WO1999024545A2

WO1999024545A2 - Method for producing stable, rapidly decomposing shaped bodies of detergent

Info

Publication number: WO1999024545A2
Application number: PCT/EP1998/006891
Authority: WO
Inventors: Gerhard Blasey; Christian Block; Monika Böcker; Ingo Hardacker; Heinke Jebens; Hans-Friedrich Kruse; Andreas Lietzmann; Antoni Machin; Fred Schambil; Sandra WITT-NÜSSLEIN
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1997-11-11
Filing date: 1998-10-30
Publication date: 1999-05-20
Also published as: WO1999024545A3; CA2305563A1; DE19749749A1

Abstract

The invention relates to a method for producing shaped bodies of detergent by compressing a particulate detergent composition into shapes. Said composition is obtained by mixing a detergent granulate produced according to a known method with powder treatment components. Particularly stable shaped bodies, characterised in that they decompose rapidly, can be obtained by mixing the granulate with the powder treatment components in a mixer and circulating the mixture at least four times after the last component has been added, with detention times of between 1 and 300 seconds.

Description

^ Process for the production of stable and rapidly disintegrating detergent tablets'

The present invention relates to the production of detergent tablets. In particular, the invention relates to a process for the production of washing and cleaning-active moldings which can be obtained by compression-molding of particulate detergent and cleaning agent compositions and which are distinguished by high strengths and nevertheless good decay and solubility characteristics.

The production of washable and cleaning-active molded articles is carried out by applying pressure to a mixture to be pressed, which is located in the cavity of a press. In the simplest case of molded article production, which is simply called tableting below, the mixture to be tabletted is directly, i.e. pressed without prior granulation. The advantages of this so-called direct tableting are its simple and inexpensive application, since no further process steps and consequently no further plants are required. However, these advantages are offset by disadvantages. For example, a powder mixture which is to be tabletted directly must have sufficient plastic deformability and have good flow properties; furthermore, it must not show any tendency to segregate during storage, transport and filling of the die. These three requirements are extremely difficult to master with many substance mixtures, so that direct tableting is not often used, particularly in the manufacture of detergent tablets.

The usual way to manufacture detergent tablets starts with powdery components ("primary particles"), which are transformed into secondary particles with a larger particle diameter are agglomerated or granulated. These granules or mixtures of different granules are then mixed with individual additives and fed to the tableting. The properties of the granules are of crucial importance for the physical properties of the shaped bodies - particle sizes, moisture content and other parameters which can be controlled in the granules make a decisive contribution to the later properties of the shaped bodies. In particular, two physical properties of moldings are of crucial importance, especially in the case of detergent tablets: the hardness and the rate of disintegration. While one can obtain molded articles of any desired stability by correspondingly high pressure during tableting, the time required for the molded article to disintegrate increases at the same time as the pressing pressure. Since the desired properties of a hard, transport- and handling-stable tablet, on the one hand, and a rapidly disintegrating tablet, on the other hand, conflict, there is generally a problem in the manufacture of detergent tablets to overcome the dichotomy between hardness and disintegration as far as possible.

In the prior art, there is an almost unlimited number of fonts for the production of granules, which range from the patent specification to the complete monograph of the granulation technology.

EP-B-642 576 (Henkel) discloses a process for the continuous production of granules, in which in a first low-speed mixer / granulator through which the product flows horizontally (peripheral speeds of the mixing tools 2-7 m / s) and pre-granulated second high-speed mixer granulator, through which the product flows vertically (peripheral speeds of the mixing tools> 8 m / s) is completely granulated.

The combination of slow- and fast-running mixers with different residence times of the products in the mixing granulators is also widely described in the prior art. For example, European patent application EP-A-264 049 (BAYER AG) describes a process for the production of granules, in which the powder to be granulated is subsequently other is granulated in a high-speed and slow-speed mixing granulator with the addition of a granulating liquid and then dried in a fluidized bed. The residence times in the high-speed mixer (speed range 800-3000 rpm) are in the range from 0.5 to 60 seconds, while the powder in the slow-speed mixer (speed range 60 to 250 rpm) remains for 60 to 300 seconds.

