DE10254313A1 - Process for the production of filled detergent tablets - Google Patents

Abstract

A large-scale production process for filled moldings, which allows the quick, clean and safe production of filled moldings, comprises the following steps: DOLLAR A a) pressing a particulate premix into a pressed part (basic molded body) which has at least one cavity, DOLLAR A b) filling one or more active substances in liquid, gel-like, pasty or solid form in the said cavity (s), DOLLAR A c) sealing the openings of the (filled) cavities with a foil, DOLLAR A whereby a foil tube or envelope is produced which is placed around the filled tablet.

Description

The present invention relates to a process for the production of filled and then sealed Detergent tablets. It affects in particular a process for the manufacture of filled detergent tablets, which a base molding enclose with a trough, which is filled and closed.

Lately there have been forms of offers for washing or cleaning agents have proven to be advantageous in which different Active substances are localized in different areas. outgoing of the two-layer tablet or multi-chamber bags are in the Literature describes various mixed forms in which tablets with other bodies can be combined, or in which water-soluble or -dispersible Packaging filled with tablets and / or other forms of preparation. A viable way is to provide a hollow mold (for example a tablet with a trough or a through hole, a deep-drawn part made of water-soluble Material, an injection molded part from water soluble Material etc.), which filled and subsequently is sealed, the seal for hollow molds made of polymers plays an outstanding role.

Filled and filled in large series production closed molds, however, have problems. So they can filled hollow body can only be moved with difficulty without the filling partially escaping and on the edges the hollow form the application of adhesion promoters or liability the occlusive Foil difficult. In addition, the application of adhesives to the edges of the Shape prone to failure if the filling is metered in before the adhesive is applied, since the filling Application tools can contaminate.

Shaped bodies in which both temperature- and pressure-sensitive ingredients can be introduced into delimited regions, the size of the delimited region being unrestricted with regard to the overall shaped body and additionally achieving a visual differentiation from conventional two-layer tablets are described in the German patent application DE 199 32 765 A1 (Henkel KGaA). This document also discloses a manufacturing process for the filled moldings.

However, in large series production here too the problems just described. So they can filled moldings can be moved only with difficulty, without the filling partially on the Tablet top emerges and there the application of adhesion promoters or the adhesion of the film difficult. In addition, the order is from Adhesives on the tablet surface prone to failure when filling the adhesive application is metered in, since the filling is the application tools can contaminate. Another problem is the exact cut the film after sticking, as protruding film seams affect the appearance of the tablet.

The present invention was the Based on the task, a large-scale production Manufacturing process for filled hollow or molded body to provide the type described above, which is free of disadvantages mentioned.

• a) Herstellung einer offenen Hohlform („Basisformkörper"), welche mindestens eine Kavität aufweist;
• b) Einfüllen einer oder mehrerer Aktivsubstanzen in flüssiger, gelförmiger, pastöser oder fester Form in die besagte(n) Kavität(en),
• c) Verschließen der Öffnungen der (befüllten) Kavitäten mit einer Folie,

bei dem ein Folienschlauch oder -umschlag hergestellt wird, welcher um die befüllte Tablette gelegt wird.The invention relates to a method for producing detergent tablets by

• a) production of an open hollow mold (“base molding”) which has at least one cavity;
• b) filling one or more active substances in liquid, gel-like, pasty or solid form into said cavity (s),
• c) sealing the openings of the (filled) cavities with a film,

in which a film tube or envelope is produced, which is placed around the filled tablet.

According to the invention, a fillable is first body manufactured. This is then filled and sealed. The production of the fillable body can preferably be made of materials that are used in the washing or Cleaning process one Perform function, the tableting of active substance mixtures is an outstanding Role. However, greater shape variability can result from using materials that are used in washing or Cleaning process none perform specific function. Here have water soluble or dispersible polymers are of outstanding importance. The Disadvantage that additional "ballast" is used, is shaped by the advantage of greater variability and possible ingredients as well as a high aesthetic Claim compensated.

Preferred variants of the method according to the invention are therefore characterized in that the manufacture of the open Hollow mold in step a) pressing a particulate premix to a pressed one Part (base molding), the at least one cavity has comprises.

Another preferred embodiment are methods according to the invention, which are characterized in that the manufacture of the open Hollow mold in step a) by deep drawing and / or casting and / or injection molding and / or blow molding a water soluble or dispersible Polymer or polymer mixture takes place.

Regardless of the type of manufacture the fillable body in the first step of the method according to the invention, open hollow molds are used manufactured, which have at least one cavity. The open according to the invention Can mold are also designed so that they have several cavities, which one after the other or simultaneously with the same or with different Active substances filled become.

Process step a) is explained below using the preferred process variant for producing tablets with cavities:
It has proven to be advantageous if the premix pressed into basic shaped bodies in step a) meets certain physical criteria. Preferred processes are characterized, for example, in that the particulate premix in step a) has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.

The particle size of the in Step a) pressed Premix is sufficient preferably certain criteria: methods in which the particulate premix in step a) particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 μm, are preferred according to the invention. A further restricted particle size in the ones to be compressed Premixing can be used to obtain advantageous molded body properties can be set. In preferred variants for the method according to the invention shows that pressed in step a) particulate Premix a particle size distribution at which less than 10% by weight, preferably less than 7.5 % By weight and in particular less than 5% by weight of the particles larger than 1600 μm or smaller than 200 μm are. Narrower particle size distributions are further preferred here. Particularly advantageous process variants are characterized in that that this pressed in step a) particulate Premix a particle size distribution in which more than 30% by weight, preferably more than 40% by weight and in particular more than 50% by weight of the particles have a particle size between 600 and 1000 μm exhibit.

When performing the procedural step a) is the inventive method not limited to that only a particulate Premix to a shaped body pressed becomes. Rather, the Process step a) also expand to the extent that in in a manner known per se produces multilayered shaped articles by two or prepares several premixes which are pressed together. in this connection will be filled in first Premix slightly pre-compressed, around a smooth top surface that runs parallel to the molded body base to get, and after filling of the second premix to the finished molded article. at three-layer or multi-layer moldings there is a further pre-compression after each premix addition, before the shaped body is finally pressed after the addition of the last premix. The cavity described above is preferably in the base molding Trough, so preferred embodiments of the first method according to the invention are characterized in that in Step a) multi-layer molded articles, which have a trough, manufactured in a manner known per se by mixing several different particulate premixes pressed become.

The moldings according to the invention are produced in step a) first by dry mixing the ingredients, all or part can be pre-granulated and then Inform, in particular pressing into tablets, whereby conventional Procedure can be. The premix is prepared in a so-called die between two stamps into a fixed one Compressed compressed. This process, briefly referred to below as Tabletting is divided into four sections: Dosage, compression (elastic deformation), plastic deformation and expelling.

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

Tableting takes place in standard commercial form Tablet presses, basically with single or double stamps equipped could be. In the latter case, it is not only the upper stamp that builds up pressure used, the lower punch also moves during the pressing process towards the upper stamp during the Upper stamp presses down. For little ones Production quantities are preferably eccentric tablet presses, where the stamp or stamps are attached to an eccentric disc are, in turn, on an axis with a certain rotational speed is mounted. The movement of this ram is with the way of working of a usual Four-stroke engine comparable. The pressing can be done with an upper and lower stamps can be made but also several stamps can be attached to an eccentric disc, the number of die holes is expanded accordingly. The throughputs of eccentric presses vary from a few hundred to depending on the type maximum 3000 tablets per hour.

For one chooses larger throughputs Rotary tablet presses on a so-called die table A larger number of matrices circular is arranged. The number of matrices varies depending on the model 6 and 55, including larger matrices available in the stores are. Each die on the die table is an upper and lower stamp assigned, again the pressure is active only by the Upper or lower stamp, but also built up by both stamps can be. The matrix table and the stamps move by one common vertical axis, using the stamp rail-like curves during of circulation in the positions for filling, Compression, plastic deformation and discharge are brought. In the places where a particularly serious increase or decrease in Stamp is required (filling, Compression, ejection), these cam tracks are replaced by additional low-pressure pieces, low-tension rails and lift tracks supported. The filling the die is made over a rigidly arranged feed device, the so-called filling shoe, the one with a storage container for the Premix is connected. The pressure on the premix is above that compression paths for top and Lower stamp individually adjustable, whereby the pressure build-up by the rolling of the stamp shaft heads on adjustable pressure rollers happens.

Rotary presses can be used to increase the Throughput also with two filling shoes be provided, with only one to produce a tablet Semicircle must be run through. Several filling shoes are used to produce two- and multi-layer molded articles arranged one behind the other without the slightly pressed first Shift before further filling pushed out becomes. Appropriate litigation are on in this way, coated tablets and tablets can also be produced, some have onion skin-like structure, being in the case of the point tablets the top of the core or core layers is not covered and remains visible. Rotary tablet presses are also available can be equipped with single or multiple tools, so that for example an outer circle with 50 and an inner circle with 35 holes simultaneously for pressing to be used. The throughputs modern rotary tablet presses are over one million tablets per Hour.

• – Verwendung von Kunststoffeinlagen mit geringen Dickentoleranzen
• – Geringe Umdrehungszahl des Rotors
• – Große Füllschuhe
• – Abstimmung des Füllschuhflügeldrehzahl auf die Drehzahl des Rotors
• – Füllschuh mit konstanter Pulverhöhe
• – Entkopplung von Füllschuh und Pulvervorlage

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

• - Use of plastic inserts with small thickness tolerances
• - Low number of revolutions of the rotor
• - Big filling shoes
• - Matching the filler paddle speed to the speed of the rotor
• - Filling shoe with constant powder height
• - Decoupling of filling shoe and powder feed

To reduce the build-up of stamps they all offer themselves non-stick coatings known from the art. Particularly advantageous are plastic coatings, plastic inserts or plastic stamps. Rotating punches have also proven to be advantageous, whereby if possible The upper and lower stamps should be rotatable. With rotating Stamping can usually be done without a plastic insert become. The stamp surfaces should be electropolished here.

It continued to show that long pressing times are advantageous. these can with pressure rails, several pressure rollers or low rotor speeds can be set. Because the fluctuations in hardness the tablet should be caused by the fluctuations in the pressing forces Systems are used that limit the pressing force. Here elastic Stamps, pneumatic compensators or spring elements in the force path be used. The pressure roller can also be designed to be resilient.

Preferred methods within the scope of the present invention are characterized in that the Compression in step a) is carried out at pressures from 0.01 to 50 kNcm ^-2 , preferably from 0.1 to 40 kNcm ^-2 and in particular from 1 to 25 kNcm ^-2 .

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

The cavity in the produced in step a) moldings can have any shape. It can cut through the molded body, i.e. an opening have on the top and bottom of the molded body, but it can also be a cavity that does not go through the entire molded body, their opening only on one side of the molding is visible.

The moldings produced according to the invention can be any take on a geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylindrical segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five, hexagonal and octagonal prismatic and rhombohedral shapes preferred are. Completely too irregular base areas like arrow or animal shapes, trees, Clouds etc. will be realized. If the shaped bodies according to the invention have corners and edges, so they are preferably rounded. As an additional optical differentiation is an embodiment with rounded corners and chamfered ("gripped") edges preferred.

Of course, those made in accordance with the invention moldings can also be produced in multiple phases. For reasons of process economy two-layer moldings have proven particularly useful here.

The shape of the cavity can also be in wide limits freely chosen become. For reasons process economics have through holes, their openings on opposite one another surfaces the molded body lying, and troughs with an opening on one side of the molding proven. In preferred laundry detergent and cleaning product tablets, the cavity has the shape a through hole, the openings of which are located at two opposite Molded surfaces are. The shape of such a through hole can be chosen freely, being molded are preferred in which the through hole is circular, elliptical, triangular, rectangular, square, pentagonal, has hexagonal, heptagonal or octagonal horizontal sections. Completely too irregular Hole shapes such as arrow or animal shapes, trees, clouds, etc. can be realized become. As with the moldings are in the case of square holes those with rounded corners and edges or with rounded corners and chamfered edges preferred.

The above geometric Realization forms can be combined with one another as desired. So can moldings with a rectangular or square base and circular holes as well are produced like round shaped bodies with octagonal holes, whereby the variety of possible combinations there are no limits. For reasons of process economy and the aesthetic consumer feeling are shaped bodies with hole particularly preferred in which the shaped body base and the hole cross section have the same geometric shape, for example moldings with a square base and centrally integrated square hole. Particularly preferred are shaped rings, i.e. circular shaped body with a circular hole.

