EP1660623A1

EP1660623A1 - Washing or cleaning agents

Info

Publication number: EP1660623A1
Application number: EP04764486A
Authority: EP
Inventors: Thomas Holderbaum; Maren Jekel; Alexander Lambotte
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2003-09-04
Filing date: 2004-08-26
Publication date: 2006-05-31
Anticipated expiration: 2024-08-26
Also published as: US20060223738A1; DE10340683A1; EP1660623B1; WO2005023974A1; PL1660623T3

Abstract

The invention relates to combination products consisting of at least one washing or cleaning agent shaped body and of at least one liquid-filled hollow body, which is an injection molded and/or blow-molded and/or deep-drawn part, and which is, at least proportionately, comprised of one or more water-soluble or water-dispersible polymers. The combination product is characterized in that the liquid-filled hollow body/bodies is/are joined to the washing or cleaning agent shaped body and makes it possible to prepare combined solid/liquid products with a minimized packaging effort. Combination products of this type are characterized by having an improved stability during production, storage and transport.

Description

"Detergents or cleaning agents'

The present invention relates to detergents or cleaning agents, in particular detergent or cleaning agent combination products, which in addition to one or more solid constituents also comprises liquids.

Detergents and cleaning agents and processes for their preparation are well known and are therefore widely described in the prior art. They are usually made available to the consumer in the form of spray-dried or granulated powder products or as liquid goods. Following the consumer's desire for simple dosing, in addition to these two classic variants, products in pre-portioned form have become established on the market and are also described comprehensively in the prior art, in particular pressed molded articles, i.e. tablets, blocks, briquettes and the like, as well as packaged in bags Portions of solid or liquid detergents and cleaning agents are described.

In the case of the single-dose quantities of detergents and cleaning agents that come onto the market packaged in bags, bags made of water-soluble film have again become established, making the tearing of the packaging by the consumer unnecessary. In this way, convenient dosing of a single portion is possible by inserting the bag directly into the washing machine or dishwasher or into its washing-up chamber, or by throwing it into a predetermined amount of water, for example in a bucket or in the hand wash or sink. Detergents and cleaning agents packed in bags made of water-soluble film are therefore described in large numbers in the prior art.

For example, German patent application DE 11 30 547 (Procter & Gamble) discloses packages made of water-soluble polyvinyl alcohol films which are filled with non-liquid synthetic detergents. This document does not comment on the particle sizes of the packaged detergents.

A single dose of a washing or bleaching agent in a bag, which has one or more seams made of water-sensitive material, is described in European patent application EP 143 476 (Akzo N.V.). In this publication, a mixture of anionic and / or nonionic water-binding polymer and cationic polymer adhesive material is proposed as the water-sensitive suture material.

Solid, in particular compressed washing or cleaning agents, are often characterized by a delayed release of their ingredients as a result of the pressing. This disadvantageous property is contrasted by the high density and thus low dosage volume of this form of offer as well as its high active ingredient content. Liquid detergents or cleaning agents, on the other hand, dissolve comparatively quickly, but as a rule they cannot be assembled without the addition of solvents without washing or cleaning activity. A goal of the development of modern detergents or cleaning agents is therefore the provision of supply forms which combine the advantages of solid detergents or cleaning agents with those of the liquid forms of supply.

For example, international application WO 02/42401 (Procter & Gamble) discloses bag packaging with at least two receiving chambers, one chamber of which contains a solid and the other chamber contains an anhydrous gel.

EP 1319706 (Unilever), on the other hand, describes a bag made of water-soluble polymer film with liquid filling, in which there is at least one solid body, the rate of dissolution of the solid body in the liquid filling being greater than the speed of dissolution of the water-soluble polymer film in the liquid filling at storage temperature.

All such combination products are characterized by a high proportion of packaging and high manufacturing costs. Furthermore, detergents or cleaning agents provided with water-soluble or water-dispersible packaging generally require a special form of packaging or additional outer packaging in order to avoid damage during production, storage or transport.

International application WO 00/55068 (Unilever) describes special "dome-shaped" thermoformed bags for packaging liquid detergents or cleaning agents.

WO 03/55767 (Reckitt Benckiser) finally discloses water-soluble containers which are formed from a water-soluble laminate which comprises an extruded and a cast film.

The object of the present application was therefore to provide a washing or cleaning agent combination product which enables the separate packaging of solid and liquid constituents with minimal packaging expenditure. The solid and liquid components of the detergent or cleaning agent should be made up as separate components of a compact and easily metered body.

A first subject of the present application is therefore a combination product of at least one shaped detergent or cleaning agent and at least one liquid-filled hollow body, which is an injection molding and / or blow molding and / or deep-drawn part and which at least partially consists of one or more water-soluble or water-dispersible polymers . characterized in that the liquid-filled hollow body (s) is / are connected to the washing or cleaning agent shaped body.

In a preferred embodiment of the present application, the connection of the liquid-filled hollow body (s) to the detergent or cleaning product shaped body takes place by means of a plug and / or snap and / or latching and / or adhesive connection.

combination product

The dimensions of preferred combination products according to the invention ensure safe dosing in commercially available dosing devices for washing machines or dishwashers. Characteristic of the spatial shape of combination products according to the invention are their width, height and depth. Combination products are preferred whose dimensions in none of the three spatial directions is more than 45 mm, preferably more than 42 mm, particularly preferably more than 39 mm. If the largest dimension of the combination product is defined as its width, the shortest dimension of the combination product as its height, the preferred ratio of width to height of combination products according to the invention is between 4: 1 and 1.1: 1, preferably between 3: 1 and 1.2 : 1, very particularly preferably between 2.8 and 1.4: 1 and in particular between 2.5: 1 and 1.8: 1.

In order to ensure dosing in different machines, the maximum volume of the combination products in a preferred embodiment of the present invention is less than 30 ml. Particularly preferred are embodiments in which the volume of the combination product is less than 26 ml, particularly preferably less than 22 ml, very particularly preferably less than 18 ml and in particular less than 16 ml. In the context of the present application, preference is given to combination products in which the volume ratio of detergent tablets (s) to the liquid-filled (m / n) hollow body (s) is between 8: 1 and 1: 8, preferably between 5: 1 and 1: 5, particularly is preferably between 3: 1 and 1: 3. The liquid-filled hollow body preferably takes up the smaller volume in comparison to the detergent or cleaning product tablet. In this way, i.a. minimize the expenditure for the packaging of the hollow body and thus also the manufacturing costs of the combination product according to the invention. Combination products in which the volume ratio of detergent or cleaning product shaped body (s) to liquid-filled (m / n) hollow body (s) 8: 1 to 1: 1, preferably 5: 1 to 1.5, are therefore particularly preferred in the context of the present application : 1 and in particular 4: 1 to 2: 1. The internal volume of hollow bodies which are particularly preferred according to the invention is less than 6 ml, preferably less than 4 ml, particularly preferably between 0.5 and 3 ml and in particular between 1 and 2 ml.

Combination products according to the invention are particularly suitable for assembling detergent or cleaning agent portions with a total weight below 35 g. Are particularly preferred the combination products with a total weight below 30 g, preferably below 27 g, particularly preferably below 25 and in particular below 23 g. The weight ratio of detergent tablets to liquid-filled hollow bodies in preferred combination products according to the invention is 11: 1 to 1:11, preferably 5: 1 to 1: 5 and in particular 3: 1 to 1: 3 is.

The weight of combination products according to the invention is preferably between 10 and 50 g, preferably between 12 and 40 g, particularly preferably between 14 and 30 g and in particular between 16 and 25 g.

In the combination products preferred according to the invention, the detergent tablets are connected by plug-in and / or snap-in and / or latching and / or adhesive connection, but preferably by gluing.

In addition to other substances, polymers or polymerizing substance mixtures are particularly suitable for bonding combination products according to the invention. The choice of adhesive or glue is among others determined by the size of the adhesive surface, the weight and the shape of the components bonded to one another, but in particular also by the chemical composition of the detergent tablet.

