Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3932—Inorganic compounds or complexes

Definitions

• the present invention relates to the use of bleach-activating transition metal complex compounds, which are enclosed in cage connections to reinforce the Bleaching effect of inorganic peroxy compounds in particular during bleaching of colored soiling on textiles and hard surfaces, and washing, Disinfectant and cleaning agent for hard surfaces in cage connections included bleach-activating transition metal complexes.
• 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.
• the oxidation effect of the inorganic peroxygen compounds can be improved by the addition of so-called bleach activators, for which numerous suggestions, especially 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, Hydrotriazine, urazoles, diketopiperazines, sulfuryl amides and cyanurates, also carboxylic anhydrides, especially phthalic anhydride, Carbonklareester, especially sodium nonanoyloxybenzenesulfonate, sodium isononanoyloxybenzenesulfonate and acylated sugar derivatives, such as pentaacetylglucose, are known in the literature.
• the bleach activators for which numerous suggestions
• the present invention also has the improvement of the oxidation and bleaching effect of inorganic Peroxygen compounds at low temperatures below 80 ° C, especially in the temperature range of approx. 15 ° C to 55 ° C.
• transition metal complexes are enclosed in the cavities of cage connections a significant contribution to cleaning performance compared to colored ones Soiling can do.
• Objects of the invention are the use of in cavities of cage connections included bleach-activating transition metal complexes that do not contain Mn (II) bipyridyl complexes are, as activators for in particular inorganic peroxygen compounds, preferably selected from the group comprising organic peracids, hydrogen peroxide and hydrogen peroxide-providing substances such as percarbamide, perborate and Percarbonate and mixtures thereof, in oxidation, washing, cleaning or disinfection solutions, and their use for bleaching paint stains when washing Textiles.
• inorganic peroxygen compounds preferably selected from the group comprising organic peracids, hydrogen peroxide and hydrogen peroxide-providing substances such as percarbamide, perborate and Percarbonate and mixtures thereof, in oxidation, washing, cleaning or disinfection solutions, and their use for bleaching paint stains when washing Textiles.
• Another object of the invention is the use of in cavities of cage connections included bleach-activating transition metal complexes, which none Mn (II) bipyridyl complexes are used to bleach color stains when cleaning hard surfaces or for disinfection.
• the selection of the suitable cage connection depends on the size of the transition metal complex to be included. It is it is essential that both the Transition metal ion as well as the ligands necessary for complex formation in the Cavity of the cage connection must be able to reach the forming bleach-enhancing complex but must no longer fit through the opening of the cavity, to ensure stable inclusion of the complex.
• Zeolite Y Cavities with a diameter of approx. 1.3 nm, the openings of which have a diameter of 0.74 nm.
• Stable inclusion should be understood to mean that under Conditions of use, that is in the washing, cleaning, rinsing or Disinfectant liquor, no amounts of free complex influencing bleaching catalysis are detectable.
• the formed within the cavities of cage connections and then enclosed transition metal complexes are much more stable and thus over effective for a longer period than the same transition metal complexes that affect the Surface of carrier materials have been applied, even if these are Carrier materials are corresponding cage connections.
• Transition metal complexes suitable according to the invention are preferably selected from the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes and mixtures thereof.
• Suitable ligands in the transition metal complexes which can be used according to the invention are customary substances of both inorganic and organic nature.
• the organic ligands in such complexes include, in addition to carboxylates, in particular compounds with primary, secondary and / or tertiary amine and / or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, triazole, 2,2'-bispyridylamine , Tris (2-pyridylmethyl) amine, 1,4,7-triazacyclononane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-trimethyl-1,5,9-triazacyclododecane, (Bis - ((1-methylimidazol-2-yl) methyl)) - (2-pyridylmethyl) amine, N, N '- (bis (1-methylimidazol-2-yl) methyl) ethylenediamine, N - bis (2-benzimidazolylmethyl) aminoethanol, 2,6-bis (bis-
• the inorganic neutral ligands include, in particular, ammonia and water.
• the central atom is normally present with the coordination number 6, the presence of at least 1 ammonia ligand is preferred.
• a complex to be used in the enclosed form according to the invention contains further, preferably anionic and among these in particular mono- or bidentate ligands.
• these include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO 2 ) - group.
