WO2005103217A1

WO2005103217A1 - Consumption indicator for machine dishwashing agents

Info

Publication number: WO2005103217A1
Application number: PCT/EP2005/003931
Authority: WO
Inventors: Arnd Kessler; Wolfgang Barthel; Ion Canavoiu-Opritescu; Ingo Hardacker
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2004-04-21
Filing date: 2005-04-14
Publication date: 2005-11-03
Also published as: DE102004020033A1

Abstract

Metered quantities of a cleaning agent or auxiliary cleaning agent that are introduced into the interior of a dish washer and are completely used only during a plurality of cleaning processes can be reliably and economically metered when combined with a consumption indicator. Said indicator comprises an alkali polyphosphate which, based on the entire weight of the indicator, comprises at least 45 % by weight of phosphorpentoxide (P2O5) and at least 5 % by weight of alkali oxide (M2O), and indicates to the user that the cleaning agent or auxiliary cleaning agent is used up.

Description

"Consumption indicator for automatic dishwashing detergents"

The present application relates to a consumption indicator for automatic dishwashing detergents. In particular, the present application relates to consumption indicators for cleaning or cleaning aids in automatic dishwashing.

With automatic dishwashing in the home, detergents are usually introduced into a dosing chamber in powder or tablet form for a rinse cycle, i.e. Detergent must be dosed again for each new cleaning process. In addition, there are cleaning aids and, in particular, cleaning aids that survive several rinse cycles. For cleaning aids, which are dosed by the dishwasher, there is a consumption display in most commercial dishwashers, which signals the consumer that the corresponding product must be refilled. In this way, for example, the consumption of rinse aid or regeneration salt is recorded and a certain condition is signaled to the consumer via acoustic or visual displays.

In contrast, there are no consumption indicators in the dishwasher for cleaning agents and the consumption of these cleaning agents. In the meantime, there are also a large number of cleaning aids that are also not dosed by the machine, but that are consumed over several rinse cycles, for example deodorants for the interior of the machine, glass protection products or additional products for silver protection, increased cleaning performance, etc.

The problem here is to indicate the exhaustion of cleaning or cleaning aids when the consumer is to buy a corresponding new product and put it in the dishwasher.

To solve this problem, the cleaning aids are added, for example, to corresponding single-dose cleaning agents, so that the consumer receives a new cleaning aid when buying a new package of the cleaning agent. This has the disadvantage that one is bound to certain pack sizes for the cleaning agent; in addition, a separate sale of the cleaning aid is not possible in this way.

The object of the present application was therefore to provide a consumption indicator which indicates the exhaustion of the cleaning or cleaning aid to the user of a cleaning or cleaning aid which is introduced into the interior of a dishwasher and is only used there in the course of several cleaning processes. In order to adapt it to the requirements of the different cleaning or cleaning aids, the consumption indicator should be able to be produced in a simple manner, preferably in any size and shape. A first subject of the present application is therefore an agent in the form of a measured amount of a cleaning or cleaning aid, which is introduced into the interior of a dishwasher and is only completely used up there in the course of several cleaning processes, comprising a consumption indicator which tells the user that the appliance is exhausted Indicates cleaning or cleaning aids and comprises an alkali polyphosphate containing, based on the total weight of the consumption indicator, at least 45 wt .-% phosphorus penide (P ₂ 0 ₅ ) and at least 5 wt .-% alkali oxide (M ₂ 0).

The agents according to the invention comprise, as the first component, a measured amount of a cleaning or cleaning aid. This cleaning or cleaning aid for automatic dishwashing can be an automatic dishwashing agent and / or an additive for automatic dishwashing. In addition to the compact machine dishwashing detergents, cleaning boosters can also be used as machine dishwashing agents. Enzyme concentrates, bleach concentrates, water softeners or rinse aid concentrates can be used as cleaning enhancers. Additives whose effects go beyond simply cleaning the dishes are, for example, fragrances for scenting the interior of the machine, disinfectants or agents to prevent the corrosion of silver or glass. In the context of the present application, it is preferred to use one of the abovementioned cleaning boosters and / or one of the abovementioned additives as cleaning or cleaning aids.

Agents according to the invention, characterized in that the cleaning or cleaning aid is a glass corrosion inhibitor and / or a silver protective agent and / or a fragrance and / or a disinfectant and / or a rinse aid and / or a water softener and / or an enzyme and / or a bleaching agent are particularly preferred.

If the cleaning or cleaning aid is a cleaning enhancer, from the group of enzymes or enzyme concentrates, the proportion by weight of the enzyme in the total weight of the cleaning or cleaning aid is preferably more than 5% by weight, preferably more than 8% by weight. %, particularly preferably more than 11% by weight and in particular more than 14% by weight. If bleaching agent concentrates are used as cleaning or cleaning aids, the proportion by weight of these agents in bleaching agent is more than 30% by weight, preferably more than 50% by weight, particularly preferably more than 60% by weight and in particular more than 70% by weight .-%. Cleaning or cleaning aids which serve as water softeners or rinse aid concentrates preferably contain more than 12% by weight, preferably more than 18% by weight, particularly preferably more than 24% by weight and in particular more than 30% by weight of one organic polymer, preferably a cationic, anionic or amphoteric polymer. If the cleaning or cleaning aid comprises an additive for automatic dishwashing from the group of fragrances, disinfectants, silver preservatives or glass corrosion inhibitors, the proportion by weight of the cleaning or cleaning aid in perfume or disinfectant or silver protection agents or glass corrosion inhibitor is at least 3% by weight, preferably at least 7% by weight, particularly preferably at least 12% by weight and in particular at least 18% by weight. The additive content of perfume is preferably between 20 and 60% by weight, preferably between 25 and 50% by weight and in particular between 30 and 40% by weight.

Cleaning enhancers and additives, but in particular the additives, preferably have a water-soluble or water-insoluble polymeric carrier material as a further ingredient.

All polymers or polymer mixtures are generally suitable as polymeric carrier materials for the cleaning enhancers or additives. Cleaning enhancers or additives preferred in the context of the present application are characterized in that the polymeric carrier material comprises at least one substance from the group comprising ethylene / vinyl acetate copolymers, polyethylene of low or high density (LDPE, HDPE) or mixtures thereof, polypropylene, poly ethylene / polypropylene copolymers, polyether / polyamide block copolymers, styrene / butadiene (block) copolymers, styrene / isoprene (block) copolymers, styrene / ethylene / butylene copolymers, acrylonitrile / - butadiene / styrene copolymers, acrylonitrile / Butadiene copolymers, polyether esters, polyisobutene, polyisoprene, ethylene / ethyl acrylate copolymers, polyamides, polycarbonate, polyester, polyacrylonitrile, polymethyl methacrylate, polyurethanes, polyvinyl alcohols.

Polyethylene (PE) is a collective name for polymers belonging to the polyolefins with groupings of the type

CH ₂ - CH ₂

as a characteristic basic unit of the polymer chain. Polyethylenes are generally produced by polymerizing ethylene using two fundamentally different methods, the high pressure u. the low pressure process. The resulting products are accordingly often referred to as high-pressure polyethylenes or low-pressure polyethylenes; they differ mainly in their degree of branching and, related to this, in their degree of crystallinity and density. Both processes can be carried out as solution polymerization, emulsion polymerization or gas phase polymerization.

The high-pressure process produces branched polyethylenes with low density (approx. 0.915-0.935 g / cm ³ ) and degrees of crystallinity of approx. 40-50%, which are referred to as LDPE types (low density polyethylene). Products with higher molecular weight and. resulting improved strength u. Stretchability has the short name HMW-LDPE (HMW = high molecular weight). By copolymerizing ethylene with longer-chain olefins, especially with butene and the like. Octene, the pronounced degree of branching of the polyethylenes produced in the high-pressure process can be reduced; the copolymers have the symbol LLD-PE (linear low density polyethylene).

The macromolecules of the polyethylenes from low-pressure processes are largely linear and unbranched. These polyethylenes, abbreviations HDPE (from E high density polyethylene) have degrees of crystallinity of 60-80% u. a density of approx. 0.94-0.965 g / cm3. They are called products with high or ultra-high molar mass (approx. 200,000-5,000,000 g / mol or 3,000,000-6,000,000 g / mol) under the short designation HD-HMW-PE or UHMW-HD-PE offered. Medium density (MDPE) products made from blends of low and high density polyethylenes are also commercially available. Linear P. with densities <0.918 g / cm3 (VLD-PE, from E very Iow density polyethylene) are only slowly gaining market importance.

Polyethylenes have a very low water vapor permeability, the diffusion of gases as well as aromas and the like. ethereal substances through polyethylene is relatively high. The mechanical properties strongly depend on the molecular size and structure of the polyethylenes. In general, Kristal I increase in degree of Density of polyethylene with decreasing degree of branching and with shortening of the side chains. The shear modulus, hardness, yield strength and so on increase with density. Melting range; it decrease from shock resistance, transparency, swellability u. Solubility. At the same density, the tensile strength, elongation, shock resistance, impact resistance and the like increase with increasing molecular weight. Fatigue strength too. Depending on the method of polymerization, products with paraffin wax-like properties (MR around 2000) and. Get products with the highest toughness (MR over 1 million).

The processing of the polyethylene types can be carried out according to all methods usual for thermoplastics.

Polypropylene (PP) is the name for thermoplastic polymers of propylene with the general formula:

- (CH ₂ -CH [CH3]) _n -

The basis for polypropylene production was the development of the process for the stereospecific polymerization of propylene in the gas phase or in suspension by Natta. This is initiated with Ziegler-Natta catalysts, but increasingly also with metallocene catalysts, and leads either to highly crystalline isotactic or to less crystalline syntactic or to amorphous atactic polypropylenes Polypropylene is characterized by high hardness, resilience, rigidity and heat resistance. Short-term heating of objects made of polypropylene is even possible up to 140 ° C. At temperatures below 0 ° C, the polypropylenes become somewhat brittle, but can be shifted to much lower temperature ranges by copolymerizing the propylene with ethylene (EPM, EPDM). Gen. the impact strength of P. can be improved by modification with elastomers. As with all polyolefins, the chemical resistance is good. The mechanical properties of P. can be improved by reinforcing with talc, chalk, wood flour or glass fibers. P. are to an even greater extent than PE oxidations- u. sensitive to light, which is why the addition of stabilizers (antioxidants, light stabilizers, UV absorbers) is necessary.

