EP3625319B1 - Coated granules, use thereof, and washing and cleaning agents containing same - Google Patents

Description

The present invention relates to granules and their use in detergents and cleaning agents, in particular in agents for cleaning dishes.

Persalts such as perborates and percarbonates are used in dishwashing detergents for cleaning in order to obtain spotless dishes. To activate these bleaches and to achieve a satisfactory bleaching effect when cleaning at temperatures of 60 ° C. and below, the dishwashing detergents generally also contain bleach activators and / or bleach catalysts.

Bleach catalysts and / or bleach activators are used in dishwashing detergents, preferably in the form of prefabricated granules, in order to increase their storage stability. In addition to the active substances, these granulates usually also contain binders. Bleach granules are for example in the EP 2966161 A1 , US 2011/245136 A1 , US 2007/072787 A1 , EP 0 985 728 A1 , WO 2007/012451 A1 , WO 2010/115581 A1 , WO 2010/115582 A1 , WO 2014/198368 A1 , and WO 2014/198369 A1 described.

It is also known to provide these granules with a coating in order to increase their storage stability. The amount of coating is generally 1 to 30% by weight, typically 5 to 30% by weight. Fatty acids, alcohol ethoxylates and film-forming polymers, including polyvinyl alcohol, are proposed as materials for the formation of coatings.

DE 2263939 describes tablets containing bleach activators which are coated with up to 5% by weight of film-forming water-soluble polymers, up to 15% by weight of a water-soluble or swellable starch or carboxymethyl starch and up to 1.5% by weight of Mg or Ca salts of saturated Contain C ₁₆ -C ₂₀ fatty acids. Bleach catalysts are not included in these tablets.

DE 199 16 187 A1 describes granular bleaching auxiliaries containing bleach activators from the class of the N-acyl and O-acyl compounds. These contain at least one granulating aid from the class of polyvinyl alcohols. These granules do not contain bleach catalysts.

DE 10 2009 017 724 A1 describes bleach co-granules which, in addition to bleach activators and metal-containing bleach catalysts, additionally contain at least 3% by weight of one or more organic acids. These co-granules can optionally be provided with a coating. A wide variety of substances, which are also used as binders, are used as coating materials. In addition to various film-forming polymers, including polyvinyl alcohol, fatty acids are also mentioned.

When using larger amounts of polyvinyl alcohol as a coating material, it has been found that the granules can stick to one another during production and storage. Attempts have therefore been made to reduce the amount of coating material. It has been found that, in addition to reducing the tendency for the granulate particles to stick together, a significantly increased bleaching performance, in particular with respect to tea stains, can surprisingly be achieved if the granulates have bleach catalysts.

It has also been shown that granules containing bleach catalysts and coated with small amounts of polyvinyl alcohol have a significantly improved storage stability compared with uncoated granules. This effect also occurs with granules that contain bleach activators in addition to bleach catalysts, but not with granules that do not contain bleach catalysts.

The present invention was therefore based on the object of providing bleach-activating granules which, compared with granules known from the prior art, are distinguished by increased storage stability and increased bleach activation.

The present invention relates to granules which contain one or more bleach catalysts from the group of the manganese salts or the manganese complexes and contain at least one binder from the group of acidic organic compounds, the granules being coated with 0.1 to 3% by weight, based on the total amount of the granules, with a coating containing polyvinyl alcohol, the coating being at least 80% by weight % of polyvinyl alcohol or mixtures thereof, based on the total weight of the envelope.

The performance of bleaches in detergents and cleaning agents can be significantly increased if the per compound is brought into contact with a combination of bleach catalyst and bleach activator. Here, the bleaching effect of the catalyst is effectively supported by the peroxycarboxylic acid formed from the activator. At the same time, the peroxycarboxylic acid makes a significant contribution to killing germs on the items to be cleaned, improves the odor of the washing liquor and prevents the formation of a biofilm in the washing machine or dishwasher. The combination of bleach catalysts and bleach activators is therefore useful to increase the bleaching effect and to ensure hygiene when using bleaches in detergents and cleaning agents.

However, the use of bleach activators and bleach catalysts as separate particles or granules also has disadvantages that can have a negative effect on the bleaching effect. The reactions of the per compound or the hydrogen peroxide released therefrom with the bleach activator and the bleach catalyst take place in parallel. If the bleach catalyst granulate dissolves faster than the bleach activator granulate, then the per compound is already consumed before it can react with the bleach activator. The same applies to the reverse case.

Granules containing bleach activators and bleach catalysts are also advantageous in order to ensure the homogeneous distribution of both components in the detergent and cleaning agent and to save space in the formulation. Furthermore, the production costs are cheaper, since only one granulate has to be produced instead of two different granulates.

Preferred granules according to the invention therefore contain bleach activators and bleach catalysts from the group of the manganese salts or the manganese complexes.

In addition to the bleach activators and / or bleach catalysts from the group of the manganese salts or the manganese complexes, the granules according to the invention contain at least one binder from the group of the acidic organic compounds.

The amount of bleach activator (s) in the granules according to the invention is usually 1 to 90% by weight, based on the total amount of granules. Preferred amounts of bleach activator (s) range from 50 to 85% by weight.

The amount of bleach catalyst (s) in the granules according to the invention is usually from 0.01 to 30% by weight, based on the total amount of granules. Preferred amounts of bleach catalyst (s) range from 0.1 to 20% by weight.

The amount of binder (s) in the granules according to the invention is usually 1 to 30% by weight, based on the total amount of granules. Preferred amounts of binder (s) range from 1 to 20% by weight.

The amount of other additives in the granules according to the invention is usually 0 to 25% by weight, preferably 0.1 to 25% by weight, based on the total amount of granules. Particularly preferred amounts are in the range from 2 to 20% by weight.

1. a) 1 bis 90 Gew.-% eines oder mehrerer Bleichaktivatoren
2. b) 0,01 bis 30 Gew.-% eines oder mehrerer Bleichkatalysatoren aus der Gruppe der Mangansalze oder der Mangankomplexe, und
3. c) 1 bis 30 Gew.-% eines oder mehrerer Bindemittel.

