EP1192241A1 - Method for producing washing and cleaning agent shaped bodies - Google Patents

Abstract

The invention relates to a method for producing washing and cleaning agent shaped bodies which improves upon prior art tabletting and extrusion technology with regard to protecting the constituents from thermal stress, pressure and shearing. The inventive method is also technically less complex, more economical, enables higher rates of production and requires little effort to produce three-phase or multiphase shaped bodies. The method includes the production of (a) shapeable material(s), the feeding of this material under a pressure of less than 40 bar to outlet openings, as well as the cutting off of the exiting strands of material and permitting the same to harden.

Description

 "Process for the production of detergent tablets"

The present invention relates to a novel method for producing single-phase and multi-phase detergent tablets.

Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage. Tableted cleaning agents have a number of advantages over powdered products: They are easier to dose and handle and, thanks to their compact structure, have advantages in terms of storage and transport. There is therefore an extremely broad state of the art for detergent tablets, which is also reflected in an extensive patent literature. At an early stage, the developers of tablet-shaped products came up with the idea of releasing certain ingredients through differently composed areas of the molded bodies only under defined conditions in the washing or cleaning cycle, in order to improve cleaning success. In addition to the core / shell tablets and ring / core tablets, which are well known in pharmacy, multi-layered shaped bodies, which are now offered for many areas of washing and cleaning or hygiene, have become established. The optical differentiation of the products is also becoming increasingly important, so that single-phase and single-color moldings in the field of washing and cleaning have largely been displaced by multi-phase moldings. Two-layer molded bodies with a white and a colored phase or with two differently colored layers are currently customary on the market. There are also point tablets. Toroidal tablets. Coated tablets etc., which currently have a rather minor meaning. The production of the shaped bodies mentioned always comprises at least one tabletting step in which a particulate premix is converted into a compact shaped body using pressure. In the case of the two-layer tablets, coated / core tablets, etc., different premixes are pressed onto or into one another. In addition, there are proposals to produce tablets by means of conventional pressing technology and to fill cavities in these tablets with melts or the like in order to arrive at compositional molded articles made from pressed and non-pressed parts.

Another process that is used to produce compact detergent and cleaning agent pieces is extrusion. Here, a premix is plasticized under high pressures and discharged through hole molds, after which shaping takes place by cutting off and possible post-treatment. In contrast to tabletting, in which the particle bed is quasi “sintered” and in which the molded bodies still have a hollow volume, the extrusion leads to very compact particles or pieces, the internal hollow volume of which is significantly reduced, due to the high pressures of 100 bar and above is.

Multi-layer detergent tablets for machine dishwashing are described, for example, in European patent application EP 224 128 (Henkel KGaA). The two layers show differences in solubility. which leads to advantageous application properties.

Multi-phase cleaning tablets for the toilet are described for example in EP 05S 100 (Jeyes Group). This document discloses blocks of toilet detergent comprising a molded body of a slowly soluble detergent composition in which a bleach tablet is embedded. At the same time, this document discloses the most varied forms of configuration of multi-phase shaped bodies. According to the teaching of this document, the moldings are produced either by inserting a pressed bleach tablet into a mold and pouring the detergent composition into this tablet, or by pouring part of the detergent composition into the mold, followed by inserting the pressed bleach tablet and possibly subsequent pouring over with further detergent composition.

EP 481 547 (Unilever) also describes multi-phase detergent tablets which are to be used for automatic dishwashing. These shaped bodies are in the form of core / shell tablets and are produced by gradually compressing the constituents: First, a bleaching composition is pressed into a shaped body, which is inserted into a matrix half-filled with a polymer composition, which is then filled with another polymer composition and into one provided with a polymer jacket bleaching mold body is pressed. The process is then repeated with an alkaline detergent composition, so that a three-phase molded body results.

Another way of producing optically differentiated detergent tablets is described in international patent applications WO99 / 06522, WO99 / 27063 and WO99 / 27067 (Procter & Gamble). According to the teaching of these documents, a molded body is provided which has a cavity which is filled with a solidifying melt. Alternatively, a powder is filled in and fixed in the cavity by means of a coating layer. All three applications have in common that the area filling the cavity should not be pressed, since in this way .. pressure-sensitive "ingredients should be protected.

Both the tableting and the extrusion lead to a high pressure load on the premixes to be processed, which makes it difficult or impossible to incorporate pressure-sensitive ingredients. The production of three-phase or multi-phase molded bodies is no longer possible with both methods without any problems, since the technical effort increases sharply with an increasing number of phases.

The extrusion or co-extrusion of several premixes is hardly possible with a very different proportion of the individual phases. The conventional tableting of multilayer tablets also finds its limits in the field of detergent tablets when one layer only makes up a small proportion of the total tablet should have. If one falls below a certain layer thickness, it is increasingly difficult to press a layer adhering to the rest of the molded body.

The present invention was based on the object of providing a production method for single-phase and multi-phase molded articles, in which pressure-sensitive ingredients can also be introduced into delimited regions, the size of the delimited region being subject to no restrictions with respect to the overall molded article. On the one hand, an optical differentiation from conventional two-layer tablets should be achieved, on the other hand, the production of the molded body should work safely without large technical effort, even in large series, without the molded body having disadvantages in terms of stability or inaccuracies in the dosage.

In particular, the present invention was based on the object of providing a novel production process for detergent tablets which is superior to the previous tableting and extrusion technology in terms of protecting the ingredients from thermal stress, pressure and shear. which is less expensive in terms of equipment and is more economical in terms of process engineering, and enables higher throughputs. In addition, the process should also be usable for the production of three-phase or multi-phase molded bodies without great effort.

It has now been found that the low-pressure strand processing of deformable, hardenable compositions is suitable for the production of detergent tablets and fulfills the requirement profiles mentioned.

The invention relates to a process for the production of detergent tablets. in which one (a) deformable mass (s) is produced and these are supplied at a pressure below 40 bar outlet openings and the exiting material strands are cut to shaped body dimensions and allowed to harden.

The deformable masses which harden after the deformation are preferably fed to the outlet openings at even lower pressures in order to be pressure-sensitive To protect ingredients. Preferred processes are characterized in that the deformable mass (es) at the outlet openings are at a pressure below 35 bar, preferably below 30 bar. fed particularly preferably below 20 bar and in particular below 10 bar.

Depending on the packaging of the deformable masses (see below) and the configuration of the processing machines, even lower pressures can be achieved or an unpressurized procedure is possible. Processes in which the deformable mass (es) are fed to the outlet openings with a pressure below 8.5 bar, preferably below 7.5 bar, particularly preferably below 6.5 bar and in particular below 5 bar, are another important embodiment of the present invention.

In the following, technical parameters and special features of the process according to the invention are described before the ingredients and physical parameters of the masses to be processed are discussed.

The method according to the invention provides for the processing of deformable masses which harden or solidify after forming into compact shaped bodies. In contrast to the extrusion of detergents and cleaning agents, where solid, free-flowing premixes are plasticized by high pressures and processed to give shape, the process according to the invention is operated at low pressures and assumes deformable masses. These deformable masses are not particulate, but rather dough-like or plastic and harden after the shaping processing.

A preferred procedure within the scope of the present invention for feeding the deformable masses to the outlet openings is to draw them in between two rollers which have opposite directions of rotation. As a result, the mass which is located between the rollers is conveyed in the direction of the outlet openings under low pressure as a function of the width of the gap between the rollers and of the roller speed. Depending on the number of pairs of rollers and outlet openings as well as the design of these openings, single or multi-phase material strands result. ge, which can have different shapes and / or colors. These strands of material are cut into sections of predetermined length and the individual strand sections are left to harden to form the finished detergent and molded article.

Single-phase molded bodies are advantageously produced by feeding a deformable mass with a pair of rollers to an outlet opening. Preferred methods are characterized in that a deformable mass is drawn in between two rollers, discharged as a strand of material from outlet openings, cut to the desired shape and dimensioned and allowed to harden.

Apparatus suitable for the preferred processes are available, for example, from Hosokava Bepex GmbH under the name ..Drehstab-Walzenpresse DP ". The outlet openings of such apparatus can be circular, triangular, square, rectangular, heart-shaped, crescent-shaped, etc., for example. The first-mentioned openings then require cylindrical, prismatic, cubic or tetragonal, tetragonal or orthorhombic shaped bodies. The drawings in FIGS. 27 and 29 to 42 exemplarily show some possible designs for outlet openings.

It is also possible to turn the material strands before cutting to the desired shape body dimensions in the processable state after leaving the openings. In this way, shaped bodies are created with irregular, spiral-shaped side surfaces that offer special optical stimuli.

Two-phase molded bodies can be produced in a corresponding manner with two pairs of rollers. Preferred methods for this are characterized in that two differently formable, deformable masses are drawn in between two pairs of rollers and discharged as filled, hollow or multi-layered material strands from outlet openings, cut to the desired shape and allowed to harden. Of course, it is also possible to process two identically composed masses analogously. This then does not serve to separate the active ingredient or to achieve certain washing and cleaning effects, but rather to provide a visual incentive. Also Apparatus suitable for such processes according to the invention are available from Hosokava Bepex GmbH under the name "Double Torsion Roll Press DDP". The outlet openings of such apparatus can be arranged side by side or one inside the other, which results in multi-layered or multi-phase molded bodies. Figures 15 to Examples of some cross sections of outlet openings for different masses are shown in Figures 26 and 28. Figures 15, 16, 17, 19, 21, 23 and 25 result in strands and shaped bodies in which one part, apart from the cut surfaces, is completely enclosed by the other part The other figures mentioned show strands or shaped bodies in which one part is embedded on or only partially in the other part, and here too the material strands can be rotated before being cut to length in order to achieve special optical effects.

The method according to the invention can also be used without problems for the production of three-phase shaped bodies. Such methods according to the invention are carried out completely analogously to the previous embodiments, in that three differently composed, plastically deformable masses are drawn in between three pairs of rollers and discharged as single, double or triple-filled, hollow, two-layer or three-layer material strands from outlet openings to the desired shaped body dimension cut off and allowed to harden.

Of course, it is also possible to process two or even three identically composed masses analogously. This, in turn, does not (only) serve to separate active ingredients or to achieve certain washing and cleaning effects, but rather to provide a visual incentive. Apparatus suitable for the production of three-phase molded articles are also available from Hosokava Bepex GmbH under the name "Dreifach-Drehstab- Walzenpresse DP / 3". The outlet openings of such apparatus can be arranged side by side or one inside the other, which results in multi-layer or multi-phase molded articles. Examples of cross-sections of outlet openings for different masses are shown in Figures 1 to 14. Here, too, the material strands can be rotated before being cut to length to produce special optical effects. The possibilities of discharging several strands of material onto, next to, above, below or inside one another from the apparatus are unlimited, so that four-phase or multi-phase molded bodies can also be produced in a simple manner. Since the apparatus and the associated nozzle systems are simple and robust, changing the product shape and adapting to different market requirements is quick and easy. The appropriate treatment of the material strands before cutting also allows shape changes to be made to the resulting shaped bodies without any problems. If, for example, according to FIG. 1, three material strands are discharged from one another from three outlet openings with a round cross-section, shaped bodies which have the shape of three stacked cylinders result after being cut to length. By simply rotating the three strands of material about their longitudinal axis before cutting to length, one obtains detergent shaped articles; which have the shape of intertwined segments and are reminiscent of rope or braids. The flexibility of the method according to the invention with regard to changing shapes and aesthetic design is thus far above the previously known method.

