EP1791939B1 - Bleach activator mixtures - Google Patents

Description

The invention relates to improved bleach activator and bleach compositions for use in detergents, cleaners and disinfectants. In particular, the invention also relates to compositions in the form of bleach activator co-granules having improved bleaching performance on a variety of bleachable soils.

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, the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators. For this purpose, numerous proposals have been worked out in the past, especially from the classes of N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine and tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles. Diketopiperazines, sulfurylamides and cyanurates, as well as carboxylic anhydrides, in particular phthalic anhydride and substituted maleic anhydrides, carboxylic acid esters, especially sodium acetoxy-benzenesulfonate, sodium benzoyloxybenzenesulfonate (BOBS), sodium nonanoyloxy-benzenesulfonate (NOBS), sodium isononoyloxybenzenesulfonate (ISONOBS) and acylated sugar derivatives, such as pentaacetylglucose , By adding these substances, the bleaching effect of aqueous peroxide solutions can be increased so much that already 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, in particular being used in granulated form. As a result, their storage stability is significantly increased. The achievable bleaching result is essentially determined by the water solubility of the activator, the structure of the perhydrolysierenden compound, the type and reactivity of the peracid formed, the Granulierhilfsmittels and the type of Granulatherstellung.

Bleach activators can be classified into two classes for their reactivity to certain soils, hydrophilic and hydrophobic. In particular, hydrophilic bleach activators remove tea or red wine stains, while hydrophobic activators preferentially discolor oily discolorations such as ketchup and barbecue sauce. However, many of the soils that occur in daily life do not fall into these classes (e.g., grass, curry) or are mixtures of various soils (e.g., baby food). Here, the application of a single bleach activator usually leads to unsatisfactory results. In view of further decreasing wash temperatures and more volume-efficient formulations, synergistically acting mixtures of detergent ingredients will be of particular interest in the future.

The use of special activator mixtures consisting of a hydrophilic and a hydrophobic activator is state of the art. The hydrophobic component used are predominantly derivatives of the readily water-soluble sodium phenolsulfonate. For example, in EP-A-0 257 700 Mixtures of Nonanoyloxybenzolsulfonat with tetraacetylethylenediamine, Benzoyloxybenzolsulfonat or Acetoxybenzolsulfonat claims. WO-02/083 829 describes improved efficacy of mixtures consisting of tetraacetylethylenediamine and sodium 4- (sulfophenyl octyl) carbonate. Similar mixtures are also in EP-A-098129 and EP-A-0 120 591 described.

The bleaching optimum of the activator mixtures depends on the type and the mixing ratio of the activators used and on the type of stains to be removed and, according to experience, can not theoretically be calculated in advance. Therefore, there is still much interest in novel bleach activator blends with which synergistic effects can be achieved.

Surprisingly, it has now been found that mixtures of bleach activators based on hydroxybenzoic acids and certain peracetic acid-releasing activators have significant synergistic effects on hard-to-remove soils such as grass and curry.

1. a) ein Hydroxybenzoesäurederivat der Formel
   
   worin R C₈-C₁₁-Alkyl bedeutet, und
2. b) Tetraacetylethylendiamin und/oder 1,5-Diacetyl-2,4-dioxo-1,3,5-hexahydrotriazin.

The invention relates to bleach activators containing, in the form of co-granules

1. a) a Hydroxybenzoesäurederivat of the formula
   
   wherein R is C ₈ -C ₁₁ alkyl, and
2. b) tetraacetylethylenediamine and / or 1,5-diacetyl-2,4-dioxo-1,3,5-hexahydrotriazine.

Preferred from the group of compounds of formula (I) are nonanoyloxybenzoic acid and decanoyloxybenzoic acid.

In a preferred embodiment, these activator mixtures are used in the form of co-granules as bleach component together with a hydrogen peroxide-generating substance in detergents, cleaners and disinfectants.

Corresponding hydroxybenzoic acid derivatives are, for example, in EP-A-0 337 274 and DOS 196 54 780 , Tetraacetylethylenediamine in GB 907,356 and 1,5-diacetyl-2,4-dioxo-1,3,5-hexahydrotriazine in DD 229 696 and DD 253 634 described. The US Pat. No. 6,444,634 B1 discloses bleaching compositions containing a mixture of several bleach activators.