Polyether is a general term in the field of macromolecular chemistry for polymers whose organic repeating units are held together by ether functionalities (C-O-C). According to this definition, a large number of structurally very different polymers belong to the polyethers, e.g. B. the polyalkylene glycols (polyethylene glycols, polypropylene glycols and polyepichlorohydrins) as polymers of 1, 2-epoxides, epoxy resins, polytetrahydrofuran (polytetramethylene glycols), polyoxetanes, polyphenylene ethers (see polyaryl ether) or polyether ether ketones (see polyether ketones) (see polyether ketones) Polymers with pendant ether groups are not counted among the polyethers, as u. a. the cellulose ethers, starch ethers u. Vinyl ether polymers.

The group of polyethers also includes functionalized polyethers, i.e. H. Compounds with a polyether backbone that have other functional groups attached to their main chains, such as. B. carboxy, epoxy, allyl or amino groups, etc. Block copolymers of polyethers and polyamides (so-called polyether amides or polyether block amides, PEBA) are very versatile.

Polyamides (PA) are polymers whose basic building blocks are held together by amide bonds (-NH-CO-). Naturally occurring polyamides are peptides, polypeptides and the like. Proteins (e.g. protein, wool, silk). With a few exceptions, the synthetic polyamides are thermoplastic, chain-shaped polymers, some of which are of great technical importance as synthetic fibers and. Have obtained materials. According to the chemical structure, the so-called homo-polyamides can be divided into two groups, the aminocarboxylic acid types (AS) and the diamine-dicarboxylic acid types (AA-SS; A denotes amino groups and S carboxy groups). The former are made from only a single monomer by e.g. B. polycondensation of a D-aminocarboxylic acid 1 (polyamino acids) or by ring-opening polymerization of cyclic amides (lactams) 2. In addition to homopolyamides, some copolyamides have also become important. A qualitative u. quantitative indication of the composition z. B. PA 66/6 (80:20) for from 1, 6-hexanediamines, adipic acid and. Polyamides produced by e-caprolactam in a molar ratio of 80:80:20.

Because of their special properties, P. which are exclusively aromatic. Contain residues (e.g. those from p-phenylenediamine and terephthalic acid), under the generic name. Aramids or polyamides combined (example: Nomex®).

The most commonly used types of polyamide (especially PA 6 and PA 66) consist of unbranched chains with average molecular weights of 15,000 to 50,000 g / mol. They are partially crystalline in the solid state and have degrees of crystallization of 30-60%. An exception are polyamides from building blocks with side chains or copolyamides from widely different components that are largely amorphous. In contrast to the generally milky-opaque, partially crystalline polyamides, these are almost crystal-clear. The softening temperature of the most common HomoPolyamides are between 200 u. 260 ° C (PA 6: 215-220 ° C, PA 66: 255-260 ° C).

Polyester is the collective name for polymers whose basic building blocks are held together by ester bonds (-CO-0-). According to their chemical structure, the so-called homopolyesters can be divided into two groups, the hydroxycarboxylic acid types (AB polyester) and the like. the dihydroxy-dicarboxylic acid types (AA-BB polyester). The former are made from only a single monomer by e.g. B. polycondensation of a D-hydroxycarboxylic acid 1 or by ring-opening polymerization of cyclic esters (lactones) 2.

Branched and crosslinked polyesters are obtained in the polycondensation of trihydric or polyhydric alcohols with polyfunctional carboxylic acids. Polyesters generally include polycarbonates (carbonic acid polyesters).

AB-type P. (I) are u. a. Polyglycolic acids, polylactic acids, polyhydroxybutyric acid [poly (3-hydroxybutyric acid), poly (e-caprolactone) e and polyhydroxybenzoic acids.

Purely aliphatic AA-BB type polyesters (II) are polycondensates made from aliphatic diols and dicarboxylic acids, which are used, inter alia, as products with terminal hydroxyl groups (as polydiols) for the production of polyester polyurethanes [e.g. B. Polytetramethylene adipate. In terms of quantity, AA-BB type polyesters made from aliphatic diols and aromatic dicarboxylic acids, in particular the polyalkylene terephthalates, with polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and poly (1,4-cyclohexanedimethylene terephthalate) e (PCDT) as most important representative. These types of P. can be obtained by using other aromatic dicarboxylic acids (e.g. isophthalic acid) or by using diol mixtures in the The properties of polycondensation vary widely and can be adapted to different areas of application.

Purely aromatic polyesters are the polyarylates, to which u. a. which include poly (4-hydroxybenzoic acid). In addition to the previously mentioned saturated polyesters, unsaturated polyesters can also be produced from unsaturated dicarboxylic acids which have gained technical importance as polyester resins, in particular as unsaturated polyester resins (UP resins).

Polyesters are usually thermoplastics. Products based on aromatic dicarboxylic acids have a distinct material character. The purely aromatic polyarylates are characterized by high thermal stability.

Polymers, in whose macromolecules the repeating units are linked by urethane groups -NH-CO-O-, are referred to as polyurethanes (PUR). Polyurethanes are generally obtained by polyaddition from di- or higher alcohols and isocyanates.

Depending on the choice and stoichiometric ratio of the starting materials, polyurethanes with very different mechanical properties are created, which are used as components of adhesives and varnishes (P. -Harze), as ionomer, as thermoplastic material for bearing parts, rollers, tires, rollers and more or less hard elastomers in fiber form (elasto fibers, short PUE for these elastane or spandex fibers) or as polyether or polyester urethane rubber (EU or AU)

Polyurethane foams are created during polyaddition when water and / or. Carboxylic acids are present, because they react with the isocyanates with the elimination of carbon dioxide, which has a foaming and foaming effect. With polyalkylene glycol ethers as diols u. Water as a reaction component leads to flexible polyurethane foams with polyols and the like. CFC propellants (esp. R 11) give rigid polyurethane foams and structural or integral foams. Additional auxiliaries required here are e.g. B. catalysts, emulsifiers, foam stabilizers (esp. Polysiloxane-polyether copolymers), pigments, aging u. Flame retardants. The so-called RIM technique (reaction injection molding) was developed in the 1970s for the production of even complex shaped objects made of polyurethane foam. The RIM process relies on rapid dosing u. Mixing the components, injection of the reactive mixture into the mold u. rapid curing; the cycle time is only a few minutes. Using RIM technology u. a. Car body parts, shoe soles, window profiles and television housings produced.

Polyvinyl alcohols (PVAL, occasionally also PVOH) is the name for polymers of the general structure

- CH ₂ CH - CH ₂ - CH - which in small proportions (approx. 2%) also structural units of the type

contain.

Commercially available polyvinyl alcohols are offered as white-yellowish powders or granules with degrees of polymerization in the range from approximately 100 to 2500 (molar masses from approximately 4000 to 100,000 g / mol). The manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax. The polyvinyl alcohol coatings are largely impervious to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

Polyvinyl alcohols of a certain molecular weight range are preferably used, it being preferred according to the invention that the molecular weight is in the range from 10,000 to 100,000 gmol ^"1 , preferably from 11,000 to 90,000 gmol ^{" 1} , particularly preferably from 12,000 to 80,000 gmol ^"1 and in particular from 13,000 to 70,000 gmol ^"1 lies.

In a particularly preferred embodiment of the present invention, the polymeric carrier material of the particles consists at least in part of ethylene / vinyl acetate copolymer. Another preferred subject of the present application is therefore a cleaning enhancer or additives, characterized in that the polymeric carrier material contains at least 10% by weight, preferably at least 30% by weight, particularly preferably at least 70% by weight, of ethylene / vinyl acetate copolymer , preferably made entirely of ethylene / vinyl acetate copolymer.

Ethylene / vinyl acetate copolymers is the name for copolymers of ethylene and vinyl acetate. This polymer is generally produced in a process comparable to the production of low density polyethylene (LDPE; Iow density polyethylene). With a too Taking vinyl acetate, the crystallinity of the polyethylene is interrupted and the melting and softening points or the hardness of the resulting products are reduced in this way. The vinyl acetate also makes the copolymer more polar and thus improves its adhesion to polar substrates.

The ethylene / vinyl acetate copolymers described above are widely available commercially, for example under the tradename Elvax ^® (Dupont). Polyvinyl alcohols which are particularly suitable in the context of the present invention are, for example, Elvax ^® 265, Elvax ^® 240, Elvax ^® 205 W, Elvax ^® 200 W and Elvax ^® 360.

Some particularly suitable copolymers and their physical properties can be found in the table below:

In the context of the present invention, cleaning enhancers or additives are particularly preferred in which ethylene / vinyl acetate copolymer is used as the polymeric carrier material and this copolymer contains 5 to 50% by weight of vinyl acetate, preferably 10 to 40% by weight of vinyl acetate and in particular 20 to 30 wt .-% vinyl acetate, each based on the total weight of the copolymer contains.

