EP1298195A1 - Semi-automatic dosage method - Google Patents

Abstract

Dosing of active compositions is effected using a water-insoluble container with ≥ 2 hollows containing the active composition and each hollow covered with a separate water-insoluble protective film, the dosing process involving removing at least one of the separate films and contacting the container with water or an aqueous solution so as to release the active composition. <??>Independent claims are also included for <??>(i) water-insoluble containers having actives-containing hollows closed by protective films, there also being a water-soluble film between the insoluble protective film and the container; and <??>(ii) a kit of parts including the container and a fixing device.

Description

The present application relates to the semi-automatic dosage of active substances. Especially The present application relates to a method for semiautomatic dosing of Detergents and cleaning agents such as those used for dishwashing in dishwashers be used.

Detergents and cleaning agents and processes for their preparation are well known and in the state the technology thus broadly described. Usually, they are the consumer in the form of spray-dried or granulated powder products or provided as a liquid product. the Following the consumer's request for simple dosing, in addition to these two classic variants products in pre-portioned form established in the market and are in the state of the art Technique also comprehensively described, wherein in particular compressed molded articles, ie tablets, Blocks, briquettes and the like, and sachets packed in sachets solid or liquid Washing and cleaning agents are mentioned.

Although such pre-portions facilitate the dosage of the corresponding washing and Detergent, however, does not relieve the consumer of the need to wash and Separate detergent for each washing and cleaning cycle separately, wherein This dosage usually includes a series of operations, in addition to the selection of the desired washing and cleaning agent and the removal of an outer packaging and the Insert the detergent into the washing machine or dishwashing machine. In many cases, the consumer is in direct contact with the appropriate Waschund Exposed to cleaning agents.

The devices for the dosing of active substances, hitherto disclosed in the prior art, especially washing and cleaning substances, often only allow one Single dosage of these substances.

In DE 39 34 123 (Henkel) and DE 39 22 342 (Fischer-Werke, Henkel) detergent receiving containers are described, which are fixedly attached to the laundry drum. This attachment is effected by means of pins or latching hooks. The containers must be removed from the washing machine after each wash cycle and refilled.

EP 0 215 366 describes a detergent container with a melting closure, in which the melting closure melts at a certain operating temperature, whereby the cleaning agent is released. In particular, the closure of the container is not reusable, also a multiple dosing with this system is not possible.

DE 39 02 356 discloses a Dosierspeicher, which can also be used only for a wash cycle, and its operating principle is also based on a temperature-dependent release of the detergent. By a resulting in increasing temperature overpressure in the dispenser a slide valve is moved to its open position and allows the exit of the detergent in the washing machine.

Methods for the multiple dosing of detergents and cleaners are by the state Although the technology also described, but are integrated into the machine and thus to a tied to specific device model.

Thus, the published patent application DE 195 40 608 (Bosch-Siemens) discloses a device for adding block-shaped dishwashing detergents, which allows multiple dosing, wherein the individual dosages are controlled by a command of the dishwasher. A user-selected work program of the dishwasher regulates the time of Dosierfreigabe.

The object of the present application was therefore to provide a metering method for active substances, preferably for active ingredients in the field of detergents and cleaners, which substantially simplifies the metering of these active substances, in particular in a reliable manner the prerequisites for a simple and time-saving repeated metering or Multiple dosing of these active ingredients creates, it was preferred to combine such a multiple dose in addition with mechanisms for the time-delayed release of the active substances (controlled release). The time required for the dosage of the funds should be minimized. The aim was also to provide funds for carrying out such a procedure. The possibility of direct contact of the consumer with the active substance should preferably be avoided. Finally, the process should be as flexible as possible to different requirements in the various conceivable application areas. Also, the means for performing the method should not limit the applicability of the method, in particular not, as in the case of DE 195 40 608 , be bound to a combination with another device.

The subject of the present application is therefore a process for the dosage of active substances and / or active-substance preparations, characterized in that from a water-insoluble container, comprising at least two receiving troughs and at least one (n) in these receiving troughs active ingredient and / or active ingredient preparation, each of these receiving wells is closed by a single water-insoluble protective film, at least one of these water-insoluble protective films is removed and the container so with water or aqueous Solutions or water-containing solutions is brought into contact, that the / the active substance (s) and / or the active ingredient preparation (s) by dispersion and / or dissolution processes in the water or the aqueous solutions or water-containing solutions is / are released.

In such a process form the combination of water insoluble receiving trough and water-insoluble protective film, a dosing unit and it requires pre-portioned for the dosage Active ingredients merely to remove a single water-insoluble protective film. By the arrangement of at least two individual receptacles is the possibility of a repeated Dosing of the active ingredients, for example in a second cycle or in the form of a Given multiple dosing. Since an extension of this principle to more than two washing and Cleaning operations is obviously desirable, it is in a preferred embodiment the process of the invention provided that the water-insoluble container not only two but three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty, twenty-one, twenty-two, twenty-three, includes twenty-four or more receiving troughs and each of these receiving troughs is closed by a single water-insoluble protective film.

The aforementioned receiving troughs of the water-insoluble container not only allow the multiple portioning of active ingredients within a container, but allow it For example, to separate active ingredients and / or active substance preparations spatially from each other. This separation may be due, for example, to chemical incompatibility, but as in one the following paragraphs in detail, also with the purpose of controlled release of active substances or active substance preparations. A method characterized is that the water-insoluble container three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty, twenty-one, twenty-two, twenty-three, twenty-four or more receptacles, and respectively two, three, four or more of these receptacles by a single water-insoluble Protective film are therefore excluded in the context of the present application prefers.

According to the methods described above, by removing a single water-insoluble Protective film one or more receiving wells and thus one or more different Washing and cleaning functions, such as pre-, intermediate-, main- and / or rinse-off functions be "activated" during automatic dishwashing. This way you can relax These methods dose both complex substance and active mixtures, as well as simple additives. The dosing method according to the invention can consequently be used both for routine applications (Eg .: dishwashing), which require a constant dosage of certain active substances as well as for special applications (eg corrosion protection), which are not always parallel to such routine operations should be performed. Dosing units for such different Applications can be in accordance with the inventive method both in separate water-insoluble containers as well as in combination in a single such container realize. Furthermore, by means of the method according to the invention also one of the problem (Ex: heavy pollution) oriented multiple dosing by simply removing several water-insoluble protective films possible. Finally, it may be for specific uses but also be advantageous if the used in the process according to the invention Water-insoluble container Dosage units (combination of one or more receiving wells) and associated water-insoluble protective film) characterized by the number of distinguished by the water-insoluble protective film covered receiving troughs. With help of a Such containers can be incompatible active ingredients or active substance preparations or Active substance or mixtures of active substances for different purposes, for example, in a time sequence to be performed in a container combine. (The possibilities The controlled release of active substances will be explained in more detail in a later section.)

The dosing method described above is then particularly time-saving and consumer-friendly and thus in the context of the present application particularly preferred when the water-insoluble Before removing the protective film, the container is fixed inside the device, in which the subsequent contact with the water or the aqueous solution or the water-containing Solution should be done and after removing the protective film during the course of a manual and / or semiautomatic method and / or fully automatic method with water or aqueous Solutions or water-containing solutions is brought into contact. Such an approach Reduces the necessary operations for dosing the active ingredient (s) on the removal of the water-insoluble protective film. In the said device can depending on the field of application of the method according to the invention, for example dishwashing machines, Piping systems, mixers, spraying and pumping devices, storage tanks, Washers or washing machines act. In a further preferred embodiment In the present application, the device is a dishwasher, in the process of a cleaning program. Preferred subject of the present application is thus also a method which is characterized in that the water-insoluble Before removing the protective film, place the container inside a dishwasher and after Remove the protective film during the course of a cleaning program with water or aqueous Solutions or water-containing solutions is brought into contact, depending on the device (dishwasher) may be advantageous, the attachment by a holding device inside this device (dishwasher) or by one on the water-insoluble Container located holding device takes place. The attachment of the holding device in the Machine can be done for example on locking, clamping, plug or snap closures. Also conceivable is the permanent bonding of the holding device, the use of Velcro fasteners or suction cups. The attachment can be made to the inside of the device, the door or the cutlery or crockery baskets. Finally, it is possible to use the water-insoluble dosing container or a second container contained in this container to make it on easy way in a cutlery basket or dish rack can be accommodated.

The holding device described above is not only suitable, the water-insoluble Dosierbehältnis permanently, so at least for the number of feasible by means of the dosing Washing and cleaning operations, but protects in another preferred Embodiment also the water-insoluble dosing container before mechanical effects within the dishwasher, as for example by the rinsing liquor during the cleaning cycle caused. For this purpose, such holding devices are particularly preferred that not only attach the metering container but also clad, where a panel preferably only the part of the water-insoluble Dosierbehältnisses from the outside accessible for the respective cleaning cycle by removing the water-insoluble Protective film should be activated. In such a case, it may be necessary to activate the dosing device by removing the water-insoluble protective film to facilitate, be advantageous the previously described water-insoluble metering container in the holding device relative to this Holding device or a part of this holding device is to move.

Prerequisite for a permanent attachment of the dosing in any device and the repeated use in a dosing process, in addition to the mechanical stability, the preferred by the stability of the dosing itself or a dosing this included holding device is ensured, including the chemical stability of this container or the holding device against external influences of importance. Since the invention semiautomatic dosing the contact of the dosing with water or aqueous Solutions or water-containing solutions involves an obvious need This container made of a water-insoluble material to the possibility of a to ensure repeated use of this container. Plastics, in particular polymers Plastics are among the most versatile materials for manufacturing industrial goods. Important Properties of Kunstoffen are, for example, their high mechanical strength, the favorable ratio of strength and density and high resistance to chemicals. in the Therefore, within the scope of the present invention, a method is preferred, characterized in that in that the water-insoluble container consists of water-insoluble polymers and / or polymer mixtures consists.

The term "polymers" in the context of the present application polymers, Polyadducts and polycondensates summarized.

As polymers in this application are referred to such high molecular weight compounds, whose construction is based on a chain growth mechanism. Preferred polymers are in the context of the present application polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, Polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile and / or polystyrene.

Polyadducts are formed by polyaddition, ie polyreactions in which many times repeating and independent linking reactions of bis- or polyfunctional Educts (monomers) via reactive oligomers eventually polymers arise. preferred Polyadducts are polyurethanes.

Like the polyadducts, polycondensates are formed by repetitive and mutually repeating processes independent linking reactions of discrete oligomers and monomers, but in the Contrary to the polyaddition simultaneously a cleavage of low molecular weight compounds takes place. Preferred polycondensates in the context of the present invention are polyamides, polycarbonates and polyester.