In the bleach activator mixtures according to the invention, the ratio of hydroxybenzoic acid derivative to N-acyl compound is generally 95: 5 to 5:95 wt.%, Preferably 75:25 to 25:75 wt.%, But in particular 60:40 to 40: 60% by weight. In a particularly preferred embodiment, these mixtures are prepared in ready-made form. Here, the use of additives and / or coating agents may be beneficial. In such formulated preparations, the proportion of bleach activator mixtures is generally 5-98% by weight, preferably 40-95% by weight. The remainder is attributable to additives and / or coating agents.
In the detergents, cleaners and disinfectants according to the invention, the bleach activator mixtures are used in combination with hydrogen peroxide or inorganic peroxy compound. For this purpose, all alkali metal perborates, preferably in the form of mono- or tetrahydrate and / or alkali percarbonates, are considered in the first place, with sodium being the preferred alkali metal. The ratio of bleach activator mixture 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 mixtures are used in the detergents according to the invention or, if the detergents are machine dishwashing detergents, in concentrations of 0.1-15%, preferably 1-8%. In stain salts or disinfectants, however, the proportion of the bleach activator mixture can also be up to 50%.

In addition, such detergents, cleaners and disinfectants may contain organic-based oxidizers in the concentration range of 1 to 20%. These include all known peroxycarboxylic acids, for example monoperoxyphthalic acid, dodecanediperoxyacid, but especially phthalimidoperoxycarboxylic acids (PAP).

The term bleaching is understood here to mean both the bleaching of dirt located on the textile surface and the bleaching of dirt located in the wash liquor and detached from the textile surface. The same applies mutatis mutandis to the bleaching of stains on hard surfaces. Further potential applications are in the personal care field, for example in the bleaching of hair and to improve the effectiveness of denture cleaners. Furthermore, the mixtures according to the invention are used in commercial laundries, in wood and paper bleaching, in the bleaching of cotton and in disinfectants.
Furthermore, the invention relates to a process for the cleaning of textiles as well as hard surfaces, in particular dishes, using said bleach activator mixtures in combination with the peroxide compound in aqueous, optionally further detergent or cleaning agent components, containing solution, and detergent and cleaning agent for hard surfaces, especially dishwashing detergents, such being preferred for use in machine processes.

The preparation of the bleach activator mixtures can be carried out in different ways, wherein the physical state of the active substance at the beginning of the packaging can be of essential importance for the choice of method. The term packaging is to be understood here in particular as the granulation of the bleach activator mixture.

Activator mixtures as a solid:

If the activator mixture is in the form of a solid, different routes of preparation are available. Usually, one or more additives which can have binding, stabilizing and / or supplementary function are added in these processes. The binder material is often added in liquid form, but can also be registered as a solid, which is activated in the granulator by an auxiliary liquid (usually water).

Build-up granulation in mixing apparatuses:

The mixer granulation of the components can be carried out in conventional, batchwise or continuously operating mixing devices, which are generally equipped with rotating mixing devices. As a mixer, moderately working apparatus such as plowshare mixers (Lödige KM types, Drais KT types) or intensive mixers (eg Eirich, Schugi, Lödige CB types, Drais K-TT types) can be 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.
Depending on the granulating liquid used (solvent or melt-shaped binder), a drying (for solvent) or cooling step (for melting) adjoins the granulation stage in order to avoid sticking of the granules. The aftertreatment preferably takes place in a fluidized bed apparatus. Subsequently, the coarse grain and the fine grain fraction is separated by sieving. The coarse grain fraction is comminuted by grinding and, like the fine grain fraction, fed to a renewed granulation process.

Granulation with the aid of a plasticizer:

In a further preferred embodiment, the solid activator mixture is admixed with one or more plastification substances. Other solid and liquid additives are also possible. The plasticizing substances can be introduced in liquid form (solvent or usually water) or in melt form. Depending on the plastification system, a particularly careful temperature control (mixture with melt) or precise control of the process is required Moisture balance (mixture with solvent / water) to ensure an undesirable change in the plasticity of the mixture (especially decrease by cooling, solidification or drying) to avoid.