Detergent tablets which contain sodium percarbonate as bleaching agents have a reduced stability and durability of the bonds compared to tablets with another bleaching agent (e.g. sodium perborate etc.). A further object of the present application was therefore to provide combination products containing sodium percarbonate according to the invention which have permanent adhesion between the detergent or cleaning product shaped body and the liquid-filled hollow body. It has now been found that this problem can be solved in addition to the use of larger amounts of adhesive by changing the surfactant content of the detergent tablets containing sodium percarbonate.

Another object of the present application is therefore a combination product according to the invention consisting of at least one shaped detergent or cleaning agent containing sodium percarbonate and at least one liquid-filled hollow body which is an injection molding and / or blow molding and / or deep-drawn part and which at least partially consists of one or more water-soluble or water-dispersible polymers , wherein the liquid-filled hollow body (s) is / are connected to the detergent tablet by an adhesive connection, characterized in that the sodium percarbonate-containing detergent tablet does not contain any anionic surfactants and / or cationic surfactants and / or nonionic surfactants and / or amphoteric surfactants. It is of course not always possible to completely dispense with surfactants in the formulations for the detergent tablets. In particular, the washing or cleaning performance of the combination products according to the invention is impaired by a reduction in the surfactant content. In the context of the present application, preference is therefore given in particular to those detergent tablets as a constituent of combination products according to the invention, in which the detergent tablet, in addition to a sodium percarbonate content, has a surfactant content, preferably a nonionic surfactant content, below 7% by weight, preferably between 0 , 1 and 6% by weight, preferably between 0.2 and 5% by weight, particularly preferably between 0.4 and 4% by weight and in particular between 0.6 and 3% by weight. Particularly preferred detergent tablets have a surfactant content below 2% by weight. Such detergent tablets with a low nonionic surfactant content have permanent and stable bonds when bonded to liquid-filled hollow bodies using conventional adhesives. In the context of the present application, preference is therefore given to those combination products in which the liquid-filled hollow body has at least 40% by weight, preferably at least 60% by weight, particularly preferably at least 80% by weight and in particular at least 90% by weight of the in the Combination product contains surfactants, wherein it is also very particularly preferred that the liquid filling of the hollow body to at least 30 wt .-%, preferably at least 50 wt .-%, particularly preferably at least 70 wt .-%, very particularly preferably at least 90 wt .-% and in particular at least 95 wt .-% of surfactants, preferably nonionic surfactants.

In general, the use of combination products according to the invention offers the possibility of separating incompatible constituents or the targeted individual packaging of certain active substances. Those embodiments of the combination products according to the invention in which the proportion by weight of at least one of the active substance contained in the combination product in the liquid-filled hollow body is greater than in the detergent tablets are preferred. In the context of the present application, preference is given to those combination products in which the detergent tablet or the liquid-filled hollow body is at least 60% by weight, preferably at least 70% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight. % and in particular at least 95% by weight of the bleaching agents and / or bleach activators and / or silver protection agents and / or corrosion protection agents and / or polymers and / or enzymes contained in the combination product.

Embodiments according to the invention are particularly preferred in which the liquid-filled hollow body has at least 80% by weight, preferably at least 90% by weight and in particular the total amount of the enzymes and / or polymers contained in the combination product, but especially the enzymes. Embodiments are further preferred in which at least a partial separation of the silver protection agent (s) contained from the bleaching agent (s) and / or the bleaching activator (s) is realized. For example, combination products can be produced which contain at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 90% by weight, very particularly preferably at least 95% by weight, and in particular the total amount of, in the liquid-filled hollow body have silver protection agents contained in the combination products, while the liquid-filled hollow body is at the same time essentially free of bleaching agents and / or bleach activators.

In addition to the detergent tablet or detergent tablets and the liquid-filled hollow bodies), the combination product according to the invention can comprise further constituents, preferably from the group of gelatin capsules and / or the coated tablets.

Another object of the present application is a process for the production of combination products from at least one detergent or cleaning product body and at least one liquid-filled hollow body, characterized by the steps a) production of washing or cleaning product bodies; b) production of liquid-filled hollow bodies by injection molding and / or blow molding and / or deep drawing; c) Connection of at least one product from step a) with at least one product from step b).

In a preferred embodiment of the method according to the invention, the detergent tablet is connected to the liquid-filled hollow body in step c) by a plug-in and / or snap-in and / or latching and / or adhesive connection, preferably by gluing.

The combination product according to the invention comprises detergent tablets as well as at least one liquid-filled hollow body. Both components will be described in more detail below.

Detergent tablets

The detergent tablets can be any solid and dimensionally stable confection form known to the person skilled in the art for active washing or cleaning agents. Detergent or cleaning agent tablets, washing or cleaning agent casting bodies, but also extruded or extruded washing or cleaning agent bodies can be used, for example.

In a preferred embodiment of the present application, the detergent tablet is one or more single-phase or multiphase detergent tablets. Detergent or cleaning agent tablets of this type are produced in a manner known to the person skilled in the art by pressing particulate starting substances. To produce the tablets, the premix is compacted in a so-called die between two punches to form a solid compressed product. This process, which is briefly referred to below as tableting, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, the filling quantity and thus the weight and the shape of the resulting tablet or shaped body being determined by the position of the lower punch and the shape of the pressing tool. The constant dosing, even at high molding throughputs, is preferably achieved by volumetric dosing of the premix. As the tableting continues, the upper punch touches the premix and lowers further towards the lower punch. During this compression, the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix), the plastic deformation begins, in which the particles flow together and the molded body is formed. Depending on the physical properties of the premix, some of the premix particles are also crushed and sintering of the premix occurs at even higher pressures. With increasing pressing speed, that is to say high throughput quantities, the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting, the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.).

Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down. For small production quantities, eccentric tablet presses are preferably used, in which the stamp or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine. The pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disc, the number of die holes being correspondingly increased. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour. For larger throughputs, rotary tablet presses are selected in which a larger number of matrices are arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available. Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps. The die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation. At locations where a particularly serious lifting or lowering of the punches is required (filling, compacting, ejecting), these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks. The die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix. The pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.

Rotary presses can also be provided with two filling shoes to increase the throughput, only a semicircle having to be run through to produce a tablet. For the production of two- and multi-layer molded articles, several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling. With suitable process control, jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible. Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing. The throughputs of modern rotary tablet presses are over one million tablets per hour.

When tableting with rotary presses, it has proven to be advantageous to carry out the tabletting with the smallest possible fluctuations in the weight of the tablet. The fluctuations in hardness of the tablet can also be reduced in this way. Small fluctuations in weight can be achieved in the following ways:

- Use of plastic inserts with small thickness tolerances

- Low number of revolutions of the rotor

- Big filling shoes

- Matching the filler paddle speed to the speed of the rotor

- Filling shoe with constant powder height

- Decoupling of filling shoe and powder feed All non-stick coatings known from the art can be used to reduce stamp caking. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotating punches have also proven to be advantageous, with the upper and lower punches being designed to be rotatable if possible. In the case of rotating punches, a plastic insert can generally be dispensed with. The stamp surfaces should be electropolished here.

It was also shown that long pressing times are advantageous. These can be set with pressure rails, several pressure rollers or low rotor speeds. Since the fluctuations in the hardness of the tablet are caused by the fluctuations in the pressing forces, systems should be used which limit the pressing force. Here elastic stamps, pneumatic compensators or spring elements can be used in the force path. The pressure roller can also be designed to be resilient.

Processes preferred in the context of the present invention are characterized in that the pressing is carried out at pressures of from 0.01 to 50 kNcm ^"2 , preferably from 0.1 to 40 kNcm ^{" 2} and in particular from 1 to 25 kNcm ^"2 .

Tableting machines suitable in the context of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Hörn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (Sl ). For example, the hydraulic double pressure press HPF 630 from LAEIS, D. Tablettierwerkzeuge are, for example, from the companies Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Hörn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharmatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers are e.g. Senss AG, Reinach (CH) and Medicopharm, Kamnik (Sl).

