EP1192241B1 - 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

The present invention relates to a novel process for the preparation of single- and multi-phase detergent tablets.

Detergent tablets are widely described in the art and are becoming increasingly popular with consumers because of their ease of use. Tableted detergents have a number of advantages over powdered products: they are easier to dose and handle and, due to their compact structure, have advantages in storage and transport. There is therefore an extremely wide state of the art for washing and Reinigungsmittelformkörpem. which is also reflected in an extensive patent literature. Early on, developers of tablet-shaped products came up with the idea of releasing certain ingredients in the washing or cleaning process via differently shaped areas of the moldings in order to improve cleaning success. In this case, in addition to the well-known from pharmaceutics core / shell tablets and ring / core tablets in particular multilayer molded bodies have prevailed that are offered today for many areas of washing and cleaning or hygiene. Also, the optical differentiation of the products is becoming increasingly important, so that single-phase and monochrome shaped body in the field of washing and cleaning were largely displaced by multi-phase moldings. Commercially available two-layer molded articles with one white and one colored phase or with two differently colored layers are currently commercially available. In addition, there are point tablets, toroidal tablets, coated tablets, etc., which currently have a rather minor importance.

The production of said moldings always comprises at least one tabletting step in which a particulate premix is converted into a compact mold by applying pressure. In the two-layer tablets mentioned, coat / core tablets, etc., different premixes are pressed up or pressed into one another. There are also proposals to prepare tablets by means of conventional pressing technology and to fill cavities in these tablets with melts or the like in order to obtain composition moldings from compressed and not compressed portions.

Another method used to make compact detergent and cleaner items is extrusion. Here, a premix is plasticized under high pressure and discharged by hole forming, followed by shaping by cutting and eventual post-treatment. In contrast to the tabletting, which is the particle bed "sintered" quasi, and in which the moldings still have a hollow volume. Due to the high pressures of 100 bar and above, the extrusion leads to very compact particles or pieces whose inner hollow volume is significantly reduced.

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

Multi-phase cleaning tablets for the WC are described for example in EP 055 100 (Jeyes Group). This document discloses toilet cleaner blocks comprising a molded body of a slow-dissolving detergent composition. in which a bleach tablet is embedded. This document simultaneously discloses the most varied embodiments of multiphase moldings. The production of the moldings is carried out according to the teaching of this document either by inserting a compressed bleach tablet into a mold and molding this tablet with the detergent composition, or by pouring a portion of the detergent composition into the mold. followed by insertion of the compressed bleach tablet and possibly subsequent pouring 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 stepwise compression of the constituents. First, the compression of a bleaching composition into a shaped body which is placed in a semi-filled with a polymer composition die, which is then filled with another polymer composition and a bleach molded body is pressed with a polymer jacket. The process is then repeated with an alkaline detergent composition to give a three-phase molded body.

Another way to prepare 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 shaped 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 cavity filling area should not be pressed. because in this way "pressure-sensitive" ingredients should be spared.

A process for the preparation of solid anionic surfactant-containing detergents and cleaners with high bulk content is described in the European application EP 0 814 152 A2, which is characterized by an improved solution and gel behavior. For this purpose, the premix is pressed with plasticizer at pressures of 25 to 200 bar.

British Patents GB 2 298 867 A and GB 1 048 831 disclose laundry detergent tablets which have improved hardness properties due to partially or fully hydrated builders. Simple production processes are described without going into the applied extruding pressures.

The document US 3 455 834 describes a high speed manufacturing process for detergent tablets, which are therefore characterized by improved hardness. However, this prior art is silent about the pressures used and is limited to the mention of the required temperature and time.

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

The extrusion or coextrusion of several premixes is hardly possible with a very different proportion of the individual phases. The conventional tabletting of multilayer tablets also finds its limits in the field of detergent tablets in the case of one layer only a small proportion of the overall tablet should have. If one falls below a certain layer thickness, it is increasingly difficult to compress a layer adhering to the remainder of the shaped article.

It is an object of the present invention to provide a production process for mono- and multiphase moldings in which pressure-sensitive ingredients can also be introduced into delimited regions, wherein the delimited region should not be restricted in terms of its size in relation to the overall mold. On the one hand, optical differentiation to conventional two-layer tablets should be achieved, on the other hand, the production of moldings should work safely without large technical effort in large series without the moldings have disadvantages in terms of stability or inaccuracies in the dosage would be feared.

In particular, the present invention was based on the object. to provide a novel manufacturing process for detergent tablets, which is superior to the previous Tablettier- and extrusion technology with respect to the protection of the ingredients from thermal stress, pressure and shear, the apparatus is less expensive and procedural economical cheaper and higher throughputs. In addition, the process should be used without much effort for the production of three- or multi-phase moldings.

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

The invention relates to a process for the preparation of detergent tablets in which one produces a deformable mass (s) and feeds them at a pressure of less than 10 bar outlet openings and cuts off the exiting material strands on molded body dimensions and allowed to harden.

Preferably, the deformable and post cure thermosetting masses are supplied to the orifices at even lower pressures to be pressure sensitive To protect ingredients. Preferred processes are characterized in that the deformable mass (s) are fed to the outlet openings at a pressure below 35 bar, preferably below 30 bar, more preferably below 20 bar.

Depending on the configuration of the deformable masses (see below) and depending on the configuration of the processing machines even lower pressures can be realized, or a non-pressurized procedure is possible. Processes in which the deformable mass (s) are fed to the outlet openings at a pressure below 8.5 bar, preferably below 7.5 bar, more preferably below 6.5 bar and in particular below 5 bar, are another important embodiment of the present invention.

Apparatus-specific parameters and process-specific features of the method according to the invention will be described below, before discussing the ingredients and physical parameters of the masses to be processed.

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

A preferred way in the context of the present invention to supply the deformable masses to the outlet openings, is to feed them between two rollers, which have opposite directions of rotation. This will cause the mass to be between the rollers. depending on the width of the gap between the rollers and the roller speed promoted under low pressure in the direction of the outlet openings. Depending on the number of roller pairs and outlet openings and depending on the configuration of these openings result in single or multi-phase material strands, which may have different shapes and / or colors. These strands of material are cut into sections of predetermined length and allowed to harden the individual strand sections to the finished detergent tablets.

Single-phase moldings are advantageously produced by supplying a deformable mass with a roller pair to an outlet opening. Preferred methods are characterized in that a deformable mass drawn between two rolls, discharged as a strand of material from outlet openings, cut to the desired shape of the molded body and allowed to cure.

For the preferred method suitable apparatuses are available for example from the company Hosokava Bepex GmbH under the name "torsion bar roller press DP". The outlet openings of such apparatus can be configured, for example, circular, triangular, square, rectangular, heart-shaped, crescent-shaped, etc. The first-mentioned openings then require cylindrical, prismatic, cubic or tetragonal, tetragonal or orthorhombic shaped bodies. The drawings show in the figures 27 and 29 to 42 by way of example some possible embodiments for outlet openings.

It is also possible to rotate the strands of material before cutting to the desired shape dimensions in the shaping workable state after exiting the openings. In this way, moldings with irregular, spiral-shaped side surfaces, which offer special optical stimuli.

Two-phase moldings can be produced in a corresponding manner with two pairs of rollers. For this purpose, preferred processes are characterized in that two deformable masses of different composition are drawn in between two pairs of rolls and discharged from outlet openings as filled, hollow or multi-layered strands of material, cut to the desired shape dimension and allowed to harden. Of course it is also possible. to process two identically assembled masses analogously. This is then not the separation of active ingredients or the achievement of certain washing and cleaning effects, but the visual incentive. Also Apparatuses suitable for such processes according to the invention are available from Hosokava Bepex GmbH under the name "Double Torsion Roller Press DDP". The outlet openings of such apparatuses can be arranged side by side or inside each other, resulting in multilayer or multi-phase moldings. Figures 15 to 26 and 28 show an example of some cross-sections of outlet openings for different masses. In FIGS. 15, 16, 17, 19, 21, 23 and 25, strands and moldings result, in which one part, except for the cut surfaces, is completely enclosed by the other part. The other cited figures show strands or shaped bodies in which one part is or only partly embedded in the other part. Again, a rotation of the strands of material prior to cutting to achieve special optical effects is possible.

The process according to the invention can also be used without difficulty for the preparation of three-phase molded bodies. Completely analogous to the previous embodiments, such methods according to the invention are carried out by three differently composite, plastically deformable masses drawn between three pairs of rollers and discharged as one-, two- or three-fold, hollow, two- or three-layer strands of material from outlet openings, to the desired shape of the molded body be cut off and allowed to cure.