Plastics are characterized by a special versatility also with regard to their processability out. Plastics can also be shaping by extrusion or injection molding be processed as by drawing process. When pulling (thermoforming) is a preheated Plastic sheet or foil between the two parts of the tool, the positive and the negative, introduced and then compressed, whereby the plastic part receives its shape. Similar runs the so-called cold deformation; Here is the plate or foil to be deformed but not preheated. If no negative tool is available, it is called deep drawing. In the context of the present invention, it is now particularly preferred that the water-insoluble Container is a thermoforming mold.

Regardless of the type of molding process has a preferred water-insoluble container depending on the water-insoluble plastic used and the nature of the use of the dosing container has a wall thickness between 5 μm and 2000 μm, preferably between 10 μm and 1000 μm and in particular between 50 μm and 500 μm.

The watertight cover of the receiving trough of the dosing with one or more water-insoluble protective films is a basic requirement for the use of this container for repeated dosing of active substances. For the reasons mentioned above have become also proven for the production of these protective films water-insoluble polymers. In a preferred Embodiment of the method according to the invention consists of the aforementioned water-insoluble Film therefore of water-insoluble polymers and / or polymer blends. For this Polymers and polymer mixtures are subject to the same explanations as already mentioned with regard to made the water-insoluble container forming preferred polymers and polymer blends were. To avoid repetition reference is made to these sections.

To increase the stability (e.g., tear strength), reduce the permeability, or the like To improve the external appearance of these protective films, these can be in a preferred Variant of the method according to the invention be provided with a Metallevampfung or with be connected to a metal foil. The Metallevampfung or the metal foil can be up the receiving trough facing side or facing away from the receiving trough Side of the protective film or on both sides of this protective film.

For visual enhancement or to simplify the method according to the invention it is furthermore preferred to print the water-insoluble films. Refer to possible print motifs thereby using text or symbols on the field of application in which the dosing used is, give information about the ingredients (Ex .: Hazard symbols) or hints on the professional implementation of the procedure. Also decorative or advertising imprints are possible.

In order to minimize the packaging costs, it is advantageous the thickness of said protective film to adapt to the respective procedural requirements. Are preferred in the context of the present Application of water-insoluble protective films having a thickness between 1 μm and 1000 μm, preferably between 5 μm and 500 μm and in particular between 10 μm and 200 μm exhibit.

As described above, form the water-insoluble receiving trough and the covering them water-insoluble protective film one dosing unit. The waterproof sealed in this way Volumes are determined by the size of the receiving wells and may vary depending strongly different from the application of the method according to the invention. As part of In this application, it is preferable that the ones sealed with the water-insoluble protective film Receiving wells a volume of 1 ml to 1000 ml, preferably from 1 ml to 100 ml and especially from 1 ml to 50 ml.

For the advantageous implementation of the method according to the invention is in addition to the by the water-insoluble protective film in the receiving cavity sealed volume and thereby defined amount of an active substance or an active ingredient preparation and the depth of the receiving trough significant. It has been shown that the depth of the receiving trough, in particular however, the ratio of the opening area of the receiving trough to its depth, among others Factors the duration of the solution and / or dispersion process of the active ingredients in the receiving trough affected. Particularly preferred methods according to the invention have now been found characterized in that the quotient of the dimensionless opening area of the receiving troughs and the dimensionless volume of the receiving wells at least 0.1, especially preferably at least 0.2 and in particular at least 0.4.

It should be noted that in the determination of the quotient, although the calculated values for the opening area and the volume of the receiving well are used as dimensionless variables, these calculated values must have the same unit length (Ex: cm ² and cm ³ , or mm ² and mm ³ ).

With regard to the active substances present in the receiving troughs of the water-insoluble container in principle no restrictions are imposed on the present process according to the invention, that is, in addition to solid and gel-like liquid, preferably liquid, non-aqueous active ingredients and / or active substance preparations are present in the receiving troughs. Furthermore, the active substance preparations can be used as dispersions, that is, for example in the form of Suspensions or emulsions are present.

As solid active ingredients and / or active substance preparations are all amorphous, semi-crystalline and / or crystalline substances or substance mixtures, for example in the form of powders, Tablets or extrudates. The confectioning process of the particulate active substance and / or the particulate active substance preparation is responsible for the effectiveness of the method according to the invention not significant. Nevertheless, it is preferred that the particulate located in the receiving wells Active substances by molding processes, such as thermoplastic processes or Pressing process, preferably by spray-drying, granulation, agglomeration, pelleting, Roll compaction, (co) extrusion, crimping, pasting, injection molding, molding, calendering, Crystallization, tabletting or a combination of these methods to assemble, as These methods are characterized by both high flexibility and high reliability. In addition, preferred particulate compounds prepared by said processes may be used Active ingredients / Active substance preparations, one, two, three, four or more phases, wherein these multiphase solid confections, for example, by common tableting various powdery premixes, by coextrusion of various deformable By mass or by gluing different ingredients (e.g., tablet, extrudate and / or Casting) can be obtained. Regarding the spatial form of the above-mentioned confectioning produced solid active ingredients / active substance preparations, it applies only to the compatibility of the dimension of the solids with the dimensions of the receiving well (s) of the water-insoluble container. For example, the solids can be made by compaction or other methods suitable for the receiving troughs or parts of these Receiving troughs (bottom plate, side plate) are made. Finally, it is possible the Kompaktate produce within the wells, for example by tableting in the receiving trough. Furthermore, the receiving troughs or parts of the receiving troughs with liquid Active substances or active substance preparations, which are subsequently solidified, Solidify crystallization or similar processes. Both through the tableting and through the molding can be realized in addition to single-phase and multiphase mixtures of substances become. Finally, the combination of particulate substances with compactates and / or by solidification or crystallization solidified substances in the context of the invention Dosing process preferred type of packaging of active ingredients or active substance preparations. For example, it is advantageous to seal a receiving trough containing particulate or gel-like active substances or active substance preparations, by pouring on and then Solidification of a fusible substance or the incorporation of compacts (tablets, Extrudates, etc.) in powdered, gelatinous and / or waxy active substances or active substance mixtures, for example, by pressing or sticking, wherein the inserted compactates preferably an added benefit, for example by (delayed release) release of a provide additional active substance.

The term "gel-like" active ingredients and / or active-substance preparations are used in the context the present application viscous and highly viscous substances or mixtures of substances summarized to dimensionally stable gels, which understood as "dimensionally stable" such preparations which have an intrinsic dimensional stability which enables them, under usual conditions the manufacture, storage, transport and handling by the consumer to have a stable, non-disintegrating spatial form against breakage and / or pressure, which does not change even under the conditions mentioned for a long time, that is under the usual conditions of manufacture, storage, transport and handling by the consumer in the spatio-geometric shape resulting from the production persists, or after the end of the action of an external under the conditions of manufacture, the storage, transport and handling usual force, in these spatial geometric Form returns. The viscosity of the gel-like active substances and / or active substance preparations can by standard methods (for example, Brookfield LVT-II viscometer at 20 U / min and 20 ° C, spindle 3) are measured and is in the case of gel-like active substances and / or active mixtures in the context of the present invention at viscosities above or equal to 10000 mPas

In order to adjust the desired viscosities of such gels, it is within the scope of the present invention Invention, as thickening agent contains one or more thickening agents. preferred Thickeners are, for example, substances from the group agar-agar, carrageenan, tragacanth, Gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, Starch, Dextrins, Gelatin, Casein, Carboxymethylcellulose, Kernmehlether, Polyacryl- u. Polymethacrylic Conn., Vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, Clay minerals such as montmorillonites, zeolites and silicas in the active ingredients and / or To incorporate active mixtures, wherein it has proved to be particularly advantageous if this Gels the thickener in amounts between 0.2 and 8 wt .-%, preferably between 0.3 and 6 Wt .-% and particularly preferably between 0.4 and 4 wt .-% based on the total weight of the active substance or the active substance preparation.

Naturally derived polymers used as thickening agents in the context of the present invention are preferably used, as described above, for example, agar-agar, carrageenan, Tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, Starch, dextrins, gelatin and casein. Preferred modified natural products come from especially from the group of modified starches and celluloses, examples being carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propyl cellulose, and gum ethers called.

A large group of thickeners, widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, Vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes. Thickeners from these classes of compounds are commercially available and are widely available for example under the trade names Acusol®-820 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral® GT-282-S (alkyl polyglycol ether, Akzo), Deuterol® polymer 11 (dicarboxylic acid copolymer, Schöner GmbH), Deuteron® XG (Anionic heteropolysaccharide based on β-D-glucose, D-mannose, D-glucuronic acid, more beautiful GmbH), Deuteron®-XN (nonionic polysaccharide, Schöner GmbH), Dicrylan®-thickener-O (Ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA®-81 and EMA®-91 (Ethylene-maleic anhydride copolymer, Monsanto), thickener-QR-1001 (polyurethane emulsion, 19-21% in water / diglycol ether, Rohm & Haas), Mirox®-AM (anionic Acrylic acid-acrylic acid ester copolymer dispersion, 25% in water, Stockhausen), SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo®-S (high molecular weight polysaccharide, stabilized with formaldehyde, Shell) and Shellflo®-XA (xanthan biopolymer, with Stabilized formaldehyde, Shell).

Due to their manufacturing process, as well as to optimize their dissolution and / or dispersion behavior For example, preferred gel forms may contain various solvents, wherein active ingredients or active substance preparations have proved to be particularly advantageous, the Water and / or one or more water-miscible solvents in amounts of from 25 to 70 Wt .-%, preferably from 30 to 65 wt .-% and particularly preferably from 35 to 60 wt .-% contain. In addition, it has proven particularly advantageous if the water-miscible solvents one or more substances from the group of the group ethanol, n- or i-propanol, n- or sec- or tert-butanol, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, Hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, Ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl, or ethyl ether, diisopropylene glycol monomethyl, or -ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether.

As liquid active ingredients and / or active mixtures are used in the context of the present inventions denotes substances or mixtures of substances with a viscosity below 10000 mPas exhibit. The determination of the viscosity can be carried out by conventional standard methods (for example Brookfield viscometer LVT-II at 20 rpm and 20 ° C, spindle 3).

In the context of the present invention, a method is preferred which is characterized in that the active substance (s) are in solid and / or gel and / or non-aqueous liquid form present in the receiving trough.

As mentioned above, in addition to providing a simple and reliable method for the multiple dosing of active substances, a further object of the present invention in linking such a method with mechanisms for time-controlled Release of active substances and / or active substance preparations (controlled release). It became now found that this object by a preferred in the context of the present invention Method for dosing active substances and / or active substance preparations can be solved characterized in that of a water-insoluble container comprising at least two receiving troughs and at least one (s) located in these receiving troughs Active ingredient and / or active ingredient preparation, each of these receiving wells by a single water-insoluble protective film is sealed and located between the water-insoluble film and the water-insoluble container is a water-soluble and / or water-dispersible film which, after removing the water-insoluble protective film, the receiving trough (s) completely closes, however, on contact with water or aqueous solutions or water-containing Dissolves solutions, at least one of these water-insoluble protective films is removed and the container in such a way with water or aqueous solutions or water-containing solutions in Contact is made that the / the active substance (s) and / or the active ingredient preparation (s) by Dispersion and / or dissolution processes in the water or the aqueous solutions or Water-containing solutions is / are released.