If the above Principle of two opposite Moldings pages open holes on an opening is reduced, mold bodies are obtained. Manufactured according to the invention Detergent tablets, at which the cavity having the shape of a trough are also preferred. As with the "perforated bodies", the produced according to the invention moldings also in this embodiment assume any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylindrical segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five, hexagonal and octagonal prismatic and rhombohedral shapes are preferred. Completely too irregular base areas like arrow or animal shapes, trees, Clouds etc. will be realized. If the molding has corners and edges, so they are preferably rounded. As an additional optical differentiation is an embodiment with rounded corners and chamfered ("chamfered") edges preferred.

The shape of the trough can also be chosen freely, preference being given to shaped bodies in which at least one trough has a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylindrical segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, seven-sided and octagonal-prismatic and rhombohedral in shape. Completely irregular trough shapes such as arrow or animal shapes, trees, clouds, etc. can also be realized. As with the molded bodies, troughs with rounded corners and edges or with rounded corners and chamfered edges are preferred. Trough shapes such as those in the German patent application are particularly preferred DE 198 22 973 A1 (Henkel KGaA), to which express reference is made here.

The size of the trough or the through hole in comparison to the entire molded article depends on the intended use of the molded article. The size of the cavity can vary depending on whether the cavity is to be filled with further active substance and whether a smaller or larger amount of active substance is to be contained. Regardless of the intended use, detergent tablets are preferred in which the volume ratio of molded article to cavity is 2: 1 to 100: 1, preferably 3: 1 to 80: 1, particularly preferably 4: 1 to 50: 1 and in particular 5: 1 to 30: 1. The volume ratio is calculated from the volume of the finished molded body according to the invention, ie the molded body which has the cavity which is closed with the film and the volume of the cavity. The difference between the two volumes results in the volume of the molded body with a cavity in which the cavity is not closed with film. In other words: if the shaped body has an orthorhombic shape with the side lengths 2, 3 and 4 cm and has a trough with a volume of 2 cm ³ , the volume of this “basic shaped body” is 22 cm ^3. This is for calculating the ratio The volume used is 24 cm ³ , since the trough is closed with film and therefore an orthorhombic molded body without a trough is present on the outside. In this example, the ratio of the volumes is therefore 12: 1. With volume ratios of molded body: cavity below 2: 1, which can of course also be implemented according to the invention, the instability of the walls can increase.

Similar statements can be made about the surface proportions that the shaped body with the cavity (“basic shaped body”) or the opening area of the cavity make up on the entire surface of the shaped body. Here, detergent tablets are preferred, in which the area of the openings) of the cavity (en) accounts for 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface of the molded body. The total surface of the molded body again corresponds to the total surface of the molded body with a closed cavity, in the example above that is, regardless of the opening area of the depression 52 cm ^{2. In} such an exemplary shaped body, the openings) of the cavity in preferred embodiments of the present invention therefore have an area of 0.52 to 13 cm ² , preferably of 1.04 to 10.4 cm ² , particularly preferably 1.56 to 7.8 cm ² and in particular 2.08 to 5.2 cm ² .

In step b) the cavity is filled with active substance (s), Active substance mixtures or active substance preparations filled. Unless the cavity is more than an opening has, it is procedurally appropriate, the second, third and any further openings to close to fill in this way technically easier to design. While it is possible in principle, too a ring shaped body to fill first then the top opening to close the hole the molded body including filling turn around and also close the second hole, but this requires mechanical Devices that prevent the filling from falling out. So point the cavity the shaped body produced in step a) has more than one opening, it is preferred to carry out the optional step b) - the filling - only after the (n-1) execution of the Perform step c), if the number of openings n is. The closing the last opening then corresponds to the last time the method step was carried out c), which can be followed by further steps.

The moldings produced according to the invention consist from a base molding, the one or more cavities has, film (s) that seal (s) these cavity (s) and optional in the cavity (s) contained active substance (s). The film materials and preferred physical parameters of the films are described below. There now follows a description of the ingredients of the base molding, the at the same time active substances contained in the cavity are, can be as well as a list of more preferred physical parameter for Basic tablet and filling the cavity. By incorporating certain components, on the one hand, the solubility the filling the cavity targeted acceleration, on the other hand, the release of certain Ingredients from this filling lead to advantages in the washing or cleaning process. Ingredients preferred at least partially in the cavity are localized, for example, those described below Surfactants, enzymes, soil-release polymers, builders, bleaches, bleach activators, Bleaching catalysts, optical brighteners, silver preservatives, etc.

In preferred embodiments of the present invention, the base molding has a high specific weight. Detergent tablets which are characterized in that the base tablet has a density above 1000 kgdm ^-3 , preferably above 1025 kgdm ^-3 , particularly preferably above 1050 kgdm ^-3 and in particular above 1100 kgdm ^-3 are in accordance with the invention prefers.

Process step a) is described below using the second preferred process variant of producing the open hollow mold by deep drawing and / or casting and / or injection molding and / or blow molding of a water-soluble or water-dispersible polymer or polymer mixture:
The production of unfilled hollow bodies by means of shaping processing takes place in accordance with the methods customary in the plastics processing industry, with film production and further processing, blow molding and injection molding being preferred in particular. All processes have in common that a plastic granulate is melted with the help of an extruder and fed to shaping tools.

In a preferred embodiment In the present invention, the melt leaving the extruder blow molded. Suitable according to the invention Blow molding processes include extrusion blow molding, coextrusion blow molding, Injection stretch blow molding and plunge blowing. Leave the wall thickness of the moldings produce different areas by blow molding, by looking at the wall thicknesses the preform, preferably along its vertical axis, accordingly different thicknesses, preferably by regulation the amount of thermoplastic material, preferably by means of a Adjusting spindle forms when the preform is removed from the extruder nozzle.

The powder or liquid-filled solid can one with areas of different outer perimeter and more consistent Wall thickness blow molding by changing the wall thicknesses the preform, preferably along its vertical axis, accordingly different thicknesses, preferably by regulation the amount of thermoplastic material using an adjusting spindle when the preform is removed from the extruder nozzle.

In this way, different geometric configurations of the molded body with and without compartments blow molding. In a single cycle, bottles can be Balls, Santa Clauses, Easter bunnies or other figures blow molds that are filled with funds can.

It is particularly advantageous that the moldings emboss and / or decorate in the blow mold during blow molding. By appropriate design of the blow mold, a motif can be mirrored transferred to the molded body. That way the surface of the shaped body design practically any. For example, the molded body Information such as calibration marks, application notes, hazard symbols, Brands, weight, filling quantity, Apply expiry date, pictures, etc.

The preform and / or the hollow body can tubular, spherical or bubble-shaped his. A spherical one moldings preferably has a shape factor of> 0.8, preferably of> 0.82, preferably> 0.85, more preferably> 0.9 and particularly preferably from> 0.95.

The shape factor in the sense of the present invention can be precisely determined using modern particle measurement techniques with digital image processing. A common method is, for example, the Camsizer ^® system from Retsch Technology or the KeSizer ^® from Kemira. These methods are based on the fact that the bodies are irradiated with a light source and the shaped bodies are recorded, digitized and processed by computer technology as projection surfaces. The surface curvature is determined by an optical measurement method in which the “shadow cast” of the body to be examined is determined and converted into a corresponding form factor. The underlying principle for determining the form factor was described, for example, by Gordon Rittenhouse in "A visual method of estimating two-dimensional sphericity" in the Journal of Sedimentary Petrology, Vol. 13, No. 2, pages 79-81. The measuring limits of this optical analysis method are 15 μm to 90 mm Methods for determining the form factor for larger particles are known to the person skilled in the art and are generally based on the principles of the aforementioned methods.

The walls of the by means of blow molding manufactured hollow body have a wall thickness from between 0.05 - 5 mm, preferably from between 0.06-2 mm, preferably from between 0.07-1.5 mm, more preferably from between 0.08-1.2 mm, more preferably from between 0.09 - 1 mm and most preferably between 0.1-0.6 mm.

The filling opening of the hollow body after filling let yourself in step c) liquid-tight close, it being preferred to have corresponding edges around the blow molding to provide the filling opening ..

In another preferred embodiment In the present invention, the melt leaving the extruder from water soluble Polymer blend processed using an injection molding process. The injection molding takes place according to known procedures at high pressures and Temperatures with the steps of closing the to the extruder injection molding connected mold, injection of the polymer at high temperature and high pressure, cooling of the injection molded molding, opening the Shape and remove the molded blank. Other optional steps such as the application of release agents, demolding etc. Known in the art and can be carried out according to technology known per se.

The advantages of the procedure manufacturing by injection molding lie in the mature technology of this procedure, the high flexibility in terms of the materials that can be used, the ability to have exactly the desired wall thickness s To obtain shaped or dimensionally stable hollow body and the possibility of a dimensionally stable in one step with high reproducibility hollow body with one or more integral compartmentalization device (s) manufacture.

In preferred methods, one up to 5000 bar, preferably between 2 and 2500 bar, particularly preferably between 5 and 2000 bar, more preferably between 10 and 1500 and especially between 100 and 1250 bar injection molded.

The temperature of the material that to be injection molded, is preferably above the melting or softening point of the material and thus also depends on the type and composition of the polymer blend. In preferred methods according to the invention is at temperatures between 100 and 250 ° C, preferably between 120 and 200 ° C and especially injection molded between 140 and 180 ° C.

The tools, the materials record, are preferably preheated and have temperatures above room temperature, with temperatures between 25 and 60 ° C and especially from 35 to 50 ° C are preferred.

Regardless of the material used for the Hollow body but dependent of the ones you want dissolution properties the thickness of the wall can be varied. The wall should be chosen so thin on the one hand that a speedy resolution or disintegration is achieved and the ingredients quickly into the application fleet released, but a certain minimum thickness is also required, the desired shape around the hollow shape Stability, especially dimensional stability, to rent.

Preferred wall thicknesses of injection molded articles are in the range from 100 to 5000 μm, preferably from 200 to 3000 μm, particularly preferably from 300 to 2000 μm and in particular from 500 to 1500 μm.

Regularly, the one made by injection molding moldings not closed walls on all sides and is on at least one of its sides - at a spherical one or elliptical body in the area of part of its shell - open due to manufacturing. Through the remaining opening is / are in the compartment (s) formed inside the molded body (s) one or preparations). This also happens in a way known per se, for example within the confectionery industry known manufacturing processes; in several steps are also conceivable current procedures. A one step process is particularly preferred if in addition to solid preparations liquid components comprehensive preparations (dispersions or emulsions, suspensions) or even gaseous Formulations comprising components (foams) introduced should be.

A film is made during deep drawing appropriate material about a shape, which has recesses, if necessary heated and then pulled into the depression by means of negative pressure. alternative or in addition this can be done by applying pressure from the top or pressed into the mold by a stamp. Preferred wall thicknesses are deep-drawn moldings are in the range from 100 to 5000 μm, preferably from 200 to 3000 μm, particularly preferably from 300 to 2000 μm and in particular from 500 to 1500 μm.

As materials for the hollow body from water-soluble or -dispersible polymers are all polymers, who also for the occlusive Foil can be used. These are described below.

Regardless of whether the open hollow body produced by tableting or by other processes, they are used in step b) of the process according to the invention with active substances) filled. In the case where tablets form the open hollow bodies, you can various active substances can be contained in the tablets. Become the open hollow body produced by other methods, it is also possible that the hollow body already Contains active substance (for example dyes, enzymes, optical brighteners, redispersants, Complexing agents etc., so-called small components), the main amount however, the active substance will be in the filling.

The preferred ones are shown below Ingredients of the basic tablet. Of course can all of the substances mentioned also form part of the filling - during manufacture the hollow form made of water-soluble or dispersible polymers will be the bulk of those listed below Substances in the filling are located. The information below is therefore provided that it is explicitly on "the Base moldings "refer to as" base moldings and / or Filling "to understand.

Within the scope of the present invention are preferably manufactured detergent tablets characterized in that the Basic tablet builders in amounts of 1 to 100% by weight, preferably 5 to 95% by weight, particularly preferably from 10 to 90% by weight and in particular from 20 up to 85 wt .-%, based in each case on the weight of the base molding.

In the manufactured according to the invention Detergent tablets can all common builders used in washing and cleaning agents, in particular So zeolites, silicates, carbonates, organic cobuilders and -wo no ecological There are prejudices against their use - including 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 sheet silicates of the formula given are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

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

Within the scope of the present invention are preferably manufactured detergent tablets characterized in that the Basic tablet Silicate (s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, in amounts of 10 to 60% by weight, preferably from 15 to 50% by weight and in particular from 20 to 40% by weight, in each case based on the weight of the base molding.