Of course it is also possible here. to process two or even three identically composed masses analogously. This in turn is then not (only) the separation of active ingredients or the achievement of certain washing and cleaning effects, but the visual incentive. Apparatuses which are also suitable for the production of three-phase moldings are available from Hosokava Bepex GmbH under the name "triple-roll bar press DP / 3". The outlet openings of such apparatuses can be arranged side by side or inside each other, resulting in multilayer or multi-phase moldings. Figures 1 to 14 show examples of some cross sections of outlet openings for different masses. Again, a rotation of the strands of material prior to cutting to achieve special optical effects is possible.

The possibilities of discharging several strands of material from one another to and from one another over the apparatuses are unlimited, so that it is also possible to produce four-phase or multiphase moldings in a simple manner. Since the apparatus and the associated nozzle systems are simple and robust, a change of the product form and the adaptation to different market requirements is possible quickly and easily. Even by the appropriate treatment of the material strands prior to cutting, changes in shape of the resulting moldings can be easily cause. If, for example, according to FIG. 1, three strands of material from three aortic openings with a round cross-section are carried out against one another, shaped bodies, which have the shape of three stacked cylinders, result after cutting to length. By simply rotating the three strands of material about their longitudinal axis before cutting to length, washing and cleaning agent tablets are obtained; which have the shape of interlaced segments and reminiscent of rope or braids. The flexibility of the method according to the invention with regard to the change of shapes and aesthetic design is thus far superior to the previously known methods.

In the production of multiphase shaped bodies, the ratio of the phases with 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 molding) or in the range from 1 : 1.1 to 1: 100: 100, preferably from 1: 1: 2 to 1:75:75 and especially from 1: 1: 2.5 to 1:30:30 (three-phase molding). The ratio of the surfaces of the individual molded body phases is preferably in similar ranges.

Depending on the formulation 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 comply with certain exit speeds for the material strands. In preferred methods, the strands of material become at a speed of 0.2 m / min to 30 m / min, preferably between 0.25 m / min to 20 m / min, more preferably from 0.5 m / min to 15 m / min and especially 1 m / min up to 10 m / min discharged from the outlet openings.

In principle, the method according to the invention is not limited in terms of the shape and size of the outlet openings. With regard to the products to be produced and their size or mass, which in the case of such products is usually in the range from 5 to 500 g, preferably from 10 to 250 g, more preferably from 15 to 100 g and in particular between 20 and 50 g, methods are preferred in which the outlet openings opening areas of 50 mm ² to 2500 mm ² , preferably from 100 mm ² to 2000 mm ² , more preferably from 200 mm ² to 1500 mm ² and in particular from 300 mm ² to 1000 mm ² under particular Preferred 350 mm ² to 750 mm ² , have.

However, these values can be undershot for individual outlet openings, for example if one outlet opening serves to lay a thin "tube" over another strand, so that it is virtually coated as a result. Such strand cross sections are outlined for example in Figures 15, 17, 21 and 23, wherein the respective outer part may well be thinner. In the finished molded body then strands are present, which are coated with the exception of the end faces (cut surfaces), from which effects regarding the delayed or accelerated release can be achieved. However, with the exception of such coating strands, methods are 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 cutting of the material strands emerging from the outlet openings can take place according to the known methods of the prior art, for example by rotating knives, lowerable blades or wires etc. The mass of the finished shaped bodies depends on the one hand on the size of the outlet openings, on the other hand on the length the sections. If conventional washing and cleaning agent tablets are to be provided for conventional purposes, such as detergent tablets or automatic dishwashing detergent tablets, processes are preferred in which the material strands emerging from the outlet openings are placed on 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 to 50 mm, are cut off.

Depending on the composition or the intended use, however, the limits mentioned can also be exceeded or fallen short of. Thus, it is possible, for example, to process less soluble masses after curing and cut them to lengths of 100 to 1000 mm, preferably from 120 to 750 mm and in particular from 150 to 500 mm. The hardened "bars" 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 wash or rinse cycle, while the remainder remains in the machine or its dosing system for the next cleaning cycle.

After cutting to the desired molding dimensions, the strand sections are allowed to harden. Depending on the composition of the compositions, the curing takes place in different ways (see below), so that the curing can optionally be assisted or accelerated by suitable measures. It is thus possible, for example, to superficially initiate or accelerate a reactive curing process by activating activators. The irradiation with radioactive rays can also be used for radiation-curing compounds. as well as UV radiation for UV-active masses. In preferred processes, the curing is carried out by internal and external drying and / or cooling, so that preferred methods are characterized in that the curing of cut on molded body material strands by superficial drying and / or cooling, in particular by blowing with cold air, is supported.

After the presentation of the apparatus preferred embodiments, a description of the deformable and hardening materials to be processed follows. Here, both the composition and physical parameters are discussed as well as possible curing mechanisms described.

The hardening of the deformable mass (s) can be effected by different mechanisms, the time-delayed water binding, the cooling below the melting point, the evaporation of solvents, the crystallization, by chemical reaction (s), in particular polymerization and the change of rheological properties, e.g. by altered shearing of the mass (s) as the most important hardening mechanisms in addition to the already mentioned beam softening by UV, alpha-beta or gamma rays are mentioned.

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

In preferred in the context of the present invention, the curing of the deformable mass (s) takes place by time-delayed water binding.

The time-delayed water binding in the inventively processed masses can be realized in turn in different ways. For example, masses that contain hydratable, anhydrous raw materials or low hydration grade raw materials that can convert into stable higher hydrates, as well as water, are suitable. The formation of the hydrates, which does not occur spontaneously, then leads to the binding of free water, which in turn leads to a hardening of the masses. A shaping processing with low pressures is then no longer possible, and there are handling stable shaped body, which can optionally be further treated and / or packaged.

The staggered water binding can also be effected, for example, by incorporating hydrated water-containing salts, which dissolve in their own water of crystallization when the temperature increases, into the masses. If the temperature drops later, the water of crystallization becomes tied again, which leads to a loss of shaping processability by simple means and to a solidification of the masses.

The swelling of natural or synthetic polymers as time-delayed water binding mechanism can be used in the context of the method according to the invention. Here, blends of unswollen polymer and suitable swelling agent, e.g. Water, diols, glycerol, etc., are incorporated into the masses, wherein a swelling and curing takes place after shaping.

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

It is particularly preferred if the resulting hydrate forms 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 (s) 10 to 95 wt .-%, preferably 15 to 90 wt .-%, particularly preferably 20 to 85 wt .-% and in particular 25 to 80 wt. % anhydrous substances which pass through hydration in a hydrate form having 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 the addition of plasticizing aids such as polyethylene glycols, polypropylene glycols, waxes, paraffins, nonionic surfactants, etc. Further information on the mentioned classes of substances can be found below.

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

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

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

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

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.

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

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates. where cyclic representatives. the sodium or potassium metaphosphates and chain types that can distinguish sodium and potassium polyphosphates, respectively. Especially for the latter, a variety of names are in use: Melted or calcined phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

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

These phosphates are used according to the invention exactly as 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) comprise phosphate (s), preferably alkali metal phosphate (s), more 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.

If phosphates are used as sole hydratable substances in the masses, then the amount of added water should not exceed their water-binding capacity in order to keep the content of the shaped bodies in free water low. Overall, in order to comply with the abovementioned limit values, methods have been found to be preferred 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 which may be present in place of or in addition to phosphates in the deformable masses are carbonates and / or bicarbonates, wherein the alkali metal salts, and especially the potassium and / or sodium salts are preferred. In preferred processes, the deformable mass (s) contain carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonates, more preferably sodium carbonate, in amounts of from 5 to 50% by weight, preferably from 7.5 to 40 Wt .-% and in particular from 10 to 30 wt .-%, each based on the mass.

Again, with regard to the water content of the masses, the above applies. In particular, processes have proven to be preferred in which the weight ratio of carbonate (s) and / or bicarbonate (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 : Is 0.1.

Other ingredients which may be present in the deformable masses instead of or in addition to the said phosphates and / or carbonates / bicarbonates. are silicates, with the alkali metal silicates and including particularly the amorphous and / or crystalline potassium and / or sodium disilicates are preferred.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} ^· H ₂ O, where M is sodium or hydrogen, x is an integer from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline sheet 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 is sodium and x assumes the values 2 or 3. In particular both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ ^· yH ₂ O are preferred, with β-sodium disilicate being obtainable for example by the method / described in the international patent application WO-A-91 08,171th

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray-amorphous silicates, which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 . Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

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

Again, with regard to the water content of the masses, the above applies. In particular, methods 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.

