EP2417240B1 - Bleach granules comprising an active coating - Google Patents

Bleach granules comprising an active coating Download PDF

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Publication number
EP2417240B1
EP2417240B1 EP10712904.1A EP10712904A EP2417240B1 EP 2417240 B1 EP2417240 B1 EP 2417240B1 EP 10712904 A EP10712904 A EP 10712904A EP 2417240 B1 EP2417240 B1 EP 2417240B1
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EP
European Patent Office
Prior art keywords
granules
weight
coating
bleach
acid
Prior art date
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Active
Application number
EP10712904.1A
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German (de)
French (fr)
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EP2417240A1 (en
Inventor
Georg Borchers
Gerd Reinhardt
Andreas Schottstedt
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Weylchem Switzerland AG
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Weylchem Switzerland AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected

Definitions

  • 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.
  • automatic dishwashing detergents In order to obtain spotless dishes, persalts such as perborates and percarbonates are used in automatic dishwashing 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 and EP 0 530 870 Bleach catalysts based on various manganese-containing transition metal complexes.
  • bleach catalysts are 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.
  • the bleaching effect of the catalyst is effectively supported by the peroxycarboxylic acid formed from the activator.
  • 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.
  • 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.
  • 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 0 835 926 discloses a process for preparing a coated bleach activator granule by coating a bleach activator base granule with a coating substance and simultaneously and / or subsequently annealing.
  • the bleach activator base granules may contain other additives besides the bleach activator and the granulation aid.
  • additives for example, metal complexes and organic catalysts are called to increase the performance of peracid.
  • EP 1 499 702 describes co-granules consisting of a bleach catalyst, a bleach activator, and optionally a coating.
  • stabilizers such as antioxidants, reducing agents or acids may be present in amounts up to 2.5% by weight.
  • the catalyst is mainly responsible for the low-temperature bleaching performance, the activator in particular for the hygiene during the bleaching process.
  • the focus of new bleach granules is mainly in the field of low temperature bleaching.
  • the activator present in the granule core is preferably in particle form.
  • the catalyst present in the coating layer is preferably dissolved and / or in particle form.
  • the granule core may optionally contain one or more additives, preferably one or more organic acids.
  • the coating layer may optionally contain one or more further additives and optionally one or more dyes.
  • the granule core may optionally contain one or more organic acids, preferably in an amount of from 0 to 30% by weight and more preferably in an amount of from 0.1 to 30% by weight.
  • the coating or coating layer may optionally contain one or more further additives, preferably in an amount of from 0 to 30% by weight and more preferably in an amount of from 0.1 to 30% by weight.
  • the coating or coating layer may optionally also comprise one or more dyes, preferably in an amount of 0 to 5% by weight and more preferably in an amount of 0.1 to 5% by weight.
  • the granule core may optionally contain one or more organic acids, preferably in an amount of from 0 to 10% by weight and more preferably in an amount of from 0.1 to 10% by weight.
  • the coating or coating layer may optionally contain one or more further additives, preferably in an amount of 0 to 15% by weight, particularly preferably in an amount of 0.1 to 15% by weight. and particularly preferably in an amount of 5 to 15 wt .-%.
  • the coating or coating layer may optionally also comprise one or more dyes, preferably in an amount of 0 to 5% by weight and more preferably in an amount of 0.1 to 5% by weight.
  • the quantities given above for the bleach activators of component a) and the binders of component c) and the organic acids optionally present in the granule core of the inventive co-granules are based on the total amount of the granule core of the co-granules according to the invention.
  • the co-granules according to the invention are characterized in that the granule core comprises 0% by weight of the total amount of the one or more bleach catalysts contained in the co-granules and the coating layer comprises 100% by weight of the total amount of the one or more in the Co Granules containing bleach catalysts.
  • the weight ratio of granule core to shell or coating layer is from 95: 5 to 50:50.
  • the weight ratio of granule core to shell or coating layer is particularly preferably from 90:10 to 60:40.
  • the granules according to the invention can 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-lauroylxibenzene sulfonate (NOBS or LOBS), acylated phenolcarboxylic acids, in particular nonanoyloxy or decanoyloxibenzoic acid (NOBA or DOBA), carboxylic acid anhydrides, in particular phthalic anhydr
  • Hydrophilic substituted acyl acetals and acyl lactams are also preferably used.
  • nitrile derivatives such as n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA) or cyanomorpholine (MOR) can be used as bleach activators.
  • MMA n-methyl-morpholinium-acetonitrile-methyl sulfate
  • MOR cyanomorpholine
  • 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.
  • 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.
  • complexes of the iron in the oxidation state II or III and manganese in the oxidation state II, III, IV or IV preferably one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and /. or S included.
  • 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 are 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 cyclene, such as 1,8-dimethylcyclam, 1,7-dimethylcycles, 1,8-diethylcycl
  • 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 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (TACN) 2 ] (PF 6 ) 2 , [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (PF 6 ) 2 , [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (SO 4 ), [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (OAc) 2 , [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (Cl) 2 , [Mn IV 2 ( ⁇ -O) 3 (Me4-DTE)] (PF 6 ) 2 , [Mn IV 2 ( ⁇ -O ) 3 (Me4-DTE)] Cl 2, [Mn IV 2 ( ⁇ -O) 3 (Me4-DTE)] (SO 4) [Mn IV 2 ( ⁇ -O) 3 (Me4-DTE)] (OA
  • 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 IV 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (TACN) 2 ] (PF 6 ) 2 , [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (PF 6 ) 2 , [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (SO 4 ), [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (OAc) 2 , [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (Cl) 2 , [Mn IV 2 ( ⁇ -O) 3 (Me4-DTE)] (PF 6 ) 2
  • organic acid both monomeric and polymeric acids can be used either in the form of the free acid or in partially neutralized form.
  • organic acid therefore includes both the organic acids in free form and in partially neutralized form.
  • Preferred counterions are Na ions.
  • Preferred 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, fatty acids and mixtures thereof.
  • Particularly preferred organic acids are oxalic acid, ascorbic acid, citric acid and fatty acids.
  • polymeric acids are polymers of acrylic acid and copolymers of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid use.
  • Particularly preferred organic acids are citric acid, ascorbic acid and oxalic acid.
  • the co-granules according to the invention contain one or more binders in order to ensure cohesion of the co-granules.
  • binders substances selected from fatty acids, alcohol ethoxylates, polymers and natural clay minerals may preferably be used.
  • polymers here are synthetic and natural polymers understood as well as modified polymers of natural origin.
  • the natural clay minerals are again preferred.
  • Suitable are, inter alia, organic fatty acids having 8 to 22 carbon atoms, such as lauric acid, myristic acid, stearic acid or mixtures thereof.
  • organic 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, in particular those having a relative molecular mass of 500 to 70,000 g / mol.
  • 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 having molecular weights of 2,000 to 10,000 g / mol, and preferably from 3,000 to 5,000 g / mol.
  • 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.
  • the polymers may also contain structural units derived from allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid.
  • 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.
  • copolymers are those which have structural units derived from acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • 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 optionally further ionogenic or nonionogenic monomers.
  • 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 Clariant or carboxymethyl.
  • bentonite is particularly preferred.
  • the materials already used as binders can also be used as coating materials.
  • 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 content of the total granules is at least 10 wt .-%.
  • the coating layer envelops the granule core as completely and uniformly as possible.
  • the coating materials correspond to the aforementioned preferred binders (with the exception of the natural clay minerals such as bentonite).
  • the coating materials are therefore selected from fatty acids, alcohol ethoxylates and polymers.
  • the polymers synthetic and natural polymers are understood as well as modified polymers of natural origin.
  • the fatty acids are again preferred, in particular fatty acids having 8 to 22 carbon atoms.
  • 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.
  • 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.
  • water-insoluble dyes are more stable to oxidation than water-soluble dyes.
  • concentration of the dye varies in the washing or Detergents. 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 to use dyes which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic dyes, for. B. anionic nitrosofarbstoffe.
  • additives which may be present in the co-granules according to the invention, in particular in their coating or coating layer, are additives which are known from the prior art in such granules, in particular those intended for use in detergents and cleaners are to be used.
  • the granutant core of the co-granules according to the invention consists of the bleach activators of component a) and the binders of component c).
  • the granule core of the co-granules according to the invention consists of the bleach activators of component a), the binders of component c) and organic acids.
  • the coating or coating layer of the co-granules according to the invention consists of the bleach catalysts of component d) and the coating agents of component e).
  • the coating or coating layer of the co-granules according to the invention consists of the bleach catalysts of component d), the coating agents of component e) and dyes.
  • the co-granules of the invention consist of the bleach activators of component a), the binders of component c), the bleach catalysts of component d), the Coatsmittein the component e) and one or more substances selected from in Granule core of the inventive co-granules contained organic acids and contained in the coating or coating layer of the co-granules of the invention dyes and other additives.
  • a build-up granulation is carried out in mixing apparatus.
  • the components are processed in conventional, batch or continuous mixing devices, which are usually equipped with rotating mixing devices.
  • a mixer moderately operating devices such.
  • plowshare mixer Lödige KM types, Drais KT types
  • intensive mixers eg Eirich, Schugi, Lödige CB types, Drais K-TT types
  • mixing all mixed variants are conceivable that ensure adequate mixing of the components.
  • all components are mixed simultaneously.
  • 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 mixer and fast mixer 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.
  • 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 is separated by sieving. The coarse grain fraction is comminuted by grinding and, like the fine grain fraction, fed to a renewed granulation process.
  • the pulverulent components 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.
  • cylindrical Granules is the particle diameter 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 granulate can then be rounded again in a rounding device (eg from Glatt, Schlüter, Fuji-Paudal).
  • a final solidification step is required in which the solvent is removed or the melt is solidified.
  • this step is carried out in a fluidized bed apparatus operating as a dryer or condenser as required.
  • 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.
  • 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.
  • liquid additives may also be added to the mixture to a certain extent (eg up to 10% by weight).
  • 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).
  • roll compactors eg from Hosokawa-Bepex, Alexanderwerk, Köppern.
  • 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 fines, the puddles be crushed in a mill to the desired particle size. Typically come as a mill type preferably gentle grinding apparatus, such.
  • sieve and hammer mills eg from the company Hosokawa-Alpine, Hosokawa-Bepex
  • roll mills eg., Fa. Bauermeister, Bühler
  • 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.
  • common screening machines such as tumble screen or vibrating screens (eg., From Allgaier, Sweco, Vibra) are used.
  • the granules prepared by one of the processes described above are provided in the second step with the so-called active coating.
  • the granules are coated in an additional step according to methods known per se with a film-forming substance, wherein the coating shell contains one or more bleach catalysts and optionally further additives.
  • the maximum particle size of the milled bleach catalyst to be set is defined inter alia by the starting particle size of the bleach catalyst, the dimensions of the coating layer to be applied and the process conditions of the coating process.
  • the maximum particle size of the bleach catalyst can be limited to ⁇ 100 .mu.m, preferably ⁇ 50 .mu.m.
  • the grinding of the bleach catalyst is required, in principle all common milling principles and grinding units are conceivable. For example, an impact crushing can be done in a pin mill. Ultimately, especially determine the grinding properties of the bleach catalyst, such. Brittleness, and the desired fineness of the mill selection.
  • the prepared bleach catalyst is incorporated in the next process step in the coating substance.
  • the coating liquid is placed in a container and the bleach catalyst is added with stirring.
  • stirrers to avoid sedimentation of solids or, in the case of highly viscous systems, mixers for introducing shear energy are advantageous in the case of rather low-viscosity systems.
  • the coating materials in a preferred embodiment of the invention are selected from fatty acids, alcohol ethoxylates and polymers.
  • the coating materials are selected from film-forming substances, such as waxes, silicones, fatty acids, fatty alcohols, soaps, anionic surfactants, nonionic surfactants, cationic surfactants, anionic and cationic polymers, and also polyalkylene glycols. Preference is given to using coating substances having a melting point of 30-100 ° C.
  • C 8 -C 31 -fatty acids for example lauric, myristic, stearic acid
  • C 8 -C 31 fatty alcohols Polyethylene glycols having a molecular weight of 1,000 to 50,000 g / mol
  • Fatty alcohol polyalkoxylates with 1 to 100 moles of EO EO: ethylene oxide unit
  • polymers for example polyvinyl alcohols, waxes, for example montan waxes, paraffin waxes, ester waxes, polyolefin waxes, silicones.
  • further substances which do not soften or melt in this area can be present in dissolved or suspended form, for example homopolymers, copolymers or propylene copolymers of unsaturated carboxylic acids and / or sulfonic acids and their derivatives Alkali salts, cellulose ethers, starch, starch ethers, polyvinylpyrrolidone; mono- and polybasic carboxylic acids, hydroxycarboxylic acids or ether carboxylic acids having 3 to 8 carbon atoms and salts thereof; Silicates, carbonates, bicarbonates, sulfates, phosphates, phosphonates.
  • mixers mechanically induced fluidized bed
  • fluidized bed apparatuses pneumatically induced fluidized bed
  • mixers mechanically induced fluidized bed
  • fluidized bed apparatuses pneumatically induced fluidized bed
  • a mixer z. B. plowshare mixer continuous and batchwise
  • ring layer mixers or Schugi mixer possible.
  • the tempering can be carried out using a mixer in a granule preheater and / or in the mixer directly and / or in a fluidized bed downstream of the mixer.
  • Granulated coolers or fluid bed coolers can be used to cool the coated granules.
  • the heat treatment takes place via the hot gas used for fluidization.
  • the granules coated by the fluidized-bed method can be cooled by a granulate cooler or a fluidized-bed cooler, similar to the mixing method. Both in the mixing process and in the fluidized bed process, the coating substance can be sprayed on a single-component or a Zweistoffdüsvorraum.
  • the optional tempering consists in a heat treatment at a temperature of 30 to 100 ° C, but equal to or below the melting or softening temperature of the respective shell substance. Preference is given to working at a temperature which is just below the melting or softening temperature.
  • the coating agents can be applied in the form of solutions or suspensions to the primary particle, which is possible in principle with the aforementioned apparatuses.
  • Fluidized bed apparatuses can preferably be used here, since they offer the advantage that liquid can be sprayed in at the same time and moisture dried off. This often results in increased flexibility in the process and in the achievable product quality.
  • 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 also on the influence of physical parameters such as the particle size, the fines content and the Bleach catalyst content of selected Siebfr hopeen can be favorably influenced.
  • 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.
  • Another object of the present invention is therefore the use of a co-granule according to the invention for the production of detergents and cleaners and preferably of agents 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 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 washing and cleaning agents according to the invention in particular the means for the automatic cleaning of dishes, may 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.
  • Water-soluble builder components 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 commonly employed 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 range up to about 60% by weight, preferably from 5 to 20% by weight, based on the total agent.
  • 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.
  • organic polymers of the type of the polycarboxylates of native or synthetic origin which act as co-builders, in particular in hard water regions.
  • polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids are, for example, Sokalan TM CP 5, CP 10 and PA 30 from BASF.
  • co-builder polymers of native origin include oxidized starch and polyamino acids such as polyglutamic acid or polyaspartic acid.
  • 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.
  • citric acid especially sodium citrate.
  • 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.
  • the acids corresponding to the said co-builder salts may also be present.
  • Preferred peroxygen compounds are perborates and percarbonates, especially the corresponding sodium salts of these compounds.
  • the enzymes present in the detergents and cleaners of the invention include proteases, amylases, pullulanases, cutinases and / or lipases, for example proteases such as BLAP TM, Optimase TM, Opticlean TM, Maxacal TM, Maxapem TM, Durazym TM, Purafect TM OxP, Esperase TM and / or Savinase TM, amylases such as Termamyl TM, Amylase-LT TM, Maxamyl TM, Duramyl TM and / or lipases such as Lipolase TM, Lipomax TM, Lumafast TM and / or Lipozyme TM.
  • proteases such as BLAP TM, Optimase TM, Opticlean TM, Maxacal TM, Maxapem TM, Durazym TM, Purafect TM OxP, Esperase TM and / or Savinase TM
  • the enzymes used may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are in the washing and cleaning agents according to the invention, in particular the means for the machine cleaning of dishes, 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 to using enzymes which are stabilized against oxidative degradation.
  • 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.
  • 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, in an amount of up to 50% by weight and preferably from 5 to 40 wt .-% may be included.
  • 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 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 Granulieryaku.
  • Their amount can be up to 20 wt .-%, preferably up to 10 wt .-% and is particularly preferably in the range of 0.5 to 5 wt .-%.
  • extremely low-foam compounds are used in particular in the means for the automatic cleaning of dishes.
  • C 12 -C 18 -alkylpolyethylene glycol-polypropylene glycol ethers having in each case up to 8 mol of ethylene oxide and propylene oxide units in the molecule.
  • 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 alkyl polyglycoside with fatty alcohol ethoxylates or glucamide with alkyl polyglycosides. The presence of amine oxides, betaines and ethoxylated alkylamines is also possible.
  • detergents and cleaning agents 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.
  • 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.
  • crystalline layered silicates and / or zinc salts are sold, for example, by the company Clariant under the trade name Na-SKS, z. 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. ⁇ H 2 O, makatite).
  • 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
  • Na-SKS-13 NaHSi 2 O 5
  • Na-SKS-6 delta-Na 2 Si 2 O 5
  • the washing and cleaning agents according to the invention in particular the means for the machine cleaning of dishes, an amount of the crystalline layered silicate of preferably 0.1 to 20 wt .-%, particularly preferably 0.2 to 15 wt .-% and particularly preferably 0.4 to 10 wt .-%, each based on the total weight of these agents on.
  • detergents and cleaners according to the invention may comprise 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, in particular preferably 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 valerate and zinc p-toluenesulfonate.
  • bismuth salts such.
  • B. bismuth acetates are used.
  • washing and cleaning agents 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 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 can be used in detergents and cleaners according to the invention, in particular the detergents for dishwashing.
  • 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.
  • 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 Bisfettklareamide, and other further known commercially available defoamer added.
  • 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 Bisfettklareamide, and other further known commercially available defoamer added.
  • the detergents and cleaners according to the invention may contain, as further ingredients, for example from the prior art, sequestrants, electrolytes, additional peroxygen activators, dyes or fragrances, for example perfume oils.
  • Inventive detergents and cleaners in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
  • the washing and cleaning agents according to the invention are preferably in the form of powdered, granular or tablet-shaped preparations which are prepared in a manner known per se, for example by mixing, granulating, roll compacting and / or by spray-drying the thermally stable components and admixing the more sensitive components, to which in particular enzymes, bleaching agents and the bleach catalyst are to be expected can.
  • 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 to 1500 105 Pa pressed.
  • 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 done 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.
  • the industrially available bleach activator TAED (tetraacetylethylenediamine) was obtained from Clariant in powder form, the manganese salts were purchased from Sigma-Aldrich and the metal complexes used were prepared according to literature.
  • Example 1 Preparation of co-granules according to the invention with active coating These are co-granules containing TAED and a bleach catalyst, such. B. Mn (II) sulfate, which is applied specifically as an active coating.
  • the co-granules contain the necessary granulation aids, such as binders and coating substance, but optionally also other additives such. B. stabilizers.
  • the bleach catalyst is added to the stirred melt and distributed uniformly.
  • the bleach catalyst was previously comminuted in a laboratory mill.
  • the basic granulate for the active coating is a TAED granulate (Peractive CB - commercial product from Clariant containing bentonite) in a laboratory mixer submitted.
  • the granules are heated with moderate stirring to the required starting temperature of T> 70 ° C.
  • the melt mixture is metered in evenly and slowly with the bleach catalyst, so that the mixture is evenly distributed on the base granules and excessive overgranulation is avoided.
  • the coated granules are briefly emptied from the mixer emptied and cooled. The product is then sieved to remove coarse and fine fractions of 200-1600 ⁇ m.
  • Table 1 shows an overview of the prepared co-granules according to the invention with active coating, which were provided for further investigations.
  • Table 1 Co-granules according to the invention with active coating
  • Example co-granules A B C D substances bleach TAED TAED TAED TAED bleach catalyst Mn (II) sulfate Mn (II) sulfate Complex 1 Complex 2
  • the statement "[K, 84.3]" for the bleach activator of the co-granule A means that the bleach activator is contained in the granule core and its amount is only 84.3% by weight, based on the total mass of the granule core , Accordingly, for example, the specification "[H;50.0]” for the bleach catalyst of the co-granule A means that the bleach catalyst is contained in the coating layer and its amount - based only on the total mass of the coating layer - 50.0 wt .-% is.
  • the hygroscopic behavior is tested at elevated relative humidity.
  • 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 Hygroscopicity - 65% RH Example co-granules A B C D Moisture absorption% 1.5 1.8 3.3 2.5 Note (free-flowing) 1 1 1 1 Review Granules very well very well very well rH: relative humidity
  • Example 3 Storage Tests in Basic Washing Powder - Chemical Storage Stability To check the physical stability of the co-granules according to the invention, the storage behavior is determined in a typical manner
  • washing powder formulation examined.
  • the coated co-granules incorporated in IEC-A base wash powder so that the finished formulation contains 5% of the invention co-granules.
  • 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 Storage stability in base wash powder IEC-A Example co-granules A B C D Storage duration room climate [Days] 20 20 13 13 Note (discoloration) 2 1 1 2 Review sample Good very well very well Good Storage time 40 ° C, 75% rH [Days] 20 20 13 13 Note (discoloration) 2 2 3 3 Review sample Good Good acceptable acceptable rH: relative humidity