Granules according to the invention containing, based on the total weight of the granules, are particularly advantageous and therefore preferred with regard to their performance and storage stability,

1. a) 1 to 90% by weight of one or more bleach activators
2. b) 0.01 to 30% by weight of one or more bleach catalysts from the group of the manganese salts or the manganese complexes, and
3. c) 1 to 30% by weight of one or more binders.

1. a) 50 bis 85 Gew.-% eines oder mehrerer Bleichaktivatoren
2. b) 0,1 bis 20 Gew.-% eines oder mehrerer Bleichkatalysatoren aus der Gruppe der Mangansalze oder der Mangankomplexe, und
3. c) 1 bis 20 Gew.-% eines oder mehrerer Bindemittel.

The granules according to the invention particularly preferably contain, based on the total weight of the granules,

1. a) 50 to 85% by weight of one or more bleach activators
2. b) 0.1 to 20% by weight of one or more bleach catalysts from the group of the manganese salts or the manganese complexes, and
3. c) 1 to 20% by weight of one or more binders.

1. a) 50 bis 85 Gew.-% eines oder mehrerer Bleichaktivatoren,
2. b) 0,1 bis 20 Gew.-% eines oder mehrerer Bleichkatalysatoren aus der Gruppe der Mangansalze oder der Mangankomplexe,
3. c) 5 bis 20 Gew.-% eines Bindemittels ausgewählt aus der Gruppe einer niedermolekularen und/oder polymeren organischen Säure,
4. d) 0 bis 20 Gew.-% eines Bindemittels, das keine organische Säure gemäß Komponente c) ist, und
5. e) 1 bis 3 Gew.-% einer Umhüllung aus Polyvinylalkohol.

The granules according to the invention preferably contain, based on the total weight of the granules, 1 to 3% by weight of a coating made of polyvinyl alcohol. In a particularly preferred embodiment of the invention, the granules according to the invention contain, based on the total weight of the granules,

1. a) 50 to 85% by weight of one or more bleach activators,
2. b) 0.1 to 20% by weight of one or more bleach catalysts from the group of manganese salts or manganese complexes,
3. c) 5 to 20% by weight of a binder selected from the group of a low molecular weight and / or polymeric organic acid,
4. d) 0 to 20 wt .-% of a binder that is not an organic acid according to component c), and
5. e) 1 to 3% by weight of a coating made of polyvinyl alcohol.

The granules according to the invention can contain compounds known per se from the prior art as bleach activators. These are preferably polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated trlazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU ), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyloxi- or n-lauroyloxibenzenesulfonate (NOBS or LOBS), acylated phenolcarboxylic acids, especially nonanoyloxi- or decanoyloxibenzoic acid (NOBA), in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaxyacetyl fructose and tetraxyacetyl fructose, tetraxacetlose and octaetyl fructose acetylated optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams can also be preferred can be used. In addition, nitrile derivatives such as n-methyl morpholinium acetonitrile methyl sulfate (MMA) or cyanomorpholine (MOR) can be used as bleach activators. Combinations of bleach activators can also be used.

Particularly preferred bleach activators are TAED and DOBA.

The granules according to the invention from the prior art contain bleach-enhancing transition metal salts or complexes of manganese which are known per se as bleach catalysts.

When using metal salts, manganese salts in the oxidation states +2 or +3 are particularly preferred, for example manganese halides, the chlorides being preferred, or the manganese salts of organic acids, such as manganese acetates, manganese acetylacetonates, manganese oxalates or manganese nitrates.

Bleach catalysts which are also preferably used are complexes of manganese in the II, III, IV or IV oxidation state, which preferably contain one or more macrocyclic ligand (s) with the N, NR, PR, O and / or S donor functions. Preference is given to using bleach catalysts with ligands which have nitrogen donor functions.

Bleach catalysts preferably used as transition metal complexes in the granules according to the invention are complexes which, as macromolecular ligands, are 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1 , 5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1,4,7-triazacyclononane (MeMeTACN) and / or 2-methyl-1 , 4,7-triazacyclononane (Me / TACN) or bridged ligands such as 1,2-bis- (4,7-dimethyl-1,4,7-triazacyclonono-1-yl) ethane (Me4-DTNE) or derivatives of cyclam or cyclens such as 1,8-dimethylcyclam, 1,7-dimethylcyclen, 1,8-diethylcyclam, 1,7-diethylcyclen, 1,8-dibenzylcyclam and 1,7-dibenzylcyclen. Examples are in EP 0 458 397 , EP 0 458 398 , EP 0 549 272 , WO 96/06154 , WO 96/06157 or WO 2006/125517 to find. Bleach catalysts are used in the granules according to the invention preferably used manganese complexes as they come from EP 1 445 305 , EP 1 520 910 or EP 1 557 457 are known.

mit R = H, CH₃, C₂H₅, oder C₃H₇ enthalten.Mono- or dinuclear complexes of manganese which contain at least one ligand of the general formulas A or B are particularly preferably used as bleach catalysts in the granules according to the invention

with R = H, CH ₃ , C ₂ H ₅ , or C ₃ H ₇ .

Preferred ligands are 1,4,7-trimethyl-1,4,7-triazacyclononane (Me ₃ -TACN), 1,4,7-triazacyclononane (TACN) or bridged ligands such as 1,2-bis- (4,7- Dimethyl-1,4,7-triazacyclonono-1-yl) ethane (Me4-DTNE), as e.g. B. in EP 0 458 397 , EP 0 458 398 , EP 0 549 272 , WO 96/06154 , WO 96/06157 or WO 2006/125517 are described.

