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
  • C11D3/16—Organic compounds
  • C11D3/168—Organometallic compounds or orgometallic complexes
• • 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

• a dendritic polyamine and its cobalt complex are described in Chem. Ber. 1993, Pp. 2133-2135.
• DE-A-196 21 510 describes dendrimers with planarchiral or axial-chiral end groups.
• transition metal complexes with dendrimers of Polyalkylenimine type the bleaching effect of the peroxygen compounds during bleaching of colored stains both on textiles and on hard surfaces improve without destroying colors and fibers. It was also found that the use of dendrimers that are not complex with transition metals are bound in washing and cleaning agents, the oxidation and Increase the bleaching power of the agents in aqueous solution.
• the invention furthermore relates to detergents and cleaning agents containing Complexes of the compounds defined above with cobalt, manganese, iron, Ruthenium, vanadium, molybdenum or tungsten. Manganese complexes are preferred.
• These compounds and the corresponding metal complexes are suitable as Bleaching and oxidation catalysts for peroxygen compounds, especially in detergents and cleaning agents containing such peroxygen compounds, for example heavy duty detergents or machine dishwashing detergents.
• This Catalysts improve the oxidation and bleaching effects of the inorganic Peroxygen compounds at temperatures below 80 ° C, especially in Temperature range from 15 to 45 ° C while reducing the color and Textile fiber damage.
• the connections defined above and their metal complexes are also used in paper bleaching.
• the production of the poly-salen dendrimers of the formula I was carried out using a method described in the specialist literature (R. Moors, F. Vögtle, Chem. Ber. 1993, 126, 2133-2135).
• the initiator core here is ethylenediamine, which is reacted with acrylonitrile by a Michael addition.
• the terminal nitrile groups are reduced to the amine, which enables a further addition of acrylonitrile. Repeating this synthesis frequency doubles the number of functionalities.
• the amino groups can be reacted with salicylaldehyde, whereby compounds of formula I with group A are obtained. Reaction of the amino groups with a derivative of ⁇ , ⁇ -diamino-propionic acid and subsequent reaction with salicylaldehyde gives the compounds of the formula I which contain groups of the formula -COCHNA-CH 2 NA.
• the products are produced as yellow solids or oils.
• the complexation with metal cations can be done in three different ways.
• the ligand is prepared as described by Moors and Vögtle.
• the reaction with the metal cation for example to give the dendritic complex, is then carried out in a suitable solvent, for example chloroform, methylene chloride, ethanol, methanol, dimethylformamide, water, dimethyl sulfoxide or mixtures thereof.
• salicylaldehyde, dendritic polyamine and metal salt in a suitable solvent, for example chloroform, methylene chloride, ethanol, methanol, dimethylformamide, water, dimethyl sulfoxide or mixtures thereof, are combined in a one-pot reaction, thereby forming the catalysts according to the invention.
• the metal-free poly-salen dendrimer can be used.
• the dendrimer absorbs the metal cations in the water during use and acts as a catalyst.
• the metal-free poly-salen dendrimer, optionally enclosed in a matrix, and a suitable metal salt separately in a detergent formulation. By dissolving the detergent formulation, the reactants can come together and form the catalyst.
• Such dendrimers can be used with stoichiometrically different amounts Transition metal can be loaded. In the maximum case, all nitrogen atoms of the dendrimer saturated with transition metal.
• inner nitrogen atoms of the dendrimer can also complex and the resulting complex can have a catalytic effect.
• the total number of peripheral and internal nitrogen atoms are: generation 0 1 2 3rd 4th 5 ... Number of N atoms 2 6 14 30th 62 126
• the transition metals in the complexes to be used according to the invention can have oxidation states in the range from + II to + V.
• Manganese, cobalt and molybdenum are among the preferred transition metals. Multinuclear systems with mixed oxidation numbers and / or several different transition metals are also possible.
• the complex compounds to be used according to the invention can also carry further ligands, generally of a simpler structure, in particular neutral or mono- or polyvalent anion ligands.
• oligomeric multinuclear complexes are formed with at least one dendrimer ligand.
• the transition metal dendrimer complexes described, but also the Dendrimers as such are excellent as bleaching and Oxidation catalysts, especially in washing and cleaning agents for Cleaning textiles as well as hard surfaces, especially dishes and in textile and paper bleaching.
• Textile detergents in the form of powder detergents or as liquid formulations and dish detergent.