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Description

Die vorliegende Erfindung betrifft Bleichmittelgranulate, ein Verfahren zu deren Herstellung sowie deren Verwendung in Wasch- und Reinigungsmitteln, insbesondere in Mitteln für die maschinelle Reinigung von Geschirr.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.

Um fleckenloses Geschirr zu erhalten, werden in maschinellen Geschirrspülmitteln Persalze wie Perborate und Percarbonate eingesetzt. Zur Aktivierung dieser Bleichmittel und um beim Reinigen bei Temperaturen von 60 °C und darunter eine verbesserte Bleichwirkung zu erreichen, enthalten maschinelle Geschirrspülmittel in der Regel weiterhin Bleichaktivatoren oder Bleichkatalysatoren, wobei sich insbesondere die Bleichkatalysatoren als besonders wirkungsvoll erwiesen haben.In order to obtain spotless dishes, persalts such as perborates and percarbonates are used in automatic dishwashing 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.

Bleichkatalysatoren werden in maschinellen Geschirrspülmitteln vorzugsweise in Form vorgefertigter Granulate eingesetzt um ihre Lagerstabilität zu erhöhen. So beschreiben EP 0 458 397 , EP 0 458 398 und EP 0 530 870 Bleichkatalysatoren auf Grundlage verschiedener Mangan-haltiger Übergangsmetallkomplexe.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 and EP 0 530 870 Bleach catalysts based on various manganese-containing transition metal complexes.

Verfahren zur Herstellung von Bleichkatalysatorgranulaten werden in EP 0 544 440 , WO 95/06710 und WO 2008/069935 offenbart. Kennzeichnend für die dort beschriebenen Verfahren ist der Einsatz großer Mengen an Inertmaterialien als Träger sowie Bindemittel, die gegebenenfalls als Schmelzen eingesetzt werden, wobei diese Verfahrensweise Kühl- und/oder Trocknungsstufen einschließt, welche den Einsatz zusätzlicher Apparate wie Wirbelschichtanlagen bedingt.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.

Die keimabtötende Wirkung von Bleichkatalysatoren ist in den meisten Fällen allerdings gering. Die Leistung von Bleichmitteln in Maschinengeschirrspülmitteln ist daher höher, wenn sie aus einer Kombination eines Bleichkatalysators mit einem Bleichaktivator bestehen. Hierbei wird die bleichende Wirkung des Katalysators durch die aus dem Aktivator gebildete Peroxicarbonsäure wirksam unterstützt. Zugleich trägt die Peroxicarbonsäure signifikant zur Keimabtötung auf dem Spülgut bei, verbessert den Geruch der Waschlauge und unterbindet die Ausbildung eines Biofilms in der Spülmaschine. Die Kombination von Bleichkatalysatoren und Bleichaktivatoren ist deshalb sinnvoll zur Steigerung der Bleichperformance und Gewährleistung der Hygiene bei der Verwendung von Bleichmitteln in Wasch- und Reinigungsmitteln. So beschreibt EP 0 616 029 ein Bleichmitteladditiv bestehend aus einer Trockenmischung aus Percarbonat, einem TAED-Granulat und einem Bleichkatalysator-Granulat. Auch in diesem Fall weist das Bleichkatalysator-Granulat nur einen Aktivgehalt von 1,2 Gew.-% auf, der Rest besteht aus Trägermaterialien und/oder Bindemittel.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.

Der Einsatz von Aktivatoren und Katalysatoren in getrennten Granulaten bietet jedoch Nachteile, die sich auf die Bleichperformance negativ auswirken können. Die Reaktionen des Persalzes, bzw. des daraus freigesetzten Wasserstoffperoxides mit Aktivator und Katalysator laufen parallel ab. Löst sich das Katalysator-Granulat schneller als das Aktivator-Granulat, ist das Persalz bereits verbraucht, bevor es mit dem Aktivator reagieren kann. Entsprechendes trifft für den umgekehrten Fall zu. Co-Granulate aus Aktivatoren und Katalysatoren sind weiterhin von Vorteil, um die homogene Verteilung beider Komponenten im Wasch- und Reinigungsmittel zu gewährleisten und um Platz in der Formulierung zu sparen. Weiterhin verbilligen sich die Herstellkosten, da an Stelle zweier verschiedener Granulate nur ein Co-Granulat hergestellt werden muss.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 0 835 926 offenbart ein Verfahren zur Herstellung eines gecoateten Bleichaktivatorgranulats, wobei man ein Bleichaktivatorbasisgranulat mit einer Coatingsubstanz umhüllt und gleichzeitig und/oder anschließend tempert. In der EP 0 835 926 wird beschrieben, dass die Bleichaktivatorbasisgranulate neben dem Bleichaktivator und dem Granulierhilfsmittel noch weitere Zusatzstoffe enthalten können. Als Zusatzstoffe werden beispielsweise Metallkomplexe und organische Katalysatoren zur Leistungssteigerung der Persäure genannt. EP 0 835 926 discloses a process for preparing a coated bleach activator granule by coating a bleach activator base granule with a coating substance and simultaneously and / or subsequently annealing. In the EP 0 835 926 It is described that the bleach activator base granules may contain other additives besides the bleach activator and the granulation aid. As additives, for example, metal complexes and organic catalysts are called to increase the performance of peracid.

EP 1 499 702 beschreibt Co-Granulate bestehend aus einem Bleichmittelkatalysator, einem Bleichmittelaktivator und wahlweise einer Beschichtung. Optional können Stabilisatoren wie Antioxidantien, Reduktionsmittel oder Säuren in Mengen bis zu 2,5 Gew.-% vorhanden sein. 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.

Bei diesem und anderen literaturbekannten Herstellprozessen für Aktivator-Katalysator-Co-Granulate liegen Bleichaktivator und Katalysator räumlich nebeneinander im Granulat vor. Löst sich das Granulat während des Waschprozesses auf, sollten bei gleicher Lösegeschwindigkeit der Komponenten Aktivator und Katalysator im gleichen Mengenverhältnis aufgelöst werden und zur Reaktion mit Wasserstoffperoxyd, freigesetzt aus einem Persalz, zur Verfügung stehen. Die Reaktionen laufen dann parallel ab und Aktivator und Katalysator nehmen damit im gleichen Mengenverhältnis am Bleichprozess teil. Dies ist nicht der Fall, wenn die Lösegeschwindigkeit einer der beiden Komponenten, Aktivator oder Katalysator, verzögert ist, was häufig auftritt. Ist die Lösegeschwindigkeit des Katalysators deutlich geringer als die des Aktivators, wird das Wasserstoffperoxyd bzw. das Persalz bereits durch Umsetzung mit dem Aktivator aufgebraucht, so dass kein oder nur eine untergeordnete Menge an Wasserstoffperoxyd für die Reaktion mit dem Katalysator zur Verfügung steht. Wie bereits oben angedeutet, ist der Katalysator aber hauptsächlich für die Niedertemperatur-Bleichperformance, der Aktivator insbesondere für die Hygiene während des Bleichprozesses verantwortlich. Der Focus neuer Bleichmittelgranulate liegt vor allem auf dem Gebiet der Niedertemperaturbleiche.In this and other literature-known manufacturing processes for activator catalyst co-granules are bleach activator and catalyst spatially next to each other in the granules. If the granules dissolve during the washing process, at the same rate of dissolution of the components activator and catalyst should be dissolved in the same quantitative ratio and be available for reaction with hydrogen peroxide released from a persalt. The reactions then proceed in parallel and activator and catalyst take part in the bleaching process in the same proportions. This is not the case if the dissolution rate of either component, activator or catalyst, is delayed, which is common. If the rate of dissolution of the catalyst is significantly lower than that of the activator, the hydrogen peroxide or the persalt is already consumed by reaction with the activator, so that no or only a minor amount of hydrogen peroxide is available for the reaction with the catalyst. As indicated above, however, the catalyst is mainly responsible for the low-temperature bleaching performance, the activator in particular for the hygiene during the bleaching process. The focus of new bleach granules is mainly in the field of low temperature bleaching.

Es besteht daher Bedarf an neuartigen Waschmittelgranulaten, die gute Niedertemperatur-Performance aufweisen und erst in zweiter Hinsicht den Hygieneaspekt und die Mitteltemperatur-Performance sichern. Es muss deshalb sichergestellt sein, dass sich Aktivator/Katalysator-Co-Granulate so auflösen, dass zunächst der Katalysator und in einem zweiten Schritt der Aktivator in der Waschlauge freigesetzt wird. Diese Anforderung wird durch den Stand der Technik nicht erfüllt.There is therefore a need for novel detergent granules which have good low-temperature performance and ensure the hygiene aspect and the medium-temperature performance only in the second respect. It must therefore be ensured that activator / catalyst co-granules dissolve so that first the catalyst is released and in a second step, the activator in the wash liquor. This requirement is not met by the prior art.

Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, Bleichaktivator-Bleichkatalysator-Co-Granulate bereitzustellen, die sich gegenüber aus dem Stand der Technik bekannten Granulaten dadurch auszeichnen, dass während der Anwendung in der Waschlauge zunächst der Katalysator und dann in einem zweiten Schritt der Aktivator freigesetzt wird.It is an object of the present invention to provide bleach activator bleach catalyst co-granules which are distinguished from granules known from the prior art by first liberating the catalyst during use in the wash liquor and then releasing the activator in a second step becomes.

Die gestellte Aufgabe konnte überraschenderweise gelöst werden durch die Bereitstellung von Co-Granulaten, enthaltend einen Granulatkern und eine den Granulatkern umgebende Hüll- oder Coatingschicht, dadurch gekennzeichnet, dass der Granulatkern

  • a) einen oder mehrere Bleichaktivatoren,
    • a2) 0 Gew.-% der Gesamtmenge eines oder mehrerer im Co-Granulat
      enthaltener Bleichkatalysatoren und
  • c) ein oder mehrere Bindemittel
    enthält und die Hüll- oder Coatingschicht
  • d) 100 Gew.-% der Gesamtmenge des einen oder der mehreren im Co-Granulat enthaltenen Bleichkatalysatoren und
  • e) ein oder mehrere Coatingmittel
enthält und das Gewichts-Verhältnis von Granulatkern zu Hüll- oder Coatingschicht von 95:5 bis 50:50 beträgt.The stated object could surprisingly be solved by the provision of co-granules containing a granule core and a granulate core surrounding shell or coating layer, characterized in that the granule core
  • a) one or more bleach activators,
    • a2) 0% by weight of the total amount of one or more in the co-granules
      contained bleach catalysts and
  • c) one or more binders
    contains and the coating or coating layer
  • d) 100% by weight of the total amount of the one or more bleach catalysts contained in the co-granulate, and
  • e) one or more coating agents
and the weight ratio of granule core to shell or coating layer is from 95: 5 to 50:50.