With particular preference in the context of the present application, two- or multi-phase detergent or cleaning agent tablets are used as detergent tablets. The individual phases of these two-phase or multi-phase detergent or cleaning agent tablets differ in terms of their chemical composition, and the distribution of the ingredients contained among the individual phases can be carried out in any way within the scope of the present application. In the context of the present application, preference is given to combination products according to the invention in which the individual phases of the two-phase or multi-phase washing or cleaning agent tablets differ with regard to their surfactant content, in particular with regard to their nonionic surfactant content, and / or with regard to their bleaching agent content, in particular with regard to their sodium percarbonate content.

In a further preferred embodiment of the present application, the shaped detergent or cleaning product is a casting. Casting bodies of this type are generally produced by pouring a washing- or cleaning-active preparation into a mold and then demolding the solidified cast body.

Tools which have cavities which can be filled with pourable substances are preferably used as the “mold”. Such tools can be designed, for example, in the form of individual cavities, but also in the form of plates with a plurality of cavities. In industrial processes, the individual cavities or cavity plates are preferably mounted on horizontally rotating conveyor belts, which enable the cavities to be transported continuously or discontinuously, for example, along a number of different workstations (e.g .: casting, cooling, filling, sealing, demolding etc.).

The active washing or cleaning preparations are cast in the preferred process and subsequently solidify to a dimensionally stable body. In the context of the present invention, "solidification" denotes any hardening mechanism which, from a deformable, preferably flowable mixture or such a substance or mass, provides a body which is solid at room temperature, without the need for pressing or compacting forces. "Solidification" in the sense of the present invention is therefore, for example, the curing of melts of substances which are solid at room temperature by cooling. "Solidification processes" in the sense of the present application are also the hardening of deformable masses through time-delayed water binding, through evaporation of solvents, through chemical reaction, crystallization etc. as well as the reactive hardening of flowable powder mixtures to form stable hollow bodies,

In summary, methods according to the invention are preferred in which the cast body is delayed by water binding, by cooling below the melting point, by evaporation of solvents, by crystallization, by chemical reaction (s), in particular polymerization, by changing the rheological properties, e.g. is produced by changing shear, by sintering or by means of radiation curing, in particular by UV, alpha-beta or gamma rays.

In the context of the present application, methods are preferred in which the solidification of the cast bodies takes place by cooling below the melting point. Cooling under the melting Point can be done, for example, by giving off heat to the environment, in particular to the mold. However, it is particularly preferred to support the heat emission by using a cooling medium. Consequently, methods according to the invention are particularly preferred in which the mold is cooled. Cold air, dry ice or liquid nitrogen, for example, are suitable as a cooling medium. With particular preference, however, circulating, preferably liquid, coolants are used in the mold. The mold is preferably cooled to temperatures below 20 ° C., preferably below 17 ° C., particularly preferably below 14 ° C., very particularly preferably below 11 ° C. and in particular below 8 ° C.

In general, all washing-active or cleaning-active preparations that can be processed by casting techniques are suitable for processing in the described method. However, washing or cleaning preparations in the form of dispersions are used with particular preference. In a particularly preferred embodiment of the present application, the wash-active or cleaning-active preparation poured into the receiving recess of the molding tool is a dispersion of solid particles in a dispersant, dispersions which, based on their total weight i), 10 to 85% by weight Dispersants and ii) contain 15 to 90 wt .-% dispersed substances, are particularly preferred.

In this application, dispersion is a system consisting of several phases, one of which is continuous (dispersant) and at least one other is finely divided (dispersed substances). Particularly preferred active detergent or cleaning preparations are characterized in that they contain the dispersant in amounts above 11% by weight, preferably above 13% by weight, particularly preferably above 15% by weight, very particularly preferably above 17% by weight. and in particular above 19% by weight, based in each case on the total weight of the dispersion. Dispersions which have a dispersion with a proportion by weight of dispersant above 20% by weight, preferably above 21% by weight and in particular above 22% by weight, in each case based on the total weight of the dispersion, can also be used with preference. The maximum dispersant content of preferred dispersions, based on the total weight of the dispersion, is preferably less than 63% by weight, preferably less than 57% by weight, particularly preferably less than 52% by weight, very particularly preferably less than 47% by weight .-% and in particular less than 37 wt .-%. In the context of the present invention, in particular those active washing or cleaning preparations which, based on their total weight, contain dispersing agents in amounts of 12 to 62% by weight, preferably 17 to 49% by weight and in particular 23 to 38% by weight. % contain.

The dispersants used are preferably water-soluble or water-dispersible. The solubility of these dispersants is preferably more than 200 g / l, preferably at 25 ° C. more than 300 g / l, particularly preferably more than 400 g / l, very particularly preferably between 430 and 620 g / l and in particular between 470 and 580 g / l.

Suitable dispersants in the context of the present invention are preferably the water-soluble or water-dispersible polymers, in particular the water-soluble or water-dispersible nonionic polymers. The dispersant can be either a single polymer or a mixture of different water-soluble or water-dispersible polymers. In a further preferred embodiment of the present invention, the dispersant or at least 50% by weight of the polymer mixture consists of water-soluble or water-dispersible nonionic polymers from the group of polyvinylpyrrolidones, vinylpyrrolidone / vinyl ester copolymers, cellulose ethers, polyvinyl alcohols, polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol.

Dispersions are particularly preferably used which contain a nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, the weight fraction of the poly (ethylene) glycol being used the total weight of all dispersants is preferably between 10 and 90% by weight, particularly preferably between 30 and 80% by weight and in particular between 50 and 70% by weight. Dispersions in which the dispersant is more than 92% by weight, preferably more than 94% by weight, particularly preferably more than 96% by weight, very particularly preferably more than 98% by weight are particularly preferred. and in particular 100% by weight consists of a poly (alkylene) glycol, preferably poly (ethylene) glycol and / or poly (propylene) glycol, but in particular poly (ethylene) glycol. Dispersing agents which, in addition to poly (ethylene) glycol, also contain poly (propylene) glycol, preferably have a ratio by weight of poly (ethylene) glycol to poly (propylene) glycol of between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, particularly preferably between 10: 1 and 1, 5: 1 and in particular between 7: 1 and 2: 1.

Other preferred dispersants are the nonionic surfactants, which are used both alone, but particularly preferably in combination with a nonionic polymer. Detailed information on the nonionic surfactants that can be used can be found below in the description of detergent or cleaning substances.

Suitable dispersed substances in the context of the present application are all wash or cleaning-active substances which are solid at room temperature, but in particular washing or cleaning-active substances from the group of builders (builders and cobuilders), the washing or cleaning-active polymers, the bleaching agents and the bleach activators , the glass corrosion protection agent, the silver protection agent and / or the enzymes. A more detailed description of these ingredients can be found below in the text. The detergents which are preferably used as detergent tablets are distinguished by a high density. Moldings with a density above 1.040 g / cm ³ are particularly preferably used. Agents preferred according to the invention are characterized in that they have a density above 1.040 g / cm ³ , preferably above 1.15 g / cm ³ , particularly preferably above 1.30 g / cm ³ and in particular above 1.40 g / cm ³ exhibit. This high density not only reduces the total volume of a dosing unit but also improves its mechanical stability. Particularly preferred combination products according to the invention are therefore characterized in that the detergent tablets have a density between 1,050 and 1,670 g / cm ³ , preferably between 1,120 and 1,610 g / cm ³ , particularly preferably between 1,210 and 1,570 g / cm ³ , entirely particularly preferably between 1, 290 and 1.510 g / cm ³ , and in particular between 1.340 and 1.480 g / cm ^3. The information on the density relates in each case to the densities of the compositions at 20 ° C.