• a (NO 2 ) - group is understood to mean a nitro ligand which is bonded to the transition metal via the nitrogen atom or a nitrito ligand which is bonded to the transition metal via an oxygen atom.
• the (NO 2 ) - group can also be chelated to a transition metal or it can bridge two transition metal atoms asymmetrically or ⁇ 1 -O-.
• the transition metal complexes to be used in the activator system according to the invention can also carry further ligands, generally of a simpler structure, in particular mono- or polyvalent anion ligands.
• nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, perchlorate and complex anions such as hexafluorophosphate are suitable.
• the anion ligands are intended to balance the charge between the transition metal central atom and the ligand system.
• the presence of oxo ligands, peroxo ligands and imino ligands is also possible.
• Such ligands in particular can also act as bridges, so that multinuclear complexes are formed. In the case of bridged dinuclear complexes, both metal atoms in the complex do not have to be the same.
• the use of dinuclear complexes in which the two transition metal central atoms have different oxidation numbers is also possible.
• anion ligands are missing or the presence of anion ligands is not used to balance the charge in the complex can in the form according to the invention in enclosed form using transition metal complex compounds present anionic counterions that neutralize the cationic transition metal complex.
• anionic Counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, Perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, Acetate, benzoate or citrate.
• the charge balance can also at least partially through the cage connection if it is able to make cationic connections to include. To such cage connections, which in the present context Zeolites belong in particular to the role of anionic counterions.
• transition metal complex compounds to be used according to the invention in enclosed form are Mn (IV) 2 ( ⁇ -O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) -, Mn (IV) 4 ( ⁇ -O) 6 (1,4,7-trimethyl-1,4,7-triazacyclononane) -, [N, N'-bis [(2-hydroxy-5-vinylphenyl) methylene] -1,2-diaminocyclohexane] -manganese (III) -, [N, N'-bis [(2-hydroxy-5-nitrophenyl) -methylene] -1,2-diaminocyclohexane] -manganese (III) -, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-phenylenediamine] manganese (III) -, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-phen
• Mn (IV) 4 ( ⁇ -O) 6 (1,4,7-trimethyl-1,4,7-triazacyclononane) complex and / or Mn (IV) 2 ( ⁇ ) enclosed in zeolite Y is particularly preferred -O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) complex which, for example, as in the publication by DEDeVos, JL Meinertshagen and T. Bein in Angewandte Chem. Volume 108 (1996), Pages 2355 to 2357 specified is available.
• the transition metal complexes enclosed in cavities of cage connections become preferably for bleaching color stains when washing textiles, used in particular in an aqueous, surfactant-containing liquor.
• bleaching of Color soiling is to be understood in its broadest meaning and includes both the bleaching of dirt on the textile, the bleaching of in the Wash liquor, dirt detached from the textile as well as oxidative destruction of textile dyes in the wash liquor, which are under the washing conditions detach from textiles before they can be drawn onto textiles of a different color.
• Another preferred application form according to the invention is the use of the in Cavities of caged compounds enclosed transition metal complexes that have no Mn (II) bipyridyl complexes are, for example, in cleaning solutions for hard surfaces for dishes, for bleaching colored stains.
• bleaching means both the bleaching of what is on the hard surface Dirt, in particular tea, as well as the bleaching of Dirt detached from the hard surface understood.
• the invention further relates to a method for cleaning hard surfaces, in particular of dishes using enclosed in cavities of cage connections
• Transition metal complexes which are not Mn (II) bipyridyl complexes
• aqueous optionally further detergent components, in particular oxidizing agents Peroxygen based, containing solution, as well as washing, disinfecting and cleaning agents for hard surfaces, especially detergents for dishes and preferably among them those for use in mechanical cleaning processes that are in cavities of Cage compounds contain enclosed transition metal complexes, which none Mn (II) bipyridyl complexes are.
• the use according to the invention consists essentially in the presence of a colored stains to create contaminated surface conditions under which a peroxidic oxidant and those trapped in cavities of cage joints Transition metal complexes can react with each other, with the aim of being stronger to obtain oxidizing secondary products. Such conditions are in particular then when the reactants meet in aqueous solution. This can be done by separate addition of the peroxygen compound and in the cavities of cage connections included transition metal complex to a possibly containing detergent Solution happen.