Der im Granulatkern vorliegende Aktivator liegt vorzugsweise in Partikelform vor.The activator present in the granule core is preferably in particle form.

Der in der Coatingschicht vorliegende Katalysator liegt vorzugsweise gelöst und/oder in Partikelform vor.The catalyst present in the coating layer is preferably dissolved and / or in particle form.

Gegenstand der vorliegenden Erfindung sind daher Co-Granulate, die einen Granulatkern und eine den Granulatkern umgebende Hüll- oder Coatingschicht enthalten, dadurch gekennzeichnet, dass der Granulatkern

  • a) einen oder mehrere Bleichaktivatoren,
    • a2) 0 Gew.-% der Gesamtmenge eines oder mehrerer im Co-Granulat
      enthaltener Bleichkatalysatoren und
  • c) ein oder mehrere Bindemittel
    enthält und die Hüll- oder Coatingschicht
  • d) 100 Gew.-% der Gesamtmenge des einen oder der mehreren im Co-Granulat enthaltenen Bleichkatalysatoren und
  • e) ein oder mehrere Coatingmittel
enthält und das Gewichts-Verhältnis von Granulatkern zu Hüll- oder
Coatingschicht von 95:5 bis 50:50 beträgt.The present invention therefore relates to co-granules which comprise a granule core and an enveloping or coating layer surrounding the granule core contain, characterized in that the granule core
  • a) one or more bleach activators,
    • a2) 0% by weight of the total amount of one or more in the co-granules
      contained bleach catalysts and
  • c) one or more binders
    contains and the coating or coating layer
  • d) 100% by weight of the total amount of the one or more bleach catalysts contained in the co-granulate, and
  • e) one or more coating agents
contains and the weight ratio of granule core to shell or
Coating layer of 95: 5 to 50:50.

In diesen erfindungsgemäßen Co-Granulaten kann der Granulatkern gegebenenfalls einen oder mehrere Zusatzstoffe, vorzugsweise eine oder mehrere organische Säuren, enthalten. Die Hüll- oder Coatingschicht kann gegebenenfalls ein oder mehrere weitere Additive und optional einen oder mehrere Farbstoffe enthalten.In these co-granules according to the invention, the granule core may optionally contain one or more additives, preferably one or more organic acids. The coating layer may optionally contain one or more further additives and optionally one or more dyes.

Vorzugsweise enthält der Granulatkern des erfindungsgemäßen Co-Granulats

  • a) 1 bis 99 Gew.-%, vorzugsweise 69,1 bis 99 Gew.-% und besonders bevorzugt 70 bis 99 Gew.-%, eines oder mehrerer Bleichaktivatoren und
  • c) 0,9 bis 30 Gew.-% und vorzugsweise 1 bis 30 Gew.-% eines oder mehrerer Bindemittel
    und die Hüll- oder Coatingschicht des erfindungsgemäßen Co-Granulats
  • d) 1 bis 99 Gew.-%, vorzugsweise 1 bis 98,9 Gew.-% und besonders bevorzugt 1 bis 98,8 Gew.-% eines oder mehrerer Bleichkatalysatoren, und
  • e) 1 bis 99 Gew.-%, vorzugsweise 1 bis 98,9 Gew.-% und besonders bevorzugt 1 bis 98,8 Gew.-% eines oder mehrerer Coatingmittel.
Preferably, the granule core of the co-granules according to the invention contains
  • a) 1 to 99 wt .-%, preferably 69.1 to 99 wt .-% and particularly preferably 70 to 99 wt .-%, of one or more bleach activators and
  • c) 0.9 to 30 wt .-% and preferably 1 to 30 wt .-% of one or more binders
    and the coating or coating layer of the co-granules according to the invention
  • d) 1 to 99 wt .-%, preferably 1 to 98.9 wt .-% and particularly preferably 1 to 98.8 wt .-% of one or more bleach catalysts, and
  • e) 1 to 99 wt .-%, preferably 1 to 98.9 wt .-% and particularly preferably 1 to 98.8 wt .-% of one or more coating agents.

In den soeben genannten erfindungsgemäßen Co-Granulaten kann der Granulatkern gegebenenfalls eine oder mehrere organische Säuren enthalten, vorzugsweise in einer Menge von 0 bis 30 Gew.-% und besonders bevorzugt in einer Menge von 0,1 bis 30 Gew.-%.In the co-granules according to the invention just mentioned, the granule core may optionally contain one or more organic acids, preferably in an amount of from 0 to 30% by weight and more preferably in an amount of from 0.1 to 30% by weight.

In den soeben genannten erfindungsgemäßen Co-Granulaten kann die Hüll- oder Coatingschicht gegebenenfalls ein oder mehrere weitere Additive enthalten, vorzugsweise in einer Menge von 0 bis 30 Gew.-% und besonders bevorzugt in einer Menge von 0,1 bis 30 Gew.-%.In the co-granules according to the invention just mentioned, the coating or coating layer may optionally contain one or more further additives, preferably in an amount of from 0 to 30% by weight and more preferably in an amount of from 0.1 to 30% by weight. ,

In den soeben genannten erfindungsgemäßen Co-Granulaten kann die Hüll- oder Coatingschicht gegebenenfalls auch einen oder mehrere Farbstoffe enthalten, vorzugsweise in einer Menge von 0 bis 5 Gew.-% und besonders bevorzugt in einer Menge von 0,1 bis 5 Gew.-%.In the co-granules according to the invention just mentioned, the coating or coating layer may optionally also comprise one or more dyes, preferably in an amount of 0 to 5% by weight and more preferably in an amount of 0.1 to 5% by weight. ,

Besonders bevorzugt enthält der Granulatkern des erfindungsgemäßen Co-Granulats

  • a) 50 bis 95 Gew.-%, vorzugsweise 79,9 bis 95 Gew.-% und besonders bevorzugt 80 bis 95 Gew.-% eines oder mehrerer Bleichaktivatoren und
  • c) 4,9 bis 20 Gew.-%, vorzugsweise 5 bis 20 und besonders bevorzugt 5 bis 15 Gew.-% eines oder mehrerer Bindemittel und die Hüll- oder Coatingschicht des erfindungsgemäßen Co-Granulats
  • d) 2 bis 60 Gew.-%, vorzugsweise 2 bis 59,9 Gew.-% und besonders bevorzugt 2 bis 59,8 Gew.-% eines oder mehrerer Bleichkatalysatoren und
  • e) 40 bis 98 Gew.-%, vorzugsweise 40 bis 97,9 Gew.-% und besonders bevorzugt 40 bis 97,8 Gew.-% eines oder mehrerer Coatingmittel.
Particularly preferably, the granule core of the co-granules according to the invention contains
  • a) 50 to 95 wt .-%, preferably 79.9 to 95 wt .-% and particularly preferably 80 to 95 wt .-% of one or more bleach activators and
  • c) 4.9 to 20 wt .-%, preferably 5 to 20 and particularly preferably 5 to 15 wt .-% of one or more binders and the coating or coating layer of the co-granules of the invention
  • d) 2 to 60 wt .-%, preferably 2 to 59.9 wt .-% and particularly preferably 2 to 59.8 wt .-% of one or more bleach catalysts and
  • e) 40 to 98 wt .-%, preferably 40 to 97.9 wt .-% and particularly preferably 40 to 97.8 wt .-% of one or more coating agents.

In den soeben genannten erfindungsgemäßen Co-Granulaten kann der Granulatkern gegebenenfalls eine oder mehrere organische Säuren enthalten, vorzugsweise in einer Menge von 0 bis 10 Gew.-% und besonders bevorzugt in einer Menge von 0,1 bis 10 Gew.-%.In the co-granules according to the invention just mentioned, the granule core may optionally contain one or more organic acids, preferably in an amount of from 0 to 10% by weight and more preferably in an amount of from 0.1 to 10% by weight.

In den soeben genannten erfindungsgemäßen Co-Granulaten kann die Hüll- oder Coatingschicht gegebenenfalls ein oder mehrere weitere Additive enthalten, vorzugsweise in einer Menge von 0 bis 15 Gew.-%, besonders bevorzugt in einer Menge von 0,1 bis 15 Gew.-% und insbesondere bevorzugt in einer Menge von 5 bis 15 Gew.-%.In the co-granules according to the invention just mentioned, the coating or coating layer may optionally contain one or more further additives, preferably in an amount of 0 to 15% by weight, particularly preferably in an amount of 0.1 to 15% by weight. and particularly preferably in an amount of 5 to 15 wt .-%.

In den soeben genannten erfindungsgemäßen Co-Granulaten kann die Hüll- oder Coatingschicht gegebenenfalls auch einen oder mehrere Farbstoffe enthalten, vorzugsweise in einer Menge von 0 bis 5 Gew.-% und besonders bevorzugt in einer Menge von 0,1 bis 5 Gew.-%.In the co-granules according to the invention just mentioned, the coating or coating layer may optionally also comprise one or more dyes, preferably in an amount of 0 to 5% by weight and more preferably in an amount of 0.1 to 5% by weight. ,

Die oben angegebenen Mengenangaben für die Bleichaktivatoren der Komponente a) und die Bindemittel der Komponente c) sowie der gegebenenfalls im Granulatkern der erfindungsgemäßen Co-Granulate enthaltenen organischen Säuren sind auf die Gesamtmenge des Granulatkerns der erfindungsgemäßen Co-Granulate bezogen. Demgegenüber sind die oben angegebenen Mengenangaben für die Bleichkatalysatoren der Komponente d), die Coatingmittel der Komponente e) sowie der gegebenenfalls in der Hüll- oder Coatingschicht der erfindungsgemäßen Co-Granulate enthaltenen weiteren Additive und Farbstoffe auf die Gesamtmenge der Hüll- oder Coatingschicht der erfindungsgemäßen Co-Granulate bezogen.The quantities given above for the bleach activators of component a) and the binders of component c) and the organic acids optionally present in the granule core of the inventive co-granules are based on the total amount of the granule core of the co-granules according to the invention. In contrast, the quantities given above for the bleach catalysts of component d), the coating agent of component e) and the further additives and dyes optionally contained in the coating or coating layer of the co-granules of the invention to the total amount of the coating or coating layer of the inventive Co Granules related.

Die erfindungsgemäßen Co-Granulate sind dadurch gekennzeichnet, dass der Granulatkern 0 Gew.-% der Gesamtmenge des einen oder der mehreren im Co-Granulat enthaltenen Bleichkatalysatoren und die Hüll- oder Coatingschicht 100 Gew.-% der Gesamtmenge des einen oder der mehreren im Co-Granulat enthaltenen Bleichkatalysatoren enthält.The co-granules according to the invention are characterized in that the granule core comprises 0% by weight of the total amount of the one or more bleach catalysts contained in the co-granules and the coating layer comprises 100% by weight of the total amount of the one or more in the Co Granules containing bleach catalysts.

Das Gewichts-Verhältnis von Granulatkern zu Hüll- oder Coatingschicht beträgt von 95:5 bis 50:50.The weight ratio of granule core to shell or coating layer is from 95: 5 to 50:50.

Das Gewichts-Verhältnis von Granulatkern zu Hüll- oder Coatingschicht beträgt besonders bevorzugt von 90:10 bis 60:40.The weight ratio of granule core to shell or coating layer is particularly preferably from 90:10 to 60:40.

BleichaktivatorenBleach activators

Als Bleichaktivatoren können die erfindungsgemäßen Granulate mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyloxi- oder n-Lauroyloxibenzolsulfonat (NOBS bzw. LOBS), acylierte Phenolcarbonsäuren, insbesondere Nonanoyloxi- oder Decanoyloxibenzoesäure (NOBA bzw. DOBA), Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat und 2,5-Diacetoxy-2,5-dihydrofuran sowie acetyliertes Sorbitol und Mannitol beziehungsweise deren Mischungen (SORMAN), acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfruktose, Tetraacetylxylose und Octaacetyllactose sowie acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton, und/oder N-acylierte Lactame, beispielsweise N-Benzoylcaprolactam enthalten. Hydrophil substituierte Acylacetale und Acyllactame werden ebenfalls bevorzugt eingesetzt. Daneben können Nitrilderivate wie n-Methyl-Morpholinium-Acetonitril-Methylsulfat (MMA) oder Cyanomorpholin (MOR) als Bleichaktivatoren Verwendung finden. Auch Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden. Besonders bevorzugte Bleichaktivatoren sind TAED und DOBA.As bleach activators, the granules according to the invention can 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-lauroylxibenzene sulfonate (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 as well as acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated 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.

Bleichkatalysatorenbleach catalysts

Als Bleichkatalysatoren werden im Rahmen der vorliegenden Erfindung vorzugsweise bleichverstärkende Übergangsmetallsalze bzw. -komplexe des Mangans, Eisens, Kobalts, Rutheniums, Molybdäns, Titans oder Vanadiums verwendet.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.

Bei Verwendung von Metallsalzen sind insbesondere Mangansalze in den Oxidationsstufen +2 oder +3 bevorzugt, beispielsweise Manganhalogenide, wobei die Chloride bevorzugt sind, Mangansulfate, Mangansalze organischer Säuren wie Manganacetate, Manganacetylacetonate, Manganoxalate sowie Mangannitrate.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.

Weiterhin bevorzugt sind Komplexe des Eisens in den Oxidationsstufen II oder III und Mangans in der Oxidationsstufe II, III, IV oder IV, die vorzugsweise einen oder mehrere makrocyclische(n) Ligand(en) mit den Donorfunktionen N, NR, PR, O und/oder S enthalten. Vorzugsweise werden Liganden eingesetzt, die Stickstoff-Donorfunktionen aufweisen.Also preferred are complexes of the iron in the oxidation state II or III and manganese in the oxidation state II, III, IV or IV, preferably one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and /. or S included. Preferably, ligands are used which have nitrogen donor functions.

Als Übergangsmetallkomplexe in den erfindungsgemäßen Co-Granulaten bevorzugt eingesetzt werden Komplexe, welche als makromolekularen Liganden 1,4,7-Trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-Triazacyclononan (TACN), 1,5,9-Trimethyl-1,5,9-triazacyclododecan (Me-TACD), 2-Methyl-1,4,7-trimethyl-1,4,7-triazacyclononan (MeMeTACN) und/oder 2-Methyl-1,4,7-triazacyclononan (Me/TACN) oder verbrückte Liganden wie 1,2-bis-(4,7-Dimethyl-1,4,7-triazacyclonono-1-yl) ethan (Me4-DTNE) oder Derivate des Cyclams oder Cyclens, wie 1,8-Dimethylcyclam, 1,7-Dimethylcyclen, 1,8-Diethylcyclam, 1,7-Diethylcyclen, 1,8-Dibenzylcyclam und 1,7-Dibenzylcyclen enthalten, wie sie z. B. in EP 0 458 397 , EP 0 458 398 , EP 0 549 272 , WO 96/06154 , WO 96/06157 oder WO 2006/125517 beschrieben sind, daneben aber auch Mangankomplexe, wie sie aus EP 1 445 305 , EP 1 520 910 oder EP 1 557 457 bekannt sind.Complexes which are preferably used as transition metal complexes in the co-granules according to the invention are complexes which are 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 cyclene, such as 1,8-dimethylcyclam, 1,7-dimethylcycles, 1,8-diethylcyclam, 1,7-diethylcycles, 1,8-dibenzylcyclam and 1,7-dibenzylcycles contain, as z. 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.

