WO2000078910A1

WO2000078910A1 - Moulding method for detergent and cleansing agent tablets

Info

Publication number: WO2000078910A1
Application number: PCT/EP2000/005369
Authority: WO
Inventors: Hans-Friedrich Kruse; Andreas Lietzmann; Dieter Jung; Claus-Peter Thiessies; Torsten Wietholz
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1999-06-19
Filing date: 2000-06-10
Publication date: 2000-12-28
Also published as: CA2311989A1; AU5680400A

Abstract

The invention relates to detergent and cleansing agent shaped bodies which have a high degree of mechanical resistance to impact, shock and friction and a high active-substance content, which also extends to their coating. Said bodies are produced when at least one ram of a pressure ram pair is rotated about its vertical axis during the tablet-compressing process. This avoids additional stages of the method and reduces the production costs of the shaped bodies.

Description

PRESS PROCESS FOR DETERGENT AND DETERGENT TABLETS

The present invention relates to a process for the production of detergent tablets and molded articles produced by this process and their use. In particular, the invention relates to moldings and manufacturing processes such as detergent tablets, detergent tablets, bleaching tablets or water softening tablets and their respective production.

In addition to liquid and particulate products, detergent tablets have firmly established themselves as a form of supply for such compositions, since they have a number of advantages such as easy metering, safe handling, high compaction and, as a result, reduced packaging, transport and storage costs and aesthetic stimuli.

These advantages are offset by disadvantages. Compression into sufficiently stable tablets often results in a reduced solubility or disintegration rate, which is undesirable, especially with detergent tablets. If, on the other hand, the molded articles are only weakly pressed in order to achieve better solubility, problems such as breakage, edge breakage and abrasion occur which are perceived by the consumer as undesirable.

One solution that is proposed in the prior art for this purpose is the use of coated tablets, in which a “casing” envelops the internal detergent tablet (“core”) and gives it stability. Coated detergent tablets are described, for example, in European patent application EP 716 144 (Unilever). According to the teaching of this document, a coating of water-soluble material should reduce the abrasion and friability of the tablets without influencing the solubility. In this document, film-forming materials such as water-soluble polymers or sugar are mentioned as coating materials. The coating is applied in a process following the tabletting process and accounts for a few percent by weight of the finished molded article.

Coated detergent tablets are also described in European patent applications EP 846 754, EP 846 755 and EP 846 756 (all Procter & Gamble). According to the teaching of this document, coatings which contain dicarboxylic acids are applied as a melt or solution to pre-compressed moldings. Here, too, the coating makes up a few percent of the finished molded body by weight and must be applied in a separate processing step.

In the cited cases of the prior art, the coating fulfills the task of a protective layer around the previously produced shaped body and does not fulfill any tasks in the later washing or cleaning process. In relation to the total weight of the molded articles, a certain percentage of active substance-free material is sold to the consumer. In addition, the technology described requires the use of two different process stages: tableting on the one hand and coating on the other. This places an unfavorable burden on process economics.

The present invention was based on the object of providing detergent tablets which achieve the advantages of coated tablets without being used in the washing or cleaning cycle of useless materials. A high mechanical stability against impact, impact and friction, i.e. a high breaking strength and low friability as well as tendency to abrasion, should also be achieved with high active substance contents in the coating.

In addition, further process steps should be avoided in order to reduce the costs for the production of the shaped bodies. Another task was to To achieve layering of the moldings, which brings the advantages mentioned above, without a special coating step after the pressing is necessary.

It has now been found that surface-treated detergent tablets can be produced by means of a special pressing process, the outer layers of which have the quality of a conventional coating and have the advantages mentioned.

The present invention relates to a process for the production of detergent tablets by pressing one or more particulate detergent compositions in a tablet press, in which at least one die of a pair of dies is rotated about its vertical axis during the tabletting process.

Without wishing to be bound by theory, the applicant assumes that the rotation of at least one punch of a pair of press punches during the tableting process causes the surface of the shaped bodies to become harder than the rest of the shaped bodies due to friction. In this way, even with low pressing forces, a thin, harder layer is produced on the surface of the tablet in a shell-like manner, which significantly increases the stability of the shaped body and its resistance to abrasion. It is particularly advantageous here that the harder "shell" consists of the same premix as the rest of the tablet, that is to say it has the same composition. In this way, the use of coating layers free of active substance is avoided. At the same time, the coating is already produced during the pressing process, which later coating - makes procedural steps superfluous.

