Co-granulat, washing and cleaning agents containing same and use thereof

Abstract

The following are described: coated or uncoated co-granules containing a) 10 to 40 wt% cyclic sulfonimine, b) 20 to 60 wt% bleach activator selected from the group consisting of tetraacetylethylenediamine, decanoyloxybenzoic acid or mixtures thereof, c) 0.1 to 5 wt% organic acid in the form of the free acid and / or a salt thereof, d) 1 to 15 wt% polyvinyl alcohol as a binder, e) 10 to 25 wt% drying agent selected from the group consisting of alkali sulfate, alkali carbonate, alkaline earth sulfate, alkaline earth carbonate, alkaline earth oxide, aluminum oxide, hydrates of these compounds or mixtures of two or more thereof, f) 0 to 0.5 wt% dye and / or pigment, and g) 0 to 5 wt% water, wherein the percentages refer to the sum of the components a) to g) and the sum of the components a) to g) equals 100 percent.These co-granules are stable for extended storage periods and contain ingredients that do not tend to discolor during storage or, in the case of colored co-granules, do not tend to change color.

Description

[0001] The present invention relates to co-granules, washing and cleaning agents for textiles and surfaces and their use for disinfection and for washing or cleaning at low temperatures.

[0002] To achieve a bleaching effect, persalts such as perborates and percarbonates are added to detergents and cleaning agents. To activate these bleaching agents and achieve a satisfactory bleaching effect when cleaning at temperatures of 60°C and below, these agents usually also contain bleach activators and / or bleach catalysts.

[0003] Bleach activators and bleach catalysts are preferably used in detergents and cleaning agents in the form of preformed granules. This is done partly to increase their storage stability and partly to ensure homogeneous incorporation of tiny amounts of catalyst into the formulations.

[0004] Sulfonimines and their use in detergents and cleaning agents have already been described in the patent literature.

[0005] DE 691 04 405 T2 corresponding to EP 0 453 003 B1 discloses bleaching compositions for detergents containing 1 to 60 wt.% of a peroxygen compound, 0.05 to 10 wt.% of a selected sulfonimine and 0.5 to 50 wt.% of a surfactant.

[0006] DE 691 04 751 T2, corresponding to EP 0 446 982 B1, describes bleaching compositions containing 1 to 60 wt. % of a peroxygen compound, 0.05 to 10 wt. % of a selected sulfonimine, and 0.1 to 40 wt. % of a bleach precursor that reacts with the peroxide anion. Bleaching compositions that are effective even at low temperatures are known from this document. The examples describe combinations of sulfonimine with the bleach activator tetraacetylethylenediamine (TAED) and perborate, and their effect on textiles treated with tea stains. The bleaching agent is applied at temperatures of 40°C.

[0007] In SOFW Journal 140 9-2014, G. Reinhardt, M. Best, I. Herrgen, and M. Ladwig describe sulfonimines and quaternary iminium salts as novel bleaching catalysts. These compounds serve as precursors to dioxiranes, oxaziridines, and oxaziridinium salts, which, even at low concentrations in combination with peroxide compounds, achieve excellent bleaching effects. This publication already proposed using sulfonimines and quaternary iminium salts in the form of granules with other bleach activators, such as TAED or nonanoyloxybenzenesulfonate sodium (NOBS), and also using film-forming binders. However, such granules are often not sufficiently stable during storage.

[0008] EP 3,345,989 A1 discloses granules containing sulfonimines or quaternary iminium salts and an acid that is solid at 25 °C as a stabilizer. These granules can be used to formulate detergents and cleaning agents that can be used at temperatures below 35 °C.

[0009] DE 10 2020 001 458 A1 discloses cogranules containing selected bleach activators and sulfonimines. These are cellulose ether-coated cogranules containing cyclic sulfonimine, a selected bleach activator, such as tetraacetylethylenediamine (TAED), and cellulose ether as a binder. These cogranules are particularly suitable for wet granulation.

[0010] Tests have shown that cellulose ethers, such as carboxymethyl cellulose, used as binders in combination with bleach activators, sulfonimines, and driers, such as calcium sulfate, do not produce stable granules. The addition of driers appears problematic in this context. Furthermore, problems arose with the dosing of powder mixtures of driers and sulfonimines, as these mixtures adhered and remained in the pipes. Furthermore, difficulties were encountered with coloring granules using cellulose ether as a binder. Ultimately, small particles of the granules could only be insufficiently coated and discolored yellow to brown during storage in detergent and cleaning agent formulations.

[0011] Surprisingly, it was found that these problems could be solved by replacing the cellulose ether binder with polyvinyl alcohol.

[0012] EP 3,345,989 A1 generally proposes the use of non-acidic binders, mentioning polyvinyl alcohol as a binder, among others. In the examples of this document, microcrystalline cellulose was also used as a binder in addition to polyvinyl alcohol. However, the latter does not permit wet granulation. Surprisingly, it was found that stable co-granules can be produced by wet granulation using polyvinyl alcohol as the sole binder. Furthermore, all of the granules described in EP 3,345,989 A1 exhibit a slight yellow tinge after storage. The co-granules of the present invention exhibit no change in color even after prolonged storage.

