EP2417238B1 - Bleach granules - Google Patents

Description

The present invention relates to bleach granules, to a process for their preparation and to their use in detergents and cleaners, in particular in detergents for dishwashing.

In order to obtain spotless dishes, persalts such as perborates and percarbonates are used in automatic dishwasher detergents. In order to activate these bleaching agents and to achieve an improved bleaching effect during cleaning at temperatures of 60 ° C. and below, automatic dishwashing detergents generally also contain bleach activators or bleach catalysts, with the bleach catalysts in particular having proven to be particularly effective.

Bleach catalysts are used in automatic dishwasher detergents, preferably in the form of prefabricated granules, in order to increase their storage stability. So describe EP 0 458 397 . EP 0 458 398 . EP 0 530 870 . EP 0 710 714 and WO 03/093405 Bleach catalysts based on various manganese-containing transition metal complexes. Process for the preparation of bleach catalyst granules are described in EP 0 544 440 . WO 95/06710 and WO 2008/069935 disclosed. Characteristic of the processes described therein is the use of large amounts of inert materials as carriers and binders, which are optionally used as melts, this method includes cooling and / or drying stages, which requires the use of additional equipment such as fluidized bed plants.

However, the germicidal effect of bleach catalysts is low in most cases. The performance of bleaching agents in automatic dishwashing detergents is therefore higher if they consist of a combination of a bleach catalyst with a 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 significantly contributes to germ killing on the dishes, improves the smell of the wash liquor and prevents the Training a biofilm in the dishwasher. The combination of bleach catalysts and bleach activators is therefore useful for increasing the bleaching performance and ensuring hygiene in the use of bleaching agents in laundry detergents and cleaners. So describes EP 0 616 029 a bleaching additive consisting of a dry mixture of percarbonate, a TAED granules and a bleach catalyst granules. Also in this case, the bleach catalyst granules only has an active content of 1.2 wt .-%, the rest consists of support materials and / or binder.

The use of activators and catalysts in separate granules, however, has disadvantages that may adversely affect the bleaching performance. The reactions of the persalt, or of the hydrogen peroxide released therefrom with activator and catalyst take place in parallel. Dissolves the catalyst granules faster than the activator granules, the persalt is already consumed before it can react with the activator. The same applies to the opposite case. Co-granules of activators and 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 manufacturing costs are reduced, since instead of two different granules, only one co-granulate must be produced.

EP 1 499 702 describes co-granules consisting of a bleach catalyst, a bleach activator, and optionally a coating. Optionally, stabilizers such as antioxidants, reducing agents or acids may be present in amounts up to 2.5% by weight. The co-granules are characterized in that the particles have a moisture content of <0.5 wt .-% and a moisture absorption of not more than 0.5 wt .-%. To ensure this, the humidity in the ambient air during manufacture must be kept below 40%, preferably below 25%. This naturally results in production-related disadvantages.

The present invention therefore an object of the invention to provide bleach activator bleach catalyst co-granules, which compared to the State of the art known granules characterized by increased storage stability and simplified manufacturability.

Surprisingly, it has now been found that this object is achieved and the storage stability and thus the preservation of the bleaching activity in such co-granules in detergents and cleaners can be increased if the co-granules, based on the total weight of the co-granules, a) B) from 0.1 to 20% by weight of one or more metal-containing bleach catalysts, c) from 5 to 20% by weight of one or more organic acids selected from citric acid, ascorbic acid, oxalic acid , Adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids and aminocarboxylic acids and d) from 1 to 20% by weight of one or more binders which are not organic acids according to component c).

The moisture absorption during production and storage does not matter. In the co-granules according to the invention it is also possible to incorporate slightly hygroscopic components without their storage stability being impaired.

1. a) 50 bis 85 Gew.-% eines oder mehrerer Bleichaktivatoren
2. b) 0,1 bis 20 Gew.-% eines oder mehrerer metallhaltiger Bleichkatalysatoren
3. c) 5 bis 20 Gew.-% einer oder mehrerer organischen Säuren ausgewählt aus Citronensäure, Ascorbinsäure, Oxalsäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren und Aminocarbonsäuren und
4. d) 1 bis 20 Gew.-% eines oder mehrerer Bindemittel, die keine organischen Säuren gemäß Komponente c) sind.

The present invention therefore relates to co-granules containing, based on the total weight of the co-granules,

1. a) 50 to 85 wt .-% of one or more bleach activators
2. b) 0.1 to 20 wt .-% of one or more metal-containing bleach catalysts
3. c) 5 to 20 wt .-% of one or more organic acids selected from citric acid, ascorbic acid, oxalic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids and aminocarboxylic acids and
4. d) 1 to 20 wt .-% of one or more binders which are not organic acids according to component c).

Bleach activators

As bleach activators, the co-granules according to the invention may be polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyloxy or n-lauroyl oxbenzenesulfonate (NOBS or LOBS), acylated phenolcarboxylic acids, in particular nonanoyloxy or decanoyloxibenzoic acid (NOBA or DOBA), Carboxylic acid anhydrides, 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 mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfraktose, tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated it contains glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably 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 conventional bleach activators can also be used. Particularly preferred bleach activators are TAED and DOBA.

bleach catalysts

Bleach catalysts used in the context of the present invention are preferably bleach-enhancing transition metal salts or complexes of manganese, iron, cobalt, ruthenium, molybdenum, titanium or vanadium.