Particularly preferred bleach catalysts are, for example, the polynuclear complexes [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) _2] (PF ₆ ) ₂ , [Mn ^IV ₂ (μ-O) ₃ (Me ₃ -TACN ) ₂₁ (PF ₆ ) ₂ , [Mn ^IV ₂ (µ-O) ₃ (Me ₃ -TACN) _2] (SO ₄ ), [Mn ^IV ₂ (MO) ₃ (Me ₃ -TACN) ₂ ] (OAc) ₂ , [Mn ^IV ₂ (MO) ₃ (Me ₃ -TACN) _2] (Cl) ₂ , [Mn ^IV Mn ^III ₂ (µ-O) ₂ (OAc) (Me ₄ -DTE)] (Cl) ₂ , [Mn ^IV Mn ^III ₂ (µ-O) ₂ (OAc) (Me ₄ -DTE)] (PF ₆ ) ₂ or the mononuclear complexes [Mn ^IV (Me ₃ -TACN) (OCH ₃ ) ₃ ] PF ₆ , ( produced according to EP 544 519), [Mn ^IV (Me ₃ -TACN) (OC ₂ H ₅ ) ₃ ] PF ₆ and [Mn ^IV (Me ₃ -TACN) (acac) OH] PF ₆ or [Mn ^III (Me ₃ -TACN) (acac) OC ₂ H ₅ ] PF ₆ , the latter prepared according to K. Wieghardt et al., Zeitschrift für Naturforschung 43b, 1184-1194 (1988 ). Since some of these complexes crystallize in hydrated form (with crystal water), these forms are preferred, an example of this is. [Mn ^IV ₂ (µ-O) ₃ (Me ₃ -TACN) _2] (PF ₆ ) ₂ * H ₂ O.

Particularly preferred manganese complexes are, for example, [Mn ^III ₂ (µ-O) ₁ (µ-OAC) ₂ (TACN) _2] (PF ₆ ) ₂ , [Mn ^IV ₂ (µ-O) ₃ (Me-TACN) ₂ ] ( PF ₆ ) ₂ , [Mn ^IV ₂ (µ-O) ₃ (Me-TACN) ₂ ] (SO ₄ ), [Mn ^IV ₂ (µ-O) ₃ (Me-TACN) ₂ ] (OAc) ₂ , [ Mn ^IV ₂ (µ-O) ₃ (Me-TACN) ₂ ] (Cl) ₂ , [Mn ^IV ₂ (µ-O) ₃ (Me4-DTE)] (PF ₆ ) ₂ , [Mn ^IV ₂ (µ- O) ₃ (Me4DTE)] (Cl) ₂ , [Mn ^IV ₂ (µ-O) ₃ (Me4-DTE)] (SO) ₄ ), [Mn ^IV ₂ (µ-O) ₃ (Me4-DTE)] (OAc) ₂ , 1,8-diethyl-1, 4,8,11-tetraazacyclotetradecane manganese (II) chloride or 1, 4,8,1 1-tetraazacyclotetradecane manganese (II) chloride.

The granules according to the invention contain a binder as a further ingredient in order to improve the cohesion of the granules.

Substances selected from fatty acids, alcohol ethoxylates and organic polymers can preferably be used as binders. Mixtures of different binders or different binders of the same type can also be used.

In the context of the present description, organic polymers are understood to mean synthetic and natural polymers, as well as modified polymers of natural origin.

The binders can be neutral or acidic organic polymers or else low molecular weight organic compounds. It is preferred to use acidic organic compounds, that is to say acidic low molecular weight organic compounds or acidic polymeric organic compounds. These can be used either in the form of the free acid or in partially neutralized form. In the context of the present invention, the term “organic acid” therefore includes both the organic acids in free form and in partially neutralized form.

Alkali metal ions, in particular Na ions, are preferred as counterions.

Suitable binders include organic fatty acids with 8 to 22 carbon atoms, such as lauric acid, myristic acid, stearic acid or mixtures thereof. Farther organic polymers are preferred. The organic polymers can be anionic, cationic or amphoteric in nature. Natural organic polymers and modified organic polymers of natural origin can be used as well as synthetic organic polymers.

The group of organic polymers used with particular preference as binders include polyvinyl alcohols including their acetalized derivatives, polyvinylpyrrolidones and polyalkylene glycols, in particular polyethylene glycols.

Polyvinyl alcohols, which can preferably be used as binders, are described in more detail below in the description of the polyvinyl alcohols which form the coating.

The anionic polymers used with particular preference as binders are, in particular, homo- or copolymeric polycarboxylates. For example, polyacrylic acid or polymethacrylic acid, in particular those with a relative molecular weight of 500 to 70,000 g / mol, are preferably used.

Preferred among these are polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their solubility, the short-chain polyacrylates, which have molar masses from 2,000 to 10,000 g / mol and preferably from 3,000 to 5,000 g / mol, are again preferred from this group.

Also preferred among these are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven particularly suitable. Their relative molecular weight, based on free acids, is preferably 2,000 to 70,000 g / mol, particularly preferably 20,000 to 50,000 g / mol and particularly preferably 30,000 to 40,000 g / mol.

To improve the water solubility, the polymers can also have structural units derived from allylsulfonic acids. such as allyloxybenzenesulfonic acid and methallylsulfonic acid. Biological are also particularly preferred Degradable polymers from more than two different monomer units, for example those, the structural units from salts of acrylic acid and maleic acid and from vinyl alcohol or vinyl alcohol derivatives and sugar derivatives or the structural units from salts of acrylic acid and 2-alkylallylsulfonic acid and from sugar derivatives contain.

Further preferred copolymers are those which have structural units derived from acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Further anionic polymers used with preference as binders are polymers containing sulfonic acid groups, in particular copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers.

Further preferred binders are C ₈ -C ₂₂ alcohol ethoxylates which _{are solid at room temperature, preferably C 8} -C ₂₂ alcohol ethoxylates with an average of 10 to 100 ethylene oxide units in the molecule, such as Genapol® T 500 from Clariant or carboxymethyl celluloses.

The low molecular weight organic acids likewise preferably used as binders can likewise be used either in the form of the free acid or in partially neutralized form. Low molecular weight organic acids used with preference are citric acid, ascorbic acid, oxalic acid and adipic acid. Succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, fatty acids and mixtures of these.

Low molecular weight organic acids which are particularly preferably used are oxalic acid, ascorbic acid, citric acid and fatty acids.

The granulate according to the invention has a small amount of coating made of polyvinyl alcohol, which ensures storage stability even in tablet formulations. According to the invention, the proportion of the protective or coating layer in the total granulate is 0.1 to 3% by weight, and in particular 1 to 3% by weight.

Typical polyvinyl alcohols used according to the invention to form the envelope or as a binder have a number average molecular weight in the range from 10,000 to 200,000 (measured at 20 ° C. using the gel permeation chromatography (GPC) method) (corresponding to the viscosity of a 4% aqueous solution 20 ° C from approx. 2 to 70 mPa * s; measured with the falling ball viscometer according to Höppler, DIN 53015).