• An advantage of the bleaching catalysts according to the invention is their stability against hydrolysis and oxidation as well as their catalytic Effect already at low temperatures. You improve in such Formulations not only the bleaching effect of hydrogen peroxide, but also of organic and inorganic peroxy compounds.
• the present invention accordingly also relates to a method for Bleaching soiled substrates, taking the soiled substrate in aqueous bleaching liquor with peroxy compounds and an effective amount of one or more of the compounds of formula I, or the corresponding metal complexes as bleaching catalysts in contact.
• aqueous solutions also come in mixtures of water and suitable ones organic solvents as a reaction medium in question.
• the quantities used Peroxygen compounds are generally chosen so that in the Solutions between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm active oxygen are present. Also the amount used on compounds of the formula I according to the invention or their metal complexes depends on the application.
• the washing and cleaning agents according to the invention thus contain them Bleaching catalysts, in amounts by weight from 0.0001 to 0.5% by weight, in particular 0.00025 to 0.25% by weight, especially 0.0005 to 0.1% by weight on the weight of the formulations.
• detergents and cleaning agents which are powdered, granular or tablet-like solids, homogeneous solutions or suspensions are present can, in addition to the bleach catalysts used according to the invention in Principle of all known ingredients common in such agents, such as Peroxygen compounds, bleach activators, other conventional ones Bleaching catalysts, surfactants, builders, water-miscible organic solvents, Enzymes, sequestering agents, electrolytes, pH regulators and other aids such as Silver corrosion inhibitors, foam regulators, thickeners, Preservatives, pearlescent agents and emulsifiers, as well as colors and fragrances contain.
• Peroxygen compounds such as Peroxygen compounds, bleach activators, other conventional ones Bleaching catalysts, surfactants, builders, water-miscible organic solvents, Enzymes, sequestering agents, electrolytes, pH regulators and other aids such as Silver corrosion inhibitors, foam regulators, thickeners, Preservatives, pearlescent agents and emulsifiers, as well as colors and fragrances contain.
• Suitable peroxygen compounds in particular come into question organic peracids or peracid salts of organic acids.
• Examples include peroxynaphthoic acid, peroxylauric acid, peroxystearic acid, N, N-phthaloylaminoperoxycaproic acid, perbenzoic acid, diperdodecanedioic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, Diperoxyisophthalic acid, 2-decyldiperoxybutane-1,4-diacid and 4,4'-sulfonylbisperoxybenzoic acid.
• Hydrogen peroxide is also suitable Washing and cleaning conditions
• Compounds releasing hydrogen peroxide such as alkali metal peroxides, organic peroxides such as urea-hydrogen peroxide adducts, and inorganic persalts, such as the alkali perborates, percarbonates, -perphosphates, -persilicates and -persulfates.
• alkali metal peroxides such as urea-hydrogen peroxide adducts
• inorganic persalts such as the alkali perborates, percarbonates, -perphosphates, -persilicates and -persulfates.
• Sodium perborate tetrahydrate and especially sodium perborate monohydrate.
• Sodium perborate monohydrate is because of its good shelf life and its good solubility in water preferred.
• Sodium percarbonate can be made Environmental reasons may be preferred.
• Alkyl hydroperoxides are another suitable group of peroxide compounds.
• Cumene hydroperoxide and butyl hydroperoxide are also suitable as Peroxy compounds inorganic peroxyacid salts, e.g. B. Potassium monopersulfate. Mixtures of two or more of these compounds are also suitable.
• the detergent and cleaning agent formulations according to the invention contain usually 1 to 30% by weight, in particular 2 to 25% by weight Peroxy compounds.
• bleach stabilizers such as of phosphonates, borates, metaborates and metasilicates as well as magnesium salts such as magnesium sulfate can be useful.
• bleach activators which, under perhydrolysis conditions, give aliphatic percarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms and / or optionally substituted perbenzoic acid.
• Suitable substances are those 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 triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran, sodium nonanoyloxy-benzenes
• Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1 to 10% by weight, in particular 2 to 8% by weight, based on the total agent.
• sulfonimines and / or further bleach-enhancing transition metal salts or transition metal complexes may also be present.
• the transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from DE 195 29 905 and DE 196 05 688.
• the detergents and cleaning agents according to the invention can contain anionic surfactants in amounts of approximately 1 to 50% by weight, based on the total amount of all surfactants, as surface-active agents.
• anionic surfactants are C 8 -C 20 fatty acid alpha-methyl ester sulfonates, alkyl ether sulfates and sec. Alkanesulfonates.