Dispersions preferably used as detergent tablets according to the invention are distinguished in that they disperse in water (40 ° C.) in less than 9 minutes, preferably less than 7 minutes, preferably in less than 6 minutes, particularly preferably in less than 5 minutes and especially dissolve in less than 4 minutes. To determine the solubility, 20 g of the dispersion are introduced into the interior of a dishwasher (Miele G 646 PLUS). The main wash cycle of a standard wash program (45 ° C) is started. The solubility is determined by measuring the conductivity, which is recorded by a conductivity sensor. The dissolving process ends when the maximum conductivity is reached. In the conductivity diagram, this maximum corresponds to a plateau. The conductivity measurement begins with the insertion of the circulation pump in the main wash cycle. The amount of water used is 5 liters.

Both compact bodies and hollow molds can be produced by casting processes. If a cast, active washing or cleaning preparation solidifies in the cavity of the mold, simple, compact bodies are produced. However, detergent tablets in the form of cast hollow bodies are more advantageous and preferred in the context of the present application.

A preferred subject of the present application is therefore a method for producing a cast hollow body from a washing or cleaning active preparation, comprising the steps: a) pouring a washing or cleaning active preparation into a mold; b) shaping the active washing or cleaning preparation; c) demoulding the cast body from the mold.

The washing or cleaning active preparation can be brought into shape using different techniques. In the simplest case, a flowable mixture is poured into an appropriate mold, left to harden there and then removed from the mold. The disadvantage here is the design the shape, because the desired wall thicknesses of the resulting hollow bodies do not allow complicated geometries to be filled quickly.

Alternatively, the solidifying mixture can be filled into a mold that is designed only as a cavity. If you let the mixture solidify there, you would get a compact body, not a hollow shape. Appropriate process control can ensure that the mixture first solidifies on the wall of the mold. If the mold is turned over after a certain time t, the excess mixture flows off and leaves a lining of the mold, which itself is a hollow mold, which can be removed from the mold after complete solidification.

A method for producing such cast hollow body from a wash or cleaning active preparation comprises the steps: a) pouring a wash or cleaning active preparation into the cavity of a molding tool; b) turning the cavity after a time t between 0 and 5 minutes and pouring out the excess preparation; c) demoulding the cast body from the mold.

As an alternative to completely filling the cavity and pouring excess mixture, the cavity can only be partially filled. In these cases, the mixture is pressed against the wall of the cavity with a suitable stamp, where it solidifies to form the hollow body. This process variant represents an intermediate form between the "casting technique" and the casting technique in negative forms of the hollow body.

Corresponding methods for producing a cast hollow body from a preparation that is active in washing or cleaning comprise the steps: a) pouring a preparation that is active in washing or cleaning into the cavity of a mold; b) displacement of the active washing or cleaning preparation by means of a stamp; c) demoulding the cast body from the mold.

Liquid-filled hollow body

In addition to the washing or cleaning agent shaped body (s), the combination products according to the invention also comprise at least one liquid-filled hollow body. This hollow body can be an injection molded and / or blow molded and / or deep drawn part. In the context of the present application, products manufactured by deep-drawing processes are referred to as “deep-drawn parts”. In these deep-drawing processes, a first film-like wrapping material is generally deformed after being brought into contact with a receiving trough located in a die forming the deep-drawing plane and molding the wrapping material into this receiving trough by the action of pressure and / or vacuum. The casing material can be pretreated before or during the molding in by the action of heat and / or solvent and / or conditioning by means of relative atmospheric humidity and / or temperature changes compared to ambient conditions. The pressure can be exerted by two parts of a tool, which behave like positive and negative to each other and deform a film placed between these tools when pressed together. However, the action of compressed air and / or the weight of the film and / or the weight of an active substance placed on the top of the film are also suitable as pressure forces.

After deep-drawing, the deep-drawn envelope materials are preferably fixed by using a vacuum within the receiving troughs and in the spatial shape achieved by the deep-drawing process. The vacuum is preferably applied continuously from deep drawing to filling, preferably to sealing and in particular to the separation of the receiving chambers. With comparable success, however, it is also possible to use a discontinuous vacuum, for example for deep-drawing the receiving chambers and (after an interruption) before and during the filling of the receiving chambers. The strength of the continuous or discontinuous vacuum can also vary and, for example, assume higher values at the beginning of the process (when thermoforming the film) than at the end (when filling or sealing or separating).

As already mentioned, the wrapping material can be pretreated by the action of heat before or during molding into the receiving troughs of the dies. The coating material, preferably a water-soluble or water-dispersible polymer film, is kept at temperatures above 60 ° C. for up to 5 seconds, preferably for 0.1 to 4 seconds, particularly preferably for 0.2 to 3 seconds and in particular for 0.4 to 2 seconds. preferably heated above 80 ° C, particularly preferably between 100 and 120 ° C and in particular to temperatures between 105 and 115 ° C. In order to dissipate this heat, but in particular also to dissipate the heat introduced by the means filled into the deep-drawn receiving chambers (eg melting), it is preferred to cool the dies used and the receiving troughs located in these dies. The cooling is preferably carried out at temperatures below 20 ° C., preferably below 15 ° C., particularly preferably at temperatures between 2 and 14 ° C. and in particular at temperatures between 4 and 12 ° C. The cooling is preferably carried out continuously from the start of the deep-drawing process to the sealing and separation of the receiving chambers. Cooling liquids, preferably water, which are circulated in special cooling lines within the die are particularly suitable for cooling. This cooling, like the continuous or discontinuous application of a vacuum described above, has the advantage of preventing the deep-drawn containers from shrinking back after deep-drawing, which not only improves the appearance of the process product, but at the same time also escapes the agents filled into the receiving chambers the edge of the receiving chamber, for example in the sealing areas of the chamber, is avoided. This prevents problems with the sealing of the filled chambers.

In the deep-drawing process, a distinction can be made between processes in which the wrapping material is fed horizontally into a molding station and from there in a horizontal manner for filling and / or sealing and / or separating, and processes in which the wrapping material is fed via a continuously rotating die-forming roller (if necessary optionally with a counter-rotating male mold roll, which guides the shaping upper punches to the cavities of the female mold roll). The first-mentioned process variant of the flatbed process is to be operated both continuously and discontinuously; the process variant using a shaping roller is generally carried out continuously. All of the deep-drawing processes mentioned are suitable for producing the agents preferred according to the invention. The receiving troughs located in the matrices can be arranged “in series” or offset.

"Injection molded parts" are made by injection molding. Injection molding refers to the shaping of a molding compound in such a way that the mass contained in a mass cylinder for more than one injection molding process plastically softens under the action of heat and flows under pressure through a nozzle into the cavity of a previously closed tool. The process is mainly used for non-hardenable molding compounds that solidify in the mold by cooling. Injection molding is a very economical, modern process for the production of non-cutting shaped objects and is particularly suitable for automated mass production. In practical operation, the thermoplastic molding materials (powder, granules, cubes, pastes, etc.) are heated to liquefaction (up to 180 ° C) and then injected under high pressure (up to 140 MPa) into closed, two-part, that is, from dies (formerly Matrix) and core (formerly patrix), preferably water-cooled hollow molds, where they cool and solidify. Piston and screw injection molding machines can be used. Suitable molding compounds (injection molding compounds) are water-soluble polymers such as, for example, the above-mentioned cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch.

Combination products according to the invention which are particularly preferred are characterized in that the liquid-filled hollow body (s) has a wall thickness of 100 to 1000 μm, preferably 110 to 800 μm and in particular 120 to 600 μm. ingredients

The combination products according to the invention are detergents or cleaning agents, preferably textile cleaning agents, dishwashing agents or surface cleaning agents. The group of textile cleaning agents includes in particular the universal detergents, color detergents, mild detergents, fabric softeners or ironing aids. The group of dishwashing detergents includes machine dishwashing detergents and machine rinse aids as well as manual dishwashing detergents. Surface cleaning agents include Descaler, agent for disinfecting or sterilizing surfaces or objects and agent for cleaning metal or glass surfaces. In the context of the present application, preferred detergents or cleaning agents of this type contain at least one substance from the group consisting of builders, surfactants, polymers, bleaching agents, bleach activators, enzymes, dyes, fragrances, electrolytes, pH adjusting agents, perfume carriers, fluorescent agents, hydrotopes, foam inhibitors, silicone oils, Anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating agents, and swellings and anti-slip agents. These substances will be described in more detail below.