Cleaning enhancers or additives according to the invention contain the polymeric carrier materials in the form of particles. The spatial shape of these particles is only limited by the technical possibilities in their manufacture. All sensibly manageable configurations are thus considered as the spatial shape, for example, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment comprises tablet-shaped particles up to compact cylindrical pieces with a ratio of height to diameter above 1. Further possible spatial shapes are spheres, hemispheres or "elongated spheres" in the form of elipsoid capsules as well as regular polyhedra, for example tetrahedra, hexahedra, Octahedron, dodecahedron, icosahedron. Star-shaped training courses are also conceivable three, four, five, six or more peaks or completely irregular bodies, which can be motivated, for example. Depending on the field of use of the agents according to the invention, suitable motifs are, for example, animal figures such as dogs, horses or birds, floral motifs or the representation of fruits. The motivic design can also refer to inanimate objects such as vehicles, tools, household items or clothing. The surface of the solid particles can have bumps depending on the type of manufacturing process chosen and / or a coating selected. Because of the numerous design options for the particles, the agents according to the invention are not only distinguished by advantages in their manufacture. On account of the wide variety of configurations, the fragrance-containing particles are also clearly visually perceptible to the consumer and, through the targeted spatial configuration of these particles, enable a visualization of the active ingredients contained in the agents according to the invention, or other active substances optionally contained in these agents, which is particularly advantageous for product acceptance. The optically perceptible multiphase nature of these agents can, for example, illustrate the different mode of action of individual active substances (e.g. cleaning and additional functions such as glass protection, silver protection, etc.).

In the context of the present application, particles are summarized as particles which have a consistency which is solid at room temperature, that is to say dimensionally stable and not flowable. Preferred particles have an average diameter of 0.5 to 20 mm, preferably 1 to 10 mm and in particular 3 to 6 mm.

The polymeric carrier materials can be made up into the particles described above by all methods known to those skilled in the art for processing these substances. In the context of the present invention, extrusion, injection molding and spraying into polymer granules are preferred.

The measured amount of the cleaning or cleaning aid contained in the agent according to the invention is only completely consumed in the course of several cleaning processes. The agents according to the invention are therefore not used for simple dosing for a single rinse cycle, but rather are more suitable for releasing the corresponding active ingredients over several rinse cycles. Agents according to the invention whose content of cleaning or cleaning aids, preferably from the group of enzymes, bleaching agents, cationic or amphoteric polymers, fragrances, disinfectants, silver protection agents or glass corrosion inhibitors, are preferred only in the course of at least 4 rinsing cycles, preferably at least 8 rinsing cycles, preferably at least 16 Rinse cycles and in particular at least 24 rinse cycles is reduced to less than 40% by weight of the original content of these cleaning or cleaning aids. Particularly preferred are agents whose content of cleaning or cleaning aids, preferably from the group of enzymes, bleaching agents, cationic or amphoteric polymers, fragrances, disinfectants, silver preservatives or glass corrosion inhibitors, after 4 rinse cycles, preferably 8 rinse cycles, preferably 16 rinse cycles and in particular 24 rinse cycles, still corresponds to at least 10% by weight of the original content of these cleaning or cleaning aids.

Another component of agents according to the invention is the consumption indicator. The consumption indicator is an essentially inorganic matrix which, in the course of use, that is to say with increasing number of wash cycles in the dishwasher, is increasingly dissolved and thus consumed. Consumption indicators according to the invention contain at least 45% by weight of phosphorus pentoxide (P ₂ 0 ₅ ). The proportion by weight of the phosphorus pentoxide makes it possible to control the processability and formability and the “service life”, that is to say the number of rinses until the inorganic matrix is completely dissolved. Such cleaning or cleaning aids according to the invention have proven to be advantageous in which the consumption indicator, based on its total weight, is at least 55% by weight, preferably at least 60% by weight, particularly preferably at least 65% by weight, very particularly preferably contains at least 70 wt .-% and in particular at least 75 wt .-% phosphorus pentoxide.

In addition to the phosphorus pentoxide, the consumption indicator also contains at least 5% by weight of alkali oxide (M ₂ O). The weight fraction of alkali oxide is used in particular to influence the "service life" of the consumption indicator. Cleaning or cleaning aids are preferred in the context of the present application, characterized in that the consumption indicator, based on its total weight, is at least 9% by weight, preferably at least 12% by weight, particularly preferably at least 15% by weight, very particularly preferably contains at least 18% by weight and in particular at least 21% by weight of alkali oxide.

Alkaline oxides from the group of sodium oxide and / or potassium oxide are preferred. Cleaning or cleaning aids are preferred, characterized in that the alkali oxide in the consumption indicator is at least 25% by weight, preferably at least 50% by weight, preferably at least 70% by weight, very particularly preferably at least 80% by weight. -% and in particular at least 90 wt .-% consists of Na ₂ 0.

To optimize the processability and the "service life" of consumption indicators according to the invention, the weight ratio of the phosphorus pentoxide contained in the indicator to the alkali oxide also contained is preferably kept within narrow limits. Cleaning or cleaning aids according to the invention are preferred, characterized in that the weight ratio of phosphorus pentoxide (P ₂ 0 ₂ ) to alkali oxide (M ₂ 0) in the consumption indicator is between 1: 1 and 12: 1, preferably between 3: 2 and 10: 1 , preferably between 2: 1 and 8: 1 and in particular between 5: 2 and 6: 1. Cleaning or cleaning aids and consumption indicators are present separately in the agents according to the invention. It is further preferred that the consumption indicator has no active substances for the cleaning process. In particular, it is preferred that the consumption indicator does not contain any active substances from the group of enzymes, bleaches, water softeners, rinse aids, fragrances, disinfectants, or agents for preventing corrosion of silver or glass.

The processing and shaping of the consumption indicator is preferably carried out by melting and then casting the ingredients contained in the consumption indicator. Consumption indicators according to the invention can be produced, for example, by melting the corresponding amounts of ammonium dihydrogen phosphate and alkali carbonate, preferably sodium or potassium carbonate, before, simultaneously with or after the addition of further ingredients, such as the dyes described below, and pouring them into a casting mold. This processing and shaping process enables the cost-effective production of the consumption indicator in a wide variety of spatial shapes. Cleaning or cleaning aids according to the invention, characterized in that the consumption indicator is a cast body, are particularly preferred.

The agents according to the invention are placed in the interior of a dishwasher, where they remain for the course of several rinsing cycles. The interior of the dishwasher taken up by the agent according to the invention cannot be used to hold dishes. In order to maximize the interior volume of the dishwasher remaining for the dishes to be cleaned, the volume of the agents according to the invention is preferably reduced to a minimum. As the volume of the agents according to the invention decreases, however, the "lifespan" of these products also generally decreases. An embodiment has proven to be technically particularly advantageous in which the volume of the agent according to the invention plus an optionally used metering container is less than 350 ml, preferably less than 250 ml, particularly preferably between 5 and 200 ml and in particular between 10 and 150 ml. The volume proportion of the consumption indicator in the total volume of the agent according to the invention is preferably less than 40% by volume, preferably less than 25% by volume and in particular between 5 and 20% by volume. Agents according to the invention, characterized in that the volume of the consumption indicator is between 0.5 and 35 ml, preferably between 1.0 and 30 ml, preferably between 2.0 and 25 ml, very particularly preferably between 3.0 and 20 ml and in particular between 4.0 and 15 ml is particularly preferred.

Agents according to the invention are preferably placed in the cutlery basket or in the racks for dishes and glasses. Another possibility is to provide the means according to the invention with a holding device, which the attachment of these means in the interior of the Dishwashers, for example on one of the inner walls, the inside of the door or on one of the frames for dishes and glasses. Adhesive, latching, snap, clamping or plug devices are preferred for fastening. The holding device is preferably part of a dosing container for the cleaning or cleaning aid and the consumption indicator.

The agents according to the invention, which comprise at least one of the cleaning or cleaning aids described above and at least one of the consumption indicators described above, are preferably combined with a metering container. Cleaning or cleaning aids according to the invention, characterized in that the cleaning or cleaning aid is present in a dosing container in which the consumption indicator is integrated are particularly preferred. Those agents according to the invention are preferred, for example, in which the cleaning or cleaning aid and the consumption indicator are arranged in spatially separate areas. Preferred embodiments include, for example, dosing containers for cleaning aids or cleaning aids, the housing of the dosing container having a receptacle which is adapted in its shape to the spatial shape of the consumption indicator, in which the consumption indicator with the aid of an adhesive and / or a detent, snap, clamp - or plug fastener is fixed. The receiving trough can be located both inside the metering container, ie on the inside of the housing facing the cleaning or cleaning aid, and outside the metering container, ie on the outside of the housing facing away from the cleaning or cleaning aid.

In order to prevent contact between cleaning or cleaning aids and consumption indicators and to increase the visual perception of the consumption indicator, cleaning or cleaning aids and consumption indicators are preferably separated from one another by spacers. The latch, snap, clamp or plug closure with which the consumption indicator is fixed in the metering container is preferably used as a spacer.

In a preferred embodiment, the previously described colored indicator is also an integral part of the dosing container. All devices are suitable as dosing containers which guarantee a permanent absorption of cleaning or cleaning aids or consumption indicators. In order to ensure optimum access to the rinsing liquor and thus optimal release of the active substances, the cleaning or cleaning aid and the consumption indicator preferably do not completely fill the inside volume of the dosing container. Agents according to the invention are preferred in which the internal volume of the metering container is 98% by volume, preferably 40 to 98% by volume, particularly preferably 60 to 98% by volume and in particular 80 to 98% by volume Cleaning or cleaning aids and / or consumption indicators must be filled out. The dosing container is preferably from one of the above-mentioned water-insoluble polymers. The access of the washing liquor to the cleaning or cleaning aid or to the consumption indicator can be controlled not only by the degree of filling of the dosing container but also by the spatial configuration of the dosing container.

Openings in the housing of the dosing container enable contact between the rinsing liquor and the cleaning or cleaning aid or the consumption indicator. Dosing containers preferred according to the invention have more than one opening in the dosing container. These openings can have the same or different sizes.

In the context of the present application, preference is given in particular to a metering container which has a plurality of openings, characterized in that the receiving space of the essentially rotationally symmetrical container has a crescent-like cross-sectional shape with an outwardly curved front wall and an inwardly curved rear wall. Both the front and the rear wall of the metering container preferably have openings.

