2002523558A

Abstract

Manganese complexes of formula (1) or (2) are used as activators for peroxygenated compounds in dishwashing detergents, wherein Y represents linear or branched alkylene of formula -C(R1)2]m, wherein m is a whole number ranging from 2-8 and the radicals R1 represent independently from each other hydrogen or C1-C4-alkyl, -CX=CX-, whereby X is cyano, linear or branched C1-C8 -alkyl or di-(linear or branched C1-C8 alkyl)-amino; -(CH2)q-NR1-(CH2)q-, wherein R1 has the meaning thus cited and q is 1, 2, 3 or 4 or stands for a 1,2-cyclohexylene or 1,2 phenyl radical of formula (a) or (b), wherein R8 represents hydrogen, CH2OH, CH2NH2 or SO3M, wherein M represents hydrogen, an alkaline metal atom, ammonium or the cation of an organic amine, R?5 and R6¿ represent independently from each other hydrogen, linear or branched C¿1?-C4 -lkyl; linear or branched C1-C8alkene-R2, wherein R2 is OR1, COOR1 or NR3R4, unsubstituted aryl or aryl that is substituted by cyano, halogen, OR1, COOR1, nitro, linear or branched C1-C8-alkyl, NR3R4, wherein R3 and R4 mean independently from each other hydrogen or linear or branched C1-C12-alkyl; or substituted by -N?oR¿1R3R4, wherein R1, R3, R4 have the meanings thus cited, the radicals R7 represent independently from each other hydrogen or C1-C4 alkyl, Z1 and Z2 represent independently from each other hydrogen, hydroxy, C1-C4 alkoxy or di-(C1-C4-alkyl)amino and A stands for a charge-equalising anion ligand.

Description

MANGANE COMPLEXES AS CATALYSTS FOR PERCENTAGE COMPOUNDS FOR CLEANING HARD SURFACES, IN PARTICULAR DISHES

The present invention relates to the use of certain manganese complexes as catalysts for reactions with peroxygen compounds for bleaching colored stains on hard surfaces. Hard surface cleaners containing such catalysts are another subject of the invention.

Inorganic peroxygen compounds, especially 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 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 proposals have become known in the literature. These are primarily compounds from the substance 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, diketopamide and sulfuryl cyanuryl amides , in addition to carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as pentaacetyl glucose. 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 dishes, and are usually not always reached even in automatic dishwashing processes. In the past few years, application temperatures of below 60 ° C., in particular below 50 ° C., down to the cold water temperature have become increasingly important in the search for energy-saving methods for machine cleaning of dishes. At these low temperatures, the effect of the activator compounds known to date generally diminishes noticeably, particularly in the case of soiling which is difficult to bleach, such as, for example, tea residues on porcelain or glass. There has been no shortage of efforts to develop more effective activators for this temperature range without convincing success to date.

One starting point could be the use of transition metal salts and complexes as so-called bleaching catalysts. From DE-A-19529904 and WO 97/07191 cleaning agents for dishes are already known which contain transition metal complexes of the salen type as an activator for peroxygen compounds. However, even these are not yet able to meet all requirements.

It has now been found that, surprisingly, manganese complexes of the formulas below have a significantly improved bleach-catalyzing effect on colored soils which are found on hard surfaces. If these complexes are added in catalytic amounts to a dishwashing detergent which contains a peroxygen compound and optionally TAED (N, N, N ', N'-tetraacetylethylenediamine), tea stains on porcelain at 45 ° C. are largely removed in the dishwasher. This also applies when using hard water, where it is known that the removal of tea deposits is more difficult to achieve than in soft water.