The liquid plasticizer is intensively mixed with the powdered activator mixture and possibly 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 (for example 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), edge mills (eg from Amandus-Kahl) and extruders, designed as single-shaft machines (eg from Hosokawa-Bepex, Fuji-Paudal) or preferably as twin-screw extruders (eg from Fa. 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 adjustment of the granules can be done for example by fixed scraper blades, rotating blades, cutting wires or blades. To round off the cut edges, the granules can subsequently be rounded again in a rounding device (for example from Glatt, Schlüter, Fuji-Paudal).

In another preferred embodiment, the extrudate is only roughly chipped and the extrudate strands are transferred directly to a ripper. The further granulation (cylindrical to spherical particles are possible) takes place in the Rondierschritt, in a preferred embodiment, the process in Cascade operation performed. The size and shape of 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 Rondier, by the rotation speed of the Rondierscheibe, as well as by the plastic deformability of the mixture. With decreasing filling volume in the rounding device, shorter cylindrical granules and a narrower distribution of the particle sizes are obtained. With decreasing plasticity initially longer granules are obtained, with a further decrease in plasticity, the dust content increases sharply and targeted particle formation can not be achieved.

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

compacting

In a further preferred embodiment, the pulverulent activator mixture is optionally mixed with further preferably solid additives, and this mixture is compacted, then ground and then optionally sieved into individual grain fractions. Optionally, the mixture may also be added to some extent (eg up to 10%) liquid additives. Examples of compacting aids are water glass, polyethylene glycols, nonionic surfactants, anionic surfactants, polycarboxylate copolymers, modified and / or unmodified celluloses, bentonites, hectorites, saponites and / or other detergent ingredients.

The compacting is preferably carried out on so-called roll compactors (for example 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 Preßschülpen. While the lumpy briquettes are usually separated only from the fines, the slugs must be crushed in a mill to the desired particle size. Typically, the mill type used is preferably mild grinding machines, such as e.g. Sieve and hammer mills (for example from Hosokawa-Alpine, Hosokawa-Bepex) or roll mills (for example from Bauermeister, Bühler) are used.

From the granules thus produced is separated by screening the fine grain content and possibly 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, e.g. Screening machines of the companies Allgaier, Sweco, Rhewum are used.

Activator mixtures as solution or suspension:

If the activator mixture is present in the form of a solution or suspension, spray-drying or fluidized-bed granulation may be used in particular for the preparation. In spray drying, usually a spray powder with a particle size <200 microns is achieved, this powder can then be processed in a further confectioning step to larger particles. In a preferred embodiment, the solution or suspension is transferred directly into a granulate in a fluidized-bed granulation process. Depending on the processing properties of the activator mixture or the desired granulate formulation, one or more additives may be added to the spray liquid, it being possible for these additives to be mixed both liquid and solid. In addition to a binder function, the additives can also have the task of stabilizing or supplementing the actual active substance. Especially when admixing solid additives, optimum preparation of the spray slurry for the spraying process is advantageous, such as, for example, a grinding step for comminuting solid particles, frequently Zahnscheibenkolloidmühlen can be used. For specific adjustment of the viscosity of the spray liquid, a dilution and / or temperature control can be carried out.

According to another preferred embodiment, one or more additives may be separately metered into the process in solid form. The stubble portions 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 e.g. the targeted supply of a carrier material for receiving sticky active substances. In addition, the separate solid feed may prove to be a control tool for granule growth in the process.

The described fluidized bed processes can be carried out in apparatuses which are designed both with round and with rectangular geometries.

additives:

As mentioned several times, it is necessary in many cases during the granulation of the active substance to add one or more additives. In particular, these additives can have the following function.

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 layered alkali metal silicates of the formula

MM'Six0 (2x-1) * yH ₂ O (M, M '= Na, K, H, x = 1.9 to 23; y = 0-25), preferably sodium silicates, for example under the trade name SKS-6 and Nabion 15 available 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 Handetsprodukten Tonsil ^® EX 519, Tonsil Optimum 210 FF, Tonsil Standard 310 FF and 314 FF, and Opazil ^® SO Fa. Suedchemie available.

Other suitable support materials are alkali metal phosphates, which may be 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, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and mixtures of sodium and potassium salts.
Useful organic support materials are, for example, the carboxylic acids preferably used in the form of their sodium salts, such as citric acid and nitriloacetate (NTA), ethylenediaminetetraacetic acid. Analogously, it is also possible to use polymeric carboxylates and their salts. These include, for example, the salts of homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those of 50% to 10% of maleic acid, polyaspartic acid and also polyvinylpyrrolidone and urethanes. The molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid. In particular, water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a molecular weight of more than one million are also suitable. Examples of these are the polymers available under the name Carbopol 940 and 941.