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

Of course, there is also a stake of the well-known phosphates possible as builder substances, provided that such use is not avoided for ecological reasons should be. Among the variety of commercially available The alkali metal phosphates have a particular preference for phosphates Pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) of greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid 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 and lime incrustations in fabrics and also contribute to 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, water-soluble powders that lose water of crystallization when heated and at 200 ° C into the weakly acidic 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 (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , 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 easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to the diphosphate Na ₄ P ₂ O ₇ when heated to a greater extent. Disodium hydrogen phosphate is prepared by neutralizing 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 easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 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 ) a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when Thomas slag is heated with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ³ , melting point 94 ° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating 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 formers 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 of which is 1% Solution at 25 ° is 10.4.

Higher mols are formed by condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ . Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. About 17 g of the salt of water free of water of crystallization dissolve in 100 g of water at room temperature, about 20 g at 60 ° and around 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these are accurate such as sodium tripolyphosphate, potassium tripolyphosphate or mixtures usable from these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and are potassium tripolyphosphate and sodium potassium tripolyphosphate usable according to the invention.

Within the scope of the present invention are preferably manufactured detergent tablets characterized in that the Basic tablet Phosphate (s), preferably alkali metal phosphate (s), particularly preferred Pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 20 to 80% by weight, preferably 25 to 75% by weight us in particular from 30 to 70 wt .-%, each based on the weight the basic molded body, contains.

Alkali carriers can be present as further constituents his. As an alkali carrier apply, for example, alkali metal hydroxides, alkali metal carbonates, Alkali metal bicarbonates, alkali metal sesquicarbonates, the aforementioned Alkali silicates, alkali metasilicates, and mixtures of the aforementioned Substances, in the sense of this invention preferably the alkali carbonates, especially sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate be used. A builder system is particularly preferred a mixture of tripolyphosphate and sodium carbonate. Likewise a builder system containing a mixture is particularly preferred from tripolyphosphate and sodium carbonate and sodium disilicate.

Manufactured in a particularly preferred manner Detergent tablets contains the basic molded body Carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably sodium carbonate, in amounts of 5 to 50% by weight, preferably from 7.5 to 40% by weight and in particular from 10 to 30 % By weight, in each case based on the weight of the base molding.

As organic cobuilders in the detergent tablets according to the invention In particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are described below.

Usable organic builders are, for example, those that can be used in the form of their sodium salts polycarboxylic being under polycarboxylic acids such carboxylic acids can be understood that carry more than one acid function. For example these are citric acid, adipic acid, Succinic acid, Glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), unless such use for ecological reasons objectionable, and mixtures of these. Preferred salts are the salts of polycarboxylic acids like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used become. The acids In addition to their builder effect, they typically also have the property an acidifying component and thus also serve to set a lower and milder one pH value of detergents or cleaning agents. In particular, here are citric acid, Succinic acid, glutaric, adipic acid, gluconic and to name any mixtures of these.

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

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

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

Copolymers are also suitable Polycarboxylates, especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been particularly suitable maleic proven to contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative molecular mass, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

To improve water solubility can the polymers also allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as Contain monomer.

Are also particularly preferred biodegradable polymers from more than two different monomer units, for example those which are salts of acrylic acid and monomers the maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Acrylic acid salts and 2-alkylallylsulfonic acid as well as sugar derivatives.

Other preferred copolymers are those that preferably contain acrolein and acrylic acid / acrylic acid salts as monomers or acrolein and vinyl acetate.

Are also preferred as others Builder substances polymeric aminodicarboxylic acids, their salts or their precursors to call. Polyaspartic acids or their salts and derivatives, which in addition to cobuilder properties have a bleach-stabilizing effect.

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

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

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 at C _{6 of} the saccharide ring can be particularly advantageous.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are others suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates are also preferred in this context and glycerol trisuccinates. Suitable amounts are those containing zeolite and / or silicate-containing formulations at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which optionally also in lactone form and which at least 4 carbon atoms and at least one hydroxyl group and maximum two acid groups contain.

Another class of substances with cobuilder properties represent the phosphonates. These are in particular around hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9) reacts. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), Diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reactions Sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta- and octa sodium salt the DTPMP. As a builder, the class becomes the Phosphonates preferably used HEDP. The aminoalkane phosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the agent also bleach contain, be preferred, aminoalkanephosphonates, in particular DTPMP, to use, or to use mixtures of the phosphonates mentioned.

In addition, everyone can Compounds capable of complexes with alkaline earth ions train as cobuilders.

The amount of builders is usually between 10 and 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50 wt .-%, each based on the base molding. In turn the amount of builders used depends on the intended use, so that bleach tablets higher Amounts of builders can have (for example between 20 and 70% by weight, preferably between 25 and 65 wt .-% and in particular between 30 and 55 wt .-%), as for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 to 45% by weight and in particular between 17.5 and 37.5% by weight).

The substances mentioned from the Group of builders and cobuilder can part of course the one in the cavity contained compositions.

Preferred washing and Cleaning tablets also contain one or more surfactants. In the manufactured according to the invention Detergent tablets can anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these are used. Prefers are mixtures from a technical point of view for detergent tablets made of anionic and nonionic surfactants and for detergent tablets nonionic surfactants. The total surfactant content of the moldings is in the case of detergent tablets at 5 to 60 wt .-%, based on the molded body weight, where surfactant levels above 15% by weight are preferred, while Detergent tablets for machine dishwashing preferably contain less than 5% by weight of surfactant (s).

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Among fatty acid glycerol esters are the mono-, di- and triesters and their mixtures to understand how they in the manufacture by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerin be preserved. Preferred sulfonated fatty acid glycerol esters are included 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.

The alkali and, in particular, the sodium salts of the sulfuric acid semiesters are used as alk (en) yl sulfates the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C, s-alkyl sulfates and C, ₂ -C, _S -alkyl sulfates as well as C, ₄ -C, _5- alkyl sulfates are preferred for reasons of washing technology. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

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

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

Other anionic surfactants especially soaps. Saturated fatty acid soaps are suitable, like the salts of lauric acid, myristic, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and especially from natural ones fatty acids, e.g. Coconut, palm kernel or tallow derived soap mixtures.

The anionic surfactants including the Can soaps in the form of their sodium, potassium or ammonium salts and as soluble salts organic bases, such as mono-, di- or triethanolamine, are present. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

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

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

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as they are for example in the Japanese patent application JP 58/217598 or which are preferably produced by the method described in international patent application WO-A-90/13533.

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 alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of 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.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

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

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 0xy-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 propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or a 0xy-alkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this remainder.

[Z] is preferably by reductive Obtained amination of a reduced sugar, for example glucose, Fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy substituted Connections can then for example according to the teaching of international application WO-A-95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

Within the scope of the present invention are preferred detergent tablets in the production of detergent tablets, which contain anionic (s) and nonionic surfactants), where application-related advantages from certain proportions, in which the individual classes of surfactants are used result can.

Thus, for example, are manufactured according to the invention Detergent tablets particularly preferred where the ratio of anionic surfactant (s) to Nonionic surfactant (s) between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2. Prefers are also detergent tablets, the surfactant (s), preferably anionic (s) and / or nonionic surfactant (s), in amounts of 5 to 40% by weight, preferably 7.5 to 35% by weight, particularly preferably from 10 to 30% by weight and in particular from 12.5 to 25% by weight, in each case based on the weight of the molded article, contain.

It can be applied Viewpoint advantages when certain classes of surfactants in some phases the detergent tablets or in the entire tablet, i.e. in all phases, are not included. Another important embodiment The present invention therefore provides that at least one phase of the moldings is free of non-ionic surfactants.

Conversely, the Content of individual phases or of the entire molded body, i.e. all phases certain surfactants have a positive effect. The bringing in the alkyl polyglycosides described above have proven to be advantageous proven so that washing and detergent tablets are preferred in which at least one phase of the shaped body alkyl polyglycosides contains.

Similar as with the nonionic surfactants can also be omitted of anionic surfactants from individual or all phases of washing and detergent tablets result that are for certain areas of application are better suited. It is therefore in the frame of the present invention, detergent tablets are also conceivable, in which at least one phase of the moldings is free from anionic surfactants is.

As already mentioned, the use of surfactants in detergent tablets for machine dishwashing is preferably limited to the use of nonionic surfactants in small amounts. In the context of the present invention, detergent tablets preferably to be produced as detergent tablets are characterized in that the base tablet has total surfactant contents below 5% by weight, preferably below 4% by weight, particularly preferably below 3% by weight and in particular below 2% by weight, based in each case on the weight of the base molding. Usually only weakly foaming nonionic surfactants are used as surfactants in automatic dishwashing detergents. By contrast, representatives from the groups of anionic, cationic or amphoteric surfactants are of lesser importance. The detergent tablets according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In particular in the production according to the invention of detergent tablets or detergent tablets for the machine dishwashing it is preferred that the Detergent tablets contain a nonionic surfactant that has a melting point above Has room temperature. Accordingly, at least one of the deformable contains Masses in the process according to the invention preferably a nonionic surfactant with a melting point above of 20 ° C. Nonionic surfactants to be used preferably have melting points above 25 ° C have, particularly preferably to be used nonionic surfactants Melting points between 25 and 60 ° C, especially between 26.6 and 43.3 ° C.

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

Preferred than at room temperature fixed nonionic surfactants come from the groups of alkoxylated Nonionic surfactants, especially ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants stand out about it good foam control.

In a preferred embodiment The present invention is the nonionic surfactant with a Melting point above room temperature an ethoxylated nonionic surfactant, that from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferred at least 15 moles, especially at least 20 moles of ethylene oxide per Mol alcohol or alkylphenol has emerged.

A particularly preferred nonionic surfactant which is solid at room temperature 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 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide , Among these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

The nonionic surfactant that is solid at room temperature preferably has additional Propylene oxide units in the molecule. Such PO units preferably make up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or Alkylphenols additionally Have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules makes preferably more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such Nonionic surfactants.

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

Nonionic surfactants that can be used with particular preference are, for example, un Available ter the name Poly Tergent ^® SLF-18 from Olin Chemicals.

Another preferred surfactant can be represented by the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ] describe in which R ^{1 represents} 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 denotes values between 0.5 and 1, 5 and y represents a value of at least 15.

Further 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 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. N, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula can be different if x ≥ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = N) or propylene oxide (R ³ = CH ₃ ) units which can be joined together in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula can be used R ¹ 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 stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 represents} H and x assumes values from 6 to 15.

To prevent the decomposition of highly compressed moldings facilitate, it is possible Disintegration aids, so-called tablet disintegrants, in the basic moldings to incorporate to reduce disintegration times. Under tablet disintegrants or decay accelerators are according to Römpp (9th edition, Vol. 6, p. 4440) and Voigt "textbook pharmaceutical technology "(6. Edition, 1987, pp. 182-184) understood auxiliaries for rapid Disintegration of tablets in water or gastric juice and for release of the pharmaceuticals in a resorbable form.

These substances, also because of their Effect called "explosive" medium increase with water ingress their volume, on the one hand increasing their own volume (swelling), on the other hand also about the Release of gases creates a pressure on the tablet can disintegrate into smaller particles. Well-known Disintegration aids include carbonate / citric acid systems, taking other organic acids can be used. Swelling disintegration aids are, for example, synthetic Polymers such as polyvinylpynolidone (PVP) or natural polymers or modified Natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration aids, each based on the weight of the molded body. contains only the base molding Disintegration aids, so refer to the information given only on the weight of the base molding.

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

As a swellable disintegration aid Bentonites or other swellable silicates come in Consideration. Also synthetic polymers, especially those in the hygiene sector superabsorbers or cross-linked polyvinylpyrrolidone used, can be used.

With particular advantage as swellable Disintegration aid polymers based on starch and / or Cellulose used. These basic substances can be used alone or in a mixture with more natural and / or synthetic polymers to swellable disintegrants are processed.

In the simplest case, a cellulosic Material or pure cellulose through granulation, compacting or other application of pressure can be converted into secondary particles, which on contact swell with water and serve as an explosive. As a cellulosic Material wood pulp has proven itself, by thermal or chemical-thermal processes from wood or wood chips (Sawdust, sawmill waste) is accessible. This cellulose material from the TMP process (thermo mechanical pulp) or the CTMP (chemo-thermo mechanical pulp) process can then be used Application of pressure compiled, preferably roller-compensated and be converted into particle form. Of course let yourself completely similarly also use pure cellulose, but from the raw material base is more expensive. Here you can both microcrystalline and amorphous fine cellulose and Mixtures of the same can be used.