Also suitable as an important component in the compositions to be processed according to the invention are substances from the group of zeolites. In particular, in the manufacture of detergent tablets, these substances are preferred builders. Zeolites have the general formula

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

in which M is a cation of valency n, x stands for values which 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 ₄ tetrahedra, this network being occupied by cations and water molecules. The cations in these structures are relatively mobile and can be exchanged to varying degrees by other cations. Depending on the type of zeolite, the intercrystalline "zeolitic" water can be released continuously and reversibly, while with some zeolite types, structural changes are accompanied by water release or uptake.

In the structural subunits, the "primary binding units" (AlO ₄ tetrahedra and SiO ₄ tetrahedra) form so-called "secondary binding units", which are in the form of single or multiple rings. For example, in various zeolites, 4-. 6- and 8-membered rings (referred to as S4R, S6R, and S8R), other types are linked by four- and six-membered double-ring prisms (most common types: D4R as a square or D6R as a hexagonal prism). These "secondary subunits" combine different polyhedra called Greek letters. Most common here is a Vielflächner, consisting of six squares and eight equilateral hexagons and is referred to as "β". With these units, a variety of different zeolites can be realized. So far, 34 natural zeolite minerals and about 100 synthetic zeolites have been known.

The best known zeolite, zeolite 4 A, is a cubic composite of β-cages linked by D4R subunits. It belongs to the zeolite structure group 3 and its three-dimensional network has pores of 2.2 Å and 4.2 Å size, the formula unit in the unit cell can be with Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] · 27 H ₂ O describe.

Preferably, zeolites of the faujasite type are used in the process according to the invention. Together with 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-membered subunit D6R (cf. 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 structural group 4 also includes the minerals chabazite and gmelinite as well as the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5. The latter two synthetic zeolites have no mineral analogs.

Faujasite-type zeolites are composed of β-cages linked tetrahedrally via D6R subunits, with the β-cages resembling the carbon atoms in the diamond. The three-dimensional network of the faujasite-type zeolites used in the process according to the invention has pores of 2.2 and 7.4 Å, the unit cell also contains 8 cavities of about 13 Å diameter and can be represented by the formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] ^. 264 H ₂ O. The network of zeolite X contains a void volume of about 50%, based on the dehydrated crystal. which represents the largest empty space of all known zeolites (zeolite Y: about 48% void volume, faujasite: about 47% void volume). (All data from: Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto 1974. pp. 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 zeolite structure group 4. In addition to zeolite X, zeolite Y and faujasite as well as mixtures of these compounds can therefore also be used according to the invention, the pure zeolite X being preferred.
Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which need not necessarily belong to the zeolite structure group 4, can be used according to the invention, with the advantages of the process according to the invention becoming 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 one uses the minimum amount of a zeolite of the faujasite type (0.5 wt .-%, based on the weight of the resulting shaped body) and used as a residual powdering agent conventional zeolite A. In any case, however, it is preferred that the powdering agent consist exclusively of one or more faujasite-type zeolites, zeolite X in turn 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 ) ₁₀₆ ] ^.xH ₂ O,



K ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] ^.xH ₂ O,



Ca ₄₀ Na ₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] ^xH ₂ O,



Sr ₂₁ Ba ₂₂ [(AlO _{2) 86} (SiO _{2) 106]} ^· x H ₂ O,

where x can take values between 0 and 276 and have pore sizes of 8.0 to 8.4 Å.

For example, a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) which is marketed by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® is also commercially available and preferably usable in the context of the process according to the invention and by the formula

nNa ₂ O ^• (1-n) K ₂ O ^• Al ₂ O ₃ ^• (2 - 2.5) SiO ₂ ^• (3.5-5.5) H ₂ O

can be described.

Also Y-type zeolites are commercially available us can be, for example, by the formulas

Na ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] ^xH ₂ O,



K ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] ^xH ₂ O,

where x is numbers between 0 and 276 and has pore sizes of 8.0 Å.

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

The particle sizes of the faujasite-type zeolites preferably used in the process according to the invention are preferably in the range from 0.1 to 100 .mu.m, preferably between 0.5 and 50 .mu.m and in particular between 1 and 30 .mu.m, in each case 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 cited zeolites or other builders or bleaches, bleach activators or other solids. Very generally, process variants are preferred in which the average 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 may still vary. 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 wt .-%, preferably less than 10 wt .-% and in particular less than 5 wt .-% of the deformable Mass (s) of 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, ie the particle sizes are minimally 0.7 and, at most, 1.3. times the mean particle size.

Above, the weight ratio of water to certain ingredients in accordance with the invention preferably to be processed masses. After processing, this water is preferably bound in the form of water of hydration, so that the Verfahrensendprodukte preferably have a significantly lower free water content. Preferred end products of the process according to the invention are essentially anhydrous, ie in one state. in which the content of liquid, ie not in the form of water of hydration and / or water of constitution present water below 2 wt .-%, preferably below 1 wt .-% and in particular even below 0.5 wt .-%, in each case based on the moldings , lies. Accordingly, methods according to the invention preferred in which the shaped bodies less than 10 wt .-%, preferably less than 5 wt .-%, more 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 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 production process according to the invention, the moldings advantageously have a total water content of not more than 15% by weight, with this water not being present in liquid free form, but chemically and / or physically bound, and it is particularly preferred that the Content of not bound to zeolite and / or silicates water in the solid premix not more than 10 wt .-% and in particular not more than 7 wt .-% is.

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 themselves still able to bind further free water. In preferred processes, the water content of the moldings 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 chemically stable form and ultimately indicates. How much water in the form of stable hydrates can be bound by a substance or a shaped body. The dimensionless value of the water-binding capacity (WBV) is calculated from: $$\mathit{\text{WBV}}\text{=}\frac{\mathit{\text{n}}\text{· 18}}{\mathit{\text{M}}}\text{.}$$ where n is the number of water molecules in the corresponding hydrate of the substance and M is the molecular weight of the non-hydrated substance. This results in a value of, for example, the water binding capacity of anhydrous sodium carbonate (formation of sodium carbonate monohydrate) $$\mathit{\text{WBV}}\text{=}\frac{\text{1 · 18}}{\text{2 · 23 + 12 + 3 x 16}}\text{= 0.17.}$$

The value WBV can be calculated for all hydrate-forming substances which are used in the compositions to be processed according to the invention. About the percentage of these substances then gives the total water binding capacity of the recipe. In preferred Verfahrensendprodukten the water content is then between 50 and 100% of this calculated value.

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

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

Under the influence of temperature softenable masses can be easily assembled by mixing the desired other ingredients with a meltable or softenable material and the mixture is heated to temperatures in the softening of this substance and processed molding at these temperatures. In this case, waxes, paraffins, polyalkylene glycols, etc. are particularly preferably used as meltable or softenable substances. These are described below.

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

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

The above properties are usually met by so-called waxes. "Waxing" is understood to mean a series of naturally or artificially produced substances which generally melt above 40 ° C. without decomposition and are already relatively low-viscosity and non-stringy just above the melting point. They have a strong temperature-dependent consistency and solubility.

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

Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japan wax, Esparto grass wax, cork wax, guaruma wax, rice germ oil wax. Sugarcane wax, ouricury wax, or montan wax, animal waxes such as beeswax. Shellac wax, spermaceti, lanolin (wool wax), or raffia fat, mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum. Paraffin waxes or microwaxes.

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

Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. It is also possible to use as meltable or softenable substances for the compositions which cure by cooling, and compounds from other substance classes which meet the stated requirements with regard to the softening point. Suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll® 66 (Bayer AG), proved. Also suitable are synthetically produced waxes from lower carboxylic acids and fatty alcohols, for example dimyristyl tartrate, which is available under the name Cosmacol® ETLP (Condea). Conversely, synthetic or partially synthetic esters of lower alcohols can be used with fatty acids from natural sources. This class of substances includes, for example, Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Shellac, for example shellac KPS three-ring SP (Kalkhoff GmbH) can also be used according to the invention as meltable or softenable substances.

Likewise to the waxes in the context of the present invention, for example, the so-called wax alcohols are calculated. Wax alcohols are higher molecular weight. water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols are, for example, in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent 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 may optionally also contain wool wax alcohols, among which triterpenoid and steroid alcohols, for example lanolin. which is available, 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 optionally also water-insoluble or only slightly water-soluble polyalkylene glycol bonds may also be used as part of the meltable or softenable substances.