The invention accordingly relates to the use of manganese complexes of the formula (1) or (2)

or wherein

Y is linear or branched alkylene of the formula - [C (R ₁ ) ₂ ] _m , where m is an integer from 2 to 8 and R is independently hydrogen or CrC ₄ alkyl, -CX = CX-, where X is cyano , linear or branched C 1 -C ₈ alkyl or di (linear or branched C 1 -C ₈ alkyl) l-amino; - (CH ₂ ) q-NR ₁ - (CH ₂ ) q-, wherein Ri has the meaning given and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene or 1,2-phenylene radical of the formula

wherein R _{8 is} hydrogen, CH ₂ OH, CH ₂ NH ₂ or SO ₃ M, where M is hydrogen, an alkali metal atom, ammonium or the cation of an organic amine,

R ₅ and R _{6 are} independently hydrogen, linear or branched CC ₄ alkyl; linear or branched C ₁ -C ₈ alkylene-R ₂ , in which R _{2 is} ORi, COORi or NR ₃ R ₄ , mean unsubstituted aryl or aryl which is substituted by cyano, halogen, ORi, COORi, nitro, linear or branched -C ₈ -alkyl, NR ₃ R ₄ , wherein R ₃ and R ₄ independently of one another are hydrogen or linear or branched CC ₂ -alkyl, or by -N ^® RιR ₃ R ₄ , wherein R _1t R ₃ and R _{4 are} the have the meanings given,

R ₇ independently of one another are hydrogen or -CC alkyl,

Zi and Z ₂ independently of one another are hydrogen, hydroxy, dC ₄ alkoxy or di (C ₁ -C ₄ alkyl) amino, and

A stands for a charge-balancing anion ligand, as catalysts for reactions with peroxygen compounds in cleaning solutions for hard surfaces, in particular for dishes, wherein not all of the substituents Z _1f Z ₂ , R ₅ and R ₆ in the compounds of the formula (1) may simultaneously be hydrogen if Y 1, 2-phenylene is.

The preferred compounds according to formula (1) include those in which 7. _\ and / or Z ₂ independently of one another denote hydrogen, hydroxyl, methoxy, ethoxy, dimethylamino or diethylamino.

The preferred compounds of the formulas (1) and (2) also include those in which Y is ethylene, 1,2- or 1,3-propylene, 1-methyl-1,2-propylene, 2-methyl-1,2 propylene, 1,2-cyclohexylene or 1,2-phenylene. Particularly preferred meanings of Y are ethylene, 1,3-propylene, 2-methyl-1,2-propylene, 1,2-cyclohexylene or 1,2-phenylene.

If Y is a 1,2-cyclohexylene radical, this can be present in any of its stereoisomeric cis / trans forms.

R ₅ and R ₆ independently of one another are preferably hydrogen, methyl, ethyl or unsubstituted phenyl, in particular hydrogen.

The alkyl residues with 1 to 4 carbon atoms include in particular the methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl and tert-butyl group.

Preferred meanings of ^ are methyl or especially hydrogen.

R ₇ preferably denotes hydrogen, methyl or ethyl, especially methyl.

R ₈ is preferably hydrogen.

The charge-balancing anion ligand A in the compounds of the formulas (1) and (2) can be mono- or polyvalent, in which case it can neutralize a number of manganese 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 (1) or (2) used according to the invention are known or can be prepared by processes known in principle by the reaction of salicylaldehyde, which optionally carries the substituents Z ₁ or Z ₂ defined above, or two fused rings as in the compounds of the formula (2), with diamines H ₂ NY-NH ₂ and reaction of the salen ligand thus obtainable with manganese salts, as described, for example, in European patent application EP-A-630964.

The compounds of the formula (1) or (2) can be used individually or in mixtures with two or more compounds of the formula (1) or (2). In addition, they can also be used together with one or more uncomplexed salen ligands, for example with those ligands which are contained in the compounds of the formula (1) or (2).