Another way is that Cellulose-containing material with the addition of granule auxiliaries to granulate. As pelletizers, for example solutions synthetic polymers or non-ionic surfactants.

To remove residues with those produced according to the invention To avoid washed textiles, the primary fiber length should be the used cellulose or the cellulose in the cellulose-containing material less than 200 μm lie, with primary fiber lengths below 100 μm, especially below 50 μm are preferred. The secondary particles ideally have a particle size distribution where more than 90% by weight of the particle sizes above of 200 μm to have. A certain amount of dust can improve storage stability manufactured tablets contribute. Part of a fine dust part from less than 0.1 mm up to 10% by weight, preferably up to 8% by weight can in those used according to the invention Disintegrant granules are present.

The finely divided cellulose preferably has bulk densities from 40 g / l to 300 g / l, very particularly preferably from 65 g / l to 170 g / l. If already granulated types are used, lies whose bulk density is higher and can be in an advantageous embodiment 350 g / l to 550 g / l. The bulk weights of the cellulose derivatives are typically in the range from 50 g / l to 1000 g / l, preferably in Range of 100 g / l and 800 g / l.

As already stated, leave also use cellulose-based disintegration aids, which contain other active ingredients or auxiliaries besides cellulose. For example, compacted disintegrant granules are suitable from 60 - 99 % By weight not water-soluble, water-swellable cellulose and optionally other modified ones water-swellable polysaccharide derivatives, 1 - 40% by weight at least one polymeric binder in the form of a polymer or copolymer the (meth) acrylic acid and / or their salts, and 0-7 % By weight of at least one liquid, with water-forming surfactants. These disintegrants preferably have a moisture content of 2 to 8% by weight.

The proportion of cellulose in such disintegrant granules is between 60 to 99% by weight, preferably between 60 to 95% by weight. Regenerated celluloses such as viscose can also be used in these explosives. Particularly regenerated celluloses in powder form are characterized by very good water absorption. The viscose powder can be made from cut viscose fiber or by precipitation of the dissolved viscose. Low molecular weight cellulose degraded by electron beam is also suitable, for example, for producing such disintegrant granules. Furthermore, the swellable disintegration aids contained according to the invention in the washing or cleaning agent tablets can contain water-swellable cellulose derivatives such as cellulose ethers and cellulose esters and starch or starch derivatives as well as other swellable polysaccharides and polygalactomannans, for example ionically modified celluloses and starches such as carboxymethyl-modified cellulose and starch, non-ionically modified Starches such as alkoxylated celluloses and starches such as hydroxypropyl and hydroxyethyl starch or hydroxypropyl and hydroxyethyl cellulose and alkyl etherified products such as methyl cellulose as well as mixed modified celluloses and starches from the aforementioned modifications, optionally combined with a modification which leads to crosslinking. Suitable starches are also cold-swelling starches, which are formed by mechanical or degrading reactions on the starch grain. Above all, this includes swelling starches from extruder and drum dryer processes as well as enzymatically, oxidizing or acid-degrading modified products. Chemically derivatized starches preferably contain substituents which are linked to the polysaccharide chains in sufficient numbers by ester and ether groups. Starches which have ionic substituents such as Carboxylate, hydroxyalkyl or phosphate groups have been modified, have proven to be particularly advantageous and are therefore preferred. The use of slightly cross-linked starches has also proven itself to improve the swelling behavior. Alkaline-treated starches can also be used because of their good swellability in cold water. In an advantageous embodiment, the combination of cellulose with cellulose derivatives and / or starch and / or starch derivatives has proven itself. The proportions can vary within wide limits, based on the combination the proportion of cellulose derivatives and / or starch and / or starch derivatives is preferably 0.1 to 85% by weight, particularly preferably 5 to 50% by weight.

As a binder in preferred disintegration aid granules become polymers or copolymers of (meth) acrylic acid or mixtures of such Polymers or copolymers used. The polymers are selected from the group of homopolymers of (meth) acrylic acid, from the group of copolymers with the following monomer components ethylenically unsaturated dicarboxylic acids and / or their anhydrides and / or ethylenically unsaturated sulfonic acids and / or acrylic esters and / or vinyl esters and / or vinyl ethers or their saponification products and / or crosslinking agents and / or graft bases based on polyhydroxy compounds.

Have proven to be particularly suitable uncrosslinked polymers or copolymers of (meth) acrylic acid, with weight-average ones Molecular weights of 5,000 to 70,000 proven. For the copolymers it is preferably copolymers of (meth) acrylic acid and ethylenically unsaturated dicarboxylic acids or their anhydrides, such as maleic acid or maleic anhydride, which, for example, 40 to 90% by weight (meth) acrylic acid and 60 to 10% by weight maleic acid or maleic anhydride contain, whose relative molar mass, based on free acids, between 3,000 and 100,000, preferably 3,000 to 70,000 and very particularly is preferably 5,000 to 50,000. Ter- and quattropolymers have also proven to be suitable binders Proven polycarboxylates, built up from (meth) acrylic acid, maleic acid and optionally fully or partially saponified vinyl alcohol derivatives, or from (meth) acrylic acid, ethylenically unsaturated sulfonic acids and Polyhydroxy units, such as sugar derivatives, or such (Meth) acrylic acid, maleic acid, Vinyl alcohol derivatives and monomers containing sulfonic acid groups.

The polymeric binders will preferably used in the production in the form of their aqueous solutions, but can can also be used in the form of fine powder. The binder polymers are preferably in partially or fully neutralized form, whereby salt formation preferably with cations of alkali metals, ammonia and amines, or their mixtures.

The percentage of polymers / copolymers in preferred disintegrants, between 1 and 40% by weight is preferred between 1 and 20% by weight, particularly preferably between 5 and 15% by weight. Polymer contents above 15% in the disintegrant lead to harder disintegrant granules, while Polymer contents below 1% tend to form soft granules that less abrasion resistant are.

Suitable polymer binders are also cross-linked polymers made from (meth) acrylic acid. They are preferred as finely divided powders are used and preferably have average particle sizes of 0.045 mm to 0.150 mm and are preferably 0.1 to 10% by weight used. Particles with average particle sizes over 0.150 mm also result good disintegrant granules but after dissolving of tablets made with the granules too visually as particles visible source bodies, which, for example, is clearly visible in the case of textile washes the textile in disruptive Deposit way. A special embodiment of the invention provides the combination of soluble Poly (meth) acrylate homo- and copolymers and the aforementioned finely divided crosslinked polymer particles.

Included as another ingredient preferably used disintegrant granules one or more liquid, with Water-gelling surfactants selected from the group of non-ionic, anionic or amphoteric surfactants, which are used in quantities of up to 7% by weight. %, preferably up to 3.5% by weight. If the surfactant content in the explosive is too high, in addition to increased abrasion the tablets made with it also have poor swelling properties.

The nonionic surfactants were detailed above described.

Disintegration aids preferably used according to the invention are characterized by a special swelling kinetics, whereby the expansion depending does not change linearly over time, but reached a very high level after a very short time. The swelling behavior in the first is of particular interest 10 seconds after touch with water. The specific water absorption capacity is preferably used Disintegration aids can be determined gravimetrically and is preferably 500 to 2000 The fluid intake (also as specific porosity preferred) explosive is in a range of over 600 ml / kg, preferably of over 750 ml / kg, especially in the range 800 to 1000 ml / kg.

The production of granulated disintegrant granules is done first by mixing the granulate components with conventional mixing methods. For example can Mixers from Vomm, Lödige, Schugi, Eirich, Henschel or Fukae can be used. With this The first step in mixing and granulating are pre-compounds produced by agglomeration processes.

In the next step, these pre-compounds are mechanically compressed. The condensing under An Pressure can be applied in various ways. The products can be placed between two pressure surfaces in roller compressors, e.g. B. smooth or profiled. The compactate is ejected as a strand. Compaction methods in matrices with punches or cushion rollers result in compact forms such as tablets or briquettes. Roller compactors, extruders, roller or cube presses, but also pelletizing presses can be used as compaction machines.

The has proven to be particularly suitable Compaction with pelleting presses has been proven, using a suitable Litigation of granules are obtained, which are dried without further comminution can. suitable Pelleting presses are e.g. from the companies Amandus Kahl and Fitzpatrick manufactured.

The coarse, compacted particles are crushed, e.g. mills, Schnitzler or roller mills are suitable. The shredding can be done before or after drying carried out become. Can in the drying process preferred water content of 2 - 8 % By weight, preferably 2.5-7 % By weight and particularly preferably 3-5% by weight. Therefor are common Dryers such as Roller dryer (temperatures e.g. from 95 - 120 ° C) or fluid bed dryer (Temperatures e.g. from 70 - 100 ° C).

As a swellable disintegration aid coprocessates which are made of polysaccharide material are also suitable and insoluble Explosives are obtained. As polysaccharide materials are here the above-mentioned substances from the groups powdered cellulose, microcrystalline cellulose and mixtures thereof are particularly suitable; as insoluble Disintegrants come here in particular insoluble polyacrylic acid monopolymer, insoluble Polyacrylamide Monopolymerisat, insoluble Polyacrylic acid polyacrylamide copolymer and mixtures thereof.

The content of each component in these explosives can vary within wide limits, for example from 1 to 60% by weight insoluble polyacrylic product disintegrant and 40 to 99% by weight cellulose. A content of 3 is preferred up to 60 wt .-% insoluble Polyacrylprodukt-explosive and 40 to 97% by weight cellulose. A salary is more preferred from 5 to 30% by weight insoluble Polyacrylic product disintegrant and 70 to 95 wt .-% cellulose. Optional can this disintegrant still contains small amounts of other disintegrants, for example various strengths, Shower mixes e.g. from sodium carbonate and sodium hydrogen sulfate, etc. are added, these amounts by appropriate deductions at the Balanced amount of cellulose i.e. be compensated.

This suitable disintegrant can by coprocessing a cellulose as defined above with a insoluble as defined above Disintegrant by damp or dry compression under pressure be preserved. Under the term "coprocessing" is a dry compression e.g. between opposing Compacting rollers at pressures from 20-60 kN, preferably from 30-50 kN, or wet compaction after adding water, by kneading or pressing wet plastic Masses through a sieve, a perforated disc or via an extruder and then drying Roger that.

The washing and Cleaning tablets can about that addition, both in the base molding as well as in the cavity contain a gas-developing shower system. The gas evolving Shower system can consist of a single substance, which at Contact with water releases a gas. Among these connections The magnesium peroxide is particularly worth mentioning, that on contact releases oxygen with water. Usually there is the gas-releasing one Bubble system, however, in turn from at least two components, that react with each other to form gas. While here a variety of systems conceivable and executable is, for example, nitrogen, oxygen or hydrogen release, the will be used in the detergent tablets according to the invention Bubble system based on both economic as well as ecological Select points of view to let. Preferred shower systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent that is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.

In the case of the alkali metal carbonates or -hydrogen carbonates are the sodium and potassium salts for reasons of cost compared to other salts clearly preferred. Of course, they don't have to pure alkali metal carbonates or bicarbonates used become; rather can Mixtures of different carbonates and hydrogen carbonates are preferred his.

In preferred laundry detergent and cleaning product tablets as a shower system 2 to 20 wt .-%, preferably 3 to 15 wt .-% and in particular 5 to 10% by weight of an alkali metal carbonate or hydrogen carbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10 % By weight of an acidifying agent, in each case based on the total Moldings, used.

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

Are preferred within the scope of the present Invention detergent tablets, in which as an acidifying agent in the shower system a substance from the group of organic di-, tri-and oligocarboxylic or mixtures of these are used.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaches which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidohexanoic acid (peroxycaproic acid), and )], o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, phthalic acids diperoxy-1,9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic acid, the 2-Decyldiperoxybutan- 1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

As a bleaching agent in those produced according to the invention Reinigungsmittelfomkörpern for the machine dishwashing can chlorine or bromine-releasing substances can also be used. Under the appropriate chlorine or bromine-releasing materials come for example heterocyclic N-bromine and N-chloramides, for example trichloroisocyanuric, tribromoisocyanuric, Dibromo isocyanuric acid and / or dichloroisocyanuric (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.

The bleaching agents are made in machine Dishwashing detergents usually in amounts of 1 to 30% by weight, preferably 2.5 to 20% by weight and in particular from 5 to 15% by weight, in each case based on the composition, used. In the context of the present invention, the mentioned proportions on the weight of the base molding.