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 commercial products acrylic acid, and the Salts of these polymer acids. Commercial products are, for example Sokalan ^® CP 5 or 45, Sokalan CP 12 S or 13 S. CP

Surfactants, in particular anionic and nonionic surfactants, surfactant compounds, di- and polysaccharides, cyclodextrins, meltable polyesters, polyalkylene glycols, in particular polyethylene, polypropylene glycols, particularly preferably polyethylene glycols having molecular weights of from 1000 to 10,000, preferably from 3,000 to 6,000, may also be used as binders and granulating aids , particularly preferably 4000, fatty acids, in particular saturated fatty acids, such as lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, eg Coconut, palm kernel or tallow fatty acids derived mixtures, soaps, especially saturated fatty acid soaps and waxes are used.

Preferred anionic surfactants are alkali salts, ammonium salts, amine salts and salts of amino alcohols of the following compounds: alkyl sulfates, alkyl ether sulfates, alkylamide sulfates and ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkanesulfonates, α-olefinsulfonates, alkylarylsulfonates, arylsulfonates, in particular 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 such as oleic acid, ricinoleic acid, palmitic acid, stearic acid, coconut oil acid salt or hydrogenated coconut oil acid salts. The alkyl group of all these compounds normally contains 8-32, preferably 8-22 carbon 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).

coating:

The granules obtained according to the invention are suitable directly for use in detergents and cleaners. In a particularly preferred However, they can be provided with a coating shell according to methods known per se. For this purpose, the granules are coated in an additional step with a film-forming substance, whereby 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 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 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 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 in dissolved or suspended form, for example homo-, cobalt- or graft 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.

Depending on the desired properties of the coated granules, the content of coating substance can be from 1 to 30% by weight, preferably from 5 to 15% by weight, based on the coated granules.

For applying the coating substances, mixers (mechanically induced fluidized bed) and fluidized bed apparatus (pneumatically induced fluidized bed) can be used. to be used. As mixers, for example, plowshare mixers (continuous and batchwise), ring layer mixers or even Schugi mixers are 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.

The bleach activator mixtures according to 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 will be listed below.

Surface-active substances Anionic surfactants

The detergents and cleaners may comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants. Such surfactants are present in inventive detergents in proportions of preferably 1 wt .-% to 50 wt .-%, in particular from 3 to 30 wt .-%, whereas in hard surface cleaners usually lower levels, that is amounts up to 20 wt .-%, in particular up to 10 wt .-% and preferably in the range of 0.5 to 5 wt .-% are included. Dishwashing detergents typically use low-foam compounds.

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 of 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. Are suitable also the sulfuric acid monoesters of the straight-chain or branched alcohols ethoxylated with 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 having 1 to 4 EO.

The preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfoccinates or as sulfosuccinic acid esters, and which are 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 anionic surfactants, including soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts. Anionic surfactants are preferably present in detergents according to the invention in amounts of from 0.5 to 10% by weight and in particular in amounts of from 5 to 25% by weight.

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 is linear or preferably methyl-branched in the 2-position can, 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. with 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl having 3 to 1 0 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 in which (II) is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 is} a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R ⁵ is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, wherein C ₁ -C ₄ alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is at least is substituted two 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-allyloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, especially 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-dihydroxyethylaminoxid. and the fatty acid alkanolamide may be suitable.

Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is usually one Carbon chain, which should be long enough that the hydrophilic groups have a sufficient distance so that they can act independently. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. However, it is also possible to use 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 to be discribed. Other surfactant types may have dendrimeric structures.

BUILDER Inorganic builders

A detergent according to the invention preferably contains 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 is generally 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 silicates useful as builders have Preferably, 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 amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates with a molar ratio of Na ₂ O: SiO, of 1: 2 to 1: 2.8. As crystalline silicates which may be present alone or in a mixture with amorphous silicates, preference is given to using crystalline sheet silicates of the general formula NA ₂ Si _x O _{2 × + 1} : YH ₂ O, in which x, the so-called module, has a number of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. 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. 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, can be used. In a further preferred embodiment of such agents, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention. In a preferred embodiment of compositions according to the invention, a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion®. 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 silicate, preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1. Such builder substances are preferably present in compositions according to the invention in amounts of up to 60% by weight, in particular from 5% by weight to 40% Wt .-%, contained.