The invention further relates to detergents for hard surfaces, in particular detergents for dishes, and preferably those for use in machine cleaning processes which contain one of the compounds of the formula (1) or (2) described above as a bleaching catalyst, and a process for cleaning hard surfaces 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 peroxide-containing oxidizing agent and the bleaching catalyst according to formula (1) or (2) can react with one another with the aim of producing secondary products with a stronger oxidizing action receive. Such conditions exist particularly 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 method 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 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 selected 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 bleaching catalyst used also depends on the application. Depending on the desired degree of activation, 0.00001 mol to 0.025 mol, preferably 0.0001 mol to 0.02 mol, of activator are used per mol of peroxygen compound, but these limits can also be exceeded or fallen below in special cases.

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 according to formula (1) or (2) in addition to the usual ingredients compatible with the bleaching catalyst. The bleaching catalyst can be adsorbed on carriers in a manner known in principle and / or embedded in coating substances.

The cleaning agents according to the invention, which can be in the form of solids or suspensions in powder or tablet form, homogeneous solutions or suspensions, can, in addition to the bleaching catalyst used according to the invention, in principle contain all the known ingredients which are customary in such agents. The agents according to the invention can contain, in particular, 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 as well as colorants and fragrances.

A cleaning agent according to the invention for hard surfaces can also contain abrasive components, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and micro-glass balls, and mixtures thereof. 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 machine 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, 3% by weight to 25% by weight, in particular 5% by weight to 15% by weight, oxygen-based bleaching agent, in each case based on the total agent comprising a bleaching catalyst according to formula (1) or (2), in particular in amounts of 0.005% by weight to 0.1% by weight.

In principle, all builders commonly used in machine dishwashing detergents, for example polymeric alkali metal phosphates, which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts, are suitable as water-soluble builder components, in particular in such low-alkaline cleaning agents. Examples include tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, sodium tripolyphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts and mixtures of sodium and potassium salts. Their amounts can range up to about 35% by weight, based on the total agent. 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.

For example, polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids are suitable. 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- and di-hydroxy succinic acid, α-hydroxypropionic acid and gluconic acid. In addition, the salts of citric acid, in particular sodium citrate, are suitable as builder components. Anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable as sodium citrate. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder. Depending on the ultimately in the The pH adjusted to the mean can also be the acids corresponding to the co-builder salts mentioned.

Suitable bleaches based on oxygen are primarily alkali perborate or tetrahydrate and / or alkali percarbonate, with sodium being the preferred alkali metal. The use of sodium percarbonate has advantages in particular in cleaning agents for dishes, since it has a particularly favorable effect on the corrosion behavior on glasses. 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, and magnesium salts such as magnesium sulfate may also be useful.

In addition to the bleaching catalysts according to formula (1) or (2), other transition metal salts or complexes known as bleach-activating active substances and / or conventional bleach activators, that is to say compounds which contain perbenzoic and / or peroxocarboxylic acids which are optionally substituted under perhydrolysis conditions, with 1 to 10 C atoms, especially 2 to 4 carbon atoms, can be 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. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N, N-diacetyl-N, N-dimethylurea (DDU), acylated triazine derivatives, in particular 1, 5-diacetyl-2, 4-dioxohexahydro-1, 3,5-triazine (DADHT), acylated phenyl sulfonates, especially nonanoyloxy- or isononanoyloxybenzenesulfonate, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol acylated sugar derivatives, in particular pentaacetylgiucose (PAG), sucrose polyacetate (SUPA), 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-A-4443 177 can also be used.

The low-alkaline machine dishware according to the invention preferably contains cleaning agents the usual alkali carriers such as alkali silicates, alkaicarbonates and / or alkali hydrogen carbonates. The alkali carriers commonly used include carbonates, hydrogen carbonates and alkali silicates with a SiO ₂ / M ₂ O (M = alkali atom) molar ratio of 1.5: 1 to 2.5: 1. Alkali silicates can be used 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 avoided 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, which is contained in an amount of up to 60% by weight, preferably 10% by weight to 40% by weight. Depending on which pH value is ultimately desired, the ratio of carbonate to bicarbonate used varies, but an excess of sodium bicarbonate is usually used, so that the weight ratio between bicarbonate 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 builder, in particular alkali citrate, 5% by weight to 15% by weight alkali carbonate and 20% by weight to 40% by weight alkali silicate are contained.