• the method according to the invention is particularly advantageous however using a cleaning agent according to the invention for hard surfaces, the transition metal complex enclosed in cavities of cage connections and optionally contains an oxidizing agent containing peroxy.
• the peroxygen compound can also be separately, in bulk or as a preferably aqueous solution or Suspension, added to the solution if a peroxide-free detergent 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 are generally chosen so that between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm active oxygen, are present in the solutions.
• the amount of bleach-enhancing transition metal complex enclosed in the cavities of cage connections also depends on the intended use. Depending on the desired degree of activation, it is used in amounts such that 10 -5 mol to 2.5 ⁇ 10 -2 mol, preferably 10 -4 mol to 2, 10 -2 mol, of transition metal are used per mol of peroxygen compound, but in particular If these limits are exceeded or fallen short of.
• 0.0001% by weight is preferably up to 10 wt .-%, in particular 0.01 wt .-% to 0.5 wt .-% in cavities of cage connections included bleach-activating transition metal complexes, wherein this weight information here and unless otherwise stated is the total from cage compound and complex enclosed therein.
• the invention Agents which are in the form of granules, powdered or tablet-shaped solids, other shaped articles, homogeneous solutions or suspensions can be present in addition to the above included transition metal complex in principle all known and in such Contain common ingredients.
• the agents according to the invention can in particular Builder substances, surfactants, peroxygen compounds, water-miscible organic solvents, sequestering agents, electrolytes, pH regulators and others Auxiliaries, such as silver corrosion inhibitors, foam regulators, additional peroxygen activators as well as dyes and fragrances.
• a cleaning agent for hard surfaces according to the invention can also be abrasive active components, in particular from the group comprising quartz flours, wood flours, Plastic flours, chalks and micro glass balls and their mixtures.
• Abrasives are preferably not more than 20% by weight in the cleaning agents according to the invention, in particular from 5% by weight to 15% by weight.
• Another object of the invention is a means for machine cleaning of dishes, containing 15 wt .-% to 65 wt .-%, in particular 20 wt .-% to 60 wt .-% water-soluble Builder component, 5% by weight to 25% by weight, in particular 8% by weight to 17% by weight Oxygen-based bleach, based in each case on the total agent, which is 0.01% by weight up to 10% by weight of bleach activators enclosed in cavities of cage connections Contains transition metal complex.
• a medium is particularly low alkaline, that his 1% by weight solution has a pH of 8 to 11.5, preferably 9 to 11 on.
• alkali phosphates in the form of their alkaline, neutral or acidic sodium or potassium salts.
• examples for this 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.
• Your quantities can range of up to about 60% by weight, in particular 5% by weight to 20% by weight, based on the total Means.
• water-soluble builder components are polyphosphonates and phosphonate alkyl carboxylates for example native or organic polymers synthetic origin of the type of polycarboxylates, particularly in hard water regions act as a co-builder.
• examples include polyacrylic acids and copolymers from maleic anhydride and acrylic acid as well as the sodium salts of these polymer acids.
• Commercial products are, for example, Sokalan® CP 5, CP 10 and PA 30 from the company BASF.
• Polymers of native origin that can be used as co-builders include, for example oxidized starch, such as from the international patent application WO 94/05762 known, and polyamino acids such as polyglutamic acid or Polyaspartic acid.
• the preferred builder components include the salts citric acid, especially sodium citrate.
• Anhydrous trisodium citrate is used as sodium citrate and preferably trisodium citrate dihydrate.
• Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
• the enzymes contained in agents according to the invention include proteases, amylases, Pullulanases, cutinases and / or lipases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®.
• proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®
• amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramy
• the used Enzymes can, as for example in international patent applications WO 92/11347 or WO 94/23005 described, adsorbed on carriers and / or in coating substances embedded to protect them against premature inactivation. They are in the cleaning agents according to the invention preferably in amounts of up to 10% by weight, in particular from 0.05% by weight to 5% by weight, with particular preference against oxidative degradation stabilized enzymes, such as those from the international Patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350, known, can be used.
• Transition metal complex can be conventional transition metal complexes known as bleach activators in non-enclosed form and / or conventional bleach activators, that is, compounds that may be under perhydrolysis conditions substituted perbenzoic acid and / or peroxocarboxylic acids with 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms are used.
