DE102004043359A1 - Bleaching activator-granulates, useful e.g. in washing-, cleaning- and disinfecting agents, comprises hydroxybenzoicacid derivatives, quaternary hydroxyalkyl ammonium compounds and granulation auxiliary- and/or coating agents - Google Patents

Abstract

Bleaching activator-granulates (A) comprises a hydroxybenzoicacid derivative (I), a quaternary hydroxy alkyl ammonium compound (II) and at least a granulation auxiliary agent (III) and/or a coating agent (IV). Bleaching activator-granulates (A) comprises a hydroxybenzoic acid derivative of formula (I), a quaternary hydroxyalkyl ammonium compound of formula (II) and at least a granulation auxiliary agent (III) and/or a coating agent (IV). R : 8-11C alkyl; R1>5-22C alkyl, 5-22C alkenyl, 5-22C alkylamidopropyl, 5-22C alkenyl-amidopropyl, 8-22C alkoxypropyl or 5-22C alkenyloxypropyl; R2>1-22C alkyl or 2-22C alkenyl; R3>1-22C-alkyl, 2-22C alkenyl or a group of formula -A-(OA)n-OH; R4>a group of formula -A-(OA)n; A : -C2H4- and/or -C3H6-; n : 0-20; and X : anion. An independent claim is also included for a washing-, cleaning- and disinfecting agent comprising (A). [Image].

Description

object The invention provides improved bleach activators in granular form and their use in detergents, cleaners and disinfectants.

Inorganic peroxygen compounds, particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes. The oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H ₂ O ₂ or perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles.

at lower temperatures can reduce the oxidation effect of the inorganic Peroxygen compounds by addition of so-called bleach activators be improved. Therefor In the past, numerous proposals were drawn up, especially from the classes of N- or O-acyl compounds, for example, several times acylated alkylenediamines, especially tetraacetylethylenediamine and tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, Hydrotriazines, urazoles. Diketopiperazines, sulfurylamides and cyanurates, as well as carboxylic acid anhydrides, in particular phthalic anhydride and substituted maleic anhydrides, Carbonsäureester, especially sodium acetoxybenzenesulfonate, Sodium benzoyloxybenzenesulfonate (BOBS), sodium nonanoyloxy-benzenesulfonate (NOBS), sodium isononanoyloxybenzenesulfonate (ISONOBS) and acylated sugar derivatives, such as pentaacetyl glucose. By adding these substances, the bleaching effect of aqueous peroxide be increased so much that even at temperatures around 40 - 60 ° C substantially the same effects as with the peroxide solution alone at 95 ° C occur.

Bleach activators are essential ingredients in powdered or tableted detergents, spot salts or machine dishwashing detergents, wherein they are used in particular in granulated form. hereby will their storage stability clearly increased. The achievable bleaching result is essentially determined by the water solubility the activator, the structure of the compound to be perhydrolyzed, Nature and reactivity the formed peracid, granulating agent and type of granule production.

Bleach activators can be considered in terms of their reactivity to certain soils into two classes, hydrophilic and hydrophobic. Hydrophilic Bleach activators in particular remove tea or red wine stains, while hydrophobic activators preferably oily discoloration How to discolor ketchup and barbecue sauce. Many of the daily Life occurring stains do not fall into these classes (e.g., grass, curry) or are mixtures of various soils (e.g., baby food). Here leads the use of a single bleach activator usually unsatisfactory Results. With regard to further sinking wash temperatures and More volume-efficient formulations will be synergistic in the future Detergent ingredient mixtures of particular interest.

The Use of special activator mixtures consisting of a hydrophilic and a hydrophobic activator is prior art. As hydrophobic Component become predominant Derivatives of the highly water-soluble Sodium phenolsulfonates used. Thus, e.g. in EP-A-0 257 700 mixtures of nonanoyloxybenzenesulfonate with tetraacetylethylenediamine, Benzoyloxybenzolsulfonat or acetoxybenzenesulfonate claims. WO 02/083 829 (Warwick) describes improved efficacy of mixtures consisting of tetraacetylethylenediamine and sodium 4- (sulfophenyl octyl) carbonate. Similar Mixtures are also described in EP-A-098129 and EP-A-0120591.

Next Mixtures of two bleach activators can also be mixtures of a Bleach activator synergistic with other detergent ingredients Have properties. An example of this are mixtures of activators based on good water-soluble Phenolsulfosäure salts (Nonanoyloxybenzolsulfonat or Octamidooxybenzolsulfonaten) with Bis-alkoxylated ammonium quats. Furthermore, mixtures consisting of alkoxylated ammonium quats with lactam-based activators (benzoylcaprolactam) or water-soluble Derivatives of phenolsulfonic acids known.

The bleaching optimum of synergistic mixtures of an activator with other detergent ingredients is dependent on the nature and the mixing ratio of the two components and on the type of soils to be removed. The bleaching results can not theoretically be calculated in advance. There is therefore still much interest in novel mixtures with which syner gistic effects can be achieved. There is particular interest in storage-stable mixtures in granulated form, since they are used in powdery or tableted detergents and cleaners.

One Disadvantage of using quaternary hydroxyalkylammonium compounds is that they are mostly just as watery solutions available in relatively low concentrations and solid in this form for the production Washing and cleaning agents are problematic. Concentrating one the watery Solutions, receives hard-to-handle high-viscosity gels. To quaternary hydroxyalkylammonium compounds In granular form, various methods have been used. Examples of this can be found in WO 96/17042, WO 98/53037 and WO 01/81528.

Special Problems arise when these quaternary hydroxyalkylammonium compounds with a good water-soluble Bleach activator such as e.g. Granulated derivatives of salts of phenolsulfonic acid should always be the risk of hydrolysis of the Part solved Activator is connected under granulation.