Bleach activators that have the effect who support bleach, can also be part of the base molding. Known bleach activators are compounds which contain one or more N- or O-acyl groups, like substances from the class of anhydrides, esters, imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylene diamine TAMD and tetraacetylhexylene diamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

As bleach activators, compounds the aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid result can be used. Suitable substances are the O- and / or N-acyl groups of the above Number of carbon atoms and / or optionally substituted benzoyl groups wear. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), enol esters and acetylated sorbitol and mannitol respectively their mixtures (SORMAN), acylated sugar derivatives, in particular Pentaacetylglucose (PAG), Pentaacetylfruktose, Tetraacetylxylose and octaacetyl lactose and acetylated, optionally N-alkylated Glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl. Hydrophilically substituted acylacetals and acyllactams are also preferred. Combinations of conventional ones Bleach activators can be used. The bleach activators are made in machine Dishwashing detergents usual travel in amounts from 0.1 to 20% by weight, preferably from 0.25 to 15% by weight and in particular from 1 to 10% by weight, in each case based on the composition, used. In the context of the present invention, the mentioned proportions on the weight of the base molding.

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

Bleach activators are preferred from the group of multi-acylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonate (or iso-NOBS), n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight up to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 up to 6 wt .-% based on the total agent used.

Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferred selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate in usual Amounts, preferably in an amount up to 5 wt .-%, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01 % By weight to 0.25% by weight, in each case based on the total composition, used. But in special cases more bleach activator can also be used.

Detergent tablets produced according to the invention which are characterized in that the Basic tablet Bleaches from the group of oxygen or halogen bleaches, especially chlorine bleach, with particular preference of sodium perborate and sodium percarbonate, in amounts from 2 to 25% by weight, preferably from 5 to 20% by weight and in particular from 10 to 15% by weight, based in each case on the weight of the base molding, contains are preferred according to the invention embodiment of the present invention.

It is also preferred that the base molding and / or the active substances) contain bleach activators in the cavity. Manufactured according to the invention Detergent tablets, where the base molding Bleach activators from the groups of multiply acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), the N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), in amounts from 0.25 to 15% by weight, preferably from 0.5 to 10 wt .-% and in particular from 1 to 5 wt .-%, each based on the weight of the base molding, contains are also preferred.

The detergent tablets produced according to the invention can in particular in the base molding to protect the dishes or the machine contain corrosion inhibitors, especially Silver protective agents in the field of automatic dishwashing have special meaning. The known substances can be used the state of the art. In general, silver protection agents in particular selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or - complex be used. Benzotriazole are particularly preferred and / or alkylaminotriazole. One finds in cleaner formulations about that out often Active chlorine-containing agents that clearly corrode the silver surface can reduce. Chlorine-free cleaners contain oxygen and nitrogen in particular organic redox-active compounds, such as di- and trihydric phenols, z. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, 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. Prefers here are the transition metal salts, the selected are from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used for prevention corrosion on the wash ware be used.

In the context of the present invention The shaped tablets preferably contain silver protective agents from the group of triazoles, benzotriazoles, bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes, particularly preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.01 to 5% by weight, preferably 0.05 to 4% by weight and in particular from 0.5 to 3% by weight, in each case based on the weight of the base molding.

Of course, the trough filling can also contain silver protection agents included, the base molding either also contains silver protection agents or free of such compounds is.

In addition to the ingredients mentioned above there are further classes of substances for incorporation in washing and cleaning agents. Thus, detergent tablets produced according to the invention are preferred where the base molding one or more substances from the groups of enzymes, Corrosion inhibitors, scale inhibitors, cobuilders, paint and / or Fragrances in a total amount of 6 to 30 wt .-%, preferably of 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the base molding, contains.

In addition to the constituents mentioned, builder, surfactant, disintegration aid, bleach and bleach activator, the detergent tablets according to the invention can be used in detergents. and cleaning agents contain common ingredients from the group of dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

The enzymes in particular come in the base moldings those from the classes of hydrolases such as proteases, esterases, Lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of soiling such as protein, fat or starchy Stains on. Can bleach oxidoreductases can also be used. Are particularly well suited from bacterial strains or mushrooms such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and from their genetically modified variants of enzymatic substances obtained. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. There are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytically active enzymes, in particular however, protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples for such lipolytic acting enzymes are the well-known cutinases. Peroxidases or Oxidases have been found in some cases proven suitable. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.

The enzymes can be adsorbed on carriers or in coating substances embedded to protect them against premature decomposition. The Proportion of the enzymes, enzyme mixtures or enzyme granules can, for example about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight. Preferred detergent tablets are within the scope of the present invention characterized in that the Basic tablet Contains protease and / or amylase.

Farb- und Duftstoffe können den erfindungsgemäßen Wasch- und Reinigungsmittelformkörpern sowohl im Basisformkörper als auch in den in der Kavität enthaltenen Zubereitungen zugesetzt werden, um den ästhetischen Eindruck der entstehenden Produkte zu verbessern und dem Verbraucher neben der Leistung ein visuell und sensorisch "typisches und unverwechselbares" Produkt zur Verfügung zu stellen. Als Parfümöle bzw. Duftstoffe können einzelne Riechstoffverbindungen, z.B. die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden. Riechstoffverbindungen vom Typ der Ester sind z.B. Benzylacetat, Phenoxyethylisobutyrat, p-tert.-Butylcyclohexylacetat, Linalylacetat, Dimethylbenzylcarbinylacetat, Phenylethylacetat, Linalylbenzoat, Benzylformiat, Ethylmethylphenylglycinat, Allylcyclohexylpropionat, Styrallylpropionat und Benzylsalicylat. Zu den Ethern zählen beispielsweise Benzylethylether, zu den Aldehyden z.B. die linearen Alkanale mit 8-18 C-Atomen, Citral, Citronellal, Citronellyloxyacetaldehyd, Cyclamenaldehyd, Hydroxycitronellal, Lilial und Bourgeonal, zu den Ketonen z.B. die Jonone, α-Isomethylionon und Methylcedrylketon, zu den Alkoholen Anethol, Citronellol, Eugenol, Geraniol, Linalool, Phenylethylalkohol und Terpineol, zu den Kohlenwasserstoffen gehören hauptsächlich die Terpene wie Limonen und Pinen. Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen. Solche Parfümöle können auch natürliche Riechstoffgemische enthalten, wie sie aus pflanzlichen Quellen zugänglich sind, z.B. Pine-, Citrus-, Jasmin-, Patchouly-, Rosen- oder Ylang-Ylang-Öl. Ebenfalls geeignet sind Muskateller, Salbeiöl, Kamillenöl, Nelkenöl, Melissenöl, Minzöl, Zimtblätteröl, Lindenblütenöl, Wacholderbeeröl, Vetiveröl, Olibanumöl, Galbanumöl und Labdanumöl sowie Orangenblütenöl, Neroliol, Orangenschalenöl und Sandelholzöl.Because the detergent tablets according to the invention can contain the enzyme (s) in two fundamentally different areas (in the base tablet and / or as an active substance or mixture of active substances in the cavity), moldings with a very precisely defined enzyme release and action can be provided. The table below gives an overview of possible enzyme distributions in detergent tablets according to the invention:

Dyes and fragrances can be added to the detergent tablets according to the invention both in the base tablet and in the preparations contained in the cavity, in order to improve the aesthetic impression of the resulting products and, in addition to the performance, give the consumer a visually and sensorially "typical and unmistakable" To provide product. As perfume oils or fragrances, individual fragrance compounds, for example the synthetic products of the ester, ether, Al type dehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzylatepylpropionate, stally. The ethers include, for example, benzyl ethyl ether, the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the jonones, α-isomethylionone and methylcedryl ketone the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be used directly in the washing and cleaning agents can be incorporated, but it can also be advantageous be the fragrances on carriers to apply, which increase the adhesion of the perfume to the laundry and due to a slower fragrance release for a long-lasting fragrance Take care of textiles. As such carrier materials Cyclodextrins have proven themselves, for example, the cyclodextrin-perfume complexes additionally can be coated with other auxiliaries.

To the aesthetic impression of the agent according to the invention To improve it (or parts of it) with suitable dyes colored become. Preferred dyes, the selection of which no expert Difficulties have a high storage stability and insensitivity across from the other ingredients of the means and against light as well as no pronounced substantivity towards the with substrates to be treated such as textiles, glass, Ceramic or plastic dishes so as not to stain them.

The detergent tablets according to the invention can be one or contain several optical brighteners. These substances that also called "white tones" are used in modern detergents, since they are even freshly washed and bleached white Laundry has a slight yellow tinge. Optical brighteners are organic Dyes that contain part of the invisible UV radiation from sunlight longer wavelength convert blue light. The emission of this blue light complements the "gap" in the light reflected by the textile, so that a Textile treated with an optical brightener makes the eye whiter and appears brighter. Because the mechanism of action of brighteners Assembling on the fibers presupposes, depending on the "dyed" fibers, for example Brightener for Cotton, polyamide or polyester fibers. The standard ones for the Incorporation in brighteners suitable for detergents is one of them essentially five structure groups on the stilbene, the diphenylstilbene, the coumarin-quinoline, the Diphenylpyrazoline group and the group of the combination of benzoxazole or benzimidazole with conjugated systems. An overview of common brighteners is for example in G. Jakobr, A. Loehr "Detergents and Textile Washing", VCH-Verlag, Weinheim 1987, pages 94 to 100. Suitable are e.g. Salts of 4,4'-bis [(4-anilino-6-morpholino-s-triazin-2-yl) amino] -stilbene-2,2'-disulfonic acid or a similar structure Compounds that have a diethanolamino group instead of the morpholino group, a methylamino group, an anilino group or a 2-methoxyethylamino group wear. Can continue Present brighteners of the substituted diphenylstyryl type, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brighteners can also be used.

In addition, the detergent tablets can also Contain components that have oil and fat washability positive effects from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty that has been previously washed several times with a detergent according to the invention, that this oil and fat-dissolving Component contains was washed. Among the preferred oil and fat dissolving components counting for example nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose containing methoxyl groups from 15 to 30% by weight and hydroxypropoxyl groups from 1 to 15 % By weight, based in each case on the nonionic cellulose ether, and the polymers of phthalic acid and / or known from the prior art of terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic and of terephthalic acid polymers.

As foam inhibitors used in the agents according to the invention can be used for example, soaps, paraffins or silicone oils can be used, which, if applicable, on carrier materials may be upset.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, Glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof in amounts of 0.1 to 5% by weight, based on the composition, are preferably used. Textile fabrics, in particular made of rayon, rayon, cotton and their blends, can be wrinkled because the individual fibers prevent bending, kinking. If pressing and squeezing across the direction of the fibers are sensitive, the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

To fight microorganisms can the agents according to the invention contain antimicrobial agents. A distinction is made here depending on the antimicrobial spectrum and mechanism of action between Bacteriostatics and bactericides, fungiostatics and fungicides etc. Important substances from these groups are, for example, benzalkonium chlorides, Alkylarlyl sulfonates, halophenols and phenol mercuric acetate, wherein also entirely these connections can be dispensed with.

To unwanted, due to exposure to oxygen and other oxidative processes caused changes in the agents and / or To prevent the treated textiles, the agents can have antioxidants contain. This class of compounds includes, for example, substituted ones Phenols, hydroquinones, pyrocatechols and aromatic amines as well organic sulfides, polysulfides, dithiocarbamates, phosphites and Phosphonates.

Increased wearing comfort can result from the additional use of antistatic agents, which are additionally added to the agents according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. External antistatic agents are, for example, in the patent applications FR 1,156,513 . GB 873 214 and GB 839 407 described. The lauryl (or SteaRYl) dimethylbenzylammonium chlorides disclosed here are suitable as antistatic agents for textiles or as an additive to detergents, with an additional softening effect being achieved.

To improve water absorption, the Re-wettability of the treated textiles and for relief of ironing of the treated textiles can in the agents according to the invention, for example Silicone derivatives are used. These also improve that rinse behavior the agent due to its foam-inhibiting properties. preferred Silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes, in which the alkyl groups have one to five carbon atoms and quite or are partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may or may not be derivatized and then amino functional or are quaternized or Si-ON, Si-N and / or Si-Cl bonds exhibit. The viscosities the preferred silicones are at 25 ° C in the range between 100 and 100,000 centistokes, the silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.