Polyvinyl alcohol is generally made by saponifying polyvinyl acetate.

Particularly suitable polyvinyl alcohol has a degree of hydrolysis of 70 to 100 mol% and its aqueous solution has a Höppler viscosity at 20 ° C. of 2 to 70 mPa * s.

Further suitable polyvinyl alcohols can have been modified hydrophobically or hydrophilically in any way.

Examples of hydrophobically modified polyvinyl alcohols which contain water-insoluble monomer units in their main chain are ethylene-containing polyvinyl alcohols of the Exceval® type from Kuraray.

Another possibility is the modification by grafting reactions on the alcohol groups, such as the partial acetalization of the alcohol groups of the polyvinyl alcohol, whereby the polyvinyl alcohols can be equipped with any radicals that can be either hydrophobic or hydrophilic, such as polyvinyl alcohols of the Mowiflex® type from Kuraray.

The modified radicals can be arranged in blocks or randomly.

Polyvinyl alcohols and acetalized polyvinyl alcohols used with preference have molecular weights in the range from 10,000 to 200,000 g / mol, preferably from 11,000 to 90,000 g / mol, particularly preferably from 12,000 to 80,000 g / mol and particularly preferably from 13,000 to 70,000 g / mol. Polyethylene glycols used with preference have molar masses in the range from 200 to 5,000,000 g / mol, corresponding to degrees of polymerization from 5 to> 100,000.

In the production of the casing, mixtures of different polyvinyl alcohols or mixtures of polyvinyl alcohols with other organic polymers or low molecular weight compounds can be used. The casing consists to a by far predominant proportion of polyvinyl alcohol or mixtures thereof, that is to say at least 80% by weight of polyvinyl alcohol or mixtures thereof, based on the total weight of the casing.

Colorants can optionally also be added to the granules according to the invention. Dyes can be in the granulate core and / or in the casing. Dyes are preferably added to the granulate before it has been provided with a coating.

In a further preferred embodiment, the invention relates to granules containing, in addition to the components described above, further additives.

In this embodiment, the granules according to the invention can thus have bleach catalysts and / or bleach activators, optionally binders and further additives.

As further additives, for example, siccatives, such as calcium sulfate, come into consideration.

The granules according to the invention can be produced by processes known per se and have already been described in detail in the patent documents mentioned above. In principle, different granulation processes are possible.

In a first preferred variant of the process, build-up granulation takes place in mixing apparatus. Here, the components are processed in conventional, batch-wise or continuously working mixing devices, which are usually with rotating mixing elements are equipped. When mixing, all mixing variants that ensure sufficient mixing of the components are conceivable.

In a preferred embodiment, all components are mixed at the same time. However, multi-stage mixing processes are also conceivable in which the individual components are introduced into the overall mixture in various combinations, either individually or together with other additives.

The sequence of slow and high-speed mixers can be reversed as required. The residence times in the mixer granulation are preferably 0.5 s to 20 min, particularly preferably 2 s to 10 min. The granulating liquid can be pumped into the mixing apparatus via simple guide tubes. For better distribution, nozzle systems (single-fluid or multi-fluid nozzles) are also conceivable.

Depending on the granulation liquid used (solvent or molten binder), the granulation stage is followed by a drying (for solvents) or cooling step (for melts) in order to prevent the granules from sticking together. The coarse grain and fine grain fraction is then separated off by sieving. The coarse grain fraction is comminuted by grinding and, like the fine grain fraction, fed to a new granulation process. The coating is preferably applied in a fluidized bed apparatus, for example in a fluidized bed mixer, provided with a coating.

In a further preferred variant of the method, one or more plasticizers are added to the pulverulent constituents (bleach activator and / or bleach catalyst and, if appropriate, further auxiliaries). These can be entered as a liquid or as a melt, with melt-like substances being preferred.

The liquid plasticizer is intensively mixed with the powdery active substance and, if necessary, the other additives, so that a plastically deformable mass is created. The mixing step can take place in the above-mentioned mixing apparatus, but kneaders or special types of extruders are also conceivable. The granulating mass is then fed through the nozzle bores of a press die using tools pressed so that cylindrically shaped extrudates are produced. The emerging extrudates are to be comminuted to the desired length or particle size in a post-processing step. in many cases a length / diameter ratio of L / D = 1 is desired. In the case of cylindrical granules, the particle diameter is typically between 0.2 and 2 mm, preferably between 0.5 and 0.8 mm, and the particle length in the range from 0.5 to 3.5 mm. ideally between 0.9 and 2.5 mm. The length or size of the granules can be adjusted, for example, by fixed scraper blades, rotating cutting blades, cutting wires or blades. To round off the cut edges, the granulate can then be rounded again in a rounder.

After adjusting the size of the granules, a final solidification step is required in which the solvent is removed or the melt solidifies and then the coating is applied. This step is usually carried out in a fluidized bed apparatus which, depending on the requirements, is operated as a dryer or cooler. The coarse grain and fine grain fraction is then separated off by sieving. The coarse grain fraction is comminuted by grinding and, like the fine grain fraction, fed to a new granulation process. The granulate produced is then provided with a coating in a fluidized bed apparatus, for example in a fluidized bed mixer.

In a further preferred variant of the method, the powdered active substances are optionally mixed with other, preferably solid, additives and this mixture is compacted, then ground and then optionally sieved into individual particle size fractions. If necessary, liquid additives can also be added to the mixture to a certain extent (for example up to 10% by weight). Examples of compacting aids are water glass, polyethylene glycols, nonionic surfactants, anionic surfactants, polycarboxylate copolymers, modified and / or unmodified celluloses, bentonites, hectorites, saponites and / or other detergent ingredients.

The compaction is preferably carried out on so-called roller compactors (for example from Hosokawa-Bepex, Köppern). By choosing the roller profile, lumpy pellets or briquettes on the one hand and press sockets on the other hand can be produced.

While the lumpy compacts are usually only separated from the fines, the flakes have to be comminuted in a mill to the desired particle size. Typically, gentle types are preferably used as the type of mill. The comminuted particles are then provided with a coating in a fluidized bed apparatus, for example in a fluidized bed mixer.