In such a process, the release of those in the receiving trough (s) is located Active ingredients / active substance preparations delayed for the period required for the disintegration of the water-soluble and / or water-dispersible film is needed. In a modification of the aforementioned preferred embodiment of the method according to the invention is further a method preferred, which is characterized in that between the water-insoluble film and the water-insoluble container two, three, four or more identical and / or different ones water-soluble and / or water-dispersible films, which after removal of the water-insoluble Completely seal one, two, three or more receiving troughs, However, in contact with water or aqueous solutions or water-containing Resolve solutions.

It is necessary depending on the scope of the method according to the invention or desired different or identical active ingredients and / or active substance preparations To dose time delay, this may be in a further preferred modification of the aforementioned inventive method by different mechanisms or, with others Words, due to different "switches" happen.

• die Zeit, d. h. der Ablauf einer bestimmten Zeit, in der die Wände der formstabilen Hohlkörper und/oder die Kompartimentierungs-Einrichtungen mit einem bestimmten Medium, beispielsweise mit einer wäßrigen Flotte, in Kontakt stehen, wobei eine zuverlässige Zeitsteuerung eine lineare Lösungskinetik voraussetzt;
• die Temperatur, d. h. das Erreichen eines bestimmten Temperaturwertes im Verlauf des Temperaturprofils des Wasch-, Reinigungs- oder Spülvorgangs; die Steuerung über die Temperatur stellt insbesondere bei Geschirrspülmitteln wegen der mit jeder Stufe des Spülvorgangs steigenden Temperatur eine zuverlässige und damit bevorzugte Ausführungsform dar;
• der pH-Wert, d. h. die Einstellung eines bestimmten pH-Wertes im Verlauf eines Wasch-, Reinigungs- oder Spülvorgangs durch Komponenten der waschaktiven, reinigungsaktiven oder spülaktiven Zubereitung oder das Verlassen eines bestimmten pH-Wertes nach Zerfall einer den pH-Wert beeinflussenden oder bestimmenden Komponente;
• die lonenstärke;
• die mechanische Stabilität, welche - in Abhängigkeit von der Zeit, von der Temperatur oder von anderen Parametern - ein die Desintegration bestimmender Faktor sein kann;
• die Permeabilität für eine bestimmte - vornehmlich gasförmige oder flüssige - Komponente; usw..

Possible "switches" which influence the disintegration of the water-soluble film are, in particularly preferred embodiments, physicochemical parameters. Examples thereof, which should not be construed as limiting, are

• the time, ie the passage of a certain time in which the walls of the dimensionally stable hollow body and / or the compartmentalization devices in contact with a certain medium, for example with an aqueous liquor, wherein a reliable timing requires a linear solution kinetics;
• the temperature, ie the achievement of a certain temperature value in the course of the temperature profile of the washing, cleaning or rinsing process; the control over the temperature represents a reliable and therefore preferred embodiment, in particular for dishwashing detergents, because of the rising temperature with each stage of the flushing process;
• the pH value, ie the setting of a specific pH value during the course of a washing, cleaning or rinsing process by components of the detergent-active, cleaning-active or rinse-active preparation or the leaving of a specific pH value after decomposition of a pH influencing or determining agent Component;
• the ionic strength;
• the mechanical stability, which - depending on time, temperature or other parameters - may be a factor determining disintegration;
• the permeability for a particular - primarily gaseous or liquid - component; etc..

The aforementioned parameters are only examples that are not intended to limit the invention.

For the preparation of the water-soluble and / or water-dispersible film are in principle suitable All substances or substance mixtures that can be made up in the form of a film. However, particularly preferred is a method in which the water-soluble and / or water-dispersible Foil of (acetalised) polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, Starch and starch derivative (s), cellulose and cellulose derivative (s), especially methylcellulose and / or mixtures of these substances, this list being exemplary and the The invention is not limiting.

In a further, likewise preferred embodiment, it is advantageous according to the invention if the film (s) contains one or more materials from the group of acrylic acid-containing polymers, polyacrylamides, Oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters and polyethers and their mixtures include / include.

• Mischungen aus 50 bis 100 % Polyvinylalkohol oder Poly(vinylalkohol - co - vinylacetat) mit Molekulargewichten im Bereich von 10.000 bis 200.000 g/mol und Acetatgehalten von 0 bis 30 Mol-%; diese können Verarbeitungszusätze wie Weichmacher (Glycerin, Sorbit, Wasser, PEG usw.), Gleitmittel (Stearinsäure und andere Mono-, Di- und Tricarbonsäuren), sogenannte "Slipmittel" (z. B. "Aerosil"), organische und anorganische Pigmente, Salze, Blasformmittel (Citronensäure-Natriumbicarbonat-Mischungen) enthalten;
• Acrylsäure-haltige Polymere, wie z.B. Copolymere, Terpolymere oder Tetrapolymere, die mindestens 20 % Acrylsäure enthalten und ein Molekulargewicht von 5.000 bis 500.000 g/mol besitzen; als Comonomere sind besonders bevorzugt Acrylsäureester wie Ethylacrylat, Methylacrylat, Hydroxy-ethylacrylat, Ethylhexylacrylat, Butylacrylat, und Salze der Acrylsäure wie Natriumacrylat, Methacrylsäure und deren Salze und deren Ester wie Methylmethacrylat, Ethylmethacrylat, Trimethylammoniummethylmethacrylatchlorid (TMAEMC), Methacrylat-amidopropyl-trimethylammoniumchlorid (MAPTAC). Weitere Monomere wie Acrylamid, Styrol, Vinylacetat, Maleinsäureanhydrid, Vinylpyrrolidon sind ebenfalls mit Vorteil verwendbar;
• Polyalkylenoxide, bevorzugt Polyethylenoxide mit Molekulargewichten von 600 bis 100.000 g/mol und deren durch Pfropfcopolymerisation mit Monomeren wie Vinylacetat, Acrylsäure und deren Salzen und deren Estern, Methacrylsäure und deren Salzen und deren Estern, Acrylamid, Styrol, Styrolsulfonat und Vinylpyrrolidon modifizierte Derivate (Beispiel: Poly-(ethylenglykol - graft - vinylacetat). Der Polyglykol-Anteil sollte 5 bis 100 Gew.-% betragen, der Pfropfanteil sollte 0 bis 95 Gew.-% betragen; letzterer kann aus einem oder aus mehreren Monomeren bestehen. Besonders bevorzugt ist ein Pfropfanteil von 5 bis 70 Gew.-%; dabei sinkt die Wasserlöslichkeit mit dem Pfropfanteil;
• Polyvinylpyrrolidon (PVP) mit einem Molekulargewicht von 2.500 bis 750.000 g/mol;
• Polyacrylamid mit einem Molekulargewicht von 5.000 bis 5.000.000 g/mol;
• Polyethyloxazolin und Polymethyloxazolin mit einem Molekulargewicht von 5.000 bis 100.000 g/mol;
• Polystyrolsulfonate und deren Copolymere mit Comonomeren wie Ethyl-(meth-)acrylat, Methyl-(meth-)acrylat, Hydroxyethyl(meth-)acrylat, Ethylhexyl(meth-)acrylat, Butyl(meth-)acrylat und den Salzen der (Meth-) Acrylsäure wie Natrium-(meth-)acrylat, Acrylamid, Styrol, Vinylacetat, Maleinsäureanhydrid, Vinylpyrrolidon; der Comonomer-Gehalt sollte 0 bis 80 Mol-% betragen, und das Molekulargewicht sollte im Bereich von 5.000 bis 500.000 g/mol liegen;
• Polyurethane, insbesondere die Umsetzungsprodukte von Diisocyanaten (z. B. TMXDI) mit Polyalkylenglykolen, insbesondere Polyethylenglykolen des Molekulargewichts 200 bis 35.000, oder mit anderen difunktionellen Alkoholen zu Produkten mit Molekulargewichten von 2.000 bis 100.000 g/mol;
• Polyester mit Molekulargewichten von 4.000 bis 100.000 g/mol, basierend auf Dicarbonsäuren (z.B. Terephthalsäure, Isophthalsäure, Phthalsäure, Sulfoisophthalsäure, Oxalsäure, Bernsteinsäure, Sulfobernsteinsäure, Glutarsäure, Adipinsäure, Sebacinsäure usw.) und Diolen (z.B. Polyethylenglykole, beispielsweise mit Molekulargewichten von 200 bis 35.000 g/mol);
• Celluloseether/ester, z.B. Celluloseacetate, Cellulosebutyrate, Methylcellulose, Hydroxypropylcellulose, Hydroxyethylcellulose, Methylhydroxypropylcellulose usw.;
• Polyvinylmethylether mit Molekulargewichten von 5.000 bis 500.000 g/mol.

With particular advantage, one or more materials may be cited from the following illustrative but non-limiting list:

• Mixtures of 50 to 100% polyvinyl alcohol or poly (vinyl alcohol-co-vinyl acetate) having molecular weights in the range of 10,000 to 200,000 g / mol and acetate contents of 0 to 30 mol%; these may include processing additives such as plasticizers (glycerine, sorbitol, water, PEG, etc.), lubricants (stearic acid and other mono-, di- and tricarboxylic acids), so-called "slip agents" (eg "Aerosil"), organic and inorganic pigments, Salts, blowing agents (citric acid-sodium bicarbonate mixtures);
• Acrylic acid-containing polymers, such as copolymers, terpolymers or tetrapolymers, which contain at least 20% of acrylic acid and have a molecular weight of 5,000 to 500,000 g / mol; Particularly preferred comonomers are acrylates such as ethyl acrylate, methyl acrylate, hydroxyethyl acrylate, ethylhexyl acrylate, butyl acrylate, and salts of acrylic acid such as sodium acrylate, methacrylic acid and their salts and their esters such as methyl methacrylate, ethyl methacrylate, trimethylammonium methylmethacrylate chloride (TMAEMC), methacrylate-amidopropyltrimethylammonium chloride (MAPTAC ). Other monomers such as acrylamide, styrene, vinyl acetate, maleic anhydride, vinyl pyrrolidone are also useful with advantage;
• Polyalkylene oxides, preferably polyethylene oxides having molecular weights of 600 to 100,000 g / mol and their derivatives by graft copolymerization with monomers such as vinyl acetate, acrylic acid and their salts and their esters, methacrylic acid and its salts and their esters, acrylamide, styrene, styrenesulfonate and vinylpyrrolidone modified derivatives (Example: The amount of polyglycol should be from 5 to 100% by weight, the amount of graft should be from 0 to 95% by weight, the latter being composed of one or more monomers Graft content of from 5 to 70% by weight, in which case the solubility in water drops with the grafting component;
• Polyvinylpyrrolidone (PVP) having a molecular weight of 2,500 to 750,000 g / mol;
• Polyacrylamide having a molecular weight of 5,000 to 5,000,000 g / mol;
• Polyethyloxazoline and polymethyloxazoline having a molecular weight of 5,000 to 100,000 g / mol;
• Polystyrenesulfonates and their copolymers with comonomers such as ethyl (meth) acrylate, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, butyl (meth) acrylate and the salts of (meth) ) Acrylic acid such as sodium (meth) acrylate, acrylamide, styrene, vinyl acetate, maleic anhydride, vinylpyrrolidone; the comonomer content should be 0 to 80 mol%, and the molecular weight should be in the range of 5,000 to 500,000 g / mol;
• Polyurethanes, in particular the reaction products of diisocyanates (eg TMXDI) with polyalkylene glycols, in particular polyethylene glycols of molecular weight 200 to 35,000, or with other difunctional alcohols to products with molecular weights of 2,000 to 100,000 g / mol;
• Polyesters having molecular weights of 4,000 to 100,000 g / mol, based on dicarboxylic acids (eg terephthalic acid, isophthalic acid, phthalic acid, sulfoisophthalic acid, oxalic acid, succinic acid, sulfosuccinic acid, glutaric acid, adipic acid, sebacic acid etc.) and diols (eg polyethylene glycols, for example with molecular weights of 200 to 35,000 g / mol);
• Cellulose ethers / esters, eg, cellulose acetates, cellulose butyrates, methylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, methylhydroxypropylcellulose, etc .;
• Polyvinyl methyl ether with molecular weights of 5,000 to 500,000 g / mol.

Consider particularly preferred embodiments of the water-soluble films according to the invention also, that with particular advantage - although not mandatory - the in the receiving troughs contained active ingredients and / or active substance preparations by a - preferably controllable - water solubility of the film material at a certain point in time of the washing, Cleaning or rinsing, for example, when reaching a certain temperature, or upon reaching a certain pH or ionic strength of the wash liquor or also fed into the aqueous liquor due to other controllable events or conditions can be.

The quality of the material as well as its quantity / strength take on these solubility properties direct influence. It is therefore within the scope of the present invention, such a method particularly preferred, which is characterized in that the thickness of the water-soluble Film between 1 .mu.m and 1000 .mu.m, preferably between 5 .mu.m and 500 .mu.m and in particular between 10 .mu.m and 200 .mu.m. Different film thicknesses with the goal of a delayed Release of active substances and / or active substance preparations can also be advantageous, for example by the multiple sealing of one or more receiving wells by means of one or more realize several identical or different water-soluble films. The thickness of the water-soluble Film in the sense of the present invention then results as the sum of the thicknesses the one receiving trough sealing, superimposed water-soluble individual sheets.

Particularly preferred are materials for the water-soluble films, which are - a certain, the Stability with determining thickness - at certain temperatures, pH values, Lonenstärken, or solve after a certain residence time in the aqueous liquor. It can be a such dissolving process, the film as a whole or only a part of it, so that parts release the foil when setting a specific combination of parameters, while other parts not yet (but later) or not at all. The latter can be different Quality of the material as well as by different amounts of material (thickness) or also different geometries of the water-insoluble container can be achieved. For example it is possible through the outer shape of the water-insoluble container to the water access complicate and thus delay the dissolution process. In another preferred embodiment It is possible, the foils of different thicknesses (nevertheless of the same material) too design and thus allow earlier dissolving at the thinner areas. Be such different thickness water-soluble films to cover different receiving troughs used, the active substances contained in these receiving wells to different Times released. In a further likewise preferred embodiment, the films are made of materials of different water solubility, for example Polyvinalalkoholen (PVAL) with different residual acetate content.

In a particularly preferred embodiment, the water-soluble and / or water-dispersible Foil in addition to the ingredients mentioned also one or more washing and cleaning active Contain substances or consist of these substances (ex .: polyvinyl alcohols as Sheeting and builder). In the former case, for example, washing active, cleaning active or active ingredients which are present in the preparations and which are present only in small amounts are and their uniform incorporation therefore not unproblematic, in the film or a part of the film, for example one which is in the state of washing, cleaning or rinsing dissolves, in which just the active ingredient is needed to be incorporated, thereby it is released into the liquor at the right time when the film is dissolved. An example this may be fragrances in the last phase of the washing or cleaning or rinsing process but also optical brighteners, UV protectants, dyes and other detergent-active, cleansing or rinse-active preparations.

Another in the context of the present application also preferred embodiment of inventive method for semiautomatic dosing in combination with a time controlled release of the active substances and / or active substance preparations, consists in the use of Active substances and / or active substance preparations whose rate of release by dispersion and / or solution processes in water or aqueous solutions or water-containing Solutions are different. Preferred is therefore a method which is characterized that the receiving trough contains at least two active substances and / or active substance preparations whose Release rate by dispersion and / or dissolution processes in the water or the aqueous solutions or water-containing solutions are different. Also by means of Such an embodiment can be controlled in the context of the present invention Release of active ingredients, wherein it is further preferred that the release rate the active ingredients and / or active substance preparations augrund different Solubility, different melting temperature, different coating and / or different spatial arrangement of these active substances in the receiving trough different. It is on it to point out that referred to in the context of the present inventions as active ingredient preparations Mixtures of substances in addition to the actually active substance (s) (Ex .: cleaning active Substance) may optionally contain other materials such as carrier or matrix substances.

According to the above, differences in the rate of release of active substances can be and / or active substance mixtures realize by their different melting temperatures, these different melting temperatures being at the melting temperatures relate to different matrices and / or different coatings. As special preferred in the process according to the invention is the use of meltable or softenable Substances as matrix or coating material for the active substances or active substance preparations. (The term "coating" means in the context of the present invention in addition to the coating of one or more sides or surfaces of an object such as a solid particulate agent, the one complete coating, ie the wrapping of this particulate object. Also the sealing of a receiving trough by a fusible substance by pouring such a substance on a particulate (s) or gel-like active / active-substance preparation is referred to as coating.) According to the Invention preferred fusible substances have a melting point above 30 ° C on. If active ingredient preparations by the inventive method to different Times, for example, during the various rinses of a cleaning process can be released, for example, through the use of various fusible Matrices or coatings are made, which differ in their melting point, wherein the melting points of these substances preferably to the temperature profile of this Cleaning process adapted and the difference of the melting points is sufficient to the separate Dissolve the individual matrices or coatings to ensure. Will the invention Dosing, for example, for the dosage of cleaning agents for the machine dishwashing and continue to be two or more different Matrices or coatings as a carrier material or coating material of active substances and / or active substance preparations with the aim of the time-separated release in the different Matrices or coatings included active ingredients and / or active ingredient preparations used, such substances for the different matrices and / or Coatings preferred with respect to their melting point by at least 5 ° C, preferably differ by 10 ° C, more preferably by 15 ° C and especially by at least 20 ° C, it being further preferred that the melting point of at least one of the fusible Substances that form a matrix or coating below 30 ° C while the melting point of at least one further substance, which is another matrix or coating form, is above 30 ° C.

Is it provided a softenable substance as a matrix for an active ingredient or an active ingredient preparation to be used, this can be made up under the action of heat softenable mass, by the desired further ingredients with this meltable or softenable Mixture mixed and the mixture heated to temperatures in the softening range of this substance and is processed molding at these temperatures. Be the softening substances used as a coating agent, such a coating, for example by dipping, spraying or tumbling in a drum coater or coating pan. Particularly preferred as meltable or softenable substances for the matrices or Coatings waxes, paraffins, polyalkylene glycols, etc. used.

It has proved to be advantageous if the meltable or softenable substances are not sharp defined melting point, as it usually occurs in pure, crystalline substances, but may have a range of several degrees Celsius melting range. The Meltable or softenable substances preferably have a melting range which is between about 45 ° C and about 75 ° C. That is, in the present case, that the melting range within the specified temperature interval occurs and does not designate the width of the melting range. The width of the melting region is preferably at least 1 ° C., preferably about 2 to about 3 ° C.

The above properties are usually met by so-called waxes. Under "Waxing" is understood to mean a number of natural or artificial substances, usually melt above 40 ° C without decomposition and relatively little above the melting point low viscosity and non-stringy. They have a strong temperature-dependent consistency and solubility.

According to their origin, the waxes are divided into three groups, the natural waxes, chemical modified waxes and the synthetic waxes.

Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japan wax, Esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, Ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, Spermaceti, lanolin (wool wax), or raffia fat, mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or microwaxes.

The chemically modified waxes include, for example, hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes are generally polyalkylene waxes or polyalkylene glycol waxes Understood. As meltable or softenable substances for the hardening by cooling Compounds which can also be used are compounds from other substance classes which meet the stated requirements regarding the softening point. As suitable synthetic compounds have For example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, the commercial under the name Unimoll® 66 (Bayer AG). Also suitable are synthetic waxes prepared from lower carboxylic acids and fatty alcohols, for example dimyristyl tartrate, which is available under the name Cosmacol® ETLP (Condea). Conversely, synthetic ones too or partially synthetic esters of lower alcohols with fatty acids from natural sources. In For example, this class of substances includes Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Shellac, for example shellac KPS three-ring SP (Kalkhoff GmbH) is inventively as meltable or softenable substances used.

Likewise to the waxes in the context of the present invention are, for example, the so-called Wax alcohols counted. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols come for example in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent of many natural waxes in front. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, Myristyl alcohol or melissyl alcohol. The envelope of the invention enveloped Solid particles may optionally also contain wool wax alcohols, of which triterpenoid and Steroidal alcohols, for example lanolin, understands, for example, under the trade name Argowax® (Pamentier & Co) is available. Also at least partially as part of the Meltable or softenable substances can be used in the context of the present invention fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only sparingly water-soluble polyalkylene glycol compounds.

Particularly preferred meltable or softenable substances in the masses to be processed are those from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) Polyethylene glycols having molecular weights between 1500 and 36,000 are preferred, those with Molar masses of 2000 to 6000 are particularly preferred and those having molecular weights of 3000 to 5000 are particularly preferred. Also corresponding methods characterized that the plastically deformable mass (s) at least one substance from the group of Polyethylene glycols (PEG) and / or polypropylene glycols (PPG) are / are preferred.

genügen, wobei n Werte zwischen 10 und 2000 annehmen kann. Bevorzugte PPG weisen Molmassen zwischen 1000 und 10.000, entsprechend Werten von n zwischen 17 und ca. 170, auf.Here, according to the invention, masses to be processed are particularly preferred, which contain propylene glycols (PPG) and / or polyethylene glycols (PEG) as sole meltable or softenable substances. Polypropylene glycols which can be used according to the invention (abbreviated PPG) are polymers of propylene glycol which have the following general formula

satisfy, where n can take values between 10 and 2000. Preferred PPG have molecular weights between 1000 and 10,000, corresponding to values of n between 17 and about 170.