Organic Builder

The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and 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, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain polymerized small amounts of polymerizable substances 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 generally have a relative Molecular weight between 1000 and 200 000 on. Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.

The organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50% strength by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

If desired, such organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1 to 8% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular water-containing agents.

Suitable water-soluble builder components in hard surface cleaners according to the invention are in principle all builders customarily used in detergents for dishwashing, for example the abovementioned alkali metal phosphates. Their amounts may be in the range of up to about 60 wt .-%, in particular 5 to 20 wt .-%, based on the total mean. Other possible water-soluble builder components are, in addition to polyphosphonates and Phosphonatalkylcarboxylaten for example, organic polymers of native or synthetic origin of the above-mentioned type of polycarboxylates, which act especially in hard water regions as a co-builder, and naturally occurring hydroxycarboxylic acids such as mono-, dihydroxysuccinic, alpha-hydroxypropionic and gluconic. Preferred organic builder components include the salts of citric acid, especially sodium citrate. As sodium citrate, anhydrous tri-sodium citrate and preferably trisodium citrate dihydrate are suitable. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder. Depending on the ultimate in the invention Detergents adjusted pH value can also be present corresponding to the said co-builder salts acids.

enzymes

The enzymes optionally contained in the agents according to the invention 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 such as Termamy®, amylase-LT, Maxamyl®, Duramyl®, Purafectel OxAm, cellulases such as Celluzyme®, Carezyme®, K-AC® and / or lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®. The enzymes used may be adsorbed to carriers and / or embedded in encapsulants to protect 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 to 5% by weight, enzymes which are particularly preferably stabilized against oxidative degradation being 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 from 3 to 30% by weight, based on the total agent. 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 to 40% by weight.

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

To effect silver corrosion protection, silver corrosion inhibitors can be used in dishwashing detergents according to the invention. 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, molybdenum, vanadium or Cersalze_und / or complexes, and salts and / or complexes of the metals present in the complexes suitable according to the invention with other than in formula (I) predetermined ligands.

If the agents foam too much during use, they may still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-regulating compound, preferably from the group consisting of silicones, paraffins, paraffin-alcohol combinations , Hydrophobicized silicic acids, Bisfettsäureamide and mixtures thereof and other other known commercially available foam inhibitors are added. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred. Further optional ingredients in the compositions according to the invention are, for example, perfume oils.

Among the organic solvents which can be used in the compositions according to the invention, especially if they are in liquid or pasty form, are alcohols having 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, and mixtures thereof and the derivable from said classes of compounds ethers. Such water-miscible solvents are preferably not present in the cleaning agents according to the invention
20 wt .-%, in particular from 1 to 15 wt .-%, present.

In order to establish a desired pH, which does not naturally result from the mixture of the other components, the compositions according to the invention may contain system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid or alkali metal hydrogensulfates, or bases, in particular ammonium or alkali metal hydroxides, such pH regulators are preferably not more than 10 wt .-%, in particular from 0.5 wt .-% to 6 wt .-%, contain.

The compositions according to the invention are preferably in the form of pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roll compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and the bleach catalyst are to be expected, can be prepared. Solutions according to the invention 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.

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 mixed with increasing the bulk density of this premix and subsequently - if desired after a Intermediate drying - the other ingredients of the composition, 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 Exzeriteipressen 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.

Examples example 1 Bleaching performance of nonanoyloxybenzoic acid (NOBA) in combination with tetaacetylethylenediamine (TAED)