Geeignete Mangankomplexe sind beispielsweise [MnIII 2(µ-O)1 (µ-OAc)2(TACN)2](PF6)2, [MnIV 2(µ-O)3(Me-TACN)2](PF6)2, [MnIV 2(µ-O)3(Me-TACN)2](SO4), [MnIV 2(µ-O)3(Me-TACN)2](OAc)2, [MnIV 2(µ-O)3(Me-TACN)2](Cl)2, [MnIV 2(µ-O)3(Me4-DTE)](PF6)2, [MnIV 2(µ-O)3(Me4-DTE)]Cl2, [MnIV 2(µ-O)3(Me4-DTE)](SO4), [MnIV 2(µ-O)3(Me4-DTE)](OAc)2, cis-(1,4,8,11-Tetraazacyclotetradecan)dichloro-eisen (III) chlorid, trans-(1,4,8,11-Tetraazacyclotetradecan)dichloro-eisen (III) chlorid, 1,8-Diethyl-1,4,8,11-Tetraazacyclotetradecan-eisen(II)chlorid, 1,8-Diethyl-1,4,8,11-Tetraazacyclotetradecan-mangan(II)chlorid und 1,4,8,11-Tetraazacyclotetradecan-mangan(II)chlorid.Suitable 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 (Me4-DTE)] Cl 2, [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) dichloro-iron (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.

Besonders bevorzugte metallhaltige Bleichkatalysatoren sind ausgewählt aus Mangansalzen und Mangankomplexen, wobei unter den Mangansalzen wiederum Salze ausgewählt aus Mangansulfat, Manganacetat und Manganoxalat bevorzugt sind und unter den Mangankomplexen wiederum Komplexe ausgewählt aus [MnIV 2(µ-O)1(µ-OAc)2(TACN)2](PF6)2, [MnIV 2(µ-O)3(Me-TACN)2](PF6)2, [MnIV 2(µ-O)3(Me-TACN)2](SO4), [MnIV 2(µ-O)3(Me-TACN)2](OAc)2, [MnIV 2(µ-O)3(Me-TACN)2](Cl)2, [MnIV 2(µ-O)3(Me4-DTE)](PF6)2, [MnIV 2(µ-O)3(Me4-DTE)]Cl2, [MnIV 2(µ-O)3(Me4-DTE)](SO4), [MnIV 2(µ-O)3(Me4-DTE)](OAc)2, cis-(1,4,8,11-Tetraazacyclotetradecan)dichloro-eisen (III) chlorid, trans-(1,4,8,11-Tetraazacyclotetradecan)dichloro-eisen (III) chlorid, 1,8-Diethyl-1,4,8,11-Tetraazacyclotetradecan-eisen(II)chlorid, 1,8-Diethyl-1,4,8,11-Tetraazacyclotetradecan-mangan(II)chlorid und 1,4,8,11-Tetraazacyclotetradecan-mangan(II)chlorid bevorzugt sind.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 IV 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 (μ-O) 3 (Me4-DTE)] (OAc) 2, cis- (1,4,8,11-tetraazacyclotetradecane) dichloro iron ( 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.

Organische SäurenOrganic acids

Als organische Säure können sowohl monomere als auch polymere Säuren entweder in Form der freien Säure oder in teilneutralisierter Form verwendet werden. Im Rahmen der vorliegenden Erfindung umfasst der Begriff "organische Säure" daher sowohl die organischen Säuren in freier Form als auch in teilneutralisierter Form.As the organic acid, both monomeric and polymeric 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.

Als Gegenionen bevorzugt sind Na-Ionen.Preferred counterions are Na ions.

Bevorzugte organische Säuren sind Citronensäure, Ascorbinsäure, Oxalsäure, Adipinsäure, Bemsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren, Aminocarbonsäuren, Fettsäuren sowie Mischungen aus diesen. Besonders bevorzugte organische Säuren sind Oxalsäure, Ascorbinsäure, Citronensäure und Fettsäuren. Als polymere Säuren finden Polymere der Acrylsäure sowie Copolymere der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure Verwendung.Preferred 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, fatty acids and mixtures thereof. Particularly preferred organic acids are oxalic acid, ascorbic acid, citric acid and fatty acids. As polymeric acids are polymers of acrylic acid and copolymers of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid use.

Insbesondere bevorzugte organische Säuren sind Citronensäure, Ascorbinsäure und Oxalsäure.Particularly preferred organic acids are citric acid, ascorbic acid and oxalic acid.

Bindemittelbinder

Als weiteren Inhaltsstoff enthalten die erfindungsgemäßen Co-Granulate ein oder mehrere Bindemittel, um den Zusammenhalt des Co-Granulates zu gewährleisten.As a further ingredient, the co-granules according to the invention contain one or more binders in order to ensure cohesion of the co-granules.

Als Bindemittel können vorzugsweise Substanzen ausgewählt aus Fettsäuren, Alkoholethoxylaten, Polymeren und natürlichen Tonmineralien verwendet werden. Unter den Polymeren werden hierbei synthetische und natürliche Polymere verstanden wie auch modifizierte Polymere natürlichen Ursprungs. Unter diesen Substanzen sind wiederum die natürlichen Tonmineralien bevorzugt.As binders, substances selected from fatty acids, alcohol ethoxylates, polymers and natural clay minerals may preferably be used. Among the polymers here are synthetic and natural polymers understood as well as modified polymers of natural origin. Among these substances, the natural clay minerals are again preferred.

Geeignet sind u. a. organische Fettsäuren mit 8 bis 22 Kohlenstoffatomen, wie Laurinsäure, Myristinsäure, Stearinsäure oder Mischungen davon. Weiterhin bevorzugt sind organische Polymere. Die Polymere können nichtionischer, anionischer, kationischer oder amphoterer Natur sein. Natürliche Polymere und modifizierte Polymere natürlichen Ursprungs sind ebenso einsetzbar wie synthetische Polymere.Suitable are, inter alia, organic fatty acids having 8 to 22 carbon atoms, such as lauric acid, myristic acid, stearic acid or mixtures thereof. Farther 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.

Zur Gruppe der mit besonderem Vorzug als Bindemittel eingesetzten nichtionischen Polymere zählen Polyvinylalkohole, acetalisierte Polyvinylalkohole, Polyvinylpyrrolidone und Polyalkylenglykole, insbesondere Polyethylenoxide. Bevorzugte Polyvinylalkohole und acetalisierte Polyvinylalkohole weisen Molekulargewichte im Bereich von 10.000 bis 100.000 g/mol, vorzugsweise von 11.000 bis 90.000 g/mol, besonders bevorzugt von 12.000 bis 80.000 g/mol und insbesondere bevorzugt von 13.000 bis 70.000 g/mol auf. Bevorzugte Polyethylenoxide haben Molmassen im Bereich von ca. 200 bis 5.000.000 g/mol, entsprechend Polymerisationsgraden n von ca. 5 bis >100.000.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.

Bei den mit besonderem Vorzug als Bindemittel eingesetzten anionischen Polymeren handelt es sich insbesondere um homo- oder copolymere Polycarboxylate. Bevorzugt eingesetzt werden beispielsweise Polyacrylsäure oder Polymethacrylsäure, insbesondere solche mit einer relativen Molekülmasse von 500 bis 70.000 g/mol.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, in particular those having a relative molecular mass of 500 to 70,000 g / mol.

Darunter bevorzugt sind Polyacrylate, die bevorzugt eine Molekülmasse von 2.000 bis 20.000 g/mol aufweisen. Aufgrund ihrer überlegenen Löslichkeit bevorzugt aus dieser Gruppe sind wiederum die kurzkettigen Polyacrylate, die Molmassen von 2.000 bis 10.000 g/mol, und bevorzugt von 3.000 bis 5.000 g/mol aufweisen.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 having molecular weights of 2,000 to 10,000 g / mol, and preferably from 3,000 to 5,000 g / mol.

Darunter weiterhin bevorzugt sind copolymere Polycarboxylate, insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt vorzugsweise 2.000 bis 70.000 g/mol, besonders bevorzugt 20.000 bis 50.000 g/mol und insbesondere bevorzugt 30.000 bis 40.000 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.

Zur Verbesserung der Wasserlöslichkeit können die Polymere auch Struktureinheiten hervorgegangen aus Allylsulfonsäuren, wie beispielsweise Allyloxybenzolsulfonsäure und Methallylsulfonsäure, enthalten. Insbesondere bevorzugt sind auch biologisch abbaubare Polymere aus mehr als zwei verschiedenen Monomereinheiten, beispielsweise solche, die Struktureinheiten aus Salzen der Acrylsäure und der Maleinsäure sowie aus Vinylalkohol bzw. Vinylalkohol-Derivaten und Zucker-Derivaten oder die Struktureinheiten aus Salzen der Acrylsäure und der 2-Alkylallylsulfonsäure und aus Zucker-Derivaten enthalten.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.

Weitere bevorzugte Copolymere sind solche, die Struktureinheiten hervorgegangen aus Acrolein und Acrylsäure/Acrylsäuresalze bzw. Acrolein und Vinylacetat aufweisen.Further preferred copolymers are those which have structural units derived from acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Weitere mit Vorzug als Bindemittel eingesetzte anionische Polymere sind Sulfonsäuregruppen-haltige Polymere, insbesondere Copolymere aus ungesättigten Carbonsäuren, Sulfonsäuregruppen-haltigen Monomeren und gegebenenfalls weiteren ionogenen oder nichtionogenen Monomeren.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 optionally further ionogenic or nonionogenic monomers.

Weitere bevorzugte Bindemittel sind bei Raumtemperatur feste C8-C22 Alkoholethoxylate, vorzugsweise C8-C22 Alkoholethoxylate mit im Mittel 10 bis 100 Ethylenoxid-Einheiten im Molekül, wie z. B. Genapol® T 500 der Firma Clariant oder Carboxymethylcellulosen.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 Clariant or carboxymethyl.

Unter den natürlichen Tonmineralien ist insbesondere Bentonit bevorzugt.Among the natural clay minerals, bentonite is particularly preferred.

Coatingschicht und CoatingmaterialienCoating layer and coating materials

Die bereits als Bindemittel verwendeten Materialien (ausgenommen die natürlichen Tonmineralien wie beispielsweise Bentonit) können auch als Coatingmaterialien eingesetzt werden. Hierbei werden die Co-Granulate nach ihrer Herstellung in einem separaten Schritt mit einem oder mehreren Coatingmaterialien umhüllt, so dass eine gleichmäßige Schutzschicht entsteht. In einer bevorzugten Ausführungsform der Erfindung beträgt deren Gehalt am Gesamtgranulat mindestens 10 Gew.-%.The materials already used as binders (except the natural clay minerals such as bentonite) 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. In a preferred embodiment of the invention, the content of the total granules is at least 10 wt .-%.

In einer weiteren bevorzugten Ausführungsform umhüllt die Coatingschicht den Granulatkern möglichst vollständig und gleichmäßig.In a further preferred embodiment, the coating layer envelops the granule core as completely and uniformly as possible.

Die als Coatingmaterialien bevorzugten Substanzen entsprechen den zuvor genannten bevorzugten Bindemitteln (ausgenommen die natürlichen Tonmineralien wie beispielsweise Bentonit). In einer weiteren bevorzugten Ausführungsform der Erfindung sind die Coatingmaterialien daher ausgewählt aus Fettsäuren, Alkoholethoxylaten und Polymeren. Unter den Polymeren werden hierbei wiederum synthetische und natürliche Polymere verstanden wie auch modifizierte Polymere natürlichen Ursprungs. Unter den soeben genannten Substanzen sind wiederum die Fettsäuren bevorzugt, insbesondere Fettsäuren mit 8 bis 22 Kohlenstoffatomen.The substances preferred as coating materials correspond to the aforementioned preferred binders (with the exception of the natural clay minerals such as bentonite). In a further preferred embodiment of the invention, the coating materials are therefore selected from fatty acids, alcohol ethoxylates and polymers. Among the polymers, synthetic and natural polymers are understood as well as modified polymers of natural origin. Among the substances just mentioned, the fatty acids are again preferred, in particular fatty acids having 8 to 22 carbon atoms.

Farbstoffedyes

Die erfindungsgemäßen Co-Granulate enthalten in einer weiteren bevorzugten Ausführungsform der Erfindung einen oder mehrere Farbstoffe. Bevorzugte Farbstoffe, deren Auswahl dem Fachmann keinerlei Schwierigkeit bereitet, besitzen eine hohe Lagerstabilität und Unempfindlichkeit gegenüber den übrigen Inhaltsstoffen der Mittel und gegen Licht sowie keine ausgeprägte Substantivität gegenüber den mit den farbstoffhaltigen Mitteln zu behandelnden Substraten wie beispielsweise Textilien, Glas, Keramik oder Kunststoffgeschirr, um diese nicht anzufärben.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.

Bei der Wahl des Farbstoffs muss beachtet werden, dass die Farbstoffe eine hohe Lagerstabilität und Unempfindlichkeit gegenüber Licht aufweisen. Gleichzeitig ist auch bei der Wahl geeigneter Farbstoffe zu berücksichtigen, dass Farbstoffe unterschiedliche Stabilitäten gegenüber Oxidation aufweisen. Im Allgemeinen gilt, dass wasserunlösliche Farbstoffe gegen Oxidation stabiler sind als wasserlösliche Farbstoffe. Abhängig von der Löslichkeit und damit auch von der Oxidationsempfindlichkeit variiert die Konzentration des Farbstoffs in den Wasch-oder Reinigungsmitteln. Es werden Farbstoffe bevorzugt, die im Waschprozess oxidativ zerstört werden können sowie Mischungen derselben mit geeigneten blauen Farbstoffen, sog. Blautönern. Es hat sich als vorteilhaft erwiesen, Farbstoffe einzusetzen, die in Wasser oder bei Raumtemperatur in flüssigen organischen Substanzen löslich sind. Geeignet sind beispielsweise anionische Farbstoffe, z. B. anionische Nitrosofarbstoffe.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 varies in the washing or Detergents. 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 to use dyes which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic dyes, for. B. anionic nitrosofarbstoffe.

Weitere AdditiveOther additives

Weitere Additive, die in den erfindungsgemäßen Co-Granulaten enthalten sein können, insbesondere in deren Hüll- oder Coatingschicht, sind Additive, die bekanntermaßen aus dem Stand der Technik in derartigen Granulaten, insbesondere in solchen, die für den Einsatz in Wasch- und Reinigungsmitteln gedacht sind, eingesetzt werden.Further additives which may be present in the co-granules according to the invention, in particular in their coating or coating layer, are additives which are known from the prior art in such granules, in particular those intended for use in detergents and cleaners are to be used.

In einer weiteren bevorzugten Ausführungsform der Erfindung besteht der Granutatkern der erfindungsgemäßen Co-Granulate aus den Bleichaktivatoren der Komponente a) und den Bindemitteln der Komponente c).In a further preferred embodiment of the invention, the granutant core of the co-granules according to the invention consists of the bleach activators of component a) and the binders of component c).

In einer weiteren bevorzugten Ausführungsform der Erfindung besteht der Granulatkern der erfindungsgemäßen Co-Granulate aus den Bleichaktivatoren der Komponente a), den Bindemitteln der Komponente c) und organischen Säuren.In a further preferred embodiment of the invention, the granule core of the co-granules according to the invention consists of the bleach activators of component a), the binders of component c) and organic acids.

In einer weiteren bevorzugten Ausführungsform der Erfindung besteht die Hüll- oder Coatingschicht der erfindungsgemäßen Co-Granulate aus den Bleichkatalysatoren der Komponente d) und den Coatingmitteln der Komponente e).In a further preferred embodiment of the invention, the coating or coating layer of the co-granules according to the invention consists of the bleach catalysts of component d) and the coating agents of component e).

In einer weiteren bevorzugten Ausführungsform der Erfindung besteht die Hüll- oder Coatingschicht der erfindungsgemäßen Co-Granulate aus den Bleichkatalysatoren der Komponente d), den Coatingmitteln der Komponente e) und Farbstoffen.In a further preferred embodiment of the invention, the coating or coating layer of the co-granules according to the invention consists of the bleach catalysts of component d), the coating agents of component e) and dyes.