The adaptation of the above Process for the production of detergent granules is described in EP-A-367 339 (Unilever). This document discloses the production of detergent granules with bulk densities above 650 g / 1 by treating a powdery starting material in a high-speed mixer (speed range 100-2500 rpm, residence time 5-30 s), followed by mixing in a slow-running mixer (speed range 40 -160 rpm, dwell time 60-600 s) and final drying.

EP-A-390 251 (Unilever) extends the latter method in that 0.1 to 40% by weight of a powder is added between the high-speed and the slow-speed mixer. This procedure is intended to minimize the formation of particles with too large particle diameters.

The production of detergent tablets is carried out by pressing particulate detergent compositions which are at least partially composed of granules. Detergent tablets and processes for their production are also described in detail in the prior art. For example, EP-A-0 522 766 (Unilever) discloses moldings made from a compact, particulate detergent composition containing surfactants, builders and disintegration aids (for example based on cellulose), at least some of the particles being coated with the disintegration agent, which is both binder and also shows disintegration effects when the moldings are dissolved in water. This document also indicates the general difficulty of producing moldings with adequate stability and good solubility at the same time. The particle size in the mixture to be pressed should be above 200 μm, the upper and lower limits of the individual particle sizes should not differ from one another by more than 700 μm. The molded bodies are produced by mixing one Detergent and cleaning agent granules produced in a manner known per se with powder-form processing components and subsequent shaping pressing.

Further documents which deal with the production of detergent tablets are EP-A-0 716 144 (Unilever), which describes tablets with an external shell made of water-soluble material, and EP-A-0 711 827 (Unilever), which contain a citrate with a defined solubility as an ingredient.

The use of binders which may have an explosive effect (in particular polyethylene glycol) is disclosed in EP-A-0 711 828 (Unilever), which describes detergent tablets which are formed by pressing a particulate detergent composition at temperatures between 28 ° C. and the melting point of the binder material be produced, always being pressed below the melting temperature. From the examples in this document it can be seen that the moldings produced in accordance with their teaching have higher breaking strengths when compression is carried out at elevated temperature.

Detergent tablets in which individual ingredients are present separately from others are also described in EP-A-0 481 793 (Unilever). The detergent tablets disclosed in this document contain sodium percarbonate, which is spatially separated from all other components that could influence its stability.

The manufacturing processes for washing and cleaning-active moldings mentioned in the prior art are shaping pressing, which takes place in part at different temperatures. In the state of the art, only physical properties of the mixture to be pressed, such as, for example, the particle size, the spatial distribution of individual components or the physical properties of individual components, are mentioned as further influencing variables.

Nowhere in the state of the art is it described how a specific preparation of the particulate detergent and cleaning agent composition to be compressed is based on the physical sical properties of the resulting detergent tablets can have an advantageous effect.

The object of the present invention was to provide, in addition to the selection of individual constituents, a further influencing variable with which the physical properties of detergent tablets can be improved. In particular, the object of the present invention was to provide a method which, by means of specific pretreatment of the mixture to be compressed, delivers hard and nevertheless rapidly disintegrating detergent tablets.

It has now been found that, in the production of the particulate detergent and cleaning composition to be compressed, certain mixing times have to be observed when mixing the granular constituents with the powdery mixing components in order to obtain tablets with high hardness and good disintegration properties.

The invention therefore relates to a process for the production of detergent tablets by mixing detergent granules, prepared in a manner known per se, with pulverulent preparation components and subsequent molding, wherein the granules are mixed with the pulverulent preparation components in a mixer and after the addition of the last component, the mixture is circulated at least four times with dwell times between one and 300 seconds.

The detergent and cleaning agent granules used in the process according to the invention can be produced in a wide variety of ways and can contain the usual ingredients of detergents and cleaning agents in varying amounts. The granulate particles can have a wide variety of shapes, depending on the production process, with approximately spherical granules often being referred to as pellets.