Surprisingly it has now been found that mixtures of bleach activators based on of hydroxybenzoic acids and certain quaternary Hydroxyalkylammonium compounds not only significant synergistic Have effects on difficult to remove soils, but due to the poor water solubility of Hydroxybenzoesäurederivate granulate well.

wobei in Formel (I)
R = eine C₈-C₁₁ Alkylgruppe bedeutet, und in Formel (II) R¹ lineares oder verzweigtes C₅-C₂₂-Alkyl, C₅-C₂₂-Alkenyl, C₅-C₂₂-Alkylamidopropyl, C₅-C₂₂-Alkenyl-amidopropyl, C₈-C₂₂-Alkoxypropyl oder C₅-C₂₂-Alkenyloxypropyl, R² C₁-C₂₂-Alkyl oder C₂-C₂₂-Alkenyl, R³ C₁-C₂₂-Alkyl, C₂-C₂₂-Alkenyl oder eine Gruppe der Formel -A-(OA)_n-OH bedeutet, wobei A -C₂H₄- und/oder -C₃H₆- ist und n für eine Zahl von 0 bis 20 steht, und R⁴ eine Gruppe der Formel -A-(OA)_n-OH und X ein Anion bedeutet, beispielsweise Chlorid, Bromid, Iodid, Fluorid, Sulfat, Hydrogensulfat, Carbonat, Hydrogencarbonat, Phosphat, Mono- und Di-Hydrogenphosphat, Pyrophosphat, Metaphosphat, Nitrat, Methylsulfat, Phosphonat, Methylphosphonat, Methandisulfonat, Methylsulfonat, Ethansulfonat oder eine anionische Verbindung der Formeln R⁶SO₃⊝, R⁷SO₄⊝ oder R⁶COO⊝, worin R⁶ und R⁷ C₈-C₂₀-, vorzugsweise C₁₀-C₁₈-Alkyl, und R⁷ zusätzlich auch C₇-C₁₈-Alkylphenyl bedeuten.The present invention therefore granules consisting of a Hydroxybenzoesäurederivat of the general formula (I), a quaternary hydroxyalkylammonium compound of the general formula (II) and at least one Granulierhilfs- and / or Coatingmittel,

in formula (I)
R = a C ₈ -C ₁₁ alkyl group, and in formula (II) R ¹ linear or branched C ₅ -C ₂₂ alkyl, C ₅ -C ₂₂ alkenyl, C ₅ -C ₂₂ alkylamidopropyl, C ₅ -C ₂₂ alkenyl amidopropyl, C ₈ -C ₂₂ alkoxypropyl or C ₅ -C ₂₂ alkenyloxypropyl, R ² C ₁ -C ₂₂ alkyl or C ₂ -C ₂₂ alkenyl, R ³ C ₁ -C ₂₂ alkyl, C ₂ -C ₂₂ alkenyl or a group of the formula -A- (OA) _n -OH, where A is -C ₂ H ₄ - and / or -C ₃ H ₆ - and n is a number from 0 to 20 and R ^{4 is} a group of the formula -A- (OA) _n -OH and X is an anion, for example chloride, bromide, iodide, fluoride, sulfate, hydrogensulfate, carbonate, bicarbonate, phosphate, mono- and di-hydrogen phosphate, Pyrophosphate, metaphosphate, nitrate, methylsulfate, phosphonate, methylphosphonate, methanedisulfonate, methylsulfonate, ethanesulfonate or an anionic compound of the formulas R ⁶ SO ₃ ⊝, R ⁷ SO ₄ ⊝ or R ⁶ COO⊝, wherein R ⁶ and R ^{7 are} C ₈ -C ₂₀ -, preferably C ₁₀ -C ₁₈ -alkyl, and R ⁷ additionally also C ₇ -C ₁₈ -alk mean ylphenyl.

From the group of Hydrobenzoesäurederivate particularly preferred are decanoyloxybenzoic and Nonanoyloxybenzoesäure. Corresponding compounds are described, for example, in EP-A-0 337 264 and DOS 196 54 780. Of the group of quaternary hydroxyalkylammonium compounds, C ₅ -C ₁₁ -alkyldimethylhydroxyethylammonium and C ₁₂ -C ₁₄ -alkyldimethylhydroxyethylammonium salts are of particular interest.

In the bleach activator co-granules of the invention, the ratio of hydroxybenzoic acid derivative to quaternary hydroxyalkylammonium compound is 95: 5 to 5:95 wt%, preferably 90:10 to 20:80 wt%, but more preferably 85:15 to 40:60 wt .-%. In the granules according to the invention, the proportion of the bleach activator-quat mixture is 5 to 98% by weight, preferably 40 to 90%, the remainder being accounted for by Gra auxiliary auxiliary and / or coating agent.

In the washing, Cleaning and disinfecting agents become the bleach activator granules in combination with hydrogen peroxide or an inorganic peroxy compound used. These are primarily all alkali metal perborates, preferably in the form of mono- or tetrahydrates and / or alkali metal percarbonates with sodium as the preferred alkali metal. The relationship bleach activator blends and peroxide compound is 1: 0.5 to 1: 20 parts by weight, preferably 1: 1 to 1: 5 parts by weight.

The Bleach activator granules are used in detergents or machine dishwashing detergents in concentrations of 0.1 - 15 %, preferably 1-8 % used. In stain salts or disinfectants, the However, the proportion of bleach activator granules but also be up to 50%.

Additionally or alternatively you can the washing, Cleaning and disinfecting agent oxidizing agent on organic Base contained in the concentration range of 1 - 20%. These include all known ones peroxycarboxylic e.g. monoperoxyphthalic, dodecanediperoxy, but especially phthalimidoperoxycarboxylic acids (PAP).

Under The term bleaching here is used to describe bleaching the textile surface Dirt as well as the bleaching of in the wash liquor Understanding, detached from the textile surface dirt understood. For the bleaching on hard surfaces located stains applies mutatis mutandis the same. Other potential Applications can be found in the personal care field, e.g. at the bleaching of hair and improve the effectiveness of denture cleaners. Furthermore, the complexes of the invention find use in commercial laundries, in the wood and paper bleach, the bleaching of cotton and in Disinfectants.

Farther The invention relates to a method for cleaning textiles as well as hard surfaces, in particular dishes, using said bleach activator granules in combination with the peroxide compound in aqueous, optionally further Detergent ingredients, containing Solution, and detergents and hard surface cleaners, in particular detergents for dishes, with such for the use in mechanical processes are preferred.