In the production of multi-phase molded bodies, the ratio of the phases to one another can be chosen freely, and it can be advantageous from an aesthetic point of view if one phase is at least 1/100, preferably at least 1/20 and in particular at least 1/10 of the volume or weight of the other Phase (s). In preferred process end products, the weight ratio of the masses to one another is in the range from 1: 1 to 1: 100, preferably from 1: 2 to 1:75 and in particular from 1: 2.5 to 1:30 (two-phase shaped body) or in the range from 1 : 1.1 to 1: 100: 100, preferably from 1: 1: 2 to 1:75:75 and in particular from 1: 1: 2.5 to 1:30:30 (three-phase molded body). The ratio of the surfaces of the individual molded bodies is preferably in similar ranges.

Depending on the packaging of the deformable masses (see below), ie depending on the ingredients and the physical parameters of the masses to be processed, different throughputs can be achieved, which also depend on the size of the outlet openings. It is preferred to adhere to certain exit speeds for the material strands. In preferred processes, the strands of material at a speed of 0.2 m min to 30 m / min, preferably between 0.25 m / min to 20 m / min, particularly preferably from 0.5 m / min to 15 m min and in particular from 1 m / min to Discharged 10 m min from the outlet openings.

In principle, the method according to the invention is not limited with regard to the shape and size of the outlet openings. With regard to the products to be manufactured and their size or mass, which for such products is usually in the range from 5 to 500 g, preferably from 10 to 250 g, particularly preferably from 15 to 100 g and in particular between 20 and 50 g, Methods are preferred in which the outlet openings have opening areas of from 50 mm ^" to 2500 mm", preferably from 100 mm to 2000 mm ", particularly preferably from 200 mm ^" to 1500 mm ² and in particular from 300 mm ^: to 1000 mm " particularly preferred from 350 mm "to 750 mm ² .

These values can, however, be fallen short of for individual outlet openings, for example if an outlet opening serves to place a thin “tube” over another strand so that it is thereby coated, as it were. Such strand cross sections are, for example, in FIGS. 15, 17, 21 and 23 sketches, but the outer part can be thinner. In the finished molded body there are strands that are coated with the exception of the end faces (cut surfaces), from which effects with regard to the delayed or accelerated release can be achieved. However, with the exception of such coating strands are processes preferred, in which the thickness of at least one of the material strands emerging from the outlet openings is at least 5 mm, preferably at least 7.5 mm and in particular at least 10 mm.

The material strands emerging from the outlet openings can be cut to length according to the known methods of the prior art, for example by rotating knives, countersinkable cutters or wires etc. The mass of the finished molded body depends on the one hand on the size of the outlet openings and on the other hand on the length of the sections. If conventional detergent tablets are to be provided for conventional purposes, such as detergent tablets or detergent tablets for automatic dishwashing, methods are preferred in which the strands of material emerging from the outlet openings are aligned with one another Length from 10 to 100 mm, preferably from 12.5 to 75 mm, particularly preferably from 15 to 60 mm and in particular from 20 to 50 mm, are cut off.

Depending on the composition or the intended use, the limits mentioned can also be exceeded or fallen short of. For example, it is possible to process poorly soluble compositions after curing and to cut them to lengths of 100 to 1000 mm, preferably 120 to 750 mm and in particular 150 to 500 mm. The cured “rods” obtained in this way can then be introduced as depot blocks in washing machines or dishwashers, where a defined part of the block dissolves per washing or rinsing cycle, while the rest remains in the machine or its metering system for the next cleaning cycle.

After being cut to the desired shape body dimensions, the strand sections are allowed to harden. Depending on the composition of the masses, curing takes place in different ways (see below), so that curing can be supported or accelerated if necessary by suitable measures. For example, it is possible to initiate or accelerate reactive hardening by spraying activators on the surface. Irradiation with radioactive rays can also be used with radiation-curing compositions, just like UV radiation for UV-active compositions. In preferred processes, the hardening is carried out by internal and external drying and / or cooling, so that preferred processes are characterized in that the hardening of the material strands cut to the form body dimensions is supported by superficial drying and / or cooling, in particular by blowing with cold air.

After the presentation of the preferred embodiments in terms of apparatus, a description of the deformable and hardening compositions to be processed now follows. The composition and physical parameters as well as possible curing mechanisms are described. The deformable mass (es) can be cured by various mechanisms, the time-delayed water binding, cooling below the melting point, evaporation of solvents, crystallization, by chemical reactions), in particular polymerization, and the change in theological properties, for example by changing Shear of the mass (es) are the most important hardening mechanisms in addition to the radiation softening mentioned above by UV, alpha beta or gamma rays.

In all cases, a deformable, preferably plastic, mass is produced, which can be shaped without great pressure. After the shaping processing, the hardening then takes place by suitable initiation or waiting for a certain period of time. If masses are processed that have self-curing properties without further initiation, this must be taken into account during processing in order to avoid hardening during the shaping processing and thus blockages and disruptions in the process sequences.

In methods preferred in the context of the present invention, the deformable mass (s) are cured by time-delayed water binding.

The time-delayed water binding in the masses processed according to the invention can in turn be implemented in different ways. There are, for example, compositions which contain hydratable, water-free raw materials or raw materials in low hydration levels, which can be converted into stable, higher hydrates, and water. The formation of the hydrates, which does not occur spontaneously, then leads to the binding of free water, which in turn leads to hardening of the masses. A shaping processing with low pressures is then no longer possible, and there are shaped bodies which are stable in handling and which, if appropriate, can be further processed and / or packed.

The time-delayed water binding can also take place, for example, by incorporating hydrate-containing salts, which dissolve in their own crystal water when the temperature rises, into the masses. If the temperature drops later, the stall water bound again, which leads to a loss of formability with simple means and to a solidification of the masses.

The swelling of natural or synthetic polymers as a time-delayed water binding mechanism can also be used in the process according to the invention. Mixtures of unswollen polymer and suitable swelling agent, e.g. Water, diols, glycerin, etc., are incorporated into the masses, swelling and hardening taking place after shaping.

The most important mechanism of hardening through time-delayed water binding is the use of a combination of water and water-free or low-water raw materials that slowly hydrate. For this purpose, there are in particular substances which contribute to the cleaning performance in the washing or cleaning process. In the process according to the invention, preferred ingredients of the deformable compositions are, for example, phosphates, carbonates, silicates and zeolites.

It is particularly preferred if the hydrate forms formed have low melting points, since in this way a combination of the curing mechanisms is achieved by internal drying and cooling. Preferred processes are characterized in that the deformable mass (es) 10 to 95% by weight, preferably 15 to 90% by weight, particularly preferably 20 to 85% by weight and in particular 25 to 80% by weight. % contain anhydrous substances which, by hydration, change into a hydrate form with a melting point below 120 ° C., preferably below 100 ° C. and in particular below 80 ° C.

The deformable properties of the compositions can be influenced by adding plasticizing aids such as polyethylene glycols, polypropylene glycols, waxes, paraffins, nonionic surfactants etc. Further information on the substance classes mentioned can be found below.

Raw materials to be preferably incorporated into the deformable materials come from the group of phosphates, with alkali metal phosphates being particularly preferred. This Fabrics are used in the manufacture of the masses in anhydrous or low-water form and the desired plastic properties of the masses are set with water and optional plasticizing aids. After the shaping processing, the shaped and cut strands are then cured by hydration of the phosphates.

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 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 tissues and also contribute to cleaning performance.

Sodium. NaH ₂ PO exists as a dihydrate (density 1.91 ^'3 , melting point 60 °) and as a monohydrate (density 2.04 ^{' 3} ). Both salts are white, water-soluble powders which, when heated, cause water of crystallization lose and at 200 ° C in the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ HPO ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ Oc _> ) and Maddrell's salt (see below), NaH ₂ PO reacts acidic: it arises when phosphoric acid is adjusted to pH 4.5 with sodium hydroxide solution and the mash is sprayed in. 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 likes ^{' 3} , has a melting point of 253 ° [decomposes to form potassium polyphosphate (KPO ₃ ) _x ] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO, 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 like ^{" 3} , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 ^"3. Melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ θ7 when heated more. Disodium hydrogenphosphate is obtained by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator posed. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO, is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals that like a dodecahydrate a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as a 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 ^"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, 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 is formed, for example, when heating Thomas slag 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 PO ₇ . exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 like ^'3rd melting point 94 ° with loss of water). Colorless substances 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 dehydrating the solution by spraying.The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 ^"3 " which is soluble in water, the pH value being 1% Solution at 25 ° 10.4.

Condensation of the NaH ₂ PO or the KH PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. For the latter in particular, a large number of names are used in need: melting 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 Oι ₀ (sodium tripolyphosphate), is an anhydrous or 6 HO crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 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 Oιo (potassium tripolyphosphate), for example in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25%) K ₂ O) on the market. 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 trimethosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH - »Na ₃ K ₂ P ₃ Oι ₀ + H ₂ O

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

In preferred processes, the deformable mass (s) contain phosphate (s), preferably alkali metal phosphate (s). particularly preferably pentasodium or pentapotassium tri phosphate (sodium or potassium tripolyphosphate), in amounts of 20 to 80% by weight, preferably 25 to 75% by weight and in particular 30 to 70% by weight, in each case based on the mass.

If phosphates are used as the only hydratable substances in the masses, the amount of water added should not exceed their water-binding capacity in order to keep the content of free water in the moldings low. In total, methods have been found to be preferred for complying with the limit values mentioned above, in which the weight ratio of phosphate (s) to water in the deformable mass is less than 1: 0.3, preferably less than 1: 0.25 and in particular less than 1: 0, 2 is.

Other ingredients that can be contained in the deformable compositions instead of or in addition to phosphates are carbonates and / or hydrogen carbonates, the alkali metal salts and, in particular, the potassium and / or sodium salts being preferred. In preferred processes, the deformable mass (es) contain carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably sodium carbonate, in amounts of 5 to 50% by weight, preferably 7.5 up to 40 wt .-% and in particular from 10 to 30 wt .-%, each based on the mass.

The statements made above also apply here with regard to the water content of the masses. In particular, processes have been found to be preferred in which the weight ratio of carbonate (s) and / or hydrogen carbonate (s) to water in the deformable mass is less than 1: 0.2, preferably less than 1: 0, 15 and in particular less than 1 : 0.1 is.

Further ingredients which may be contained in the deformable compositions instead of or in addition to the phosphates and or carbonates / bicarbonates mentioned are silicates, the alkali metal silicates and in particular the amorphous and or crystalline potassium and / or sodium disilicate being preferred.

Suitable crystalline ^'-shaped sodium silicates have the general formula NaMSi 0 ₂ + ^ι' schichtfb H ₂ 0 where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si O ₅ 'yH ₂ O are preferred, with β-sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171.

Amoφhe sodium silicates with a module Na O: SiO ₂ from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are delayed in dissolution, can also be used 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 / compaction or by overdrying. In the context of this invention, the term "amoφh" is also understood to mean "roentgenamoφh". This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be integrated in such a way that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried x-ray silicates.

In processes preferred within the scope of the present invention, the deformable mass (es) contain silicate (s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates. in amounts of 10 to 60% by weight. preferably from 15 up to 50 wt .-% and in particular from 20 to 40 wt .-%, each based on the mass.