[0013] Based on this prior art, the object of the present invention was to provide co-granules which are stable in storage over a longer period and which contain larger amounts of highly active bleach activators, bleach catalysts and siccatives which do not tend to discolor during storage or, in the case of colored co-granules, do not tend to change the color tone.

[0014] A further object of the present invention was to provide further stable co-granules which contain highly active bleach activators and bleach catalysts and which do not decompose into their powdery components after wet granulation.

[0015] These tasks are solved by providing coated or uncoated co-granules containing a) 10 to 40% by weight of cyclic sulfonimine, b) 20 to 60% by weight of bleach activator selected from the group consisting of tetraacetylethylenediamine, decanoyloxybenzoic acid or mixtures thereof, c) 0.1 to 5% by weight of organic acid in the form of the free acid and / or in the form of a salt thereof, d) 1 to 15% by weight of polyvinyl alcohol as a binder, e) 10 to 25% by weight of drying agent selected from the group consisting of alkali sulfate, alkali carbonate, alkaline earth sulfate, alkaline earth carbonate, alkaline earth oxide, aluminum oxide, hydrates of these compounds or mixtures of two or more thereof, f) 0 to 0.5% by weight of dye and / or pigment, and g) 0 to 5% by weight of water, where the percentages refer to the sum of components a) to g) and the sum of components a) to g) equals 100 percent.

[0016] Furthermore, the invention relates to washing and cleaning agents containing A) bleaching agent selected from the group consisting of perborate, percarbonate or mixtures thereof, and B) the co-granulate described above, preferably a cellulose ether coated co-granulate.

[0017] In the detergent and cleaning agent according to the invention, selected per compounds are used as component A). These are perborate, percarbonate, or mixtures thereof.

[0018] Preferably, the corresponding sodium salts of perborates and percarbonates are used as component A), in particular sodium percarbonate.

[0019] The amount of component A) in the detergent and cleaning agent according to the invention is typically 5 to 30 wt. %, based on the total amount of detergent and cleaning agent. Preferred amounts of component a) are in the range from 5 to 20 wt. %, in particular in the range from 8 to 12 wt. %.

[0020] In the detergent and cleaning agent according to the invention, cogranules with selected components are used as component B). These cogranules are coated with a cellulose ether. These cogranules contain selected amounts of the above-defined components a) to g) as ingredients.

[0021] The amount of component B) in the detergent and cleaning agent according to the invention is typically 0.05 to 10 wt.%, based on the total amount of detergent and cleaning agent. Preferred amounts of component B) are in the range from 0.2 to 8 wt.%, in particular from 0.5 to 6 wt.%, particularly preferably from 0.5 to 3 wt.%, and most preferably in the range from 0.5 to 2 wt.%.

[0022] The cyclic sulfonimines used according to the invention as component a) are cyclic compounds with a structural unit =N-SO 2 - in the molecule.

[0023] Cyclic sulfonimines preferably used as component a) are compounds of the formula I wherein R 1 and R 2 are independently hydrogen, C 1 -C 6 alkyl or phenyl.

[0024] Of the compounds of formula I, those in which R 1 is hydrogen and R 2 is C 1 -C 6 alkyl, in particular methyl or ethyl, or phenyl are very particularly preferred.

[0025] The most preferred sulfonimine of formula I is 3-methyl-1,2-benzisothiazole-1,1-dioxide.

[0026] If in this description one of the radicals is C 1 -C 6 alkyl, the alkyl group can be either branched or unbranched. An alkyl group contains one to six carbon atoms. Examples of alkyl groups are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert .-Butyl, pentyl or n-hexyl.

[0027] The amount of component a) in the co-granulate according to the invention is between 10 and 40 wt. %, based on the total amount of components a) to g) in the co-granulate. Preferred amounts of component a) are in the range from 25 to 35 wt. %, in particular in the range from 27 to 33 wt. %.

[0028] According to the invention, tetraacetylethylenediamine or decanoyloxybenzoic acid is used as bleach activator b). Mixtures thereof can also be used. The preferred component b) is tetraacetylethylenediamine.

[0029] The amount of component b) in the co-granulate according to the invention is between 20 and 60 wt. %, based on the total amount of components a) to g) in the co-granulate. Preferred amounts of component b) are in the range from 20 to 50 wt. %, in particular in the range from 25 to 45 wt. %, and most preferably in the range from 30 to 40 wt. %.

[0030] Both monomeric and polymeric acids can be used as organic acids c), either in the form of the free acid or in the form of their salts. For the purposes of the present invention, the term "organic acid" therefore encompasses both organic acids in free form and in salt form.

[0031] Preferred counterions of organic acids are alkali ions and especially Na ions.

[0032] Preferred organic acids c) are citric acid, ascorbic acid, oxalic acid, adipic acid, sebacic acid, malonic acid, succinic acid, glutaric acid, malic acid, tartaric acid, lactic acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, C 8 -C 22 fatty acids, and mixtures thereof. Particularly preferred organic acids are oxalic acid, ascorbic acid, citric acid, and C 8 -C 22 fatty acids, for example lauric acid, myristic acid, palmitic acid, or stearic acid.

[0033] Preferred polymeric organic acids c) are polymers of acrylic acid or methacrylic acid and copolymers of acrylic acid with methacrylic acid or copolymers of acrylic acid and / or methacrylic acid with maleic acid.