In einer weiteren bevorzugten Ausführungsform der Erfindung bestehen die erfindungsgemäßen Co-Granulate aus den Bleichaktivatoren der Komponente a), den Bindemitteln der Komponente c), den Bleichkatalysatoren der Komponente d), den Coatingmittein der Komponente e) und aus einer oder mehreren Substanzen ausgewählt aus im Granulatkern der erfindungsgemäßen Co-Granulate enthaltenen organischen Säuren und in der Hüll- oder Coatingschicht der erfindungsgemäßen Co-Granulate enthaltenen Farbstoffen und weiteren Additiven.In a further preferred embodiment of the invention, the co-granules of the invention consist of the bleach activators of component a), the binders of component c), the bleach catalysts of component d), the Coatsmittein the component e) and one or more substances selected from in Granule core of the inventive co-granules contained organic acids and contained in the coating or coating layer of the co-granules of the invention dyes and other additives.

Herstellung der erfindungsgemäßen Co-GranulateProduction of the Co-Granules According to the Invention

Zur Bereitstellung der erfindungsgemäßen Co-Granulate sind grundsätzlich verschiedene Granulierverfahren möglich.To provide the co-granules according to the invention, fundamentally different granulation processes are possible.

In einer ersten bevorzugten Verfahrensvariante erfolgt eine Aufbaugranulierung in Mischapparaten. Hierbei werden die Komponenten in üblichen, chargenweise oder kontinuierlich arbeitenden Mischvorrichtungen verarbeitet, die in der Regel mit rotierenden Mischorganen ausgerüstet sind. Als Mischer können moderat arbeitende Apparate wie z. B. Pflugscharmischer (Lödige KM-Typen, Drais K-T-Typen) aber auch Intensivmischer (z. B. Eirich, Schugi, Lödige CB-Typen, Drais K-TT-Typen) zum Einsatz kommen. Beim Mischen sind alle Mischvarianten denkbar, die eine ausreichende Durchmischung der Komponenten gewährleisten. Bei einer bevorzugten Ausführungsform werden alle Komponenten gleichzeitig vermischt. Es sind jedoch auch mehrstufige Mischprozesse denkbar, bei denen die einzelnen Komponenten in verschiedenen Kombinationen einzeln oder zusammen mit anderen Additiven in die Gesamtmischung eingetragen werden. Die Reihenfolge von Langsam- und Schnellmischer kann je nach Erfordernis vertauscht werden. Die Verweilzeiten in der Mischergranulierung betragen bevorzugt 0,5 s bis 20 min, besonders bevorzugt 2 s bis 10 min. Die Granulierflüssigkeit kann über einfache Leitrohre in den Mischapparat gepumpt werden. Zur besseren Verteilung sind aber auch Düsensysteme (Einstoff- oder Mehrstoffdüsen) denkbar.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 KT 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 mixer and fast mixer 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.

In Abhängigkeit der verwendeten Granulierflüssigkeit (Lösemittel oder schmelzeförmiges Bindemittel) schließt sich an die Granulierstufe ein Trocknungs-(für Lösemittel) bzw. Kühlungsschritt (für Schmelzen) an, um ein Verkleben der Granulate zu vermeiden. Die Nachbehandlung findet vorzugsweise in einem Fließbett-Apparat statt. Anschließend wird durch Sieben der Grobkorn- und der Feinkornanteil abgetrennt. Der Grobkornanteil wird durch Vermahlen zerkleinert und ebenso wie der Feinkornanteil einem erneuten Granulierungsprozess zugeführt.Depending on the granulation 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 is separated by sieving. The coarse grain fraction is comminuted by grinding and, like the fine grain fraction, fed to a renewed granulation process.

Granulierung mit Hilfe eines PlastifizierungsmittelsGranulation with the aid of a plasticizer

In einer weiteren bevorzugten Ausführungsform werden die pulverförmigen Bestandteile (Bleichaktivator, Bleichkatalysator und gegebenenfalls weitere Hilfsstoffe) mit einem oder mehreren Plastifizierungssubstanzen versetzt. Die Plastifizierungsmittel können als Flüssigkeit oder als Schmelze eingetragen werden, wobei schmelzeförmige Substanzen erfindungsgemäß bevorzugt sind.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.

Das flüssige Plastifiziermittel wird intensiv mit der pulverförmigen Aktivsubstanz und gegebenenfalls den weiteren Additiven gemischt, so dass eine plastisch verformbare Masse entsteht. Der Mischschritt kann in den o. g. Mischapparaten erfolgen, aber auch Kneter oder spezielle Extrudertypen (z. B. Extrud-o-mix der Fa. Hosokawa-Bepex Corp.) sind denkbar. Die Granuliermasse wird anschließend mittels Werkzeugen durch die Düsenbohrungen einer Pressmatrize gepresst, so dass zylindrisch geformte Extrudate entstehen. Geeignete Apparate für den Extrusionsprozess sind Ringkollerpressen (z. B. von Fa. Schlüter, Salmatec, Bühler), Kollergänge (z. B. von Fa. Amandus-Kahl) und Extruder, ausgeführt als Einwellenmaschine (z. B. von Fa. Hosokawa-Bepex, Fuji-Paudal) oder bevorzugt als Doppelschneckenextruder (z. B. von Fa. Händle). Die Wahl des Durchmessers der Düsenbohrung ist vom Einzelfall abhänging und liegt typischerweise im Bereich von 0,7 - 4 mm.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.

Die austretenden Extrudate sind durch einen Nachbearbeitungsschritt auf die gewünschte Länge bzw. Partikelgröße zu zerkleinern. In vielen Fällen ist ein Längen/Durchmesser-Verhältnis von L/D = 1 gewünscht. Bei zylinderförmigen Granulaten liegt der Partikeldurchmesser zwischen 0,2 und 2 mm, bevorzugt zwischen 0,5 und 0,8 mm, die Teilchenlänge im Bereich von 0,5 bis 3,5 mm, idealerweise zwischen 0,9 und 2,5 mm. Die Längen bzw. Größeneinstellung der Granulate kann beispielsweise durch feststehende Abstreifermesser, rotierende Schnittmesser, Schnittdrähte oder -klingen erfolgen. Zum Abrunden der Schnittkanten kann das Granulat anschließend nochmals in einem Rondierer (z. B. von Fa. Glatt, Schlüter, Fuji-Paudal) verrundet werden.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 L / D = 1 is desired. For cylindrical Granules is the particle diameter 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 granulate can then be rounded again in a rounding device (eg from Glatt, Schlüter, Fuji-Paudal).

Nach der Größeneinstellung der Granulate ist ein abschließender Verfestigungsschritt erforderlich bei dem das Lösemittel entfernt bzw. die Schmelze erstarrt wird. Üblicherweise wird dieser Schritt in einem Fließbett-Apparat durchgeführt, der je nach den Erfordernissen als Trockner oder Kühler betrieben wird. Anschließend wird durch Sieben der Grobkorn- und der Feinkornanteil abgetrennt. Der Grobkornanteil wird durch Vermahlen zerkleinert und ebenso wie der Feinkornanteil einem erneuten Granulierungsprozess zugeführt.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.

Kompaktierungcompacting

In einer weiteren bevorzugten Ausführungsform werden die pulverförmigen Aktivsubstanzen gegebenenfalls mit weiteren vorzugsweise festen Additiven gemischt und diese Mischung kompaktiert, danach gemahlen und anschließend gegebenenfalls in einzelne Kornfraktionen gesiebt. Gegebenenfalls können der Mischung auch in gewissem Umfang (z. B. bis zu 10 Gew.-%) zusätzlich flüssige Additive zugesetzt werden. Beispiele für Kompaktierhilfsmittel sind Wasserglas, Polyethylenglykole, nichtionische Tenside, anionische Tenside, Polycarboxylatcopolymere, modifizierte und/oder unmodifizierte Cellulosen, Bentonite, Hectorite, Saponite und/oder andere Waschmittelinhaltsstoffe.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.

Die Kompaktierung wird vorzugsweise auf sog. Walzenkompaktoren (z. B. von Fa. Hosokawa-Bepex, Alexanderwerk, Köppern) durchgeführt. Durch die Wahl des Walzenprofils lassen sich einerseits stückige Pellets oder Briketts und andererseits Pressschülpen erzeugen. Während die stückigen Presslinge üblicherweise nur noch vom Feinanteil abgetrennt werden, müssen die Schülpen in einer Mühle auf die gewünschte Partikelgröße zerkleinert werden. Typischerweise kommen als Mühlentyp vorzugsweise schonende Mahlapparate, wie z. B. Sieb- und Hammermühlen (z. B. von Fa. Hosokawa-Alpine, Hosokawa-Bepex) oder Walzenstühle (z. B. von Fa. Bauermeister, Bühler) zum Einsatz.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 fines, the puddles 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.

Von dem so erzeugten Granulat wird durch Siebung der Feinkornanteil und gegebenenfalls der Grobkornanteil abgetrennt. Der Grobkornanteil wird erneut der Mühle zugeführt, der Feinkornanteil erneut der Kompaktierung zugeführt. Zur Klassierung der Granulate können gängige Siebmaschinen wie z. B. Taumelsieb- oder Vibrationssiebe (z. B. von Fa. Allgaier, Sweco, Vibra) zum Einsatz kommen.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.

Coating-Verfahren:Coating method:

Die nach einem der zuvor beschriebenen Verfahren hergestellten Granulate werden im zweiten Schritt mit dem so genannten Aktivcoating versehen. Hierzu wird das Granulat in einem zusätzlichen Schritt nach an sich bekannten Verfahren mit einer filmbildenden Substanz umhüllt, wobei die Coatinghülle einen oder mehrere Bleichkatalysatoren sowie gegebenenfalls weitere Additive enthält.The granules prepared by one of the processes described above are provided in the second step with the so-called active coating. For this purpose, the granules are coated in an additional step according to methods known per se with a film-forming substance, wherein the coating shell contains one or more bleach catalysts and optionally further additives.

Für eine gleichmäßige Verteilung in der Coatinghülle einerseits und eine bessere Verarbeitung andererseits, kann es sich als vorteilhaft erweisen, dass der Bleichkatalysator vor der Einarbeitung in das Coating zerkleinert wird. Die dabei einzustellende maximale Partikelgröße des gemahlenen Bleichkatalysators wird unter anderem von der Ausgangspartikelgröße des Bleichkatalysators, den Abmessungen der aufzubringenden Coatingschicht und den Prozessbedingungen des Coatingprozesses definiert. Typischerweise kann die maximale Partikelgröße des Bleichkatalysators auf < 100 µm, bevorzugt < 50 µm, begrenzt werden.For a uniform distribution in the coating shell on the one hand and a better processing on the other hand, it may prove advantageous that the bleach catalyst is comminuted prior to incorporation into the coating. The maximum particle size of the milled bleach catalyst to be set is defined inter alia by the starting particle size of the bleach catalyst, the dimensions of the coating layer to be applied and the process conditions of the coating process. Typically, the maximum particle size of the bleach catalyst can be limited to <100 .mu.m, preferably <50 .mu.m.

Sofern die Mahlung des Bleichkatalysators erforderlich ist, sind prinzipiell alle gängigen Mahlprinzipien und Mahlaggregate denkbar. Beispielsweise kann eine Prallzerkleinerung in einer Stiftmühle erfolgen. Letztendlich bestimmen vor allem die Mahleigenschaften des Bleichkatalysators, wie z. B. Sprödigkeit, und die gewünschte Mahlfeinheit die Mühlenauswahl.If the grinding of the bleach catalyst is required, in principle all common milling principles and grinding units are conceivable. For example, an impact crushing can be done in a pin mill. Ultimately, especially determine the grinding properties of the bleach catalyst, such. Brittleness, and the desired fineness of the mill selection.

Der aufbereitete Bleichkatalysator wird im nächsten Prozessschritt in die Coatingsubstanz eingearbeitet. Hierzu wird die Coatingflüssigkeit in einem Behälter vorgelegt und der Bleichkatalysator unter Rühren zugemischt. Je nach Fluidsystem sind bei eher niedrigviskosen Systemen Rührorgane zur Vermeidung der Feststoffsedimentation oder bei hochviskosen Systemen Mischer zum Einbringen von Scherenergie von Vorteil.The prepared bleach catalyst is incorporated in the next process step in the coating substance. For this purpose, the coating liquid is placed in a container and the bleach catalyst is added with stirring. Depending on the fluid system, stirrers to avoid sedimentation of solids or, in the case of highly viscous systems, mixers for introducing shear energy are advantageous in the case of rather low-viscosity systems.

Wie bereits zuvor erwähnt sind die Coatingmaterialien in einer bevorzugten Ausführungsform der Erfindung ausgewählt aus Fettsäuren, Alkoholethoxylaten und Polymeren.As already mentioned before, the coating materials in a preferred embodiment of the invention are selected from fatty acids, alcohol ethoxylates and polymers.

In einer weiteren bevorzugten Ausführungsform der Erfindung sind die Coatingmaterialien ausgewählt aus filmbildenden Substanzen, wie Wachse, Silikone, Fettsäuren, Fettalkohole, Seifen, anionische Tenside, nichtionische Tenside, kationische Tenside, anionische und kationische Polymere, sowie Polyalkylenglykole. Bevorzugt werden Coatingsubstanzen mit einem Schmelzpunkt von 30 - 100 °C verwendet. Beispiele hierfür sind: C8-C31-Fettsäuren, beispielsweise Laurin-, Myristin-, Stearinsäure; C8-C31-Fettalkohole; Polyethylenglykole mit einer Molmasse von 1.000 bis 50.000 g/mol; Fettalkoholpolyalkoxylate mit 1 bis 100 Mol EO (EO: Ethylenoxid-Einheit); Alkansulfonate, Alkylbenzolsulfonate, α-Olefinsulfonate, Alkylsulfate, Alkylethersulfate mit C8-C31-Kohlenwasserstoffresten, Polymere, beispielsweise Polyvinylalkohole, Wachse, beispielsweise Montanwachse, Paraffinwachse, Esterwachse, Polyolefinwachse, Silikone.In a further preferred embodiment of the invention, the coating materials are selected from film-forming substances, such as waxes, silicones, fatty acids, fatty alcohols, soaps, anionic surfactants, nonionic surfactants, cationic surfactants, anionic and cationic polymers, and also polyalkylene glycols. Preference is given to using coating substances having a melting point of 30-100 ° C. Examples of these are: C 8 -C 31 -fatty acids, for example lauric, myristic, stearic acid; C 8 -C 31 fatty alcohols; Polyethylene glycols having a molecular weight of 1,000 to 50,000 g / mol; Fatty alcohol polyalkoxylates with 1 to 100 moles of EO (EO: ethylene oxide unit); Alkanesulfonates, alkylbenzenesulfonates, α-olefinsulfonates, alkyl sulfates, alkyl ether sulfates with C 8 -C 31 -hydrocarbon radicals, polymers, for example polyvinyl alcohols, waxes, for example montan waxes, paraffin waxes, ester waxes, polyolefin waxes, silicones.

In der im Bereich von 30 bis 100 °C erweichenden oder schmelzenden Coatingsubstanz können darüber hinaus weitere in diesem Bereich nicht erweichende oder schmelzende Substanzen in gelöster oder suspendierter Form vorliegen, beispielsweise Homo-, Co-, oder Propfencopolymerisate ungesättigter Carbonsäuren und/ oder Sulfonsäuren sowie deren Alkalisalze, Celluloseether, Stärke, Stärkeether, Polyvinylpyrrolidon; ein- und mehrwertige Carbonsäuren, Hydroxycarbonsäuren oder Ethercarbonsäuren mit 3 bis 8 C-Atomen sowie deren Salze; Silikate, Carbonate, Bicarbonate, Sulfate, Phosphate, Phosphonate.In the coating substance which softens or melts in the range from 30 to 100 ° C., further substances which do not soften or melt in this area can be present in dissolved or suspended form, for example homopolymers, copolymers or propylene copolymers of unsaturated carboxylic acids and / or sulfonic acids and their derivatives Alkali salts, cellulose ethers, starch, starch ethers, polyvinylpyrrolidone; mono- and polybasic carboxylic acids, hydroxycarboxylic acids or ether carboxylic acids having 3 to 8 carbon atoms and salts thereof; Silicates, carbonates, bicarbonates, sulfates, phosphates, phosphonates.