The statements made above also apply here with regard to the water content of the masses. In particular, processes have been found to be preferred in which the weight ratio of silicate (s) to water in the deformable mass is less than 1: 0.25, preferably less than 1: 0.2 and in particular less than 1: 0.15.

Substances from the group of zeolites are also suitable as an important component in the compositions to be processed according to the invention. These substances are preferred builders in particular in the production of detergent tablets. Zeolites have the general formula

M _{2 / n} O ^• Al ₂ O ₃ ^• x SiO ₂ ^• y H ₂ O

where M is a cation of valence n, x stands for values that are greater than or equal to 2 and y can assume values between 0 and 20. The zeolite structures are formed by linking AlO ₄ tetrahedra with SiO tetrahedra, this network being occupied by cations and water molecules. The cations in these structures are relatively mobile and can be exchanged for other cations in different degrees. Depending on the type of zeolite, the intercrystalline “zeolitic” water can be released continuously and reversibly, while for some types of zeolite structural changes are also associated with the water release or uptake.

In the structural subunits, the “primary binding units” (AlO ₄ tetrahedra and SiO tetrahedra) form so-called “secondary binding units”, which have the form of one or more rings. For example, 4-, 6- and 8-membered rings appear in different zeolites (referred to as S4R, S6R and S8R), other types are connected via four- and six-membered double ring prisms (most common types: D4R as a square prism or D6R as a hexagonal prism ). These "secondary subunits" connect different polyhedra, which are denoted by Greek letters. The most common is a polyhedra of six squares and eight equilateral hexagons is constructed and which is referred to as "ß". With these units, a variety of different zeolites can be realized. So far 34 natural zeolite minerals and about 100 synthetic zeolites are known.

The best known zeolite, zeolite 4 A, is a cubic combination of ß-cages that are linked by D4R subunits. It belongs to the zeolite structure group 3 and its three-dimensional network has pores of 2.2 Ä and 4.2 Ä size, the formula unit in the unit cell can be with Naι ₂ [(AlO ₂ ) ι ₂ (SiO ₂ ) ι ₂ ] ^• Describe 27 H ₂ O.

Zeolites of the faujasite type are preferably used in the process according to the invention. Together with the zeolites X and Y, the mineral faujasite belongs to the faujasite types within the zeolite structure group 4, which is characterized by the double six-ring subunit D6R (compare Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons. New York, London, Sydney, Toronto. 1974. Page 92). In addition to the faujasite types mentioned, the zeolite structure group 4 also includes the minerals chabazite and gmelinite as well as the synthetic zeolites R (chabazite type), S (gmelithite- Type), L and ZK-5. The latter two synthetic zeolites have no mineral analogues.

Faujasite-type zeolites are made up of ß-cages which are tetrahedral linked by D6R subunits, the ß-cages being arranged similar to the carbon atoms in the diamond. The three-dimensional network of the zeolites of the faujasite type used in the process according to the invention has pores of 2.2 and 7.4 Å, the unit cell also contains 8 cavities with a diameter of approximately 13 Å and can be represented by the formula Na86 [(AlO) ₈₆ ( iO ₂ ) ιo6] ^' 264 H ₂ O describe. The network of the Zeolite X contains a void volume of approximately 50%. based on the dehydrated crystal, which represents the largest empty space of all known zeolites (zeolite Y: approx. 48% o void volume. Faujasite: approx. 47% void volume). (All data from: Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons. New York. London, Sydney. Toronto. 1974. Pages 145. 176. 177). In the context of the present invention, the term “faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolim structure group 4. In addition to the zeolite X, zeolite Y and faujasite and mixtures of these compounds can also be used according to the invention, the pure zeolite X is preferred.

Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites which do not necessarily have to belong to the zeolite structure group 4 can also be used according to the invention, the advantages of the process according to the invention being particularly evident when at least 50% by weight of the powdering agent consist of a zeolite of the faujasite type. It is also conceivable, for example, that the minimum amount of a faujasite-type zeolite (0.5% by weight, based on the weight of the molded body formed) is used and conventional zeolite A is used as the remaining powdering agent. In any case, however, it is preferred that the powdering agent consists exclusively of one or more zeolites of the faujasite type, zeolite X again being preferred.

The aluminum silicates which are preferably used in the process according to the invention are commercially available and the methods for their preparation are described in standard monographs.

Examples of commercially available X-type zeolites can be described by the following formulas:

Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀ 6] ^• x H ₂ O,

K ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] ^• x H ₂ O,

Ca4oNa6 [(AlO ₂ ) g6 (SiO ₂ ) ιo6] ^" x H ₂ O,

Sr ₂₁ Ba ₂₂ [(AlO ₂ ) ₈ 6 (SiO ₂ ), o6] ^" x H ₂ O, in which x can have values between 0 and 276 and the pore sizes range from 8.0 to 8.4 Å.

Preferably commercially available and within the scope of the inventive method is used, for example, a co-crystallizate of zeolite X and zeolite A (ca. 80 wt .-% zeolite X) which is marketed by CONDEA Augusta SpA under the trade name VEGOBOND AX ^® and through the formula

nNa ₂ O ^• (ln) K ₂ O ^• Al ₂ O ₃ ^• (2 - 2.5) SiO ₂ "(3.5 - 5.5) H ₂ O

can be described.

Y-type zeolites are also commercially available and can be expressed, for example, by the formulas

Na ₅₆ [(AlO ₂ ) ₅ 6 (SiO ₂ ) ₁₃₆ ] ^• x H ₂ O,

K ₅₆ [(AlO ₂ ) 56 (SiO ₂ ) ι ₃₆ ] ^■ x H ₂ O,

in which x stands for numbers between 0 and 276 and have a pore size of 8.0 Å.

Preferred processes are characterized in that the deformable mass (es) zeolite (s), preferably zeolite A, zeolite P, zeolite X and mixtures thereof, in amounts of 10 to 60% by weight, preferably 15 to 50 wt .-% and in particular from 20 to 40 wt .-%, each based on the mass.

The particle sizes of the zeolites of the faujasite type which are preferably used in the process according to the invention are preferably in the range from 0.1 to 100 μm, preferably between 0.5 and 50 μm and in particular between 1 and 30 μm, each measured using standard particle size determination methods. It is generally preferred to use finely divided solids in the compositions to be processed according to the invention, regardless of whether these are the zeolites mentioned or other builders or bleaching agents. Bleach activators or other solids. Process variants are very generally preferred in which the mean particle size of the solids used in the deformable mass (s) is below 400 μm, preferably below 300 μm and in particular below 200 μm.

The mean particle size represents the arithmetic mean of the individual particle sizes, which can still fluctuate. Particularly preferred processes are characterized in that less than 10% by weight, preferably less than 5% by weight and in particular less than 1% by weight of the solids used in the deformable mass (s) have particle sizes above 1000 μm , The upper particle size range can be narrowed even further, so that particularly preferred processes are characterized in that less than 15% by weight, preferably less than 10% by weight and in particular less than 5% by weight, of the materials which can be deformed Mass (s) solids used have particle sizes above 800 microns.

In general, however, even narrower particle size distributions are preferred, in which the fluctuation range around the average particle size is at most 50%, preferably at most 40% and in particular at most 30% of the average particle size, that is to say the particle sizes are at least 0.7 times and at most 1.3 times that make up average particle size.

The weight ratio of water to certain ingredients has been given above in masses which are preferably to be processed according to the invention. After processing, this water is preferably bound in the form of water of hydration, so that the end products of the process preferably have a significantly lower free water content. Preferred end products of the process according to the invention are essentially water-free, ie in a state in which the content of liquid water, ie water not present in the form of hydrate water and / or constitutional water, is below 2% by weight. preferably below 1% by weight and in particular even below 0.5% by weight. each based on the molded body. lies. Accordingly, the inventive drive preferred, in which the molded body contain less than 10 wt .-%, preferably less than 5 wt .-%, particularly preferably less than 1 wt .-% and in particular less than 0.5 wt .-% free water. Accordingly, water can essentially only be present in chemically and / or physically bound form or as a constituent of the raw materials or compounds present as a solid, but not as a liquid, solution or dispersion in the end products of the process according to the invention. At the end of the manufacturing process according to the invention, the molded articles advantageously have a total water content of not more than 15% by weight, this water therefore not being in liquid free form but chemically and / or physically bound, and it is particularly preferred. that the content of water not bound to zeolite and or to silicates in the solid premix is not more than 10% by weight and in particular not more than 7% by weight.

Process end products which are particularly preferred in the context of the present invention not only have an extremely low proportion of free water, but are preferably also themselves capable of binding further free water. In preferred methods, the water content of the molded body is 50 to 100% of the calculated water binding capacity.

The water binding capacity is the ability of a substance (here: the end product of the process). To absorb water in a chemically stable form and ultimately indicates. how much water can be bound in the form of stable hydrates by a substance or a molded body. The dimensionless value of the water binding capacity (WBV) is calculated from:

«• 18th

WBV = -

M

where n is the number of water molecules in the corresponding hydrate of the substance and M is the molar mass of the non-hydrated substance. This gives, for example, a value of the water-binding capacity of anhydrous sodium carbonate (formation of sodium carbonate monohydrate) 1-18

WBV = - = 0.17.

2 - 23 + 12 + 3 - 16

The W ^τ ert loggers can thereby for all hydrate substances that are used in the invention to be processed masses are calculated. The total water-binding capacity of the formulation then results from the percentage of these substances. In preferred end products of the process, the water content is then between 50 and 100% of this calculated value.

In addition to the water content of the end products of the process and the ratio of water to certain raw materials, information can also be given about the absolute water content of the masses to be processed according to the invention. In particularly preferred processes, the deformable mass (es) have / have a water content of 2.5 to 30% by weight, preferably 5 to 25% by weight and in particular 7.5 to 20% by weight during processing .-% o, each based on the mass.

Another mechanism for curing the masses processed in the process according to the invention is the cooling during processing of the masses above their softening point. Methods in which the deformable mass (s) are cured by cooling below the melting point are therefore preferred.

Masses softenable under the influence of temperature can be easily assembled by mixing the desired further ingredients with a meltable or softenable substance and heating the mixture to temperatures in the softening range of this substance and shaping it at these temperatures. Waxes are particularly preferred as meltable or softenable substances. Paraffins, polyalkylene glycols etc. are used. These are described below.

The meltable or softenable substances should have a melting range (solidification range) in such a temperature range in which the others Ingredients of the masses to be processed are not exposed to excessive thermal stress. On the other hand, however, the melting range must be sufficiently high to still provide a manageable molded body at at least a slightly elevated temperature. In preferred compositions according to the invention, the meltable or softenable substances have a melting point above 30 ° C.

It has proven to be advantageous if the meltable or softenable substances do not have a sharply defined melting point, as is usually the case with pure, crystalline substances, but instead have a melting range that may include several degrees Celsius. The meltable or softenable substances preferably have a melting range which is between approximately 45 ° C. and approximately 75 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range. The width of the melting range is preferably at least 1 ° C., preferably about 2 to about 3 ° C.

The properties mentioned above are usually fulfilled by so-called waxes. "Waxing" is understood to mean a number of natural or artificially obtained substances which generally melt above 40 ° C. without decomposition and which are relatively low-viscosity and not stringy even a little above the melting point. They have a strongly temperature-dependent consistency and solubility.

The waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes.