• the alkyl ether sulfates used in the agents according to the invention are water-soluble salts or acids of the formula RO (A) m SO 3 M, in which R is an unsubstituted C 10 -C 24 -alkyl or C 10 -C 24 -hydroxyalkyl radical, preferably a C 12 -C 20 alkyl or C 12 -C 20 hydroxyalkyl radical, particularly preferably C 12 -C 18 alkyl or C 12 -C 18 hydroxyalkyl radical.
• A is an ethoxy or propoxy unit
• m is a number greater than 0, preferably between 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3
• M is a hydrogen atom or a cation such as, for example a metal cation (e.g. sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or a substituted ammonium cation.
• substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine.
• alkyl ether sulfates are C 12 -C 18 alkyl polyethoxylate (1.0) sulfate, (C 12 -C 18 E (1.0) M), C 12 -C 18 alkyl polyethoxylate (2.25) sulfate (C 12 -C 18 E (2.25) M), C 12 -C 18 alkyl polyethoxylate (3.0) sulfate, (C 12 -C 18 E (3.0) M), C 12 - C 18 alkyl polyethoxylate (4.0) sulfate (C 12 -C 18 E (4.0) M), where E is an ethoxy unit.
• the alkyl group can either be saturated or unsaturated, branched or linear and optionally with a hydroxyl group be substituted.
• the sulfo group is statistically distributed over the entire C chain, with the primary methyl groups at the beginning and end of the chain none Possess sulfonate groups.
• the preferred secondary alkanesulfonates contain linear alkyl chains with 9 to 25 carbon atoms, preferably from 10 to 20 Carbon atoms and particularly preferably 13 to 17 carbon atoms.
• the cation is sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. Sodium as a cation is simplicity preferred for the sake of it.
• the Formulations according to the invention also other types of anionic surfactants contained within the limits specified above, such as Alkyl sulfates, sulfonates, carboxylates, phosphates and mixtures of the mentioned connections.
• Suitable cations are e.g. Sodium, potassium, calcium or magnesium, as well as ammonium, substituted ammonium compounds, including mono-, di- or triethanolammonium cations, as well as mixtures of these cations.
• the anionic surfactants for the present invention are suitable, have surfactant properties and are water-soluble or in Water dispersible.
• alkyl sulfates are water-soluble salts or acids of the formula ROSO 3 M, in which R is preferably a C 10 -C 24 -hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical with C 10 -C 20 -alkyl components, particularly preferably a C12-C18-alkyl or hydroxyalkyl radical represents.
• R is preferably a C 10 -C 24 -hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical with C 10 -C 20 -alkyl components, particularly preferably a C12-C18-alkyl or hydroxyalkyl radical represents.
• M is hydrogen or a cation, for example sodium, potassium, lithium or ammonium or substituted ammonium, for example methyl, dimethyl and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations, derived from alkylamines such as ethylamine, diethylamine, triethylamine and Mixtures of these.
• alkylamines such as ethylamine, diethylamine, triethylamine and Mixtures of these.
• alkylbenzenesulfonate Another suitable anionic surfactant is alkylbenzenesulfonate.
• the alkyl group can be either saturated or unsaturated, branched or linear and optionally substituted with a hydroxyl group.
• the preferred alkylbenzenesulfonates contain linear alkyl chains of 9 to 25 carbon atoms, preferably of 10 to 13 carbon atoms, the cation is sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof.
• Suitable anionic surfactants are carboxylates, for example fatty acid soaps and comparable surfactants.
• the soaps can be saturated or unsaturated and can contain various substituents, such as hydroxyl groups or alpha sulfonate groups. Linear saturated or unsaturated hydrocarbon residues are preferred as the hydrophobic component in the soaps.
• the hydrophobic components usually contain 6 to 30 carbon atoms, preferably 10 to 18 carbon atoms.
• anionic surfactants are salts of acylaminocarboxylic acids, which are formed by reacting fatty acid chlorides with sodium sarcosinate in an alkaline medium (acylsarcosinates), and fatty acid-protein condensation products, which are obtained by reacting fatty acid chlorides with oligopeptides.
• the salts of alkylsulfamidocarboxylic acids and the salts of alkyl and alkylaryl ether carboxylic acids also have surfactant properties.