The agents according to the invention enable the consumer to easily determine the exhaustion of the cleaning or cleaning aids included. The previously described consumption indicator, which is also used up, serves as an indicator of the degree of wear of the cleaning or cleaning aids. The indicator effect of this consumption indicator can be improved by different preferred embodiments.

In a first preferred embodiment, the consumption indicator is colored. Suitable dyes are, in particular, those substances which do not absorb onto the dishes to be cleaned, that is to say onto glass, ceramic, metal or plastic surfaces, and discolor them. Such dyes are used, for example, as a component of commercial machine dishwashing detergents. In this preferred embodiment, the dye is an integral part of the consumption indicator. When such agents are used, the dye, together with the inorganic backbone of the consumption indicator, dissolves in the course of several rinsing cycles. The agent according to the invention is completely exhausted as soon as the colored consumption indicator is completely dissolved. The basis for this embodiment is the use of dyes which, due to the action of the washing liquor in the interior of the machine, are not removed or washed out of the inorganic basic structure of the consumption indicator. In order to prevent the dyes from dissolving out of the consumption indicator, dyes with low water solubility and water dispersibility are particularly preferred. The pigments are particularly suitable as a dye for the consumption indicator. Pigments are inorganic or organic, colored or achromatic colorants. These pigments are preferably poorly soluble or insoluble in water. The insolubility preferred for the pigments can be achieved by excluding solubilizing groups, by forming insoluble salts ("laking") of carboxylic and in particular sulfonic acids, and by introducing groups which reduce solubility (e.g. carboxamide groups).

Inorganic pigments are naturally occurring pigments, which burnt substances obtained by mechanical treatment such as grinding, slurrying, drying, such as chalk, ocher, umber, green earth, Terra di Siena or graphite.

Synthetic inorganic pigments, in particular white, black, colored and glossy pigments, which are obtained from inorganic raw materials by chemical and / or physical conversion, such as digestion, precipitation, annealing, etc., are, for example, white pigments such as titanium white (titanium dioxide), lead white, zinc white , Lithopone, antimony white; Black pigments such as carbon black (over 90% market share), iron oxide black, manganese black as well as cobalt black and antimony black. Suitable colored pigments are lead chromate, red lead, zinc yellow, zinc green, cadmium red, cobalt blue, Berlin blue, ultramarine, manganese violet, cadmium yellow, Schweinfurt green, molybdate orange and molybdate red, chrome orange and red, iron oxide red, chrome oxide green, strontium yellow and many others. Also suitable are luster pigments with metallic effect pigments and pearlescent pigments, vapor deposition layers, luminescent pigments with fluorescent and phosphorescent pigments.

A distinction can therefore be made between groups in the case of inorganic pigments: metal oxides, hydroxides and oxide hydrates; Mixed phase pigments; Sulfur-containing silicates; Metal sulfides and the like -selenide; complex metal cyanides; Metal sulfates, chromates and molybdates; Mixed pigments (inorganic-organic) and the metals themselves (bronze pigments). Inorganic pigments from the group of the metal salts of iron, copper, titanium, cobalt, zinc, molybdenum and manganese are particularly preferred in the context of the present application.

The coloration of consumption indicators according to the invention by ion coloring is preferred. Sub-group elements, in particular 3d elements, such as e.g. Fe, Co, Ni, Cu, Cr or others. These sub-group elements have easily mobile electrons. Installed in the consumption indicator, this causes resonance absorption of its electron shell and thus coloring when irradiated with white light.

Organic pigments are naturally occurring pigments such as umber, gum, bone charcoal, Kasseler brown, indigo or chlorophyll. Synthetic organic pigments are, for example, azo pigments, indigoids, dioxazine, quinacridone, phthalocyanine, isoindolinone, perylene and perinone, metal complex, alkali blue and recently the diketopyrrolopyrrole (DPP) -P., The extreme light and They have weather fastness and are used a lot in paints as clear, pure orange to red tones.

Alternatively, the consumption indicator according to the invention can also be combined with a water-insoluble, colored indicator, preferably a colored plastic surface. In this embodiment, the consumption indicator is applied to the colored indicator, preferably a colored plastic surface, in such a way that the colored indicator, preferably the colored plastic surface, is at least partially, preferably completely, covered. With increasing exhaustion of the cleaning or cleaning aid and increasing wear and tear of the consumption indicator, the colored indicator becomes increasingly visible to the consumer. The agent according to the invention is completely exhausted as soon as the indicator which is initially covered by the consumption indicator is completely visible. The colored indicator can also be combined with a colorless as well as with a colored consumption indicator described above. In a preferred embodiment, the consumption indicator and the colored indicator have complementary colors. Combinations of red consumption indicator and green indicator or blue consumption indicator and orange indicator are preferred.

The colored indicator is preferably made from a water-insoluble polymer. Particularly suitable as water-insoluble polymers are polymers from the group comprising ethylene / vinyl acetate copolymers, low or high density polyethylene (LDPE, HDPE) or mixtures thereof, polypropylene, polyethylene / polypropylene copolymers, polyether / polyamide block copolymers, styrene / butadiene ( Block) copolymers, styrene / isoprene (block) copolymers, styrene / ethylene / butylene copolymers, acrylonitrile / butadiene / styrene copolymers, acrylonitrile / butadiene copolymers, polyether esters, polyisobutene, polyisoprene, ethylene / ethyl acrylate -Copolymers, polyamides, polycarbonate, polyester, polyacrylonitrile, polymethyl methacrylate, contains polyurethanes.

Another object of the present application is the use of alkali polyphosphates which, based on their total weight, contain at least 45% by weight phosphorus pentoxide (P ₂ 0 ₅ ) and at least 5% by weight alkali oxide (M ₂ 0) to indicate the exhaustion of a for several rinsing cycles in a dishwasher or cleaning agent.

The cleaning or cleaning aids according to the invention contain, as active substance, washing or cleaning-active compounds, in particular washing and cleaning-active compounds from the group of bleaching agents, bleach activators, polymers, builders, surfactants, Enzymes, pH regulators, fragrances, perfume carriers, dyes, foam inhibitors, disinfectants, corrosion inhibitors and glass corrosion inhibitors.

builders

In the context of the present application, the builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x 0 _{2x +} ι 'H ₂ 0, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ θ ₅ 'yH ₂ 0 are preferred.

Amorphous sodium silicates with a module Na ₂ 0: Si0 ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

In the context of the present invention, it is preferred that these silicate (s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, in detergents or cleaning agents in amounts of 10 to 60% by weight, preferably 15 to 50% by weight .-% and in particular from 20 to 40 wt .-%, each based on the weight of the detergent or cleaning agent, are included. If the silicates are used as a component of automatic dishwashing detergents, these detergents preferably contain at least one crystalline layered silicate of the general formula NaMSi _x 0 _{2x +} ι 'y H ₂ 0, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, is preferably from 1.9 to 4 and y is a number from 0 to 33. The crystalline layered silicates of the formula NaMSi _x 0 _{2x +} ι ^' y H ₂ 0 are, for example, from Clariant GmbH

(Germany) sold under the trade name Na-SKS, e.g. Na-SKS-1 (Na ₂ Si22Ö 5-xH2θ, Kenyait), Na-SKS-2 (Na ₂ Si ₁₄ 0 ₂₉ -χH ₂ 0, magadiite), Na- SKS-3 (Na ₂ Sig0 _{1 7} -χH ₂ 0) or Na-SKS-4 (Na ₂ Si ₄ 0 ₉ -χH ₂ 0, makatite).

For the purposes of the present invention, crystalline sheet silicates of the formula (I) in which x is 2 are particularly suitable. Of these, Na-SKS-5 (α- a Si ₂ 0), Na-

SKS-7 (β-Na ₂ Si ₂ 0 ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ 0 ₅ Η ₂ 0), Na-SKS-10 (NaHSi ₂ 0 ₅ '3H ₂ 0, kanemite), Na -SKS-11 (t-Na Si ₂ 0 ₅ ) and Na-SKS-13 (NaHSi O), but especially Na-SKS-6 (δ- Na Si O). 2 2 5 '

If the silicates are used as a component of automatic dishwashing detergents, these detergents contain, in the context of the present application, a proportion _by weight of the crystalline layered silicate of the formula NaMSi _x 0 _{2x +.} ^' y H ₂ 0 from 0.1 to 20 wt .-%, preferably from 0.2 to 15 wt .-% and in particular from 0.4 to 10 wt .-%, each based on the total weight of these agents. It is particularly preferred if such automatic dishwashing detergents have a total silicate content below 7% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably below 4% by weight, very particularly preferably below 3% by weight .-% and in particular below 2.5 wt .-%, with this silicate, based on the total weight of the silicate contained, preferably at least 70 wt .-%, preferably at least 80 wt .-% and in particular at least 90 wt .-% is silicate of the general formula NaMSi _x 0 _{2x +} ι 'y H ₂ 0.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and is represented by the formula nNa ₂ 0 ^• (1-n) K ₂ 0 ^■ Al ₂ 0 ₃ - (2 - 2.5) Si0 ₂ ^■ ( 3.5 - 5.5) H ₂ 0 can be described. The zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. This applies in particular to the use of agents according to the invention as automatic dishwashing agents, which is particularly preferred in the context of the present application. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric acid H ₃ P0 _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance.