If appropriate, surfactants, in particular low-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 for use in machine dishwashing processes. These preferably include C ₁₂ -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 Glycol-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 ethers and the foaming but ecologically attractive C ₈ -C ₁₄ -alkyl polyglucosides with a degree of polymerization of about 1 to 4 and / or C ₁₂ -Cι ₄ - 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 consists of a fatty alcohol with the C chain length C ₆ -C ₁₄ . It is partially advantageous if the surfactants described are used as mixtures, for example the combination of alkyl polyglycoside with fatty alcohol ethoxylates or glucamide with alkyl polyglycosides.

Although manganese complexes are known to counteract the corrosion of silver, the compounds of the formula (1) or (2) are generally used in amounts which are too low to provide protection against silver corrosion, so that silver corrosion inhibitors are additionally present in dishwashing detergents according to the invention can be used, the effect of which can be enhanced by the compounds of the formula (1) or (2). 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 are in one of the oxidation states II , III, IV, V or VI are present.

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®, Opticiean®, 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 enzymes which may be used, as described, for example, in international patent applications WO 92/11347 or WO 94/23005, can be adsorbed on carriers and / or embedded in coating substances in order 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 1.2% by weight.

If the cleaning agents foam too much during use, they can contain up to 6% by weight, preferably about 0.5% to 4% by weight, of a foam-suppressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica , Paraffin, paraffin-alcohol combinations, hydrophobized silica, the bis fatty 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 with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms , in particular ethylene glycol and propylene glycol, as well as their mixtures and the ethers derivable 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 contain mineral acids, especially sulfuric acid, or alkali hydrogen sulfates, or bases, especially ammonium or alkali hydroxides. Such pH regulators are preferably not contained in the agents according to the invention in excess of 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, 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. To produce 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 pressed. In this way, unbreakable tablets are obtained which, under operating conditions, dissolve sufficiently quickly and have a flexural strength of normally more than 150 N. 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 / l in a first process step by adding the builder components with at least a portion of liquid mixture components Increasing the bulk density of this premix is mixed and subsequently - 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 / l, preferably 2 to 5 g / l.

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 the agents according to the invention, completely clean and hygienically perfect dishes are obtained. Examples:

The following substances have been tested:

Substance Y Zi z ₂

(101) 1,2-Cyclohexylene -N (C ₂ H ₅ ) ₂ -N (C ₂ H ₅ ) ₂

(102) 1, 2-Ethylene -N (C ₂ H ₅ ) ₂ -N (C ₂ H ₅ ) ₂

(103) 1,2-Ethylene -OH -OH

(104) 1, 2-Ethylene -N (CH ₃ ) ₂ -N (CH ₃ ) ₂

(105) 1,2-ethylene -H -H

(106) 1,2-ethylene -OCH ₃ -OCH ₃

(107) 1,3-propylene -N (C ₂ H ₅ ) ₂ -N (C ₂ H ₅ ) ₂

(108) 2-methyl-1,2-propylene -N (C ₂ H ₅ ) ₂ -OCH3

(109) 2-methyl-1,2-propylene -N (C ₂ H ₅ ) ₂ -H

(110) 1,2-phenylene OH OH

The connections (108) and (109) have the following structure:

The following substances were also tested:

Substance R ₇

(111) 1,2-cyclohexylene CH ₃

(112) 1,2-ethylene CH ₃

Example 1: Soiling procedure: A tea infusion (12 g tea leaves / liter) is made from black tea (Twinings brand) and hard water (total hardness: 18 ° dH) with stirring at 99 ° C. Allow to infuse for five minutes and filter the tea. Then about 100 ml of tea are poured into a porcelain cup. The tea is left in the cups for 30 minutes. The cups are then emptied in three steps of approx. 35 ml. There is a waiting period of five minutes between the emptying steps. The completely empty cups are dried at 70 ° C for 60 minutes. Reiniαunαsprozedere: The cups were cleaned in a Miele G-690 D dishwasher with the Fθin program at 45 ° C using hard water. In each cleaning program, 12 cups soiled with tea were cleaned. There were also six glasses with milk soiling, 24 clean plates and 60 g of a mixture of different foods (including spinach, eggs, minced meat, starch) in the machine. The dosage of the dishwashing detergent was: 17.2 g of a basic formulation containing phosphate, 1.72 g of sodium perborate monohydrate, 0.8 g of TAED and possibly 50 ppm of catalyst (ppm based on the metal). After cleaning, the removal of the tea topping was assessed visually on a scale from 0 (= unchanged very thick deposit) to 10 (= no deposit). Table 1 compares the scores for our catalysts with a reference (TAED only, no catalyst). The notes given in the table are the median values from several cleaning programs with 12 cups each. The table shows that the marks for the catalysts used according to the invention are significantly better than the reference value.

Table 1. Sheet removal marks

Similar results can be achieved if you put the dishwasher in the middle! following composition together with 50 ppm of the catalysts used in the table above, 1.72 g of sodium perborate monohydrate and 0.8 g of TAED.

Ingredient% by weight

Sodium tripolyphosphate 30

Sodium carbonate 25

Hydrated 2.0r silicate 18.5

Nonionic surfactant 2.5

Polymer (60% acrylic acid, 20% maleic acid, 20% ethyl acrylate) 5

Protease (4% active) 1

Amylase (0.8% active) 0.5

Water, sodium sulfate, etc. rest up to 100%

Example 2:

10.1 mg (30 μmol) of morin dihydrate was dissolved in 1000 ml of a borax buffer solution (9 mmol disodium tetraborate / liter, pH = 9.4). At t = 0 min. 295 mg (2.5 mmol) sodium perborate monohydrate and, depending on the, 3.4 μmol catalyst or 137 mg (0.6 mmol) TAED added. The extinction E of the solution at 400 nm was measured every minute at 27 ° C. over a period of 30 minutes. Table 2 shows the values for the percent decolorization D (t), calculated according to D (t) = [E (0) -E (t)] / E (0) ^* 100.

It can be seen that the bleaching action in solution for compounds (101) to (104) is better than that of TAED, although the concentration of TAED was much higher. You can also see that after 30 minutes a better decolorization is achieved than with the compound M2.

EXAMPLE 3 The procedure is as described in Example 1, but an equivalent amount of the compound of the formula is used as the catalyst

this also gives a good cleaning effect. Example 4: The procedure is as described in Example 1 of EP-A-630964, but instead of salicylaldehyde, an equivalent amount of the 1: 1 mixture of salicylaldehyde and 2-hydroxy-4-diethylamino-benzaldehyde and instead of ethylenediamine, an equivalent amount of 2-amino-2-methyl-3-aminopropane. The manganese complex is then formed as described there, and a mixture of the following 4 manganese complexes is obtained:

If the procedure described in Example 1 is followed, but an equivalent amount of this mixture is used as the catalyst, a good cleaning action is also obtained.

Example 5: Another good cleaning effect is achieved if, instead of the mixture from Example 4, one is used which contains only the last two of the complexes listed. This mixture is accessible by purifying the mixture of the uncomplexed ligands from the first stage of the preparation according to Example 4.