Particularly preferred meltable or softenable substances in the masses to be processed include those from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG), with polyethylene glycols having molecular weights of between 1500 and 36,000 being preferred, and those having molecular weights of from 2000 to 6000 being particularly preferred and those having molecular weights of 3,000 to 5,000 are particularly preferred. Also, corresponding processes, which are characterized in that the plastically deformable mass (s) at least one substance from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) contains / are preferred.

Here, according to the invention, masses to be processed are particularly preferred, which contain propylene glycols (PPG) and / or polyethylene glycols (PEG) as sole meltable or softenable substances. Polypropylene glycols which can be used according to the invention (abbreviated PPG) are polymers of propylene glycol which correspond to the general formula I satisfy, where n can take values between 10 and 2000. Preferred PPG have molecular weights between 1000 and 10,000, corresponding to values of n between 17 and about 170.

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

H- (O-CH ₂ -CH ₂ ) _n -OH (II)

satisfy, where n can take values between 20 and about 1000. The abovementioned preferred molecular weight ranges correspond to preferred ranges of the value n in formula IV of about 30 to about 820 (exactly: from 34 to 818), especially preferably from about 40 to about 150 (exactly: from 45 to 136) and especially from about 70 to about 120 (exactly: from 68 to 113).

In a further preferred embodiment, the masses to be processed according to the invention contain in the predominant proportion paraffin wax. That is, at least 50% by weight of the total contained meltable or softenable substances, preferably more, consist of paraffin wax. Particularly suitable are paraffin wax contents (based on the total amount of meltable or softenable substances) of about 60% by weight, about 70% by weight or about 80% by weight, with 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 the meltable or softenable substances used of at least one mass consists exclusively of paraffin wax.

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

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

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

Preferably, the content of the paraffin wax used at ambient temperature (usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible. The more solid wax constituents in a wax at room temperature. the more useful it is in the context of the present invention. As the proportion of solid wax constituents increases, the end-of-processability of the process end products increases against impacts or friction on other surfaces, resulting in longer-lasting protection. High levels of oils or liquid wax components can lead to a weakening of the moldings or moldings areas, whereby pores are opened and the active ingredients are exposed to the aforementioned environmental influences.

The meltable or softenable substances may contain, in addition to paraffin as the main constituent, one or more of the abovementioned waxes or waxy substances. 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 / l at a temperature of about 30 ° C and preferably be below 5 mg / l.

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

The principle described above is the delayed release of ingredients at a certain time in the cleaning cycle and can be particularly advantageous when rinsing in the main rinse at a lower temperature (for example 55 ° C), so that the active substance from the rinse aid particles only in the rinse cycle at higher Temperatures (about 70 ° C) is released.

Preferred compositions to be processed according to the invention are characterized in that they comprise, as meltable or softenable substances, one or more substances having a melting range from 40 ° C. to 75 ° C. in amounts of from 6 to 30% by weight, preferably from 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 curing of the masses can take place 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, after the shaping processing step, release and harden the solvent (s). Suitable solvents are, for example, lower alkanols, aldehydes, ethers, esters, etc., the selection of which is carried out depending on the further composition of the masses to be processed. Particularly suitable solvents for such processes in which the hardening of the deformable mass (s) takes place 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 abovementioned alcohols, in particular ethyl acetate.

The evaporation of said solvents can be accelerated by the shaping and cutting subsequent heating, or by air movement. Combinations of the measures mentioned are suitable for this purpose, for example, the blowing of the cut moldings with hot or hot air.

Another mechanism that can underlie the hardening of the molding and cut masses. is the crystallization. Methods in which the hardening of the deformable mass (s) occurs by crystallization are also preferred.

The crystallization as a mechanism underlying the curing can be used, for example, by melting of crystalline substances as the basis of one or more molding masses. After processing such systems go into a higher order state, which in turn leads to the curing of the entire formed body. The 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, in a closed system, more of a substance is present than is required for saturation. A supersaturated solution obtained, for example, by supercooling thus contains more solute than it is likely to contain in thermal equilibrium. The excess of dissolved matter may be made by seeding with germs or dust particles or by shaking the system for instant crystallization. In the context of the present invention, the term "supersaturated" always refers to a temperature of 20 ° C. Dissolve in a particular solvent at a temperature of 20 ° C of a substance x grams in liters, the solution in the context of the present invention is to be described as "supersaturated" if it contains (x + y) grams of the substance in liters where y> 0. For example, in the context of the present invention, solutions which are used with an increased temperature as the basis of a mass to be processed and are processed at this temperature at which more dissolved substance is in the solution than those which are present are also to be termed "supersaturated" 20 ° C in the same amount of solvent would solve.

By the term "solubility", the present invention means the maximum amount of a substance. which can absorb the solvent at a certain temperature, ie the proportion of the solute in a saturated at the temperature of the solution. If a solution contains more solute than it should be in thermodynamic equilibrium at a given temperature (eg, supercooling), it is called supersaturated. By seeding with germs can cause the excess precipitates as a bottom body of the now only saturated solution. However, a solution that is saturated with respect to a substance can dissolve other substances (eg you can dissolve sugar in a saturated saline solution).

The state of supersaturation can, as described above, be achieved by slow cooling or by supercooling of a solution, as long as the solute is more soluble in the solvent at higher temperatures. Other ways to achieve supersaturated solutions, for example, include the combination of two solutions whose ingredients react to another substance, which does not precipitate immediately (prevented or delayed precipitation reactions). The latter mechanism is particularly suitable as a basis for the formation of compositions to be processed according to the invention.

In principle, the state of supersaturation can be achieved with any type of solution, although the application of the principle described in the present application, as already mentioned, is used in the production of detergents and cleaners. As a result, some systems tend to form supersaturated solutions in principle. According to the invention less well used, since the underlying material systems ecologically, toxicologically or for economic reasons can not be used. In addition to nonionic surfactants or common nonaqueous solvents, therefore, processes according to the invention with the last-mentioned curing mechanism are particularly preferred in which a supersaturated aqueous solution is used as the basis for at least one mass to be processed.

As already mentioned above, the state of supersaturation in the context of the present invention refers to the saturated solution at 20 ° C. By using solutions that have a temperature above 20 ° C, the state of supersaturation can be easily reached. Processes according to the invention in which the composition which sets by crystallization has a temperature between 35 and 120 ° C, preferably between 40 and 110 ° C, more preferably between 45 and 90 ° C and especially between 50 and 80 ° C. are preferred in the context of the present invention.

Since the prepared detergent tablets are usually neither stored at elevated temperatures nor later applied at these elevated temperatures, cooling of the mixture results in precipitation of the solute content from the supersaturated solution contained above the saturation limit at 20 ° C in the solution. The supersaturated solution can thus be divided on cooling into a saturated solution and a bottom body. But it is also possible that by recrystallization and hydration phenomena the supersaturated solution solidifies on cooling to a solid. This is the case, for example, when certain hydrazine-containing salts dissolve on heating in their water of crystallization. On cooling, supersaturated solutions are often formed here, which solidify by mechanical action or addition of seed to give a solid-the salt containing water of crystallization as the thermodynamically stable state at room temperature. This phenomenon is known, for example, from sodium thiosulfate pentahydrate and sodium acetate trihydrate, it being possible in particular for the latter hydrazine-containing salt in the form of the supersaturated solution to be used advantageously in the process according to the invention. Special detergent ingredients, such as phosphonates, also show this phenomenon and are outstandingly suitable as granulation aids in the form of the solutions. For this purpose, the corresponding phosphonic acids (see below) are neutralized with concentrated alkali metal hydroxide solution, the solution heating up by the heat of neutralization. Upon cooling, these solutions form solids of the corresponding alkali phosphonates. By incorporating further detergent ingredients in the still warm solutions can be prepared according to the invention processable masses of different composition. Particularly preferred methods according to the invention are characterized. that the supersaturated solution used as the basis of the hardening mass solidifies at room temperature to a solid. It is preferred here that the previously supersaturated solution can not be reconverted into a supersaturated solution after solidification to a solid by heating to the temperature at which the supersaturated solution was formed. This is the case, for example, with the phosphonates mentioned.

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

It is also possible to dehydrate salts containing water of hydration by "dry" heating and to dissolve it in its own water of crystallization (see above). This, too, is a method for producing supersaturated solutions which can be used in the context of the present invention.