Natural waxes include, for example, vegetable waxes such as candelilla wax. Carnauba wax. Japanese wax, esparto grass wax. Cork wax, guaruma wax, rice germ oil wax. Sugar cane wax, Ouricury wax. or montan wax, animal waxes like beeswax. Shellac wax. Walrate, lanolin (wool wax), or pretzel fat, mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum. Paraffin waxes or micro waxes. The chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material which meet the stated softening point requirements can also be used as meltable or softenable substances for the masses hardening by cooling. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is available under the name Unimoll 66 ^® (Bayer AG) commercially. proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ^® ETLP (Condea). Conversely, synthetic or partially synthetic esters from lower alcohols with fatty acids from native sources can also be used. Tegin ^® 90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances. Shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used according to the invention as meltable or softenable substances.

The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol. Myristyl alcohol or melissyl alcohol. The coating of the solid particles coated according to the invention can optionally also contain wool wax alcohols, including Triteφenoid and steroid alcohols. for example, lanolin, which is obtainable for example under the trade name Argowax ^® (Pamentier & Co). In the context of the present invention, fatty acid glycerol esters or fatty acid alkanolamides but also, if appropriate, water-insoluble or only slightly water-soluble polyalkylene glycol compounds can likewise be used at least in part as a constituent of the meltable or softenable substances. Particularly preferred meltable or softenable substances in the compositions to be processed are those from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG), polyethylene glycols with molecular weights between 1500 and 36,000 being preferred, those with molecular weights from 2000 to 6000 particularly preferred and those with molecular weights of 3000 to 5000 are particularly preferred. Corresponding processes which are characterized in that the plastically deformable mass (es) contain / contain at least one substance from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) are preferred.

Here, compositions to be processed according to the invention are particularly preferred which contain propylene glycols (PPG) and / or polyethylene glycols (PEG) as the only meltable or softenable substances. Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the general formula I

H- (O-CH-CH ₂ ) "- OH (I)

I CH ₃

are sufficient, where n can take values between 10 and 2000. Preferred PPGs have molar masses between 1000 and 10,000, corresponding to values of n between 17 and approximately 170.

Polyethylene glycols (abbreviation PEG) which can preferably be used according to the invention are polymers of ethylene glycol which have the general formula II

H- (O-CH ₂ -CH ₂ ) _π -OH (II)

are sufficient, where n can have values between 20 and approx. 1000. The preferred molecular weight ranges mentioned above correspond to preferred ranges of the value n in formula IV from approximately 30 to approximately 820 (exactly: from 34 to 818). especially preferably from about 40 to about 150 (exactly: from 45 to 136) and in particular from about 70 to about 120 (exactly: from 68 to 113).

In a further preferred embodiment, the masses to be processed according to the invention predominantly contain paraffin wax. This means that at least 50% by weight of the total meltable or softenable substances contained, preferably more, consist of paraffin wax. Paraffin wax contents (based on the total amount of meltable or softenable substances) of approximately 60% by weight, approximately 70% by weight or approximately 80% by weight are particularly suitable, even higher proportions of, for example, more than 90% by weight. are particularly preferred. In a particular embodiment of the invention, the total amount of meltable or softenable substances used consists of at least one mass consisting exclusively of paraffin wax.

Paraffin waxes have the advantage over the other natural waxes mentioned in the context of the present invention that there is no hydrolysis of the waxes in an alkaline detergent environment (as is to be expected, for example, from the wax esters), since paraffin wax contains no hydrolyzable groups.

Paraff waxes consist mainly of alkanes, as well as low levels of iso- and cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C. Portions of high-melting alkanes in the paraffin can leave undesired wax residues on the surfaces to be cleaned or the goods to be cleaned if the melting temperature in the detergent solution drops below this. Such wax residues usually lead to an unsightly appearance on the cleaned surface and should therefore be avoided.

Masses to be processed preferably contain at least one paraffin wax with a melting range of 50 ° C. to 60 ° C. as meltable or softenable substances. being Preferred processes are characterized in that the deformable mass (es) contain a paraffin wax with a melting range of 50 ° C to 55 ° C.

Preferably, the paraffin wax content of alkanes solid at ambient temperature (usually about 10 to about 30 ° C.). Isoalkanes and cycloalkanes as high as possible. The more solid wax components present in a wax at room temperature, the more useful it is within the scope of the present invention. As the percentage of solid wax components increases, the process end products' ability to withstand impacts or friction on other surfaces increases, which leads to longer-lasting protection. High proportions of oils or liquid wax components can lead to a weakening of the molded body or molded body areas, whereby pores are opened and the active substances are exposed to the environmental influences mentioned at the beginning.

In addition to paraffin, the meltable or softenable substances can also contain one or more of the above-mentioned waxes or wax-like substances as the main constituent. In a further preferred embodiment of the present invention, the mixture forming the meltable or softenable substances should be such that the mass and the molded body or molded body component formed therefrom are at least largely water-insoluble. The solubility in water should not exceed about 10 mg / 1 at a temperature of about 30 ° C. and should preferably be below 5 mg / 1.

In such cases, however, the meltable or softenable substances should have the lowest possible solubility in water, even in water at an elevated temperature, in order to largely avoid a temperature-independent release of the active substances.

The principle described above is used to delay the release of ingredients at a certain point in the cleaning cycle and can be used particularly advantageously when washing in the main rinse cycle at a lower temperature (for example 55 ° C.), so that the active substance from the rinse aid particles only in the rinse cycle at a higher level Temperatures (approx. 70 ° C) is released. Preferred compositions to be processed according to the invention are characterized in that, as meltable or softenable substances, they contain one or more substances with a melting range from 40 ° C to 75 ° C in amounts of 6 to 30% by weight, preferably 7.5 to 25% Wt .-% and in particular from 10 to 20 wt .-%>, each based on the weight of the mass.

Another mechanism by which the compositions can be cured is the evaporation of solvents. For this purpose, solutions or dispersions of the desired ingredients can be prepared in one or more suitable, volatile solvents, which release these solvents after the shaping processing step and thereby harden. Examples of suitable solvents are lower alkanols, aldehydes, ethers, esters, etc., the selection of which is made depending on the further composition of the materials to be processed. Particularly suitable solvents for processes in which the deformable composition (s) are cured by evaporation of solvents are 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 and the acetic acid esters of the above-mentioned alcohols, especially ethyl acetate.

The evaporation of the solvents mentioned can be accelerated by heating following the shaping and cutting to length, or by air movement. Combinations of the measures mentioned are also suitable for this purpose, for example blowing the cut-to-length molded body with warm or hot air.

Another mechanism that can underlie the hardening of the molded and cut masses is crystallization. Methods in which the deformable mass (s) are cured by crystallization are also preferred. Crystallization as the mechanism on which the hardening is based can be used, for example, by melting melted crystalline substances as the basis for one or more moldable masses. After processing, such systems go into a higher order state, which in turn leads to curing of the entire molded body formed. However, crystallization can also be carried out by crystallization from supersaturated solution. In the context of the present invention, supersaturation is the term for a metastable state in which more of a substance is present in a closed system than is required for saturation. A supersaturated solution obtained, for example, by hypothermia therefore contains more solute than it should contain in thermal equilibrium. The excess of dissolved substance can be brought to instantaneous crystallization by seeding with germs or dust particles or by shaking the system. In the context of the present invention, the term “oversaturated” always refers to a temperature of 20 ° C. If a substance dissolves x gram per liter in a certain solvent at a temperature of 20 ° C, the solution in the context of the present invention can be described as "supersaturated" if it contains (x + y) gram of the substance per liter , where y> 0 applies. Thus, in the context of the present invention, solutions are also to be referred to as "oversaturated", which serve as the basis of a mass to be processed at an elevated temperature and are processed at this temperature at which there is more of a solute in the solution than in Would dissolve 20 ° C in the same amount of solvent.

The term “solubility” is understood by the present invention to mean the maximum amount of a substance that the solvent can absorb at a certain temperature, ie the proportion of the solute in a solution saturated at the temperature in question. If a solution contains more solute than it should contain in the thermodynamic equilibrium at a given temperature (e.g. under hypothermia), it is called supersaturated. Vaccinating with germs can cause the excess to fail as the bottom body of the now only saturated solution. However, a solution saturated with one substance can also dissolve other substances (for example, sugar can still be dissolved in a saturated saline solution). As described above, the state of supersaturation can be achieved by slow cooling or by subcooling a solution as long as the solute is more soluble in the solvent at higher temperatures. Other ways of achieving supersaturated solutions are, for example, combining two solutions, the ingredients of which react to form another substance that does not immediately fail (prevented or delayed precipitation reactions). The latter mechanism is particularly suitable as the basis for the formation of masses to be processed according to the invention.

In principle, the state of supersaturation can be achieved with any type of solution, although, as already mentioned, the principle described in the present application is used in the production of detergents and cleaning agents. As a result, some systems, which in principle tend to form supersaturated solutions, can be used less well according to the invention. because the underlying substance systems cannot be used ecologically, toxicologically or for economic reasons. In addition to non-ionic surfactants or common non-aqueous solvents, methods according to the invention with the last-mentioned curing mechanism are therefore particularly preferred, in which a supersaturated aqueous solution is used as the base for at least one mass to be processed.

As already mentioned above, the state of supersaturation in the context of the present invention relates to the saturated solution at 20 ° C. By using solutions with a temperature above 20 ° C, the state of supersaturation can easily be reached. Processes according to the invention, in which the mass hardening by crystallization during processing has a temperature between 35 and 120 ° C. preferably between 40 and 110 ° C. particularly preferably between 45 and 90 ° C and in particular between 50 and 80 ° C. has are preferred in the context of the present invention.

Since the detergent tablets produced are generally neither stored at elevated temperatures nor used later at these elevated temperatures, the cooling of the mixture leads to the precipitation of the proportion of solute from the supersaturated solution which was present in the solution above the saturation limit at 20 ° C. The supersaturated solution can thus be divided into a saturated solution and a bottom body when it cools down. However, it is also possible that the supersaturated solution solidifies to a solid on cooling due to recrystallization and hydration phenomena. This is the case, for example, when certain hydrated salts dissolve in their crystal water when heated. When cooling, supersaturated solutions are often formed here, which solidify through mechanical action or the addition of germs to a solid - the salt containing water of crystallization as the state that is thermodynamically stable at room temperature. This phenomenon is known, for example, from sodium thiosulfate pentahydrate and sodium acetate trihydrate. the latter salt in the form of the supersaturated solution, in particular, being advantageously used in the process according to the invention. Special detergent and cleaning agent ingredients, such as phosphonates, also show this phenomenon and are ideally suited as granulation aids in the form of solutions. For this purpose, the corresponding phosphonic acids (see below) are neutralized with concentrated alkali water, whereby the solution heats up due to the heat of neutralization. On cooling, solids of the corresponding alkali metal phosphonates are formed from these solutions. By incorporating further detergent and cleaning agent ingredients into the still warm solutions, masses of different composition that can be processed according to the invention can be produced. Particularly preferred methods according to the invention are characterized in that the supersaturated solution serving as the basis for the hardening mass solidifies to a solid at room temperature. It is preferred here that the previously supersaturated solution, after solidification to a solid by heating to the temperature at which the supersaturated solution was formed, cannot be converted back into a supersaturated solution. This is the case, for example, with the phosphonates mentioned.