Overall, the method according to the invention makes it possible to further reduce the molding pressure, which in any case is significantly lower in the case of detergent tablets, compared to other tableting mixtures, without having to fear disadvantages with regard to handling or transport stability. The overall further reduced compression pressure advantageously leads to tablets which dissolve even more quickly.

In order to achieve the most homogeneous possible structure of the "shell" around the entire molded body, it is advantageous if not only one press die of a pair of dies rotates, but the upper and lower punches rotate around their vertical axis during the tableting process. Accordingly, methods in which both punches of a pair of compression punches are rotated about their vertical axis during the tabletting process are preferred.

The rotation of two stamps, the pressing surfaces of which face each other, can take place in the same direction or in opposite directions. In addition, the angle of rotation and with it the speed of rotation of the stamp can differ. Although all six conceivable embodiments (same direction of rotation, upper stamp rotates faster / further, same direction of rotation, lower stamp rotates faster / further, different direction of rotation, upper stamp rotates faster / further, different direction of rotation, lower stamp rotates faster / further, same direction of rotation, both Stamps rotate at the same speed / distance, opposite direction of rotation, both stamps move at the same speed / distance) according to the invention lead to success and can be used, process variants have proven to be preferred in which the rotation of the stamps takes place in opposite directions.

The speed of rotation or the amount by which the stamps are rotated can be the same or different. It has proven to be advantageous to choose the same speed as the stamp in the production of single-phase tablets, while in the production of multi-layer tablets the speed of a stamp can be matched to the mixture composition of the premix that comes into contact with it. The physical properties of the coating layer can be varied in a targeted manner by varying the parameters of the mixture composition, circulation speed and surface quality of the press ram.

In principle, the tabletting punch (s) can be rotated at any point in the tabletting process. A suitable point in time is, for example, a stamp rotation when the pressed detergent and cleaning agent tablet is discharged from the die and is surface-treated by the stamp (s) during discharge. Methods in which the rotation of the press ram (s) takes place after the pressing in the discharge area of the tablet press are preferred embodiments. Particularly suitable points in time to form stable coating layers are those in which the stamps are under pressure, that is to say, for example, when pre-compressing the filled premix and / or during the final addressing to the finished detergent molded article. After the particulate premix (= the particulate detergent and cleaning agent composition) has been filled in, the lower punch can be raised, the upper punch lowered and by rotating the punch (s) a uniform distribution of the premix in the die can be made possible. At the same time, the bed is vented, which improves the homogeneity of the tablet and its uniform stability in all areas of the molded body. Venting the bed enables the tablet to be less friable and the tablet press to perform better. Methods in which the rotation of the press ram (s) takes place in the filling and / or pressure area of the tablet press, preferably in the filling and pressure area, are therefore preferred.

The above-mentioned times of rotation of the stamp (s) can be combined with one another as desired. It is particularly advantageous here if the stamp (s) are rotated both during the pre-addressing (in the filling area) and during the main addressing (in the printing area) as well as after the addressing (in the discharge area). Preferred methods are therefore characterized in that a rotation of the press ram (s) takes place during the pre-addressing and the main addressing and optionally after the addressing.

The disintegration of the tablets can be greatly reduced by incorrectly choosing the time of rotation. It has been observed that there is a marked deterioration in the disintegration times when the plunger (s) are rotated at the point in time at which the pressing force is between 40 to 100% of the maximum pressing force. Accordingly, times of rotation are preferred at which the pressing forces applied to the die (s) are 0 to 40% of the maximum pressing force, preferably 0 to 20% of the maximum pressing force.

The stamp can be rotated constructively by cams on the stamp, the rotation being carried out via stop bars on the press. Furthermore, the rotary on also be done by driven plastic rollers that rest against the punches at certain times. It is also possible to provide the stamp with a ring gear. The rotation is effected via toothed racks fixed to the press. The material pairing Zaru wreath / rack is preferably to be chosen so that the rack is subject to greater wear during operation. It is advisable, for example, to resiliently mount the toothed rack in order to slowly build up the forces acting on the tooth flanks.

The above statements related verbally strongly to the production of single-phase tablets from a particulate premix, which is a detergent and cleaning agent composition. However, the method according to the invention is in no way limited to this; rather, multi-phase molded bodies can also be produced with the advantages of the method according to the invention. Another object of the present invention is therefore a process for the production of multi-phase detergent tablets by pressing several particulate detergent compositions in a tablet press, in which at least one die of a pair of dies is rotated about its vertical axis during the tabletting process.

Completely analogous to the above statements, methods are also preferred in the production of multi-phase tablets, in which both punches of a pair of compression punches are rotated about their vertical axis during the tableting process. Processes which are characterized in that the rotation of the punches takes place in opposite directions are preferred embodiments of the process according to the invention for producing multi-phase tablets.