[0034] Particularly preferred components c) are citric acid, ascorbic acid and oxalic acid or alkali salts of these acids, very particularly preferably citric acid or an alkali salt thereof.

[0035] The amount of component c) in the co-granulate according to the invention is between 0.1 and 5 wt. %, based on the total amount of components a) to g) in the co-granulate. Preferred amounts of component c) are in the range from 0.3 to 0.5 wt. %, in particular in the range from 0.39 to 0.41 wt. %.

[0036] According to the invention, polyvinyl alcohol is used as binder d). Mixtures of polyvinyl alcohols can also be used.

[0037] To characterize polyvinyl alcohol, the viscosity of a 4% aqueous solution at 25°C (measured with a Höppler viscometer) is often preferred instead of the molecular weight. Particularly suitable polyvinyl alcohol d) has a viscosity in aqueous solution at 25°C of 2 to 60 mPa*s, in particular 5 to 10 mPa*s.

[0038] Polyvinyl alcohol is typically produced by saponification of polyvinyl acetate. Particularly preferred polyvinyl alcohol has a degree of saponification of 70 to 100 mol%, especially 80 to 90 mol%.

[0039] Other suitable polyvinyl alcohols d) may be hydrophobically or hydrophilically modified in any way.

[0040] The amount of component d) in the co-granulate according to the invention is between 1 and 15 wt. %, based on the total amount of components a) to g) in the co-granulate. Preferred amounts of component c) are in the range from 1 to 5 wt. %, in particular in the range from 2 to 4 wt. %, most preferably in the range from 3 to 4 wt. %.

[0041] As drying agents e), compounds selected from the group consisting of alkali metal sulfate, alkali metal carbonate, alkaline earth metal sulfate, alkaline earth metal carbonate, alkaline earth metal oxide, aluminum oxide, and / or hydrates of these compounds are used. Mixtures of two or more of these compounds can also be used.

[0042] These compounds are preferably used as hydrates, especially as dihydrates.

[0043] Preferably used siccatives e) are selected from the group consisting of sodium sulfate, magnesium sulfate, calcium sulfate, hydrates of these compounds or mixtures of two or three thereof.

[0044] Calcium sulfate, in particular calcium sulfate dihydrate, is particularly preferably used as drier e).

[0045] The amount of component e) in the co-granulate according to the invention is between 10 and 25 wt. %, based on the total amount of components a) to g) in the co-granulate. Preferred amounts of component e) are in the range from 15 to 20 wt. %, in particular in the range from 15 to 16 wt.

[0046] In addition to the components a) to e) described above, the co-granules according to the invention may also contain dyes and / or pigments f) and / or water g) as further ingredients.

[0047] Dyes are color-providing compounds that can be dissolved in a solvent, such as water. Solubility in this context is defined as a solubility of at least 1 g of dye in 1 L of solvent at 25 °C.

[0048] The pigments are color-giving compounds that cannot be dissolved in a solvent, for example in water, i.e. they have a solubility at 25 °C of less than 1 g of pigment in 1 L of solvent.

[0049] The proportion of component f) is 0 to 0.5 wt.%, preferably 0 to 0.1 wt.%, in particular 0.03 to 0.07 wt.%, based on the total amount of components a) to g) in the co-granulate.

[0050] The proportion of component g) is 0 to 5 wt.%, preferably 0 to 1 wt.%, based on the total amount of components a) to g) in the co-granulate.

[0051] No other ingredients other than components a) to g) and the coating are present in the co-granules according to the invention.

[0052] Preferably, the co-granules according to the invention contain no further ingredients besides components a to e), optionally f) and / or optionally the coating.

[0053] The co-granules according to the invention can be coated (so-called protective layer), which further improves storage stability. Furthermore, the co-granules can be colored with this coating; however, it is also possible to formulate dye and / or pigment together with components a) to e).

[0054] In the simplest embodiment of the invention, the co-granulate according to the invention is not provided with a coating.

[0055] In a preferred embodiment of the invention, the co-granulate according to the invention is provided with a coating.

[0056] Preferred substances for the coating are organic compounds with film-forming properties, such as fatty acids, waxes, polyvinyl alcohols, acetalized polyvinyl alcohols, polyvinylpyrrolidones, polyalkylene glycols, cellulose derivatives, polymeric organic acids, such as polymers of acrylic acid or methacrylic acid and copolymers of acrylic acid with methacrylic acid or copolymers of acrylic acid and / or methacrylic acid with other comonomers, such as maleic acid.

[0057] Optionally, the coating may also contain small amounts of water-soluble dyes or water-insoluble pigments.

[0058] Suitable fatty acids for the coating have 8 to 22 carbon atoms. These include, for example, lauric acid, myristic acid, palmitic acid, stearic acid, or mixtures thereof. Organic polymers containing acid groups are also preferred.

[0059] The proportion of the coating in the total amount of co-granules can vary widely, but should not exceed 30 wt.%, based on the total mass of the coated co-granules. Preferably, the proportion of the coating is between 5 and 20 wt.%, based on the total mass of the coated co-granules.

[0060] Preferably, the coating of the co-granules according to the invention is formed from cellulose ethers or contains cellulose ethers.