For example, wet granulation, dry granulation or melt solidification granulation are suitable as granulation processes, of which wet granulation is the most common granulation technique, since this technique has the fewest restrictions. is subjected to and most surely leads to granules with favorable properties. With this granulation technology, a distinction is made between adhesive and crust granulation and between build-up and breakdown granulation. In the first case, a distinction is made between whether the powder mixtures to be granulated are granulated with solutions of binders or adhesives or with pure solvent or solvent mixtures; in the second case, a distinction is made as to whether finer particles are built up into coarser aggregates or coarser pieces into finer pieces Granules are crushed.

A wide variety of apparatuses are suitable for carrying out the granulation, for example fluidized-bed granulators, high-speed and slow-speed mixing granulators, roller compactors, ring die presses, pellet presses and many others. Extrusion, which can be carried out both as wet and as dry granulation, is also suitable for producing the granules used in the process according to the invention.

The granules can be post-treated in a manner known per se. For example, a drying step may be necessary after wet granulation, or the granules are further treated to improve their surface properties, for example by powdering with finely divided substances that prevent the granules from sticking together.

All the usual ingredients of detergents and cleaning agents can be considered as ingredients from which the granules are made. In particular, builders and surfactants are to be mentioned here, but also bleaching agents and bleach activators, enzymes, cobuilders, foam inhibitors, optical brighteners, phosphonates, polymers and colorants and fragrances. In the context of the present invention, a method is preferred in which the detergent and cleaning agent granules, which are produced in a manner known per se, contain surfactant (s), builders (s) and, optionally, further ingredients customary in detergents and cleaning agents.

The person skilled in the art will have no difficulty in incorporating individual detergent and cleaning agent ingredients either in the production of the granules or in the mixing thereof with the powdery processing components. Depending on the Desired properties of the moldings, the ingredients of detergents and cleaning agents can be introduced into the moldings via the granules or via the pulverulent preparation components. It is preferred that the ingredients of detergents and cleaning agents, which could be damaged during granulation, are introduced into the moldings via the pulverulent preparation components.

In a preferred process for the production of detergent tablets, one or more substances from the group of the surfactants, surfactant compounds, builders, bleaching agents, bleach activators, enzymes, foam inhibitors, dyes and fragrances as well as binding and disintegration aids are added to the granules as a powdery processing component .

The proportions of granules and powdered processing components can also be varied within wide limits. In the context of the present invention, a method is preferred in which, when blended, 30 to 80% by weight, preferably 40 to 75% by weight and in particular 50 to 70% by weight of granules and 20 to 70% by weight , preferably 25 to 60% by weight and in particular 30 to 50% by weight of pulverulent constituents, in each case based on the amount of the mixture to be tabletted, and the mixture after the addition of the last component with residence times between one and 300 seconds , preferably between 10 and 180 seconds and in particular between 20 and 120 seconds, at least four times.

In order to make better use of existing granulating devices or to be able to use existing types of granules, the detergent and cleaning agent granules produced in a manner known per se can also consist of two or more separately produced individual granules. For example, a nonionic surfactant zeolite granulate can be mixed with an anionic surfactant silicate granulate and the pulverulent processing components without any loss of quality compared to a single granulate which is composed of all four components. Within the scope of the present invention, preferred in a process in which the detergent and cleaning agent granules produced in a manner known per se consist of two or more granules produced separately.

In order to achieve an even distribution of granulate (s) and powdery processing components, the mixture to be tabletted must be circulated in the mixer at least four times. The time required for the circulation is not important. Both high-speed, high-speed mixers and slower-running mixers can be used. The residence time of the granules must also be less than 300 seconds, regardless of the mixer type. Although the granules are circulated much more frequently in a high-speed mixer than in a slow-speed mixer, the time limit above which the tablet properties are negatively influenced is 300 seconds. For economic reasons, however, it may be preferable to adapt the residence times of the mixture to be tabletted in the mixer to the circulation speed. When using slow-running mixers with circulation speeds between 10 and 250 rpm, residence times between 1 and 300 seconds, preferably between 20 and 180 seconds and in particular between 30 and 150 seconds are preferred, while preferred residence times in high-speed mixers with circulation speeds between 250 and 3000 RPM are between one and 300 seconds, preferably between 2 and 180 seconds and in particular between 3 and 90 seconds.