The bleaching performance of the individual activators and of the mixtures according to the invention was investigated in a Linitest apparatus (Fa. Out) at 40.degree. For this purpose, 2 g / l of a bleach-free basic detergent (WMP, WFK, Krefeld) and 0.5 g / l of sodium percarbonate (Degussa) were dissolved in water of hardness grade 3. Subsequently, 250 mg / l activator or activator mixture were added. The washing time was 30 min. Curry, grass and tea on cotton (BC-4, CS-8 and BC-1, WFK, Krefeld) were used as bleaching test cloth. As a bleaching result, the remission difference, measured with an Elrepho machine, after washing compared to a fabric washed with a base detergent and percarbonate was evaluated. Remission difference (ddR%) Activators / solvent mixture BC-4 CS-8 BC-1 100% TAED 1.3 0.9 3.7 75% TAED, 25% NOBA 3.4 3.9 4.8 50% TAED, 50% NOBA 4.7 5.2 5.0 25% TAED, 75% NOBA 4.1 4.4 4.7 100% NOBA 4.1 4.1 4.2 ( All% data here and in the following examples as wt% )

It can be seen that the mixtures according to the invention achieve a significantly better bleaching effect than the individual activators alone. Substantially similar results were obtained when replacing sodium percarbonate with sodium perborate monohydrate.

Example 2 Bleaching performance of decanoyloxybenzoic acid (DOBA) in combination with tetaacetylethylenediamine (TAED)

The bleaching performance of the individual activators and of the mixtures according to the invention was investigated in a Linitest apparatus (Fa. Out) at 40.degree. For this purpose, 2 g / l of a bleach-free basic detergent (WMP, WFK, Krefeld) and 0.5 g / l of sodium percarbonate (Degussa) were dissolved in water of hardness grade 3. Subsequently, 250 mg / l activator or activator mixture were added. The washing time was 30 min. Grass and tea on cotton (CS-8 and BC-1, WFK, Krefeld) were used as bleaching test cloth. As a bleaching result, the remission difference, measured with an Elrepho machine, after washing compared to a fabric washed with a base detergent and percarbonate was evaluated. Remission difference (ddR%) Activators / solvent mixture CS-8 BC-1 100% TAED 0.9 3.7 75% TAED, 25% DOBA 3.9 4.8 50% TAED, 50% DOBA 5.2 5.0 25% TAED, 75% DOBA 4.4 4.7 100% DOBA 4.1 4.2

It can be seen that the mixtures according to the invention achieve a significantly better bleaching effect than the individual activators alone.
Substantially similar results were obtained when tetraacetylethylenediamine was substituted for 1,5-diacetyl-2,4-dioxo-1,3,5-hexahydrotriazine (DADHT).

Example 3 Bleaching performance of decanoyloxybenzoic acid (DOBA) in combination with tetaacetylethylenediamine (TAED) in the washing machine

The experiments were carried out in a Miele Novotronic W927 in a short cycle at 40 ° C. For this purpose, 72 g basic wash detergent (WMP, WFK, Krefeld), 12 g percarbonate (Degussa) and 2.5 g activator or a mixture of 1.5 g TAED and 1.0 g DOBA were used per wash. The test soiling was a multi-stem swatch (EMPA). As a bleaching result, the remission difference, measured with an Elrepho device, after washing compared to the unwashed test soil was evaluated. Remission difference (ddR%) Activators / solvent mixture Make up carotene baby food butter 2.5 g TAED 50.3 40.6 37.0 56.6 1.5 g TAED, 1; 0 g DOBA 58.8 42.9 39.3 60.2 2.5 g DOBA 47.6 41.4 36.1 59.3

It can be seen that the mixtures according to the invention achieve a significantly better bleaching effect than the individual activators alone.

Example 4

Bleaching performance of nonanoyloxybenzoic acid (NOBA) in combination with 1,5-diacetyl-2,4-dioxo-1,3,5-hexahydrotriazine (DADHT) in the washing machine The experiments were carried out in a Miele Novotronic W927 in a short cycle at 40 ° C. For this purpose, 72 g basic wash detergent (WMP, WFK, Krefeld), 12 g percarbonate (Degussa) and 2.5 g activator or a mixture of 1.5 g TAED and 1.0 g NOBA were used per wash. The test soiling was a multi-stem swatch (EMPA). As a bleaching result, the remission difference, measured with an Elrepho device, after washing compared to the unwashed test soil was evaluated. Remission difference (ddR%) Activators / solvent mixture Make up curry carotene grass 2.5 g DADHT 63.5 41.6 28.9 59.0 1.5 g DADHT, 1.0 g NOBA 72.2 44.3 37.4 62.0 2.5 g of NOBA 57.7 41.7 36.0 58.6

It can be seen that the mixtures according to the invention achieve a significantly better bleaching effect than the individual activators alone.