• bleach activators in non-enclosed form
• bleach activators compounds that may be under perhydrolysis conditions substituted perbenzoic acid and / or peroxocarboxylic acids with 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms are used.
• the usual ones cited at the beginning are suitable Bleach activators, the O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
• Multi-acylated alkylenediamines are preferred, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenyl sulfonates, especially nonanoyl or Isononanoyloxybenzenesulfonate, acylated polyhydric alcohols, especially triacetin, Ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and Mannitol, and acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, Tetraacetylxylose
• the weight ratio of peroxocarboxylic acid under perhydrolysis conditions Cleaving compound to transition metal complex (without cage connection) is preferably in the range of 1 000 000: 1 to 1: 1, being in hard detergents Surfaces preferably in the range from 8,000: 1 to 1: 1, in particular from 1,000: 1 to 10: 1 and in detergents for use in textile washing, preferably in the range of 1,000,000: 1 to 500: 1, in particular from 500,000: 1 to 1,000: 1.
• oxygen-based bleaching agents are also used primarily alkali perborate or tetrahydrate and / or alkali percarbonate into consideration, with sodium being the preferred alkali metal.
• the use of sodium percarbonate has particular advantages in detergents for dishes, as it is special has a positive effect on the corrosion behavior of glasses.
• the oxygen-based bleach is therefore preferably an alkali percarbonate, especially sodium percarbonate.
• known peroxycarboxylic acids for example Dodecanediperic acid or phthalimidopercarboxylic acids, which are optionally substituted on aromatics can be included.
• Bleach stabilizers such as phosphonates, borates, respectively Metaborates and metasilicates as well as magnesium salts such as magnesium sulfate are useful be.
• Machine dishwashing detergents according to the invention preferably contain the customary alkali carriers such as, for example, alkali silicates, alkali carbonates and / or alkali hydrogen carbonates.
• Alkali silicates can be used in amounts of up to 40% by weight, in particular 3% by weight to 30% by weight, based on the total composition, can be present.
• 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 are contained in an amount of up to 50% by weight, preferably 5% by weight to 40% by weight can.
• agents according to the invention 20% by weight to 60% by weight water-soluble organic builder, in particular alkali citrate, 3% by weight to 20% by weight Contain alkali carbonate and 3 wt .-% to 40 wt .-% alkali disilicate.
• surfactants in particular anionic surfactants, zwitterionic surfactants and preferably 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 preparation of the cleaning agents.
• Their amount can be up to 20% by weight, in particular up to 10% by weight, and is preferably in the range from 0.5% by weight to 5% by weight.
• Extremely low-foaming compounds are usually used in particular in cleaning agents for use in automatic dishwashing processes.
• C 12 -C 18 alkyl polyethylene glycol polypropylene glycol ethers each containing up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
• you can also use other known low-foaming nonionic surfactants such as C 12 -C 18 alkyl polyethylene 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 (e.g.
• surfactants from the family of glucamides such as, for example, alkyl-N-methyl-glucamides, in which the alkyl part preferably originates from 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. The presence of amine oxides, betaines and ethoxylated alkylamines is also possible.
• silver corrosion inhibitors can be used for dishes.
• Preferred silver corrosion inhibitor are organic sulfides such as cystine and cysteine, divalent or trivalent Phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, Manganese, titanium, zirconium, hafnium, vanadium or cerium salts and / or complexes, in which the metals mentioned, depending on the metal, in one of the oxidation states II, III, IV, V or VI are present.
• the cleaning agents for example in the presence of anionic surfactants, at the Application foam too much, they can still up to 6 wt .-%, preferably about 0.5 wt .-% to 4 wt .-% 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 bis fatty acid amides, and other other known commercially available defoamers can be added.
• 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 bis fatty acid amides, and other other known commercially available defoamers can be added.
• a foam suppressing compound preferably from the Group of silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffins, Paraffin-alcohol combinations, hydropho
• Organic solvents that can be used include alcohols with 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 aforementioned classes of derivable ether.
• Such water miscible Solvents are preferably not present in the cleaning agents according to the invention 20% by weight, in particular from 1% by weight to 15% by weight, is present.