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

Also preferred are complexes of iron in oxidation states II or III and manganese in oxidation state II, III, IV or IV, preferably one or more macrocyclic ligand (s) having the donor functions N, NR, PR, O and / or S included. Preferably, ligands are used which have nitrogen donor functions.

Complexes which are preferably used as transition metal complexes in the co-granules according to the invention are complexes which contain, as macromolecular ligands, 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 the cyclam or Cyclens such as 1,8-dimethyl cyclam, 1,7-dimethylcycles, 1,8-diethyl cyclic, 1,7-diethyl, 1,8-dibenzyl cyclam and 1,7-dibenzyl contain such. In EP 0 458 397 . EP 0 458 398 . EP 0 549 272 . WO 96/06154 . WO 96/06157 or WO 2006/125517 but also manganese complexes, as they are EP 1 445 305 . EP 1 520 910 or EP 1 557 457 are known.

Suitable manganese complexes are, for example, [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (PF ₆ ) ₂ , [Mn ^IV (μ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ] ₂ , [Mn ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (SO ₄ ), [Mn ^IV ₂ (NO) 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 ( Me4-DTE)] Cl2, [Mn ^IV ₂ (μ-O) ₃ (Me4-DTE)] (SO ₄₎ [Mn ^IV ₂ (μ-O) ₃ (Me4-DTE)] (OAc) _2, cis - (1,4,8,11-tetraazacyclotetradecane) dichloroiron (III) chloride, trans- (1,4,8,11-tetraazacyclotetradecane) dichloro-iron (III) chloride, 1,8-diethyl-1,4,8 , 11-tetraazacyclotetradecane-iron (II) chloride, 1,8-diethyl-1,4,8,11-tetraazacyclotetradecane manganese (II) chloride and [Mn ^IV ₂ (μ-O) ₃ (Me4-DTE)] (OAc) 2, cis- (1,4,8,11-tetraazacyclotetradecane) dichloroiron (III) chloride, trans (1,4,8,11 Tetraazacyclotetradecane) dichloro-iron (III) chloride, 1,8-diethyl-1,4,8,11-tetraazacyclotetradecane-iron (II) chloride, 1,8-diethyl-1,4,8,11-tetraazacyclotetradecane manganese (II) chloride and 1,4,8,11-tetraazacyclotetradecane manganese (II) chloride.

Particularly preferred metal-containing bleach catalysts are selected from manganese salts and manganese complexes, wherein among the manganese salts in turn salts selected from manganese sulfate, manganese acetate and manganese oxalate are preferred, and among the manganese complexes complexes turn is selected from: [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 (Me4-DTE)] Cl ₂ , [Mn ^IV ₂ (μ-O) ₃ (Me4-DTE)] (SO ₄₎ [Mn ^IV ₂ (NO) ₃ (Me4-DTE)] (OAc) _2, cis- (1,4,8,11-tetraazacyclotetradecane) dichloroeisen (III) chloride, trans- (1,4,8,11-tetraazacyclotetradecane) dichloro-iron (III) chloride, 1,8-diethyl-1,4,8,11-tetraazacyclotetradecane-iron (II) chloride, 1,8-diethyl-1 , 4,8,11-tetraazacyclotetradecane manganese (II) chloride and 1,4,8,11-tetraazacyclotetradecane manganese (II) chloride are preferred.

Organic acids

As the organic acid, acids 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.

Particularly preferred counterions are Na ions.

Suitable organic acids are citric acid, ascorbic acid, oxalic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids and mixtures of these. Particularly preferred organic acids are citric acid, ascorbic acid and oxalic acid.

binder

As a further ingredient, the co-granules according to the invention preferably contain a binder in order to ensure the cohesion of the co-granules.

As binders, substances selected from alcohol ethoxylates and polymers can preferably be used. Among the polymers here are synthetic and natural polymers understood as well as modified polymers of natural origin.

Suitable are u. a. organic fatty acids having 8 to 22 carbon atoms, such as lauric acid, myristic acid, stearic acid or mixtures thereof. Further preferred are organic polymers. The polymers may be nonionic, anionic, cationic or amphoteric in nature. Natural polymers and modified polymers of natural origin are usable as well as synthetic polymers.

The group of nonionic polymers used with particular preference as binders include polyvinyl alcohols, acetalated polyvinyl alcohols, polyvinylpyrrolidones and polyalkylene glycols, in particular polyethylene oxides. Preferred polyvinyl alcohols and acetalated polyvinyl alcohols have molecular weights in the range from 10,000 to 100,000 g / mol, preferably from 11,000 to 90,000 g / mol, more preferably from 12,000 to 80,000 g / mol and particularly preferably from 13,000 to 70,000 g / mol. Preferred polyethylene oxides have molecular weights in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000.