Another way is to add a non-supersaturated solution with a gas or other liquid or solution so that the solute in the solution reacts to a less soluble substance or dissolves more poorly in the mixture of solvents. The combination of two solutions, each containing two substances which react with each other to a poorly soluble substance, is also a method for producing supersaturated solutions, as long as the less soluble material fails instantaneously. Processes which are likewise preferred in the context of the present invention are characterized in that the supersaturated solution which serves as the basis of the hardening composition is prepared by combining two or more solutions. Examples of such ways of producing supersaturated solutions are discussed below.

Preferred methods according to the invention are characterized. in that the supersaturated aqueous solution is obtained by combining an aqueous solution of one or more acidic ingredients of detergents and cleaners, preferably from the group of surfactant acids, builder acids and complexing acids, and an aqueous alkali solution, preferably an aqueous alkali hydroxide solution, especially an aqueous sodium hydroxide solution becomes.

Among the representatives of the aforementioned classes of compounds already mentioned above, in particular the phosphonates occupy 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 above 55 wt .-%, each based on the phosphonic acid and an aqueous sodium hydroxide solution with concentrations above 35 wt .-%, preferably above 40 wt .-% and in particular above 45 wt .-%, each based on the sodium hydroxide solution.

The curing of the deformable mass (s) according to the invention can also be effected 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). In particular, chemical reactions that do not abruptly lead to the mentioned state change, are suitable. From the variety of chemical reactions that lead to the solidification phenomenon, particularly reactions are suitable in which the construction of larger molecules is made of smaller molecules. These, in turn, preferably include reactions in which many small molecules react to (a) 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 finished cut molded article its strength.

With regard to the intended use of the products according to the invention, it is preferable to use as hardening mechanism the formation of such solid substances from liquid or pasty raw materials, which in the washing and cleaning agent anyway as ingredients, such as co-builders, soil repellents or soil-release Polymers are to be used. Such co-builders may be selected, for example, from the groups of the polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid. Polyacetals, dextrins, etc. come. These classes of substances are described below.

Another mechanism by which the hardening of the deformable mass (s) can take place in the context of the method according to the invention is curing by changing the rheological properties.

It makes use of the property that certain substances under the influence of shear forces change their rheological properties in some cases drastically. Examples of such systems which are familiar to the person skilled in the art are, for example, sheet silicates which, when sheared in suitable matrices, have a strong thickening effect and can lead to sliceable masses.

Of course, in a mass and two or more curing mechanisms are connected or used simultaneously. Here, for example, the crystallization with simultaneous solvent evaporation, the cooling with simultaneous crystallization, the water binding ("internal drying") with simultaneous external drying, etc. offer.

The general description of mechanisms which may underlie the curing process according to the invention is followed by a detailed description of the ingredients otherwise 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 surfactants. Accordingly, it is preferred that at least one of the masses to be processed contains surfactant (s). In the detergent tablets according to the invention can anionic. nonionic, cationic and / or amphoteric surfactants or mixtures thereof are used. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants. The total surfactant content of the tablets in the case of detergent tablets is 5 to 60% by weight, based on the tablet weight, with surfactant contents above 15% by weight being preferred, whereas automatic dishwashing detergent tablets preferably contain less than 5% by weight of surfactant (e ) contain.

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

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

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which is a synthetic. contain on a petrochemical basis produced straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also, 2,3-alkyl sulfates prepared, for example, according to U.S. Patents 3,234,258 or 5,075,041, which can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.

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

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

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

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

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

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol. which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Another class of preferred nonionic surfactants 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 from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters. as described for example in Japanese Patent Application JP 58/217598 or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylaminoxid, and the fatty acid alkanolamides may be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula (III) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (IV) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms. R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms. wherein C _1-4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical. its alkyl chain with at least two hydroxyl groups 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, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides according to the teaching of international application WO-A-95/07331, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

In the context of the present invention, preference is given to the production of detergent tablets which contain anionic (s) and nonionic surfactant (s), with technical advantages resulting from specific proportions in which the individual classes of surfactant are used.

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

It may be advantageous from an application point of view if certain classes of surfactant are present in some phases of the detergent tablets or in the entire tablet, i. in all phases, not included. Another important embodiment of the present invention therefore provides that at least one phase of the moldings is free of nonionic surfactants.

Conversely, however, can also by the content of individual phases or the entire molding. ie all phases, on certain surfactants a positive effect can be achieved. The incorporation of the alkylpolyglycosides described above has proven to be advantageous proven, so that detergent tablets are preferred in which at least one phase of the moldings contains alkylpolyglycosides.

Similar to the nonionic surfactants, the omission of anionic surfactants from individual or all phases may result in washing and cleaning agent tablets which are more suitable for certain fields of application. It is therefore within the scope of the present invention also possible to use detergent tablets in which at least one phase of the tablets is free of anionic surfactants.

As already mentioned, the use of surfactants in automatic dishwashing detergent tablets is preferably restricted to the use of small amounts of nonionic surfactants. Detergent tablets preferably to be used as detergent tablets are characterized in that they contain total surfactant contents below 5% by weight, preferably below 4% by weight, more preferably below 3% by weight and in particular below 2 wt .-%, each based on their total weight, have. As surfactants, only weakly foaming nonionic surfactants are usually used in automatic dishwashing detergents. Representatives from the groups of anionic, cationic or amphoteric surfactants, however, have less importance. With particular preference, detergent tablets for automatic dishwashing produced according to the invention contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut. Palm, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 Alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

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

Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants. in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complexed 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 having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.

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

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. 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 constitutes 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.

More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 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 may be used with particular preference are available, for example, under the name Poly Tergent® SLF-18 from Olin Cfhemicals.

A further preferred surfactant can be defined by the formula

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

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

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

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

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

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

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

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

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

The above information related in part to the final process products, which - as mentioned above - can also be designed in two, three or four phases. Relative to the individual mass to be processed containing surfactant (s), in the production of automatic dishwashing detergent tablets, methods are preferred in which the deformable mass (s) of total surfactant contents are below 5% by weight, preferably below of 4 wt .-%, more preferably below 3 wt .-% and in particular below 2 wt .-%, each based on the mass, have.

In addition to the constituents builder and surfactant, the detergent tablets according to the invention may contain further ingredients customary in detergents and cleaners from the group of bleaches. Bleach activators, disintegration aids, Dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, anti redeposition agents, grayness inhibitors, color transfer inhibitors and corrosion inhibitors. These substances can be used in all masses to be processed, but it is also possible to make beneficial properties usable by the separation of certain ingredients.

In order to facilitate the disintegration of highly compacted moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrating agents, in order to shorten the disintegration times. These substances are suitable, for example, for accelerating the release of individual shaped body regions in relation to other regions. This can be realized in the method according to the invention in that only one of the masses to be processed contains such substances, or 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, pp. 182-184), excipients are understood to mean excipients which are suitable for rapid disintegration of tablets in water or gastric juice and for the release of the drugs in resorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume upon ingress of water, on the one hand increasing the intrinsic volume (swelling), and on the other hand creating a pressure via the release of gases which can break the tablet into smaller particles decays. 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 substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preferred detergent tablets contain from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, of one or more disintegration aids, in each case based on the weight of the tablet. Contains only one mass Disintegration aids, so the above information refers only to the weight of this mass.

Preferred disintegrating agents in the context of the present invention are cellulose-based disintegrating agents, so that preferred washing and cleaning agent tablets contain such cellulose-based disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular 4 contain up to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bound by an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use pure cellulose as a cellulose-based disintegrant. which is free of cellulose derivatives.

The cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. Detergent tablets and detergent tablets which contain disintegrating agents in granular or optionally cogranulated 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). Further details of the production of granulated, compacted or cogranulated cellulose explosives can be found in these publications. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns. The above-mentioned coarser disintegration aids based on cellulose described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from Rettenmaier.

Microcrystalline cellulose may be used as another cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact. Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 μm and can be compacted, for example, into granules having an average particle size of 200 μm.

In the context of the present invention, preferred detergent tablets also contain a disintegration aid, preferably a cellulose-based disintegration assistant, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight. -% and in particular from 4 to 6 wt .-%, each based on the molding weight.

The detergent tablets according to the invention may additionally comprise a gas-evolving effervescent system which is incorporated in one or more of the masses to be processed. The gas-developing effervescent system can consist of a single substance. which releases a gas on contact with water. Among these compounds, mention should be made in particular of magnesium peroxide, which on contact with water Oxygen releases. Usually, however, the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas. While here a variety of systems is thinkable and executable that release, for example, nitrogen, oxygen or hydrogen, the bubble system used in the detergent tablets according to the invention can be selected both on the basis of economic as well as ecological aspects. Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating 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 relevant pure alkali metal carbonates or bicarbonates do not have to be used; Rather, mixtures of different carbonates and bicarbonates may be preferred for washing technical interest.