[0061] The cellulose ethers preferably used as coating components are cellulose derivatives formed by partial or complete substitution of the hydrogen atoms of the hydroxy groups in the cellulose. The type of substituents, the number of substituted hydroxy groups, and their distribution in the cellulose ethers used according to the invention can be varied within wide limits.

[0062] Preferably, cellulose ethers are used that are soluble in water. This means a solubility of at least 1 g of cellulose ether in 1 L of water at 25 °C.

[0063] Examples of cellulose ethers that can be used as coating components are carboxymethylcellulose (CMC), methylcellulose (MC), ethylcellulose (EC), hydroxyethylcellulose (HEC) or hydroxypropylcellulose (HPC).

[0064] Further examples of cellulose ethers that can be used as coating components are cellulose mixed ethers such as methylethylcellulose (MEC), hydroxyethylmethylcellulose (HEMC), hydroxypropylmethylcellulose (HPMC), ethylhydroxyethylcellulose or carboxymethylhydroxyethylcellulose

[0065] Preferred shell components are HEMC and HPMC.

[0066] Optionally, the coating may also contain small amounts of additives, such as organic dyes or pigments, and / or other film-forming polymers. However, the total proportion of such additives and / or other film-forming polymers in the total mass of the coating should not exceed 10 wt.%, preferably 5 wt. Preferably, the coating contains no additives, i.e., no dyes or pigments, and no other film-forming polymers.

[0067] In a further embodiment, the co-granulate according to the invention can be provided with two or more coatings, at least one of which consists of cellulose ether. Thus, the co-granulate according to the invention can be provided with a first coating, preferably made of hydroxypropylmethylcellulose (HPMC) and / or hydroxyethylmethylcellulose (HEMC), and with a second protective layer, preferably made of a fatty acid or a fatty acid mixture, most preferably of stearic acid and palmitic acid.

[0068] Particularly preferred in terms of their performance and storage stability are co-granules coated with cellulose ether which, based on the total mass of components a) to g), consist of 25 to 35 wt.% of component a), 30 to 40 wt.% of component b), 0.3 to 0.5 wt.% of component c), 2 to 4 wt.% of component d), 15 to 20 wt.% of component e), 0.03 to 0.07 wt.% of component f) and 0 to 1 wt.% of component g).

[0069] Other co-granules which are particularly preferred in terms of their performance and storage stability are coated with 5 to 20 wt.% cellulose mixed ether, in particular with methylethylcellulose (MEC), hydroxyethylmethylcellulose (HEMC), hydroxypropylmethylcellulose (HPMC), ethylhydroxyethylcellulose or carboxymethylhydroxyethylcellulose.

[0070] In principle, various granulation processes are possible for the production of the co-granules according to the invention.

[0071] Both degradation and granulation processes can be used. Degradation is defined by experts as the aggregation of powder through moisture or pressure, followed by degradation through division to a desired particle size. Degradation can be carried out as wet or dry granulation.

[0072] In the preferred wet granulation process, a dough-like, homogeneous mass is produced from the individual components and a granulation liquid, which is then comminuted into the granules. Polyvinyl alcohol dissolved in water is used as the granulation liquid. The aqueous solution generally has a polyvinyl alcohol content of between 10 and 30 wt.%. Polyvinyl alcohol contents of 15 to 25 wt.% are preferred. These solutions can be sprayed into the granulation device. The resulting base mass is then comminuted into the co-granules, using aggregates known to those skilled in the art. A distinction can be made between perforated disc, compressed, and shaken granules. Finally, the solvents in the granulation liquids can be removed by heat treatment.

[0073] In dry granulation, co-granules are produced by compacting a powder using pressure. Roller compactors, for example, can be used for this purpose. The resulting pressed material is then further reduced to the desired size.

[0074] In build-up granulation, which is also possible, the co-granules are produced directly from powder particles. For example, powder particles can be swirled in an air stream in a fluidized bed and sprayed with a granulating liquid. The powder particles aggregate to form agglomerates, which are then dried by the air stream. Alternatively, co-granules can be produced using high-speed mixers. For this purpose, the components of the co-granules are added in powder form at the beginning of processing. Granulating liquid is added during the process. The high shear forces and friction on the walls of the high-speed mixer produce uniform co-granules.

[0075] The fine grain fraction and, if necessary, the coarse grain fraction can be separated from the resulting co-granules by sieving. Preferably, the coarse grain fraction is returned to the granulation apparatus, and the fine grain fraction is again subjected to compaction.

[0076] The co-granules produced in this way are coated in a separate step, for example in a fluidized bed mixer.

[0077] The co-granules according to the invention are primarily characterized by their chemical composition. Nevertheless, it has been shown that the effectiveness of these co-granules can also be advantageously influenced by influencing physical parameters, such as particle size, fines content, and the bleach catalyst and bleach activator content of selected sieve fractions.

[0078] For this reason, preferred co-granules according to the invention have an average particle size between 0.1 and 1.6 mm, preferably between 0.2 and 1.5 mm and particularly preferably between 0.4 and 1.2 mm, each measured by sieve analysis.

[0079] Preferred co-granules according to the invention furthermore have a water content of less than 5 wt.%, in particular less than 2 wt.% (measured according to Karl Fischer), based on the total amount of the co-granules.