Suitable phosphates are, for example, sodium dihydrogen phosphate, NaH ₂ PO ₄ , in the form of the dihydrate (density 1.91, preferably ^"3 , melting point 60 °) or in the form of the monohydrate (density 2.04, preferably ^{" 3} ), the disodium hydrogen phosphate (secondary sodium phosphate) , Na ₂ HP0 ₄ , which is anhydrous or with 2 mol. (Density 2.066 like ^"3 , water loss at 95 °), 7 mol. (Density 1, 68 like ^'3 , melting point 48 ° with loss of 5 H ₂ 0) and 12 mol. Water (density 1, 52 like ^"3 , melting point 35 ° with loss of 5 H ₂ 0) can be used, but especially the trisodium phosphate (tertiary sodium phosphate) Na ₃ P0 ₄ , which as dodecahydrate, as decahydrate (corresponding to 19 -20% P ₂ 0 ₅ ) and in anhydrous form (corresponding to 39-40% P ₂ 0 ₅ ) can be used.

Another preferred phosphate is tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ P0 ₄ . Also preferred are the tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ 0 ₇ , which is given in anhydrous form (density 2.534, preferably ³ , melting point 988 °, also 880 °) and as decahydrate (density 1, 815-1, 836 gladly ^"3 , melting point 94 ° with water loss) exists, as well as the corresponding potassium salt potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ 0 ₇ . Condensation of NaH ₂ P0 or KH ₂ P0 ₄ produces higher mols. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (0) (ONa) -0] _n that crystallizes with 6 H ₂ 0 -Na with n = 3. The corresponding potassium salt, pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (> 23% P ₂ 0 ₅ , 25% K ₂ 0). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can likewise be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaP0 ₃ ) ₃ + 2 KOH - »Na ₃ K ₂ P ₃ O ₁₀ + H ₂ 0

According to the invention, these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

If, in the context of the present application, phosphates are used as washing or cleaning-active substances in washing or cleaning agents, preferred agents contain these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) , in amounts of 5 to 80 wt .-%, preferably from 15 to 75 wt .-% and in particular from 20 to 70 wt .-%, each based on the weight of the detergent or cleaning agent.

It is particularly preferred to use potassium tripolyphosphate and sodium tripolyphosphate in a weight ratio of more than 1: 1, preferably more than 2: 1, preferably more than 5: 1, particularly preferably more than 10: 1 and in particular more than 20: 1. It is particularly preferred to use exclusively potassium tripolyphosphate without admixtures of other phosphates.

Other builders are the alkali carriers. Examples of alkali carriers include alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, the alkali silicates mentioned, alkali metal silicates, and mixtures of the abovementioned substances, the alkali metal carbonates, in particular sodium carbonate, sodium hy- bicarbonate or sodium sesquicarbonate can be used. A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred. A builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred. Because of their low chemical compatibility with the other ingredients of detergents or cleaning agents compared to other builder substances, the alkali metal hydroxides are preferably used only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, particularly preferably below 4 wt .-% and in particular below 2 wt .-%, each based on the total weight of the detergent or cleaning agent used. Agents which contain less than 0.5% by weight and in particular no alkali metal hydroxides, based on their total weight, are particularly preferred.

It is particularly preferred to use carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonate (s), particularly preferably sodium carbonate, in amounts of 2 to 50% by weight, preferably 5 to 40% by weight and in particular from 7.5 to 30% by weight, based in each case on the weight of the detergent or cleaning agent. Agents which, based on the weight of the washing or cleaning agent (ie the total weight of the combination product without packaging) are less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and contain in particular less than 9% by weight of carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably sodium carbonate.

Organic cobuilders include, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Polymeric polycarboxylates are also suitable as builders; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information, for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.

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

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in washing or cleaning agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers , Further preferred copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and are particularly preferred.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders. Ethylenediamine-N, ^{N'-disuccinate} (EDDS) is preferably in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as builders.

surfactants

Surfactants are preferably used as the rinse aid. In addition to the nonionic surfactants described at the beginning, the anionic, cationic and amphoteric surfactants are also included in the group of surfactants.

All nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants in the context of the present application. Alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol are used, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and may contain methyl branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ . ₁ alcohols with 3 EO or 4 EO, Cg-n alcohol with 7 EO, C ₁₃ . ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ . ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ . ₁₄ alcohol with 3 EO and C ₁₂ . ₁₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these Nonionic surfactants can also use fatty alcohols with more than 12 EO. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula, R ¹ I

R-CO-N- [Z] in the RCO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula R ¹ -0-R ² I R-CO-N- [Z] in which R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ² for a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 6 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or Propxylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Low-foaming nonionic surfactants are used as preferred surfactants. The agents according to the invention particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ . ₁ alcohols with 3 EO or 4 EO, Cg-n alcohol with 7 EO, C ₁₃ . ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ . ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ . ₁₄ alcohol with 3 EO and C ₁₂ . ₁₈ - alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. 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 alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO nonionic surfactants, are used with particular preference in the context of the present application.

Agents according to the invention which contain a nonionic surfactant which has a melting point above room temperature are particularly preferred. Accordingly, preferred dishwashing detergents are characterized in that they contain nonionic surfactant (s) with a melting point above 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants which are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature originate from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms, (Cι _Θ - ₂ o--alcohol), a C preferably ₁₈ alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide won. Among these, the so-called "narrow rank ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) which consist of C ₆ . ₂₀ monohydroxyalkanols or C _{_6-20} alkylphenols or Cι. ₆ ₂₀ fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.

The nonionic surfactant, which is solid at room temperature, preferably has additional propylene oxide units in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70 wt .-% of the total molecular weight of such nonionic surfactants. Preferred dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic Make up surfactants.

Further nonionic surfactants with melting points above room temperature which are particularly preferably used contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which contains 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals.

Another preferred agent according to the invention contains nonionic surfactant (s) of the formula

R ¹ 0 [CH ₂ CH (CH ₃ ) 0] _x [CH ₂ CH ₂ 0] _y CH ₂ CH (OH) R ² ,

in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y stands for a value of at least 15.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x> 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15. As described above, each R ³ in the above formula can be different if x> 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which can be joined together in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula can be used

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 represents} H and x assumes values from 6 to 15.

If the latter statements are summarized, dishwashing detergents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

contain, in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ²

in which x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

Low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants within the scope of the present invention. Among these, surfactants with EO-AO-EO-AO blocks are preferred, with one to ten EO or AO groups being bonded to one another before a block follows from the other groups. Here, automatic dishwashing agents according to the invention are preferred which are nonionic surfactant (s) of the general formula

contain, in which R ¹ for a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . _{24 is} alkyl or alkenyl; each group R ² or R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently represent integers from 1 to 6.

The preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula can vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is generally not shown, the linear radicals being of alcohols of native origin with 12 to 18 carbon atoms, for example coconut, palm, tallow or Oleyl alcohol are preferred. Alcohols accessible from synthetic sources are, for example, Guerbet alcohols or residues which are methyl-branched in the 2-position or linear and methyl-branched residues in a mixture, as are usually present in oxo alcohol residues. Regardless of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, preferred dishwasher detergents according to the invention are those in which R ¹ in the above formula for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit. However, other alkylene oxides in which R ² or R ³ are selected independently of one another from - CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are also suitable. Preferred automatic dishwashing agents are characterized in that R ² or R ³ for a radical -CH ₃ , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.

In summary, nonionic surfactants which have a Cg- _15- alkyl radical with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, are particularly preferred for use in the agents according to the invention. These surfactants have the required low viscosity in aqueous solution and can be used with particular preference according to the invention. Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x R ²

in which R ^{1 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{2 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which is preferably between 1 and 5 have hydroxyl groups and are preferably further functionalized with an ether group, R ³ for H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2 -ButyIrest stands, x for values between 1 and 40.

Agents which nonionic surfactant (s) of the general formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x R ²

contain in which R ^{1 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{2 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which are preferably have between 1 and 5 hydroxyl groups and are preferably further functionalized with an ether group, R ³ for H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl 2-butyl and x represents values between 1 and 40 are also particularly preferred.

In particularly preferred nonionic surfactants of the above formula, R ^{3 is} H. In the resulting end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH ₂ 0] _x R ²

those nonionic surfactants are particularly preferred in which R ^{1 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, R ^{2 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and x stands for values between 1 and 40.

In particular, those end group-capped poly (oxyalkylated) nonionic surfactants are preferred which conform to the formula

R ¹ 0 [CH ₂ CH ₂ 0] _x CH ₂ CH (0H) R ² in addition to a radical R ¹ , which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, which is adjacent to a monohydroxylated intermediate group -CH ₂ CH (OH) -. In this formula, x stands for values between 1 and 90.

In the context of the present application, particular preference is given to those agents which contain nonionic surfactant (s) of the general formula

R ¹ 0 [CH ₂ CH ₂ Oj _x CH ₂ CH (OH) R ²

contain which, in addition to a radical R ¹ , which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, a linear or branched, saturated or unsaturated, aliphatic or aromatic Have hydrocarbon radical R ² with 1 to 30 carbon atoms, which is adjacent to a monohydroxylated intermediate group - CH ₂ CH (OH) - and in which x stands for values between 60 and 80.

The corresponding end-capped poly (oxyalkylated) nonionic surfactants of the above formula can be obtained, for example, by reacting a terminal epoxide of the formula R ² CH (0) CH ₂ with an ethoxylated alcohol of the formula R ¹ 0 [CH ₂ CH ₂ 0] _x - ₁ CH ₂ Get CH ₂ OH.

End-capped poly (oxyalkylated) nonionic surfactants of the formula are also particularly preferred

R ¹ 0 [CH ₂ CH ₂ 0] _x [CH ₂ CH (CH ₃ ) 0] _y CH ₂ CH (OH) R ²

in which R ¹ and R ² independently of one another represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} selected independently of one another from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ , but preferably represents -CH ₃ , and x and y independently of one another have values between 1 and 32, nonionic surfactants having values for x from 15 to 32 and y from 0.5 and 1.5 are very particularly preferred.