The Granulation of the two compounds of formulas I and II can on take different ways, the state of aggregation of Active substance at the beginning of the granulation process of essential Meaning of can be the procedural choice.

active substance as a solution or suspension

Lies provide the active ingredient in the form of a solution or suspension especially the spray drying or fluidized bed granulation. In the spray drying becomes common a spray powder achieved with a particle size <200 microns, with this powder subsequently processed in a further confectioning step to larger particles can be. Corresponding processes are described below further explained.

In a preferred embodiment the liquid containing the active substance is in a fluidized bed granulation process transferred directly into a granule. ever according to processing properties of the active substance or the desired Granule formulation can the spray liquid one or more additives are added, these additives both liquid as well as can be mixed. In addition to a binder function can the additives also the task of stabilization or a supplementary component to the actual active substance. Especially when mixed firmer Additives is an optimum preparation of the spray slurry for the spraying process advantageous, such. a grinding step for the comminution of solid particles, often using Zahnscheibenkolloidmühlen for Use can come. For a specific adjustment of the viscosity of the spray liquid, a dilution and / or Tempering be made.

According to another preferred embodiment, one or more additives may be separately metered into the process in solid form. The dust content of finished granules, as they are usually incurred, can be recycled as a solid in the fluidized bed. This recycling of the dust content is basically possible in all process variants for granulation. The separate solids dosage allows, for example, the targeted supply of a carrier material for receiving sticky active substances. Furthermore For example, separate solid feed may prove to be a control tool for granule growth in the process.

The fluidized bed processes described in apparatuses, both are executed with round as well as with rectangular geometries, carried out become.

active substance as a solid

Lies the active substance as a solid, e.g. from a spray-drying process, There are also different ways of packaging here at. Usually In the processes, one or more additives are added, which as mentioned before, Binder, stabilization, and / or supplementary function may have. The Tying material becomes common in liquid Form added, but can also be registered as a solid, in the granulator by an auxiliary liquid (usually water) activated becomes.

Build-up granulation in Mixing apparatuses:

The Mixer granulation of the components can be carried out in the usual, batchwise or continuously operating mixing devices, which are usually are equipped with rotating mixing elements done. As a mixer can moderately operating apparatus such as e.g. Ploughshare mixer (Lödige KM types, Drais K-T types) but also intensive mixers (for example Eirich, Schugi, Lödige CB types, Drais K-TT types) are used. When mixing are all mixed variants conceivable that have a sufficient mixing ensure the components. In a preferred embodiment All components are mixed simultaneously. There are, however multi-stage mixing processes conceivable in which the individual components in different combinations individually or together with others Additives are added to the overall mixture. The chronological order of slow and fast mixers can be reversed as required become. The residence times in the mixer granulation are preferred 0.5 second to 20 minutes, more preferably 2 seconds to 10 minutes.

In dependence the granulating liquid used (Solvent or melted Binder) closes at the granulation a drying (for solvent) or cooling step (for melting) to prevent sticking of the granules. The aftertreatment preferably takes place in a fluidized bed apparatus. Subsequently, will separated by sieving the coarse grain and the fine grain content. The coarse grain fraction is crushed by grinding and as is the fine grain content fed to a renewed granulation process.

granulation with the help of a plasticizer

In a further preferred embodiment will the powdery Active substance with one or more plastification substances added. Other solid and liquid Additives are also possible. The plasticizing substances can liquid (Solvent or usually water) or melted. ever After Plastifizierungssystem is in the process on a particularly careful temperature control (mixture with melt) or on a precise control of the moisture balance (Mixture with solvent / water) to pay attention to an unwanted change plasticity the mixture (especially decrease by cooling, solidification or drying out) to avoid.

The liquid Plasticizer is intensively mixed with the powdered active substance and possibly the other additives mixed, so that a plastically deformable Mass arises. The mixing step may be in the o.g. mixing apparatuses kneaders or special extruder types (e.g., Extrud-o-mix the company Hosokawa-Bepex Corp.) are conceivable. The granulation mass is subsequently using tools through the nozzle holes pressed a pressing die, so that cylindrically shaped extrudates arise. Suitable apparatus for the extrusion process are ring roller presses (e.g., from Schlüter), mullets (e.g. from Amandus-Kahl) and extruders, designed as single-shaft machines (e.g. from Hosokawa-Bepex, Fuji-Paudal) or preferably as a twin-screw extruder (for example from Händle). The choice of the diameter of the nozzle bore depends on the individual case and is typically in the range of 0.7 - 4 mm.

The exiting extrudates are to be comminuted by a post-processing step to the desired length or particle size. In many cases, a length / diameter ratio of L / D = 1 is desired. For cylindrical granules, the particle diameter is between 0.2 mm and 2 mm, preferably between 0.5 mm and 0.8 mm, the particle length in the range of 0.5 mm to 3.5 mm, ideally between 0.9 mm and 2 , 5 mm. The lengths or size setting of the granules can be fixed, for example, by fixed Scraper blades, rotating blades, cutting wires or blades are made. To round off the cut edges, the granulate can then be rounded again in a raking device (eg from Glatt, Schlüter, Fuji-Paudal).

In another preferred embodiment the extrudate is only roughly ruptured and the extrudate strands directly transferred to a Rondierer. The further granulation (cylindrical to spherical particles are possible) takes place in Rondierschritt, in a preferred embodiment, the process carried out in cascade operation. Size and shape the particles can be influenced and brought about in the Rondierverfahren by several parameters. The forming process is determined by the filling quantity, the temperature of the Mixture, the residence time of the mixture in the Rondierer, by the rotation speed the Rondierscheibe, as well as by the plastic deformability of Mixture. With decreasing capacity in the scrubber become shorter Cylindrical granules and a narrower distribution of particle sizes obtained. With decreasing plasticity be first longer Granules, with a further decrease in plasticity takes the Dust too strong and a targeted particle formation can not more can be achieved.