The fine-grain fraction and, if necessary, the coarse-grain fraction are separated from the granulate produced in this way. The coarse grain fraction is fed back into the mill, the fine grain fraction is fed back into the compaction process. To classify the granules, common screening machines such as B. tumbler or vibrating screens are used.

The granules according to the invention are primarily characterized by their chemical composition. Nevertheless, it has been shown that the action of these granulates can also be advantageously influenced by influencing physical parameters, such as, for example, the particle size, the fine fraction and the content of bleach catalyst and / or bleach activator.

For this reason, preferred granules according to the invention have an average particle size between 0.1 and 1.6 mm, preferably between 0.2 and 1.2 mm and particularly preferably between 0.3 and 1.0 mm, each measured by sieve analysis.

In particularly granules according to the invention the volume Average primary particle size in the range of 1 preferred moves _f jm to 150 microns, and the final granules have a mean particle size of 0.1 to 1.6 mm.

Preferred granules according to the invention are further characterized in that their water content is less than 5% by weight (measured according to Karl Fischer), based on the total amount of the granules.

Particularly preferred granules according to the invention have a water content of less than 3% by weight, particularly preferably 0 to 2% by weight, based on the total amount of the granules.

The granules according to the invention are suitable for use in all detergents or cleaning agents, their use in agents for cleaning dishes, in particular for machine cleaning of dishes, having proven particularly advantageous.

The present invention therefore furthermore relates to the use of the granules according to the invention for the production of detergents and cleaning agents and, preferably, of agents for cleaning dishes.

The present invention also relates to detergents and cleaning agents, preferably agents for cleaning dishes, containing a granulate according to the invention.

Preferred washing and cleaning agents according to the invention, in particular the agents for cleaning dishes, contain the granules according to the invention in amounts between 0.1 and 10% by weight, preferably in amounts between 0.2 and 8% by weight and particularly preferably in Amounts between 0.5 and 6% by weight.

The detergents and cleaning agents according to the invention, in particular the agents for cleaning dishes, which can be in the form of granules, powder or tablet-like solids, but also in liquid or paste form, can, in addition to the granules according to the invention, in principle contain all known ingredients that are usual in such agents contain. The detergents and cleaning agents according to the invention, in particular the agents for cleaning dishes, can in particular contain builder substances, peroxygen compounds, enzymes, alkali carriers, surface-active surfactants, pH regulators, organic solvents and other auxiliaries such as glass corrosion inhibitors, silver corrosion inhibitors and foam regulators. The cogranulates according to the invention are suitable for use in both phosphate-containing and phosphate-free formulations.

1. i) 15 bis 65 Gew.-%, vorzugsweise 20 bis 60 Gew.-% einer wasserlöslichen Builderkomponente,
2. ii) 5 bis 20 Gew.-%, vorzugsweise 8 bis Gew.-%, einer Persauerstoffverbindung,
3. iii) 0,5 bis 6 Gew.-% eines erfindungsgemäßen Granulates, und
4. iv) 0 bis 50 Gew.-% weitere Zusatzstoffe wie Enzyme, Alkaliträger, oberflächenaktive Tenside, pH-Regulatoren, organische Lösungsmittel oder weitere Hilfsstoffe, wie Glaskorrosionsinhibitoren, Silberkorrosionsinhibitoren und Schaumregulatoren, jeweils bezogen auf das Gesamtgewicht des Wasch- und Reinigungsmittels.

Particularly preferred washing and cleaning agents, in particular agents for cleaning dishes, contain

1. i) 15 to 65% by weight, preferably 20 to 60% by weight of a water-soluble builder component,
2. ii) 5 to 20% by weight, preferably 8 to% by weight, of a peroxygen compound,
3. iii) 0.5 to 6% by weight of a granulate according to the invention, and
4. iv) 0 to 50% by weight of other additives such as enzymes, alkali carriers, surface-active surfactants, pH regulators, organic solvents or other auxiliaries such as glass corrosion inhibitors, silver corrosion inhibitors and foam regulators, each based on the total weight of the detergent and cleaning agent.

Such an agent is in particular lower alkaline, i. H. its 1% by weight solution has a pH in the range from 8 to 11.5 and preferably from 9 to 11.

Water-soluble builder components in the detergents and cleaning agents according to the invention, in particular the agents for cleaning dishes, are in principle all builders typically used in such agents. Examples are alkali metal phosphates, which can be 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 be in the range from 15 to about 65% by weight, preferably from 20 to 60% by weight, based on the total agent. In addition to polyphosphonates and phosphonate alkyl carboxylates, other possible water-soluble builder components are, for example, organic polymers of native or synthetic origin of the polycarboxylate type, which act as co-builders in hard water regions in particular. For example, polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids are suitable. Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF. The polymers of native origin which can be used as co-builders include, for example, oxidized ones Starch and polyamino acids such as polyglutamic acid or polyaspartic acid. Further possible water-soluble builder components are naturally occurring hydroxycarboxylic acids such as, for example, mono-, dihydroxysuccinic acid, alpha-hydroxypropionic acid and gluconic acid. The preferred organic water-soluble builder components include the salts of citric acid, in particular sodium citrate. Anhydrous trisodium citrate and preferably trisodium citrate dihydrate come into consideration as sodium citrate. Trisodium citrate dihydrate can be used as a finely or coarsely crystalline powder. Depending on the pH value ultimately set in the detergents and cleaning agents according to the invention, in particular the agents for cleaning dishes, the acids corresponding to the co-builder salts mentioned can also be present. Particularly preferred builder components in phosphate-free formulations are methyl glycine diacetate (MDGA, e.g. Trilon® M, BASF), L-glutamic acid, N, N, (biscarboxymethyl) tert-sodium salt (GLDA, Dissolvine® DL, Akzo Nobel), sodium -Polyaspartates (Baypure®, Lanxess) or salts of iminodisuccinic acid (Baypure®, Lanxess).

Preferred peroxygen compounds used in the detergents and cleaning agents according to the invention, in particular the agents for cleaning dishes, are perborates and percarbonates, in particular the corresponding sodium salts of these compounds.