Agent, characterized in that it is nonionic surfactant (s) of the general formula

R ¹ 0 contains [CH ₂ CH ₂ 0] _x [CH ₂ CHO] _y CH ₂ CH (OH) R ² IR ³ , in which R ¹ and R ² independently of one another represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical with 2 to 26 carbon atoms R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ , but preferably represents -CH ₃ , and x and y independently of one another have values between 1 and 32, nonionic surfactants having values for x from 15 to 32 and y from 0.5 and 1.5 are very particularly preferred.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the above-mentioned nonionic surfactants represent statistical mean values which can be an integer or a fraction for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned usually do not consist of an individual representative, but of mixtures, which can result in mean values and fractional numbers both for the C chain lengths and for the degrees of ethoxylation or alkoxylation.

Of course, the agents according to the invention can contain the aforementioned nonionic surfactants not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants. In this context, surfactant mixtures are not mixtures of nonionic surfactants which in their entirety fall under one of the general formulas mentioned above, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different of the aforementioned general formulas ,

If the agent according to the invention contains two, three, four or more nonionic surfactants, the quantitative ratio of the nonionic surfactants contained in the agent is preferably within narrow limits. If a mixture of two nonionic surfactants (surfactant 1 and surfactant 2) is used, the weight ratio of the nonionic surfactants used to one another (weight ratio of surfactant 1 to surfactant 2) is preferably between 10: 1 and 1:10, preferably between 8: 1 and 1 : 8, particularly preferably between 6: 1 and 1: 6 and in particular between 4: 1 and 1: 4.

If the agent according to the invention contains a surfactant mixture of two, three, four or more surfactants, it is preferred if at least one of the surfactants has a weight fraction above 2.0% by weight, preferably above 3.0% by weight and in particular above 4% by weight. 0% by weight.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C _{_9-13} alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C _12th ₁₈ -monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates, from C ₂ - _.8 alkanes, for example by sulfochlorination or sulfoxidation and subsequent hy- drolysis or neutralization can be obtained. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures, such as those used in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles Glycerin can be obtained. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 mol of ethylene oxide. ₂₁ alcohols, such as 2-methyl-branched

with an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ . ₁₈ fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _a -ι ₈ fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are suitable, 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 the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

If the anionic surfactants are part of machine dishwashing detergents, their content, based on the total weight of the detergents, is preferably less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight. Automatic dishwashing detergents that do not contain anionic surfactants are particularly preferred.

Instead of the surfactants mentioned or in conjunction with them, cationic and / or amphoteric surfactants can also be used.

Cationic compounds of the formulas IX, X or XI, for example, can be used as cationic active substances:

R ¹ R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (IX) (CH ₂ ) _n -TR ²

R ¹ R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -CH-CH ₂ (X) R ¹ TTR ² RR ¹ R ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (XI) R ⁴ wherein each group R ^{1 is} independently selected from C ^ alkyl, alkenyl or

hydroxyalkyl; each group R -.2 is independently selected from C ₈ . ₂₈ alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O- CO- or -CO-O- and n is an integer from 0 to 5. In automatic dishwashing detergents, the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. %. Automatic dishwashing detergents that do not contain cationic or amphoteric surfactants are particularly preferred.

polymers

The group of polymers includes in particular the wash- or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. In general, in addition to nonionic polymers, cationic, anionic and amphoteric polymers can also be used in washing or cleaning agents.

Cationic or amphoteric polymers are used with particular preference.

“Cationic polymers” in the sense of the present invention are polymers which carry a positive charge in the polymer molecule. This can be achieved, for example, by means of (alkyl) ammonium groups or other positively charged groups present in the polymer chain. Particularly preferred cationic polymers come from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives the dialkylaminoacrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

In the context of the present invention, “amphorere polymers” also have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups can be, for example, carboxylic acids, sulfonic acids or phosphonic acids.

Agents, characterized in that they contain a polymer which has monomer units of the formula R ¹ R ² C = CR ³ R ⁴ , in which each radical R ¹ , R ² , R ³ , R ^{4 is} independently selected from hydrogen, derivatized Hydroxy group, C1 to C30 linear or branched alkyl groups, aryl, aryl-substituted C ^ o linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups with at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group with a positive charge in the pH range from 2 to 11, or salts here- of, with the proviso that at least one radical R ¹ , R, R, R is a heteroatomic organic group with at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group with a positive charge particularly preferred in the context of the present application.

Cationic or amphoteric polymers which are particularly preferred in the context of the present application contain a compound of the general formula R ¹ R ² R ⁴ as the monomer unit

H ₂ C = C (CH ₂ ) _x N ⁺ (CH ₂ ) _y C = CH ₂ X ^" R ³ in which R ¹ and R ⁴ independently of one another represent H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ³ independently of one another represent an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl radical is linear or branched and has between 1 and 6 carbon atoms, which is preferably a methyl group; x and y independently of one another are integers between 1 and 3. X represents a counter ion, preferably a counter ion from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylene sulfonate, phosphate, citrate, Formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula (VII) are selected from -CH ₃ , -CH ₂ - CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, - CH ₂ -CH (OH) -CH ₃ , -CH (OH ) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -0) _n H.

In the context of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ¹ and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer units of the formula

H ₂ C = CH (CH ₂ ) N ⁺ (CH ₃ ) ₂ (CH ₂ ) CH = CH ₂ X ^"

are also referred to as DADMAC (diallyldimethylammonium chloride) in the case of X ^" . = chloride.

Further cationic or amphoteric polymers which are particularly preferred in the context of the present application contain a monomer unit of the general formula

R ¹ HC = CR ² C (0) NH (CH ₂ ) _x N ⁺ R ³ R ⁴ R ⁵ X ^"

in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of one another are preferably a linear or branched, saturated or unsaturated alkyl, or hydroxyalkyl radical having 1 to 6 carbon atoms for a linear or branched alkyl radical selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , - CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , - CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -0) _n H and x represents an integer between 1 and 6.

In the context of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ^{1 is} H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula

H ₂ C = C (CH ₃ ) C (0) NH (CH ₂ ) _x N ⁺ (CH) ₃ ) ₃ X ^"

In the case of X ^" . = Chloride are also referred to as MAPTAC (methyacrylamidopropyl trimethylammonium chloride).

Agents preferred according to the invention are characterized in that the polymer contains diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.

The aforementioned amphoteric polymers have not only cationic groups, but also anionic groups or monomer units. Such anionic monomer units come, for example, from the group of the linear or branched, saturated or unsaturated carboxylates, the linear or branched, saturated or unsaturated phosphonates, the linear or branched, saturated or unsaturated sulfates or the linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are acrylic acid, (meth) acrylic acids, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinyl acetic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.

Preferred amphoteric polymers that can be used come from the group of alkyl acrylamide / acrylic acid copolymers, alkyl acrylamide / methacrylic acid copolymers, alkyl acrylamide / methyl methacrylic acid copolymers, alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, and alkyl acrylamide / Methacrylic acid / alkylaminoalkyl (meth) -acrylic acid copolymers, the alkyl acrylamide / methyl methacrylic acid / alkyIaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers as well as the copolymers from unsaturated derivatized carboxylic acids unsaturated carboxylic acids and optionally other ionic or nonionic monomers. Zwitterionic polymers which can be used with preference come from the group of the acrylamidoalkyl trialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.

Also preferred are amphoteric polymers which, in addition to one or more anionic monomers, comprise methacrylamidoalkyl-trialkylammonium chloride and dimethyl (diallyl) ammonium chloride as cationic monomers.

Particularly preferred amphoteric polymers come from the group of methacrylamidoalkyl-trialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, which

MethacryI-amidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl- (meth) acrylic acid copolymers as well as their alkali and ammonium salts.

Particularly preferred are amphoteric polymers from the group of methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the

MethacrylamidopropyltrimethyIammoniumchlorid / DimethyI (diallyl) ammonium chloride / acrylic acid copolymers and the Methacrylamidopropyltrimethylammonium chloride / Dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers and their alkali and ammonium salts.

In a particularly preferred embodiment of the present invention, the polymers contained in the agents according to the invention are in pre-assembled form with a molecular weight of 2000 gmol ^"1 or above

the encapsulation of the polymers by means of water-soluble or water-dispersible coating agents, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;

the encapsulation of the polymers by means of water-insoluble, meltable coating agents, preferably by means of water-insoluble coating agents from the group of waxes or paraffins with a melting point above 30 ° C .;

the cogranulation of the polymers with inert carrier materials, preferably with carrier materials from the group of active washing or cleaning substances, particularly preferably from the group of builders (builders) or cobuilders.

Polymers effective as softeners are, for example, the polymers containing sulfonic acid groups, which are used with particular preference. Copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers can be used with particular preference as polymers containing sulphonic acid groups.

In the context of the present invention, unsaturated carboxylic acids of the formula X are preferred as the monomer

R ¹ (R ² ) C = C (R ³ ) COOH

in which R ¹ to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids that can be described by formula XII are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H; R ³ = CH ₃ ) and / or maleic acid (R = COOH; R ² = R ³ = H) preferred.

The monomers containing sulfonic acid groups are of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H

preferably in which R ⁵ to R ⁷ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is optional available spacer group is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas H ₂ C = CH-X-S0 ₃ HH ₂ C = C (CH ₃ ) -X-S0 ₃ H H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X -S0 ₃ H

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which selected is from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) -NH- CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, vinyl sulfonic acid, 3 -Sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide (X = - C (0) NH- in formula Xlllb), sulfomethyl methacrylamide and water-soluble salts of the acids mentioned.

Other suitable ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. The group iii) monomer content of the polymers used according to the invention is preferably less than 20% by weight, based on the polymer. Polymers to be used with particular preference consist only of monomers of groups i) and ii).

In summary, copolymers of i) unsaturated carboxylic acids of the formula

R ¹ (R ² ) C = C (R ³ ) C00H in which R ¹ to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, one or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical with 1 to 12 carbon atoms,

ii) sulfonic acid group-containing monomers of the formula R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H in which R ⁵ to R ⁷ independently of one another for -H -CH ₃ , a straight-chain or branched saturated alkyl radical 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH ₂ , -OH or -COOH as defined above or for -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X for an optionally present Spacer group, which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) -NH-CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers

particularly preferred.