[0080] The co-granules are used to produce the washing or cleaning agents according to the invention.

[0081] The washing and cleaning agents according to the invention can be in the form of granules, powdered or tablet-shaped solids, but also in liquid or pasty form in pouches and multi-chamber bottles.

[0082] The washing and cleaning agents according to the invention are preferably powdered or tablet-shaped solids, in particular powders.

[0083] In addition to components A) and B), the washing and cleaning agents according to the invention can in principle contain all known ingredients which are customary in such agents.

[0084] The washing and cleaning agents according to the invention, in particular the agents for cleaning dishes, can contain in particular builder substances, enzymes, alkali carriers, surface-active surfactants, pH regulators, organic solvents and other auxiliaries, such as glass corrosion inhibitors, silver corrosion inhibitors and foam regulators.

[0085] Preferred washing and cleaning agents are powdered and contain i) 15 to 65% by weight, preferably 20 to 60% by weight of water-soluble builder component, ii) 5 to 20% by weight, preferably 8 to 10% by weight, of component A), iii) 0.5 to 6% by weight of co-granulate B), and iv) 0 to 50% by weight of further additives, in particular enzymes, alkali carriers, surface-active surfactants, pH regulators, organic solvents or further auxiliaries, such as glass corrosion inhibitors, silver corrosion inhibitors and foam regulators, in each case based on the total weight of the washing and cleaning agent.

[0086] Such an agent is in particular low alkaline, ie its 1% by weight solution has a pH in the range from 8 to 11.5 and preferably from 9 to 11.

[0087] In principle, all builders commonly used in such agents are suitable as water-soluble builder components in the detergents and cleaning agents according to the invention. Examples include alkali metal phosphates, which may be present in the form of their alkaline, neutral, or acidic sodium or potassium salts, in particular 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. Their amounts can range from 15 to about 65% by weight, preferably from 20 to 60% by weight, based on the total agent. Other possible water-soluble builder components, in addition to polyphosphonates and phosphonate alkylcarboxylates, include, for example, organic polymers of native or synthetic origin of the polycarboxylate type, which act as co-builders, particularly in hard-water regions.Examples of suitable co-builders include polyacrylic acids and copolymers of maleic anhydride and acrylic acid, as well as the sodium salts of these polymer acids. Commercially available products include Sokalan® CP 5, CP 10, and PA 30 from BASF. Polymers of native origin that can be used as co-builders include oxidized starch and polyamino acids such as polyglutamic acid or polyaspartic acid. Other possible water-soluble builder components are naturally occurring hydroxycarboxylic acids such as mono- and dihydroxysuccinic acid, alpha-hydroxypropionic acid, and gluconic acid. Preferred organic water-soluble builder components include citric acid salts, particularly sodium citrate. Suitable sodium citrates include anhydrous trisodium citrate and, preferably, trisodium citrate dihydrate. Trisodium citrate dihydrate can be used as a fine or coarse-crystalline powder.Depending on the pH ultimately set in the detergents and cleaning agents according to the invention, in particular dishwashing agents, the acids corresponding to the co-builder salts mentioned may also be present. Particularly preferred builder components in phosphate-free formulations are methylglycine diacetate (MDGA, e.g., Trilon®< M, BASF), L-glutamic acid, N,N,(biscarboxymethyl)-tetrasodium salt (GLDA, Dissolvine®< DL, Akzo Nobel), sodium polyaspartate (Baypure®< , Lanxess), or salts of iminodisuccinic acid (Baypure®< , Lanxess).

[0088] The enzymes optionally contained in washing and cleaning 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, EXCELLENZ™< P 1250, Esperase™< and / or Savinase™< , amylases such as Termamyl™< , Amylase-LT™< , Maxamyl™< , Duramyl™< and / or lipases such as Lipolase™< , Lipomax™< , Lumafast™< and / or Lipozym ™< . The enzymes used can be adsorbed on carriers and / or embedded in coating substances to protect them against premature inactivation. They are typically present in the detergents and cleaning agents according to the invention in amounts of 0 to 10 wt.%, and preferably in amounts of 0.05 to 5 wt.%, with particular preference being given to using enzymes stabilized against oxidative degradation.

[0089] The washing and cleaning agents according to the invention preferably contain the customary alkali carriers such as, for example, alkali metal silicates, alkali metal carbonates and / or alkali metal bicarbonates. The customarily used alkali carriers include carbonates, bicarbonates and alkali metal silicates with a molar ratio SiO 2 / M 2 O (M = alkali atom) of 1:1 to 2.5:1. Alkali metal silicates can be present in amounts of up to 40% by weight, in particular from 3 to 30% by weight, based on the total weight of the washing and cleaning agent. The alkali carrier system preferably used in the washing and cleaning agents according to the invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and sodium bicarbonate, which can be present in an amount of up to 50% by weight and preferably from 5 to 40% by weight.

[0090] In a further preferred embodiment of the invention, the washing and cleaning agents according to the invention contain 20 to 60 wt.% water-soluble organic builder, in particular alkali citrate, 3 to 20 wt.% alkali carbonate and 3 to 40 wt.% alkali disilicate.