• anionic surfactants which are useful for use in detergents are C 8 -C 24 olefin sulfonates, sulfonated polycarboxylic acids, prepared by sulfonating the pyrolysis products of alkaline earth metal citrates, as described, for example, in GB 1 082 179, alkyl glycerol sulfates, fatty acyl glycerol sulfates, oleyl glycerol sulfates, alkylphenol ethersulfates, alkylphenol ethersulfates paraffin sulfonates, alkyl phosphates, alkyl ether phosphates, isethionates such as the acyl isethionates, N-acyl taurides, alkyl succinamates, sulfosuccinates, monoester of sulfosuccinates (especially saturated and unsaturated C 12 -C 18 monoesters) and diester
• Resin acids or hydrogenated resin acids such as rosin or hydrogenated rosin or tall oil resins and tall oil resin acids can also be used. Further examples are described in "Surface Active Agents and Detergents” (Vol. I and II, Schwartz, Perry and Berch). A large number of such surfactants are also described in US 3,929,678.
• anionic surfactants are also alkyl ether sulfonates, glycerol ether, sulfofatty acids, fatty alcohol ether sulfates, Glycerol ether, Hydroxymischethersulfate, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, alkyl oligoglucoside sulfates, Alkylaminozuckersulfate and alkyl (ether) phosphates .
• anionic surfactants contain polyglycol ether chains, they can have a conventional or narrow homolog distribution.
• Nonionic surfactants such as fatty acid alkyl ester alkoxylates, alkyl and / or alkenyl oligoglycosides, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, and fatty acid fatty acid orborbyl esters, polyglycol fatty acids or fatty acid sorbyl esters, polyglycol fatty acids or fatty acid glycobloyl esters, fatty acid polyglycol ethers, and alkoxylated triglycerides, and fatty acid fatty acid orborbates,
• co-surfactants from the group can be used in the agents according to the invention
• Alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, Imidazolinium betaines and sulfobetaines, amine oxides and fatty acid alkanolamides, especially the monoethanolamides from palm kernel and coconut oil fatty acids or Polyhydroxyamides are used in the amounts by weight of 1 to 50%.
• the total proportion of surface-active compounds can be up to 50% by weight. amount, preferably 1 to 40 wt .-%, in particular 4 to 25 wt .-% of total detergent or cleaning agent.
• Suitable and especially ecologically harmless Builder substances are crystalline, layered silicates of the general formula NaMSi (x) O (2x + 1), where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4 and y is a number from 0 to 33, for example Na-SKS-5 ( ⁇ -Na2Si2O5), Na-SKS-7 ( ⁇ -Na2Si2O5, natrosilite), Na-SKS-9 (NaHSi2O5 * H2O), Na-SKS-10 (NaHSi2O3 * 3H2O, Kanemit), Na-SKS-11 (t-Na2Si2O5) and Na-SKS-13 (NaHSi2O5), but especially Na-SKS-6 ( ⁇ -Na2Si2O5) as well. finely crystalline, synthetic water-containing zeolites, in particular of the
• Zeolites and layered silicates can be contained in an amount of up to 20% by weight.
• Non-partially or partially neutralized (co) polymeric polycarboxylic acids are also suitable. These include the homopolymers of acrylic acid or methacrylic acid or their copolymers with other ethylenically unsaturated monomers such as, for example, acrolein, dimethylacrylic acid, ethylacrylic acid, vinyl acetic acid, allylacetic acid, maleic acid, fumaric acid, itaconic acid, (meth) allylsulfonic acid, vinyl sulfonic acid, styrenesulfonic acid group, and acrylamidomethyl phosphonic acid monomers, and also acrylamidomethyl phosphonomethyl monomers such as, for example, vinyl phosphoric acid, allyl phosphoric acid and acrylamidomethylpropane phosphoric acid and their salts, and also hydroxyethyl (meth) acrylate
• Preferred (co) polymers have an average molecular weight of 1000 to 100,000 g / mol, preferably of 2000 to 75,000 g / mol and in particular of 2000 to 35,000 g / mol.
• the degree of neutralization of the acid groups is advantageously from 0 to 90%, preferably from 10 to 80% and in particular from 30 to 70%.
• Suitable polymers include above all homopolymers of acrylic acid and copolymers of (meth) acrylic acid with maleic acid or maleic anhydride.
• copolymers are derived from terpolymers that are Polymerization of 10 to 70 wt .-% monoethylenically unsaturated Dicarboxylic acids with 4 to 8 carbon atoms, their salts, 20 to 85% by weight monoethylenically unsaturated monocarboxylic acids with 3 to 10 carbon atoms or their salts, 1 to 50 wt .-% monounsaturated monomers, which according to Saponification release hydroxyl groups on the polymer chain, and 0 to 10 wt .-% further free-radically copolymerizable monomers can be obtained.