In this method according to the invention, the stamp can also be rotated at the most varied of locations or at the most varied points in time of the tablet process. Analogous to the above explanations, methods are also preferred in the production of multi-phase tablets in which the rotation of the compression die (s) takes place after the pressing in the discharge area of the tablet press. Of course, the rotation of the press ram (s) in the filling and / or pressure area of the tablet press, preferably in the filling and pressure area, which has been found to be advantageous, is also advantageous in the production of multi-phase molded bodies.

In preferred methods, therefore, the press ram (s) is rotated during the pre-addressing of the first premix and with each further previous addressing of further premixes and during the main addressing of the multi-phase molded body and optionally after the addressing.

In the production of multi-phase tablets, it can improve the adhesion of the individual phases to one another if the pre-pressing between the metering steps for the individual premixes is dispensed with. At the same time, this avoids the multiple application of pressure to the first premix, which is disadvantageous for the solubility of the first phase. A further embodiment therefore provides methods according to the invention, in which there is no intermediate addressing between the metering steps for the individual premixes.

The press rams used in the method according to the invention can have surface structures of any shape, it being necessary for the rams to be round due to the rotation of the ram. For the production of simple or multilayer round (biplanar) tablets, punches with flat surfaces can be used, as are known for the conventional tableting processes. For the production of specially shaped tablets, which can also be constructed from several layers, stamps can also be used, which have elevations or depressions, which in turn should be rotationally symmetrical along the longitudinal axis of the stamp. For example, it is possible to use a stamp in which a cylinder with a smaller diameter is applied to a base with a larger diameter. In production, such stamps deliver tablets which have a circular depression protruding into the round molded body. A corresponding cylindrical depression in the press ram leads to a tablet which has the shape of two cylinders stacked on top of one another. The ratio of the diameter to the height of such cylinders is usually above 1, preferably above 1.5 and in particular above 2. Of course, the above-mentioned modification can be carried out on the upper and lower punches, which either result in ring tablets (the attached cylinders meet in the middle of the tablet during the pressing process and form the through hole) or double trough tablets or tablets with the shape of three cylinders stacked on top of each other .

The principle described above can also be extended to two, three or more successive elevations or depressions on the stamp surface. Rings can also be placed on the stamp surface or milled into it, so that the tablets formed have annular depressions or elevations.

A particularly preferred embodiment of the present invention provides for the use of curved stamp surfaces. One stamp can be chosen to be flat, while the other stamp is convex or concave. This results in molded bodies with a concave depression or convex elevation on one side, while the other side is flat. The last-mentioned tablets with an upwardly curved “lenticular” elevation can be transported on conventional conveyor belts due to their smooth undersides and, for example, allow the tablets to be raised where desired. The combination of two convex or concave stamps is also possible and leads to biconcave or biconvex tablets, the latter again being able to have a greater overall height. Depending on the filling volume of the die, a more or less thick cylindrical “edge” between the curved surfaces can be realized. Last but not least, it is also possible to combine a convexly curved lower punch with a concavely curved upper punch (or vice versa), so that a tablet results which has the shape of a watch glass. Such tablets have a greater height than biplane tablets with the same mass and the same diameter.

Of course, smooth transitions are possible between the individual forms mentioned. Another preferred embodiment of tabletting punches provides for an annular elevation on the stamp edge, which preferably has a triangular cross section having. Such stamps can be used to produce tablets which have a facet edge (“chamfered” edges). Here too, there are hardly any limits to the variety of designs, so that the facet edge can also be quarter-circle shaped, step-like, curved several times, etc.

The production of multi-phase molded bodies can lead to different designs. Depending on the shape of the pressing tools, core / jacket or toroidal tablets can be produced. Bulleye tablets can also be produced by the pressing technology according to the invention. In all embodiments of the pressing tools, care must be taken to ensure that the rotating punches are rotationally symmetrical, so that there are no displacements in the mixture structure in the die during the rotation of the punch (s). Since the manufacture of the above-mentioned multi-phase tablets entails a high level of technical complexity, it may be advantageous for reasons of process economy to use flat, round pressing tools and to produce tablets which have a layer structure. Accordingly, methods are preferred in which the phases have the form of layers.

The following information applies regardless of whether single-phase, two-layer or multi-phase tablets are manufactured with different structures. They relate in particular to the turning process according to the invention.