The enzymes optionally contained in detergents and cleaning agents according to the invention, in particular the agents for cleaning dishes, 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 ™, Lipornax ™, Lumafast ™ and / or Lipozym ™ . The enzymes used can be adsorbed on carrier substances and / or embedded in coating substances in order to protect them against premature inactivation. They are contained in the detergents and cleaning agents according to the invention, in particular the agents for cleaning dishes, preferably in amounts of up to 10% by weight and particularly preferably in amounts of 0.05 to 5% by weight, with particular preference being given to oxidative degradation stabilized enzymes are used.

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

In a further preferred embodiment of the invention, the detergents and cleaning agents according to the invention, in particular the agents for cleaning dishes, contain from 20 to 60% by weight of water-soluble organic builders, in particular alkali citrate, from 3 to 20% by weight of alkali metal carbonate and from 3 to 40% by weight .-% contain alkali disilicate.

Surfactants, in particular anionic surfactants, zwitterionic surfactants and preferably low-foaming nonionic surfactants, which facilitate better removal of greasy soiling, as wetting agents and optionally during production, can optionally also be added to the detergents and cleaning agents according to the invention, especially the agents for cleaning dishes these agents serve as granulating 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.

Extremely low-foam compounds are usually used, especially in agents for machine cleaning of dishes. These include preferably C ₁₂ -C ₁₈ -alkyl polyethylene glycol polypropylene glycol ethers with up to 8 mol of ethylene oxide and propylene oxide units in each molecule. However, other known low-foam nonionic surfactants can also be used, such as, for example C ₁₂ -C ₁₈ alkyl polyethylene glycol polybutylene glycol ethers each with up to 8 mol ethylene oxide and butylene oxide units in the molecule, end-capped alkyl polyalkylene glycol mixed ethers and the foaming but ecologically attractive C ₈ -C ₁₄ alkyl polyglucosides with a degree of polymerization of about 1 to 4 and / or C ₁₂ -C ₁₄ alkyl polyethylene glycols with 3 to 8 ethylene oxide units in the molecule. Surfactants from the glucamides family, such as, for example, alkyl-N-methyl-glucamides, in which the alkyl moiety is preferably derived from a fatty alcohol with a carbon chain length of C ₆ -C ₁₄ , are also suitable. It is sometimes advantageous if the surfactants described are used 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.

To set a desired pH value that does not result from the mixture of the other components, the detergents and cleaning agents according to the invention, in particular the agents for cleaning dishes, acids that are compatible with the system and the environment, 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 hydrogen sulfates, or bases, in particular ammonium or alkali hydroxides. Such pH regulators are contained in the detergents and cleaning agents according to the invention, in particular the agents for cleaning dishes, preferably not more than 10% by weight and particularly preferably from 0.5 to 6% by weight, based in each case on the Total weight of the agent.

The organic solvents that can be used in the detergents and cleaning agents according to the invention, especially the agents for cleaning dishes, especially when they are in liquid or pasty form, include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert .-Butanol, diols having 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the ethers which can be derived from the classes of compounds mentioned. Such water-miscible solvents are in the detergents and cleaning agents according to the invention, in particular in the agents for cleaning dishes, preferably present in an amount not exceeding 20% by weight and more preferably from 1 to 15% by weight.

In order to prevent glass corrosion during the wash cycle, appropriate inhibitors can be used in the detergents and cleaning agents according to the invention, in particular the agents for cleaning dishes. Crystalline layered silicates and / or zinc salts are particularly advantageous here. The crystalline layered silicates are sold, for example, by WeylChem Wiesbaden GmbH under the trade name Na-SKS, z. B. Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ · H ₂ O, kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O _{29 ·} H ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ · H ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O _{9 ·} xH ₂ O, macatite). Of these, Na-SKS-5 (alpha-Na ₂ Si ₂ O ₆ ), Na-SKS-7 (beta-Na ₂ Si ₂ O ₆ , natrosilite), Na-SKS-9 (NaHSi ₂ O _{5 ·} H ₂ O), Na-SKS-10 (NaHSi ₂ O _{5 ·} 3H ₂ O, Kanemite), Na-SKS-11 (t-Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (delta-Na ₂ Si ₂ O ₅ ). An overview of crystalline sheet silicates can be found e.g. B. in the in " Seifen-Öle-Fette-Wachse, 116 year, No. 20/1990 ", on pages 805-808 published article.

In a further preferred embodiment, the detergents and cleaning agents according to the invention, in particular the agents for cleaning dishes, have an amount of the crystalline layered silicate of 0.1 to 20% by weight, particularly preferably 0.2 to 15% by weight and particularly preferably 0.4 to 10% by weight, based in each case on the total weight of the agent.

To suppress glass corrosion, detergents and cleaning agents according to the invention, in particular agents for cleaning dishes, contain at least one zinc or bismuth salt, preferably selected from the group of organic zinc salts, particularly preferably selected from the group of soluble organic zinc salts, particularly preferably selected from the group of soluble zinc salts of monomeric or polymeric organic acids and extremely preferably selected from the group of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc oxalate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate. Alternatively or in combination with these zinc salts, bismuth salts such as. B. bismuth acetates are used.

In the context of the present invention, washing and cleaning agents according to the invention, in particular agents for cleaning dishes, in which the amount of zinc salt based on the total weight of this agent is 0.1 to 10% by weight, preferably 0.2 to 7% by weight and particularly preferably 0.4 to 4% by weight, regardless of which zinc salts are used, in particular regardless of whether organic or inorganic zinc salts, soluble or insoluble zinc salts or mixtures thereof are used.

In order to provide silver corrosion protection, silver corrosion inhibitors can be used in the detergents and cleaning agents according to the invention, in particular in the agents for cleaning dishes. Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, hafnium, cobalt or cerium salts and / or complexes in which the named Metals are in one of the oxidation states II, III, IV, V or VI, depending on the metal.

If the detergents and cleaning agents according to the invention, in particular the agents for cleaning dishes, for example in the presence of anionic surfactants, foam too much during use, up to 6% by weight, preferably about 0.5 to 4% by weight, can be added to them .-% of a foam-suppressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, the bis-fatty acid amides, and other other known commercially available defoamers.

The detergents and cleaning agents according to the invention, in particular the agents for cleaning dishes, can be used as further ingredients, for example sequestering agents, electrolytes, additional peroxygen activators, dyes or fragrances, such as, for example, from the prior art for such agents. B. perfume oils contain.