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 Η 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 0 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- χ0 _{2x + 1} 'y H ₂ 0, where M represents sodium or hydrogen, x a number from 1.9 to 22 , preferably from 1, 9 to 4, and y represents a number from 0 to 33. The crystalline optically shaped silicates of the formula NaMSi _x 0 _{2x + 1} ^• y H ₂ 0 are sold, for example, by Clariant GmbH (Germany) under the trade name Na-SKS, for example Na-SKS-1 (Na ₂ Si ₂₂ 0 ₄₅ -χH ₂ 0, Kenyait), Na-SKS-2

(Na ₂ Si ₁₄ θ2g xH ₂ 0, magadiite), Na-SKS-3 (Na ₂ Sig0 ₁₇ -χH ₂ 0) or Na-SKS-4 (Na ₂ Si ₄ O _g xH 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-Na ₂ Si ₂ 0g), Na-SKS-

7 (β-Na ₂ Si ₂ 0 ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ 0 ₅ H ₂ 0), Na-SKS-10 (NaHSi ₂ 0 ₅ -3H ₂ 0, kanemite), Na-SKS -11 (t-Na ₂ Si ₂ 0 ₅ ) and Na-SKS-13 (NaHSi 0 ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ 0 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 viscous silicate of the formula NaMSi _x 0 _{2x + 1} ^' y H ₂ 0 of 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular from 0.4 to 10% by weight, in each case based on the total weight of these compositions. 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 which has 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 type 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). phat) Na ₃ P0 ₄ , which can be used as dodecahydrate, as decahydrate (corresponding to 19-20% P ₂ 0 ₅ ) and in anhydrous form (corresponding to 39-40% P ₂ 0 ₅ ).

Another preferred phosphate is tripotassium phosphate (tertiary or triphase potassium phosphate), KsP0 ₄ . Also preferred are the tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ 0 ₇ , which is in anhydrous form (density 2.534, preferably ³ , melting point 988 °, also 880 °) and as decahydrate (density 1.815-1, 836, preferably 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 the NaH ₂ P0 ₄ or the KH ₂ P0 ₄ produces higher moles. 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% strength 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 also 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 phosphates), 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 bicarbonate or sodium sesquicarbonate, preferably being used for the purposes of this invention. 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 the polycarbonate 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 action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value 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, 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.

For the purposes 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), using a UV detector. 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 (co) polymeric polycarboxylate content of 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. Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are also include glycerol disuccinates and glycerol trisuccinates. Suitable amounts for use 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 homologs. 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

In addition to the nonionic surfactants, the anionic, cationic and amphoteric surfactants are also included in the group of surfactants.

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 radical is branched linearly or preferably in the 2-position methyl may 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 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 _12-14 alcohols with 3 EO or 4 EO, C ₉ . n-alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ ι ₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁ -ι ₄ alcohol containing 3 EO and C _12-18 - alcohol with 5 EO. The degrees of ethoxylation given represent statistical mean values for a special product can be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty 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-cocoalkyl-N, N-dimethylamine oxide and N-day alkyl-N, N-dihydroxyethylamine oxide, and of 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 (I),

R I R-CO-N- [Z] (I)

in which RCO stands 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

R-CO-N- [Z]

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -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 propylated Derivatives of this remainder.

[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 cleaning agents according to the invention for machine dishwashing 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 _12-14 alcohols with 3 EO or 4 EO, C _9-1 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 Cι _2-1 alcohol with 3 EO and C ₁₂ .ι ₈ 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 which have a melting point above room temperature are particularly preferred, nonionic surfactants having a melting point above 20 ° C., preferably se above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, are particularly preferred.

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.

(. C ₁₆ ₂ o alcohol) A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms, preferably a C ₁₈ - alcohol and at least 12 moles, at least preferably 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 ethoxylated nonionic surfactants which are composed of C _6-20 monohydroxyalkanols or C ₆ . ₂₀ alkylphenols or C ₁₆ . ₂ o-fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide were obtained per mole of alcohol.

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% by weight 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.

Other 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.

In detergents or cleaning agents, preferably in dishwashing detergents, the nonionic surfactant of the formula (II)

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

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, 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, iso-propyl, 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, preferably 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.

In the context of the present application, weakly foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants. 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 composed of the respective whose groups follow. Here, automatic dishwashing agents according to the invention are preferred which contain surfactants of the general formula III as nonionic surfactant (s)

R ¹ -0- (CH ₂ -CH ₂ -0) _w - (CH ₂ -CH-0) _x - (CH ₂ -CH ₂ -0) _y - (CH ₂ -CH-0) _z -H (III ) IIR ² R ³

in which R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; 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 formula III 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 IM 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 formula III for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 is up 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 detergents are characterized in that RR ²² bbzzww .. RR ³³ for one RReesstt --CCHH ₃₃ ,, ww and xx xx uunnaabbhhäännggiigg vooo one another for values of 3 or 4 and y and z independently of one another for values of 1 or 2.

In summary, nonionic surfactants are particularly preferred which have a C _9-15 -alkyl radical having 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. 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 (IV)

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x R ² (IV)

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 is} 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 40.

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

R ¹ 0 [CH ₂ CH ₂ 0] _x R ² (V)

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 residues with 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and x stands for values between 1 and 40.

Those end group-capped poly (oxyalkylated) nonionic surfactants which, according to the formula (VI) R ¹ 0 [CH ₂ CH ₂ 0] _x CH ₂ CH (OH) R ² (VI)

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 having 1 have up to 30 carbon atoms R ² , which is adjacent to a monohydroxylated intermediate group -CH ₂ CH (OH) -. In this formula, x stands for values between 1 and 40. Such end-capped poly (oxyalkylated) nonionic surfactants can be obtained, for example, by reacting a terminal epoxide of the formula R CH (0) CH ₂ with an ethoxylated alcohol of the formula R ¹ 0 [CH ₂ CH ₂ 0] _x ιCH ₂ CH ₂ OH obtained.

The specified C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the above-mentioned nonionic surfactants represent statistical mean values which, for a specific product, represent a whole or can be a fractional number. 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.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are thereby _9- C ι ₃ preferably alkylbenzenesulfonates, te Olefinsulfona-, 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. Also suitable are alkanesulfonates obtained from C ₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. 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 meaning the mono-, di- and triesters and their mixtures as obtained 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 of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 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, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₂ -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 and C ₄ -C ₁₅ alkyl sulfates are preferred from a washing-technical point of view. 2,3-alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

Also the sulfuric acid monoesters of the straight-chain or branched C _{7- 1} alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C _9- ι alcohols 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 ₈ ιs fatty alcohol residues or mixtures thereof. 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) yl succinic acid with preferably 8 to 18 carbon atoms in the alkyl (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 from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

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 agents 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.

For example, cationic compounds of the formulas VII, VIII or IX can be used as cationic active substances:

R ¹

(CH ₂ ) _π -TR ^; 2 R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -CH-CH ₂ (VIII)

R ¹ TTIIR ² R ²

R ¹ IR ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (IX)

R ⁴

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group 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 agents which do not contain any 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.

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 optionally further ionic or nonionic monomers can be used particularly preferably 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 (X),

in which R 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 X 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 ¹ = COOH; R ² = R ³ = H) preferred.