Zum Aufbringen der Hüllsubstanzen können Mischer (mechanisch induzierte Wirbelschicht) und Wirbelschichtapparate (pneumatisch induzierte Wirbelschicht) benutzt werden. Als Mischer sind z. B. Pflugscharmischer (kontinuierlich und chargenweise), Ringschichtmischer oder auch Schugi-Mischer möglich. Die Temperung kann bei Verwendung eines Mischers in einem Granulatvorwärmer und/ oder im Mischer direkt und/ oder in einem dem Mischer nachgeschalteten Fließbett erfolgen. Zur Kühlung des gecoateten Granulates können Granulatkühler oder Fließbettkühler eingesetzt werden. Im Falle von Wirbelschichtapparaturen erfolgt die Temperung über das zur Aufwirbelung verwendete Heißgas. Das nach dem Wirbelschichtverfahren gecoatete Granulat kann ähnlich wie beim Mischverfahren über einen Granulatkühler oder einen Fließbettkühler abgekühlt werden. Sowohl beim Mischverfahren als auch beim Wirbelschichtverfahren kann die Coatingsubstanz über eine Einstoff- oder eine Zweistoffdüsvorrichtung aufgesprüht werden. Die fakultative Temperung besteht in einer Wärmebehandlung bei einer Temperatur von 30 bis 100 °C, jedoch gleich oder unterhalb der Schmelz- oder Erweichungstemperatur der jeweiligen Hüllsubstanz. Bevorzugt arbeitet man bei einer Temperatur, die knapp unterhalb der Schmelz- oder Erweichungstemperatur liegt.For applying the coating substances, mixers (mechanically induced fluidized bed) and fluidized bed apparatuses (pneumatically induced fluidized bed) can be used. As a mixer z. B. plowshare mixer (continuous and batchwise), ring layer mixers or Schugi mixer possible. The tempering can be carried out using a mixer in a granule preheater and / or in the mixer directly and / or in a fluidized bed downstream of the mixer. Granulated coolers or fluid bed coolers can be used to cool the coated granules. In the case of fluidized bed apparatuses, the heat treatment takes place via the hot gas used for fluidization. The granules coated by the fluidized-bed method can be cooled by a granulate cooler or a fluidized-bed cooler, similar to the mixing method. Both in the mixing process and in the fluidized bed process, the coating substance can be sprayed on a single-component or a Zweistoffdüsvorrichtung. The optional tempering consists in a heat treatment at a temperature of 30 to 100 ° C, but equal to or below the melting or softening temperature of the respective shell substance. Preference is given to working at a temperature which is just below the melting or softening temperature.

Weiterhin lassen sich die Coatingmittel in Form von Lösungen oder Suspensionen auf das Primärpartikel auftragen, was im Prinzip mit den zuvor genannten Apparaten möglich ist. Vorzugsweise können hier Wirbelschicht-Apparate zum Einsatz kommen, da diese den Vorteil bieten, dass simultan Flüssigkeit eingesprüht und Feuchtigkeit abgetrocknet werden kann. Damit lässt sich häufig eine erhöhte Flexibilität im Verfahren und in der erzielbaren Produktqualität erzielen.Furthermore, the coating agents can be applied in the form of solutions or suspensions to the primary particle, which is possible in principle with the aforementioned apparatuses. Fluidized bed apparatuses can preferably be used here, since they offer the advantage that liquid can be sprayed in at the same time and moisture dried off. This often results in increased flexibility in the process and in the achievable product quality.

Kennzeichnend für die erfindungsgemäßen Co-Granulate ist in erster Linie ihre chemische Zusammensetzung. Gleichwohl hat es sich erwiesen, dass die Bleichwirkung dieser Co-Granulate auch über die Beeinflussung physikalischer Parameter wie beispielsweise der Teilchengröße, des Feinanteils sowie des Bleichkatalysatorgehalts ausgewählter Siebfraktionen vorteilhaft beeinflusst werden kann.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 also on the influence of physical parameters such as the particle size, the fines content and the Bleach catalyst content of selected Siebfraktionen can be favorably influenced.

Bevorzugte erfindungsgemäße Co-Granulate sind aus diesem Grund dadurch gekennzeichnet, dass das Co-Granulat eine mittlere Teilchengröße zwischen 0,1 und 1,6 mm, vorzugsweise zwischen 0,2 und 1,2 mm und besonders bevorzugt zwischen 0,3 und 1,0 mm aufweist.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.

Die erfindungsgemäßen Co-Granulate eignen sich für den Einsatz in allen Wasch- oder Reinigungsmitteln, wobei sich ihr Einsatz in Mitteln für die maschinelle Reinigung von Geschirr als besonders vorteilhaft erwiesen hat.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.

Weiterer Gegenstand der vorliegenden Erfindung ist daher die Verwendung eines erfindungsgemäßen Co-Granulats zur Herstellung von Wasch- und Reinigungsmitteln und vorzugsweise von Mitteln für die maschinelle Reinigung von Geschirr.Another object of the present invention is therefore the use of a co-granule according to the invention for the production of detergents and cleaners and preferably of agents for the machine cleaning of dishes.

Weiterer Gegenstand der vorliegenden Erfindung sind auch Wasch- und Reinigungsmittel, vorzugsweise Mittel für die maschinelle Reinigung von Geschirr, enthaltend ein erfindungsgemäßes Co-Granulat.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.

Bevorzugte erfindungsgemäße Wasch- und Reinigungsmittel, insbesondere die Mittel für die maschinelle Reinigung von Geschirr, enthalten die erfindungsgemäßen Co-Granulate in Mengen zwischen 0,1 und 10 Gew.-%, vorzugsweise in Mengen zwischen 0,2 und 8 Gew.-% und besonders bevorzugt in Mengen zwischen 0,5 und 6 Gew.-%.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 .-%.

Die erfindungsgemäßen Wasch- und Reinigungsmittel, insbesondere die Mittel für die maschinelle Reinigung von Geschirr, die als Granulate, pulver- oder tablettenförmige Feststoffe aber auch in flüssiger oder pastöser Form vorliegen können, können außer dem erfindungsgemäßen Co-Granulat im Prinzip alle bekannten und in derartigen Mitteln üblichen Inhaltsstoffe enthalten. Die erfindungsgemäßen Wasch- und Reinigungsmittel, insbesondere die Mittel für die maschinelle Reinigung von Geschirr, können insbesondere Buildersubstanzen, Persauerstoffverbindungen, Enzyme, Alkaliträger, oberflächenaktive Tenside, pH-Regulatoren, organische Lösungsmittel und weitere Hilfsstoffe, wie Glaskorrosionsinhibitoren, Silberkorrosionsinhibitoren und Schaumregulatoren enthalten.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 washing and cleaning agents according to the invention, in particular the means for the automatic cleaning of dishes, may 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.

Besonders bevorzugte Wasch- und Reinigungsmittel, insbesondere Mittel für die maschinelle Reinigung von Geschirr, enthalten

  • i) 15 bis 65 Gew.-%, vorzugsweise 20 bis 60 Gew.-%, einer wasserlöslichen Builderkomponente,
  • j) 5 bis 25 Gew.-%, vorzugsweise 8 bis 17 Gew.-%, einer Persauerstoffverbindung, und
  • k) 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
  • i) from 15 to 65% by weight, preferably from 20 to 60% by weight, of a water-soluble builder component,
  • j) 5 to 25 wt .-%, preferably 8 to 17 wt .-%, of a peroxygen compound, and
  • k) 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.

Wasserlösliche Builderkomponente bzw. Buildersubstanzen Als wasserlösliche Builderkomponenten in den erfindungsgemäßen Wasch- und Reinigungsmitteln, insbesondere den Mitteln für die maschinelle Reinigung von Geschirr, kommen prinzipiell alle in derartigen Mitteln üblicherweise eingesetzten Builder in Frage, zum Beispiel Alkaliphosphate, die in Form ihrer alkalischen, neutralen oder sauren Natrium- oder Kaliumsalze vorliegen können. Beispiele hierfür sind Trinatriumphosphat, Tetranatriumdiphosphat, Dinatriumdihydrogendiphosphat, Pentanatriumtriphosphat, sogenanntes Natriumhexametaphosphat sowie die entsprechenden Kaliumsalze beziehungsweise Gemische aus Natrium- und Kaliumsalzen. Ihre Mengen können im Bereich von bis zu etwa 60 Gew.-%, vorzugsweise von 5 bis 20 Gew.-%, bezogen auf das gesamte Mittel, liegen. Weitere mögliche wasserlösliche Builderkomponenten sind neben Polyphosphonaten und Phosphonatalkylcarboxylaten zum Beispiel organische Polymere nativen oder synthetischen Ursprungs vom Typ der Polycarboxylate, die insbesondere in Hartwasserregionen als Co-Builder wirken. In Betracht kommen beispielsweise Polyacrylsäuren und Copolymere aus Maleinsäureanhydrid und Acrylsäure sowie die Natriumsalze dieser Polymersäuren. Handelsübliche Produkte sind zum Beispiel Sokalan™ CP 5, CP 10 und PA 30 der Firma BASF. Zu den als Co-Builder brauchbaren Polymeren nativen Ursprungs gehören beispielsweise oxidierte Stärke und Polyaminosäuren wie Polyglutaminsäure oder Polyasparaginsäure. Weitere mögliche wasserlösliche Builderkomponenten sind natürlich vorkommende Hydroxycarbonsäuren wie zum Beispiel Mono-, Dihydroxybernsteinsäure, alpha -Hydroxypropionsäure und Gluconsäure. Zu den bevorzugten organischen wasserlöslichen Builderkomponenten gehören die Salze der Citronensäure, insbesondere Natriumcitrat. Als Natriumcitrat kommen wasserfreies Trinatriumcitrat und vorzugsweise Trinatriumcitratdihydrat in Betracht. Trinatriumcitratdihydrat kann als fein- oder grobkristallines Pulver eingesetzt werden. In Abhängigkeit vom letztlich in den erfindungsgemäßen Wasch- und Reinigungsmitteln, insbesondere den Mitteln für die maschinelle Reinigung von Geschirr, eingestellten pH-Wert können auch die zu den genannten Co-Builder-Salzen korrespondierenden Säuren vorliegen.Water-soluble builder components 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 commonly employed 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 range 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. Consider, for example Polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids. 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.

Persauerstoffverbindungenperoxygen compounds

Bevorzugte Persauerstoffverbindungen sind Perborate und Percarbonate, insbesondere die entsprechenden Natriumsalze dieser Verbindungen.Preferred peroxygen compounds are perborates and percarbonates, especially the corresponding sodium salts of these compounds.

Enzymeenzymes

Zu den in erfindungsgemäßen Wasch- und Reinigungsmitteln, insbesondere den Mitteln für die maschinelle Reinigung von Geschirr, gegebenenfalls enthaltenen Enzymen gehören Proteasen, Amylasen, Pullulanasen, Cutinasen und/oder Lipasen, beispielsweise Proteasen wie BLAP™, Optimase™, Opticlean™, Maxacal™, Maxapem™, Durazym™, Purafect™ OxP, Esperase™ und/oder Savinase™, Amylasen wie Termamyl™, Amylase-LT™, Maxamyl™, Duramyl™ und/oder Lipasen wie Lipolase™, Lipomax™, Lumafast™ und/oder Lipozym™. Die verwendeten Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Inaktivierung zu schützen. Sie sind in den erfindungsgemäßen Wasch- und Reinigungsmitteln, insbesondere den Mitteln für die maschinelle Reinigung von Geschirr, vorzugsweise in Mengen bis zu 10 Gew.-% und besonders bevorzugt in Mengen von 0,05 bis 5 Gew.-%, enthalten, wobei insbesondere bevorzugt gegen oxidativen Abbau stabilisierte Enzyme eingesetzt werden.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 in the washing and cleaning agents according to the invention, in particular the means for the machine cleaning of dishes, 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 to using enzymes which are stabilized against oxidative degradation.

Alkaliträgeralkali carriers

Vorzugsweise enthalten die erfindungsgemäßen Wasch- und Reinigungsmittel, insbesondere die Mittel für die maschinelle Reinigung von Geschirr, die üblichen Alkaliträger wie zum Beispiel Alkalisilikate, Alkalicarbonate und/oder Alkalihydrogencarbonate. Zu den üblicherweise eingesetzten Alkaliträgern zählen Carbonate, Hydrogencarbonate und Alkalisilikate mit einem Molverhältnis SiO2/M2O (M = Alkaliatom) von 1 : 1 bis 2,5 : 1. Alkalisilikate können dabei in Mengen von bis zu 40 Gew.-%, insbesondere von 3 bis 30 Gew.-%, bezogen auf das gesamte Mittel, enthalten sein. Das in den erfindungsgemäßen Wasch- und Reinigungsmitteln, insbesondere in den Mitteln für die maschinelle Reinigung von Geschirr, bevorzugt eingesetzte Alkaliträgersystem ist ein Gemisch aus Carbonat und Hydrogencarbonat, vorzugsweise Natriumcarbonat und -hydrogencarbonat, das in einer Menge von bis zu 50 Gew.-% und vorzugsweise von 5 bis 40 Gew.-% enthalten sein kann.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, in an amount of up to 50% by weight and preferably from 5 to 40 wt .-% may be included.

In einer weiteren bevorzugten Ausführungsform der Erfindung sind in den erfindungsgemäßen Wasch- und Reinigungsmitteln, insbesondere den Mitteln für die maschinelle Reinigung von Geschirr, 20 bis 60 Gew.-% wasserlöslicher organischer Builder, insbesondere Alkalicitrat, 3 bis 20 Gew.-% Alkalicarbonat und 3 bis 40 Gew.-% Alkalidisilikat enthalten.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.