In order to ensure an even distribution of the components, the mixture of granules and powdery components must be thoroughly mixed. This requires a circulation at least four times, although a higher number of circulations can be useful from a process engineering point of view. In the context of the present application, the terms “circulate” and “circulations” denote the number of the minimum required revolutions of the mixer shaft which, depending on the speed, swirls the product more or less strongly and entrains it. Circulating at least four times thus means, for example, at a mixer speed of 40 revolutions per minute, a minimum dwell time of the mixture to be pressed of 6 seconds. In the context of the present invention, a method is preferred in which the mixture of granules and powdery constituents is circulated in the mixer at least four times, preferably at least eight times and in particular at least ten times.

The molded articles according to the invention are actually produced first by dry mixing the granules and the powdery constituents and then informing them, in particular compressing them into tablets, it being possible to use conventional methods. To produce the shaped bodies according to the invention, the premix is compacted in a so-called die between two punches to form a solid compact. This process, which is briefly referred to as tableting in the following, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.

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

Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down. For small production quantities, eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine. The pressing can take place with one upper and one lower stamp, but several stamps can also be attached to one eccentric disc, the number of die holes being correspondingly increased. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available. Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps. The die table and the stamps move around a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation. At locations where a particularly serious lifting or lowering of the punches is required (filling, compacting, ejecting), these cam tracks are supported by additional low-pressure pieces, low-pressure rail and lifting tracks. The die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix. The pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers. Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet. For the production of two-layer and multi-layer molded bodies, several filling shoes are arranged one behind the other without the lightly pressed first layer being ejected before further filling. Suitable process control also makes it possible to produce matte and dot tablets that have an onion-shell-like structure, the top surface of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible. Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing. The throughputs of modern rotary tablet presses are over one million molded articles per hour.

Tableting machines suitable within the scope of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy NV, Halle (BE / LU). For example, the hydraulic double pressure press HPF 630 from LAEIS, D. is particularly suitable.

The molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial form, for example, the design as a board, the rod or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the form of presentation from the tablet to compact cylinder pieces with a ratio of height to diameter above 1, a particularly homogeneous density distribution in the shaped bodies being achieved if the ratio of diameter to height is approximately 4.

The portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents equivalent. It is also possible, however, to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points. For the use of laundry detergents in machines of the type customary in Europe with horizontally arranged mechanics, the portioned compacts as tablets, in cylinder or cuboid form can be expedient, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such pressed articles.

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

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

However, it is also possible that the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous application properties of the molded body. If, for example, components are contained in the moldings that mutually influence each other negatively, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first Component has already reacted when the second goes into solution. The layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely removed, but it is also possible for the inner layer (s) to be completely encased ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).

In a further preferred embodiment of the invention, a molded body consists of at least three layers, i.e. two outer and at least one inner layer, at least one of the inner layers containing a peroxy bleaching agent, while in the case of the stacked molded body the two cover layers and in the case of the shell-shaped molded body the outermost layers, however, are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in a molded body. Such multilayer molded bodies have the advantage that they can be used not only via a dispensing chamber or via a metering device which is added to the washing liquor; rather, in such cases it is also possible to put the molded body into direct contact with the textiles in the machine without the risk of bleaching from bleaching agents and the like.

Similar effects can also be achieved by coating individual constituents of the detergent and cleaning agent composition to be treated or the entire molded body. For this purpose, the bodies to be coated can be sprayed with aqueous solutions or emulsions, for example, or by the process of melting. get a coating.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to

2P σ = ^• πDt Herein σ stands for diametral fracture stress (DFS) in Pa, P is the force in N that leads to the pressure exerted on the molded body that causes the molded body to break, D is the molded body diameter in meters and t the height of the molded body.

In preferred embodiments of the method according to the invention, the mixture to be compacted from granulate (s) and pulverulent preparation components at compression pressures between 10 and 150 N / cm, preferably between 15 and 100 N / cm and in particular between 20 and 100 N / cm and temperatures between 10 and 80 ° C, preferably between 15 and 70 ° C and in particular between 20 and 60 ° C.

The following is a brief description of the most important ingredients of detergent tablets which can be used in the process according to the invention both in the granulate and as pulverulent preparation components. The granular constituents of the mixture to be vesφress are produced in a manner known per se with a composition known per se, the selection of the ingredients depending on the intended use of the molded article.