Claims

claims

1. Use of manganese complexes of the formula (1) or (2)

or

wonn

Y is linear or branched alkylene of the formula - [C (R ₁ ) ₂ ] _m , where m is an integer from 2 to 8 and R _{1 is} independently hydrogen or dC ₄ alkyl, -CX = CX-, where X is cyano , linear or branched dC _β -alkyl or di- (linear or branched Cι-C _β -alkyl) -amino; - (CH ₂ ) _q -NRr (CH ₂ ) _q -, in which R ^ has the meaning given and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene or 1,2-phenylene radical of the formula

in which Ffe is hydrogen, CH ₂ OH, CH ₂ NH ₂ or SO ₃ M, where M is hydrogen, an alkali metal atom, ammonium or the cation of an organic amine, R ₅ and R _{β are} independently hydrogen, linear or branched C 1 -C 4 alkyl; linear or branched C ₁ -C ₈ -alkylene-R ₂₎ where R _{2 is} OR _{1 (} COOR _! or NR ₃ R ₄ , mean unsubstituted aryl or aryl which is substituted by cyano, halogen, ORi, COORi, nitro, linear or branched Ci-Cβ-alkyl, NR ₃ R ₄ , wherein R ₃ and R independently of one another are hydrogen or linear or branched CrCι ₂ alkyl; or by -N ^Θ RιR ₃ R ₄ , wherein R 1, R ₃ and R _{4 are} the have the meanings given,

R ₇ independently of one another are hydrogen or -CC ₄ alkyl,

Z and Z ₂ independently of one another are hydrogen, hydroxy, C 1 -C ₄ alkoxy or di (C 1 -C ₄ alkyl) amino, and

A stands for a charge-balancing anion ligand, as catalysts for reactions with peroxygen compounds in cleaning solutions for hard surfaces, not all of the substituents ZZ ₂ in the compounds of the formula (1),

R ₅ and R _{6 may} simultaneously be hydrogen if Y is 1,2-phenylene.

2. Use of complexes of the formula (1) or (2) as catalysts for reactions with peroxygen compounds in cleaning solutions for dishes.

3. Use according to claim 1 or 2, characterized in that in the formula (1) Z _t and Z ₂ independently of one another are hydrogen, hydroxyl, methoxy, ethoxy, dimethylamino or diethylamino.

4. Use according to one of claims 1 to 3, characterized in that in the formula (1) and (2) Y ethylene, 1,2- or 1,3-propylene, 1-methyl-1,2-propylene, 2nd -Methyl-1, 2-propylene, 1, 2-cyclohexylene or 1,2-phenylene.

5. Use according to claim 4, characterized in that Y is ethylene, 1, 3-propylene, 2-methyl-1,2-propylene, 1, 2-cyclohexylene or 1, 2-phenylene.

6. Use according to one of claims 1 to 5, characterized in that in the formula (1) and (2) R ₅ and R ₆ independently of one another are hydrogen, methyl, ethyl or unsubstituted phenyl, in particular hydrogen.

7. Use according to claim 1, characterized in that in the formula (2) R ₇ independently of one another is hydrogen, methyl or ethyl, in particular methyl.

8. Use according to one of claims 1 to 7, characterized in that the charge-balancing anion ligand A in the compounds of formula (1) or (2) is halide, hydroxide, hexafluorophosphate, perchlorate or the anion of an organic carboxylic acid.

9. Use according to one of claims 1 to 8, 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.

10. Use according to one of claims 1 to 9, characterized in that additionally a conventional bleach activator, in particular TAED, is used.

11. A method for cleaning hard surfaces, especially dishes, using a compound of formula (1) or (2).

12. 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 according to formula (1) or (2) Contains usual ingredients compatible with the bleaching catalyst.

13. Cleaning agent according to claim 12, characterized in that it additionally contains TAED.

14. Low-alkaline agent for machine cleaning of dishes whose 1% by weight solution 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, 3% by weight to 25% by weight, in particular 5% by weight to 15% by weight, oxygen-based bleaching agent, in each case based on the total agent, characterized in that it is a bleaching catalyst according to formula (1) or (2), in particular in amounts from 0.005% by weight to 0.1% by weight.

15. Agent according to one of claims 12 to 14, characterized in that it contains alkali perborate monohydrate, alkali perborate tetrahydrate, alkali percarbonate and / or as bleaching agent Peroxycarboxylic acid contains.