• Graft polymers of monosaccharides are also suitable, Oligosaccharides, polysaccharides and modified polysaccharides as well animal or vegetable proteins.
• Copolymers of sugar and other polyhydroxy compounds and a monomer mixture of 45 to 96% by weight of monoethylenically unsaturated C 3 -C 10 monocarboxylic acid or mixtures of C3 to C10 monocarboxylic acids and / or their salts with monovalent cations, 4 to 55% by weight are preferred .-% monoethylenically unsaturated monosulfonic acid groups containing monomers, monoethylenically unsaturated sulfuric acid esters, vinyl phosphoric acid esters and / or the salts of these acids with monovalent cations and 0 to 30 wt .-% water-soluble unsaturated compounds which are modified with 2 to 50 moles of alkylene oxide per mole of monoethylenically unsaturated compounds .
• polyaspartic acid or its derivatives are polyaspartic acid or its derivatives in non-neutralized or only partially neutralized form.
• Graft polymers of acrylic acid, methacrylic acid, maleic acid and other ethylenically unsaturated monomers on salts of polyaspartic acid, as are usually obtained in the previously described hydrolysis of the polysuccinimide, are also particularly suitable.
• the otherwise necessary addition of acid to produce the only partially neutralized form of polyaspartic acid can be dispensed with here.
• the amount of polyaspartate is usually chosen so that the degree of neutralization of all carboxyl groups incorporated in the polymer does not exceed 80%, preferably 60%.
• Further builders that can be used are, for example, the percarboxylic acids preferably used in the form of their sodium salts, such as citric acid, in particular trisodium citrate and trisodium citrate dihydrate, nitrilotriacetic acid and their water-soluble salts; the alkali metal salts of carboxymethyloxysuccinic acid, ethylenediaminetetraacetic acid, mono-, dihydroxysuccinic acid, ⁇ -hydroxypropionic acid, gluconic acid, mellitic acid, benzopolycarboxylic acids and as disclosed in U.S. Patents 4,144,226 and 4,146,495.
• Phosphate-containing builders for example alkali metal phosphates, which can be in the form of their alkaline, neutral or acidic sodium or potassium salts, are also suitable.
• Examples of this are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen phosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with oligomerization amounts in the range from 5 to 1000, in particular 5 to 50, and mixtures of sodium and potassium salts.
• the builder substances can be present from 5 to 80% by weight, a proportion of 10 to 60% by weight is preferred.
• the desired viscosity of the agent can be added by adding water and / or organic solvents or by adding a combination of organic Solvents and thickeners can be adjusted.
• Alcohols into consideration Alcohols with 1 to 4 carbon atoms, such as Methanol, ethanol, propanol, isopropanol, straight-chain and branched butanol, Glycerin and mixtures of the alcohols mentioned.
• Further preferred alcohols are polyethylene glycols with a molecular weight below 2000.
• polyethylene glycol with a relative Molecular mass between 200 and 600 and in amounts up to 45 wt .-% and from Polyethylene glycol with a molecular weight between 400 and 600 in Amounts of 5 to 25% by weight are preferred.
• An advantageous mix of Solvents consist of monomeric alcohol, such as ethanol and Polyethylene glycol in a ratio of 0.5: 1 to 1.2: 1.
• Suitable solvents are, for example, triacetin (glycerol triacetate) and 1-methoxy-2-propanol.
• Preferred thickeners are hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium and titanium stearates or the sodium and / or potassium salts of behenic acid, and polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, furthermore higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, Polyvinyl alcohol and polyvinyl pyrrolidone and electrolytes such as table salt and ammonium chloride are used.
• Suitable thickeners are water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above one million. Examples of these are the polymers available under the name Carbopol® 940 and 941.
• the crosslinked polyacrylates are used in amounts of not more than 1% by weight, preferably in amounts of 0.2 to 0.7% by weight.
• Enzymes come from the class of proteases such as BLAP, Optimase®, Opticlean®, Maxacal®, Maxapem®, Esperase®, Savinase®, Purifect® OxP and / or Durazym®, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®, Amylases such as Termamyl®, Ainylase® -LT, Maxamyl®, Duramyl® and / or Purafect® OxAm, as well as cutinases, pullulanases or their mixtures in question. Their share can be 0.2 to 1% by weight.
• the enzymes can be carried on carrier substances be adsorbed and / or be embedded in coating substances.