To the size adjustment the granules is a final one Solidification step required in which the solvent removed or the Melt is solidified. Usually this step is performed in a fluidized bed apparatus, which depending on the requirements as a dryer or cooler is operated. Subsequently, will separated by sieving the coarse grain and the fine grain content. Of the Coarse grain fraction is crushed by grinding and just like the Fine grain content fed to a renewed granulation process.

compacting

In a further preferred embodiment will the powdery Active substance optionally mixed with further preferably solid additives and this mixture compacted, then ground and then optionally sieved into individual grain fractions. Possibly. can also mix in some way Extent (e.g., up to 10%) in addition liquid Additives are added. Examples of Kompaktierhilfsmittel 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 performed on so-called roll compactors (e.g. from Hosokawa-Bepex, Alexanderwerk, Köppern). By the choice of roll profile can on the one hand lumpy pellets or briquettes and on the other hand produce slips. While the lumpy Compacts usually only still be separated from the fines, the slugs in a mill to the desired Particle size crushed become. Typically come as a mill type preferably gentle Milling machines, such as Sieve and hammer mills (for example from Hosokawa-Alpine, Hosokawa-Bepex) or roller mills (for example from Bauermeister, Bühler) for use.

From The granules thus produced are screened by the fine grain content and possibly the coarse grain fraction separated. The coarse grain fraction is again the mill supplied the fine grain content fed again to the compaction. to Classification of the granules can e.g. Screening machines from Allgaier, Sweco, Rhewum are used come.

Active substance as a melt:

Consists the possibility, that the active substance is also present as a melt, so can make a packaging directly from the melt. Possibly. can the melt still further additives are added, in addition to the recipe compatibility also the temperature resistance the additives must be taken into account.

To the Solidifying the melt must be exposed to a cooling medium, being in principle between the solidification on a cooled surface and the solidification in a fluid cooling medium can be distinguished. In the case of cooled surfaces usually come Cooling belts (e.g. from Fa. Sandvik), Kühlteller (for example from GMF-Gouda) or chill rolls (For example: Fa. GMF Gouda) used. For cooling with fluid cooling media can spray and Prill Towers (e.g., from Niro) or droppers (e.g., from Brace, Rieter-Automatic) be used.

The achievable particle size and shape is in addition to the product properties (especially melt viscosity) strongly dependent on the melt application or dosing. By means of spray nozzles, for example, a typical powder can be produced with particle sizes <200 microns. In the case of dropletizing units in conjunction with a falling apparatus, it is preferable to produce spherical particles in the range of about 250-4000 μm. Techniques for applying molten droplets to cooled surfaces are more likely to produce pastille-shaped particles with sizes of about> 1000 microns. Alternatively, the melt can be poured out as a layer or strip, wherein the solidified layers are comminuted in a suitable mill to the desired particle size.

The Grain size granules from the granulation described in each case is in general in the range of 100 microns - 4000 microns, preferably at 200 microns - 1800 microns, especially preferably at 400-1400 microns.

The bleach activator granules of the invention contain in addition to the compounds of formulas I and II or granulation (hereinafter called additives). In particular, these additives may have the following function to have.

Solid carriers

Suitable support materials are, for example, silicates, clays, carbonates, phosphates, sulfates and citrates. Clays are naturally occurring crystalline or amorphous silicates of aluminum, iron, magnesium, calcium, potassium and sodium, for example kaolin, talc, pyrophyllite, attapulgite, sepiolite, saponites, hectorites, smectites such as montmorillonite, in particular bentonites, bauxite and zeolites. Particularly suitable are crystalline schichfförmige alkali metal silicates of the formula MM'Six0 (2x-1) · yH ₂ O (M, M '= Na, K, H, x = 1.9-23, y = 0-25), preferably sodium silicates, for example, available under the trade names SKS-6 and Nabion 15 types. Also suitable are zeolites of the type A and P, and bentonites as they are under the name Laundrosil ^® DGA, Laundrosil ^® EX 0242 or Ikomont ^® CA white on the market. Phyllosilicates can also be used in acid-modified form as they are in the commercial products Tonsil ^® EX 519, Tonsil Optimum 210 FF, Tonsil Standard 310 FF and 314 FF, and Opazil ^® SO Fa. Suedchemie available.

Further suitable carrier materials are alkali phosphates, in the form of their alkaline, neutral or acidic sodium or potassium salts may be present. Examples are trisodium phosphate, Tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of 5 to 1000, in particular 5 to 50, and mixtures of sodium and potassium salts.

useful organic carrier materials For example, they are preferably those used in the form of their sodium salts Carboxylic acids, like citric acid and nitriloacetate (NTA), ethylenediaminetetraacetic acid. Analogous can do this also polymeric carboxylates and their salts are used. For this belong for example, the salts of homopolymeric or copolymeric polyacrylates, Polymethyacrylate and in particular copolymers of acrylic acid with maleic acid, preferably those of 50 to 10% maleic acid, polyaspartic acid and also polyvinylpyrrolidone and urethanes. The molecular weight of the Homopolymers are generally between 1000 and 100 000, the of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid. In particular, water-soluble Polyacrylates suitable, for example, with about 1% of a polyallyl ether the sucrose are crosslinked and the molecular weight above own one million. Examples are those under the name Carbopol 940 and 941 available Polymers.

binder

Suitable binders are cellulose and starch and their ethers or esters, for example carboxymethylcellulose (CMC), methylcellulose (MC) or hydroxyethylcellulose (HEC) and the corresponding starch derivatives, but also film-forming polymers, for example polyacrylic acids and copolymers of maleic anhydride and acrylic acid, and Salts of these polymer acids. Commercial products are, for example Sokalan ^® CP 5 or 45, Sokalan CP 12 S or 13 S. CP

When Binders can also surfactants, in particular anionic and nonionic surfactants, Surfactant compounds, di- and polysaccharides, cyclodextrins, fusible Polyesters, polyalkylene glycols, in particular polyethylene, polypropylene glycols, particularly preferred are polyethylene glycols having molecular weights of 1000 to 10,000, preferably 3000 to 6000, particularly preferably 4000, fatty acids, in particular saturated fat, like Lauric acid, myristic, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids derived mixtures, Soaps, especially saturated ones fatty acid soaps and waxes are used.