The anionic polymers used with particular preference as binders are in particular homo- or copolymeric polycarboxylates. Preference is given to using, for example, polyacrylic acid or Polymethacrylic acid, especially those having a molecular weight of 500 to 70,000 g / mol.

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

Of these, furthermore preferred are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of 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 to be particularly suitable. Their molecular weight relative to free acids is preferably 2,000 to 70,000 g / mol, more preferably 20,000 to 50,000 g / mol, and particularly preferably 30,000 to 40,000 g / mol.

To improve the solubility in water, the polymers may also contain structural units derived from allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid. Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain 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-alkylallyl sulfonic acid and from sugar derivatives.

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

Other anionic polymers used with preference as binders are sulfonic acid-containing polymers, in particular copolymers unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other 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 from 10 to 100 ethylene oxide units in the molecule, such as, for example, B. Genapol ^® T 500 from Clariant or carboxymethylcelluloses.

In a further preferred embodiment of the invention, the co-granules according to the invention are not provided with a protective layer (coating).

In a further preferred embodiment of the invention, the co-granules according to the invention are provided with a protective layer, whereby the storage stability is ensured even in tableted formulations. The proportion of the protective or coating layer in the total granules should then be at least 3% by weight, preferably at least 5% by weight, more preferably at least 7% by weight and especially preferably at least 15% by weight. The upper limit of the content of the protective or coating layer on the total granulate is preferably 30% by weight.

1. a) 50 bis 85 Gew.-% eines Bleichaktivators
2. b) 0,1 bis 20 Gew.-% eines metallhaltigen Bleichkatalysators
3. c) 5 bis 20 Gew.-% einer organischen Säure ausgewählt aus Citronensäure, Ascorbinsäure, Oxalsäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren, Aminocarbonsäuren sowie Mischungen aus diesen,
4. d) 1 bis 20 Gew.-% eines Bindemittels, das keine organische Säure gemäß Komponente c) ist, und
5. e) mindestens 3 Gew.-%, vorzugsweise mindestens 5 Gew.-% und besonders bevorzugt von 7 bis 30 Gew.-% einer wasserlöslichen Schutzschicht (Coating).

In a particularly preferred embodiment of the invention, the co-granules according to the invention contain, based on the total weight of the co-granules,

1. a) 50 to 85 wt .-% of a bleach activator
2. b) 0.1 to 20 wt .-% of a metal-containing bleach catalyst
3. c) 5 to 20% by weight of an organic acid selected from citric acid, ascorbic acid, oxalic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids and mixtures of these,
4. d) 1 to 20 wt .-% of a binder which is not an organic acid according to component c), and
5. e) at least 3 wt .-%, preferably at least 5 wt .-% and particularly preferably from 7 to 30 wt .-% of a water-soluble protective layer (coating).

Optionally, dyes may also be added to the co-granules according to the invention and the co-granules subsequently provided with a protective layer.

coating materials

The materials already used as binders can also be used as coating materials. Here, the co-granules are coated after their preparation in a separate step with one or more coating materials, so that a uniform protective layer is formed.

The substances preferred as coating materials correspond to the preferred binders mentioned above.

dyes

The co-granules according to the invention contain, in a further preferred embodiment of the invention, one or more dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents such as textiles, glass, ceramics or plastic dishes do not stain them.

When choosing the dye, it should be noted that the dyes have high storage stability and insensitivity to light. At the same time, it should also be taken into account when choosing suitable dyes that dyes have different stabilities to oxidation. In general, water-insoluble dyes are more stable to oxidation than water-soluble dyes. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the dye in the detergents or cleaning agents varies. Dyes which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proven to be advantageous Use dyes that are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic dyes, for. B. anionic nitrosofarbstoffe.

Production of the Co-Granules According to the Invention

To provide the co-granules according to the invention, fundamentally different granulation processes are possible.

In a first preferred process variant, a build-up granulation is carried out in mixing apparatus. Here, the components are processed in conventional, batch or continuous mixing devices, which are usually equipped with rotating mixing devices. As a mixer moderately operating devices such. As plowshare mixer (Lödige KM types, Drais K-T types) but also intensive mixers (eg Eirich, Schugi, Lödige CB types, Drais K-TT types) are used. When mixing all mixed variants are conceivable that ensure adequate mixing of the components. In a preferred embodiment, all components are mixed simultaneously. However, multistage mixing processes are also conceivable in which the individual components are introduced into the overall mixture individually or together with other additives in various combinations. The order of slow and blender mixers can be reversed as needed. The residence times in the mixer granulation are preferably 0.5 s to 20 min, more preferably 2 s to 10 min. The granulating liquid can be pumped via simple guide tubes into the mixing apparatus. For better distribution but also nozzle systems (single-fluid or multi-fluid nozzles) are conceivable.

Depending on the granulating liquid used (solvent or melt-shaped binder), a drying (for solvent) or cooling step (for melting) adjoins the granulation stage in order to avoid sticking of the granules. The aftertreatment preferably takes place in a fluidized bed apparatus. Subsequently, the coarse grain and the fine grain fraction are separated by sieving. The coarse grain fraction is crushed by grinding and, like the fine grain fraction, fed to a renewed granulation process.