• the agents according to the invention can be system and environmentally compatible Acids, especially citric acid, acetic acid, tartaric acid, malic acid, lactic acid, Glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali hydroxides.
• Acids especially citric acid, acetic acid, tartaric acid, malic acid, lactic acid, Glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali hydroxides.
• pH regulators are in the invention Averages preferably not more than 10% by weight, in particular of 0.5% by weight up to 6% by weight.
• agents for machine cleaning according to the invention of dishes contain 50% by weight to 60% by weight sodium phosphate, 15% by weight up to 25% by weight of sodium carbonate or its mixture with polymeric polycarboxylate, 5% to 15% by weight sodium perborate or percarbonate, 0.5% to 5% by weight below Perhydrolysis conditions peroxocarboxylic acid-releasing bleach activator, 0.5% by weight 7.5% by weight of surfactant, 2% by weight to 10% by weight of sodium silicate and 0.1% by weight to 0.75% by weight Silver corrosion inhibitor, especially benzotriazole.
• Cleaning agents according to the invention in the form of aqueous or other customary solvents containing solutions become particularly advantageous by simply mixing the ingredients, which can be put into an automatic mixer in bulk or as a solution, produced.
• the agents according to the invention are preferably in powder, granular or tablet form Preparations prepared in a manner known per se, for example by mixing, granulating, Roll compacting and / or spray drying the thermally resilient ones Components and admixing of the more sensitive components, to which in particular enzymes, Bleach and the bleaching catalyst can be expected to be produced.
• Preparations prepared in a manner known per se for example by mixing, granulating, Roll compacting and / or spray drying the thermally resilient ones Components and admixing of the more sensitive components, to which in particular enzymes, Bleach and the bleaching catalyst can be expected to be produced.
• 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 compression pressures in the range from 200 ⁇ 10 5 Pa to 1 500 ⁇ 10 5 Pa pressed.
• conventional tablet presses for example eccentric presses or rotary presses
• compression pressures in the range from 200 ⁇ 10 5 Pa to 1 500 ⁇ 10 5 Pa pressed.
• unbreakable tablets are obtained which, under application conditions, dissolve sufficiently quickly, with bending strengths of normally over 150 N.
• a tablet manufactured in this way 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 in the form of non-dusting, free-flowing, storage-stable Powders and / or granules with high bulk densities in the range from 800 to 1000 g / l can also be done, for example, in that the Builder components with at least a portion of liquid mixture components below Increase the bulk density of this premix and then mix - if desired after an intermediate drying - the other components of the agent, including the Bleaching catalyst, combined with the premix thus obtained.
• Agents for cleaning dishes according to the invention can be used both in household dishwashers as used in commercial dishwashers. The addition takes place by hand or by means of suitable dosing devices.
• the application concentrations in the cleaning liquor is generally about 1 to 8 g / l, preferably 2 to 5 g / l.
• a machine wash program is generally followed by some on the cleaning cycle following intermediate rinse cycles with clear water and a rinse cycle with a common one Rinse aid added and finished. After drying you get the Use of agents according to the invention a completely clean and flawless in terms of hygiene Dishes.
• the Mn (IV) 2 ( ⁇ -O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) complex enclosed in zeolite Y was tested in the sense of the invention ( E1 ) and its mixture with N, N, N ', N'-tetraacetylethylenediamine (TAED) ( E2 , TAED concentration 3% by weight).
• the conventional bleach activator N, N, N ', N'-tetraacetylethylenediamine (TAED) was also tested under otherwise identical conditions, but in a concentration of 6% by weight ( V1 ). Percentage decolorization over time substance 5 minutes 15 minutes 30 minutes E1 55 85 88 E2 92 94 95 V1 23 66 84
• a cleaning agent ( V2 ) for the automatic 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.
• the active ingredient according to the invention has a significantly better bleaching effect can be achieved than with the conventional bleach activator TAED alone. in the essentially the same results were obtained when the sodium perborate was obtained Sodium percarbonate replaced.

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• 1997
  • 1997-03-13 DE DE1997110370 patent/DE19710370A1/de not_active Withdrawn
• 1998
  • 1998-03-04 EP EP98103783A patent/EP0864641A1/fr not_active Withdrawn

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