preferred anionic surfactants are alkali metal salts, ammonium salts, amine salts and Salts of aminoalcohols of the following compounds: alkyl sulphates, Alkyl ether sulfates, alkyl amide sulfates and ether sulfates, alkylaryl polyether sulfates, Monoglyceride sulfates, alkanesulfonates, α-olefinsulfonates, alkylarylsulfonates, Arylsulfonates, especially cumene, xylene, toluenesulfonate alkylamide sulfonates, Alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkyl amide sulfosuccinates, Alkyl sulfoacetates, alkyl polyglycerol carboxylates, alkyl phosphates, Alkyl ether phosphates, alkyl sarcosinates, alkyl polypeptides, alkyl amido coppeptides, Alkyl isethionates, alkyl taurates, alkyl polyglycol ether carboxylic acids or fatty acids, like oleic acid, ricinoleic, palmitic acid, stearic acid, Kopraölsäuresalz or hydrogenated coconut oil acid salts. The alkyl group of all these compounds normally contains 8-32, preferably 8 - 22 C-atoms.

Suitable nonionic surfactants are polyethoxylated, polypropoxylated and polyglycerinated fatty acid alkyl esters, polyethoxylated esters of fatty acids and sorbitol, polyethoxylated or polyhydroxy fatty acid amides of the formula R ₂ -CO-N (R ₃ ) -Z, in which R ₂ CO is an aliphatic acyl radical with 6 to 22 carbon atoms, R _{3 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and Z is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups, but also alkyl glycosides of the general formula RO (G) _x used where R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms, and G is a glycose unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is preferably a number between 1 and 10, more preferably x is between 1.2 and 1.4.

Acid additives

Suitable acidic additives are sulfuric acid, sodium hydrogensulfate, phosphoric acid, sodium hydrogenphosphate, phosphonic acids and their salts, carboxylic acids or their salts, such as citric acid in anhydrous or hydrated form, glycolic acid, succinic acid, succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, adipic anhydride, maleic acid, maleic anhydride or Lactic acid, but also acidic polymers. Particularly suitable acidic additives are polyacrylic acid, polymaleic acid or copolymers of acrylic acid and maleic acid (Sokalan ^® grades).

The obtained according to the invention Granules are suitable for use in detergents and cleaners. In a particularly preferred form of use, however, they can be used per se known methods are provided with a coating shell. For this The granules are in an additional Step wrapped with a film-forming substance, reducing the product properties can be significantly influenced.

Suitable coating agents are all film-forming substances, such as waxes, silicones, fatty acids, fatty alcohols, soaps, anionic surfactants, nonionic surfactants, cationic surfactants, anionic and cationic polymers, and polyalkylene glycols. Preference is given to using coating substances having a melting point of 30-100 ° C. Examples for this 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 1000 to 50,000 g / mol;
Fatty alcohol polyalkoxylates with 1 to 100 moles EO; 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 in the range of 30 to 100 ° C softening or melting coating substance may further more in this Area not softening or melting substances in dissolved or in suspended form, for example homopolymers, copolymers or graft copolymers unsaturated carboxylic acids and / or sulfonic acids and their alkali metal salts, cellulose ethers, starch, starch ethers, polyvinylpyrrolidone; one- and polybasic carboxylic acids, hydroxy or ether carboxylic acids with 3 to 8 carbon atoms and their salts; Silicates, carbonates, bicarbonates, Sulfates, phosphates, phosphonates.

ever according to the desired Properties of the coated granulate may be the content of encasing substance 1 to 30 wt .-%, preferably 5 to 15 wt .-% based on the coated Granules amount.

For applying the coating substances, mixers (mechanically induced fluidized bed) and fluidized bed apparatuses (pneumatically induced fluidized bed) can be used. As mixers, for example, plowshare mixers (continuous and batchwise), ring layer mixers or even Schugi mixers are possible. The tempering can be directly and / or in the mixer when using a mixer in a granulate preheater and / or 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.

The bleach activator granules of the invention can be used in detergents, cleaners and disinfectants together with hydrogen peroxide or inorganic peroxy compounds. Essential components of such detergents, cleaners and disinfectants are listed below.

Surface-active substances

Anionic surfactants

The Detergents and cleaners can contain one or more surfactants, in particular anionic Surfactants, nonionic surfactants and their mixtures, but also cationic, zwitterionic and amphoteric surfactants come into question. such Surfactants are in detergents according to the invention in proportions of preferably 1 to 50 wt .-%, in particular from 3 to 30% by weight, whereas in detergents for hard surfaces usually lower levels, that is amounts up to 20 wt .-%, in particular up to 10% by weight and preferably in the range of 0.5 to 5% by weight are included. In detergents for use in machine dishwashing Normally low-foam connections are used.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups. As surfactants of the sulfonate type are preferably C ₉ -C ₁₃ alkylbenzenesulfonates, olefinsulfonates, that is mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those from monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C ₁₂ -C ₁₈ -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of alpha-sulfo fatty acids (ester sulfonates), for example the alpha-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by sulfonating the methyl esters of fatty acids of vegetable and / or animal origin having 8 to 20 carbon atoms be prepared in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts.

Other suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof. Examples of alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₈ -C ₂₀ -oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis. Also 2,3-alkyl sulfates, which, for example, according to the US patents US 3,234,158 and US 5 075 041 are prepared, are suitable anionic surfactants. Also suitable are the sulfuric acid monoesters of straight-chain or branched alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ -alcohols having on average 3.5 mol of ethylene oxide (EO) or C ₁₂ -C ₁₈ -fatty alcohols with 1 up to 4 EO.

The preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures of these. Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosinate). As further anionic surfactants are in particular soaps, for example in amounts of 0.2 to 5 wt .-%, into consideration. Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.

The including anionic surfactants the soaps, can in the form of their sodium, potassium or ammonium salts and as soluble salts organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts. anionic Surfactants are in detergents according to the invention preferably in amounts of 0.5 to 10 wt .-% and in particular in Amounts of 5 to 25 wt .-% included.