Other particularly preferred copolymers consist of

i) one or more unsaturated carboxylic acids from the group consisting of acrylic acid,

Methacrylic acid and / or maleic acid

ii) one or more monomers containing sulfonic acid groups of the formulas: H ₂ C = CH-X-S0 ₃ HH ₂ C = C (CH ₃ ) -X-S0 ₃ H H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H

in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and - C (0) -NH- CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers.

The copolymers can contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii). Particularly preferred polymers have certain structural units, which are described below.

For example, copolymers which have structural units of the formula are preferred

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p -

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms. men, where spacer groups in which Y for -0- (CH ₂ ) _π - with n = 0 to 4, for -0- (C ₆ H) -, for -NH- C (CH ₃ ) ₂ - or -NH -CH (CH ₂ CH ₃ ) - is preferred.

These polymers are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which is also preferred. The corresponding copolymers contain the structural units of the formula

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p -

in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, with spacer groups in which Y is -0 - (CH ₂ ) _n - with n = 0 to 4, represents -0- (C ₆ H ₄ ) -, represents -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , are preferred.

Completely analogously, acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. So are copolymers, which structural units of the formula

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p -

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H) -, for -NH- C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, just like copolymers, of the structural units of the formula

- [CH ₂ -C (CH ₃ ) COOH] _rn - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p -

in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, with spacer groups in which Y is -0 - (CH ₂ ) _n - with n = 0 to 4, represents -0- (C ₆ H) -, represents -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) -.

Instead of or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly preferred monomer from group i). In this way, copolymers preferred according to the invention are obtained, the structural units of the formula - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p -

contain, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₅ H ₄ ) -, for -NH- C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred and to copolymers preferred according to the invention, the structural units of the formula

- [HOOCCH-CHCOOH] n - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p -

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH- C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands.

The sulfonic acid groups in the polymers may be wholly or partly in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

The monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight of monomer, in the case of copolymers which contain only monomers from groups i) and ii) from group i) and 10 to 50% by weight of monomer from group ii), in each case based on the polymer.

In the case of terpolymers, those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred ,

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred detergent or cleaning agent compositions are characterized in that the copolymers have molecular weights of 2,000 to 200,000 gmol ^"1 , preferably 4,000 to 25,000 gmol ^{" 1} and in particular 5,000 to 15,000 gmol ^"1 . bleach

A first essential component of the solid machine dishwashing detergent according to the invention is the bleach. Of the compounds which serve as bleaching agents and which supply H ₂ 0 ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further usable bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ 0 ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoxythoxy acid peroxoxy acid, (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperocyseboxyacidoxyacid, Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents in the dispersions according to the invention. Suitable chlorine or bromine-releasing materials include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Bleach activators

Bleach activators are used in detergents or cleaning agents, for example, to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C and below. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylene diamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1, 5-diacetyl-2,4-dioxohexahydro-1, 3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N -Nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso- NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetiacetate and 2,5-2,5-diacetate dihydrofuran.

Further bleach activators which are preferably used in the context of the present application are compounds from the group of the cationic nitriles, in particular cationic nitriles of the formula R ¹

R ² -N ⁽⁺⁾ - (CH ₂ ) -CN X ^H ,

R ³

in R ¹ for -H, -CH ₃ , a C ₂ . ₂₄ alkyl or alkenyl radical, a substituted C ₂ - ₂₄ alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a C-ι- ₂₄ alkyl group, or a substituted alkyl or alkenylaryl radical with a C - ^ - alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, - CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ - CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -0) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion.

A cationic nitrile of the formula R ⁴ is particularly preferred

R ⁵ -N ⁽⁺⁾ - (CH ₂ ) -CN X ^H ,

R ⁶

in which R ⁴ , R ⁵ and R ⁶ are selected independently of one another from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , where R ⁴ additionally can also be -H and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ( CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{" are} particularly preferred, the cationic in turn from the group of these substances Nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , in which X ^{" represents} an anion selected from the group consisting of chloride, bromide and iodide, Hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate is selected, is particularly preferred.

As bleach activators it is also possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, especially triacetate, especially triacetate 5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholine-acetonitrile-methyl sulfate (MMA) as well as acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetacetylxylose and as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam , Hydrophilically substituted acylacetals and acyllactams are also preferably used. Combinations of conventional bleach activators can also be used.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be used. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

If further bleach activators are to be used in addition to the nitrile quats, bleach activators from the group of polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyloxy- or isononosulfonates, are preferred. n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-%, each based on the total weight of the bleach activator-containing agents used. Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin ) Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of the manganese sulfate are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular of 0 , 0025 wt .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total weight of the bleach activator-containing agents. But in special cases, more bleach activator can be used.

Glass corrosion inhibitors

Glass corrosion inhibitors prevent the appearance of cloudiness, streaks and scratches but also the iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and / or zinc salts and / or magnesium and / or zinc complexes.

A preferred class of compounds that can be used to prevent glass corrosion are insoluble zinc salts.

Insoluble zinc salts in the sense of this preferred embodiment are zinc salts which have a solubility of at most 10 grams of zinc salt per liter of water at 20 ° C. Examples of insoluble zinc salts which are particularly preferred according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn ₂ (OH) ₂ C0 ₃ ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn ₃ (P0 ₄ ) ₂ ), and zinc pyrophosphate (Zn ₂ (P ₂ 0 ₇ )).

The zinc compounds mentioned are preferably used in amounts which have a zinc ion content of between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and in particular between 0.2 and 1.0 % By weight, based in each case on the total agent containing glass corrosion inhibitor. The exact content of the zinc salt or zinc salts in the detergents naturally depends on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration in the detergents should be.

Since the insoluble zinc salts remain largely unchanged during the dishwashing process, the particle size of the salts is a criterion to be observed so that the salts do not adhere to glassware or machine parts. Means are preferred in which the insoluble zinc salts have a particle size below 1.7 millimeters.

If the maximum particle size of the insoluble zinc salts is below 1.7 mm, there is no fear of insoluble residues in the dishwasher. The insoluble zinc salt preferably has an average particle size which is clearly below this value in order to to further minimize insoluble residues, for example an average particle size of less than 250 μm. This, in turn, is all the more the less the zinc salt is soluble. In addition, the glass corrosion inhibiting effectiveness increases with decreasing particle size. In the case of very poorly soluble zinc salts, the average particle size is preferably below 100 μm. For even more poorly soluble salts it can be even lower; For example, average particle sizes below 100 μm are preferred for the very poorly soluble zinc oxide.

Another preferred class of compounds are magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid. These have the effect that even with repeated use the surfaces of glassware do not change corrosively, in particular no clouding, streaks or scratches but also no iridescence of the glass surfaces.

Although all magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids can be used, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the groups of the unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred.

The spectrum of the zinc salts of organic acids, preferably organic carboxylic acids preferred according to the invention, extends from salts which are sparingly or not soluble in water, ie have a solubility below 100 mg / L, preferably below 10 mg / L, in particular no solubility, up to such Salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, particularly preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

It is particularly preferred to use at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate, as the glass corrosion inhibitor. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

In the context of the present invention, the zinc salt content of cleaning agents is preferably between 0.1 to 5% by weight, preferably between 0.2 to 4% by weight and in particular between 0.4 to 3% by weight, or the content of zinc in oxidized form (calculated as Zn ²⁺ ) between 0.01 to 1% by weight, preferably between 0.02 to 0.5% by weight and in particular between 0.04 to 0.2% by weight, based in each case on the total weight of the agent containing glass corrosion inhibitor.

corrosion inhibitors

Corrosion inhibitors serve to protect the items to be washed or the machine, silver protection agents in particular being particularly important in the area of automatic dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bis-benzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. The following may be mentioned as examples of the 3-amino-5-alkyl-1, 2,4-triazoles which are preferably to be used according to the invention: 5, -propyl, butyl, pentyl, heptyl, octyl, nonyl -, - Decyl-, -Undecyl-, -Dodecyl-, -Isononyl-, -Versatic-10-acid alkyl-, -Phenyl-, -p-Tolyl-, - (4-tert. Butylphenyl) -, - (4- Methoxyphenyl) -, - (2-, -3-, -4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-furyl) -, - (5- oxo-2-pyrrolidinyl) -, -3-amino-1, 2,4-triazole. In dishwashing detergents, the alkylamino-1, 2,4-triazoles or their physiologically tolerable salts are used in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04 wt .-% used. Preferred acids for the salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulfurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid. 5-Pentyl-, 5-heptyl-, 5-nonyl-, 5-undecyl-, 5-isononyl-, 5-Versatic-10-acid-alkyl-3-amino-1, 2,4-triazoles and mixtures are particularly effective of these substances.

In addition, detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, chloroglucin, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

Instead of or in addition to the silver protective agents described above, for example the benzotriazoles, redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, Contains zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, the metals preferably being in one of the oxidation states II, III, IV, V or VI.

The metal salts or metal complexes used are said to be at least partially soluble in water. The counterions suitable for salt formation include all customary one, two or three times negatively charged inorganic anions, e.g. B. oxide, sulfate, nitrate, fluoride, but also organic anions such. B. stearate.

Metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and, if appropriate, additionally one or more of the abovementioned. Anions exist. The central atom is one of the above Metals in one of the above Oxidation states. The ligands are neutral molecules or anions that are monodentate or multidentate; the term "ligand" in the sense of the invention is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507" explained in more detail. If the charge of the central atom and the charge of the ligand (s) do not add up to zero in a metal complex, then depending on whether there is a cationic or an anionic excess, either one or more of the abovementioned. Anions or one or more cations, e.g. B. sodium, potassium, ammonium ions for charge balance. Suitable complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1, 1-diphosphonate.