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

As Acidifizierungsmittel that release carbon dioxide from the alkali metal salts in aqueous solution. For example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. However, it is also possible in particular to use the other solid mono-, oligo- and polycarboxylic acids. Again preferred from this group are tartaric acid. Succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid. Oxalic acid and polyacrylic acid. Organic sulfonic acids such as sulfamic acid are also usable. Commercially available and as Acidifizierungsmittel in the frame Sokalan.RTM. DCS (trademark of BASF), a mixture of succinic acid (maximum 31% by weight), glutaric acid (maximum 50% by weight) and adipic acid (maximum 33% by weight) is likewise preferably usable in the present invention. ).

In the context of the present invention, preference is given to detergent tablets and cleansing agent tablets in which a substance from the group of organic di-, tri- and oligocarboxylic acids or mixtures thereof is used as the acidifying agent in the effervescent system.

In preferred processes within the scope of the present invention, at least one of the moldable compositions contains bleaching agents selected from the group consisting of oxygen or halogen bleaches, especially chlorine bleaches, with particular preference to sodium perborate and sodium percarbonate, in amounts of from 2 to 25% by weight, preferably from 5 to 20 wt .-% and in particular from 10 to 15 wt .-%, each based on the mass. These substances are described below.

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

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

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

Further useful bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and peroxygenic salts or peracids which yield H ₂ O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid 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 tablets. When cleaning or bleaching tablets for automatic dishwashing are prepared, it is also possible to use bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids. Examples being the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids. such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxy carboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N -Terephthaloyl-di (6-aminopercapronate) can be used.

Chlorinating or bromine-releasing substances can also be used as bleaching agents in machine dishwashing moldings. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

In accordance with another preferred method of the invention contains at least one of the deformable masses bleach activators from the groups of polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), the N-acylimides, especially N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, especially n-nonanoyl or Isononanoyloxybenzolsulfonat (n- or iso-NOBS) and n-methyl-morpholinium acetonitrile-methyl sulfate (MMA), in amounts of 0.25 to 15 wt .-%, preferably from 0.5 to 10 wt .-% and in particular of 1 to 5 wt .-%, each based on the mass. These substances will also be 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 the anhydrides, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD) and tetraacetylhexylenediamine (TAHD), but also pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine (DADHT) and isatoic anhydride (ISA).

As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides. in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), and German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone. and / or N-acylated lactams, for example N-benzoyl-caprolactam. Hydrophilic substituted acyl acetals and acyl lactams 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 saline complexes or carbonyl complexes. Also Mn, Fe. Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co-. Fe, Cu and Ru ammine complexes are useful as bleach catalysts.

Bleach activators from the group of the multiply acylated alkylenediamines are preferred. in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0, 1 wt .-% to 8 wt .-%, especially 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the total agent used.

Bleach-enhancing transition metal complexes, in particular having 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 (ammine) Complexes of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in conventional amounts, preferably in an amount up to 5 wt .-%, in particular of 0.0025 wt % to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. 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 purpose, in particular, methods according to the invention for the production of multiphase moldings are suitable. Methods in which one of the deformable masses contains bleach while another deformable mass contains bleach activators are preferred.

A further preferred method is characterized in that at least one of the deformable masses silver protectants from the group of the triazoles, the benzotriazoles, the Bisbenzotriazole, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes, more preferably benzotriazole and / or alkylaminotriazole, in quantities of 0.01 to 5 wt .-%, preferably from 0.05 to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the mass contains.

The said corrosion inhibitors can also be incorporated into the masses to be processed for the protection of the items to be washed or the machine, wherein in the field of automatic dishwashing silver protectants have a special meaning. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

If corrosion inhibitors are used in multiphase moldings, it is preferred to separate them from the bleaching agents. Methods in which one of the deformable masses contains bleach while another deformable mass contains corrosion inhibitors are therefore preferred.

Also, the separation of the bleach from other ingredients may be advantageous. Inventive methods in which one of the deformable masses contains bleach. while another deformable mass contains enzymes, are also preferred. Particularly suitable enzymes are those from the classes of hydrolases, such as proteases, esterases, lipases or lipolytic enzymes. Amylases, cellulases or other Glykosylhydrolasen and mixtures of said enzymes in question. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases can be removed by removing pilling and microfibrils contribute to color retention and to increasing the softness of the textile. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer. Particularly suitable are from bacterial strains or fungi such as Bacillus subtilis. Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens, as well as enzymatically derived compounds derived from their genetically engineered variants. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases. Als-cellulases are preferably cellobiohydrolases, endoglucanases and - glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

In automatic dishwashing detergent tablets, other enzymes are naturally used to account for the different treated substrates and soils. Here are in particular those from the classes of hydrolases such as proteases. Esterases, lipases or lipolytic enzymes, amylases. Glykosylhydrolasen and mixtures of the enzymes mentioned in question. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains. For bleaching and oxidoreductases can be used. Particularly suitable are from bacterial strains or fungi such as Bacillus subtilis. Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens, as well as enzymatically derived compounds derived from their genetically engineered variants. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.

The enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation. The proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%, each based on the mass (s), amount.

Regardless of the intended use of the molded articles produced according to the invention (for example detergent tablets or detergent tablets), preference is given to processes in which one of the material strands emerging from the outlet openings contains enzymes.

Such enzyme-containing compositions are preferably processed in multi-stranded processes, i. In addition to a strand of material containing enzymes, there is at least one other strand which is preferably free of enzymes. Here, methods are particularly preferred in which the enzyme-containing material strand is enveloped by an enzyme-free material.

A separation of the bleach from the surfactants described above may also be advantageous, so that preferred processes are characterized in that one of the deformable masses contains bleach, while another deformable mass surfactants. preferably nonionic surfactants, with particular preference alkoxylated alcohols having 10 to 24 carbon atoms and 1 to 5 alkylene oxide units.

Further ingredients which may be part of one or more masses in the context of the process according to the invention are, for example, co-builders (see above) dyes, optical brighteners, fragrances, soil-release compounds, soil repellents, antioxidants, fluorescers, foam inhibitors, Silicone and / or paraffin oils, color transfer inhibitors, grayness inhibitors, detergency boosters, etc. These substances are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if 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 thereof.

The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

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

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again 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 from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 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 compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

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

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

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives, of which German Patent Application DE-A-195 40 086 discloses that they also have a bleach-stabilizing effect in addition to cobuilder properties.

Further 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 obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, 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 common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are described, for example, in European Patent Applications EP-A-0 232 202, EP-A-0 427 349, 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 . Also suitable is an oxidized oligosaccharide according to the German patent application DE-A-196 00 018. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present 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 co-builders 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 aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferable, especially when the agents also contain bleach. Aminoalkanphosphonate, in particular DTPMP use, or to use mixtures of said phosphonates.

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as co-builders.

In order to improve the aesthetic impression of the detergent tablets according to the invention, they can be wholly or partially dyed with suitable dyes. Special optical effects can be achieved if in the case of the production of moldings from several masses, the masses to be processed are colored differently. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the treated substrates such as textile fibers or dishes so as 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 mixtures thereof with suitable blue dyes, so-called blue toners. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe. 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 thereof with suitable blue dyes. Further dyeing agents used 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, it must be taken into account that the colorants do not have too high an affinity for the textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, for example the abovementioned Basacid® Green or the abovementioned Sandolan® Blue, colorant concentrations in the range from a few 10 ^-2 to 10 ^-3 % by weight are typically selected. In the case of the particularly preferred, but less readily water-soluble, pigment dyes, for example the abovementioned Pigmosol® dyes, the suitable concentration of the colorant in detergents or cleaners is typically between 10 ^-3 and 10 ^-4 % by weight. ,

The laundry detergent and cleaning product tablets produced by the process according to the invention may contain one or more optical brighteners. These fabrics, 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 of sunlight into longer-wavelength blue light. The emission of this blue light complements the "gap" in the light reflected from the textile so that a fabric treated with optical brightener appears whiter and brighter to the eye. Since the mechanism of action of brighteners requires their application to 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 detergent incorporation essentially comprise five structural groups on the stilbene, diphenylstilbene, coumarin-quinoline, diphenylpyrazoline and the combination of benzoxazole or benzimidazole with conjugated systems. An overview of common brighteners can be found, for example, in G. Jakobi, A. Lohr "Detergents and Textile Washing", VCH Verlag, Weinheim, 1987, pages 94 to 100 . Suitable examples are salts of 4,4'-bis [(4-anilino-6-morpholino-6-triazin-2-yl) amino] -stilbene-2,2'-disulfonic acid or similarly constructed compounds which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brightener can be used.