Polyethylene glycols (abbreviated to PEG) which can preferably be used according to the invention are polymers of ethylene glycol, those of the general formula H- (O-CH ₂ -CH ₂ ) _n -OH satisfy, where n can take values between 20 and about 1000. The abovementioned preferred molecular weight ranges correspond to preferred ranges of the value n in formula IV of about 30 to about 820 (exactly: from 34 to 818), more preferably from about 40 to about 150 (exactly: from 45 to 136). and especially from about 70 to about 120 (exactly: from 68 to 113).

In a further preferred embodiment, the invention to be processed contain Masses in the majority of paraffin wax. That is, at least 50% by weight of the total contained meltable or softenable substances, preferably more, of paraffin wax consist. Particularly suitable are paraffin wax contents (based on the total amount of melt or softenable substances) of about 60% by weight, about 70% by weight or about 80% by weight, wherein even higher levels of, for example, more than 90 wt .-% are particularly preferred. In a particular embodiment of the invention, the total amount of the melt used or softenable substances of at least one mass exclusively of paraffin wax.

Paraffin waxes have, compared to the other mentioned, natural waxes in the context of present invention has the advantage that in an alkaline detergent environment no hydrolysis the waxes take place (as is to be expected, for example, in the case of wax esters) Paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C, more preferably of more than 60 ° C on. shares refractory alkanes in paraffin can fall below this melting temperature in the Detergent liquor unwanted wax residue on the surfaces to be cleaned or leave the goods to be cleaned. Such wax residues usually lead to an unsightly Appearance of the cleaned surface and should therefore be avoided.

Preferably to be processed masses contain as meltable or softenable substances at least a paraffin wax having a melting range of 50 ° C to 60 ° C, preferred methods characterized in that the deformable mass (s) comprises a paraffin wax a melting range of 50 ° C to 55 ° C contains / contain.

Preferably, the content of the paraffin wax used is at ambient temperature (in the Usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible. The more solid wax components are present in a wax at room temperature, the more useful it is within the scope of the present invention. With increasing proportion of solid wax components increases the load capacity of the process end products against shocks or friction on others Surfaces on, resulting in a longer-lasting protection. High levels of oils or liquid Wax components can lead to a weakening of the molded bodies or molded body areas, whereby pores are opened and the active ingredients the aforementioned environmental influences get abandoned.

The meltable or softenable substances can in addition to paraffin as the main component or another or more of the above-mentioned waxes or waxy substances. In a Another preferred embodiment of the present invention should be the melting or softenable substances forming mixture be such that the mass and the resulting Shaped body or molded body component are at least largely water-insoluble. The Solubility in water at a temperature of about 30 ° C should not exceed about 10 mg / l, and preferably below 5 mg / l.

In such cases, however, the meltable or softenable substances should be as small as possible Water solubility, even in water at elevated temperature, to have a temperature independent Avoid release of the active substances as much as possible.

Preferred materials to be processed according to the invention are characterized in that they are used as meltable or softenable substances one or more substances with a melting range of 40 ° C to 75 ° C in amounts of 6 to 30 wt .-%, preferably from 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the mass.

Another preferred option for the delayed release of active substances or Active substance preparations is the staggered spatial arrangement of these substances in the receiving trough with the goal of a staggered release. Such a spatially staggered Arrangement is, for example, the layer or phase arrangement of the active substances or active substance preparations, for example, the layered tabletting performed above or the layered pouring liquid active substances or mixtures of active substances and their subsequent solidification by solidification and / or crystallization are suitable. As an access of the solvent to these located in the water-insoluble receptacles active substances or Active substance mixtures can only take place via the opening surface of the receiving trough, this leads layered arrangement for the release of those active substances or mixtures of active substances, which are on the surface of such a multiphase mixture. The phases become consequently removed temporally offset, whose contents are released temporally staggered.

• Einsatz einer oder mehrer wasserlöslicher Folien, wobei diese Folien bevorzugt eine temperaturabhängige Löslichkeit aufweisen.
• Einsatz von Beschichtungen, wobei diese Beschichtungen zum einen anstelle einer wasserlöslichen Folie eine Aufnahmemulde abdecken können, zum anderen aber auch in Form von Beschichtungen von in den Aufnahmemulden befindlichen partikulären Mitteln eingesetzt werden können. Die Beschichtungen können sich untereinander in ihrer Löslichkeit unterscheiden.
• Einsatz von schmelzbaren Matrizes, wobei sich diese in ihrem Schmelzpunkt oder Schmelzbereich unterscheiden.
• Kombinationen der vorgenannten Methoden.

Without limiting the scope of the present invention, the following procedures can be summarized for the time-controlled release of active substances and / or active substance preparations within the scope of the dosing method according to the invention:

• Use of one or more water-soluble films, these films preferably having a temperature-dependent solubility.
• Use of coatings, these coatings can cover a receiving trough instead of a water-soluble film on the one hand, but can also be used in the form of coatings of particulate funds located in the receiving troughs on the other hand. The coatings may differ in their solubility with each other.
• Use of fusible matrices, these differing in their melting point or melting range.
• Combinations of the aforementioned methods.

The methods for the timely release of active substances and / or Of course, mixtures of active substances are not an end in themselves, but serve targeted ones Control of the semiautomatic dosing process subsequent processes. So includes one Program for the automatic cleaning of dishes usually different cleaning cycles, the nature and number of these cleaning cycles by the consumer by means of a program selection can be determined. Examples of such cleaning operations are the pre-wash cycle, Intermediate and main rinses or the rinse cycle. All these different cleaning cycles require appropriate active ingredients for an optimal result of the targeted dosage or active mixtures. Thus, it is preferred in the context of the present invention Number of receptacles available per dosing unit of the number of desired Adjust cleaning cycles, with the timely release of the in the receiving troughs active substances or mixtures of active substances according to the mechanisms described above can be done. Without the detailed listing of the process according to the invention preferably to anticipate dosed active ingredients and without the present invention In the following, some preferred active ingredients are preferred in the case of automatic dishwashing or active substance preparations are described:

Active substance preparations produced by the process according to the invention during the prewash cycle preferably include alkali sources or caustic alkali sources, such as Silicates, carbonates, sodium or potassium hydroxide and / or cobuilders (preferably citric acid) and / or enzymes (preferably lipases or amylases). Preferred active ingredients for the Rinse are, for example, nonionic surfactants.

With regard to the semiautomatically dosed active substances by means of the method according to the invention and / or active ingredient formulations have limitations only in chemical compatibility these substances or mixtures with the. packaging-forming water-insoluble container, the water-insoluble protective film or the other optionally usable water-soluble and / or water-dispersible film. However, preferred are those methods in which the active substance (s) and / or the active substance preparation (s) from the group of paints, Medicines, disinfectants, fertilizers, animal feed, cosmetics, food, plant protection products and / or detergents and cleaners come / come.

A particularly preferred embodiment of the method according to the invention relates however, on the dosage of washing and cleaning active substances and therefore in particular a method characterized in that it is at the / Active substance (s) and / or the active substance preparation (s) (one) washing and cleaning substance (s) which is selected from the group of builders, cobuilders, surfactants, bleaches, Bleach activators, enzymes, dyes, fragrances, electrolytes, pH adjusters, perfume carriers, fluorescers, Hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, Grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, Ironing aids, repellents and impregnating agents, swelling and anti-slip agents and / or UV absorbers.

These preferred ingredients will be described in more detail below.

Builder

By the present inventive method, all commonly in washing and Detergents used, especially silicates, carbonates, organic cobuilders and also the phosphates.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} H ₂ O, 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 is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification 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 do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of the diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

As carbonates, both the monoalkali metal salts and the dialkali metal salts of Carbonic acid and sesquicarbonates may be included in the compositions. Preferred alkali metal ions represent sodium and / or potassium ions. In one embodiment, it may be preferred be, the carbonate and / or bicarbonate at least partially separately as another component or to be added later. Also compounds from, for example, carbonate, silicate and optionally further adjuvants such as anionic surfactants or others, In particular, organic builders, as a separate component in the finished Agents are present.

Of course, a use of the well-known phosphates as builders possible, unless such use should be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates have particular preference of pentasodium or Pentakaliumtriphosphat (sodium or Potassium tripolyphosphate) in the detergents and cleaning agents industry the greatest importance.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits on machine parts or limescale deposits on the items to be washed and also contribute to the cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium phosphate, KDP), KH ₂ PO ₄ , is a white salt of 2.33 gcm ^-3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is

in water under alkaline reaction readily soluble and is prepared by evaporation of a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches 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 with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry.

There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

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

In the context of the present inventions preferred active ingredients or active substance preparations may also contain sodium and / or potassium hydroxide. A waiver of sodium and / or However, potassium hydroxide as the alkali source has proved to be advantageous when used as zinc salts Zinc gluconate, zinc formate and zinc acetate are used.

builders

As organic cobuilders can in the receiving wells in the context of the present invention in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) and phosphonates used become. These classes of substances are described below.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, understood by polycarboxylic acids such carboxylic acids which carry more than one acidity 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), provided such use of ecological reasons, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, methylglycine diacetic acid, sugar acids and mixtures thereof.

The acids themselves can also be used. The acids are next to theirs Builder action typically also the property of an acidifying component and serve thus also for setting a lower and milder pH of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

As a builder further polymeric polycarboxylates are suitable, these are for example the Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70000 g / mol.

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

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol. Because of their superior solubility, this group may again, the short-chain polyacrylates, the molecular weights of 1000 to 10,000 g / mol, and especially preferably from 1200 to 4000 g / mol, have to be preferred.

Particularly preferred in the inventive compositions are both polyacrylates and Copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally further ionic or nonionic monomers used. The Sulfonic acid-containing copolymers will be described in detail below.

i) ungesättigten Carbonsäuren

ii) Sulfonsäuregruppen-haltigen Monomeren

iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

enthalten. However, it is also possible to provide products according to the invention which, as so-called "3in1" products, combine the conventional cleaners, rinse aids and a salt replacement function. For this purpose, automatic dishwashing agents according to the invention are preferred which additionally comprise from 0.1 to 70% by weight of copolymers

i) unsaturated carboxylic acids

ii) sulfonic acid group-containing monomers

iii) optionally further ionic or nonionic monomers

contain.

These copolymers cause the treated with such means tableware at subsequent cleaning operations are much cleaner than tableware, with flushed with conventional means.