Granulation with the aid of a plasticizer

In a further preferred embodiment, the pulverulent components (bleach activator, bleach catalyst and optionally further auxiliaries) are mixed with one or more plastification substances. The plasticizers can be added as a liquid or as a melt, with melt-shaped substances being preferred according to the invention.

The liquid plasticizer is intensively mixed with the powdered active substance and optionally the other additives, so that a plastically deformable mass is formed. The mixing step may be in the o. G. Mixing apparatus, but also kneaders or special extruder types (eg Extrud-o-mix from Hosokawa-Bepex Corp.) are possible. The granulation mass is then pressed by means of tools through the nozzle bores of a press die, so that cylindrically shaped extrudates are formed. Suitable apparatuses for the extrusion process are ring roller presses (eg from Schlüter, Salmatec, Bühler), edge mills (for example from Amandus-Kahl) and extruders, designed as single-shaft machines (eg from Hosokawa Bepex, Fuji-Paudal) or preferably as a twin-screw extruder (eg from Händle). The choice of the diameter of the nozzle bore depends on the individual case and is typically in the range of 0.7 - 4 mm.

The exiting extrudates are to be comminuted by a post-processing step to the desired length or particle size. In many cases, a length / diameter ratio of UD = 1 is desired. For cylindrical granules, the particle diameter is between 0.2 and 2 mm, preferably between 0.5 and 0.8 mm, the particle length in the range of 0.5 to 3.5 mm, ideally between 0.9 and 2.5 mm. The lengths or size adjustment of the granules can be done for example by fixed scraper blades, rotating blades, cutting wires or blades. To round off the Cut edges, the granules are then rounded again in a Rondierer (eg, by Fa. Glatt, Schlüter, Fuji-Paudal).

After the size adjustment of the granules, a final solidification step is required in which the solvent is removed or the melt is solidified. Usually, this step is carried out in a fluidized bed apparatus operating as a dryer or condenser as required. Subsequently, the coarse grain and the fine grain fraction is separated by sieving. The coarse grain fraction is comminuted by grinding and, like the fine grain fraction, fed to a renewed granulation process.

compacting

In a further preferred embodiment, the pulverulent active substances are optionally mixed with further preferably solid additives and this mixture is compacted, then ground and then optionally sieved into individual grain fractions. Optionally, liquid additives may also be added to the mixture to a certain extent (eg 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 roll compactors (eg from Hosokawa-Bepex, Alexanderwerk, Köppern). By choosing the roll profile can be on the one hand produce lumpy pellets or briquettes and on the other hand pressing slugs. While the lumpy pellets are usually separated only from the fine fraction, the slugs must be crushed in a mill to the desired particle size. Typically come as a mill type preferably gentle grinding apparatus, such. As sieve and hammer mills (eg from the company Hosokawa-Alpine, Hosokawa-Bepex) or roll mills (eg., Fa. Bauermeister, Bühler) are used.

From the granules thus produced is separated by screening the fine grain content and optionally the coarse grain fraction. The coarse grain fraction is again fed to the mill, the fine grain content fed again to the compaction. For classifying the granules common screening machines such. As tumble screen or vibrating screens (eg., From Allgaier, Sweco, Vibra) are used.

Characteristic of the co-granules according to the invention is primarily their chemical composition. However, it has been found that the bleaching action of these co-granules can also be advantageously influenced by influencing physical parameters such as, for example, the particle size, the fine fraction and the bleach catalyst content of selected sieve fractions.

For this reason, preferred co-granules according to the invention are characterized in that the co-granules 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.

The co-granules according to the invention are suitable for use in all detergents or cleaners, and their use in detergents for dishwashing has proven to be particularly advantageous.

It is assumed that the organic acid of the co-granules according to the invention takes on a protective function and prevents the reaction of alkaline detergent constituents with the alkali-labile and hydrolysis-sensitive bleach activators and bleach catalysts of the co-granules according to the invention.

Another object of the present invention is therefore the use of a co-granule according to the invention for the production of detergents and cleaning agents and preferably of means for the machine cleaning of dishes.

Another object of the present invention are also detergents and cleaners, preferably means for the automated cleaning of dishes, containing a co-granules according to the invention.

Preferred detergents and cleaners according to the invention, in particular the detergents for dishwashing, contain the inventive co-granules in amounts of between 0.1 and 10% by weight, preferably in amounts of between 0.2 and 8% by weight and particularly preferably in amounts between 0.5 and 6 wt .-%.

The detergents and cleaners according to the invention, in particular the compositions for the automatic cleaning of dishes, which may be in the form of granules, powdered or tablet-like solids but also in liquid or pasty form, may in principle all known and in addition to the co-granules of the invention Means usual ingredients included. The detergents and cleaners according to the invention, in particular the compositions for the automated cleaning of dishes, may in particular contain builder substances, peroxygen compounds, enzymes, alkali carriers, surface-active surfactants, pH regulators, organic solvents and further auxiliaries, such as glass corrosion inhibitors, silver corrosion inhibitors and foam regulators.