Anionic, nonionic, cationic and / or amphoteric surfactants can be used in the detergent tablets according to the invention. Mixtures of anionic and nonionic surfactants are preferred from an application point of view, the proportion of anionic surfactants being greater than the proportion of nonionic surfactants. The total surfactant content of the molded article is from 5 to 60% by weight, based on the weight of the molded article, with surfactant contents above 15% by weight being preferred.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C _9- sulfonates ι -Alkylbenzolsul-, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfide, as they, for example, Cι ι _2- ₈ -Monoolefmen with terminal or internal double bond, obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are derived from C ₂ - ₈ alkanes, for example by sulfochlorination or sulfo foxidation with subsequent hydrolysis or neutralization can be obtained. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

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

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C] ₂ -C ₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Ci _ö -C ₂ o -Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. For reasons of washing technology, the C ₂ -C ₆ alkyl sulfates and C ₂ -C ₅ alkyl sulfates and C ₄ -C ₅ alkyl sulfates are preferred. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C ₉ n-alcohols with an average of 3.5 moles of ethylene oxide (EO) or Cι _2- ι. ₈ -Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight. Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8- ι ₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

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

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

If premixes are prepared in the process according to the invention which contain fatty alcohol sulfates as anionic surfactants, it is preferred to introduce the fatty alcohol sulfates into the premix to be treated via the pulverulent preparation components. Fatty alcohol sulfate compounds which have an active substance content of at least 30% by weight are preferably used. Particularly advantageous moldings are obtained by the process according to the invention if the powder component which contains the fatty alcohol sulfate is added as the last constituent to the mixer and, after the addition of the fatty alcohol sulfate compound, mixing times of less than 3 minutes are observed. A preferred method is therefore characterized in that the last pulverulent preparation component in the mixture is a surfactant compound with at least 30% by weight of fatty alcohol sulfate, based on the surfactant compound, and the mixture is added after the addition of the fatty alcohol sulfate compound with residence times between one and 180 seconds, is preferably circulated at least four times between 10 and 150 seconds and in particular between 20 and 120 seconds.

It is also possible to introduce finely divided powder components into the process according to the invention, which adhere to the surface of the granules / granules and the other powdery processing components and “powder them”. The introduction of the “powdering agents” has the advantage that stamp caking occurs in the subsequent Addresses are minimized or avoided entirely. Suitable finely divided powdering agents are, for example, the builders described below, wherein zeolites and among them in particular the zeolite X described in detail below are particularly suitable. In a further preferred process, the powdery processing components are mixed with a surfactant compound with at least 30% by weight fatty alcohol sulfate, based on the surfactant compound, and zeolite X, the zeolite X preferably being added as the last processing component, and the mixture is added after the Addition of the zeolite X with residence times between one and 180 seconds, preferably between 10 and 150 seconds and in particular between 20 and 120 seconds, circulated at least four times.

The amount of anionic surfactant which is introduced into the molded body via the premix is, for example, between 5 and 60% by weight. However, the anionic surfactants are preferably not used alone, but rather in a mixture with nonionic surfactants, the total content of anionic surfactants in the moldings then being between 5 and 40% by weight, preferably between 5 and 30% by weight.

In a further preferred process, a fatty alcohol sulfate compound is added in the amount as a pulverulent preparation component such that the mixture to be treated contains at least 2% by weight, preferably at least 4% by weight and in particular more than 5% by weight of fatty alcohol sulfate. The nonionic surfactants used are preferably alkoxy-hardened, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linearly or preferably 2-branched methyl or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-1 alcohols with 3 EO or 4 EO, C ₉ π alcohol with 7 EO, C ₃ - ₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Cι _{-! 8} alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Cι.] ₄ alcohol with 3 EO and C _12-1 8 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

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

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

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

Rl

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

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

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

R! -OR ²

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

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

[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, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

The builders that can be contained in the detergent tablets according to the invention include, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

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

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

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the process according to the invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

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

can be described. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₂ -C ₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁ - fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; Measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. These salts are used due to their builder properties and should not be considered as a component of the shower system, especially since the salts are not suitable for releasing carbon dioxide from hydrogen carbonates, for example.