Finally, the agents according to the invention also contain UV absorbers that attach to the treated textiles and lightfastness of the fibers improve. Connections that you want Have properties are, for example, those due to non-radiation Deactivating active compounds and derivatives of benzophenone with substituents in 2 and / or 4-position. Substituted benzotriazoles are also in 3-position phenyl-substituted acrylates (cinnamic acid derivatives), if appropriate with cyano groups in the 2-position, salicylates, organic Ni complexes as well as natural substances such as umbelliferone and the body's own urocanoic acid.

The ingredients described above can Of course also in the cavity filling be incorporated. Preferred in the context of the present invention Manufactured detergent tablets are characterized in that that the contained in the space enclosed by the film and the molded body Active substance at least one active substance from the group of enzymes, Surfactants, soil-release polymers, disintegration aids, bleaches, Bleach activators, bleach catalysts, silver protective agents and mixtures from this, includes.

By dividing the detergent tablets produced according to the invention into base tablets and active substances) or active substance mixtures or preparation (s) contained in the cavity, ingredients can be separated from one another, which either leads to a storage stability-improving separation of incompatible ingredients or to a controlled release of certain active substances can be used. In detergent tablets preferably produced, the base tablet or the active substance contained in the space enclosed by the film and the tablet contains bleaching agents, while the other region of the tablet contains bleach activators.

More preferably manufactured washing and detergent tablets are characterized in that the Basic tablet or d contained in the space enclosed by the film and the molded body Contains active substance bleach, while the other area of the molded body Contains enzymes.

Also a separation of bleach and corrosion inhibitors or silver protection agents to reach. Detergent tablets in which the base tablet or contained in the space enclosed by the film and the molded body Contains active substance bleach, while the other area of the molded body deformable mass containing anti-corrosion agents are also preferred.

Last but not least are washing and Cleaning tablets preferred, in which the base molding or in the through the film and the molded body enclosed space contains active substance containing bleach, during the other area of the molded body Surfactants, preferably nonionic surfactants, with particular preference alkoxylated alcohols with 10 to 24 carbon atoms and 1 to 5 alkylene oxide units.

For all of the above ingredients can beneficial properties result from them from other ingredients to separate or share them with certain other ingredients to assemble. In the shaped bodies according to the invention, the individual areas can also have a different content of the same ingredient, whereby advantages can be achieved. Detergent tablets, at those of the base molding and contained in the space enclosed by the film and the molded body Contain the same active ingredient in different amounts, are preferred. The term "different amount" refers to not on the absolute amount of the ingredient in that Part of the molded body, but on the relative amount, based on the phase weight that is, a percentage by weight, based on the individual range, that is the base molding or the cavity filling.

The one to be optionally incorporated into the cavity Active substance is preferably particulate. The term “active substance” is used in the context of the present Invention is not limited to pure substances. Rather, it characterizes pure active substances, active substance mixtures and preparation forms, so that freedom of formulation there are no limits. If particulate substances are enclosed in the cavity (s), it is preferred if these certain particle size criteria sufficient so preferred washing and detergent tablets are characterized in that the contained in the space enclosed by the film and the molded body Active substance particle sizes between 100 and 5000 μm, preferably between 150 and 2500 μm, particularly preferably between 200 and 2000 μm and in particular between 400 and 1600 μm.

As mentioned above, is the optional in the cavity filling to be introduced preferably solid, with particulate fillings being particularly preferred are. Will the cavities the molded body with particulate Filled compositions, methods are preferred in which the particulate (s) Composition (s) in step b) a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.

According to the invention, the film that closes the cavity (s) is in shape a film tube or envelope, which around the filled Tablet is placed. film tubes can for example from flat foil webs by turning over and lengthwise Zusanmmenschweißen getting produced. In this way, hoses are obtained which have a seam. Seamless hoses can be, for example, by the method known in the prior art by extrusion blowing. Preferably the hose after flipping around the filled one The tablet is cut to the appropriate dimension, this increases the throughput of the Machines increased.

Foil envelopes are preferably formed by placing a flat sheet of film around the filled molded body and then sealing it becomes. The envelope also has a seam here. Preferably the Foil like the hoses described cut to length only after turning the tablet over there throughputs elevated become.

In preferred methods according to the invention become the hose pieces or envelopes suitable for the size of the tablet cut to length. Suitable for the size of the tablet "means that the Foil completely covers the cavity and closes and at the same time not over protrudes the edge of the tablet. With large tablet tops with small cavities it is not necessary that the Foil completely covers the entire tablet top. Here a "ring" of foil can be placed around the cavity suffice around wherein the ring is preferably at least 2 mm wider than that Diameter of the cavity.

Preferred methods according to the invention are characterized in that the Length of Foil tube or envelope maximum the length of the tablet to be wrapped equivalent.

The film tube or envelope fixes the filling of the cavity and secures it against falling out during further packaging, transport and handling. Depending on the aggregate condition of the filling and - for solid ones Fillings - depending on the size of the filling, the film must sit more or less tightly on the molded body to ensure a secure seal. If the cavity contains only coarse particles as a filling, a seat of the film tube or envelope is sufficient, which prevents the film from slipping off. With fine-particle or liquid fillings, on the other hand, a tight fit is required. Overall, methods according to the invention are preferred, in which the distance between the filled base molded body and the film tube or envelope over the entire contact surface of the film 0.1 to 500 μm, preferably 0.5 to 200 μm, particularly preferably 1 to 150 μm and in particular 2 up to 100 μm.

In preferred methods according to the invention the film from which the tube or envelope is formed, from a water soluble Polymer or polymer blend. The used as foil materials Polymers can from a single material or a blend of different materials consist. Preferred film materials come from the group (if appropriate acetalized) polyvinyl alcohol (PVAL) and / or PVAL copolymers, Polyvinyl pyrrolidone, polyethylene oxide, polyethylene glycol, gelatin and / or Copolymers and their mixtures.

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten.Polyvinyl alcohols are particularly preferred in the context of the present invention. "Polyvinyl alcohols" (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure

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

contain.

Commercial polyvinyl alcohols, the as white-yellowish Powder or granules with degrees of polymerization in the range of approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol) are offered are, have degrees of hydrolysis of 98-99 and 87-89 mol% so there is still a residual content of acetyl groups. Be characterized the polyvinyl alcohols from the manufacturer by specifying the Degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

Polyvinyl alcohols are dependent on Degree of hydrolysis soluble in water and a few strongly polar organic solvents (Formamide, dimethylformamide, dimethyl sulfoxide); from (chlorinated) They do not attack hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility can be achieved by post-treatment with aldehydes (acetalization) Complexing with Ni or Cu salts or by treatment with dichromates, boric acid or reduce borax. Polyvinyl alcohol is largely impenetrable for gases such as Oxygen, nitrogen, helium, hydrogen, carbon dioxide, however, leaves Pass water vapor through.

Within the scope of the present invention preferred methods are characterized in that the film material Polyvinyl alcohols and / or PVAL copolymers, their degree of hydrolysis 70th up to 100 mol%, preferably 80 to 90 mol%, particularly preferred 81 to 89 mol% and in particular 82 to 88 mol%.

Polyvinyl alcohols of a certain molecular weight range are preferably used, with processes according to the invention being preferred in which the film comprises polyvinyl alcohols and / or PVAL copolymers, the molecular weight of which is particularly preferably in the range from 3,500 to 100,000 gmol ^-1 , preferably from 10,000 to 90,000 gmol ^-1 is from 12,000 to 80,000 gmol ^-1 and especially from 13,000 to 70,000 gmol ^-1 .

The degree of polymerization of such preferred Polyvinyl alcohols is between about 200 to about 2100, preferably between approximately 220 to about 1890, more preferably between about 240 to about 1680 and especially between about 260 to about 1500th

Preferred methods according to the invention are characterized in that the Film comprises polyvinyl alcohols and / or PVAL copolymers, the average degree of polymerization between 80 and 700, preferably is between 150 and 400, particularly preferably between 180 and 300 and / or their molecular weight ratio MG (50%) to MG (90%) between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6.

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88 and Mowiol ^® 8-88.

The table below shows further polyvinyl alcohols which are particularly suitable as film materials refer to:

Other polyvinyl alcohols suitable as material for the film are ELVANOL ^® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX ^® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ^® NK-05, A-300, AH-22, C -500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (trademark of Nippon Gohsei KK ). ERKOL types from Wacker are also suitable.

die durch radikalische Polymerisation von 1-Vinylpyrrolidon nach Verfahren der Lösungs- oder Suspensionspolymerisation unter Einsatz von Radikalbildnern (Peroxide, Azo-Verbindungen) als Initiatoren hergestellt werden. Die ionische Polymerisation des Monomeren liefert nur Produkte mit niedrigen Molmassen. Handelsübliche Polyvinylpyrrolidone haben Molmassen im Bereich von ca. 2500-750000 g/mol, die über die Angabe der K-Werte charakterisiert werden und – K-Wert-abhängig – Glasübergangstemperaturen von 130-175° besitzen. Sie werden als weiße, hygroskopische Pulver oder als wäßrige. Lösungen angeboten. Polyvinylpyroolidone sind gut löslich in Wasser und einer Vielzahl von organischen Lösungsmitteln (Alkohole, Ketone, Eisessig, Chlorkohlenwasserstoffe, Phenole u.a.).Another preferred group of water-soluble polymers that can be used as film material according to the invention are the polyvinylpyrrolidones. These are sold, for example, under the name Luviskol ^® (BASF). Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (IV)

which are produced by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-radical formers (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer only provides products with low molecular weights. Commercial polyvinylpyrrolidones have molar masses in the range from approx. 2500-750000 g / mol, which are characterized by the specification of the K values and, depending on the K value, have glass transition temperatures of 130-175 °. They are presented as white, hygroscopic powders or as aqueous ones. Solutions offered. Polyvinylpyroolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).

Also suitable are copolymers of vinylpyrrolidone with other monomers, in particular vinylpyrrolidone / Vinylester copolymers, as are marketed, for example under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.

als charakteristischem Grundbaustein der Makromoleküle. Von diesen haben die Vinylacetat-Polymere (R = CH₃) mit Polyvinylacetaten als mit Abstand wichtigsten Vertretern die größte technische Bedeutung.The vinyl ester polymers are polymers accessible from vinyl esters with the grouping of the formula (V)

as a characteristic basic building block of macromolecules. Of these, the vinyl acetate polymers (R = CH ₃ ) with polyvinyl acetates are by far the most important technical representatives.

The vinyl esters are polymerized by free radicals using different processes (solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization). Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (IV) and (V). Further suitable water-soluble polymers are the polyethylene glycols (polyethylene oxides), which are referred to as PEG for short. PEG are polymers of ethylene glycol which have the general formula (VI) H- (O-CH ₂ -CH ₂ ) _n -OH (VI) are sufficient, where n can have values between 5 and> 100,000.

PEGs are manufactured technically by anionic ring opening polymerization of ethylene oxide (oxirane) mostly in the presence of small amounts of water. You have depending on the reaction Molar masses in the range of approx. 200-5,000,000 g / mol, corresponding to degrees of polymerization from approx. 5 to> 100 000th

The products with molar masses <approx. 25,000 g / mol are liquid at room temperature become sore as the actual polyethylene glycols, abbreviation PEG, designated. These short chain PEGs can in particular be other water soluble Polymers, e.g. Polyvinyl alcohols or cellulose ethers as plasticizers be added. The usable according to the invention at room temperature Solid polyethylene glycols are called polyethylene oxides, short marks PEOX. High molecular weight polyethylene oxides are extremely low Concentration of reactive hydroxy end groups and therefore only show still weak glycol properties.

Also suitable as foil material is also gelatin according to the invention, these preferably used together with other polymers becomes. Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol) that primarily by hydrolysis of the contained in animal skin and bones Collagen is obtained under acidic or alkaline conditions. The amino acid composition of gelatin largely corresponds to that of the collagen from which it would be obtained and varies depending on its provenance. The use of gelatin as a water soluble shell material is extremely wide, especially in pharmacy in the form of hard or soft gelatin capsules common. Gelatin is found in the form of foils because of their comparison only low for the above-mentioned high-cost polymers Use.

• – Celluloseether, wie Hydroxypropylcellulose, Hydroxyethylcellulose und Methylhydroxypropylcellulose, wie sie beispielsweise unter den Warenzeichen Culminal^® und Benecel^® (AQUALON) vertrieben werden.