• f) 15 bis 65 Gew.-%, vorzugsweise 20 bis 60 Gew.-% einer wasserlöslichen Builderkomponente,
• g) 5 bis 25 Gew.-%, vorzugsweise 8 bis 17 Gew.-%, einer Persauerstoffverbindung, und
• h) 0,5 bis 6 Gew.-% eines erfindungsgemäßen Co-Granulates, jeweils bezogen auf das gesamte Mittel. Ein derartiges Mittel ist insbesondere niederalkalisch, das heißt seine 1-gewichtsprozentige Lösung weist einen pH-Wert von 8 bis 11,5 und vorzugsweise von 9 bis 11 auf.

Particularly preferred detergents and cleaners, in particular detergents for dishwashing, contain

• f) from 15 to 65% by weight, preferably from 20 to 60% by weight, of a water-soluble builder component,
• g) 5 to 25 wt .-%, preferably 8 to 17 wt .-%, of a peroxygen compound, and
• h) 0.5 to 6 wt .-% of a co-granules of the invention, each based on the total agent. Such an agent is particularly low alkaline, that is, its 1-weight percent solution has a pH of 8 to 11.5 and preferably from 9 to 11.

Water-soluble builder component or builder substances

Suitable water-soluble builder components in the detergents and cleaners according to the invention, in particular the detergents for dishwashing, are in principle all builders customarily used in such compositions, for example alkali phosphates, in the form of their alkaline, neutral or acidic sodium or potassium salts may be present. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. Their amounts may be in the range of up to about 60% by weight, preferably from 5 to 20% by weight, based on the total agent. Further possible water-soluble builder components, in addition to polyphosphonates and phosphonate alkyl carboxylates, are, for example, organic polymers of the type of the polycarboxylates of native or synthetic origin, which act as co-builders, in particular in hard water regions. For example, polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymeric acids are suitable. Commercially available products are, for example, Sokalan ™ CP 5, CP 10 and PA 30 from BASF. Examples of co-builder polymers of native origin 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, for example, mono-, dihydroxysuccinic acid, alpha-hydroxypropionic acid and gluconic acid. The preferred organic water-soluble builder components include the salts of citric acid, especially sodium citrate. As sodium citrate, anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder. Depending on the pH ultimately set in the detergents and cleaners according to the invention, in particular the detergents for dishwashing, the acids corresponding to the said co-builder salts may also be present.

peroxygen compounds

Preferred peroxygen compounds are perborates and percarbonates, especially the corresponding sodium salts of these compounds.

enzymes

The enzymes present in the detergents and cleaners of the invention, in particular the detergents for dishwashing, include proteases, amylases, pullulanases, cutinases and / or lipases, for example proteases such as BLAP ™, Optimase ™, Opticlean ™, Maxacal ™, Maxapem ™, Durazym ™, Purafect ™ OxP, Esperase ™ and / or Savinase ™, amylases such as Termamyl ™, Amylase-LT ™, Maxamyl ™, Duramyl ™ and / or lipases such as Lipolase ™, Lipomax ™, Lumafast ™ and / or Lipozyme ™. The enzymes used may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are present in the detergents and cleaners according to the invention, in particular the detergents for dishwashing, preferably in amounts of up to 10% by weight and more preferably in amounts of from 0.05 to 5% by weight, with particular preference being given be used against oxidative degradation stabilized enzymes.

alkali carriers

The detergents and cleaners according to the invention, in particular the means for the automated cleaning of dishes, preferably contain the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali hydrogen carbonates. The alkali carriers used conventionally include carbonates, bicarbonates and alkali silicates having a molar ratio of SiO ₂ / M ₂ O (M = alkali metal) of from 1: 1 to 2.5: 1. Alkali silicates may be present in amounts of up to 40% by weight. in particular from 3 to 30 wt .-%, based on the total agent to be included. The alkali carrier system preferably used in the detergents and cleaners according to the invention, in particular in the detergents for dishwashing, is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which may be contained in an amount of up to 50% by weight and preferably from 5 to 40% by weight.

In a further preferred embodiment of the invention, in the detergents and cleaners according to the invention, in particular the detergents for dishwashing, 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 3 contain up to 40 wt .-% Alkalidisilikat.