Among the compounds which serve as bleaching agents and supply HO ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphate, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the detergent tablets. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acy- lated triazine derivatives, in particular l, 5-diacetyl-2,4-dioxohexahydro-l, 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 anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

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

As foam inhibitors, which can be part of component b) or are used alone as component b), for example soaps of natural or synthetic origin come into consideration which have a high proportion of C _8-24 fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silicic acid or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

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

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active substances obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the shaped bodies according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

The shaped bodies can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which, instead of the Moφholino group, have a diethanolamino group , a methyl amino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used.

Dyes and fragrances are added to the agents according to the invention in order to improve the aesthetic impression of the products and, in addition to the washing and cleaning performance, provide the consumer with a visually and sensorially “typical and unmistakable” product To make available. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propyl propylateylatepylionate. The ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, <χ-isomethylionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and teφineol, the hydrocarbons mainly include the teφenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The colorant content of the shaped bodies according to the invention is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the total formulation.

Examples:

For the production of detergent tablets, a detergent granulate (composition according to Table 1) was placed in different mixers, sprayed with perfume and subsequently mixed with the preparation components listed in Table 2. Before pressing into tablets, 4% by weight of cellulose (disintegrant) and 1% by weight of zeolite (powdering component), each based on the weight of the molded article, were mixed in. Three different mixer types were used, each with a total mixing time of 30 seconds or 3 minutes. The results in Table 3 show that the detergent tablets, which were produced from the longer-mixed premix, have significantly longer disintegration times, despite a much “softer” strain.

Table 1: Composition of the surfactant granules [% by weight]:

Table 2: Composition of the detergent tablets [% by weight]:

The hardness of the tablets was measured by deforming the tablet to fracture, the force acting on the side surfaces of the tablet and the maximum force that the tablet was able to withstand.

To determine the tablet disintegration, the tablet was placed in a beaker with water (600 ml of water, temperature 30 ° C.) and the time until the tablet disintegrated completely without mechanical action.

The experimental data are shown in Table 3:

Table 3: Detergent tablets [physical data]

Example 1: Lödige FM 130 D, Gebrüder Lödige Maschinenbau, D (ploughshare mixer) Example 2: Bolz Summiz ML 003, Helpman Process Engineering, Cheeks, D (conical screw mixer) Example 3: Pegasus PG 120, Dinnissen, Sevenum, NL ( Paddle mixer)

In further test series, detergent tablets containing fatty alcohol sulfate were produced, the fatty alcohol sulfate (FAS) being added last as a powdery processing component and once after the addition of the FAS in powder form, zeolite X was added to the mixer as a powdering agent. In a further experiment, the FAS was introduced into the process in the form of granules.

Table 4: Composition of the detergent tablets (Example 4) [% by weight]:

*. : Fatty alcohol sulfate compound with 96% active substance, 2% sodium carbonate and 2% water In this example, the fatty alcohol sulfate compound was added as the last component and the mixture was mixed in a Lödige FM 130 D. The mixing times after adding the FAS were measured and the physical data of the detergent tablets were determined after exposure. The experimental data are shown in Table 6.

In a further example, after the addition of 3.8% by weight of the FAS compound used in Example 4, 1% by weight of zeolite X was added as a powdering agent and the mixture was mixed in a Lödige FM 130 D. The mixing times after the addition of the zeolite X were measured and the physical data of the detergent tablets were determined after exposure. The experimental data are shown in Table 6.

According to the invention, FAS can also be used in the form of a surfactant granulate. For this purpose, the surfactant granules in Example 6 were changed as follows: Instead of 6.2% by weight of C _12-18 fatty alcohol with 7 EO, 3.2% by weight of 96% FAS compound and 3.0% by weight % C _{12-] 8} - fatty alcohol with 7 EO used. This granulate was mixed with the other components in a Lödige FM 130 D, the mixing time being measured after the addition of the zeolite X (last component, powdering agent). The composition of the detergent tablets shows Table 5, the physical data of the detergent tablets of Examples 4, 5 and 6 are shown in Table 6.