As an additional positive effect occurs a shortening of the drying time of the Detergent treated crockery items, i. the consumer can after the expiry of the Cleaning program to take the dishes earlier from the machine and reuse.

The invention is characterized by an improved "cleanability" of the treated substrates later cleaning operations and by a significant reduction in the drying time compared to comparable agents without the use of sulfonic acid-containing polymers.

Drying time in the context of the teaching according to the invention is generally understood to mean the meaning of the word, ie the time that elapses until a dish surface treated in a dishwasher has dried, but in particular the time that elapses, up to 90% with a cleaning or Rinse aid is dried in concentrated or diluted form treated surface.

In the context of the present invention, unsaturated carboxylic acids of the formula I are preferred as the monomer, R ¹ (R ² ) C = C (R ³ ) COOH

in the 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 is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the formula I 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) is preferred.

In the sulfonic acid-containing monomers, those of the formula II are preferred, R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

in 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 is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas IIIa, IIIb and / or IIIc, H ₂ C = CH-X-SO ₃ H H ₂ C = C (CH ₃ ) -X-SO ₃ H HO ₃ SX (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ CH ₃ ) in formula IIa), 2-acrylamido-2-propanesulfonic acid (X = -C ( O) NH-C (CH ₃ ) ₂ in formula IIIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula IIIa), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula IIIb), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C (O) NH-CH ₂ CH (OH) CH ₂ - in formula IIIb), allylsulfonic acid (X = CH ₂ in formula IIIa), methallylsulfonic acid (X = CH ₂ in formula IIIb), allyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula IIIa), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula IIIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid (X = CH ₂ in formula IIIb), styrenesulfonic acid (X = C ₆ H ₄ in formula IIIa), vinylsulfonic acid (X not present in formula IIIa), 3-sulfopropyl acrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula IIIa), 3-sulfopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula IIIb), sulfomethacrylamide (X = -C (O) NH- in formula IIIb), sulfomethylmethacrylamide (X = -C (O) NH-CH ₂ - in formula IIIb) and water-soluble salts of said acids.

As further ionic or nonionic monomers are in particular ethylenic unsaturated compounds into consideration. The content is preferably according to the invention used polymers of monomers of the group iii) less than 20 wt .-%, based on the Polymer. Particularly preferred polymers to be used consist only of monomers of Groups i) and ii).

i) ungesättigten Carbonsäuren der Formel I. R¹(R²)C=C(R³)COOH in der R¹ bis R³ unabhängig voneinander für -H -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, einoder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,

ii) Sulfonsäuregruppen-haltigen Monomeren der Formel II R⁵(R⁶)C=C(R⁷)-X-SO₃H in der R⁵ bis R⁷ unabhängig voneinander für -H -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-

iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

besonders bevorzugt.In summary, copolymers are made of

i) unsaturated carboxylic acids of the formula I. R ¹ (R ² ) C = C (R ³ ) COOH in the 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) sulfonic acid group-containing monomers of the formula II R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H in the 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 is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers

particularly preferred.

i) einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure

ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln IIIa, IIIb und/oder IIIc: H₂C=CH-X-SO₃H H₂C=C(CH₃)-X-SO₃H HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-

iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren.

Particularly preferred copolymers consist of

i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid

ii) one or more sulfonic acid group-containing monomers of the formulas IIIa, IIIb and / or IIIc: H ₂ C = CH-X-SO ₃ H H ₂ C = C (CH ₃ ) -X-SO ₃ H HO ₃ SX (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers.

The copolymers according to the invention in the compositions can be selected from the monomers of the Groups i) and ii) and optionally iii) in varying amounts, all Representatives from group i) with all representatives from group ii) and all representatives from group iii) can be combined. Particularly preferred polymers have certain Structural units, which are described below.

Thus, for example, agents according to the invention are preferred, which are characterized in that they contain one or more copolymers, the structural units of the formula IX - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. Copolymerizing the sulfonic acid-containing acrylic acid derivative with methacrylic acid, one arrives at another polymer whose use in the agents according to the invention is also preferred and characterized in that the agents contain one or more copolymers, the structural units of the formula V. - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, agents according to the invention which comprise one or more copolymers which are structural units of the formula VI - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, preferably, also a preferred embodiment of the present invention, just as are preferred agents which are characterized in that they contain one or more copolymers, the structural units of the formula VII - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred agents, which are characterized in that they contain one or more copolymers, the structural units of the formula VIII - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred and to agents which are characterized in that they contain one or more copolymers, the structural units of the formula IX - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In summary, machine dishwashing detergents according to the invention are preferred which comprise one or more copolymers as ingredient b), the structural units of the formulas IV and / or V and / or VI and / or VII and / or VIII and / or IX - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) OY-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In the polymers, the sulfonic acid groups can be completely or partially neutralized present, i. that the acidic hydrogen atom of the sulfonic acid group in some or all Sulfonic acid groups against metal ions, preferably alkali metal ions and in particular against Sodium ions, can be replaced. Appropriate means, which are characterized that the sulfonic acid groups are partially or fully neutralized in the copolymer, are preferred according to the invention.

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

In the case of terpolymers, particular preference is given to those which contain from 20 to 85% by weight of monomer Group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer Group iii).

The molecular weight of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the desired use. Preferred automatic dishwashing agents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

The content of one or more copolymers in the compositions of the invention may vary depending on Purpose and desired product performance vary, with preferred inventive automatic dishwashing detergents are characterized in that they contain the copolymer (s) in amounts of from 0.25 to 50% by weight, preferably from 0.5 to 35% by weight, especially preferably from 0.75 to 20 wt .-% and in particular from 1 to 15 wt .-%.

As already mentioned above, particular preference is given in the compositions according to the invention both polyacrylates and the above-described copolymers of unsaturated Carboxylic acids, sulfonic acid-containing monomers and optionally further ionic or non-ionic monomers. The polyacrylates were higher up described in detail. Particularly preferred are combinations of the above described sulfonic acid-containing copolymers with low molecular weight polyacrylates, for example, in the range between 1000 and 4000 daltons. Such polyacrylates are commercial available under the trade names Sokalan® PA15 and Sokalan® PA25 (BASF).

It has surprisingly been found that in a combination of zinc salts according to the invention, in particular of zinc stearate, zinc oleate, zinc citrate, zinc gluconate, zinc lactate and / or zinc acetate with the above-described sulfonic acid-containing copolymers in a MGSM, the corrosion-inhibiting effect of the zinc salts is markedly enhanced, thus consequently the amount of the zinc salt used can be reduced. In the context of the present invention, preferred automatic dishwashing detergents therefore comprise one or more zinc salts, preferably from the group consisting of zinc stearate, zinc oleate, zinc citrate, zinc gluconate, zinc lactate and / or zinc acetate, as well as one or more sulfonic acid groups. containing copolymers. The preferred weight ratio of zinc salt (calculated on Zn ²⁺ ) to sulfonic acid group-containing copolymer in such a preferred automatic dishwashing detergent is between 20: 1 and 1: 500, in particular between 1: 1 and 1: 400 and particularly preferably between 1:10 and 1: 250th

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As especially suitable have proven copolymers of acrylic acid with maleic acid, the 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Their molecular weight relative to free Acids, is generally 2000 to 100000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution become. The content of the (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.

To improve the solubility in water, the polymers may also be allyl sulfonic acids, such as For example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

Also particularly preferred are biodegradable polymers of more than two various monomer units, for example those containing as monomers salts of acrylic acid and the maleic acid and vinyl alcohol or vinyl alcohol derivatives or salts as monomers of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Other preferred copolymers have as monomers preferably acrolein and Acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, as further preferred builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors. Particularly preferred are polyaspartic acids or their salts and derivatives.

Further suitable builder substances are polyacetals, which are prepared by reaction of dialdehydes with polyol carboxylic acids having 5 to 7 C atoms and at least 3 hydroxyl groups, can be obtained. Preferred polyacetals are selected from dialdehydes such as glyoxal, Glutaraldehyde, terephthalaldehyde and mixtures thereof and from Polyolcarbonsäuren such Gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes be performed. Preferably, they are hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. This is a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, especially from 2 to 30 preferred, wherein DE a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is. Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called Yellow dextrins and white dextrins with higher molecular weights in the range of 2000 to 30,000 g / mol.

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. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable cobuilders. This is ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Further preferred are in Glycerol disuccinates and glycerol trisuccinates are also linked to this context. Suitable quantities are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

Further useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which at least 4 carbon atoms and at least one hydroxy group and a maximum of two Contain acid groups.

Another class of substances with co-builder properties are the phosphonates these are in particular hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkane phosphonates is the 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular Meaning as a co-builder. It is preferably used as the sodium salt, wherein the disodium salt neutral and the tetrasodium salt alkaline (pH 9). As aminoalkanephosphonates preferably, ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral sodium salts, e.g. B. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. As a builder it is from the class of Phosphonates preferably used HEDP. The aminoalkane phosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may, especially if the Agents also contain bleach, preferably, aminoalkanephosphonates, in particular DTPMP, to use or mixtures of the phosphonates mentioned.

In addition, all compounds that are capable of complexes with alkaline earth ions train as co-builders.

Preferred active ingredients and / or active substance preparations are within the scope of the present invention Notification characterized in that it builders, preferably from the group of Silicates, carbonates, organic cobuilders and / or phosphates in amounts of from 0.1 to 99.5% by weight, preferably from 1 to 95 wt .-%, particularly preferably from 5 to 90 wt .-% and in particular from 10 to 80% by weight, based in each case on the composition.

surfactants

Preferred active ingredients or active substance preparations contain in the context of a preferred Embodiment of the method according to the invention one or more surfactant (s) from the Groups of anionic, nonionic, cationic and / or amphoteric surfactants.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Among fatty acid glycerol esters are the mono-, di- and triesters and their mixtures to understand how they in the Preparation 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 with 6 to 22 Carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, Lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical having an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut- , Palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps may be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available. Preferably, the anionic surfactants are in the form of their sodium or potassium salts, especially in the form of the sodium salts.

Another group of detergent substances are the nonionic surfactants. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferred nonionic surfactants used either alone nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.

Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). Usable Alkypolyglycoside meet the general formula RO (G) _z , in which R is a linear or branched, especially in the 2-position methyl branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4. Preference is given to using linear alkyl polyglucosides, that is to say alkyl polyglycosides which consist of a glucose residue and an n-alkyl chain.

Another class of preferred nonionic surfactants used either alone nonionic surfactant or used in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably having 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-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide be suitable. The amount of these nonionic surfactants is preferably not more than the ethoxylated fatty alcohols, especially not more than half of them.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the formula (X)

wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 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.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder Propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (XI)

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having from 1 to 8 carbon atoms, with 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 propoxylated Derivatives of this residue.