Nonionic surfactants

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position , or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for. From coconut, palm, tallow fat or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ -alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ -alcohols with 7 EO, C ₁₃ -C ₁₅ -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ -C ₁₄ -alcohol with 3 EO and C ₁₂ -C ₁₈ -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

The nonionic surfactants also include alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and 6 represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula (I) in which R ^{1 is} CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen; an alkyl or hydroxyalkyl radical. having 1 to 4 carbon atoms and [Z] represents a linear or branched polyhydroxyalkyl having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.

The polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (II) for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R4 for a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R ⁵ for a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C ₁ -C ₄ alkyl or phenyl radicals being preferred, and [Z] a linear polyhydroxyalkyl radical whose alkyl chain has at least two Is substituted hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group. [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-alyloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides according to the teaching of international patent application WO 95/07331, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

A another class of preferred nonionic surfactants, the either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated Fatty alcohols and / or alkyl glycosides used alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl ester, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl ester.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide. and the fatty acid alkanolamide can be suitable.

When other surfactants are so-called gemini surfactants into consideration. this includes In general, such compounds are understood as meaning the two hydrophilic ones Groups per molecule have. These groups are usually separated by a so-called "spacer". This spacer is usually a carbon chain that is long enough should be that the hydrophilic groups have a sufficient distance have to be independent can act from each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and surface tension ability to greatly reduce the water out. But can be used also gemini polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides, as described in international patent applications WO 95/19953, WO 95/19954 and WO 95/19955. Other surfactant types can dendrimer Have structures.

BUILDER

Inorganic builders

One Detergent according to the invention contains preferably at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.

Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates and polymeric alkali metal phosphates which may be present in the form of their alkaline, neutral or acidic sodium or potassium salts. 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. As water-insoluble, water-dispersible inorganic builder materials are in particular crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50 wt .-%. Among these, preferred are the detergent grade crystalline sodium aluminosilicates, particularly zeolite A, P and optionally X, alone or in mixtures, for example in the form of a cocrystal of zeolites A and X. Their calcium binding capacity, according to the information of the German Patent DE 24 12 837 can be determined, is usually in the range of 100 to 200 mg CaO per gram. Suitable builder substances are also crystalline alkali metal silicates, which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders preferably have a molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates with a molar ratio of Na 2 O: SiO 2, of 1: 2 to 1: 2.8. Those with a molar ratio of Na 2 O: SiO 2 of 1: 1.9 to 1: 2.8 can be prepared by the process of European patent application EP 0 425 427 getting produced. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na ₂ Si _x O _{2x + 1} · y H ₂ O used in the x, the so-called module, a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in the European patent application EP 0 164 514 described. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and β-sodium disilicate (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred, whereby β-sodium disilicate can be obtained, for example, by the process described in international patent application WO 91/08171. β-Sodium silicates with a modulus between 1.9 and 3.2 can be prepared according to Japanese patent applications JP 04/238 809 or JP 04/260 6 10. Also prepared from amorphous silicates, practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, preparable as in the European patent applications EP 0 548 599 . EP 0 502 325 and EP 0425 428 described, have been used. In a further preferred embodiment of such agents, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as it is by the process of European patent application EP 0 436 835 made from sand and soda. Crystalline sodium silicates with a modulus ranging from 1.9 to 3.5, as prepared by the methods of European patents EP 0 164 552 and or EP 0 294 753 are available are used in a further preferred embodiment of the invention means. In a preferred embodiment of inventive compositions is a granular compound of alkali metal silicate and alkali metal, as described for example in international patent application WO 95/22592 or as is commercially available, for example under the name Nabion ^® commercially. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10: 1. In compositions containing both amorphous and crystalline alkali silicates, the weight ratio is from amorphous alkali metal silicate to crystalline alkali metal silicate, preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.

such Builders are preferably in agents according to the invention in Amounts up to 60% by weight, in particular from 5% by weight to 40% by weight, contain.

Organic Builder

To the water-soluble Organic builders include polycarboxylic acids, in particular citric acid and sugar acids, aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic as well as polyaspartic acid.

Polyphosphonic acids, especially aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid can also be used. Also preferred are polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides or dextrins of the international patent application WO 93/161 10 or the international patent application WO 92/18542 or the European patent specification EP 0 232 202 , polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small amounts of polymerizable substances copolymerized without carboxylic acid functionality. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF. Also suitable are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. It is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ -carboxylic acid and preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (meth) -acrylic acid.

The second acidic monomer or its salt may be a derivative of a C ₄ -C ₈ -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical. Such polymers can be prepared in particular by methods described in the German patents DE 42 21 381 and DE 43 00 772 are generally described, and generally have a molecular weight between 1000 and 200,000. Further preferred copolymers are those described in the German patent applications DE 43 03 320 and DE 44 17 734 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or vinyl acetate.

The organic builder substances can, in particular for the production of liquid Means, in the form of watery Solutions, preferably be used in the form of 30 to 50 wt .-% aqueous solutions. All mentioned acids are usually in the form of their water-soluble salts, in particular their alkali salts used.

such organic builders can if desired in amounts up to 40 wt .-%, in particular up to 25 wt .-% and preferably be contained from 1 to 8 wt .-%. Quantities close to the mentioned upper limit are preferably in pasty or liquid, especially water-containing agents used.

When water-soluble Builder components in detergents according to the invention for hard surfaces In principle all come in means for machine cleaning of dishes usually used builders, for example the abovementioned alkali metal phosphates. Your quantities can in the range of up to about 60 wt .-%, in particular 5 wt .-% to 20 wt .-%, based on the total mean. Other possible water-soluble builder components are in addition to polyphosphonates and Phosphonatalkylcarboxylaten to Example organic polymers of native or synthetic origin from the above Type of polycarboxylates, especially in hard water regions act as a co-builder, and of course occurring hydroxycarboxylic acids such as mono-, dihydroxysuccinic acid, alpha-hydroxypropionic acid and gluconic acid. To the preferred organic builder components include Salts of citric acid, in particular Sodium citrate. The sodium citrate is anhydrous tri-sodium citrate and preferably trisodium citrate dihydrate. trisodium can be used as a fine or coarse crystalline powder. In dependence ultimately adjusted in the detergents of the invention pH can also the acids corresponding to the said co-builder salts are present.