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula XI

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (XI),

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 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 ) -

Preferred among these monomers are those of the formulas Xla, Xlb and / or Xlc,

H ₂ C = CH-X-S0 ₃ H (Xla), H ₂ C = C (CH ₃ ) -X-S0 ₃ H (Xlb), H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) - X-S0 ₃ H (Xlc),

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 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 ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (0) NH-CH (CH ₂ CH ₃ ) in formula Xla), 2-acrylamido-2-propanesulfonic acid (X = -C ( 0) NH-C (CH ₃ ) ₂ in formula Xla), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (0) NH- CH (CH ₃ ) CH ₂ - in formula Xla), 2-methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (0) NH-CH (CH ₃ ) CH ₂ - in formula Xlb), 3-methacrylamido -2-hydroxy-propanesulfonic acid (X = -C (0) NH- CH ₂ CH (0H) CH ₂ - in formula Xlb), allylsulfonic acid (X = CH ₂ in formula Xlla), methallylsulfonic acid (X = CH ₂ in formula Xlb ), Allyloxybenzenesulfonic acid (X = -CH ₂ -0-C ₆ H ₄ - in formula Xla), methallyloxybenzenesulfonic acid (X = -CH ₂ -0-C ₆ H ₄ - in formula Xlb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid (X = CH ₂ in formula Xlb), styrene sulfonic acid (X = C ₆ H ₄ in formula Xla), vinyl sulfonic acid (X not present in formula Xla), 3 -Sulfopropyl acrylate (X = -C (0) NH-CH ₂ CH ₂ CH ₂ - in formula Xla), 3-sulfopropyl methacrylate (X = -C (0) NH-CH ₂ CH ₂ CH ₂ - in formula Xlb), sulfomethacry - Lamide (X = -C (0) NH- in formula Xlb), sulfomethyl methacrylamide (X = -C (0) NH-CH ₂ - in formula Xlb) 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 are made of

i) unsaturated carboxylic acids of formula X.

R ¹ (R ² ) C = C (R ³ ) C00H (X),

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,

ii) Monomers of the formula XI containing sulfonic acid groups

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (XI),

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 represents an optionally present 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 ) -

iii) optionally further ionic or nonionic monomers

particularly preferred.

Further 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 of the formulas Xla, Xlb and / or Xlc containing sulfonic acid groups:

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 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 XII are preferred

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

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 ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH- CH (CH ₂ CH ₃ ) - stands, are 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 XIII

- [CH ₂ -C (CH ₃ ) C00H] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (XIII),

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. Copolymers are those which have structural units of the formula XIV

- [CH ₂ -CHCOOH] _rn - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (XIV),

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 ) _π - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH- CH (CH ₂ CH ₃ ) - Is, just like copolymers, the structural units of the formula XV

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

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 ) - ,

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 which have structural units of the formula XVI

- [HOOCCH-CHCOOH] _rn - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (XVI), 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 for -0- (CH ₂ ) _π - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH- CH (CH ₂ CH ₃ ) -, preferred and preferred copolymers according to the invention are the structural units of the formula XVII

- [H00CCH-CHC00H] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p - (XVII),

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 ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH- CH (CH ₂ CH ₃ ) - stands.

In summary, according to the invention, those copolymers are preferred which have structural units of the formulas XII and / or XIII and / or XIV and / or XV and / or XVI and / or XVII

- [CH ₂ -CHC00H] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (XII), - [CH ₂ -C (CH ₃ ) C00H] _m - [CH ₂ -CHC ( 0) -Y-S0 ₃ H] _p - (XIII), - [CH ₂ -CHC00H] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (XIV), - [CH ₂ -C (CH ₃ ) C00H] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-SO ₃ H] _p - (XV), - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (XVI), - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p - (XVII)

The sulfonic acid groups in the polymers can be wholly or partly in neutralized form, ie the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by 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 washing or cleaning agent compositions are characterized in that the copolymers ^", preferably 4000 to 25,000 ^gmol" having molecular weights from 2000 to 200,000 gmol ¹ and in particular from 5000 to 15,000 gmol ^-1.

With particular preference, amphoteric or cationic polymers continue to be used. These particularly preferred polymers are characterized in that they have at least one positive charge. Such polymers are preferably water-soluble or water-dispersible, that is to say they have a solubility in water at 25 ° C. above 10 mg / ml.

Cationic or amphoteric polymers particularly preferably contain at least one ethylenically unsaturated monomer unit of the general formula

R ¹ (R ² ) C = C (R ³ ) R ⁴

in which R ¹ to R ⁴ 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, a heteroatomic group with at least one positively ended group, a quaternized nitrogen atom or at least one amine group with a positive charge in the pH range between 2 and 11 or for -COOH or -COOR ⁵ , where R ^{5 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Examples of the aforementioned (non-polymerized) monomer units are diallylamine, methyldiallylamin, dimethyldimethylammonium salts, acrylamidopropyl (trimethyl) ammonium salts (R ¹ , R ² , and R ³ , = H, R ⁴ = C (0) NH (CH ₂ ) ₂ N ⁺ (CH ₃ ) ₃ X ^" ), methacrylamidopropyl (trimethyl) ammonium salts (R ¹ and R ² = H, R ³ = CH ₃ H, R ⁴ = C (0) NH (CH ₂ ) ₂ N ⁺ (CH ₃ ) ₃ X ^" ). Unsaturated carboxylic acids of the general formula are particularly preferred as a constituent of the amphoteric polymers

R ¹ (R ² ) C = C (R ³ ) COOH

used, 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.

Particularly preferred amphoteric polymers contain, as monomer units, derivatives of diallylamine, in particular dimethyldiallylammonium salt and / or methacrylamidopropyl (trimethyl) ammonium salt, preferably in the form of the chloride, bromide, iodide, hydroxide, phosphate, sulfate, hydrosulfate, ethyl sulffast, methyl sulfate, mesylate, tosylate , Formates or acetates in combination with monomer units from the group of ethylenically unsaturated carboxylic acids.

Bleichrnittel

Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and supply H ₂ 0 ₂ in water. Further bleaching agents that can be used are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ 0 ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. According to the invention, bleaching agents from the group of organic bleaching agents can also be used. 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-phthalimidoperoxyiminoperacid acid (ε-phthalimidoperthoxy acid), and )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipinic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxoxyphaic acid, diperoacid-diperacrylic acid, diperoacid-diperacrylic acid, Decyl-diperoxybutane-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. Suitable chlorine or bromine-releasing materials include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid. 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 with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable. Multi-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), are preferred. N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetic alcohols, especially triac 5-diacetoxy-2,5-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 IR ² -N ⁽⁺⁾ - (CH ₂ ) -CN X ", IR ³

in which R is -H, -CH ₃ , a C _2-2 -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 having a C _1-2 alkyl group, or a substituted alkyl or alkenylaryl radical having a C _1-24 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 -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 is particularly preferred R ⁴

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 (H0-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{" are} particularly preferred, the cationic group from the group of these substances in turn 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, 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, especially tetraacetylethylene diamine (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 phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, especially triacetine, Diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA) as well as acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular penta-acetylglucose (PAG), penta-acetylfructose, tetra-acetyl-xylose and octaylylylose and ocylate , 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. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru amine complexes can 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 tetraacetylene-ethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or Isononanoyloxybenzenesulfonate (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.

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, the manganese sulfate are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular 0.0025% by weight .-% 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, in each case based on the total glass corrosion inhibitor-containing agent. The exact content of the agent in the zinc salt or zinc salts is naturally measured depending on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration in the agents 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 significantly below this value in order to further minimize the risk of 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, branched saturated or unsaturated monocarboxylic acids, saturated and unsaturated dicarboxylic acids, aromatic mono-, di- and tricarboxylic acids, sugar acids, hydroxy acids, oxo acids, amino acids and / or 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. -%, each based 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 bisbenzotriazoles, 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 very 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, phloroglucinol, 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 (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and man- gansulfats. 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 the manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, the metals preferably in one of the oxidation states II, III , IV, V or VI are present.

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 (II) - [1-hydroxyethane-1,1-diphosphonate], V ₂ Og, 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 .

These metal salts or metal complexes are generally commercially available substances which are used in the inventions for the purpose of protecting against silver corrosion without prior cleaning. Agents according to the invention can be used. For example, the mixture of pentavalent and tetravalent vanadium (V ₂ 0 ₅ , V0 ₂ , V ₂ 0 ₄ ) known from S0 ₃ production (contact process) is suitable, as is that by diluting a Ti (S0 ₄ ) ₂ - Solution resulting titanyl sulfate, TiOS0 ₄ .