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

In the case of active ingredients or active-product formulations for automatic dishwashing, all surfactants are generally suitable as surfactants. However, the nonionic surfactants described above and, above all, the low-foaming nonionic surfactants are preferred for this purpose. Particularly preferred are the alkoxylated alcohols, especially the ethoxylated and / or propoxylated alcohols. The person skilled in the art generally understands, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention, the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably between C ₁₂ and C ₁₆ , such as, for example, C ₁₁ -, C ₁₂ -, C ₁₃ -, C ₁₄ -, C ₁₅ -, C ₁₆ -, C ₁₇ - and C ₁₈ -alcohols). As a rule, n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions, form a complex mixture of addition products of different degrees of ethoxylation. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Also, if desired, by a final etherification with short-chain alkyl groups, such as preferably the butyl group, the substance class of "closed" alcohol ethoxylates reach, which can also be used in the context of the invention. Very particularly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or mixtures thereof with end-capped fatty alcohol ethoxylates.

in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃; -CH₂CH₃, -CH₂CH₂-CH₃, -CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here, machine dishwashing detergents according to the invention are preferred which contain surfactants of the general formula XII as nonionic surfactant (s)

in which R ^{1 is} 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 of one another are integers from 1 to 6.

The preferred nonionic surfactants of formula XII 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 XII may 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 usually undisplayed, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position in the mixture, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, automatic dishwasher detergents according to the invention are preferred in which R ¹ in formula I is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or -CH (CH ₃ ) ₂ are suitable. Preferred automatic dishwashing agents are characterized in that R ² and R ³ are each a residue -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.

In summary, for use as active ingredients or in active-material formulations in the process according to the invention, particular preference is given to nonionic surfactants which contain 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 exhibit.

Low-foaming nonionic surfactants are used as preferred additional surfactants. The automatic dishwashing compositions of the invention are particularly preferred nonionic surfactant having a melting point above room temperature. As a result, preferred agents are characterized by containing nonionic surfactant (s) with a Melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, included.

In addition to the nonionic surfactants contained in the compositions, nonionic surfactants are suitable which Have melting or softening points in said temperature range, such as low foaming nonionic surfactants which are solid or highly viscous at room temperature could be. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that this has a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Also nonionic surfactants, the waxy consistency at room temperature own, are preferred.

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

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

A particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred active ingredients or active compound formulations contain ethoxylated nonionic surfactant (s) consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 moles, preferably more than 15 Mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was won (n).

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Preferably make such PO units up to 25 wt .-%, particularly preferably up to 20 wt .-% and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant. Especially preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally comprise polyoxyethylene-polyoxypropylene block copolymer units. The alcohol- or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total Molar mass of such nonionic surfactants. Preferred active ingredients or active substance preparations are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the Propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant, contain.

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

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

A further preferred active substance / active substance preparation according to the invention contains nonionic surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ], in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula may 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, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. 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 may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when 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 may be joined 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 selected here by way of example and may well be greater, with the variation width 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 is to R ¹ O [CH ₂ CH (R ³ ) O] _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 is 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 is} H and x assumes values of 6 to 15.

Summarizing the last-mentioned statements, active compounds / active substance preparations are preferred in the process according to the invention, the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

In connection with the surfactants mentioned can also anionic, cationic and / or amphoteric Surfactants are used, these being because of their foaming behavior in machine Dishwashing have only minor importance and mostly only in quantities below from 10% by weight, in most cases even below 5% by weight, for example from 0.01 to 2.5% by weight, in each case based on the agent used. The active ingredients / active substance preparations can Thus, as a surfactant component and anionic, cationic and / or amphoteric surfactants.

In the context of the present inventive method, it is preferred that the Active substances / active substance preparations Surfactant (s), preferably nonionic surfactant (s), in quantities from 0.5 to 10% by weight, preferably from 0.75 to 7.5% by weight, and more preferably from 1.0 to 5 % By weight, based in each case on the total active / active substance preparation.

bleach

Bleaching agents and bleach activators are important constituents of detergents and cleaning agents, and an active substance or an active substance preparation may in the context of the present invention contain one or more substances from the groups mentioned. Among the compounds which serve as bleaches and deliver H ₂ O ₂ in water, sodium percarbonate has particular significance. Further useful bleaching agents are, for example, sodium perborate tetrahydrate and the sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

"Sodium percarbonate" is a term used in unspecified form for sodium carbonate peroxohydrates, which strictly speaking are not "percarbonates" (ie salts of percarbonic acid) but hydrogen peroxide adducts of sodium carbonate. The commercial product has the average composition 2 Na ₂ CO ₃ · 3 H ₂ O ₂ and is therefore no peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm ^-3 , which readily decomposes into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first obtained from solution in 1899 by precipitation with ethanol of sodium carbonate in hydrogen peroxide but erroneously considered as peroxycarbonate. It was not until 1909 that the compound was recognized as a hydrogen peroxide addition compound, Nonetheless, the historical name "sodium percarbonate" has prevailed in practice.

The industrial production of sodium percarbonate is predominantly produced by precipitation from aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide, Kristallisierhilfsmittel (for example, polyphosphates, polyacrylates) and stabilizers are combined and the sodium percarbonate by salting-out agent (mainly sodium chloride) (for example, Mg ²⁺ ions) like. The precipitated salt, which still contains 5 to 12 wt .-% mother liquor is then removed by centrifugation and dried in fluidized bed driers at 90 ° C. The bulk density of the finished product may vary between 800 and 1200 g / l, depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating methods and materials used for coating are widely described in the patent literature. In principle, all commercially available percarbonate types can be used according to the invention, as offered for example by the companies Solvay Interox, Degussa, Kemira or Akzo.

The active substances or active substance preparations can also bleaches from the group of organic Contain bleach. Typical organic bleaches as ingredients in the frame of the present invention, the diacyl peroxides, e.g. Dibenzoyl. Other typical organic bleaches are the peroxyacids, as examples especially the alkyl peroxyacids and the arylperoxy 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 ones or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, Diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid, N, N-Terephthaloyl-di (6-aminopercapronate) can be used.

As a bleaching agent according to the present invention, chlorine or bromine releasing substances be used. Among the suitable chlorine or bromine releasing materials come for example heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, Tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Advantageous active substances or active substance preparations are included within the scope of the present invention one or more bleaching agents, preferably from the group of oxygen or halogen bleaches, in particular the chlorine bleach, with particular preference of sodium percarbonate and / or sodium perborate monohydrate, in amounts of from 0.5 to 40% by weight, preferably from 1 to 30 wt .-%, particularly preferably from 2.5 to 25 wt .-% and in particular from 5 to 20 % By weight, in each case based on the total active / active substance preparation (s).

Bleach activators

To improve the bleaching performance when cleaning at temperatures of 60 ° C and below can achieve active ingredients or active ingredient preparations in the context of the present invention Bleach activators included. As bleach activators, compounds which are under perhydrolysis conditions aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C-atoms, and / or optionally substituted perbenzoic acid, are used become. Suitable substances are the O- and / or N-acyl groups of said C atom number and / or optionally substituted benzoyl groups. Preference is given to multiple acylated Alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or Isononanoyloxybenzolsulfonat (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to or in place of the conventional bleach activators, according to the present invention Invention also incorporated so-called bleach catalysts in the detergents become. These substances are bleach-enhancing transition metal salts or Transition metal complexes such as Mn, Fe, Co, Ru or Mo saline 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 ammine complexes are useful as bleach catalysts.

According to the invention, active substances or active substance preparations are preferred which contain one or more Substances from the group of bleach activators, in particular from groups of multiple acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), of N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), in amounts of 0.1 to 20 wt .-%, preferably from 0.5 to 15 wt .-% and in particular from 1 to 10% by weight, in each case based on the total active substance / active substance preparation (s), contain.

in denen R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist.The bleach activators preferred in the context of the present invention furthermore include the "nitrile quats", cationic nitriles of the formula (XIII),

in which R ^{1 is} -H, -CH ₃ , a C _2-24 -alkyl or -alkenyl radical, a substituted C _2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or represents 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 ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) - CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion.

The general formula (XIII) includes a variety of cationic nitriles useful in the present invention. With particular advantage, the detergent tablets according to the invention comprise cationic nitriles in which R ^{1 represents} methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-butyl Tetradecyl, n-hexadecyl or n-octadecyl stands. R ² and R ³ are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, wherein one or both radicals may advantageously also be a Cyanomethylenrest.

For ease of synthesis, preference is given to compounds in which the radicals R ¹ to R ^{3 are} identical, for example (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^-, (CH ₃ CH ₂ CH _{2) 3} N ⁽⁺⁾ CH ₂ -CN X ^-, (CH ₃ CH (CH _{3)) 3} N ⁽⁺⁾ CH ₂ -CN X ^-, or (HO -CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , where X ^{- is} preferably an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is selected.

In the context of the present invention, preferred active substances or active substance preparations are characterized in that it contains the cationic nitrile of the formula (XIII) in amounts of from 0.1 to 20 Wt .-%, preferably from 0.25 to 15 wt .-% and in particular from 0.5 to 10 wt .-%, respectively based on the total active / active substance preparation.

enzymes

As enzymes are in particular those from the classes of hydrolases such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or others Glykosylhydrolasen and mixtures of the enzymes mentioned in question. All of these hydrolases carry in the laundry to remove stains such as proteinaceous, fatty or starchy stains and graying at. Cellulases and other glycosyl hydrolases may be over it In addition, by removing pilling and microfibrils for color retention and increasing the Softness of the textile contribute. For bleaching or for inhibiting the color transfer can Oxidoreductases are also used. Particularly suitable are from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, as well as enzymatically derived from their genetically modified variants Agents. Preferably, subtilisin-type proteases and in particular proteases, used from Bacillus lentus. These are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic acting Enzymes or protease and cellulase or cellulase and lipase or lipolytic Enzymes or protease, amylase and lipase or lipolytic enzymes or Protease, lipase or lipolytic enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of special interest. Examples of such lipolytic enzymes are known Cutinases.

Peroxidases or oxidases have also proved suitable in some cases. To the appropriate Amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases. The cellulases used are preferably cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof used. That I distinguish different cellulase types by their CMCase and avicelase activities, By targeted mixtures of cellulases the desired activities can be adjusted.

The enzymes may be adsorbed to carriers or embedded in encapsulating substances to them to protect against premature decomposition. Preferred agents according to the invention contain enzymes preferably in the form of liquid and / or solid enzyme preparations, in amounts of from 0.1 to 10 Wt .-%, preferably from 0.5 to 8 wt .-% and in particular from 1 to 5 wt .-%, respectively based on the total active / active substance preparation (s).

dyes

To improve the aesthetic impression of active or Aktivstorfzubereitung, they can dyed with suitable dyes. In the context of the present invention preferred Dyes, the selection of which does not cause any difficulty for the skilled person, have a high level of Shelf life and insensitivity to the other ingredients of the product.