surfactants

Surfactants, in particular anionic surfactants, zwitterionic surfactants and preferably weakly foaming nonionic surfactants may also be added to the detergents and cleaners according to the invention, in particular the detergents for dishwashing, where appropriate, as a wetting agent and optionally in the context of Production of these agents serve as Granulierhilfsmittel. Their amount may be up to 20 wt .-%, preferably up to 10 wt .-% and is more preferably in the range of 0.5 to 5 wt .-%. Usually extremely low-foam compounds are used in particular for means for the automatic cleaning of dishes. These include preferably C ₁₂ -C ₁₈ -Alkylpolyethylenglykolpolypropylen-glycol ethers each having up to 8 moles of ethylene oxide and propylene oxide in the molecule. But you can also use other known low-foam nonionic surfactants, such as C ₁₂ -C ₁₈ alkylpolyethylene glycol polybutylenglykolether each with up to 8 moles of ethylene oxide and butylene oxide in the molecule, endgruppenverschlossene Alkylpolyalkylenglykolrnischether and foaming, but ecologically attractive C ₈ -C ₁₄ - Alkylpolyglucoside having a degree of polymerization of about 1 to 4 and / or C ₁₂ -C ₁₄ alkyl polyethylene glycols having 3 to 8 ethylene oxide units in the molecule. Also suitable are surfactants from the family of glucamides, such as, for example, alkyl-N-methylglucamides, in which the alkyl moiety preferably originates from a fatty alcohol with the C chain length C ₆ -C ₁₄ . It is partially advantageous if the surfactants described are used as mixtures, for example the combination of alkylpolyglycoside with fatty alcohol ethoxylates or Glucamide with alkyl polyglycosides. The presence of amine oxides, betaines and ethoxylated alkylamines is also possible.

pH regulators

To set a desired, by the mixture of the other components not automatically resulting pH value, detergents and cleaning agents according to the invention, in particular the means for the machine cleaning of dishes, system and environmentally compatible acids, especially citric acid, acetic acid, tartaric acid, Malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali hydroxides. Such pH regulators are present in the detergents and cleaners according to the invention, in particular the detergents for dishwashing, preferably not more than 10% by weight and more preferably from 0.5 to 6% by weight.

Organic solvents

The organic solvents which can be used in the detergents and cleaners of the invention, in particular the detergents for dishwashing, in particular when in liquid or pasty form, include alcohols having 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 derivable from said classes of compounds ethers. Such water-miscible solvents are present in the detergents and cleaners according to the invention, in particular in the detergents for dishwashing, preferably in an amount not exceeding 20% by weight and more preferably from 1 to 15% by weight.

Glass corrosion inhibitors

In order to prevent glass corrosion during the rinse cycle, can be used in the detergents and cleaning agents according to the invention, in particular the means for the machine cleaning of dishes, appropriate inhibitors are used. Particularly advantageous here are crystalline layered silicates and / or zinc salts. The crystalline layered silicates are sold, for example, by the company Clariant under the trade name Na-SKS, z. Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .XH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, Makatite). Of these, especially Na-SKS-5 (alpha-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (beta-Na ₂ Si ₂ O ₅ , 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 phyllosilicates can be found, for. In the in " Soap-Oils-Grease-Waxes, 116 vintage, no. 20/1990 ", on pages 805-808 published article.

In a further preferred embodiment of the invention, the detergents and cleaners according to the invention, in particular the detergents for dishwashing, have an amount of the crystalline layered silicate of preferably from 0.1 to 20% by weight, more preferably from 0.2 to 15 Wt .-% and particularly preferably 0.4 to 10 wt .-%, each based on the total weight of these agents on.

To suppress the glass corrosion, detergents and cleaners according to the invention, in particular means for machine dishwashing, contain at least one zinc or bismuth salt, preferably selected from the group of organic zinc salts, more preferably selected from the group of soluble organic zinc salts selected from the group of soluble zinc salts of monomeric or polymeric organic acids, and most preferably selected from zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc oxalate, zinc ricinoleate, zinc abietate, zinc cvate and zinc p-toluenesulfonate. Alternatively or in combination with these zinc salts bismuth salts such. B. bismuth acetates are used.

In the context of the present invention, preference is given to washing and cleaning agents according to the invention, in particular to means for machine dishwashing, in which the amount of zinc salt, based on the total weight of this agent, is from 0.1 to 10% by weight, preferably 0.2 up to 7 wt .-% and particularly preferably 0.4 to 4 wt .-% and regardless of which zinc salts are used, in particular therefore irrespective of whether organic or inorganic zinc salts, soluble or non-soluble zinc salts or mixtures thereof are used.

Silver corrosion inhibitors

In order to effect silver corrosion protection, silver corrosion inhibitors can be used in detergents and cleaners according to the invention, in particular detergents for dishwashing machines. 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 abovementioned Metals depending on the metal in one of the oxidation states II, III, IV, V or VI.

Foam regulators

If the detergents and cleaners according to the invention, in particular the means for the automated cleaning of dishes, for example in the presence of anionic surfactants, foam too much during use, they may still contain up to 6% by weight, preferably about 0.5 to 4 Wt .-% 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 Bisfettsäureamide, and other further known commercially available defoamer added.

The washing and cleaning agents according to the invention, in particular the means for the machine cleaning of dishes, can be known as further ingredients, for example from the prior art for such agents Sequestrants, electrolytes, additional peroxygen activators, dyes or fragrances such. B. perfume oils.

Preparation of detergents and cleaning agents according to the invention

The preparation of the solid detergents and cleaners according to the invention, in particular the means for machine dishwashing, presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation, with peroxygen compound and co-granules according to the invention optionally being separated later be added.

Inventive detergents and cleaners in the form of aqueous or other conventional solvent-containing solutions, in particular corresponding means for the automated cleaning of dishes, are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

The detergents and cleaning agents according to the invention, in particular means for the automated cleaning of dishes, are preferably in the form of powdered, granular or tablet-like preparations which are known per se, for example by mixing, granulating, roll compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, which in particular enzymes, bleaching agents and the bleach catalyst are expected, can be prepared.