enzymes

Among the optionally present in the inventive compositions enzymes include proteases, amylases, pullulanases, cellulases, cutinases and / or lipases, for example proteases such as BLAP ^®, Optimase ^®, Opticlean ^®, Maxacal ^®, Maxapem ^®, Durazym ^®, Purafect ^® OxP, Esperase ^® and / or Savinase ^®, amylases as Termamy ^®, amylase LT, Maxamyl ^®, Duramyl ^®, Purafectel OxAm, cellulases as Celluzyme ^®, Carezyme ^®, K-AC ^® and / or from international patent applications WO 96/34108 and WO 96/34092 known cellulases and / or lipases such as Lipolase ^® , Lipomax ^® , Lumafast ^® and / or Lipozym ^® . The enzymes used can be adsorbed on carriers and / or embedded in encapsulants, as described, for example, in International Patent Applications WO 92/131347 or WO 94/23005, in order to protect them against premature inactivation. They are preferably present in detergents and cleaners according to the invention in amounts of up to 10% by weight, in particular from 0.05% by weight to 5% by weight, with enzymes which are particularly preferably stabilized against oxidative degradation, as described for Example from the international patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350 are known to be used.

Machine dishwashing detergents according to the invention preferably comprise 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 3 wt .-% to 30 wt .-%, based on the total agent, be contained. The alkali carrier system preferably used in cleaning agents according to the invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which may be present in an amount of up to 50% by weight, preferably 5% by weight to 40% by weight ,

In a further embodiment inventive agent for the automatic cleaning of dishes are 20 to 60 wt .-% water-soluble organic builder, especially alkali citrate, 3 to 20 wt .-% alkali carbonate and 3 to 40 wt .-% Alkalidisilikat included.

Around can cause silver corrosion protection, in cleaning agents according to the invention for dishes Silver corrosion inhibitors are used. Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trivalent Phenols, optionally alkyl- or aryl-substituted triazoles such Benzotriazole, isocyanuric acid, Titanium, zirconium, hafnium, molybdenum, vanadium or cerium salts and / or complexes, as well as salts and / or complexes of those suitable for use in the invention Complex containing metals with other than in formula (I) given Ligands.

Provided If the agents foam too much during use, they can still give them up to 6% by weight, preferably about 0.5 to 4% by weight of a foam-regulating compound, preferably from the group comprising silicones, paraffins, paraffin-alcohol combinations, hydrophobized silicic acids, Bisfettsäureamide as well their mixtures and other other known commercially available Foam inhibitors are added. Preferably, the foam inhibitors, in particular silicone and / or paraffinic foam inhibitors, on a granular, in water soluble or dispersible carrier substance bound. Especially are mixtures of paraffins and bistearylethylenediamide prefers. Further optional ingredients in the compositions according to the invention are for example perfume oils.

To in the compositions according to the invention, especially when in liquid or pastier Form, usable organic solvents include alcohols with 1 to 4 C-atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms, in particular ethylene glycol and propylene glycol, as well as mixtures thereof and those mentioned Classes of derivable ether. Such water-miscible solvent are in the cleaning agents according to the invention preferably not over 20 wt .-%, in particular from 1 to 15 wt .-%, present.

to Setting a desired, through the mixture of the rest Non-self-inflicting pH components can be used agents according to the invention System and environmentally compatible acids, in particular citric acid, Acetic acid, Tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, especially sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or Alkali hydroxides. Such pH regulators are in the agents according to the invention preferably not over 10 wt .-%, in particular from 0.5 to 6 wt .-%, contained.

The agents according to the invention are preferably in powder form, granular or tablet-shaped preparations, in a conventional manner, for example by mixing, granulating, Roll compaction and / or by spray drying the thermally stable Components and mixing of the more sensitive components, which include In particular, enzymes, bleaches and the bleach catalyst are to be expected, can be produced. Efindungsgemäße means in the form of aqueous or other usual solvent containing solutions become particularly advantageous by simply mixing the ingredients, in substance or as a solution can be placed in an automatic mixer made.

For the production of particulate agents having an increased bulk density, in particular in the range of 650 g / l to 950 g / l, is one of the European patent specification EP 0 486 592 known method comprising an extrusion step is preferred. Another preferred preparation by means of a granulation process is in the European patent specification EP 0 642 576 described. The preparation of compositions according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range from 800 to 1000 g / l can also be achieved by using the builder components with at least a proportion of liquid mixture components in a first process stage while increasing the bulk density of this premix and subsequently - if desired after an intermediate drying - the other constituents of the agent, including the bleach catalyst, combined with the thus obtained premix.

For the preparation of compositions according to the invention in tablet form, the procedure is preferably such that all ingredients are mixed together in a mixer and the mixture by means of conventional tablet presses, such as Exzeriterpressor or rotary presses, with pressing pressures in the range of 200 · 10 ⁵ Pa to 1500 · 10 ⁵ Pa pressed. This gives unbreakable, yet sufficiently rapidly soluble tablets under application conditions with flexural strengths of normally over 150 N. So preferably, a tablet produced in this way has a weight of 1-5 g to 40 g, in particular from 20 g to 30 g; at a diameter of 3-5 mm to 40 mm.

example 1

Bleaching performance of decanoyloxybenzoic acid (DOBA) in combination with C ₁₂ -C ₁₄ -Alkyldimethylhydroxyethylammoniumchlorid (Praepagen HY ^® - commercial product Clariant GmbH, hereinafter referred to as HY)

The Bleaching performance of the individual activators and the mixtures according to the invention were in a linitest device (Fa Out) at 40 ° C examined. To this was added 5 g / l of a bleach-free basic detergent (WMP, WFK, Krefeld) and 0.1 g / l sodium percarbonate (Degussa) in water of the hardening stage 3 solved. Subsequently were 250 mg / l DOBA, HY (calculated on 100% activity) or DOBA-HY mixture added. The washing time was 30 min. The bleaching test fabric was grass, Tea, curry and chlorophyll on cotton (CS-8, BC-1, BC-4, AS-4 from WFK, Krefeld). The bleaching result was the remission difference, measured with an Elrepho device, after the wash compared to unwashed tissue.

you recognizes that the mixtures according to the invention, with a DOBA content from 20% a significantly better bleaching effect and thus have synergistic effects than HY alone.