The common definition in chemistry for "oxidation level" is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1991, page 3168" reproduced.

Particularly preferred metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V ₂ 0 ₅ , V ₂ 0 ₄ , V0 ₂ , TiOS0 ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoS0 ₄ , Co (N0 ₃ ) ₂ , Ce (N0 ₃ ) ₃ and mixtures thereof ., so that preferred automatic dishwashing agents according to the invention are characterized in that the metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn ( ll) - [1-hydroxyethane-1, 1-diphosphonate], V ₂ 0 ₅ , V ₂ 0 ₄ , V0 ₂ , TiOSOψ K ₂ TiF ₆ , K ₂ ZrF ₆ , CoS0 ₄ , Co (N0 ₃ ) ₂ , Ce (N0 ₃ ) ₃ .

These metal salts or metal complexes are generally commercially available substances which can be used in the agents according to the invention for the purpose of protecting against silver corrosion without prior cleaning. For example, that's from S0 ₃ production

(Contact method) known mixture of pentavalent and tetravalent vanadium (V ₂ 0 ₅ , V0 ₂ , V ₂ 0 ₄ ) is suitable, as is the titanyl sulfate formed by diluting a Ti (S0) ₂ solution,

TiOS0 ₄ . The inorganic redox-active substances, in particular metal salts or metal complexes, are preferably coated, ie completely coated with a waterproof material which is easily soluble at the cleaning temperatures in order to prevent their premature decomposition or oxidation during storage. Preferred coating materials which are applied by known processes, for example melt coating processes according to Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher-melting alcohols such as hexadecanol, soaps or fatty acids. The coating material, which is solid at room temperature, is applied in a molten state to the material to be coated, for example by spinning finely divided material to be coated in a continuous stream through a spray zone of the molten coating material which is also continuously generated. The melting point must be selected so that the coating material easily dissolves or melts quickly during the silver treatment. The melting point should ideally be in the range between 45 ° C and 65 ° C and preferably in the range 50 ° C to 60 ° C.

The metal salts and / or metal complexes mentioned are contained in cleaning agents, preferably in an amount of 0.05 to 6% by weight, preferably 0.2 to 2.5% by weight, in each case based on the total agent containing corrosion inhibitor.

enzymes

Enzymes can be used to increase the washing or cleaning performance of washing or cleaning agents. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are accordingly preferred. Agents according to the invention preferably contain enzymes in total amounts of 1 x 10 ^"6 to 5 percent by weight based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline proteins from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are under the trade names Esperase ^®, or Savinase ^® from Novozymes distributed. The variants listed under the name BLAP ^{® are} derived from the protease from Bacillus lentus DSM 5483.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, which is sold under the trade name Protosol ^® by Advanced Biochemicals Ltd., Thane, India, which is sold under the trade name Wuxi ^® by Wuxi Snyder Bioproducts Ltd., China, and in the trade name Proleather ^® and Protease P ^® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermophilus and their further developments which are improved for use in detergents and cleaning agents. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α- amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and derived variants from the α- amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes.

Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae. Another commercial product is the Amylase-LT ^® .

Lipases or cutinases can furthermore be used according to the invention, in particular because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or developed further, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^® , Lipolase ^® Ultra, LipoPrime ^® , Lipozyme ^® and Lipex ^® . Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Lipases that can also be used are from the company Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. Lipase ^® , Lipase AP ^® , Lipase M-AP ^® and Lipase AML ^® available. For example, the Genencor company can use the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products, the preparations originally sold by Gist-Brocades M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention, also the product Lumafast ^® from Genencor.

Furthermore, enzymes can be used, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and ß-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 L from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, USA , The .beta.-glucanase obtained from B. subtilis is available under the name Cereflo ^® from Novozymes.

To increase the bleaching effect, oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention , Suitable commercial products are Denilite ^® 1 and 2 from Novozymes. Advantageously, organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of greatly different redox potentials between the oxidizing enzymes and the soiling.

The enzymes originate, for example, either originally from microorganisms, for example of the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological processes known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.

The enzymes in question are preferably purified by methods which are established per se, for example by means of precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps. The enzymes can be used in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the enzyme is enclosed in a solidified gel are or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers. Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.

Furthermore, it is possible to assemble two or more enzymes together, so that a single granulate has several enzyme activities.

A protein and / or enzyme can be protected against damage, such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage, especially during storage. When the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Agents according to the invention can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.

A group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used, including above all derivatives with aromatic groups, for example ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters. Ovomucoid and leupeptin may be mentioned as peptide protease inhibitors; an additional option is the formation of fusion proteins from proteases and peptide inhibitors.

Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and their mixtures, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End group capped fatty acid amide alkoxylates are suitable. Certain organic acids used as builders can additionally stabilize an enzyme contained.

Lower aliphatic alcohols, but above all polyols, such as, for example, glycerol, ethylene glycol, propylene glycol or sorbitol are further frequently used enzyme stabilizers. Calcium salts are also used, such as calcium acetate or calcium formate, and magnesium salts.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, among other things, against physical influences or pH fluctuations. Polymers containing polyamine-N-oxide act as enzyme stabilizers. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkyl polyglycosides can stabilize the enzymatic components of the agent according to the invention and even increase their performance. Crosslinked N-containing compounds also act as enzyme stabilizers.

ctionants and antioxidants increase the stability of the enzymes against oxidative decay. A sulfur-containing reducing agent is, for example, sodium sulfite.

Combinations of stabilizers are preferably used, for example made of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The effect of peptide-aldehyde stabilizers is increased by the combination with boric acid and / or boric acid derivatives and polyols and is further enhanced by the additional use of divalent cations, such as calcium ions.

One or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, are preferred in amounts of 0.1 to 5% by weight, preferably of 0.2 to 4.5 and in particular of 0, 4 to 4 wt .-%, each based on the total enzyme-containing agent used.

fragrances

Individual perfume compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexyl propylate propylate stylatepylateyl styrene. The ethers include, for example, benzyl ethyl ether Aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetal dehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, for the ketones, for example the jonones, α-isomethylionone and methylcedryl ketone, for the alcohols anethole, citronellol , Geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be processed directly, but it can also be advantageous to apply the fragrances to carriers which ensure a long-lasting fragrance due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

dyes

Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the agents and to light, and no pronounced substantivity to the substrates to be treated with the dye-containing agents, such as glass, ceramics or plastic tableware, to say nothing of them to stain.

disinfectant

To combat microorganisms, the agents according to the invention can contain antimicrobial active ingredients. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkoniumchlor.de, alkylarlylsulfonates, halogenophenols and phenolmercuriacetate, these compounds also being dispensed with entirely in the inventive agents can.

Claims

claims:

1.Measured quantity of a cleaning or cleaning aid which is introduced into the interior of a dishwasher and is only completely used up there in the course of several cleaning processes, comprising a consumption indicator which indicates to the user the exhaustion of the cleaning or cleaning aid and comprises an alkali polyphosphate which based on the total weight of the consumption indicator contains at least 45% by weight phosphorus pentoxide (P ₂ 0 ₅ ) and at least 5% by weight alkali oxide (M ₂ 0).

2. Cleaning or cleaning aid according to claim 1, characterized in that the consumption indicator, based on its total weight, at least 55% by weight, preferably at least 60% by weight, particularly preferably at least 65% by weight, very particularly preferably at least Contains 70 wt .-% and in particular at least 75 wt .-% phosphorus pentoxide.

3. Cleaning or cleaning aid according to one of claims 1 or 2, characterized in that the consumption indicator, based on its total weight, at least 17% by weight, preferably at least 19% by weight, particularly preferably at least 21% by weight, very particularly preferably contains at least 23% by weight and in particular at least 25% by weight of alkali oxide.

4. Cleaning or cleaning aid according to one of claims 1 to 3, characterized in that the alkali oxide in the consumption indicator to at least 25 wt .-%, preferably at least 50 wt .-%, preferably at least 70 wt .-%, completely particularly preferably consists of at least 80% by weight and in particular at least 90% by weight of Na ₂ 0.

5. Cleaning or cleaning aid according to one of claims 1 to 4, characterized in that the weight ratio of phosphorus pentoxide (P ₂ 0 ₂ ) to alkali oxide (M ₂ 0) in the consumption indicator between 1: 1 and 12: 1, preferably between 3 : 2 and 10: 1, preferably between 2: 1 and 8: 1 and in particular between 5: 2 and 6: 1.

6. Cleaning or cleaning aid according to one of claims 1 to 5, characterized in that the consumption indicator has no active substances for the cleaning process.

7. Cleaning or cleaning aid according to one of claims 1 to 6, characterized in that the consumption indicator is colored.

8. Cleaning or cleaning aid according to one of claims 1 to 7, characterized in that the consumption indicator is a cast body.

9. Cleaning or cleaning aid according to one of claims 1 to 8, characterized in that the volume of the consumption indicator between 0.5 and 35 ml, preferably between 1, 0 and 30 ml, preferably between 2.0 and 25 ml, very particularly is preferably between 3.0 and 20 ml and in particular between 4.0 and 15 ml.

10. Cleaning or cleaning aid according to one of claims 1 to 9, characterized in that the cleaning or cleaning aid is a glass corrosion inhibitor and / or a silver protective agent and / or a fragrance and / or a disinfectant and / or is a rinse aid and / or a water softener and / or an enzyme and / or a bleach.

11. Cleaning or cleaning aid according to one of claims 1 to 10, characterized in that the cleaning or cleaning aid is present in a dosing container in which the consumption indicator is integrated.

12. Use of alkali polyphosphotes which, based on their total weight, contain at least 45% by weight phosphorus pentoxide (P ₂ 0 ₅ ) and at least 5% by weight alkali oxide (M ₂ 0) to indicate the exhaustion of one for several rinses in a dishwasher brought cleaning or cleaning aids.