The inorganic redox-active substances, in particular metal salts or metal complexes, are preferably coated, i.e. completely covered with a waterproof material that is easily soluble at cleaning temperatures 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, micro-waxes, waxes of natural origin such as camamauba 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, e.g. by throwing finely divided material to be coated in a continuous stream through a likewise continuously generated spray zone of the molten coating material. 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, hemicellules, 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 protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and that which can no longer be assigned to the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. Subtilisins 147 and 309 are marketed under the Men Esperase ^® , or Savinase ^{® sold} by Novozymes. 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 β. amyloliquefaciens or from ß. stearothermophilus and its further developments 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 Pu rastar ^® 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 sold by Novozymes under the name BAN ^®, and variants derived from the α-amylase from B.. stearothermophilus under the names BSG ^® and Novamyl ^® , also from Novozymes.

Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from ß. to highlight 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 also be used according to the invention, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, 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 which can also be used are from Amano under the names Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. Lipase ^® , Lipase AP ^® , Lipase M-AP ^® and Lipase AML ^® available. The Genencor company can use, for example, 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 lipo max ^® and sold by the company Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® mentioned enzymes 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 from ß. subtilis .beta.-glucanase obtained 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 (phenoloxidases, 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 enzymes are 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-capped fatty acid amide alkoxylates are also 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. Cross-linked N-containing compounds also act as enzyme stabilizers.

Reducing agents 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.

disintegration aid

In order to facilitate the disintegration of prefabricated moldings, disintegration aids, so-called tablet disintegrants, can be incorporated into these agents in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184), tablet disintegrants or disintegration accelerators are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in resorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling), and on the other hand a pressure can be generated by the release of gases, which reduces the tablet into smaller ones Particles disintegrate. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.

Disintegration aids are preferably used in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight, in each case based on the total weight of the agent containing disintegration aids.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred washing and cleaning agent compositions contain such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, from a formal point of view, is a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be pressed. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The coarser disintegration aids based on cellulose that are mentioned above and described in more detail in the cited documents are preferred as disintegration aids in the context of the present invention used and commercially available, for example, under the name Arbocel ^® TF-30-HG from Rettenmaier.

Microcrystalline cellulose can be used as another cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. Subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm.

Disintegration aids preferred in the context of the present invention, preferably a. Disintegration aids based on cellulose, preferably in granular, cogranulated or compacted form, are present in the disintegrant-containing compositions in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight. -%, each based on the total weight of the disintegrant-containing agent.

According to the invention, gas-developing effervescent systems can also preferably be used as tablet disintegration aids. The gas-developing shower system can consist of a single substance which releases a gas when it comes into contact with water. Among these compounds, magnesium peroxide should be mentioned in particular, which releases oxygen on contact with water. Usually, however, the gas-releasing bubble system itself consists of at least two components that react with one another to form gas. While a large number of systems are conceivable and executable here, which release nitrogen, oxygen or hydrogen, for example, the effervescent system used in the detergent and cleaning agent compositions according to the invention can be selected on the basis of both economic and ecological aspects. Preferred effervescent systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium salts are clearly preferred over the other salts for reasons of cost. Of course, the pure alkali metal carbonates or bicarbonates in question do not have to be used; rather, mixtures of different carbonates and hydrogen carbonates may be preferred.

The preferred shower system is 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably example 2 to 12 and in particular 3 to 10 wt .-% of an acidifying agent, based in each case on the total weight of the agent.

Acidifying agents which release carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent. However, the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are preferred from this group. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).

In the context of the present invention, preference is given to acidifying agents in the effervescent system from the group of the organic di-, tri- and oligocarboxylic acids or mixtures.

fragrances

As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropional and benylate propylate. The ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxyxitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, α-Isomethylionon and Methylcedrylketon, to the alcohols Anethol, Citronellol, Eugenol, Geraniol, Linalool, Phenylethylalkohol and Terpineol, to the hydrocarbons belong mainly the terpenes like Limonen and Pinen. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, melissa 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. As Such carrier materials have proven themselves, for example, cyclodextrins, 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, for example, glass, ceramics, plastic dishes or textiles not to stain them.

solvent

The solvents include, in particular, the non-aqueous organic solvents, with particular preference given to using non-aqueous solvents from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerin, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol , Di-ethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents.

foam inhibitors

Suitable foam inhibitors are, for example, soaps, paraffins or silicone oils, which can, if appropriate, be applied to carrier materials. Suitable antiredeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ethers and the polymers of phthalic acid and / or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of the phthalic acid and terephthalic acid polymers are particularly preferred.

Optical brighteners

Optical brighteners (so-called "white toners") can be added to detergents or cleaning agents in order to eliminate graying and yellowing of textiles treated with these agents. These substances are absorbed on the fiber and cause a lightening and pretended bleaching effect, by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and results in pure white with the yellow tone of the grayed or yellowed laundry. Suitable compounds for example, originate from the substance classes of the 4,4 ^{^{'diamino-2,2'}} - stilbenedisulfonic (flavonic), ^{4,4'-biphenylene} -Distyryl, Methylumbelliferone, coumarins, di hydrochinolinone, 1, 3-diaryl pyrazolines, naphthalimides, Benzoxazole, benzisoxazole and benzimidazole systems as well as the pyrene derivatives substituted by heterocycles.

graying

Graying inhibitors in textile cleaning agents have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. Cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof can also be used as graying inhibitors in the particulate compositions.

Antimicrobial agents

Antimicrobial agents are used to combat microorganisms. 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, benzalkonium chlorides, alkylarlylsulfonates, halogenophenols and phenol mercuric acetate, although the use of these agents can also be dispensed with entirely.

softener

The formulations can also have fabric-softening clay minerals, which can be selected from a large number of minerals, in particular the layered silicates. The smectite group has proven to be advantageous. The term smectite includes both clays in which aluminum oxide is present in a silicate grid and clays in which magnesium oxide occur in a silicate grid. Typical smectites have the following general formula: Al ₂ (Si ₂ 0 ₅ ) ₂ (OH) ₂ 'nH ₂ 0 and compounds with the following formula Mg ₃ (Si ₂ 0 ₅ ) ₂ (OH) ₂ ^« nH ₂ 0. Smectites are usually in an extensive three-layer structure. Specific examples of suitable smectites include those selected from the class of montmorillonites, hectorites, volchonskites, nontronites, saponites and sauconites, especially those with alkali or alkaline earth metal ions in the crystal lattice structure. A three-layer, expandable aluminum silicate is preferred, this is characterized by a dioctahedral crystal lattice, whereas the extensive three-layer magnesium silicate structure has a trioctahedral crystal lattice. As previously mentioned, the clay minerals contain cationic counterions such as protons, sodium ions, potassium ions, calcium ions, magnesium ions and the like. The clay minerals are usually distinguished on the basis of the cations that are predominantly or exclusively absorbed. For example, a sodium bentonot is such a clay mineral in which sodium is predominantly present as the absorbed cation. Such absorbed cations can carry out exchange reactions with other cations in aqueous solutions. A typical exchange reaction involving a smectite type is as follows:

Smectite (Na) + NH ₄ OH> smectite (NH ₄ ) + NaOH

In the aforementioned equilibrium reaction, one equivalent of ammonium ion is replaced by one equivalent of sodium ion. It is common to measure the cation exchange capacity in milliequivalents / 100 g (meq / 100 g). The cation exchange capacity of the clays can be determined in a variety of ways, for example by electrodialysis or by exchange with ammonium ions, followed by titration, as described, for example, in the book by Grimshaw, "The chemistry and physics of clays", pages 264-265, Interscience 1971. Smectites such as nontonite, for example, have an ion exchange capacity of approximately 70 meq / 100 g, and montmorillonites, which have an exchange capacity of above 70 meq / 100 g, have proven to be extremely preferred in the context of the present invention, since they are particularly effective towards them pull on the treating textiles and give them the desired soft feel. Particularly preferred clay minerals in the context of the present invention are therefore expanded three-layer smectite types with an ion exchange capacity of at least 50 meq / 100 g.