[0091] Surfactants, especially anionic surfactants, zwitterionic surfactants, and preferably low-foaming nonionic surfactants, can optionally be added to the detergents and cleaning agents according to the invention. These surfactants serve to improve the removal of greasy soils, as wetting agents, and optionally as granulation aids during the production of these agents. Their amount can be up to 20% by weight, preferably up to 10% by weight, and is particularly preferably in the range from 0.5 to 5% by weight, based in each case on the total weight of the detergent and cleaning agent.

[0092] Extremely low-foaming compounds are typically used. These preferably include C 12 -C 18 alkyl polyethylene glycol polypropylene glycol ethers, each containing up to 8 mol of ethylene oxide and propylene oxide units per molecule. However, other known low-foaming nonionic surfactants can also be used, such as C 12 -C 18 alkyl polyethylene glycol polybutylene glycol ethers, each containing up to 8 mol of ethylene oxide and butylene oxide units per 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 approximately 1 to 4 and / or C 12 -C 14 alkyl polyethylene glycols with 3 to 8 ethylene oxide units per molecule. Also suitable are surfactants from the glucamide family, such as alkyl-N-methyl-glucamides, in which the alkyl part preferably originates from a fatty alcohol with a C-chain length of C 6 -C 14.It is sometimes advantageous to use the described surfactants as mixtures, for example, the combination of alkyl polyglycosides with fatty alcohol ethoxylates or glucamide with alkyl polyglycosides. The presence of amine oxides, betaines, and ethoxylated alkylamines is also possible.

[0093] To establish a desired pH value that does not arise automatically from the mixing of the other components, the detergents and cleaning agents according to the invention can contain system- and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid, and / or adipic acid, but also mineral acids, in particular sulfuric acid or alkali metal hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably present in the detergents and cleaning agents according to the invention in amounts of no more than 10% by weight and particularly preferably in amounts of 0.5 to 6% by weight, based in each case on the total weight of the agent.

[0094] The organic solvents usable in the detergents and cleaning agents according to the invention 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; and mixtures thereof and the ethers derivable from the aforementioned classes of compounds. Such water-miscible solvents are preferably present in the detergents and cleaning agents according to the invention in an amount not exceeding 20% ​​by weight and particularly preferably from 1 to 15% by weight.

[0095] If the washing and cleaning agents according to the invention foam too much during use, for example in the presence of anionic surfactants, 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 hydrophobicized silica, paraffins, paraffin-alcohol combinations, hydrophobicized silica, bis-fatty acid amides, and other known commercially available defoamers can be added to them.

[0096] The washing and cleaning agents according to the invention can contain, as further ingredients, for example sequestering agents, electrolytes, additional peroxygen activators, dyes or fragrances, such as perfume oils, which are known from the prior art for such agents.

[0097] The production of the solid or powdered washing and cleaning agents according to the invention presents no difficulties and can in principle be carried out in a known manner, for example by spray drying or granulation, with peroxygen compound A) and co-granulate B) optionally being added separately later.

[0098] Detergents and cleaning agents according to the invention in the form of aqueous solutions or solutions containing other conventional solvents can be produced particularly advantageously by simply mixing the ingredients, which can be added in substance or as a solution into an automatic mixer.

[0099] The washing and cleaning agents according to the invention are preferably in the form of powdered, granular or tablet-shaped preparations which can be produced in a manner known per se, for example by mixing, granulating, roller compacting and / or by spray drying of thermally resilient components and admixing the more sensitive components, which include in particular enzymes, bleaching agents and the bleaching catalyst.

[0100] Detergents and cleaning agents according to the invention can be used both for hand washing and in household and commercial washing machines. Addition can be done manually or using suitable dosing devices. The application concentrations in the cleaning solution are generally approximately 1 to 8 g / l, preferably 2 to 5 g / l.

[0101] When carrying out a process for washing textiles or cleaning surfaces, the textiles or surfaces are exposed to a washing solution which has been prepared by adding a washing and cleaning agent containing the components A) and B) described above to water.

[0102] Detergents and cleaning agents according to the invention containing components A) and B) can be advantageously used at low temperatures and exhibit excellent washing and cleaning results at temperatures of 40°C or below, preferably below 30°C and most preferably below 25°C. Furthermore, these detergents and cleaning agents exhibit excellent germicidal activity even at low temperatures. These agents significantly reduce the number of bacteria and yeasts on the substrates treated with them.

[0103] The invention also relates to the use of a washing or cleaning agent containing the above-described components A) and B) for disinfecting textiles or surfaces.

[0104] Finally, the invention relates to the use of the washing or cleaning agent described above for washing textiles or for cleaning surfaces, in particular at temperatures of 40 °C and below. Examples

[0105] The following examples are intended to illustrate the invention without limiting it. Examples 1 to 5: Production of coated co-granules

[0106] The co-granules of Examples 1-4 were produced as follows: A binder solution of water, polyvinyl alcohol, and citric acid was homogenized for two hours. Sulfonimine, bleach activator, and siccative (Examples 1 and 2) or sulfonimine, bleach activator, siccative, and dye (Examples 3, 4, and 5) were then added to an Eirich EL01 intensive mixer, sprayed with the binder solution, and processed into granules. The granules were dried in a Retsch TG 200 rapid dryer at 60 °C for 40 minutes and then sieved on a Retsch AS 200 sieving machine. The 400 µm to 1200 µm fraction was isolated and sieved. This fraction was then coated in a Glatt fluidized-bed coating device. Amounts and components of the compositions used to produce the granules of Examples 1-4 are given in Table 1 below.