Table 5: Composition of the detergent tablets (Example 6) [% by weight]:

*: According to Table 1 with 3.2 wt .-% 96% FAS compound and 3.0 wt .-% Cι _2- fatty alcohol with 7 EO instead of 6.2 wt .-% Cι _2- ι ₈ fatty alcohol with 7 EO.

Table 6: Detergent tablets [physical data]

Claims

Claims:

1. A process for the production of laundry detergent and cleaning agent shaped bodies by mixing a detergent and cleaning agent granulate produced in a manner known per se with powdery processing components and subsequent shaping molding, characterized in that the mixing of the granules with the powdery processing components takes place in a mixer and the mixture after the addition of the last component with residence times between one and 300 seconds, it is circulated at least four times.

2. The method according to claim 1, characterized in that the detergent granules prepared in a conventional manner contains surfactant (s), builders (e) and optionally further ingredients customary in detergents and cleaning agents.

3. The method according to any one of claims 1 or 2, characterized in that one or more substances from the group of surfactants, surfactant compounds, builders, bleaching agents, bleach activators, enzymes, foam inhibitors, dyes and fragrances and binders as powdery processing components in the mixing. and disintegration aids are added.

4. The method according to any one of claims 1 to 3, characterized in that in the mixing 30 to 80 wt .-%, preferably 40 to 75 wt .-% and in particular 50 to 70 wt .-% granules and 20 to 70 wt. %, preferably 25 to 60% by weight and in particular 30 to 50% by weight of pulverulent constituents, in each case based on the amount of the mixture to be tabletted, are mixed with one another and the mixture after the addition of the last component with residence times between one and 300 seconds, preferably between 10 and 180 seconds and in particular between 20 and 120 seconds, is circulated at least four times.

5. The method according to any one of claims 1 to 4, characterized in that the detergent and cleaning agent granules produced in a conventional manner consists of two or more separately produced individual granules.

6. The method according to any one of claims 1 to 5, characterized in that the mixing of the granules with the powdery constituents in a slow-running mixer at circulation speeds between 10 and 250 rpm and residence times between one and 300 seconds, preferably between 20 and 180 seconds and in particular between 30 and 150 seconds.

7. The method according to any one of claims 1 to 5, characterized in that the mixing of the granules with the powdery constituents in a high-speed mixer at circulation speeds between 250 and 3000 rpm and residence times between one and 300 seconds, preferably between 2 and 180 seconds and in particular between 3 and 90 seconds.

8. The method according to any one of claims 1 to 7, characterized in that the mixture of granules (s) and powdery constituents is circulated in the mixer at least four times, preferably at least eight times and in particular at least ten times.

9. The method according to any one of claims 1 to 8, characterized in that as the last pulverulent preparation component in the mixture, a surfactant compound with at least 30% by weight of fatty alcohol sulfate, based on the surfactant compound, is added and the mixture after the addition of the fatty alcohol sulfate compound at residence times between one and 180 seconds, preferably between 10 and 150 seconds and in particular between 20 and 120 seconds, is circulated at least four times.

10. The method according to any one of claims 1 to 8, characterized in that a tensid compound with at least 30 wt .-% fatty alcohol sulfate, based on the surfactant compound, and zeolite X are added as the powdery processing components during the mixing, the zeolite X preferably being the last Processing component is added, and the mixture after the addition of the zeolite X with residence times between one and 180 seconds, preferably between 10 and 150 seconds and in particular between 20 and 120 seconds is circulated at least four times.

11. The method according to any one of claims 9 or 10, characterized in that the fatty alcohol sulfate compound is added in the amount as a powdery processing component, that the mixture to be veφressende at least 2 wt .-%, preferably at least 4 wt .-% and in particular more than 5th Wt .-% contains fatty alcohol sulfate.

12. The method according to any one of claims 1 to 11, characterized in that the shaping Veφressen the mixture at pressures between 10 and 150 N / cm ² ,. preferably between 15 and 100 N / cm ² and in particular between 20 and 100 N / cm ² and temperatures between 10 and 80 ° C, preferably between 15 and 70 ° C and in particular between 20 and 60 ° C.