The supersaturated solution serving as the basis of the hardening mass can - as mentioned above - be obtained in several ways and then processed according to the invention after optional addition of further ingredients. A simple way consists, for example, in that the supersaturated solution serving as the base of the hardening mass is prepared by dissolving the dissolved substance in heated solvent. In this way, higher amounts of the solute are in the heated solvent dissolved than would dissolve at 20 ° C, there is a supersaturated solution within the meaning of the present invention, which can either be hot (see above) or cooled and added to the mixer in the metastable state.

It is also possible to dehydrate hydrate-containing salts by "dry ^* " heating and to dissolve them in their own water of crystallization (see above). This is also a method for producing supersaturated solutions which can be used in the context of the present invention.

Another way is to add a gas or another liquid or solution to a non-supersaturated solution so that the solute reacts in the solution to a poorly soluble substance or dissolves poorly in the mixture of solvents. Combining two solutions, each containing two substances that react with each other to form a poorly soluble substance, is also a method for producing supersaturated solutions, as long as the poorly soluble substance does not immediately fail. Processes which are likewise preferred in the context of the present invention are characterized in that the supersaturated solution which serves as the basis for the hardening composition is prepared by combining two or more solutions. Examples of such ways to make supersaturated solutions are discussed below.

Preferred processes according to the invention are characterized in that the supersaturated aqueous solution by combining an aqueous solution of one or more acidic ingredients of detergents and cleaning agents, preferably from the group of surfactant acids. the builder acids and the complexing acids, and an aqueous alkali solution, preferably an aqueous alkali hydroxide solution, in particular an aqueous sodium hydroxide solution.

Among the representatives of the compound classes mentioned above, the phosphonates in particular have an outstanding position in the context of the present invention. In preferred processes according to the invention, therefore, the supersaturated aqueous solution is obtained by combining an aqueous phosphonic acid solution with concentrations above 45% by weight. preferably above 50% by weight and in particular the above 55 wt .-%. in each case based on the phosphonic acid solution and an aqueous sodium hydroxide solution with concentrations above 35% by weight, preferably above 40% by weight and in particular above 45% by weight. each based on the sodium hydroxide solution obtained.

According to the invention, the deformable mass (es) can also be cured by chemical reaction (s), in particular polymerization. In principle, all chemical reactions are suitable which, starting from one or more liquid to pasty substances, lead to solids by reaction with (another) substance (s). Chemical reactions that do not suddenly lead to the state change mentioned are particularly suitable. From the variety of chemical reactions that lead to the solidification phenomenon, reactions are particularly suitable in which larger molecules are built up from smaller molecules. Again, this preferably includes reactions in which many small molecules react to (one) larger molecule (s). These are so-called polyreactions (polymerization, polyaddition, polycondensation) and polymer-analogous reactions. The corresponding polymers, polyadducts (polyaddition products) or polycondensates (polycondensation products) then give the molded body, which has been cut to length, its strength.

With regard to the intended use of the products produced according to the invention, it is preferred to use the formation of such solid substances from liquid or pasty starting materials as the curing mechanism, which in the washing and cleaning agent are anyway present as ingredients, for example cobuilders, soil repellents or soil release Polymers are to be used. Such cobuilders can be obtained, for example, from the groups of polycarboxylates / polycarboxylic acids. polymeric polycarboxylates, aspartic acid. Polyacetals. Dextrins, etc. These classes of substances are described below.

Another mechanism by which the deformable mass (s) can be cured in the process according to the invention is the curing which takes place by changing the theological properties. This takes advantage of the property that certain substances can drastically change their rheological properties under the influence of shear forces. Examples of such systems which are known to the person skilled in the art are, for example, layered silicates which, under Schemng, have a strongly thickening effect in suitable matrices and can lead to cut-resistant materials.

Of course, two or more curing mechanisms can also be combined or used simultaneously in one mass. Here, for example, crystallization with simultaneous solvent evaporation, cooling with simultaneous crystallization, water binding ("internal drying") with simultaneous external drying etc. are appropriate.

The general description of mechanisms which can be the basis of the curing process according to the invention is followed by a detailed description of the ingredients to be used in the masses to be processed.

Preferred end products of the process according to the invention, that is to say preferred detergent tablets, furthermore contain one or more surfactant (s). Accordingly, it is preferred that at least one of the compositions to be processed contains surfactant (s). Anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these can be used in the detergent tablets according to the invention. Mixtures of anionic and nonionic surfactants are preferred from an application point of view. The total surfactant content of the molded article in the case of detergent tablets is 5 to 60% by weight, based on the weight of the molded article. wherein surfactant contents above 15% by weight are preferred, while detergent tablets for automatic dishwashing preferably contain below 5% by weight 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 - Alkylene benzene sulfonates. Olefin. ie mixtures of alkene and Hvdroxvalkansul- phonates and disulfonates. as obtained, for example, from Cι- ₈ monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonium products. Alkanesulfonates are also suitable. which are obtained from C 12-1 ₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. The mono- are among fatty acid glycerides. To understand di- and triesters and their mixtures, as they are obtained in the production 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 glycerol. Preferred sulfated fatty acid glycerol esters are the sulfate products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid. Myristic acid, lauric acid. Palmitic acid. Stearic acid or behenic acid.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₂ -C 8 fatty alcohols, for example from coconut oil alcohol. Tallow. Lauryl, myristyl, cetyl or stearyl alcohol or the Cιo-C ₂ o-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, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. For reasons of washing technology, the C ₂ -C ₆ alkyl sulfates and C ₂ -Ci ₅ alkyl sulfates and C -C ₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates. Suitable anionic surfactants, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN *.

The sulfuric acid monoesters of the straight-chain or branched C?.?! Ethoxylated with 1 to 6 mol ethylene oxide! Alcohols, such as 2-methyl-branched CQ. _Π alcohols with on average 3.5 moles of ethylene oxide (EO) or Cι ₂ -ι ₈ 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 in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cs-is 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 whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids. e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

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

Preferred nonionic surfactants are alkoxylated, advantageously ethoxylated. in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be methyl-branched linearly or preferably in the 2-position or can contain linear and methyl-branched radicals in the mixture , as they are usually present in oxo alcohol residues. In particular, however, are alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms. e.g. from coconut, palm, tallow or oleyl alcohol. and an average of 2 to 8 EO per mole of alcohol is preferred. Preferred ethoxylated alcohols include, for example, Cι ι _{2- 4} alcohols containing 3 EO or 4 EO, C ₉ n-alcohol with 7 EO, Cι _{3-] 5} alcohols containing 3 EO, 5 EO, 7 EO or 8 EO , Cι _2- ι ₈ alcohols with 3 EO. 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2-ι alcohol with 3 EO and Cι _2- ι ₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G the symbol is. that for a glycose unit with 5 or 6 carbon atoms. preferably stands 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 having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.

Also nonionic surfactants of the amine oxide type. for example N-cocoalkyl-N, N-dimethvlaminoxid and N-Talgalkvl-NN-dihvdroxvethvlaminoxid. and the fatty acid alka- nolamides may be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (III),

R ^J

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

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

The group of polyhydroxy fatty acid amides also includes compounds of the formula (IV)

R -OR ²

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

in the R for a linear or branched alkyl or alkenyl radical with 7 to 12 carbon atoms. R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R stands for a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical with 1 to 8 carbon atoms, G- -alkyl- or Phenyl radicals are preferred and [Z] stands for a linear Polvhvdroxvalkvlrest, the Alkvlkette with at least two Hvdrox- yl groups is substituted, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.

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

In the context of the present invention, the production of laundry detergent and cleaning agent moldings which contain anionic (s) and nonionic (s) surfactant (s) is preferred, with application technology advantages being able to result from certain quantitative ratios in which the individual classes of surfactants are used ,

For example, detergent tablets are particularly preferred in which the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2. Preference is also given to detergent tablets which contain surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), in amounts of 5 to 40% by weight, preferably 7.5 to 35% by weight .-%, particularly preferably from 10 to 30 wt .-%> and in particular from 12.5 to 25 wt .-%>, each based on the molded body weight.

From an application point of view, it can be advantageous if certain classes of surfactants are present in some phases of the detergent tablets or in the entire molded article, i.e. in all phases, are not included. Another important embodiment of the present invention therefore provides that at least one phase of the molded article is free of nonionic surfactants.

Conversely, the content of individual phases or the entire molded body can also be used. ie all phases, a certain effect can be achieved on certain surfactants. The introduction of the alkyl polyglycosides described above has proven advantageous proven, so that washing and cleaning agent moldings are preferred in which at least one phase of the molding contains alkyl polyglycosides.

Similar to nonionic surfactants, the omission of anionic surfactants from individual or all phases can result in detergent tablets which are more suitable for certain areas of application. It is therefore also conceivable within the scope of the present invention for detergent tablets to be made in which at least one phase of the tablet is free from anionic surfactants.

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 used as detergent tablets are characterized in that they have 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 on their total weight. Only weakly foaming nonionic surfactants are usually used as surfactants in automatic dishwashing detergents. By contrast, representatives from the groups of anionic, cationic or amphoteric surfactants are of lesser importance. Particular preference is given to the fact that shaped articles for machine dishwashing produced according to the invention contain nonionic surfactants, in particular nonionic surfactants from the group of 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 radical 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. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms. eg from coconut, palm. Taig fat or oleyl alcohol. and an average of 2 to 8 EO per mole of alcohol is preferred. The preferred ethoxylated alcohols include, for example, -C _2- alcohols with 3 EO or 4 EO, C ₉ .n alcohol with 7 EO. C ₁₃ - ₁₅ - Alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -ι ₈ - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Cι _2- ι ₄ alcohol with 3 EO and Cι ₂ -ι ₈ - alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages. These 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

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

Preferred nonionic surfactants to be used as solid at room temperature originate from the groups of alkoxylated nonionic surfactants. especially the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control. In a preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C ₆ - _2NC alcohol), preferably a cis-alcohol and at least 12 moles, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide.. Among these, the so-called "narrow ranks ethoxylates" (see above) are particularly preferred.

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

Further nonionic surfactants with melting points above room temperature that are particularly preferably used contain 40 to 70% of a polyoxypropylene-polyoxyethylene / polyoxypropylene block polymer blend. which is 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% 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, which can be used with particular preference, are available, for example, under the name Poly Tergent® SLF-18 from the company Olin Chemicals.

Another preferred surfactant can be represented by the formula

R ⁱ O [CH ₂ CH (CH ₃ ) 0] _x [CH ₂ CH ₂ 0] _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 with 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1.5 and y stands for a value of at least 15.

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

R'θ [CH ₂ CH (R ³ ) 0] [CH ₂ ] _k CH (OH) [CH ₂ ] jOR 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 stands} for H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x 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 ^J in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H. -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ^J in the above formula can be different if x> 2. This allows the alkylene oxide unit in the square brackets to be be. For example, if x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which can be joined together in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been chosen here by way of example and may well be greater, 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 formula above

R'θ [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 have} 9 to 14 carbon atoms, R ^{3 represents} H and x assumes values from 6 to 15.

The above information relates in part to the end products of the process, which - as mentioned above - can also have two, three or four phases. Based on the individual mass to be processed which contains surfactant (s), methods are preferred in the production of detergent tablets for automatic dishwashing, in which the deformable mass (es) total surfactant contents are below 5% by weight, preferably below of 4% by weight, particularly preferably below 3% by weight and in particular below 2% by weight, in each case based on the mass.