The production of the solid detergents and cleaning agents according to the invention, in particular the agents for cleaning dishes, presents no difficulties and can in principle in a known manner, for example by spray drying or Granulation, take place, with the peroxygen compound and co-granules according to the invention optionally being added later separately.

Detergents and cleaning agents according to the invention in the form of aqueous solutions or solutions containing other customary solvents, in particular corresponding agents for cleaning dishes, are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.

The detergents and cleaning agents according to the invention, in particular agents for cleaning dishes, are preferably in the form of powdery, granular or tablet-shaped preparations that can be prepared in a manner known per se, for example by mixing, granulating, roller compacting and / or by spray drying of thermally stressable components and Mixing of the more sensitive components, to which in particular enzymes, bleaching agents and the bleaching catalyst are to be included, can be produced.

To produce detergents and cleaning agents according to the invention, in particular agents for cleaning dishes, in tablet form, the preferred procedure is to mix all of the ingredients together in a mixer and to apply the mixture using conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the area from 200 · 10 ⁵ Pa to 1500 · 10 ⁵ Pa.

In this way, unbreakable tablets that dissolve sufficiently quickly under the intended use conditions and with flexural strengths of normally over 150 N are obtained without any problems. A tablet produced in this way preferably has a weight of 15 to 40 g, in particular 20 to 30 g, with a diameter of 35 up to 40 mm.

The production of detergents and cleaning agents according to the invention in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range from 800 to 1,000 g / l, in particular corresponding agents according to the invention for cleaning dishes, can be carried out in that in a first process stage, the builder components are mixed with at least a portion of liquid mixture components, increasing the bulk density of this premix, and subsequently - if desired after intermediate drying - the other constituents of the agent, including the granulate according to the invention, are combined with the premix obtained in this way.

Agents according to the invention for the machine cleaning of dishes can be used both in domestic dishwashers and in commercial dishwashers. The addition is done by hand or by means of suitable metering devices. The use concentrations in the cleaning liquor are generally about 1 to 8 g / l, preferably 2 to 5 g / l.

A machine wash program is expediently supplemented and ended by a few intermediate wash cycles with clear water and a rinse cycle with a common rinse aid. After drying, when the agents according to the invention are used, completely clean and hygienically perfect crockery is obtained.

Examples

In the following examples, percentages mean percentages by weight, unless explicitly stated otherwise.

Example 1 and comparative examples V1 and V2 example 1

Commercially available uncoated bleach activator granules were coated on a fluidized bed spray granulation system of the Glatt AG400 type by spraying on an aqueous solution of polyvinyl alcohol. Peractive® FDO-X bleach activator granules were used (commercial product from WeylChem Wiesbaden GmbH). These contained a bleach catalyst (MnTACN) and a bleach activator (TAED) as well as the acidic polymer Sokalan® CP 45 (polyacrylate, sodium salt, commercial product from BASF SE). As polyvinyl alcohol, that was Product Poval® 6-88 (commercial product from Kuraray) was used. The amount of polyvinyl alcohol was chosen so that the portion of the coating in the finished product was 3%.

Comparative example V1

The procedure was as in Example 1, with the change that the amount of polyvinyl alcohol was chosen so that the portion of the coating in the finished product was 6%.

Comparative example V2

This was the uncoated product Peractive® FDO-X (commercial product from WeylChem Wiesbaden GmbH).

Application example - storage test in machine dishwashing detergent

To check the physical stability of the granules according to the invention, the storage behavior in a typical machine dishwashing detergent was investigated. The mixtures could then be stored for several weeks in a room climate and more severe climatic conditions (T = 40 ° C, 75% relative humidity).

Application examples - bleaching performance

Corresponding amounts of the unstored granules 1, V1 and V2 were added to 20 g of the IEC-C machine dishwashing detergent, so that 4 mg of bleach catalyst (calculated as 100% active) were present in each case in the formulation. The formulations were used to put 6 teacups each (soiled according to the IKW test protocol) in an automatic dishwasher (Miele G 688 SC) according to the IKW test protocol (IKW test method; ( SOFW, 132 (8), 2006, 35 - 49 ) in the 45 ° C fine wash program. The evaluation was done optically; 0% performance = no tea removal, 100% performance: complete removal of tea stains. The tests were repeated 3 times in each case and the mean value was formed. The pH value was measured in the dishwasher during the cleaning cycle.

The following table shows an overview of the test results after 4 weeks of storage granules V1 V2 1 Pale - [%] performance 60 62 90

It was found that the granules coated according to the invention had a significantly improved performance compared to the uncoated granules or to the granules which contained a larger amount of coating.

Comparative examples C3 to C5 Comparative example C3

Commercially available uncoated bleach activator granules were coated on a fluidized bed spray granulation system of the Glatt AG400 type by spraying on an aqueous solution of polyvinyl alcohol. Bleach activator granules without a bleach catalyst were used. The granules contained bleach activator (TAED) and the acidic polymer Sokalan® CP 45 (polyacrylate, sodium salt, commercial product from BASF SE). The product Poval® 6-88 (commercial product from Kuraray) was used as the polyvinyl alcohol. The amount of polyvinyl alcohol was chosen so that the portion of the coating in the finished product was 3%.

Comparative example V4

The procedure was as in Comparative Example C3, with the change that the amount of polyvinyl alcohol was chosen so that the proportion of the coating in the finished product was 6%.

Comparative example V5

This was the uncoated bleach activator granules without a bleach catalyst which had been used as starting material in Comparative Examples C3 and C4.

Application examples - bleaching performance of coated granules with bleach activator and without bleach catalyst (MnTACN) with PVOH after storage

Corresponding amounts of the unstored granules V3, V4 and V5 were added to 20 g of the IEC-C machine dishwashing detergent, so that 4 mg of bleach activator (calculated as 100% active) were present in each case in the formulation. The formulations were used to put 6 teacups each (soiled according to the IKW test protocol) in an automatic dishwasher (Miele G 688 SC) according to the IKW test protocol (IKW test method; ( SOFW, 132 (8), 2006, 35 - 49 ) in the 45 ° C fine wash program. The evaluation was done optically; 0% performance = no tea removal, 100% performance: complete removal of tea stains. The tests were repeated 3 times in each case and the mean value was formed. The pH value was measured in the dishwasher during the cleaning cycle.