For the preparation of detergents and cleaners according to the invention, in particular detergents for dishwashing, in tablet form, the procedure is preferably such that all components are mixed together in a mixer and the mixture is compressed by means of conventional tablet presses, for example eccentric presses or rotary presses Range of 200 - 105 Pa to 1500 · 10 ⁵ Pa pressed.

You get so unbreakable and yet under

Conditions of use sufficiently quickly soluble tablets with flexural strengths of normally over 150 N. Preferably, such a tablet produced in such a way a weight of 15 to 40 g, in particular from 20 to 30 g, with a diameter of 35 to 40 mm.

The preparation of detergents and cleaners 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 of 800 to 1,000 g / l, in particular corresponding inventive means for the machine cleaning of dishes, can be carried out by in a first process step, the BuilderKomponenten mixed with at least a proportion of liquid mixture components to increase the bulk density of this premix and subsequently - optionally after an intermediate drying - the other constituents of the agent, including the inventive co-granules, combined with the thus obtained premix.

Means for the automatic cleaning of dishes according to the invention can be used both in household dishwashers and in commercial dishwashers. The addition is carried out by hand or by means of suitable metering devices. The application concentrations in the cleaning liquor are generally about 1 to 8 g / l, preferably 2 to 5 g / l.

A machine wash program is generally supplemented and terminated by a few rinses of clear water following a cleaning cycle and a rinse cycle with a common rinse aid. After drying, when using agents according to the invention, a completely clean and hygienically perfect dishes are obtained.

Examples

In the following examples, percentages% by weight (% by weight) unless explicitly stated otherwise. With regard to the stated relative humidities, the% values have the usual meaning.

Example 1: Preparation of TAED metal salt co-granules

These are co-granules containing TAED (tetraacetylethylenediamine, bleach activator) and metal salt (bleach catalyst), such as. B. Mn (II) sulfate. In addition, the co-granules contain the necessary granulation aids (especially the binder) and the organic acid. The production of the co-granules was carried out in conventional laboratory equipment with open handling without special measures to control the humidity. Comparative Example D was prepared as described in EP 1 499 702 produced.

The two active substances TAED and metal salt and the organic acid and optionally further additives are introduced according to the desired active ingredient ratio in a laboratory mixer, mixed and heated to the required starting temperature of T> 40 ° C. The melt-shaped binder Genapol ^® T is then 500 (fatty alcohol polyglycol ether, a product of Clariant Cetearyl alcohol to 50 ethylene oxide units in the molecule based with on average.) At a temperature of T = 70, with intensive stirring - 75 ° C added. The mixture is regranulated for a few minutes, then cooled to room temperature and screened to remove coarse and fines of 200-1600 microns.

In the case of co-granule sample B, the still warm product mixture was processed by means of a ring roller press (Schlüter PP 085) into cylindrical granules with a diameter of D = 1 mm.

Table 1 shows an overview of the co-granules prepared, which were provided for storage stability studies. Table 1: TAED Bleach Co-granules Co-granules A invention B invention C invention D comparison substances bleach TAED TAED TAED TAED bleach catalyst Mn (II) sulfate Mn (II) sulfate Mn (II) sulfate Mn (II) sulfate Bleach activator: bleach catalyst 8: 1 8: 1 8: 1 8: 1 binder Genapol ^® T 500 Genapol ^® T 500 Genapol ^® T 500 Genapol ^® T 500 Organic acid oxalic acid ascorbic acid citric acid - composition bleach % 68.57 68.57 69,57 76.68 bleach catalyst % 8.57 8.57 8.70 9.58 binder % 14.29 14.29 13,00 13.74 Organic acid % 8.57 8.57 8.73 -

Hygroscopicity test - physical stability

To check the physical stability of the co-granules according to the invention, the hygroscopic behavior is tested at elevated relative humidity. For this purpose, the co-granules are stored open for several hours at a relative humidity of 65% and room temperature. Over the experimental period, the moisture absorption is registered via a balance and the external change of the sample is observed. After completion of the storage experiment, the free-flowing or the degree of baking is judged by notes (grade 1: very good, free-flowing to grade 6: completely baked, no longer free-flowing).

Table 2 shows the results of the hygroscopicity test for the co-granules described above. Table 2: Hygroscopicity test Co-granules A invention B invention C invention D comparison Hygroscopicity - 65% RH moisture absorption % 5.1 3.3 1.1 0.9 Note (free-flowing) 3 2 2 2 Review co-granules acceptable Good Good Good rH: relative humidity

The results show that the co-granules, despite a detectable moisture absorption of about> 1%, remain free-flowing and do not cake under the effect of increased air humidity.