In addition to the constituents mentioned, builder and surfactant, the laundry detergent and cleaning product tablets according to the invention can contain further ingredients customary in washing and cleaning agents from the group of bleaches, bleach activators. Desintegrationshilfs- agents, dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors, color transfer inhibitors and corrosion inhibitors. These substances can be used in all the masses to be processed, but it is also possible to utilize advantageous properties by separating certain ingredients.

In order to facilitate the disintegration of highly compressed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, in order to shorten the disintegration times. These substances are suitable, for example, to accelerate the release of individual molded body areas compared to other areas. This can be achieved in the process according to the invention in that only one of the masses to be processed contains such substances, or in that several masses contain such substances in different amounts. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184), tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.

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

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 auxiliaries, in each case based on the molded article weight. Contains only one mass Disintegration aids, the information given relates only to the weight of this mass.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets form 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 to 6 % By weight. Pure cellulose has the formal composition of the composition (C _Ö H _IO O _S ^ and, formally speaking, is a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 Glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or Etherifications in which hydroxyl hydrogen atoms have been substituted, but also celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound by an oxygen atom, can be used as cellulose derivatives, in the group of cellulose derivatives fall, for example, alkali celluloses, carboxymethylce llulose (CMC). Cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free from cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated. Detergent and molded articles. the disintegrants in granular or optionally co-granulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in the present invention.

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

Detergent tablets preferred in the context of the present invention additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight. preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. each based on the molded body weight.

The detergent tablets according to the invention can also contain a gas-evolving shower system which is incorporated into one or more of the masses to be processed. The gas-developing shower system can consist of a single substance that releases a gas when it comes into contact with water. Among these compounds, particular mention should be made of magnesium peroxide, which is in contact with water This releases oxygen. Usually, however, the gas-releasing nozzle system in turn consists of at least two components that react with one another to form gas. While a large number of systems are conceivable and executable here, which release nitrogen, oxygen or hydrogen, for example, the toilet system used in the laundry detergent and cleaning product shaped bodies according to the invention can be selected on the basis of both economic and ecological considerations. Preferred effervescent systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.

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

In preferred detergent tablets, the shower system used is 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10% by weight of an acidifying agent, in each case based on the total molded body. used. The content of individual substances in the substances mentioned may well be higher.

Examples of acidifying agents which release carbon dioxide from the alkali salts in aqueous solution are boric acid and alkali metal bisulfates. Alkali metal dihydrogen phosphates and other inorganic salts can be used. 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. For this group tartaric acid is preferred. Succinic acid. Malonic acid. Adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid can also be used. Commercially available and as an acidifying agent in the men of the present invention also preferably be used is Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) and adipic acid (max. 33 by weight %).

In the context of the present invention, preference is given to shaped detergents and cleaners in which a substance from the group of organic di-, tri- and oligocarboxylic acids or mixtures thereof are used as acidifying agents in the effervescent system.

In processes preferred in the context of the present invention, at least one of the deformable compositions contains bleaches from the group of oxygen or halogen bleaches, in particular chlorine bleaches, with particular preference for sodium perborate and sodium percarbonate, in amounts of 2 to 25% by weight, preferably from 5 to 20% by weight and in particular from 10 to 15% by weight, in each case based on the mass. These substances are described below.

Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and supply H ₂ 0 ₂ in water. “Sodium percarbonate” is an unspecific term for sodium carbonate peroxohydrates, which strictly speaking are not “percarbonates” (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate. The merchandise has the average composition 2 Na ₂ C0 ₃ -3 H ₂ 0 ₂ and is therefore not peroxycarbonate. Sodium percarbonate often forms a white, water-soluble powder with a density of 2.14 ^'3 , which easily disintegrates into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first obtained in 1899 by ethanol precipitation from a solution of sodium carbonate in hydrogen peroxide, but was mistakenly regarded as peroxy carbonate. It was not until 1909 that the compound was recognized as a hydrogen peroxide addition compound, but the historical name "sodium percarbonate" has become established in practice. The industrial production of sodium percarbonate is mainly produced by precipitation from an aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg ²⁺ ions). The precipitated salt, which still contains 5 to 12% by weight of mother liquor, is then centrifuged off and dried at 90 ° C. in fluid bed dryers. The bulk density of the finished product can vary between 800 and 1200 g / 1 depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating processes and materials used for coating are widely described in the patent literature. In principle, according to the invention, all commercially available types of percarbonate can be used, such as those from Solvay Interox. Degussa. Kemira or Akzo can be offered.

Further bleaching agents which can be used are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ O-providing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the molded articles. If cleaning tablets or bleach tablets for machine dishwashing are manufactured, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxyacids. the alkyl peroxy acids and the aryl peroxy acids are mentioned as examples. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids. but also peroxy - naphthoic acid and magnesium monophthalate, (b) the aliphatic or substituted aliphatic peroxyacids. such as peroxylauric acid. Peroxystearic acid, ε- phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o- Carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate. and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassyl acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-l, 4-diacid, N, N-di-tereoyl -aminopercapronic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents in moldings for automatic dishwashing. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid,

Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium are considered. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

In processes which are further preferred according to the invention, at least one of the deformable compositions contains bleach activators from the groups of polyacylated alkylenediamines. in particular tetraacetylethylenediamine (TAED), the N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-Moφholinium-acetonitrile-acetonitrile MMA). in amounts of 0.25 to 15% by weight, preferably 0.5 to 10% by weight and in particular 1 to 5% by weight, in each case based on the mass. These substances are also described below.

In order to achieve an improved bleaching effect when washing or cleaning at temperatures of 60 ° C and below, bleach activators can be incorporated. Bleach activators which support the action of the bleaching agents are, for example, compounds which contain one or more N- or O-acyl groups, such as substances from the class of anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD) and tetraacetylhexylenediamine (TAHD), but also pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxo-hexahydro-l, 3,5-triazine (DADHT) and isatoic acid anhydride. Bleach activators which can be used are compounds which, under perhydrolysis conditions, aliphatic peroxocarboxylic acids preferably having 1 to 10 carbon atoms. in particular 2 to 4 carbon atoms, and or optionally substituted perbenzoic acid can be used. Substances which carry O- and or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable. Multi-acylated alkylenediamines are preferred. in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinim ), acylated phenol sulfonates. in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-Moφholinitronsulfetonium-acetonitrile (MMA), and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767 as well as acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG). Pentaacetylfructose. Tetraacetylxylose and Octaacetyllactose as well as acetylated. optionally N-alkylated glucamine and gluconolactone. and / or N-acylated lactams. for example N-benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams are also preferably used. Combinations of conventional bleach activators can also be used.

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

Bleach activators from the group of multi-acylated alkylenediamines are preferred. especially tetraacetylethylenediamine (TAED), N-acylimides. especially N- Nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-Moφholinium-Acetomtril-Methylsulfat (MMA), preferably in amounts up to 10% by weight, especially 0 , 1% by weight> to 8% by weight>, particularly 2 to 8% by weight> and particularly preferably 2 to 6% by weight, based on the total agent.

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

Because of their oxidizing effect, it is advantageous to separate the bleaching agents from other ingredients, for which processes according to the invention are particularly suitable for producing multi-phase moldings. Methods in which one of the deformable compositions contains bleaching agents while another deformable composition contains bleach activators are preferred.

Another preferred method is characterized in that at least one of the flammable masses of silver protection 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 from 0.01 to 5% by weight, preferably from 0.05 to 4% by weight and in particular from 0.5 to 3% by weight, in each case based on the mass.

The corrosion inhibitors mentioned can also be incorporated into the masses to be processed to protect the items to be washed or the machine, in the range of machine dishwashing silver protection agents have a special meaning. The known substances of the prior art can be used. In general, silver protective agents can be selected from the group of triazoles, benzotriazoles. the bisbenzo triazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol. Hydroxy hydroquinone. Gallic acid, phloroglucin. Pyogallol or derivatives of these classes of compounds. Also salt-like and complex-like inorganic compounds, such as salts of the metals Mn. Ti. Zr, Hf. V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes. the cobalt (acetate) complexes, the cobalt (carbonyl) complexes. the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

If anti-corrosion agents are used in multi-phase moldings, it is preferred to separate them from the bleaching agents. Processes in which one of the deformable compositions contains bleaching agents while another deformable composition contains anti-corrosion agents are therefore preferred.

The separation of the bleaching agents from other ingredients can also be advantageous. Processes according to the invention in which one of the moldable compositions contains bleaching agents while another deformable composition contains enzymes are also preferred. Enzymes in particular come from the classes of hydrolases such as proteases. Esterases. Lipases or lipolytic enzymes. Amylases. Cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases contribute to the removal of stains such as protein in the wash. greasy or starchy stains and graying. Cellulases and other glycosyl hydrolases can also be removed by removing pilling and microfi- glasses help to maintain color and increase the softness of the textile. Oxidoreductases can also be used to bleach or inhibit color transfer. Bacterial strains or fungi such as Bacillus subtilis are particularly suitable. Bacillus licheniformis. Streptomyceus griseus. Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases are preferred. which are obtained from Bacillus lentus. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytically acting enzymes or protease and cellulase or from cellulase and lipase or lipolytically acting enzymes or from protease. Amylase and lipase or lipolytically acting enzymes or protease. Lipase or lipolytic enzymes and cellulase. in particular, however, protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases are preferably used as cellulases. Endoglucanases and glucosidases, which are also called cellobiases, or mixtures of these are used. Since different types of cellulase differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

Other enzymes are naturally used in detergent tablets for machine dishwashing in order to take account of the different substrates and contaminations treated. Here come in particular those from the classes of hydrolases such as proteases. Esterases. Lipases or lipolytic enzymes. Amylases. Glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases contribute to the removal of stains such as stains containing protein, fat or starch. Oxidoreductases can also be used for bleaching. Bacterial strains or fungi such as Bacillus subtilis are particularly suitable. Bacillus licheniformis. Streptomyceus griseus. Coprinus cinereus and Humicola insolens as well as envmatic active ingredients obtained from their genetically modified variants Substances. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Here are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytically active enzymes or of protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.

The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, approximately 0.1 to 5% by weight, preferably 0.5 to approximately 4.5% by weight, in each case based on the mass (es).

Regardless of the intended use of the molded article produced according to the invention (for example detergent molded article or detergent molded article), methods are preferred in which one of the strands of material emerging from the outlet openings contains enzymes.

Such enzyme-containing compositions are preferably processed in multi-strand processes, i.e. in addition to a strand of material that contains enzymes, there is at least one further strand that is preferably free of enzymes. Methods in which the enzyme-containing material strand is encased by an enzyme-free material are particularly preferred here.

Separation of the bleaching agents from the surfactants described above can also be advantageous, so that preferred processes are characterized in that one of the deformable compositions contains bleaching agents, while another deformable composition contains surfactants. preferably nonionic surfactants. with particular preference for alkoxylated alcohols having 10 to 24 carbon atoms and 1 to 5 alkylene oxide units. contains. Other ingredients that can be part of one or more mass (es) in the process according to the invention are, for example, cobuilders (see above), dyes, optical brighteners. Fragrances, soil release compounds, soil repellents, antioxidants. Fluorescent agents. Foam inhibitors. Silicone and / or paraffin oils, color transfer inhibitors, graying inhibitors. Detergent booster etc. These substances are described below.

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

The acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of a acid component and thus also serve to set a lower and milder pH of detergents or cleaning agents. In particular, citric acid, succinic acid. Glutaric acid, adipic acid. To name gluconic acid and any mixtures of these.