• foam regulators preferably up to 6% by weight, in particular about 0.5 to 4% by weight, of foam-suppressing compounds, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffins, paraffin-alcohol combinations, hydrophobicized Silicic acid, the bis fatty acid amides and other other known commercially available defoamers are added.
• foam-suppressing compounds preferably from the group of silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffins, paraffin-alcohol combinations, hydrophobicized Silicic acid, the bis fatty acid amides and other other known commercially available defoamers are added.
• 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 to 6% by weight.
• Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, pentanediol or sorbic acid.
• pearlescent agents examples include glycol distearic acid esters such as Ethylene glycol distearate, but also fatty acid monoglycol esters into consideration.
• Sodium sulfate, sodium carbonate for example, come as salts or adjusting agents or sodium silicate (water glass).
• Typical examples of other additives are sodium borate, starch, Sucrose, polydextrose, RAED, stilbene compounds, methyl cellulose, Toluene sulfonate, cumene sulfonate, soaps and silicones.
• the bleach catalysts of this invention can be in a variety of products be used. These include textile detergents, textile bleaches, Surface cleaners, toilet cleaners, dishwasher cleaners, and also Denture cleaner.
• the detergents can be in solid or liquid form available.
• bleach activators in the form of granules, in addition to the Bleach catalyst contain a binder.
• Different methods such Producing granules are described in the patent literature, for example in Canada Pat. No. 1 102 966, GB 1 561 333, US 4 087 369, EP 240 057, EP 241 962, EP 101 634 and EP 62 523.
• the bleaching catalysts according to the invention Granules containing are generally the detergent composition along with the other dry ingredients like enzymes, added inorganic peroxide bleaching agents.
• the detergent composition, to which the catalyst granules are added can be done in various ways can be obtained, such as mixing the dry components, extruding or Spray drying.
• the bleaching catalysts according to the invention are particularly suitable for non-aqueous liquid detergents, together with a bleaching peroxide compound.
• These are compositions in Form of a non-aqueous, liquid medium in which a solid phase is dispersed can be.
• the non-aqueous, liquid medium can be a liquid, be a surface-active substance, preferably a nonionic surface-active substance Substance, a non-polar liquid medium such as liquid paraffin polar solvents, such as polyols, for example glycerol, sorbitol, Ethylene glycol, possibly in combination with low molecular weight monohydric alcohols such as ethanol or isopropanol or mixtures thereof.
• the solid phase can consist of builder substances, alkalis, abrasive substances, Polymers and solid ionic surface-active compounds, bleaches, fluorescent substances and other common solid ingredients.
• the fabric pieces were rinsed with water, dried and ironed; the bleaching effect was then quantified by determining the differences ⁇ R (KAT-TAED) of the remissions before and after bleaching using an ELREPHO 2000 whiteness measuring device (from Datacolor).
• the tests were carried out in the Linitest device with a washing time of 30 minutes carried out.
• the amounts used were 2 g / l basic detergent WMP and 1 g / l sodium percarbonate (SPC) and 10 mg / l catalyst according to Example 2.
• Test fabric WFK-BW tea (BC-1) was used as Test fabric WFK-BW tea (BC-1) as Test fabric WFK-BW tea (BC-1) was used.
• the tests were carried out in the Linitest device with a washing time of 30 minutes and a washing temperature of 23 ° C.
• the amounts used were 2 g / l Basic detergent WMP and 0.5 g / l sodium perborate monohydrate and 10 mg / l Catalyst according to Example 2.
• WFK-BW tea (BC-1) was used as the test fabric used.
• the tests were carried out in the Linitest device with a washing time of 30 minutes.
• the amounts used were 2 g / l basic detergent WMP and 1 g / l sodium percarbonate and 10 mg / l catalyst.
• Cotton with brilliant red GG and Remazol Black B was used as the test fabric.
• the manganese-dendrimer complex according to the invention like the catalyst-free detergent, causes only minor color damage. Fiber damage to the bleaching catalyst according to the invention in comparison to other detergent formulations laundry detergent Degree of depolymerization (DP) WMP / SPC / TAED 1904 + Mn-triazacyclononane 506 Mn complex according to Example 2 1490
• the degree of depolymerization (DP) of is used as a measure of the fiber damage Cotton listed. In the absence of catalysts, DP values are reduced Found in 2000. These correspond to less fiber damage. Lower values stand for greater fiber damage.
• Table 5 shows the DP values of catalyst-containing detergent formulations compared to catalyst-free Basic detergent. To determine the DP values, a five-fold wash in carried out a catalyst concentration of 2000 ppm.

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• 2000
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• 2001
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