[0107] The co-granulate of Example 5 was prepared as follows: A binder solution of water, polyvinyl alcohol, citric acid, and dye was prepared by dissolving the components. Sulfonimine, bleach activator, and siccative were then added to an Eirich EL01 intensive mixer and premixed. The binder solution was added manually over a period of four minutes and mixed for a further two minutes. The resulting granulate was dried in a Retsch TG 200 rapid dryer at 60°C for 45 minutes and then sieved on a Retsch AS 200 sieving machine. The fraction from 400 µm to 1200 µm was isolated and sieved. This fraction was then coated in a Glatt fluidized-bed coating device. The quantities and components of the compositions used to produce the granulate of Example 5 are listed in Table 1 below. Table 1: Substances used to produce the co-granules of Examples 1 to 5 Example No. 1 2 3 4 5 3-Methyl-1,2-benzisothiazole-1,1-dioxide (% by weight) 28,5 28,5 28,45 28,45 28,45 TAED (wt%) 35,5 35,5 35,5 35,5 35,5 Polyvinyl alcohol (wt%) 1)< 3,8 3,8 3,8 3,8 3,8 Citric acid (wt%) 0,4 0,4 0,4 0,4 0,4 Calcium sulfate dihydrate (% by weight) 16,6 16,6 16,6 16,6 16,6 Dye (wt%) 2)< - - 0,05 0,05 0,05 Water (wt%) 15,2 15,2 15,2 15,2 15,2 1)< In Examples 1 and 3, the product Solvadis EP 05 from Solvadis was used; in Examples 2 and 4, the product Selvol E205 from Sekisui was used; in Example 5, the product Poval 6-88 from Kuraray was used. 2)< Liquitint AMC from Milliken was used in Examples 3 and 4; Cosmenyl Carmin OC 100 from Heubach was used in Example 5.

[0108] Stable co-granules could be produced from the formulations of Examples 1 to 5 by wet granulation.

[0109] The co-granules produced according to Examples 2 to 5 were then coated in a Glatt fluidized-bed coating device. The fraction was coated in the fluidized bed with a 0.025 wt.% aqueous solution of Tylose®< MH 50 G4 (methylhydroxyethylcellulose) for four hours. Examples 6 and 7: Production of uncoated co-granules

[0110] To produce the co-granules of Example 6, the procedure described for producing the co-granules of Examples 1-4 was followed. The coating of the co-granules of Example 6 was omitted.

[0111] To produce the co-granules of Example 7, the procedure described for producing the co-granules of Example 5 was followed. The coating of the co-granules of Example 7 was omitted.

[0112] Amounts and components of the composition used to produce the granules of Examples 6 and 7 are given in Table 2 below. Table 2: Substances used to produce the co-granules of Examples 6 and 7 Example No. 6 7 3-Methyl-1,2-benzisothiazole-1,1-dioxide (% by weight) 28,45 28,45 TAED (wt%) 35,5 35,5 Polyvinyl alcohol (wt%) 3)< 3,8 3,8 Citric acid (wt%) 0,4 0,4 Calcium sulfate dihydrate (% by weight) 16,6 16,6 Dye (wt%) 4)< 0,05 0,05 Water (wt%) 15,2 15,2 3)< For example 6, the product Selvol E205 from Sekisui was used; for example 7, the product Poval 6-88 from Kuraray was used. 4)< For example 6, Liquitint AMC from Milliken was used; for example 7, Cosmenyl Carmin OC from Heubach was used.

[0113] Stable co-granules could be produced from the formulations of Examples 6 and 7 by wet granulation. Application examples - storage tests Example A1: Storage tests of the co-granules of Examples 1 - 4

[0114] To test the chemical and physical stability of the coated white and pink co-granules according to Examples 1 to 4, their storage behavior was investigated in a commercially available Vanish ®< formulation from Germany. For this purpose, 3 wt.% of these co-granules were incorporated into the Vanish ®< powder mixture. The mixture was transferred to a glass bottle and stored with the lid closed at 40°C for three months. The co-granules were then visually assessed for discoloration.

[0115] It was found that the co-granules of Examples 1 to 4 had not changed during storage. These co-granules were stable in shape and color and did not bleed. Example A2: Storage tests of the co-granulate of Example 5

[0116] To test the chemical and physical stability of the uncoated pink co-granules according to Example 5, their storage behavior was investigated in a commercially available Vanish ®< formulation from Germany. For this purpose, 3 wt.% of these co-granules were incorporated into the Vanish ®< powder mixture. The mixture was transferred to a glass bottle and stored with the lid closed at 40°C for 48 hours. The co-granules were then visually assessed for discoloration.

[0117] The co-granules of Example 5 were found to have not changed during storage. These co-granules were stable in shape and color and did not bleed. Example A3: Disaster test of the co-granulate of Example 5

[0118] 0.67 g of the co-granules from Example 5 were weighed into a glass bottle. The contents of the bottle were sprayed with 0.2 g of water. The moist granules were mixed using a glass rod and stored in a drying cabinet at 40 °C for 48 hours. The co-granules were then visually assessed for discoloration.