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

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 with the investigated polymers. This information differs significantly the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

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

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

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

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

Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,

Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and are preferred as monomers. have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in the German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.

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

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. 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 , Both maltodextrins with a DE between 3 and 20 and dry glucose simpes with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents. which are able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427349, EP-A-0 472 042 and EP-A-0 542 496 and international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

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

Further usable organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1.1 diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP) and diethylene triamine pentamethylene phosphonate

(DTPMP) and their higher homologues in question. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP. used. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, especially if the agents also contain bleach, aminoalkanephosphonates, in particular DTPMP. to use, or to use mixtures of the phosphonates mentioned. In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders.

In order to improve the aesthetic impression of the detergent tablets according to the invention, they can be colored in whole or in part with suitable dyes. Special optical effects can be achieved if the masses to be processed are colored differently in the case of the production of moldings from several masses. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to the treated substrates, such as textile fibers or dishes, in order not to stain them.

Preferred for use in detergent tablets according to the invention are all colorants which can be oxidatively destroyed in the washing process, and also mixtures thereof with suitable blue dyes, so-called blue tones. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. For example, anionic colorants, for example anionic nitroso dyes, are suitable. A possible colorant is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which is available as a commercial product, for example as Basacid Green 970 from BASF, Ludwigshafen, and mixtures of these suitable blue dyes. Other colorants are Pigmosol ^® Blue 6900 (CI 74160), Pigmosol ^® Green 8730 (CI 74260), Basonyl ^® Red 545 FL (CI 45170). Sandolan ^® Rhodamine EB400 (CI 45100), Basacid ^® Yellow 094 (CI 47005), Sicovit ^® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol ^® Blue GLW (CAS 12219-32-8, CI Acidblue 221)), Nylosan ^® Yellow N-7GL SGR (CAS 61814-57-1. CI Acidyellow 218) and / or Sandolan ^® Blue (CI Acid Blue 182. CAS 12219-26-0). When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaning agents varies. In the case of colorants which are readily water-soluble, for example the above-mentioned basacid green or the likewise above-mentioned sandolan blue, colorant concentrations in the range from a few 10 ^"2 to 10 ^{" 3} % by weight are typically chosen. In contrast, in the case of the pigment dyes which are particularly preferred on account of their brilliance, but less readily water-soluble, for example the above-mentioned pigmosol dyes, the suitable concentration of the colorant in washing or cleaning agents is typically a few 10 ^"3 to 10 ^{" 4} % by weight. %.

The laundry detergent and cleaning product tablets produced by the process according to the invention can contain one or more optical brighteners. These fabrics, which are also called "whiteners", are used in modern laundry detergents because even freshly washed and bleached white laundry has a slight yellow tinge. Optical brighteners are organic dyes that convert part of the invisible UV radiation from sunlight into longer-wave 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 appears whiter and brighter to the eye. Since the action mechanism of brighteners presupposes that they are drawn onto the fibers, a distinction is made, depending on the fibers to be "dyed", for example, brighteners for cotton, polyamide or polyester fibers. The commercially available brighteners suitable for incoφoration in detergents essentially include five structural groups: 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 can be found, for example, in G. Jakobi, A. Löhr "Detergents and Textile Washing", VCH-Verlag, Weinheim, 1987, pages 94 to 100. Suitable are, for example, salts of the 4.4 ^' bis [(4-anilino-6-moφholino-s-triazin-2-yl) amino] -stilbene 2,2'-disulfonic acid or compounds of the same structure which carry a diethanolamino group, a methylamino group, an anilino group or a 2-mefhoxyethylamino group instead of the Moφholino group. Brighteners of the substituted diphenylstyryl type may also be present. eg 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) diphenyl. Mixtures of the aforementioned brighteners can also be used.

Fragrances are added to the agents according to the invention in order to improve the aesthetic impression of the products and, in addition to the performance of the product, to provide the consumer with a visually and sensorially "typical and distinctive" product. Individual fragrance compounds can be used as perfume oils or fragrances. eg the synthetic products of the ester, ether, aldehyde, ketone type. 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. Dimethylbenzyl carbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate. Ethyl methylphenyl glycinate. Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms. Citral. Citronellal. Citronellyloxyacetaldehyde. Cyclamen aldehyde. Hydroxycitronellal. Lilial and bourgeonal. to the ketones, for example, the Jonone. <χ-Isomethylionon and methyl-cedrylketone, to the alcohols anethole. Citronellol, Eugenol. Geraniol. Linalool, phenylethyl alcohol and Teφineol. The hydrocarbons mainly include the teφene such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures, such as are obtainable from plant sources. e.g. pine, citms, jasmine. Patchouly-. Rose or ylang-ylang oil. Muscatels are also suitable. Sage oil. Chamomile oil. Clove oil. Melissa oil. Mint oil. Cinnamon leaf. Lime blossom oil. Juniper beer oil. Vetiver. Olibanum. Galbanum oil and labdanum oil as well as orange blossom oil, neroliol. Orange peel oil and sandalwood oil. The fragrance content of the detergent tablets according to the invention is usually up to 2% by weight of the total formulation. The fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

In addition, the detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight. each based on the nonionic cellulose ether. and the polymers of phthalic acid and / or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

Soaps come, for example, as foam inhibitors which can be used in the agents produced according to the invention. Paraffins or silicone oils into consideration, which can optionally be applied to carrier materials.

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 sulfone 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 (Na salt) are preferred. Methylcellulose. 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

Because textile fabrics, especially from rayon. Viscose staple fiber. Cotton and its blends can be wrinkled because the individual fibers prevent bending and kinking. If pressing and squeezing across the grain are sensitive, the agents produced 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 combat microorganisms, the agents produced according to the invention can contain antimicrobial agents. Depending on the antimicrobial spectrum and the mechanism of action, a distinction is made between bacteriostatics and bactericides, funiostatics and fungicides etc. Important substances from these groups are, for example, benzalkonium chlorides. Alkylarylsulfonates. Halogenphenols and Phenolmercuriacetat, whereby these compounds can be completely dispensed with.

In order to prevent undesirable changes in the agents and / or the treated textiles caused by the action of oxygen and other oxidative processes, the agents can contain antioxidants. This class of compounds includes, for example, substituted phenols. Hydroquinones. Catechnins and aromatic amines as well as 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 produced 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 patent applications FR 1,156,513. GB 873 214 and GB 839 407. The lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed here are suitable as antistatic agents for textiles or as an additive to detergents, an additional finishing effect being achieved.

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, for example silicone derivatives can be used in the agents produced according to the invention. These additionally improve the rinsing behavior of the agents due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes. in which the alkyl groups have one to five carbon atoms and are partially or completely fluorinated. Preferred silicones are polydimethylsiloxanes. which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 centistokes, the silicones being used in amounts between 0.2 and 5% by weight, based on the total agent.

Finally, the agents produced according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles are also available. in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives te), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid.

In the above statements, the content of the individual substances in the end products of the process according to the invention was mentioned in part. In relation to the masses to be processed, methods are generally preferred in which at least one of the deformable masses continues to contain one or more substances from the groups of the enzymes. Corrosion inhibitors, scale inhibitors, cobuilders, dyes and / or fragrances in total amounts of 6 to 30 wt .-%, preferably from 7.5 to 25 wt .-%> and in particular from 10 to 20 wt .-%, each based on the Mass, contains.

With all of the above-mentioned ingredients, advantageous properties can result from separating them from other ingredients or assembling them together with certain other ingredients. In the case of multi-phase moldings, the individual phases can also have a different content of the same ingredient, as a result of which advantages can be achieved. Methods in which at least two of the deformable compositions contain the same active ingredient in different amounts are preferred. As already explained, the term “different amount” does not refer to the absolute amount of the ingredient in the mass, but rather to the relative amount, based on the phase weight, thus represents a% by weight. Based on the individual mass, represents.

The end products of the method according to the invention can be provided in a wide variety of geometric shapes, this flexibility being one of the many advantages of the method according to the invention. However, it is also possible to produce molded articles according to the invention which are based on conventional molded articles in their appearance. For example, they can be manufactured in a predetermined spatial shape and a predetermined size, whereby practically all practical configurations can be considered as the spatial shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section. This last embodiment covers the performance form from tablets to compact cylinder pieces with a ratio of height to diameter above 1.

The end products of the method according to the invention can each be designed as separate individual elements which correspond to the predetermined dosage of the detergents and / or cleaning agents. It is also possible, however, to design the cut-to-length material strands which connect a plurality of such mass units in a compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points. For the use of textile detergents in machines of the type customary in Europe with horizontally arranged mechanics, the formation as tablets, in cylinder or cuboid form can be expedient, with a diameter / height ratio in the range from approximately 0.5: 2 to 2: 0 , 5 is preferred.

The spatial shape of another embodiment of the molded body is adapted in its dimensions to the detergent dispenser of commercially available household washing machines, so that the molded body can be metered directly into the dispenser without metering aid, where it dissolves during the dispensing process. However, it is of course also possible to use the detergent tablets without problems using a metering aid and is preferred in the context of the present invention.

Another preferred molded body. which can be produced has a plate-like or sheet-like structure with alternately thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, can be broken off and entered into the machine. This principle of the "bar-shaped ^" molded article detergent can also be implemented in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side.

Such .. bar-shaped "strand sections can be produced by a post-treatment step after cutting to length, which consists in pressing a second knife or a second set of knives into the cut strand sections without dividing them. Also a superficial shaping or production of positive or negative lettering can take place according to the invention. Accordingly, preferred methods are characterized in that the shaped bodies which have been cut to length are subjected to a post-treatment step.

In addition to embossing lettering, the post-treatment step can also include embossing patterns, shapes, etc. In this way, for example, universal detergents produced according to the invention can be identified by a T-shirt symbol, color detergents manufactured according to the invention by a wool symbol, detergent molded articles for machine dishwashing produced according to the invention by symbols such as glasses, plates, pots, pans, etc. There are no limits to the creativity of product managers. Preferred methods according to the invention therefore include an additional shaping step, in particular embossing, as a post-treatment step.

Subsequent coating of the cut-to-length molded bodies is also possible, if the application of an additional coating should be desired. In this case, methods are preferred in which the aftertreatment step involves coating the molded body with a pourable material, preferably a pourable material with a viscosity <5000 mPas. includes.

Regardless of the number of phases and the type of aftertreatment, methods are generally preferred which are characterized in that the shaped bodies have a density above 800 kgdm ^'3 , preferably above 900 kgdm ^{' 3} , particularly preferably above 1000 kgdm ^'3 and in particular above 1100 kgdm ^"3 . In such molded articles, the advantages of offering a compact washing or cleaning agent are particularly evident.

The present invention provides a method which makes it possible to produce detergent tablets in a simple manner under changing framework conditions. A preferred curing mechanism, as described above, is the time-delayed water binding, with corresponding washing and cleaning Mittelformköφer are not described in the prior art. Another object of the present invention is therefore a detergent shaped body, containing at least 30 wt .-% phosphate (s), which is characterized in that the water content of the shaped body is 50 to 100% of the calculated water binding capacity.

With regard to the definition of the water binding capacity and its calculation, reference can be made to the above explanations in order to avoid redundancies. The phosphate content of preferred molded articles produced according to the invention is higher, so that detergent molded articles are preferred which contain at least 40% by weight, preferably at least 45% by weight and in particular at least 50% by weight of phosphates), in each case based on the molded article weight, contain.