Example 2

manufacturing a co-granulate from DOBA and Präpagen HY

For laboratory experiments, a batch-working laboratory fluidized bed of the type GPCG 1.1, Fa. Glatt was used with a flow diameter of D = 150 mm, the spray nozzle sprayed from below into the fluidized bed. As a starting product, 870 g of DOBA powder and 30 g of Tylose powder as binder (Finnfix BDA Fa. Noviant) were presented in the apparatus. The powder mixture was vortexed with a gas volume flow of about 20 m ³ / h and heated to a temperature of T = 65 °. Upon reaching this temperature, the liquid metering was started and sprayed a 40% aqueous solution of the Präpagen HY on the fluidized bed. After reaching the stationary state, a total of 1500 g of Präpagen HY could be sprayed on at a metering rate of about 6 to 10 g / min. After a drying time of about 10 minutes, the removed product was fractionated on a laboratory sieve (type Retsch AS 200 control) in order to separate out fine particles <200 μm and coarse particles> 1400 μm from the target product. The finished granules were present with a composition of about 40 wt .-% Präpagen HY, about 58 wt .-% DOBA and about 2% binder.

Example 3

Production of a co-granulate from DOBA and embossing HY

3.1) Production of a Spray Slurry:

In the first step, 1200 g of a 40% aqueous C ₁₂ -C ₁₄ -Alkyldimethylhydroxethylammoniumchlorid solution (Präpagen HY Fa. Clariant) with 696 g DOBA powder, 24 g Tylose as a binder (Finnfix BDA Fa. Noviant) and 350 g water for viscosity adjustment at room temperature mixed with an Ultra-Turrax ^® and homogenized. Within a mixing time of about 5 minutes, a stirrable and pumpable, homogeneous suspension could be prepared which had no discernible sedimentation even without stirring.

3.2) Preparation of the original product

Around To be able to operate the granulation process is a turbulent mass required, to which the active ingredient solution is sprayed can. Therefore, an approach of the slurry according to Example 2.1) in a drying oven (about 100 ° C) dried and then worked up. The dried mass was to a sieve to a fine until grainy Product happens. For the granulation test was a starting mass (100 - 250 g) in the grain fraction <1400 μm.

3.3) fluidized bed granulation:

For laboratory experiments, a batch-working laboratory fluidized bed of the type GPCG 1.1, Fa. Glatt was used with a flow diameter of D = 150 mm, the spray nozzle sprayed from below into the fluidized bed. The dried product from the drying cabinet processing according to Example 2.2) was initially charged in the fluidized bed apparatus. In subsequent follow-up tests, the fine material from the previous granulation test was also used. The non-tempered slurry was atomized from below onto the moving fluidized bed via the two-substance nozzle. The amount of spray liquid delivered with a peristaltic pump was recorded gravimetrically by means of a balance. The gas volume flow for swirling the bed material was about 20 - 25 m ³ / h. The supply air temperature was set to approx. 94 - 96 ° C. With adjustment of a spray power of about 6 to 8 g / min of slurry, a temperature in the fluidized bed of about 72 to 75 ° C. was established, whereby this temperature level could be kept stable. With these operating conditions an exhaust air temperature of approx. 69 - 71 ° C resulted. After a test run time of approx. 198 min, clearly recognizable granules were produced. After a drying time of about 10 minutes, the removed product was fractionated on a laboratory sieve (type Retsch AS 200 control) in order to separate out fine particles <200 μm and coarse particles> 1400 μm from the target product. The finished granules were present with a composition of about 40 wt .-% Präpagen HY, about 58 wt .-% DOBA and about 2% binder.

Claims (9)

Bleach activator granules consisting of a hydroxybenzoic acid derivative of the general formula (I), a quaternary hydroxyalkylammonium compound of the general formula (II) and at least one granulation auxiliary and / or coating agent,

wherein in formula (I) R = a C ₈ -C ₁₁ alkyl group, and in formula (II) R ¹ linear or branched C ₅ -C ₂ 2-alkyl, C ₅ -C ₂₂ alkenyl, C ₅ -C ₂₂ -Alkylamidopropyl, C ₅ -C ₂₂ -alkenyl-amidopropyl, C ₈ -C ₂₂ -alkoxypropyl or C ₅ -C ₂₂ -alkenyloxypropyl, R ² C ₁ -C ₂₂ -alkyl or C ₂ -C ₂₂ -alkenyl, R ³ C C ₁ -C ₂₂ -alkyl, C ₂ -C ₂₂ -alkenyl or a group of the formula -A- (OA) _n -OH, where A is -C ₂ H ₄ - and / or -C ₃ H ₆ - and n is a number from 0 to 20, and R ^{4 is} a group of the formula -A- (OA) _n -OH and X is an anion. Bleach activator granules according to claim 1, characterized in that it contains decanoyloxybenzoic acid or nonanoyloxybenzoic acid Compound of formula I included. Bleach activator granules according to claim 1, characterized in that they contain a C ₅ -C ₁₁ -alkyldimethylhydroxyethylammonium salt or C ₁₂ -C ₁₄ -alkyldimethylhydroxyethylammonium salt as compound of the formula II. Bleach activator granules according to claim 1, characterized in that the weight ratio is compound of the formula I to compound of formula II is 95: 5 to 5:95. Bleach activator granules according to claim 1, characterized in that the weight ratio is compound of the formula I to compound of formula II is 90:10 to 20:80%. Bleach activator granules according to claim 1, characterized in that the weight ratio is compound of the formula I to compound of formula II is from 81:15 to 40:60%. Bleach activator granules according to claim 1, characterized in that the granulates contain 5 to 98% by weight of the sum of Compounds of formulas I and II included. Bleach activator granules according to claim 1, characterized in that the granules contain 40 to 90% by weight of the sum of Compounds of formulas I and II included. Containing detergents, cleaners and disinfectants a bleach activator granule according to claim 1.