Fragrances are added to the compositions according to the invention in order to improve the aesthetic impression of the products and to provide the consumer, in addition to the performance of the product, a visually and sensory "typical and unmistakable" product. As perfume oils or fragrances, individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral. Citronellal. Citronellyloxyacetaldehyde, cyclamenaldehyde. Hydroxycitronellal, Lilial and Bourgeonal, to the ketones eg the Jonone, α-isomethylionone and methyl-cedrylketon, to the alcohols anethol, citronellol, eugenol. Geraniol. Linalool, phenylethyl alcohol and terpineol, the hydrocarbons include mainly the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures, such as those available from plant sources, eg Pine. Citrus, jasmine, patchouly. Rose or Ylang-Ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil. Melissa oil, mint oil, cinnamon leaf oil, lime blossom oil. Juniper berry oil. Vetiver oil, Olibanum oil, Galbanum oil and Labdanum oil, as well as Orange blossom oil, Neroliol. Orange peel oil and sandalwood oil.

Usually, the content of perfume in the washing and cleaning agent tablets produced according to the invention is up to 2% by weight of the total formulation. The fragrances can be incorporated directly into the compositions of the invention, but it may also be advantageous to apply the fragrances on carriers, which enhance the adhesion of the perfume on the laundry and provide by a slower release of fragrance for long-lasting fragrance of the textiles. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.

In addition, the detergent tablets may also contain components which positively influence the oil and grease washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty, which has been previously washed several times 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 methylcellulose and methylhydroxy-propylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.

As foam inhibitors, which can be used in the compositions according to the invention, for example, soaps. Paraffins or silicone oils, which may optionally be applied to carrier materials.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids. Glue. Gelatin, salts of ether sulfonic acids starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches etc. Polyvinylpyrrolidone is also useful. However, preference is given to cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the compositions. used

Since textile fabrics, in particular of rayon, rayon, cotton and their mixtures, can crinkle, because the individual fibers against bending, Knikken. Pressing and squeezing transverse to the fiber direction are sensitive, the compositions according to the invention may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

For controlling microorganisms, the compositions prepared according to the invention may contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungiostats and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates. Halogenphenols and Phenolmercuriacetat, which can be completely dispensed with these compounds.

To prevent undesirable changes in the agents and / or the treated textiles caused by oxygen and other oxidative processes. The agents may contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides. Polysulfides. Dithiocarbamates, phosphites and phosphonates.

An increased wearing comfort can result from the additional use of antistatic agents, which are additionally added to the compositions according to the invention. Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges. External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided 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 described for example in the patent applications FR 1,156,513, GB 873 214 and GB 839 407. The lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed herein are useful as antistatics for textiles or as additives to laundry detergents, with the additional benefit of providing a softening effect.

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 compositions according to the invention. These additionally improve the rinsing behavior of the agents by their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes. which may 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 are in the range between 100 and 100,000 centistokes at 25 ° C, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.

Finally, the agents prepared according to the invention may also contain UV absorbers. which coat the treated textiles and improve the light fastness of the fibers. Links. which have these desired properties. are, for example, the compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position which are active by radiationless deactivation. Furthermore, also substituted benzotriazoles. in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural products such as umbelliferone and the body's own urocanic acid suitable.

In the above statements, the content of the end products of the process according to the invention was mentioned in part on the individual substances. Based on the masses to be processed, preference is generally given to processes in which at least one of the deformable masses furthermore contains one or more substances from the groups of enzymes, corrosion inhibitors, scale inhibitors, cobuilders, dyes and / or fragrances in total amounts of from 6 to 30% by weight. %, preferably from 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the mass.

In all of the above-mentioned ingredients, advantageous properties may result from separating them from other ingredients, or assembling them together with certain other ingredients. In the case of multiphase moldings, the individual phases can also have a different content of the same ingredient, whereby advantages can be achieved. Methods in which at least two of the deformable masses 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 on the relative amount, based on the phase weight, so represents a wt .-% statement, based on the individual mass, is.

The end products of the process according to the invention can be provided in a wide variety of geometric forms, this flexibility being one of the many advantages of the process according to the invention. However, it is also possible according to the invention to produce moldings which are similar in their appearance to conventional moldings. For example, they can be manufactured in a predetermined spatial form and a predetermined size, wherein as a space form come practically all reasonable manageable configurations come into consideration. for example, training as a blackboard. the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with a circular or oval cross-section. This last embodiment detects the presentation form from the tablet to compact cylinder pieces with a height to diameter ratio above 1.

The end products of the method according to the invention can be designed in each case as separate individual elements which corresponds to the predetermined dosage amount of the washing and / or cleaning agent. However, it is also possible to form the cut-to-length material strands which connect a plurality of such mass units in a compact, wherein in particular by predetermined predetermined breaking points the easy separability of portioned smaller units is provided. For the use of laundry detergents in machines of the type commonly used in Europe with horizontally arranged mechanism, the formation as tablets, in cylindrical or parallelepiped form may be expedient, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0 5 is preferred.

The spatial form of another embodiment of the moldings is adapted in their dimensions of the dispenser of commercial household washing machines, so that the moldings can be metered without dosing directly into the dispenser, where it dissolves during the dispensing process. Of course, however, a use of the detergent tablets via a dosing is easily possible and preferred in the context of the present invention.

Another preferred molded article which can be produced has a plate-like or tabular structure with alternately thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, which are the short thin segments, broken and in the Machine can be entered. This principle of the "bar-shaped" shaped body wash can also be realized in other geometric shapes, for example vertical triangles, which are joined together only on one side thereof.

Such "bar-shaped" strand sections can be produced by a post-treatment step after cutting to length. which consists in it. to push a second knife or a second knife set in 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 processes are characterized in that the cut-to-size moldings are subjected to a post-treatment step.

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

A subsequent coating of the cut moldings is also possible, if the application of an additional coating should be desired. Here, methods are preferred in which the post-treatment step comprises coating the shaped bodies with a pourable material, preferably a pourable material having a viscosity of <5000 mPas.

Regardless of the number of phases and the type of post-treatment, preference is generally given to processes 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 especially above 1100 kgdm ^-3 . In such moldings, the advantages of the offer form of a compact detergent or cleaning agent are particularly evident.

The present invention provides a process which makes it possible to produce washing and cleaning agent tablets simply and under varying conditions. A preferred curing mechanism is, as described above, in the time-delayed water binding, wherein corresponding washing and cleaning agent shaped bodies are not described in the prior art.

With regard to further ingredients, their quantities and physical properties, reference may also be made to the above statements as well as to the multiphase nature Inventive body, the distribution of ingredients on the individual phases and the proportions of the phases with each other.

Claims (46)