As already mentioned in the discussion of the method according to the invention, alkali metal phosphates in particular are phosphates which are to be used with preference. Completely analogously, detergent tablets are preferred, the alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 30 to 80% by weight, preferably 35 to 75 Wt .-% and in particular from 50 to 70 wt .-%, each based on the molded body weight. contain.

In the description of the process according to the invention, it was explained that, in the context of the present invention, particularly preferred process end products not only have an extremely low proportion of free water, but are preferably also capable of binding further free water. In preferred detergent tablets, the water content of the tablets is 55 to 95%, preferably 60 to 90% and in particular 65 to 85% of the calculated water binding capacity.

With regard to other ingredients, their amounts and physical properties, reference can also be made to the above explanations as to the additional phase of molded bodies according to the invention, the distribution of ingredients between the individual phases and the quantitative ratios of the phases to one another.

Claims

claims:

1. Process for the production of laundry detergent and cleaning product. characterized in that one (a) deformable mass (es) is produced and these are supplied with outlet pressure below 40 bar outlet openings and the exiting material strands are cut to shaped body dimensions and allowed to harden.

2. The method according to Anspmch 1, characterized in that the deformable mass (es) of the outlet openings with a pressure below 35 bar, preferably below 30 bar. fed particularly preferably below 20 bar and in particular below 10 bar.

3. The method according to any one of claims 1 or 2, characterized in that the deformable mass (es) the outlet openings with a pressure below 8.5 bar, preferably below 7.5 bar, particularly preferably below 6 , 5 bar and in particular below 5 bar.

4. The method according to any one of claims 1 to 3, characterized in that a deformable mass drawn between two rollers, discharged as a strand of material from outlet openings, cut to the desired shape and dimension and allowed to harden.

5. The method according to any one of claims 1 to 4, characterized in that two differently composed, deformable masses are drawn between two pairs of rollers and discharged as filled, hollow or multi-layered material strands from outlet openings, cut to the desired shape and are allowed to harden.

6. The method according to any one of claims 1 to 5, characterized in that three differently composed, plastically deformable masses drawn between three pairs of rollers and as one, two or three times filled, hollow, two or three current strands of material are discharged from the outlet openings, cut to the desired shape and allowed to harden.

7. The method according to any one of claims 1 to 6, characterized in that the material strands at a speed of 0.2 m / min to 30 m / min, preferably between 0.25 m / min to 20 m / min, particularly preferably of 0.5 m / min to 15 m / min and in particular from 1 m / min to 10 m / min are discharged from the outlet openings.

8. The method according to any one of claims 1 to 7, characterized in that the outlet openings opening areas of 50 mm ² to 2500 mm ² , preferably from 100 mm ² to 2000 mm ² , particularly preferably from 200 mm ² to 1500 mm ² and in particular from 300 mm ² to 1000 mm ^2, with particular preference from 350 mm ² to 750 mm ² .

9. The method according to any one of claims 1 to 8, characterized in that the thickness of at least one of the strands of material emerging from the outlet openings is at least 5 mm, preferably at least 7.5 mm and in particular at least 10 mm.

10. The method according to any one of claims 1 to 9, characterized in that the material strands emerging from the outlet openings to a length of 10 to 100 mm, preferably from 12.5 to 75 mm, particularly preferably from 15 to 60 mm and in particular from 20 up to 50 mm.

11. The method according to any one of claims 1 to 10, characterized in that the curing of the strands of material cut to the shape of the body is supported by superficial drying and / or cooling, in particular by blowing with cold air.

12. The method according to any one of claims 1 to 11, characterized in that the deformable mass (es) 10 to 95 wt .-%. preferably 15 to 90% by weight, particularly preferably contain 20 to 85% by weight and in particular 25 to 80% by weight of anhydrous substances which, by hydration, change into a hydrate form with a melting point below 120 ° C., preferably below 100 ° C. and in particular below 80 ° C. ,

13. The method according to any one of claims 1 to 12, characterized in that the deformable mass (es) phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate ), in amounts of 20 to 80 wt .-%, preferably from 25 to 75 wt .-% and in particular from 30 to 70 wt .-%, each based on the mass.

14. The method according to Anspmch 13, characterized in that the weight ratio of phosphate (s) to water in the deformable mass is less than 1: 0.3, preferably less than 1: 0.25 and in particular less than 1: 0.2.

15. The method according to any one of claims 1 to 14, characterized in that the deformable mass (es) carbonate (s) and or bicarbonate (s), preferably alkali carbonates, particularly preferably sodium carbonate. in amounts of 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 10 to 30% by weight, each based on the mass.

16. The method according to any one of claims 1 to 15, characterized in that the deformable mass (es) 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 wt .-% and in particular from 20 to 40 wt .-%, each based on the mass.

17. The method according to any one of claims 1 to 16, characterized in that the deformable mass (es) zeolite (s), preferably zeolite A, zeolite P, zeolite X and mixtures thereof, 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 mass.

18. The method according to any one of claims 1 to 17, characterized in that the average particle size of the solids used in the deformable mass (s) is less than 400 microns, preferably less than 300 microns and in particular less than 200 microns.

19. The method according to any one of claims 1 to 18, characterized in that less than 10 wt .-%, preferably less than 5 wt .-% and in particular less than 1 wt .-% of the deformable mass (es) Solids used have particle sizes above 1000 microns.

20. The method according to any one of claims 1 to 19, characterized in that less than 15 wt .-%, preferably less than 10 wt .-% and in particular less than 5 wt .-% of the deformable mass (es) Solids used have particle sizes above 800 microns.

21. The method according to any one of claims 1 to 20, characterized in that the water content of the molded body is 50 to 100% of the calculated water binding capacity.

22. The method according to any one of claims 1 to 21, characterized in that the deformable mass (es) during processing have a water content of 2.5 to 30% by weight, preferably 5 to 25% by weight. % and in particular from 7.5 to 20 wt .-%, each based on the mass.

23. The method according to any one of claims 1 to 22, characterized in that the hardening of the deformable mass (s) is carried out by delayed water binding.

24. The method according to any one of claims 1 to 23, characterized in that the hardening of the deformable mass (s) is carried out by cooling below the melting point.

25. The method according to any one of claims 1 to 24, characterized in that the hardening of the deformable mass (s) is carried out by evaporation of solvents.

26. The method according to any one of claims 1 to 25, characterized in that the hardening of the deformable mass (s) is carried out by crystallization.

27. The method according to any one of claims 1 to 26, characterized in that the hardening of the deformable mass (s) by chemical reaction (s), in particular polymerization, takes place.

28. The method according to any one of claims 1 to 27, characterized in that the hardening of the deformable mass (s) is carried out by changing the rheological properties.

29. The method according to any one of claims 1 to 28, characterized in that the deformable mass (es) total surfactant contents below 5 wt .-%, preferably below 4 wt .-%, particularly preferably below 3 wt .-% and in particular below 2 wt .-%, each based on the mass.

30. The method according to any one of claims 1 to 29, characterized in that at least one of the deformable masses of bleaching agents from the group of oxygen or halogen bleaching agents, in particular chlorine bleaching agents, with particular preference for sodium perborate and sodium percarbonate. in amounts of 2 to 25% by weight, preferably 5 to 20% by weight and in particular 10 to 15% by weight. each based on the mass.

31. The method according to any one of claims 1 to 30, characterized in that at least one of the deformable masses of bleach activators from the groups of polyacylated alkylenediamines. especially tetraacetylethylenediamine (TAED), the N-acylimide. especially N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates. in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-Moφholinium-acetonitrile-methyl sulfate (MMA). in amounts of 0.25 to 15 wt .-%, preferably from 0.5 to 10 wt .-% and in particular from 1 to 5 wt .-% each based on the mass.

32. The method according to any one of claims 1 to 31, characterized in that at least one of the deformable masses of silver protection agents from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes, particularly preferably benzotriazole and / or alkylaminotriazole, in amounts of from 0.01 to 5% by weight, preferably from 0.05 to 4% by weight and in particular from 0.5 to 3% by weight, in each case based on the mass.

33. The method according to any one of claims 1 to 32, characterized in that at least one of the deformable masses further one or more substances from the groups of the enzymes, corrosion inhibitors, scale inhibitors, cobuilders, dyes and / or fragrances in total amounts of 6 to 30 wt .-%, preferably from 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the mass.

34. The method according to any one of claims 5 to 33, characterized in that one of the deformable compositions contains bleaching agents, while another deformable composition contains bleach activators.

35. The method according to any one of claims 5 to 34, characterized in that one of the deformable compositions contains bleaching agents, while another deformable composition contains enzymes.

36. The method according to any one of claims 5 to 35, characterized in that one of the deformable masses contains bleaching agents, while another deformable mass contains corrosion protection agents.

37. The method according to any one of claims 5 to 35, characterized in that one of the strands of material emerging from the outlet openings contains enzymes.

38. The method according to Anspmch 37, characterized in that the enzyme-containing strand of material is encased by an enzyme-free material.

39. The method according to any one of claims 5 to 38, characterized in that one of the deformable compositions contains bleaching agents, while another deformable composition contains surfactants, preferably nonionic surfactants, with particular preference for alkoxylated alcohols having 10 to 24 carbon atoms and 1 to 5 alkylene oxide units , contains.

40. The method according to any one of claims 5 to 39, characterized in that at least two deformable masses contain the same active ingredient in different amounts.

41. The method according to any one of claims 1 to 40, characterized in that the deformable mass (es) contains / contain a paraffin wax with a melting range of 50 ° C to 55 ° C.

42. The method according to any one of claims 1 to 41, characterized in that the plastically deformable mass (es) contains / contain at least one substance from the group of polyethylene glycols (PEG) and or polypropylene glycols (PPG).

43. The method according to any one of claims 1 to 42, characterized in that the molded body less than 10 wt .-%, preferably less than 5 wt .-%, particularly preferably less than 1 wt .-% and in particular less than 0.5 % By weight of free water.

44. The method according to any one of claims 1 to 43, characterized in that the molded body have a density above 800 kgdm ^"3 , preferably above 900 kgdm °. Particularly preferably above 1000 kgdm ^{" 3} and in particular above 1100 kgdm ^"3 ,

45. The method according to any one of claims 1 to 44, characterized in that the molded body are subjected to an aftertreatment step.

46. The method according to Anspmch 45, characterized in that the after-treatment step comprises coating the molded body with a pourable material, preferably a pourable material with a viscosity <5000 mPas.

47. The method according to any one of claims 45 or 46, characterized in that the post-treatment step comprises an additional shaping step, in particular the embossing.

48. Detergent and molded articles, containing at least 30% by weight of phosphates), characterized in that the water content of the molded articles is 50 to 100% of the calculated water binding capacity.

49. Detergent molded article according to Anspmch 48, characterized in that the molded article contains at least 40% by weight, preferably at least 45% by weight and in particular at least 50% by weight of phosphate (s), in each case based on the molded article weight , contain.

50. Detergent shaped body according to one of claims 48 or 49, characterized in that the shaped body alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 30 to 80% by weight , preferably from 35 to 75 wt .-% and in particular from 50 to 70 wt .-% ₀ , each based on the molded body weight.

51. Detergent and molded article according to one of claims 48 to 50, characterized in that the water content of the molded article is 55 to 95%, preferably 60 to 90% and in particular 65 to 85% of the calculated water binding capacity.