Tensidesurfactants

Den erfindungsgemäßen Wasch- und Reinigungsmitteln, insbesondere den Mitteln für die maschinelle Reinigung von Geschirr, können gegebenenfalls auch Tenside, insbesondere Aniontenside, zwitterionische Tenside und vorzugsweise schwach schäumende nichtionische Tenside zugesetzt werden, die der besseren Ablösung fetthaltiger Anschmutzungen, als Netzmittel und gegebenenfalls im Rahmen der Herstellung dieser Mittel als Granulierhilfsmittel dienen. Ihre Menge kann bis zu 20 Gew.-%, vorzugsweise bis zu 10 Gew.-% betragen und liegt besonders bevorzugt im Bereich von 0,5 bis 5 Gew.-%. Üblicherweise werden insbesondere in den Mitteln für die maschinelle Reinigung von Geschirr extrem schaumarme Verbindungen eingesetzt. Hierzu zählen vorzugsweise C12-C18-Alkylpolyethylenglykol-polypropylenglykolether mit jeweils bis zu 8 Mol Ethylenoxid- und Propylenoxideinheiten im Molekül. Man kann aber auch andere bekannt schaumarme nichtionische Tenside verwenden, wie zum Beispiel C12-C18-Alkylpolyethylenglykol-polybutylenglykolether mit jeweils bis zu 8 Mol Ethylenoxid- und Butylenoxideinheiten im Molekül, endgruppenverschlossene Alkylpolyalkylenglykolmischether sowie die zwar schäumenden, aber ökologisch attraktiven C8-C14- Alkylpolyglucoside mit einem Polymerisierungsgrad von etwa 1 bis 4 und/oder C12-C14-Alkylpolyethylenglykole mit 3 bis 8 Ethylenoxideinheiten im Molekül. Ebenfalls geeignet sind Tenside aus der Familie der Glucamide wie zum Beispiel Alkyl-N-Methyl-Glucamide, in denen der Alkylteil bevorzugt aus einem Fettalkohol mit der C-Kettenlänge C6-C14 stammt. Es ist teilweise vorteilhaft, wenn die beschriebenen Tenside als Gemische eingesetzt werden, zum Beispiel die Kombination Alkylpolyglykosid mit Fettalkoholethoxylaten oder Glucamid mit Alkylpolyglykosiden. Auch die Anwesenheit von Aminoxiden, Betainen und ethoxlierten Alkylaminen ist möglich.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 can be up to 20 wt .-%, preferably up to 10 wt .-% and is particularly preferably in the range of 0.5 to 5 wt .-%. Usually extremely low-foam compounds are used in particular in the means for the automatic cleaning of dishes. These include, preferably, C 12 -C 18 -alkylpolyethylene glycol-polypropylene glycol ethers having in each case up to 8 mol of ethylene oxide and propylene oxide units in the molecule. But you can also use other known low-foam nonionic surfactants, such as C 12 -C 18 alkylpolyethylene glycol polybutylenglykolether with up to 8 moles of ethylene oxide and butylene oxide in the molecule, endgruppenverschlossene Alkylpolyalkylenglykolmischether and the 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 alkyl polyglycoside with fatty alcohol ethoxylates or glucamide with alkyl polyglycosides. The presence of amine oxides, betaines and ethoxylated alkylamines is also possible.

pH-RegulatorenpH regulators

Zur Einstellung eines gewünschten, sich durch die Mischung der übrigen Komponenten nicht von selbst ergebenden pH-Werts können die erfindungsgemäßen Wasch- und Reinigungsmittel, insbesondere die Mittel für die maschinelle Reinigung von Geschirr, system- und umweltverträgliche Säuren, insbesondere Citronensäure, Essigsäure, Weinsäure, Äpfelsäure, Milchsäure, Glykolsäure, Bernsteinsäure, Glutarsäure und/oder Adipinsäure, aber auch Mineralsäuren, insbesondere Schwefelsäure oder Alkalihydrogensulfate, oder Basen, insbesondere Ammonium- oder Alkalihydroxide, enthalten. Derartige pH-Regulatoren sind in den erfindungsgemäßen Wasch- und Reinigungsmitteln, insbesondere den Mitteln für die maschinelle Reinigung von Geschirr, vorzugsweise nicht über 10 Gew.-% und besonders bevorzugt von 0,5 bis 6 Gew.-% enthalten.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.

Organische LösungsmittelOrganic solvents

Zu den in den erfindungsgemäßen Wasch- und Reinigungsmitteln, insbesondere den Mitteln für die maschinelle Reinigung von Geschirr, insbesondere wenn sie in flüssiger oder pastöser Form vorliegen, verwendbaren organischen Lösungsmitteln gehören Alkohole mit 1 bis 4 C-Atomen, insbesondere Methanol, Ethanol, Isopropanol und tert.-Butanol, Diole mit 2 bis 4 C-Atomen, insbesondere Ethylenglykol und Propylenglykol, sowie deren Gemische und die aus den genannten Verbindungsklassen ableitbaren Ether. Derartige wassermischbare Lösungsmittel sind in den erfindungsgemäßen Wasch- und Reinigungsmitteln, insbesondere in den Mitteln für die maschinelle Reinigung von Geschirr, vorzugsweise in einer Menge nicht über 20 Gew.-% und besonders bevorzugt von 1 bis 15 Gew.-% vorhanden.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.

GlaskorrosionsinhibitorenGlass corrosion inhibitors

Um Glaskorrosion während des Spülganges zu verhindern, können in den erfindungsgemäßen Wasch- und Reinigungsmitteln, insbesondere den Mitteln für die maschinelle Reinigung von Geschirr, entsprechende Inhibitoren eingesetzt werden. Besonders vorteilhaft sind hier kristalline schichtförmige Silikate und/oder Zinksalze. Die kristallinen schichtförmigen Silikate werden beispielsweise von der Fa. Clariant unter dem Handelsnamen Na-SKS vertrieben, z. B. Na-SKS-1 (Na2Si22O45·×H2O, Kenyait), Na-SKS-2 (Na2Si14O29·×H2O, Magadiit), Na-SKS-3 (Na2Si8O17·×H2O) oder Na-SKS-4 (Na2Si4O9·×H2O, Makatit). Von diesen eignen sich vor allem Na-SKS-5 (alpha-Na2Si2O5), Na-SKS-7 (beta-Na2Si2O5, Natrosilit), Na-SKS-9 (NaHSi2O5·H2O), Na-SKS-10 (NaHSi2O5-3H2O, Kanemit), Na-SKS-11 (t-Na2Si2O5) und Na-SKS-13 (NaHSi2O5), insbesondere aber Na-SKS-6 (delta-Na2Si2O5). Einen Überblick über kristalline Schichtsilikate findet sich z. B. in dem in " Seifen-Öle-Fette-Wachse, 116 Jahrgang, Nr. 20/1990", auf den Seiten 805-808 veröffentlichten Artikel.In order to prevent glass corrosion during the rinse cycle, corresponding inhibitors can be used in the detergents and cleaners according to the invention, in particular the detergents for dishwashing machines. 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. × 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. × H 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 einer weiteren bevorzugten Ausführungsform der Erfindung weisen die erfindungsgemäßen Wasch- und Reinigungsmittel, insbesondere die Mittel für die maschinelle Reinigung von Geschirr, eine Menge des kristallinen schichtförmigen Silikats von vorzugsweise 0,1 bis 20 Gew.-%, besonders bevorzugt 0,2 bis 15 Gew.-% und insbesondere bevorzugt 0,4 bis 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht dieser Mittel, auf.In a further preferred embodiment of the invention, the washing and cleaning agents according to the invention, in particular the means for the machine cleaning of dishes, an amount of the crystalline layered silicate of preferably 0.1 to 20 wt .-%, particularly preferably 0.2 to 15 wt .-% and particularly preferably 0.4 to 10 wt .-%, each based on the total weight of these agents on.

Zur Unterdrückung der Glaskorrosion können erfindungsgemäße Wasch- und Reinigungsmittel, insbesondere die Mittel für die maschinelle Reinigung von Geschirr, mindestens ein Zink- oder Wismutsalz enthalten, vorzugsweise ausgewählt aus der Gruppe der organischen Zinksalze, besonders bevorzugt ausgewählt aus der Gruppe der löslichen organischen Zinksalze, insbesondere bevorzugt ausgewählt aus der Gruppe der löslichen Zinksalze monomerer oder polymerer organischer Säuren und außerordentlich bevorzugt ausgewählt aus der Gruppe Zinkacetat, Zinkacetylacetonat, Zinkbenzoat, Zinkformiat, Zinklactat, Zinkgluconat, Zinkoxalat, Zinkricinoleat, Zinkabietat, Zinkvalerat und Zink-p-toluolsulfonat. Alternativ oder in Kombination mit diesen Zinksalzen können Wismutsalze wie z. B. Wismutacetate engesetzt werden.To suppress glass corrosion, detergents and cleaners according to the invention, in particular the detergents for dishwashing, may comprise 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, in particular preferably 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 valerate and zinc p-toluenesulfonate. Alternatively or in combination with these zinc salts bismuth salts such. B. bismuth acetates are used.

Als bevorzugt gelten im Rahmen der vorliegenden Erfindung dabei erfindungsgemäße Wasch- und Reinigungsmittel, insbesondere Mittel für die maschinelle Reinigung von Geschirr, bei denen die Menge des Zinksalzes bezogen auf das Gesamtgewicht dieses Mittels 0,1 bis 10 Gew.-%, vorzugsweise 0,2 bis 7 Gew.-% und besonders bevorzugt 0,4 bis 4 Gew.-% beträgt und zwar unabhängig davon, welche Zinksalze eingesetzt werden, insbesondere also unabhängig davon, ob organische oder anorganische Zinksalze, lösliche oder nicht lösliche Zinksalze oder deren Mischungen eingesetzt werden.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 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 ,

SilberkorrosionsinhibitorenSilver corrosion inhibitors

Um einen Silberkorrosionsschutz zu bewirken, können in erfindungsgemäßen Wasch- und Reinigungsmitteln, insbesondere den Mitteln für die maschinelle Reinigung von Geschirr, Silberkorrosionsinhibitoren eingesetzt werden. Bevorzugte Silberkorrosionsinhibitoren sind organische Sulfide wie Cystin und Cystein, zwei- oder dreiwertige Phenole, gegebenenfalls alkyl- oder arylsubstituierte Triazole wie Benzotriazol, Isocyanursäure, Titan-, Zirkonium-, Hafnium-, Cobalt- oder Cersalze und/oder -komplexe, in denen die genannten Metalle je nach Metall in einer der Oxidationsstufen II, III, IV, V oder VI vorliegen.To effect silver corrosion protection, silver corrosion inhibitors can be used in detergents and cleaners according to the invention, in particular the detergents for dishwashing. 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.

SchaumregulatorenFoam regulators

Sofern die erfindungsgemäßen Wasch- und Reinigungsmittel, insbesondere die Mittel für die maschinelle Reinigung von Geschirr, zum Beispiel bei Anwesenheit von Aniontensiden, bei der Anwendung zu stark schäumen, können ihnen noch bis zu 6 Gew.-%, vorzugsweise etwa 0,5 bis 4 Gew.-% einer schaumdrückenden Verbindung, vorzugsweise aus der Gruppe der Silikonöle, Gemische aus Silikonöl und hydrophobierter Kieselsäure, Paraffine, Paraffin-Alkohol-Kombinationen, hydrophobierter Kieselsäure, der Bisfettsäureamide, und sonstiger weiterer bekannter im Handel erhältliche Entschäumer zugesetzt werden.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.

Die erfindungsgemäßen Wasch- und Reinigungsmittel, insbesondere die Mittel für die maschinelle Reinigung von Geschirr, können als weitere Inhaltsstoffe beispielsweise aus dem Stand der Technik für derartige Mittel bekannte Sequestrierungsmittel, Elektrolyle, zusätzliche Persauerstoff-Aktivatoren, Farbstoffe oder Duftstoffe wie zum Beispiel Parfümöle enthalten.The detergents and cleaners according to the invention, in particular the means for machine dishwashing, may contain, as further ingredients, for example from the prior art, sequestrants, electrolytes, additional peroxygen activators, dyes or fragrances, for example perfume oils.

Herstellung der erfindungsgemäßen Wasch- und ReinigungsmittelPreparation of detergents and cleaning agents according to the invention

Die Herstellung der erfindungsgemäßen festen Wasch- und Reinigungsmittel, insbesondere Mittel für die maschinelle Reinigung von Geschirr, bietet keine Schwierigkeiten und kann in im Prinzip bekannter Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen, wobei Persauerstoffverbindung und erfindungsgemäßes Co-Granulat gegebenenfalls später getrennt zugesetzt werden.The preparation of the solid detergents and cleaners according to the invention, in particular 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 added separately later become.

Erfindungsgemäße Wasch- und Reinigungsmittel in Form wässriger oder sonstige übliche Lösungsmittel enthaltender Lösungen, insbesondere entsprechende Mittel für die maschinelle Reinigung von Geschirr, werden besonders vorteilhaft durch einfaches Mischen der Inhaltsstoffe, die in Substanz oder als Lösung in einen automatischen Mischer gegeben werden können, hergestellt.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.

Die erfindungsgemäßen Wasch- und Reinigungsmittel, insbesondere Mittel für die maschinelle Reinigung von Geschirr, liegen vorzugsweise als pulverförmige, granulare oder tablettenförmige Präparate vor, die in an sich bekannter Weise, beispielsweise durch Mischen, Granulieren, Walzenkompaktieren und/oder durch Sprühtrocknung der thermisch belastbaren Komponenten und Zumischen der empfindlicheren Komponenten, zu denen insbesondere Enzyme, Bleichmittel und der Bleichkatalysator zu rechnen sind, hergestellt werden können.The washing and cleaning agents according to the invention, in particular means for the automatic cleaning of dishes, are preferably in the form of powdered, granular or tablet-shaped preparations which are prepared in a manner known per se, for example by mixing, granulating, roll compacting and / or by spray-drying the thermally stable components and admixing the more sensitive components, to which in particular enzymes, bleaching agents and the bleach catalyst are to be expected can.

Zur Herstellung von erfindungsgemäßen Wasch- und Reinigungsmitteln, insbesondere Mitteln für die maschinelle Reinigung von Geschirr, in Tablettenform geht man vorzugsweise derart vor, dass man alle Bestandteile in einem Mischer miteinander vermischt und das Gemisch mittels herkömmlicher Tablettenpressen, beispielsweise Exzenterpressen oder Rundläuferpressen, mit Pressdrucken im Bereich von 200 105 bis 1500 105 Pa verpresst.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 to 1500 105 Pa pressed.

Man erhält so problemlos bruchfeste und dennoch unterYou get so unbreakable and yet under

Anwendungsbedingungen ausreichend schnell lösliche Tabletten mit Biegefestigkeiten von normalerweise über 150 N. Vorzugsweise weist eine derart hergestellte Tablette ein Gewicht von 15 bis 40 g, insbesondere von 20 bis 30 g auf, bei einem Durchmesser von 35 bis 40 mm.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.

Die Herstellung erfindungsgemäßer Wasch- und Reinigungsmittel in Form von nicht staubenden, lagerstabil rieselfähigen Pulvern und/oder Granulaten mit hohen Schüttdichten im Bereich von 800 bis 1.000 g/l, insbesondere entsprechender erfindungsgemäßer Mittel für die maschinelle Reinigung von Geschirr, kann dadurch erfolgen, dass man in einer ersten Verfahrensteilstufe die BuilderKomponenten mit wenigstens einem Anteil flüssiger Mischungskomponenten unter Erhöhung der Schüttdichte dieses Vorgemisches vermischt und nachfolgend - gewünschtenfalls nach einer Zwischentrocknung - die weiteren Bestandteile des Mittels, darunter das erfindungsgemäße Co-Granulat, mit dem so gewonnenen Vorgemisch vereinigt.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.

Erfindungsgemäße Mittel für die maschinelle Reinigung von Geschirr können sowohl in Haushaltsgeschirrspülmaschinen wie in gewerblichen Spülmaschinen eingesetzt werden. Die Zugabe erfolgt von Hand oder mittels geeigneter Dosiervorrichtungen. Die Anwendungskonzentrationen in der Reinigungsflotte betragen in der Regel etwa 1 bis 8 g/l, vorzugsweise 2 bis 5 g/l.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 done 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.

Ein maschinelles Spülprogramm wird im Allgemeinen durch einige auf den Reinigungsgang folgende Zwischenspülgänge mit klarem Wasser und einem Klarspülgang mit einem gebräuchlichen Klarspülmittel ergänzt und beendet. Nach dem Trocknen erhält man beim Einsatz erfindungsgemäßer Mittel ein völlig sauberes und in hygienischer Hinsicht einwandfreies Geschirr.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.

BeispieleExamples

Im Folgenden bedeuten %-Angaben Gewichtsprozent (Gew.-%), sofern nicht explizit anders angegeben. Bezüglich der angegebenen relativen Luftfeuchten haben die %-Angaben die übliche Bedeutung.In the following, percentages% by weight (% by weight) unless explicitly stated otherwise. With regard to the stated relative humidities, the% values have the usual meaning.

Der technisch verfügbare Bleichaktivator TAED (Tetraacetylethylendiamin) wurde von Clariant in Pulverform bezogen, die Mangansalze wurden von Sigma-Aldrich bezogen und die verwendeten Metallkomplexe wurden gemäß Literatur hergestellt.The industrially available bleach activator TAED (tetraacetylethylenediamine) was obtained from Clariant in powder form, the manganese salts were purchased from Sigma-Aldrich and the metal complexes used were prepared according to literature.