Further water-soluble polymers suitable according to the invention as film material are described below:

• - cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and methylhydroxypropyl cellulose, such as are for example sold under the trademark Culminal® ^® and Benecel ^® (AQUALON).

in R für H oder einen Alkyl-, Alkenyl-, Alkinyl-, Aryl- oder Alkylarylrest steht. In bevorzugten Produkten steht mindestens ein R in Formel (III) für -CH₂CH₂CH₂-OH oder -CH₂CH₂-OH. Celluloseether werden technisch durch Veretherung von Alkalicellulose (z.B. mit Ethylenoxid) hergestellt. Celluloseether werden charakterisiert über den durchschnittlichen Substitutionsgrad DS bzw. den molaren Substitutionsgrad MS, die angeben, wieviele Hydroxy-Gruppen einer Anhydroglucose-Einheit der Cellulose mit dem Veretherungsreagens reagiert haben bzw. wieviel mol des Veretherungsreagens im Durchschnitt an eine Anhydroglucose-Einheit angelagert wurden. Hydroxyethylcellulosen sind ab einem DS von ca. 0,6 bzw. einem MS von ca. 1 wasserlöslich. Handelsübliche Hydroxyethyl- bzw. Hydroxypropylcellulosen haben Substitutionsgrade im Bereich von 0,85-1,35 (DS) bzw. 1,5-3 (MS). Hydroxyethyl- und -propylcellulosen werden als gelblich-weiße, geruch- und geschmacklose Pulver in stark unterschiedlichen Polymerisationsgraden vermarktet. Hydroxyethyl- und -propylcellulosen sind in kaltem und heißem Wasser sowie in einigen (wasserhaltigen) organischen Lösungsmitteln löslich, in den meisten (wasserfreien) organischen Lösungsmitteln dagegen unlöslich; ihre wäßrigen Lösungen sind relativ unempfindlich gegenüber Änderungen des pH-Werts oder Elektrolyt-Zusatz.Cellulose ethers can be described by the general formula (VI)

in R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products at least one R in formula (III) is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of cellulose have reacted with the etherification reagent or how many moles of etherification reagent have been attached to an anhydroglucose unit on average. Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercial hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Other polymers suitable according to the invention are water-soluble amphopolymers. Ampho-polymers are amphoteric polymers, ie polymers that contain both free amino groups and free -OOOH or SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - Contain COO ^- or -SO ₃ groups, and summarize those polymers which contain -OOOH or SO ₃ H groups and quaternary ammonium groups. An example of the present invention amphopolymer suitable is that available under the name Amphomer ^® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Methacrylic acid and its simple esters. Likewise preferred amphopolymers consist of unsaturated carboxylic acids (eg acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (eg acrylic midopropyl-trimethyl-ammonium chloride) and optionally further ionic or nonionic monomers together terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat ^® 2001 N, are particularly preferred amphopolymers according to the invention. Other suitable amphoteric polymers are for example those available under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL) octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.

• – Vinylacetat/Crotonsäure-Copolymere, wie sie beispielsweise unter den Bezeichnungen Resyn^® (NATIONAL STARCH), Luviset^® (BASF) und Gafset^® (GAF) im Handel sind.
• Diese Polymere weisen neben Monomereinheiten der vorstehend genannten Formel (II) auch Monomereinheiten der allgemeinen Formel (VII) auf: [-CH(CH₃)-CH(COOH)-]_n (VII)
• – Vinylpyrrolidon/Vinylacrylat-Copolymere, erhältlich beispielsweise unter dem Warenzeichen Luviflex^® (BASF). Ein bevorzugtes Polymer ist das unter der Bezeichnung Luviflex^® VBM-35 (BASF) erhältliche Vinylpyrrolidon/Acrylat-Terpolymere.
• – Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere, die beispielsweise unter der Bezeichnung Ultrahold^® strong (BASF) vertrieben werden.
• – Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen Solche gepfropften Polymere von Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch mit anderen copolymerisierbaren Verbindungen auf Polyalkylenglycolen werden durch Polymerisation in der Hitze in homogener Phase dadurch erhalten, daß man die Polyalkylenglycole in die Monomeren der Vinylester, Ester von Acrylsäure oder Methacrylsäure, in Gegenwart von Radikalbildner einrührt. Als geeignete Vinylester haben sich beispielsweise Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinylbenzoat und als Ester von Acrylsäure oder Methacrylsäure diejenigen, die mit aliphatischen Alkoholen mit niedrigem Molekulargewicht, also insbesondere Ethanol, Propanol, Isopropanol, 1-Butanol, 2-Butanol, 2-Methy-1-Propanol, 2-Methyl-2-Propanol, 1-Pentanol, 2-Pentanol, 3-Pentanol, 2,2-Dimethyl-1-Propanol, 3-Methyl-1-butanol; 3-Methyl-2-butanol, 2-Methyl-2-butanol, 2-Methyl-1-Butanol, 1-Hexanol, erhältlich sind, bewährt. Polypropylenglycole (Kurzzeichen PPG) sind Polymere des Propylenglycols, die der allgemeinen Formel IX
  
  genügen, wobei n Werte zwischen 1 (Propylenglycol) und mehreren tausend annehmen kann. Technisch bedeutsam sind hier insbesondere Di-, Tri- und Tetrapropylenglycol, d.h. die Vertreter mit n=2, 3 und 4 in Formel VI. Insbesondere können die auf Polyethylenglycole gepfropften Vinylacetatcopolymeren und die auf Polyethylenglycole gepfropften Polymeren von Vinylacetat und Crotonsäure eingesetzt werden.
• – gepropfte und vernetzte Copolymere aus der Copolymerisation von i) mindesten einem Monomeren vom nicht-ionischen Typ, ii) mindestens einem Monomeren vom ionischen Typ, iii) von Polyethylenglycol und iv) einem Vernetzter Das verwendete Polyethylenglycol weist ein Molkeulargewicht zwischen 200 und mehrerern Millionen, vorzugsweise zwischen 300 und 30.000, auf. Die nicht-ionischen Monomeren können von sehr unterschiedlichem Typ sein und unter diesen sind folgende bevorzugt: Vinylacetat, Vinylstearat, Vinyllaurat, Vinylpropionat, Allylstearat, Allyllaurat, Diethylmaleat, Allylacetat, Methylmethacrylat, Cetylvinylether, Stearylvinylether und 1-Nexen. Die nicht-ionischen Monomeren können gleichermaßen von sehr unterschiedlichen Typen sein, wobei unter diesen besonders bevorzugt Crotonsäure, Allyloxyessigsäure, Vinylessigsäure, Maleinsäure, Acrylsäure und Methacrylsäure in den Pfropfpolameren enthalten sind. Als Vernetzer werden vorzugsweise Ethylenglycoldimethacrylat, Diallylphthalat, ortho-, meta- und para-Divinylbenzol, Tetraallyloxyethan und Polyallylsaccharosen mit 2 bis 5 Allylgruppen pro Molekül Saccharin. Die vorstehend beschriebenen gepfropften und vernetzten Copoymere werden vorzugsweise gebildet aus: i) 5 bis 85 Gew.-% mindesten eine Monomeren vom nicht-ionischen Typ, ii) 3 bis 80 Gew.-% mindestens eines Monomeren vom ionischen Typ, iii) 2 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-% Polyethylenglycol und iv) 0,1 bis 8 Gew.-% eines Vernetzers, wobei der Prozentsatz des Vernetzers durch das Verhältnis der Gesamtgewichte von i), ii) und iii) ausgebildet ist.
• – durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltene Copolymere: i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesätigter Alkohole und ungesättigter Carbonsäuren, ii) ungesättigte Carbonsäuren, iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols Unter kurzkettigen Carbonsäuren bzw. Alkoholen sind dabei solche mit 1 bis 8 Kohlenstoffatomen zu verstehen, wobei die Kohlenstoffketten dieser Verbindungen gegebenenfalls durch zweibindige Heterogruppen wie -O-, -NH-, -S_ unterbrochen sein können.
• – Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester Diese Terpolymere enthalten Monomereinheiten der allgemeinen Formeln (IV) und (VI) (siehe oben) sowie Monomereinheiten aus einem oder mehreren Allyl- oder Methallyestern der Formel X:
  
  worin R³ für -N oder -CH₃, R² für -CH₃ oder -CH(CH₃)₂ und R¹ für -CH₃ oder einen gesättigten geradkettigen oder verzweigten C_1-6-Alkylrest steht und die Summe der Kohlenstoffatome in den Resten R¹ und R² vorzugsweise 7, 6, 5, 4, 3 oder 2 ist. Die vorstehend genannten Terpolymeren resultieren vorzugsweise aus der Copolymerisation von 7 bis 12 Gew.-% Crotonsäure, 65 bis 86 Gew.-%, vorzugsweise 71 bis 83 Gew.-% Vinylacetat und 8 bis 20 Gew.-%, vorzugsweise 10 bis 17 Gew.-% Allyl- oder Methallyletsre der Formel VII.
• – Tetra- und Pentapolymere aus i) Crotonsäure oder Allyloxyessigsäure ii) Vinylacetat oder Vinylpropionat iii) verzweigten Allyl- oder Methallylestern iv) Vinylethern, Vinylesterrn oder geradkettigen Allyl- oder Methallylestern
• – Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinymethylether, Acrylamid und deren wasserlöslicher Salze
• – Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in ☐-Stellung verzweigten Monocarbonsäure.

Water-soluble anionic polymers suitable according to the invention include:

• - vinyl acetate / crotonic acid copolymers, such as are commercially available for example under the names Resyn ^® (National Starch), Luviset ^® (BASF) and Gafset ^® (GAF).
• In addition to monomer units of the abovementioned formula (II), these polymers also have monomer units of the general formula (VII): [-CH (CH ₃ ) -CH (COOH) -] _n (VII)
• - vinylpyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF). A preferred polymer is that available under the name Luviflex VBM-35 ^® (BASF) vinylpyrrolidone / acrylate terpolymers.
• - Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, which are sold, for example, under the name Ultrahold ^® strong (BASF).
• - Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols. Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or as a mixture with other copolymerizable compounds, can be used on polyalkylene glycols obtained by hot polymerization in a homogeneous phase by stirring the polyalkylene glycols into the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid, in the presence of free-radical formers. Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as esters of acrylic acid or methacrylic acid, those which are used with low molecular weight aliphatic alcohols, in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl 1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are available. Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula IX
  
  are sufficient, where n can take values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetrapropylene glycol, ie the representatives with n = 2, 3 and 4 in formula VI. In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used.
• Grafted and crosslinked copolymers from the copolymerization of i) at least one monomer of the non-ionic type, ii) at least one monomer of the ionic type, iii) of polyethylene glycol and iv) a crosslinker The polyethylene glycol used has a molecular weight of between 200 and several million, preferably between 300 and 30,000. The nonionic monomers can be of very different types and the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-neexene. The non-ionic monomers can likewise be of very different types, of which crotonic acid, allyloxyacetic acid, vinyl acetic acid, maleic acid, acrylic acid and methacrylic acid are particularly preferably contained in the graft polymers. Ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucrose with 2 to 5 allyl groups per molecule of saccharin are preferably used as crosslinkers. The grafted and crosslinked copolymers described above are preferably formed from: i) 5 to 85% by weight of at least one monomer of the nonionic type, ii) 3 to 80% by weight of at least one ionic type monomer, iii) 2 to 50% by weight, preferably 5 to 30% by weight of polyethylene glycol and iv) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii).
• - Copolymers obtained by copolymerizing at least one monomer from each of the following three groups: i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, ii) unsaturated carboxylic acids, iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or Esters from the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol. Short-chain carboxylic acids or alcohols are to be understood as those having 1 to 8 carbon atoms, the carbon chains of these compounds being optionally by double-bonded hetero groups such as - O-, -NH-, -S_ can be interrupted.
• Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester. These terpolymers contain monomer units of the general formulas (IV) and (VI) (see above) and monomer units of one or more allyl or methallyesters of the formula X:
  
  wherein R ^{3 is} -N or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated straight-chain or branched C _1-6 alkyl radical and the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2. The above-mentioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17% by weight .-% Allyl- or Methallyletsre of formula VII.
• - Tetra- and penta-polymers of i) crotonic acid or allyloxyacetic acid ii) vinyl acetate or vinyl propionate iii) branched allyl or methallyl esters iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
• - Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts
• - Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the ☐ position.

Further, preferably according to the invention as a film material Polymers that can be used are cationic polymers. Among the cationic Polymers are preferred over the permanently cationic polymers. As "permanent become cationic " according to the invention such Polymers referred to independently have a cationic group of pH. These are in the Rule polymers that are a quaternary Contain nitrogen atom, for example in the form of an ammonium group.

• – quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat^® und Polymer JR^® im Handel erhältlich sind. Die Verbindungen Celquat^® H 100, Celquat^® L 200 und Polymer JR^®400 sind bevorzugte quaternierte Cellulose-Derivate.
• – Polysiloxane mit quaternären Gruppen, wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trimethylsilylamodimethicon), Dow Corning^® 929 Emulsion (enthaltend ein hydroxyl-amino-modifiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM-55067 (Hersteller: Wacker) sowie Abil^®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt; diquaternäre Polydime- thylsiloxane, Quaternium-80),
• – Kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosmedia^®Guar und Jaguar^® vertiebenen Produkte,
• – Polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat^®100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat^®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere.
• – Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminomethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat^®734 und Gafquat^®755 im Handel erhältlich.
• – Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere, wie sie unter der Bezeichnung Luviquat^® angeboten werden.
• – quaternierter Polyvinylalkohol sowie die unter den Bezeichnungen
• – Polyquaternium 2,
• – Polyquaternium 17,
• – Polyquaternium 18 und
• – Polyquaternium 27

bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette. Die genannten Polymere sind dabei nach der sogenannten INCI-Nomenklatur bezeichnet, wobei sich detaillierte Angaben im CTFA International Cosmetic Ingredient Dictionary and Handbook, 5^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, finden, auf die hier ausdrücklich Bezug genommen wird.Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^® . The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives.
• Polysiloxanes with quaternary groups, such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow ^Corning® 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80),
• Cationic guar derivatives, such as in particular the products marketed under the trade names Cosmedia ^® Guar and Jaguar ^® ,
• - Polymers dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products commercially available under the names Merquat ^® 100 (poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) te are examples of such cationic polymers.
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755.
• - Vinylpyrrolidone-methoimidazolinium chloride copolymers, as are offered under the name Luviquat ^® .
• - Quaternized polyvinyl alcohol and those under the names
• - polyquaternium 2,
• - polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27

known polymers with quaternary nitrogen atoms in the main polymer chain. The polymers mentioned are named according to the so-called INCI nomenclature, with detailed information in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, to which express reference is made here becomes.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers. Cationic cellulose derivatives, in particular the commercial product Polymer ^® JR 400, are very particularly preferred cationic polymers.

Together with the molded body, the at least one cavity has, forms the film bonded to the molded body those produced according to the invention Detergent tablets. In the case of closed trough shaped bodies, the structure of the produced according to the invention Molded body a "drum" in which a cavity passes through a film is closed.

When incorporating liquid, gel or more pasty Active substances or mixtures of active substances must be the composition of the shaped body and the film on the filling be matched to premature destruction of the film or loss of active substance through the molded body to avoid through. This is when solid substances are incorporated into the cavity only to a minor extent (chemical intolerance) required so that preferred produced detergent tablets further active substance in particle form, preferably in powder, granular, extruded, pelleted, prilled, flaked or tableted form.

The one closed by the foil cavity can do so completely be filled with further active substance. But it is also possible the cavity before closing to fill only partially, to move the filled particles or liquids in this way inside the cavity to enable. Especially when filling with regularly shaped larger particles attractive optical effects can be realized. Here are Manufacturing process for Detergent tablets preferred in which the volume ratio of that through the film and the molded body enclosed space to the active substance contained in this space 1: 1 to 100: 1, preferably 1.1: 1 to 50: 1, particularly preferred 1.2: 1 to 25: 1 and in particular 1.3: 1 to 10: 1. In this Terminology means a volume ratio of 1: 1 that the cavity is completely filled.

Depending on the size of the cavity, the density of the molded body, the density of the active substance in the cavity and the degree of filling of the cavity can Proportion of the other active substance in the cavity different proportions on the overall molded body turn off. Here, the production of detergent tablets is preferred, where the weight ratio of shaped body to the contained in the space enclosed by the film and the molded body Active substance 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly is preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1. at the weight ratio defined above is the relationship the mass of the unfilled molding ("Base molding") to the mass of the filling The mass of the film is not taken into account in this calculation.

Through suitable packaging of shaped body and sheet material can be the time at which the contained in the cavity Substance is released to be predetermined. For example the film is almost instantly soluble be so that the in the cavity Active substance contained right at the beginning of the washing or cleaning cycle is dosed into the washing or cleaning liquor. Alternatively the film can be so poorly soluble be that first the molded body disbanded and that in the cavity contained active substance is thereby released.

Depending on this release mechanism, it is possible, for example, to produce moldings in which the active substance contained in the cavity is dissolved in the cleaning liquor before the constituents of the molded body are dissolved or after this has happened. Thus, on the one hand, the production of detergent tablets is preferred, which are characterized in that the active substance contained in the space enclosed by the film and the tablet dissolves faster than the ba sisformkörper.

But also detergent tablets, at which are those in the one enclosed by the film and the molded body Active substance contained in the room dissolves more slowly than the basic molded body preferred embodiments of the present invention.

To accelerate the filled moldings like this to shape that a Leakage of filling on the top of the molded body is prevented, it is recommended to take appropriate design measures to take. Because filling stations and film wrapping machine are mostly staionary, the device that the moldings moved, appropriately designed. Here are methods according to the invention preferred, in which the base moldings produced in step a) a conveyor belt or film wrapping stations are fed, the conveyor belt a feed speed of 0.01 to 1 m / s, preferably of 0.02 to 0.5 m / s, particularly preferably from 0.03 to 0.3 m / s and in particular from 0.05 to 0.2 m / s.

Filling the molded body with Active substance (s), i.e. with liquids) and / or particulate preparations, is preferably carried out in such a way that several base moldings at the same time filled become. Here are methods according to the invention preferred where the filling the basic molded body by means of a filling system takes place, which with 5 to 30 cycles per minute, preferably with 10 to 25 cycles per minute and in particular with 15 to 20 cycles works per minute.

As already described above, depends on the type of filling a more or less tight fit of the film around the filled molded article is required. For critical (especially liquid or finely divided) fillings can leak the filling can be prevented even more safely if the film is additionally wrapped around the molded body at the top of the base molding attached, preferably glued. The adhesive application can for example by application rollers, which are on one side be continuously provided with adhesive. The top of the molded body or the underside of the film is then on the rotating application roller past and so provided with adhesive. An embodiment of the present The invention therefore provides that the Top of the filled Basic tablet is provided with adhesive by means of application rollers.

In the case of tableted basic tablets the tablet surface depending on the composition and manufacture of the base moldings more or less rough, so that the Technical application of adhesive to the top of the molded body can be difficult. You can also Powder residues on the tablet surface contaminate the adhesive roller and affect the system operation and the adhesion of the film to the molded body. A preferred embodiment The present invention therefore provides for the adhesives to be non-contact on the top of the molded body applied. As an alternative to the use of application rollers also used a casting plant which pours or sprays an adhesive seam around the filled cavity. Because a direct one Contact of the machine to the base molding surface is not necessary here, this method variant is a further possibility, the ones described above Problems with rough or "dusty" base moldings bypass.

Methods which are also preferred according to the invention are therefore characterized in that the top of the filled base molding means a casting plant, which can cast any line shape on the surface under computer control, is provided with adhesive.

Fabrics can be used as adhesives insert the molded body surfaces on that they are applied, have sufficient adhesiveness lend so that the films applied in the subsequent process step permanently on the surface be liable. In principle, there are those in the relevant adhesive literature and in particular in the monographs mentioned for this purpose, where in the context of the present invention the application of melts, which with increased Temperature promotes adhesion, but no longer becomes tacky after cooling, but are firm, have a special meaning.

Adhesives are particularly preferred in the context of the present invention solutions of polyvinyl alcohols (see above) and dispersions of polyacrylates. The applied per molded body Amount of adhesive can vary on the size of the molded body, its Composition and its surface roughness vary and is in preferred methods according to the invention 0.05 to 0.3 grams per tablet.

A tight fit of the film can alternatively or additionally can be achieved in that the Open the film after folding the film tube or envelope the tablet is shrunk on, for example by means of hot air or Infrared radiation can be achieved. Preferred according to the invention Methods are therefore characterized in that as a film (s) for the hose or envelope pre-stretched films are used, which after the Kill around the filled one Basic tablet to be shrunk onto it.

Another subject of the present The invention notification consists of detergent tablets compacted, particulate Detergent and cleaning agent, comprising at least one cavity, the opening (s) of which is / are closed with a film, the film tubing the molded body or enveloping like an envelope.

With regard to the ingredients of the base tablets, the cavity filling and with regard to the distribution of the ingredients and physical parameters of the ingredients or the film, reference can be made to the above guided tours.

The shape of the moldings according to the invention can also on the above statements to get expelled. Particularly preferred washing according to the invention or detergent tablets he has an orthorhombic basic shape, the film the Formrkörper only covered on four of the six sides.

"Orthorhombic basic shape" means that the moldings shows an approximately rectangular surface when viewed from each side. In particular chamfered or rounded edges, which strictly speaking do so to lead, that the moldings is not an orthorhombus not from an orthorhombic in the context of the present invention Basic shape out. The term also includes higher symmetries on. So are tetragonal basic shapes (the rectangle of the side view becomes square with two views and basic cubic shapes (all six pages are square in side view) in the term locked in.

Exemplary moldings according to the invention shown in the attached pictures. Show:

1a a top view of a tablet-shaped body according to the invention in orthorhombic basic shape with a circular trough.

1b a perspective view of the molded body 1a , It can be clearly seen that the tablet has two layers and that the film wrapping does not cover the end faces of the tablet, so that only four of the six sides of the shaped body are covered by film.

1c a side view of the end face of the molded body according to the invention 1a ,

1d a side view of the long side of the molded body according to the invention 1a , The not visible trough is outlined for an overview. It can be clearly seen that the tablet has two layers and that the film wrapping does not cover the end faces of the tablet, so that only four of the six sides of the shaped body are covered by film.

1e a vertical section through the center of the molded body according to the invention 1a parallel to the face.

2a a top view of a tablet-shaped body according to the invention in orthorhombic basic shape with a rectangular trough.

2 B a perspective view of the molded body 2a , It can be clearly seen that the tablet has two layers and that the film wrapping does not cover the end faces of the tablet, so that only four of the six sides of the shaped body are covered by film.

2c a side view of the end face of the molded body according to the invention 2a ,

2d a side view of the long side of the molded body according to the invention 2a , The not visible trough is outlined for an overview. It can be clearly seen that the tablet has two layers and that the film wrapping does not cover the end faces of the tablet, so that only four of the six sides of the shaped body are covered by film.

2e a vertical section through the center of the molded body according to the invention 2a parallel to the face.

Claims (11)

Method for producing detergent tablets by d) producing an open hollow mold (“base tablet”) which has at least one cavity; e) filling one or more active substances in liquid, gel-like, pasty or solid form into said cavity (s), f) sealing the openings of the (filled) cavities with a film, characterized in that a film tube or envelope is produced, which is placed around the filled tablet. A method according to claim 1, characterized in that. the Production of the open mold in step a) pressing a particulate Premixed to a pressed one Part (base molding), the at least one cavity has comprises A method according to claim 1, characterized in that manufacturing the open mold in step a) by deep drawing and / or casting and / or injection molding and / or blow molding a water soluble or dispersible Polymer or polymer mixture takes place. Method according to one of claims 1 to 3, characterized in that that the Length of Foil tube or envelope maximum the length of the tablet to be wrapped equivalent. Method according to one of claims 1 to 4, characterized in that that the Foil from which the tube or envelope is formed a water soluble Polymer or polymer blend. Method according to one of claims 1 to 5, characterized in that that the Distance between the filled Basic tablet and the film tube or envelope over the entire contact surface of the Film 0.1 to 500 μm, preferably 0.5 to 200 μm, particularly preferably 1 to 150 μm and in particular 2 to 100 μm, is. Method according to claims 1 to 6, characterized in that the top of the filled Basic molded body before folding the hose or envelope using application rollers is provided with adhesive. Method according to one of claims 1 to 7, characterized in that that the Top of the filled basic molded body folding the hose or envelope using a casting machine, which can cast any line shape on the surface under computer control, is provided with adhesive. Method according to one of claims 1 to 7, characterized in that that that as foil (s) for the hose or envelope pre-stretched films are used, which after the Kill around the filled one Basic tablet to be shrunk onto it. Detergent tablets compacted, particulate Detergents and cleaning agents, comprising at least one cavity, the openings of which) is / are closed with a film, characterized in that the film the molded body surrounds like a hose or envelope. Detergent tablets according to Claim 10, characterized in that it has an orthorhombic basic shape and the film has the molded body only covered on four of the six sides.