Organophilic clay minerals can also be used in the present invention. Such hydrophobically modified clay minerals in which inorganic metal ions are exchanged for organic ions by the previously described exchange process are also preferred. The modified clay minerals are very miscible with organic solvents and have the property of storing organic solvents between the layers. Suitable examples of organophilic clay minerals are Benton SD-1, SD-2 and SD-3 from Rheox.

From the group of smectites, bentonites have proven to be particularly preferred. Bentonites are contaminated clays that are formed by weathering volcanic tuffs. Due to their high montmorillonite content, bentonites have valuable properties such as swellability, ion exchange capacity and thixotropy. It is possible to modify the properties of the bentonites according to the intended use. Bentonites are a common clay component in tropical soils and are mined as sodium bentonite, for example in Wyoming / USA. Sodium bentonite has the most favorable application properties (swellability), so that its use in the context of the present invention is preferred. Naturally occurring calcium bentonites originate, for example, from Mississippi / USA or Texas / USA or from Landshut / D. The naturally obtained Ca bentonites are artificially converted into the more swellable Na bentonites by exchanging Ca for Na.

The main constituents of the bentonites are so-called montmorillonites, which can also be used in pure form in the context of the present invention. Montmorillonites belong to the phyllosilicates and here to the dioctahedral smectites clay minerals that crystallize monoclinic-pseudohexagonal. Montmorillonite predominantly form white, gray-white to yellowish, completely amorphous appearing, easily friable, swelling in the water, but not plastic, by the general formulas

AI ₂ [(OH) ₂ / Si ₄ O ₁₀ ] -nH ₂ O or AI ₂ 0 ₃ -4Si0 ₂ Η ₂ 0-nH ₂ 0 or AI ₂ [(OH) ₂ / Si ₄ O ₁₀ ] (at 150 ° dried)

can be described.

Montmorillonites have a three-layer structure, which consists of two tetrahedral layers that are electrostatically cross-linked via the cations of an intermediate octahedral layer. The layers are not rigidly connected, but can swell by reversible incorporation of water (in 2-7 times the amount) and other substances such as alcohols, glycols, pyridine, ammonium compounds, hydroxyaluminosilicate ions, etc. The above. Formulas are only approximate formulas since montmorillonites have a large ion exchange capacity. So AI can be exchanged for Mg, Fe ²⁺ , Fe ³⁺ , Zn, Cr, Cu and other ions. As a result of such a substitution, the layers are negatively charged, which is balanced by other cations, especially Na ⁺ and Ca ²⁺ .

Calcium or magnesium bentonites are usually non-swellable and usually less effective plasticizers. However, it is advantageous to combine non-swellable bentonites with carrier materials, such as, for example, polyethylene glycol, in order to achieve a considerably improved soft feel of the textiles treated with them. Calcium or magnesium bentonites, which are used in the presence of a sodium source, such as NaOH or NaC0 ₃ , are also advantageous.

In a particularly preferred embodiment, the clay is a treated montmorillonite-containing clay which has the following properties: I) Montmorillonite content of at least 85% and II) When the clay activated with sodium ions is dried and ground into particles, the ground particles do not swell more than two and a half times within a period of 24 hours when deionized water is added at room temperature.

A clay containing montmorillonite is particularly preferred, which is obtained by the following process steps: a) drying the clay to a water content of 25-35% by weight, b) extruding the dried material into a paste; c) drying the paste to a moisture content of 10-14% by weight and d) calcining at a temperature between 120 and 250 ° C.

The chemical composition of the bentonite to be used as the starting material is preferably the following:

Si0 ₂ : 55.0-61.0% by weight

Al ₂ 0 ₃ : 14.5-17.6% by weight

Fe ₂ 0 ₃ : 1.45-1.7% by weight

CaO: 2.8 - 7.0% by weight

MgO: 5.0 - 6.3% by weight

K ₂ 0: 0.5-0.58% by weight

Na ₂ 0: 0.25-0.3% by weight

Mn ₃ 0 ₄ : 0.04-0.25% by weight

A detailed description of the process for the treatment of bentonite can be found in WO 00/03959, the disclosure of which is fully incorporated in this application.

The crystalline structure of montmorillonite is more or less resistant to acid treatment. Acid treatment in the context of the invention means that a sample of the clay (for example 1 g / l) in a 1 N HCl solution is exposed to a temperature of 80 ° C. for 15 hours. It must be mentioned that most clays can be destroyed by acid treatment with, for example, fluoride. In the context of the present invention, however, acid treatment means HCI treatment. Montmorillonites (magnesium saturated / air dried) usually have a maximum diffraction distance of 14-15 in the 001 plane when treated with X-rays. This maximum diffraction distance usually does not change by treating the clay with HCI.

In the context of the present invention, however, acid-sensitive montmorillonites are preferred, for example montmorillonites, the crystalline structure of which is destroyed when they are treated with HCl. The use of such clay minerals has a soft touch-improving effect and ensures also for better dispersibility in the aqueous wash liquor or the aqueous textile treatment liquid. The destruction of the crystalline structure can be determined by measuring the diffraction distance, so that the maximum diffraction distance to be expected in the 001 plane of 14-15 does not appear for the destroyed montmorillonites in the case of crystalline montmorilonites.

Without being bound by theory, it is believed that acid sensitivity is related to an increased exchange of aluminum for magnesium in the octahedral layer of the montmorillonite clay. A ratio of Al ₂ O ₂ / MgO of less than 4, particularly preferably less than 3, is preferred. The above-mentioned acid-sensitive montmorillonites have the advantage that they enable a reduced tendency to gel and an improved dispersibility in the wash liquor. In addition, it has been observed that such clay minerals produce an improved soft feel.

Claims

claims:

1. Combination product of at least one detergent or cleaning product body and at least one liquid-filled hollow body which is an injection molding and / or blow molding and / or deep-drawn part and which at least partially consists of one or more water-soluble or water-dispersible polymers, characterized in that the / the liquid-filled hollow body (s) is / are connected to the detergent tablet.

2. Combination product according to claim 1, characterized in that the liquid-filled hollow body (s) is / are connected to the shaped detergent or detergent body by a plug and / or snap and / or latching and / or adhesive connection.

3. Combination product according to one of claims 1 or 2, characterized in that the detergent tablets are one or more single or multi-phase detergent tablets.

4. Combination product according to one of claims 1 or 2, characterized in that the / the detergent or cleaning tablets is a casting.

5. Combination product according to one of claims 1 to 4, characterized in that the volume ratio of detergent tablets (s) to liquid-filled (m / n) hollow bodies ^) 8: 1 to 1: 8, preferably 5: 1 to 1: 5 and in particular 3: 1 to 1: 3.

6. Combination product according to one of claims 1 to 5, characterized in that the weight ratio of detergent tablets (s) to liquid-filled (m / n) hollow bodies ^) 11: 1 to 1:11, preferably 5: 1 to 1: 5 and in particular 3: 1 to 1: 3.

7. Combination product according to one of claims 1 to 6, characterized in that the detergent or detergent shaped body contains sodium percarbonate, however, no anionic surfactants and / or cationic surfactants and / or nonionic surfactants and / or amphoteric surfactants.

8. Combination product according to one of claims 1 to 7, characterized in that the / the liquid-filled hollow body has a wall thickness of 100 to 1000 microns, preferably from 110 to 800 microns and in particular from 120 to 600 microns.

9. Combination product according to one of claims 1 to 8, characterized in that the combination product comprises at least a further part, preferably a gelatin capsule and / or a coated shaped body.

10. A process for the production of combination products from at least one detergent or cleaning product tablet and at least one liquid-filled hollow article, characterized by the steps a) production of washing or cleaning product tablets; b) production of liquid-filled hollow bodies by injection molding and / or blow molding and / or deep drawing; c) Connection of at least one product from step a) with at least one product from step b).

11. The method according to claim 10, characterized in that the connection in step c) by a plug and / or snap and / or latching and / or adhesive connection, preferably by gluing.