Storage Test in Basic Washing Powder - Chemical Storage Stability To test the physical stability of the co-granules according to the invention, the storage behavior in a typical detergent powder formulation is investigated. For this purpose, the co-granules are incorporated in IEC-A base wash powder, so that the finished formulation contains 5% co-granules. The mixtures are then stored in a room climate and severe climatic conditions (T = 40 ° C, 75% relative humidity) over several days. At regular intervals, the samples are evaluated for discoloration of the co-granules and rated grades (grade 1: very good, no discoloration to grade 6: strong discoloration, very dark color).

Table 3 shows the results of the storage test in base washing powder for the previously described co-granules. Table 3: Storage test in basic washing powder Co-granules A invention B invention C invention D comparison Storage duration room climate [Days] 7 7 7 7 Note (discoloration) 1 1 1 1 Review sample very well very well very well very well Storage time 40 ° C, 75% rH [Days] 7 7 7 7 Note (discoloration) 2 2 2 6 Review sample Good Good Good very bad rH: relative humidity

The results show that all investigated co-granules initially have a very good storage stability in a room climate. In the case of aggravated storage conditions under climatic conditions, Comparative Sample D without the addition of a stabilizer (i.e., an organic acid) showed very poor stability with a strong discoloration of the co-granules. In contrast, all three samples A - C with the addition of a stabilizing acid had a significantly better storage stability, so that after completion of the storage test no impairment was observed by color change of the co-granules.

The results of the storage experiments show that the co-granules according to the invention are better laberstabil than the comparison product, although they have a higher hygroscopicity.

Example 3: Preparation of TAED metal complex co-granules

The two active substances TAED (bleach activator) and metal complex (bleach catalyst) and the organic acid and optionally further additives are introduced according to the desired drug ratio in a laboratory mixer, mixed and heated to the required starting temperature of T> 40 ° C. The melt-shaped binder Genapol ^® T is then 500 (fatty alcohol polyglycol ether, a product of Clariant.) At a temperature of T = 70, with intensive stirring - 75 ° C added. The mixture is regranulated for a few minutes, then cooled to room temperature and screened to remove coarse and fines of 200-1600 microns.

The still warm product mixture is processed by means of a ring roller press (Schlüter PP 085) into cylindrical granules with a diameter of D = 1 mm.

TAED

Tetraacetylethylendiamin

DOBA

Decanoyloxibenzoesäure

Komplex 1

[Mn^IV ₂(µ-O)₃(Me-TACN)₂](PF₆)₂, hergestellt gemäß EP 0 458 397

Komplex 2

[Mn^IV ₂(N-O)₃(Me-TACN)₂](OAc)₂ hergestellt nach WO 2006/125517

Komplex 3

1,8-Diethyl-1,4,8,11-Tetraazacyclotetradecan-mangan(II)chlorid, hergestellt nach EP 1 557 457 .

Table 6 shows an overview of the co-granules G, H, I and J according to the invention Co-granules G H I J substances bleach TAED OPENING HOURS TAED TAED bleach catalyst Complex 1 Complex 1 Complex 2 Complex 3 Bleach activator: bleach catalyst 10: 1 10: 1 10: 1 10: 1 binder Genapol ^® T 500 Genapol ^® T 500 Genapol ^® T 500 Genapol ^® T 500 Organic acid oxalic acid ascorbic acid citric acid oxalic acid composition bleach % 70.6 70.25 70 70,40 bleach catalyst % 7.06 7.02 7 7.04 binder % 13.8 14.1 14.3 13.91 Organic acid % 8.54 8.63 8.7 8.65

TAED

tetraacetylethylenediamine

OPENING HOURS

Decanoyloxibenzoesäure

Complex 1

[Mn ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ prepared according to EP 0 458 397

Complex 2

[Mn ^IV ₂ (NO) ₃ (Me-TACN) ₂ ] (OAc) ₂ prepared according to WO 2006/125517

Complex 3

1,8-diethyl-1,4,8,11-tetraazacyclotetradecane manganese (II) chloride, prepared according to EP 1 557 457 ,

In the storage test according to Example 1, the co-granules G, H, I and J have a very good storage stability.

Claims (6)

1. Cogranules comprising, based on the total weight of the cogranules,

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

   b) 0.1 to 20% by weight of one or more metal-containing bleach catalysts,

   c) 5 to 20% by weight of one or more organic acids selected from citric acid, ascorbic acid, oxalic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids and aminocarboxylic acids, and

   d) 1 to 20% by weight of one or more binders which are not organic acids as per component c).
2. Cogranules as claimed in claim 1, characterized in that the one or more bleach activators are selected from tetraacetylethylenediamine and decanoyloxybenzoic acid.
3. Cogranules as claimed in claim 1 or 2, characterized in that the one or more metal-containing bleach catalysts are selected from manganese salts and manganese complexes.
4. Cogranules as claimed in one or more of claims 1 to 3, characterized in that the one or more organic acids of component c) are selected from citric acid, ascorbic acid and oxalic acid.
5. Cogranules as claimed in one or more of claims 1 to 4, characterized in that the one or more binders are selected from the group consisting of fatty acids, alcohol ethoxylates and polymers.
6. The use of cogranules as claimed in one or more of claims 1 to 5 for production of washing and cleaning compositions and preferably of compositions for the machine washing of dishware.