1. Process for producing laundry detergent and cleaning product tablets, characterized in that (a) deformable mass(es) is(are) prepared, said mass(es) is(are) supplied with a pressure below 10 bar to emergence apertures, and the emerging material strands are cut to tablet dimensions and hardened.
2. Process according to Claim 1, characterized in that the deformable mass(es) is (are) supplied to the emergence apertures with a pressure below 8.5 bar, preferably below 7.5 bar, with particular preference below 6.5 bar, and in particular below 5 bar.
3. Process according to any of Claims 1 and 2, characterized in that a deformable mass is drawn in between two rolls, discharged as a material strand from emergence apertures, cut to the desired tablet dimension, and hardened.
4. Process according to any of Claims 1 to 3, characterized in that two deformable masses of different composition are drawn in between two roll pairs and discharged as filled, hollow or multi-ply material strands from emergence apertures, cut to the desired tablet dimension, and hardened.
5. Process according to any of Claims 1 to 4, characterized in that three deformable masses of different composition are drawn in between three roll pairs and discharged as singly, doubly or triply filled, hollow, two- or three-ply material strands from emergence apertures, cut to the desired tablet dimension, and hardened.
6. Process according to any of Claims 1 to 5, characterized in that the material strands are discharged from the emergence apertures at a rate of from 0.2 m/min to 30 m/min, preferably from 0.25 m/min to 20 m/min, with particular preference from 0.5 m/min to 15 m/min, and in particular from 1 m/min to 10 m/min.
7. Process according to any of Claims 1 to 6, characterized in that the emergence apertures have aperture areas of from 50 mm² to 2500 mm², preferably from 100 mm² to 2000 mm², with particular preference from 200 mm² to 1500 mm², and in particular from 300 mm² to 1000 mm², with especial preference from 350 mm² to 750 mm².
8. Process according to any of Claims 1 to 7, characterized in that the thickness of at least one of the material strands emerging from the emergence apertures is at least 5 mm, preferably at least 7.5 mm, and in particular at least 10 mm.
9. Process according to any of Claims 1 to 8, characterized in that the material strands emerging from the emergence apertures are cut to a length of from 10 to 100 mm, preferably from 12.5 to 75 mm, with particular preference from 15 to 60 mm, and in particular from 20 to 50 mm.
10. Process according to any of Claims 1 to 9, characterized in that the hardening of the material strands, cut to tablet dimensions, is assisted by superficial drying and/or cooling, in particular by blowing with cold air.
11. Process according to any of Claims 1 to 10, characterized in that the deformable mass(es) comprise(s) from 10 to 95% by weight, preferably from 15 to 90% by weight, with particular preference from 20 to 85% by weight, and in particular from 25 to 80% by weight, of anhydrous substances which pass by hydration into a hydrate form having a melting point below 120°C, preferably below 100°C, and in particular below 80°C.
12. Process according to any of Claims 1 to 11, characterized in that the deformable mass(es) comprise(s) phosphate(s), preferably alkali metal phosphate(s), with particular preference pentasodium and/or pentapotassium triphosphate (sodium and/or potassium tripolyphosphate), in amounts of from 20 to 80% by weight, preferably from 25 to 75% by weight, and in particular from 30 to 70% by weight, based in each case on the mass.
13. Process according to Claim 12, 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.
14. Process according to any of Claims 1 to 13, characterized in that the deformable mass(es) comprise(s) carbonate(s) and/or hydrogen carbonate(s), preferably alkali metal carbonate(s), with particular preference sodium carbonate, in amounts of from 5 to 50% by weight, preferably from 7.5 to 40% by weight, and in particular from 10 to 30% by weight, based in each case on the mass.
15. Process according to any of Claims 1 to 14, characterized in that the deformable mass(es) comprise(s) silicate(s), preferably alkali metal silicates, with particular preference crystalline or amorphous alkali metal disilicates, in amounts of from 10 to 60% by weight, preferably from 15 to 50% by weight, and in particular from 20 to 40% by weight, based in each case on the mass.
16. Process according to any of Claims 1 to 15, characterized in that the deformable mass(es) comprise(s) zeolite(s), preferably zeolite A, zeolite P, zeolite X and mixtures thereof, in amounts of from 10 to 60% by weight, preferably from 15 to 50% by weight, and in particular from 20 to 40% by weight, based in each case on the mass.
17. Process according to any of Claims 1 to 16, characterized in that the average particle size of the solids used in the deformable mass(es) is below 400 µm, preferably below 300 µm, and in particular below 200 µm.
18. Process according to any of Claims 1 to 17, 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(es) have particle sizes above 1000 µm.
19. Process according to any of Claims 1 to 18, characterized in that less than 15% by weight, preferably less than 10% by weight, and in particular less than 5% by weight, of the solids used in the deformable mass(es) have particle sizes above 800 µm.
20. Process according to any of Claims 1 to 19, characterized in that the water content of the tablets is from 50 to 100% of the calculated water binding capacity.
21. Process according to any of Claims 1 to 20, characterized in that the deformable mass(es) in the course of processing has (have) a water content of from 2.5 to 30% by weight, preferably from 5 to 25% by weight, and in particular from 7.5 to 20% by weight, based in each case on the mass.
22. Process according to any of Claims 1 to 21, characterized in that the deformable mass(es) is (are) hardened by means of time-delayed water binding.
23. Process according to any of Claims 1 to 21, characterized in that the deformable mass(es) is (are) hardened by means of cooling below the melting point.
24. Process according to any of Claims 1 to 21, characterized in that the deformable mass(es) is (are) hardened by means of evaporation of solvents.
25. Process according to any of Claims 1 to 21, characterized in that the deformable mass(es) is (are) hardened by means of crystallization.
26. Process according to any of Claims 1 to 21, characterized in that the deformable mass(es) is (are) hardened by means of chemical reaction(s), especially addition polymerization.
27. Process according to any of Claims 1 to 21, characterized in that the deformable mass(es) is (are) hardened by means of a change in the rheological properties.
28. Process according to any of Claims 1 to 27, characterized in that the deformable mass(es) has (have) total surfactant contents of less than 5% by weight, preferably less than 4% by weight, with particular preference less than 3% by weight, and in particular less than 2% by weight, based in each case on the mass.
29. Process according to any of Claims 1 to 28, characterized in that at least one of the deformable masses comprises bleaches from the group of the oxygen or halogen bleaches, especially the chlorine bleaches, with particular preference being given to sodium perborate and sodium percarbonate, in amounts of from 2 to 25% by weight, preferably from 5 to 20% by weight, and in particular from 10 to 15% by weight, based in each case on the mass.
30. Process according to any of Claims 1 to 29, characterized in that at least one of the deformable masses comprises bleach activators from the groups of polyacylated alkylenediamines, especially tetra-acetylethylenediamine (TAED), N-acyl imides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulphonate (nor iso-NOBS) and N-methylmorpholiniumacetonitrile methyl sulphate (MMA), in amounts of from 0.25 to 15% by weight, preferably from 0.5 to 10% by weight, and in particular from 1 to 5% by weight, based in each case on the mass.
31. Process according to any of Claims 1 to 30, characterized in that at least one of the deformable masses comprises silver protectants from the group of the triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the transition metals salts or transition metal complexes, with particular preference 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, based in each case on the mass.
32. Process according to any of Claims 1 to 31, characterized in that at least one of the deformable masses further comprises one or more substances from the groups of enzymes, corrosion inhibitors, scale inhibitors, cobuilders, dyes and/or fragrances in total amounts of from 6 to 30% by weight, preferably from 7.5 to 25% by weight, and in particular from 10 to 20% by weight, based in each case on the mass.
33. Process according to any of Claims 4 to 32, characterized in that one of the deformable masses comprises bleaches while another deformable mass comprises bleach activators.
34. Process according to any of Claims 4 to 33, characterized in that one of the deformable masses comprises bleaches while another deformable mass comprises enzymes.
35. Process according to any of Claims 4 to 34, characterized in that one of the deformable masses comprises bleaches while another deformable mass comprises corrosion inhibitors.
36. Process according to any of Claims 4 to 34, characterized in that one of the material strands emerging from the emergence apertures comprises enzymes.
37. Process according to Claim 36, characterized in that the enzyme-containing material strand is enveloped by an enzyme-free material.
38. Process according to any of Claims 4 to 37, characterized in that one of the deformable masses comprises bleaches while another deformable mass comprises surfactants, preferably nonionic surfactants, with particular preference alkoxylated alcohols having 10 to 24 carbon atoms and from 1 to 5 alkylene oxide units.
39. Process according to any of Claims 5 to 38, characterized in that at least two deformable masses comprise the same active substance in different amounts.
40. Process according to any of Claims 1 to 39, characterized in that the deformable mass(es) comprise(s) a paraffin wax having a melting range of from 50°C to 55°C.
41. Process according to any of Claims 1 to 40, characterized in that the plastically deformable mass(es) comprise(s) at least one substance from the group of polyethylene glycols (PEG) and/or polypropylene glycols (PPG).
42. Process according to any of Claims 1 to 41, characterized in that the tablets comprise less than 10% by weight, preferably less than 5% by weight, with particular preference less than 1% by weight, and in particular less than 0.5% by weight, of free water.
43. Process according to any of Claims 1 to 42, characterized in that the tablets have a density of more than 800 kgdm^-3, preferably more than 900 kgdm^-3, with particular preference more than 1000 kgdm^-3, and in particular more than 1100 kgdm^-3.
44. Process according to any of Claims 1 to 43, characterized in that the tablets are subjected to an aftertreatment step.
45. Process according to Claim 44, characterized in that the aftertreatment step comprises the coating of the tablets with a pourable material, preferably a pourable material having a viscosity < 5000 mPas.
46. Process according to either of Claims 44 and 45, characterized in that the aftertreatment step comprises an additional shaping step, especially that of impression.