Beispiel 1: Herstellung von erfindungsgemäßen Co-Granulaten mit Aktivcoating Hierbei handelt es sich um Co-Granulate-enthaltend TAED und einen Bleichkatalysator, wie z. B. Mn (II)-sulfat, der speziell als Aktivcoating aufgebracht ist. Zusätzlich enthalten die Co-Granulate die erforderlichen Granulierhilfsmittel, wie Bindemittel und Coatingsubstanz, gegebenenfalls aber auch weitere Additive wie z. B. Stabilisatoren.Example 1: Preparation of co-granules according to the invention with active coating These are co-granules containing TAED and a bleach catalyst, such. B. Mn (II) sulfate, which is applied specifically as an active coating. In addition, the co-granules contain the necessary granulation aids, such as binders and coating substance, but optionally also other additives such. B. stabilizers.

Zur Vorbereitung des Aktivcoatings wird Stearinsäure als Hüllsubstanz bzw. Coatingmittel bei T = 95 °C in einem Rührbehälter vorgelegt und aufgeschmolzen. In die gerührte Schmelze wird der Bleichkatalysator eingetragen und gleichmäßig verteilt. Der Bleichkatalysator wurde zuvor in einer Labormühle zerkleinert.To prepare the active coating, stearic acid is initially introduced as a coating substance or coating agent at T = 95 ° C. in a stirred vessel and melted. The bleach catalyst is added to the stirred melt and distributed uniformly. The bleach catalyst was previously comminuted in a laboratory mill.

Als Basisgranulat für das Aktivcoating wird ein TAED-Granulat (Peractive CB - Handelsprodukt der Fa. Clariant enthaltend Bentonit) in einem Labormischer vorgelegt. Das Granulat wird unter moderatem Rühren auf die erforderliche Starttemperatur von T > 70 °C erwärmt. Bei etwas erhöhter Rührgeschwindigkeit wird die Schmelzemischung mit dem Bleichkatalysator gleichmäßig und langsam zudosiert, so dass die Mischung gleichmäßig auf den Basisgranulaten verteilt wird und ein übermäßiges Aufgranulieren vermieden wird. Nach dem Aufbringen der Sollmenge der Schmelzemischung wird das gecoatete Granulat kurz nachgemischt aus dem Mischer entleert und abgekühlt. Anschließend wird das Produkt zur Abtrennung von Grob- und Feinanteilen von 200 - 1.600 µm abgesiebt.The basic granulate for the active coating is a TAED granulate (Peractive CB - commercial product from Clariant containing bentonite) in a laboratory mixer submitted. The granules are heated with moderate stirring to the required starting temperature of T> 70 ° C. At a slightly higher stirring speed, the melt mixture is metered in evenly and slowly with the bleach catalyst, so that the mixture is evenly distributed on the base granules and excessive overgranulation is avoided. After application of the desired amount of the melt mixture, the coated granules are briefly emptied from the mixer emptied and cooled. The product is then sieved to remove coarse and fine fractions of 200-1600 μm.

Im Fall des erfindungsgemäßen Co-Granulats A werden anstelle der Verwendung von Peractive CB zunächst TAED, Bentonit und Oxalsäure gemischt, anschließend granuliert und die erhaltenen Granulate gecoatet.In the case of the inventive co-granule A, instead of using Peractive CB, TAED, bentonite and oxalic acid are first mixed, then granulated and the resulting granules are coated.

Die Tabelle 1 zeigt eine Übersicht der hergestellten erfindungsgemäßen Co-Granulate mit Aktivcoating, die für weitere Untersuchungen bereitgestellt wurden. Tabelle 1: erfindungsgemäße Co-Granulate mit Aktivcoating Beispiel Co-Granulat A B C D Substanzen Bleichaktivator TAED TAED TAED TAED Bleichkatalysator Mn(II)-Sulfat Mn(II)-Sulfat Komplex 1 Komplex 2 Bleichaktivator : Bleichkatalysator 8.3:1 7.7:1 11.5:1 11.5:1 Bindemittel Bentonit Bentonit Bentonit Bentonit Organische Säure Oxalsäure - - - Coatingmittel Stearinsäure Stearinsäure Stearinsäure Stearinsäure Farbstoff im Coating - - - rot Zusammensetzung Bleichaktivator % 70,08 [K; 84,3] 74,32 [K; 92,0] 75,18 [K; 90,8] 74,88 [K; 91,2] Bleichkatalysator % 8,41 [H; 50,0] 9,61 [H; 50,0] 6,54 [H; 38,0] 6,51 [H; 36,4] Bindemittel % 6,09 [K; 7,3] 6,46 [K; 8,0] 7,62 [K; 9,2] 7,26 [K; 8,8] Organische Säure % 7,01 [K; 8,4] - - - Coatingmittel % 8,41 [H; 50,0] 9,61 [H; 50,0] 10,66 [H; 62,0] 11,05 [H; 61,9] Farbstoff % - - - 0,30 [H; 1,7] Kern : Hülle [Gewichtsverhältnis] 83,2 : 16,8 80,8 : 19,2 82,8 : 17,2 82,1 : 17,9 TAED Tetraacetylethylendiamin Komplex 1 [MnIV 2(µ-O)3(Me-TACN)2](PF6)2, hergestellt gemäß EP 0 458 397 Komplex 2 1,8-Diethyl-1,4,8,11-Tetraazacyclotetradecan-mangan(II)chlorid, hergestellt nach EP 1 557 457 Table 1 shows an overview of the prepared co-granules according to the invention with active coating, which were provided for further investigations. Table 1: Co-granules according to the invention with active coating Example co-granules A B C D substances bleach TAED TAED TAED TAED bleach catalyst Mn (II) sulfate Mn (II) sulfate Complex 1 Complex 2 Bleach activator: bleach catalyst 8.3: 1 7.7: 1 5.11: 1 5.11: 1 binder bentonite bentonite bentonite bentonite Organic acid oxalic acid - - - coating agents stearic acid stearic acid stearic acid stearic acid Dye in the coating - - - red composition bleach % 70.08 [K; 84.3] 74.32 [K; 92.0] 75,18 [K; 90.8] 74.88 [K; 91.2] bleach catalyst % 8.41 [H; 50.0] 9.61 [H; 50.0] 6.54 [H; 38.0] 6.51 [H; 36.4] binder % 6.09 [K; 7,3] 6,46 [K; 8.0] 7.62 [K; 9,2] 7.26 [K; 8.8] Organic acid % 7.01 [K; 8,4] - - - coating agents % 8.41 [H; 50.0] 9.61 [H; 50.0] 10.66 [H; 62.0] 11.05 [H; 61.9] dye % - - - 0.30 [H; 1,7] Core: shell [weight ratio] 83.2: 16.8 80.8: 19.2 82.8: 17.2 82.1: 17.9 TAED tetraacetylethylenediamine Complex 1 [Mn IV 2 (μ-O) 3 (Me-TACN) 2 ] (PF 6 ) 2 prepared according to EP 0 458 397 Complex 2 1,8-diethyl-1,4,8,11-tetraazacyclotetradecane manganese (II) chloride, prepared according to EP 1 557 457

In Tabelle 1 ist sowohl die Menge der Inhaltsstoffe bezogen auf das gesamte erfindungsgemäße Co-Granulat in Gew.-% angegeben, als auch die Menge der jeweiligen Inhaltsstoffe in Gew.-% entweder bezogen auf den gesamten Granulatkern oder auf die gesamte Hüll- oder Coatingschicht, je nachdem, in welchem Teil des erfindungsgemäßen Co-Granulats der entsprechende Inhaltsstoff enthalten ist. Dabei bedeutet beispielsweise die Angabe "[K; 84,3]" für den Bleichaktivator des Co-Granulats A, dass der Bleichaktivator im Granulatkern enthalten ist und seine Menge - nur bezogen auf die Gesamtmasse des Granulatkerns - 84,3 Gew.-% ist. Dementsprechend bedeutet beispielsweise die Angabe "[H; 50,0]" für den Bleichkatalysator des Co-Granulats A, dass der Bleichkatalysator in der Hüll- bzw. Coatingschicht enthalten ist und seine Menge - nur bezogen auf die Gesamtmasse der Hüll- bzw. Coatingschicht - 50,0 Gew.-% ist.In Table 1, both the amount of ingredients based on the total inventive co-granules in wt .-% is given, as well as the amount of the respective ingredients in wt .-% either based on the entire granule core or on the entire coating or coating layer depending on in which part of the co-granules according to the invention the corresponding ingredient is contained. In this case, for example, the statement "[K, 84.3]" for the bleach activator of the co-granule A means that the bleach activator is contained in the granule core and its amount is only 84.3% by weight, based on the total mass of the granule core , Accordingly, for example, the specification "[H;50.0]" for the bleach catalyst of the co-granule A means that the bleach catalyst is contained in the coating layer and its amount - based only on the total mass of the coating layer - 50.0 wt .-% is.

Beispiel 2: Hygroskopizitätstest - physikalische StabilitätExample 2: Hygroscopicity Test - Physical Stability

Zur Überprüfung der physikalischen Stabilität der erfindungsgemäßen Co-Granulate wird das hygroskopische Verhalten bei erhöhter relativer Luftfeuchte geprüft. Dazu werden die Co-Granulate über mehrere Stunden offen bei einer relativen Luftfeuchte von 65 % und Raumtemperatur gelagert. Über den Versuchszeitraum wird die Feuchtigkeitsaufnahme über eine Waage registriert und die äußere Veränderung der Probe beobachtet. Nach Abschluss des Lagerversuchs wird neben der Gewichtszunahme auch die Rieselfähigkeit bzw. der Grad der Verbackung anhand von Noten beurteilt (Note 1: sehr gut, frei rieselfähig bis Note 6: völlig verbacken, nicht mehr rieselfähig).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).

Die Tabelle 2 zeigt die Ergebnisse des Hygroskopizitätstests für die zuvor beschriebenen Co-Granulate. Tabelle 2: Hygroskopizitätstest Hygroskopizität - 65 % rH Beispiel Co-Granulat A B C D Feuchtigkeitsaufnahme % 1,5 1,8 3,3 2,5 Note (Rieselfähigkeit) 1 1 1 1 Bewertung Granulat sehr gut sehr gut sehr gut sehr gut rH: relative Luftfeuchte Table 2 shows the results of the hygroscopicity test for the co-granules described above. Table 2: Hygroscopicity test Hygroscopicity - 65% RH Example co-granules A B C D Moisture absorption% 1.5 1.8 3.3 2.5 Note (free-flowing) 1 1 1 1 Review Granules very well very well very well very well rH: relative humidity

Die Ergebnisse zeigen, dass die erfindungsgemäßen Co-Granulate trotz einer erkennbaren Feuchtigkeitsaufnahme von > 1,5 % rieselfähig bleiben und unter Einwirkung einer erhöhten Luftfeuchte nicht verbacken.The results show that the co-granules according to the invention remain free-flowing despite a detectable moisture absorption of> 1.5% and do not cake under the effect of increased air humidity.

Beispiel 3: Lagerversuche in Basis-Waschpulver - chemische Lagerstabilität Zur Überprüfung der physikalischen Stabilität der erfindungsgemäßen Co-Granulate wird das Lagerverhalten in einer typischenExample 3: Storage Tests in Basic Washing Powder - Chemical Storage Stability To check the physical stability of the co-granules according to the invention, the storage behavior is determined in a typical manner

Waschpulverformulierung untersucht. Hierzu werden die gecoateten Co-Granulate in IEC-A Basiswaschpulver eingearbeitet, so dass die fertige Formulierung 5 % erfindungsgemäßes Co-Granulat enthält. Die Mischungen werden anschließend bei Raumklima und verschärften Klimabedingungen (T = 40 °C, 75 % relative Luftfeuchte) über mehrere Tage gelagert. In regelmäßigen Abständen werden die Proben hinsichtlich der Verfärbung der Co-Granulate beurteilt und mit Noten bewertet (Note 1: sehr gut, keine Verfärbung bis Note 6: starke Verfärbung, sehr dunkle Farbe).Washing powder formulation examined. For this purpose, the coated co-granules incorporated in IEC-A base wash powder, so that the finished formulation contains 5% of the invention 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).

Die Tabelle 3 zeigt die Ergebnisse des Lagerversuchs in Basis-Waschpulver für die zuvor beschriebenen Co-Granulate. Tabelle 3: Lagerversuch in Basis-Waschpulver Lagerstabilität in Basiswaschpulver IEC-A Beispiel Co-Granulat A B C D Lagerdauer Raumklima [Tage] 20 20 13 13 Note (Verfärbung) 2 1 1 2 Bewertung Probe gut sehr gut sehr gut gut Lagerdauer 40°C, 75 % rH [Tage] 20 20 13 13 Note (Verfärbung) 2 2 3 3 Bewertung Probe gut gut akzeptabel akzeptabel rH: relative Luftfeuchte 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 Storage stability in base wash powder IEC-A Example co-granules A B C D Storage duration room climate [Days] 20 20 13 13 Note (discoloration) 2 1 1 2 Review sample Good very well very well Good Storage time 40 ° C, 75% rH [Days] 20 20 13 13 Note (discoloration) 2 2 3 3 Review sample Good Good acceptable acceptable rH: relative humidity

Die Ergebnisse zeigen, dass alle untersuchten erfindungsgemäßen Co-Granulate sowohl bei Raumklima als auch unter verschärften Klimabedingungen eine gute bis sehr gute Lagerstabilität aufweisen. Das Aktivcoating bietet daher auch den Vorteil einer erhöhten Lagerstabilität, so dass eine Beeinträchtigung durch eine negative Farbveränderung der erfindungsgemäßen Co-Granulate vermieden werden konnte.The results show that all tested co-granules according to the invention have a good to very good storage stability both in room climate and under severe climatic conditions. The active coating therefore also offers the advantage of increased storage stability, so that impairment by a negative color change of the co-granules according to the invention could be avoided.

Claims (9)

  1. A cogranule comprising a granule core and a shell layer or coating layer surrounding the granule core, wherein the granule core comprises
    a) one or more bleach activators,
    a2) 0% by weight of the total amount of one or more bleach catalysts present in the cogranule and
    c) one or more binders
    and the shell layer or coating layer comprises
    d) 100% by weight of the total amount of the one or more bleach catalysts present in the cogranule and
    e) one or more coating agents,
    and the weight ratio of granule core to shell layer or coating layer is from 95:5 to 50:50.
  2. The cogranule as claimed in claim 1, wherein the granule core comprises
    a) 1 to 99% by weight of one or more bleach activators and
    c) 0.9 to 30% by weight of one or more binders and the shell layer or coating layer comprises
    d) 1 to 99% by weight of one or more bleach catalysts and
    e) 1 to 99% by weight of one or more coating agents.
  3. The cogranule as claimed in claim 1 or 2, wherein the granule core comprises
    a) 50 to 95% by weight of one or more bleach activators and
    c) 4.9 to 20% by weight of one or more binders and the shell layer or coating layer comprises
    d) 2 to 60% by weight of one or more bleach catalysts and
    e) 40 to 98% by weight of one or more coating agents.
  4. The cogranule as claimed in one or more of claims 1 to 3, wherein the weight ratio of granule core to shell layer or coating layer is from 90:10 to 60:40.
  5. The cogranule as claimed in one or more of claims 1 to 4, wherein the one or more bleach activators are selected from tetraacetylethylenediamine and decanoyloxybenzoic acid.
  6. The cogranule as claimed in one or more of claims 1 to 5, wherein the one or more bleach catalysts are selected from manganese salts and manganese complexes.
  7. The cogranule as claimed in one or more of claims 1 to 6, wherein the one or more binders are selected from fatty acids, alcohol ethoxylates, polymers and natural clay minerals and are preferably selected from natural clay minerals.
  8. The cogranule as claimed in one or more of claims 1 to 7, wherein the coating materials are selected from fatty acids, alcohol ethoxylates and polymers and are preferably selected from fatty acids.
  9. The use of one or more cogranules as claimed in one or more of claims 1 to 8 for producing detergents and cleaners and preferably compositions for machine dishwashing.
EP10712904.1A 2009-04-11 2010-04-01 Bleach granules comprising an active coating Active EP2417240B1 (en)

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