Preferred for use in the process according to the invention are all colorants which are used in the Washing process can be oxidatively destroyed as well as mixtures thereof with suitable blue Dyes, so-called blue toners. It has proved to be advantageous to use dyes which are in Water or at room temperature in liquid organic substances are soluble. Are suitable for example, anionic colorants, e.g. anionic nitrosofarads. A possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1, Part 2: 10020), which is referred to as Commercial product, for example, as Basacid® Green 970 from BASF, Ludwigshafen, available is, as well as mixtures of these with suitable blue dyes. As more colorants come Pigmosol® Blue 6900 (CI 74160), Pigmosol® Green 8730 (Cl 74260), Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamine EB400 (Cl 45100), Basacid® Yellow 094 (Cl 47005), Sicovit® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acid Blue 183), Pigment Blue 15 (Cl 74160), Supranol® Blue GLW (CAS 12219-32-8, Cl Acidblue 221)), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan® Blue (CI Acid Blue 182, CAS 12219-26-0).

When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for the textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, for example the abovementioned Basacid® Green or the abovementioned Sandolan® Blue, colorant concentrations in the range from a few 10 ^-2 to 10 ^-3 % by weight are typically selected. In the case of the particularly preferred, but less readily water-soluble, pigment dyes, for example the abovementioned Pigmosol® dyes, the suitable concentration of the colorant in detergents or cleaners is typically between 10 ^-3 and 10 ^-4 % by weight. ,

fragrances

Fragrances are added to the compositions in the context of the present invention in order to enhance the aesthetic Impression of the products to improve and the consumer in addition to the performance of the product a visually and sensory "typical and unmistakable" product available too put.

As perfume oils or fragrances, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester type, ethers, aldehydes, ketones, Alcohols and hydrocarbons are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl-carbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. For example, the ethers include Benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 C atoms, Citral, Citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the ionone, α-isomethylionone and methyl cedryl ketone, to the alcohols Anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the Hydrocarbons mainly include the terpenes such as limonene and pinene.

However, preference is given to using mixtures of different fragrances which together form a create an appealing scent. Such perfume oils can also be natural fragrance mixtures as 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, lime 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.

Corrosion inhibitors

Active ingredients or active-product formulations for automatic dishwashing may contain corrosion inhibitors for the protection of the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate, as well as the manganese complexes
[Me-TACN) Mn ^IV (m-0) ₃ Mn ^IV (Me-TACN)] ²⁺ (PF ₆ ^- ) ₂ ,
[Me-MeTACN) Mn ^IV (m-0) ₃ Mn ^IV (Me-MeTACN)] ²⁺ (PF ₆ ^- ) ₂ .
[Me-TACN) Mn ^III (m-0) (m-0Ac) ₂ Mn ^III (Me-TACN)] ²⁺ (PF ₆ ^- ) ₂ and
[Me-MeTACN) Mn ^III (m-0) (m-0Ac) ₂ Mn ^III (Me-MeTACN)] ²⁺ (PF ₆ ^- ) ₂ , wherein Me-TACN is 1,4,7-trimethyl-1, 4,7-triazacyclononane and Me-MeTACN stands for 1,2,4,7-tetramethyl-1,4,7-triazacyclononane. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

In the context of the present invention, active substances or active substance preparations are preferred, in addition at least one silver protecting agent selected from the group of triazoles, the Benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, preferably Benzotriazole and / or alkylaminotriazole, in amounts of 0.001 to 1 wt .-%, preferably from 0.01 to 0.5 wt .-% and in particular from 0.05 to 0.25 wt .-%, each based on the / total active / active substance preparation.

In addition to the silver protectants described above, in the context of the present invention Also such compounds referred to as corrosion inhibitors, which is a glass corrosion prevent or reduce it during machine dishwashing. In the context of the present invention, particularly preferred means are the magnesium and / or Zinc salt (s) of monomeric and / or polymeric organic acids, in particular the zinc oleate, zinc stearate, zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate.

Further objects of the present invention are the use of water-insoluble Containers comprising at least two receiving wells and at least one in this Receiving trough active and at least one of these receiving troughs occlusive water-insoluble protective film and at least one between this / these water-insoluble Foil (s) and the water-insoluble container water-soluble film for Dosing of active substances, as well as a water-insoluble container, comprising at least two Receiving troughs and at least one active substance located in these receiving troughs, at least one of these receiving wells completely occlusive water-insoluble film and at least one between this water-insoluble film (s) and the water-insoluble one Container located water-soluble film. Regarding preferred embodiment of the above disclosed use and the disclosed means to avoid repetition, on the description of the method according to the invention and the preferred embodiments there directed. All information given there, in particular with regard to the materials used of water-insoluble container, water-insoluble film, water-soluble film as well their number, size and thickness but also with respect to the holding device apply mutatis mutandis as well as for the use of a water-insoluble container according to the invention for this water-insoluble container itself.

Since according to the above embodiments, the holding device preferred according to the invention is not necessarily an integral part of the water-insoluble container according to the invention, is a
Kit of parts for the dosing of active ingredients, comprising a water-insoluble container according to the invention described above, and a holding device, a further subject of the present application.

Claims (26)

A method of dosing active ingredients and / or active substance preparations, characterized in that each of these receiving troughs is closed by a single water-insoluble protective film of a water-insoluble container, comprising at least two receiving troughs and at least one active substance and / or active substance preparation contained in these receiving troughs at least one of these water-insoluble protective films is removed and the container is brought into contact with water or aqueous solutions or water-containing solutions in such a way that the active substance (s) and / or the active ingredient preparation (s) by dispersion and / or Lösungsvorgänge is released into the water or the aqueous solutions or water-containing solutions. Method according to claim 1, characterized in that the water-insoluble container is three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty, twenty-one, Twenty-two, twenty-three, twenty-four or more receiving troughs and each of these receiving wells is closed by a single water-insoluble protective film. Process according to claims 1 or 2, characterized in that the water-insoluble container is three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty , twenty-one, twenty-two, twenty-three, twenty-four or more receiving troughs, and each two, three, four or more of these troughs are closed by a single water-insoluble protective film. A method according to claim 3, characterized in that the water-insoluble container before removal of the protective film is mounted inside a dishwasher and brought into contact after removal of the protective film at the end of a cleaning program with water or aqueous solutions or water-containing solutions. A method according to claim 4, characterized in that the fastening is effected by a holding device in the interior of the device or by a holding device located on the water-insoluble container. A method according to claim 5, characterized in that the water-insoluble container is to be moved in the holding device relative to this holding device or a part of this holding device. Method according to one of claims 1 to 6, characterized in that the water-insoluble container consists of water-insoluble polymers and / or polymer mixtures. Method according to one of claims 1 to 7, characterized in that the water-insoluble container is a thermoforming mold. Method according to one of claims 1 to 8, characterized in that the wall thickness of the water-insoluble container is between 5 μm and 2000 μm, preferably between 10 μm and 1000 μm and in particular between 50 μm and 500 μm. Method according to one of claims 1 to 9, characterized in that the water-insoluble protective film consists of water-insoluble polymers and / or polymer mixtures. Process according to one of Claims 1 to 10, characterized in that the thickness of the water-insoluble protective film is between 1 μm and 1000 μm, preferably between 5 μm and 500 μm and in particular between 10 μm and 200 μm. Method according to one of claims 1 to 11, characterized in that the receiving wells sealed with the water-insoluble protective film have a volume of from 1 ml to 1000 ml, preferably from 1 ml to 100 ml and in particular from 1 ml to 50 ml. Method according to one of claims 1 to 12, characterized in that the quotient of the dimensionless opening area of the receiving wells and the dimensionless volume of the receiving wells at least 0.1, more preferably at least 0.2 and in particular at least 0.4. Process according to one of Claims 1 to 13, characterized in that the active substance (s) / active substance preparation (s) are present in solid and / or gel and / or nonaqueous-liquid form in the receiving trough. Method according to one of claims 1 to 14, characterized in that there is a water-soluble film between the water-insoluble film and the water-insoluble container, which completely closes the receiving trough (s) after removal of the water-insoluble protective film, but on contact with water or aqueous solutions or water-containing solutions dissolves. Method according to one of claims 1 to 15, characterized in that there are two, three, four or more identical and / or different water-soluble films between the water-insoluble film and the water-insoluble container, which after removal of the water-insoluble protective film one, two, three or more receptacle (s) completely close, but dissolve on contact with water or aqueous solutions or water-containing solutions. Method according to one of claims 15 or 16, characterized in that the water-soluble films differ by their thickness and / or their composition. Process according to one of Claims 15 to 17, characterized in that the thickness of the water-soluble film is between 1 μm and 1000 μm, preferably between 5 μm and 500 μm and in particular between 10 μm and 200 μm. A method according to any one of claims 15 to 18, characterized in that the water-soluble and / or water-dispersible film of (acetalized) Polyvinylakohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, starch and starch derivative (s), cellulose and cellulose derivative (s), in particular methylcellulose, and / or mixtures of these substances. Method according to one of claims 1 to 15, characterized in that the receiving trough contains at least two active substances and / or active substance preparations whose release rate differs by dispersion and / or dissolution processes in the water or aqueous solutions or water-containing solutions. A method according to claim 20, characterized in that the release rate of the active substances and / or the active substance preparations differs due to different solubility, different melting temperature, different coating and / or different spatial arrangement of these active substances in the receiving trough. Method according to one of claims 1 to 21, characterized in that the active substance (s) and / or the active substance preparation (s) from the group of paints, pharmaceuticals, disinfectants, fertilizers, feed, cosmetics, food, plant protection products and / or Detergents and cleaning agents are / are derived. Process according to Claim 22, characterized in that the active substance (s) and / or the active substance preparation (s) contains (a) washing and cleaning substance (s) selected from the group of builders, cobuilders, surfactants, Bleaching agents, bleach activators, enzymes, dyes, fragrances, electrolytes, pH adjusters, perfume carriers, fluorescers, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, crease inhibitors, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Corrosion inhibitors, antistatic agents, ironing aids, repellents and impregnating agents, swelling and anti-sliding agents and / or UV absorbers Use of water-insoluble containers, comprising at least two receiving troughs and at least one active substance contained in this receptacle and at least a water-insoluble protective film occluding these receptacles and at least one between this water-insoluble film (s) and the water-insoluble one Contain container water-soluble film for dosing of active ingredients. Water-insoluble container, comprising at least two receiving wells and at least an active substance contained in these receiving wells, at least one of these Receptacles fully occlusive water-insoluble film and at least one between this water-insoluble film (s) and the water-insoluble container present water-soluble film. A kit of parts for the dosing of active agents, comprising an agent according to claim 26 and a holding device.