[0119] The co-granules in the bottle showed slight discoloration. Application examples - washing tests Examples B1 - B4

[0120] Lini tests for BC-4 curry staining were conducted using the co-granules from Examples 1, 2, 5, and 6 at a washing temperature of 40°C. A 200ml beaker was filled with one BC-4 cloth from CFT BV (Center for Test Materials) soiled with curry. Then, 200ml of water with a water hardness of 15dH and a powder mixture were added, resulting in a detergent concentration of 5g / L. The quantities and compositions of the individual powder mixtures are listed in Table 3 below. After sealing, the beakers were shaken for 30 minutes in a water bath at 40°C. After drying, the cloth cloths were measured with an Elrepho reflectometer (Elrepho 450, Datacolor; measuring aperture XLAV, Ø 34mm; 400nm cutoff filter). The difference in reflectance at λ=457 nm between the unwashed and washed samples was expressed as ΔR. The results are also shown in Table 3. Table 3: Washing powder formulations and results Example No. IEC-A basic washing powder (g) Sodium percarbonate (g) Peractive P TAED (g) Co-granulate according to example (g) ΔR B1 1 0,15 0,03 1 (0,01) 17,4 B2 1 0,15 0,03 2 (0,01) 17,5 B3 1 0,15 0,03 5 (0,01) 17,4 B4 1 0,15 0,03 6 (0,01) 17,6

[0121] All co-granules used show comparable bleaching performance on curry as a hydrophobic soil.

Claims

1. Coated or uncoated co-granules containing a) 10 to 40 wt.% cyclic sulfonimine, b) 20 to 60 wt.% bleach activator selected from the group consisting of tetraacetylethylenediamine, decanoyloxybenzoic acid or mixtures thereof, c) 0.1 to 5 wt.% organic acid in the form of the free acid and / or a salt thereof, d) 1 to 15 wt.% polyvinyl alcohol as binder, e) 10 to 25 wt.% drying agent selected from the group consisting of alkali sulfate, alkali carbonate, alkaline earth sulfate, alkaline earth carbonate, alkaline earth oxide, aluminum oxide, hydrates of these compounds or mixtures of two or more thereof, f) 0 to 0.5 wt.% dye and / or pigment, and g) 0 to 5 wt.% water, where the percentages relate to the sum of components a) to g) and the sum of components a) to g) 100 percent.

2. Co-granulate according to claim 1, characterized in that as bleach activator b) tetraacetylethylenediamine is used.

3. Co-granulate according to at least one of claims 1 to 2, characterized in that the cyclic sulfonimine a) is a compound of formula I wherein R1 and R2 are independently hydrogen, C1-C6 alkyl or phenyl.

4. Co-granulate according to claim 3, characterized in that R1 is hydrogen and R2 is C1-C6 alkyl or phenyl.

5. Co-granulate according to at least one of claims 1 to 4, characterized in that the binder d) is a polyvinyl alcohol with a degree of saponification of 70 to 100 mol%, which as a 4% aqueous solution has a viscosity of 2 to 60 mPa*s at 25°C (measured with the Höppler viscometer).

6. Co-granulate according to at least one of claims 1 to 5, characterized in that the drying agent e) is selected from the group consisting of sodium sulfate, magnesium sulfate, calcium sulfate, hydrates of these compounds or mixtures of two or three thereof.

7. Co-granulate according to claim 6, characterized in thatthe drying agent e) is calcium sulfate dihydrate.

8. Co-granulate according to at least one of claims 1 to 7, characterized in that the organic acid c) is citric acid and / or one of its alkali salts.

9. Co-granulate according to at least one of claims 1 to 8, characterized in that in addition to the components a) to e), dye and / or pigment f) is also present.

10. Co-granulate according to at least one of claims 1 to 9, characterized in that the amount of component a) is 25 to 35% by weight, of component b) is 30 to 40% by weight, of component c) is 0.3 to 0.5% by weight, of component d) is 2 to 4% by weight, of component e) is 15 to 20% by weight, of component f) is 0.03 to 0.07% by weight and of component g) is 0 to 1% by weight.

11. Co-granulate according to at least one of claims 1 to 10, characterized in thatthe cogranulate is coated, preferably with an organic compound having film-forming properties, in particular with a cellulose ether, and most preferably with hydroxyethylmethylcellulose or hydroxypropylmethylcellulose.

12. Washing and cleaning agents containing A) bleaching agents selected from the group consisting of perborate, percarbonate or mixtures thereof, and B) co-granules according to at least one of claims 1 to 11.

13. Washing and cleaning agent according to claim 12, characterized in that the bleaching agent A) is sodium percarbonate.

14. Washing and cleaning agent according to at least one of claims 12 or 13, characterized in that the co-granulate B) is coated with cellulose ether.

15. Washing and cleaning agent according to at least one of claims 12 to 14, characterized in that this is in the form of a powder or tablet, particularly as a powder.

16. Use of a washing or cleaning agent according to at least one of claims 12 to 15 for disinfecting textiles or surfaces.

17. Use of a washing or cleaning agent according to at least one of claims 12 to 15 for washing textiles or for cleaning surfaces, in particular at temperatures of 40°C or below.

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