The following table shows an overview of the test results after 4 weeks of storage at 40 ° C:
The following table shows an overview of the test results after 4 weeks of storage granules V3 V4 V5 Pale - [%] performance 31 32 32

Examples 2, V6 and V7 Example 2

Commercially available uncoated bleach catalyst granules were coated by spraying an aqueous solution of polyvinyl alcohol on a fluidized bed spray granulation system of the Glatt AG400 type. Bleach catalyst granules without a bleach activator were used. The granules contained bleach catalyst (MnTACN) as well as sodium sulfate, citric acid and rice starch. The product Poval® 6-88 (commercial product from Kuraray) was used as the polyvinyl alcohol. The amount of Polyvinyl alcohol was chosen so that the amount of coating in the finished product was 3%.

Comparative example C6

The procedure was as in Example 2, with the change that the amount of polyvinyl alcohol was chosen so that the portion of the coating in the finished product was 6%.

Comparative example C7

This was the uncoated bleach catalyst granulate without bleach activator, which had been used as starting material in Example 2 and in Comparative Example C6.

Application example - bleaching performance of coated granules with bleach catalyst (MnTACN) and without bleach activator with PVOH after storage

Corresponding amounts of the unstored granules 2, V6 and V7 were added to 20 g of the IEC-C machine dishwashing detergent, so that in each case 4 mg of bleach catalyst (calculated as 100% active) were present in the formulation. The formulations were used to put 6 teacups each (soiled according to the IKW test protocol) in an automatic dishwasher (Miele G 688 SC) according to the IKW test protocol (IKW test method; ( SOFW, 132 (8), 2006, 35 - 49 ) in the 45 ° C fine wash program. The evaluation was done optically; 0% performance = no tea removal, 100% performance: complete removal of tea stains. The tests were repeated 3 times in each case and the mean value was formed. The pH value was measured in the dishwasher during the cleaning cycle.

The following table shows an overview of the test results after 4 weeks of storage at 40 ° C: granules V6 V7 2 Pale - [%] performance 52 50 92

Claims (14)

1. Granules containing one or more bleaching catalysts selected from the group of manganese salts or manganese complexes and at least one binder selected from the group of acidic organic compounds, wherein the granules are coated with 0.1 to 3 % by weight, referring to the total amount of the granules, with a polyvinyl alcohol containing coating, wherein the coating comprises at least 80 % by weight of polyvinyl alcohol or mixtures thereof, in relation to the total weight of the coating.
2. Granules according to claim 1, characterized in that these contain one or more bleaching activators and one or more bleaching catalysts selected from the group of manganese salts or manganese complexes.
3. Granules according to claim 2, characterized in that these contain, in relation to the total weight of the granules,

   a) 1 to 90 % by weight of one or more bleaching activators,

   b) 0.01 to 30 % by weight of one or more bleaching catalysts selected from the group of manganese salts or manganese complexes, and

   c) 1 to 30 % by weight of one or more binders.
4. Granules according to claim 3, characterized in that these contain, in relation to the total weight of the granules,

   a) 50 to 85 % by weight of one or more bleaching activators,

   b) 0.1 to 20 % by weight of one or more bleaching catalysts selected from the group of manganese salts or manganese complexes, and

   c) 1 to 20 % by weight of one or more binders.
5. Granules according to at least one of claims 1 to 3, characterized in that these contain, in relation to the total weight of the granules, 1 to 3 % by weight of a coating of polyvinyl alcohol.
6. Granules according to claim 1, characterized in that these contain, in relation to the total weight of the granules,

   a) 50 to 85 % by weight of one or more bleaching activators,

   b) 0.1 to 20 % by weight of one or more bleaching catalysts selected from the group of manganese salts or manganese complexes;

   c) 5 to 20 % by weight of a low molecular and/or polymer organic acid,

   d) 0 to 20 % by weight of a binder that is no organic acid according to component c), and

   e) 1 to 3 % by weight of a coating made of polyvinyl alcohol.
7. Granules according to at least one of claims 1 to 6, characterized in that these contain tetraacetylethylene diamine or decanoyloxy benzoic acid as bleach activators.
8. Granules according to claim 1, characterized in that the bleaching catalysts are selected from the group consisting of manganese sulfate, manganese acetate, manganese oxalate, [Mn^III ₂(µ-O)₁(µ-OAc)₂(TACN)₂](PF₆)₂, [Mn^IV ₂(µ-O)₃(Me-TACN)₂](PF₆)₂, [Mn^IV ₂(µ-O)₃(Me-TACN)₂](SO₄), [Mn^IV ₂(µ-O)₃(Me-TACN)₂](OAc)₂, [Mn^IV ₂(µ-O)₃(Me-TACN)₂](Cl)₂, [Mn^IV ₂(µ-O)₃(Me4-DTE)](PF₆)₂, [Mn^IV ₂(µ-O)₃(Me4DTE)](Cl)₂, [Mn^IV ₂(µ-O)₃(Me4-DTE)](SO₄), [Mn^IV ₂(µ-O)₃(Me4-DTE)](OAc)₂, 1.8-diethyl-1.4.8.11-tetraazacyclotetradecane-manganese (II) chloride or 1.4.8.11-tetraazacyclotetradecane-manganese (II) chloride.
9. Granules according to claim 1, characterized in that the bleaching catalysts are selected from the group of mono- or dinuclear complexes of manganese, which contain at least one ligand of general formulae A or B

   

   with R = H, CH₃, C₂H₅, or C₃H₇.
10. Granules according to at least one of claims 1 to 9, characterized in that these contain as a binder a homo-or copolymer polycarboxylate, in particular polyacrylic acid or polymethacrylic acid.
11. Granules according to at least one of claims 1 to 10, characterized in that the polyvinyl alcohol has a degree of hydrolysis of 70 to 100 mol % and that its aqueous solution has a viscosity according to Höppler at 20 °C, determined according to DIN 53015, of 2 to 70 mPa * s.
12. Use of the granules according to at least one of claims 1 to 11 for the production of detergents and cleaning agents.
13. Detergents and cleaning agents containing granules according to at least one of claims 1 to 11.
14. Detergents and cleaning agents according to claim 13, characterized in that this is an agent for cleaning dishes.