Example 5 Production of a co-granulate from TAED and DOBA

In a laboratory mixer (type: Eirich R-02) were presented 0.9 kg of TAED powder (active content about 99%), 0.94 kg DOBA powder (active content about 95%) and 0.17 kg of bentonite (eg Ikomont NA white - commercial product of the company S & B Industrial Minerals GmbH). The products were intensively mixed at a mixing vessel speed of n = 32 min ^-1 (stage I) and a swirler speed of n = 750 min ^-1 for 2 min

The powder mixture thus prepared was then pressed in a roller compactor (type: Hosokawa-Bepex Pharmapaktor L 200/30 P). The speed of the rollers was in the range of about 3 - 6 min ^-1 and the speed of the plug screw was varied in the range of about 15 - 20 min ^{-1 in} order to achieve a sufficient compaction of the powder. The pressed pieces were then comminuted gently on a screen mill (type: Alexanderwerk SKM / NR), using a sieve insert with a mesh width of 1600 μm and a speed of 33 min ^{-1 was} worked. The comminuted product was finally fractionated on a laboratory sieve (type Retsch AS 200 control) in order to separate out fine particles <400 μm from the target product. The final compact was 44.3% TAED (active), 44.4% DOBA (active), and 8.5% bentonite.
The production of a co-granulate with NOBA can be carried out in an analogous manner.

Example 6 Production of a Co-granulate from TAED and NOBA

In a laboratory ploughshare mixer (type: Lödige M5R with knife head) are submitted to 0.6 kg of TAED powder (active content about 99%), 0.41 kg NOBA powder (active content about 97%) and 0.147 kg of carboxymethylcellulose (eg Finnfix BDA commercial product from Noviant CMC Oy, Finland). The products were premixed dry for about 30 sec at a speed of n = 100 min ^-1 . Subsequently, the mixer speed was increased to n = 225 min-1, switched on the cutter head and the dosage of the process water required for granulation started: During a period of 60 sec a total of 250 ml of water was added to the mixer. The mixing and granulating process was continued for a further 5 minutes at constant speed and with the cutter head switched on in order to achieve sufficient granulation of the mixture. Subsequently, the moist mixture was discharged from the mixer and immediately dried in a laboratory fluidized bed dryer (Retsch type TG 100) at a temperature of T = 80 ° C. The total drying time was about 15 minutes, during which the blower output was gradually lowered from level 5 to level 1. The dried product was then 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 build-up granulate was present with a composition of about 51.4% TAED (active), about 34.3% NOBA (active) and about 12.7% CMC. The production of a co-granulate with DOBA can be carried out in an analogous manner.

Claims (6)

1. A bleach activator mixture in the form of cogranules comprising

   a) a hydroxybenzoic acid derivative of the formula 1

   

   in which R is C8-C11-alkyl, and

   b) tetraacetyle-thylenediamine and/or 1,5-diac-etyl-2,4-dioxo-1,3,5-hexahydrotriazine.
2. The bleach activator mixture in the form of corgranules as claimed in claim 1, wherein the ratio of hydroxybenzoic acid derivative of the formula 1 to tetraacetylethylenediamine and/or 1,5-diacetyl-2,4-dioxo-1,3,5-hexahydrotriazine is from 95:5 to 5:95% by weight.
3. The bleach activator mixture in the form of cogranules as claimed in claim 1, wherein the ratio of hydroxybenzoic acid derivative of the formula 1 to tetraacetylethylenediamine and/or 1,5-diacetyl-2,4-dioxo-1,3,5-hexahydrotriazine is from 75:25 to 25:75% by weight.
4. The bleach activator mixture in the form of cogranules as claimed in claim 1, wherein the ratio of hydroxybenzoic acid derivative of the formula 1 to tetraacetylethylenediamine and/or 1,5-diacetyl-2,4-dioxo-1,3,5-hexahydrotriazine is from 60:40 to 40:60% by weight.
5. The bleach activator mixture in the form of cogranules as claimed in claim 1, which additionally comprises additives, granulating agents and/or coating agents.
6. A washing composition, cleaning composition and disinfectant comprising a bleach activator mixture in the form of cogranules as claimed in claim 1 and hydrogen peroxide or an inorganic peroxy oxygen compound.