For the direction of rotation of the rotating stamp (s), reference can be made to the above information. The amount by which the stamp rotates can also be varied within wide limits, all embodiments being possible from the small rotation by a few tenths of a degree to the full rotation. In view of the short dwell times of the press rams in the rotary positions at high throughputs, methods are preferred in which the press ram (s) during each turning process by 0.1 to 90 °, preferably by 0.25 to 45 ° and in particular by 0.5 to Can be turned 20 °.

The amount of rotation of a stamp, as already stated above, is not linked to the amount of rotation of the other stamp of the pair of stamps. Completely analogously, the stamp can be rotated by different amounts depending on the rotational position become. For example, it is possible to rotate a stamp in the filling area by 5 degrees, while the same stamp is rotated in the pressing area by 0.5 ° and in the discharge area by 45 °. Of course, the values mentioned are only exemplary and a rotation of a stamp is possible at any rotational position by any conceivable amount of rotation. In addition to the angle that is exceeded, the turning process can also be characterized by the intensity of the turning. This in turn depends on the time in which the turning process is completed. With regard to the throughputs of the tablet press, which should advantageously be high, the punch is only available for a limited time for the rotation. Methods which are characterized in that the rotation of the press ram (s) takes place over a period of 1 to 1000 ms, preferably 2 to 500 ms and in particular 5 to 100 ms, are preferred. Depending on the size of the angle to be exceeded, high angular speeds are achieved in this way, which lead to the desired friction on the surface of the tablet and to the formation of the coating layer.

The thickness of the coating layer can be influenced not only by the factors mentioned (time) and the intensity of the rotation, but also by the nature of the ram, the pressure and the temperature. Long turning distances, quick turns, rough stamp surfaces and increased pressing temperatures lead to a thicker and therefore more stable layer. The roughness of the stamp surfaces can be specified by the size of the roughness, which describes the difference in height between the lowest and the highest point of the stamp surface. Processes in which the pressing surfaces of the pressing dies have a roughness depth of 5 to 500 μm, preferably 10 to 250 μm and in particular 20 to 150 μm are preferred according to the invention.

Likewise, processes in which the pressing is carried out at temperatures between 10 and 60 ° C., preferably between 15 and 50 ° C. and in particular between 20 and 40 ° C. are preferred according to the invention.

The pressing forces for the method according to the invention are preferably in the range from 1 to 50 kN, in particular from 5 to 20 kN, these being the maximum forces (main pressing forces) which are applied to the punches. According to the preferred described above When the stamps are rotated, the stamp (s) are preferably rotated with applied pressing forces of 0.2 to 20, in particular of 1 to 8 kN. The stated values lead to different pressures depending on the size of the surface over which the force is distributed. In preferred process variants, these are between 50 and 2500 Ncm ^"~ , in particular between 100 and 1500 Ncm ^{" 2} , the value again representing the main pressure. The stamp according to the preferred method according to the invention is rotated at pressures between 10 and 1000 Ncm ^"2 , in particular between 20 and 600 Ncm ^{" 2} .

The method according to the invention is used to produce detergent shaped bodies and consists in the molding of one or more particulate detergent and cleaning agent compositions. Advantageous effects of the end products of the process can be achieved by suitable compositions and / or physical parameters of these detergent and detergent compositions. The following is information about physical parameters and ingredients of the detergent and cleaning agent compositions), which are also referred to as “premix” in the context of the present invention.

For a high density of the resulting molded article, it is advantageous if the premix to be compressed has a higher bulk density. In particular, processes in which the particulate detergent and cleaning composition (s) have a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1, are preferred embodiments of the present invention.

Information can also be given about the particle size or the particle size distribution of the detergent and cleaning agent composition (s) to be treated. For example, processes are preferred which are characterized in that the particulate detergent and cleaning composition (s) have particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 μm. Trends can also be recognized within the particle size ranges mentioned, which premixes are particularly suitable. Processes in which the particulate detergent and cleaning agent composition (s) has less than 20% by weight, preferably less than 10% by weight and in particular less than 5% by weight, of particles with a size below 200 μm / have are further preferred according to the invention. Similar information can also be given for the upper limit of the particle size distribution. Methods are preferred here in which the particulate detergent and cleaning agent composition (s) contains less than 20% by weight, preferably less than 10% by weight and in particular less than 5% by weight of particles with a Has / have size above 1600 μm.

Detergent tablets, for example, can be produced with particular preference by the process according to the invention. While, for example, the proportion of surfactants is low in detergent tablets for machine dishwashing and this proportion of surfactants may be completely absent in bleach tablets or water softener tablets, surfactants are an essential component of textile detergents, regardless of their form of supply. Detergent tablets are usually made by blending surfactant granules. with preparation components and subsequent pressing of this particulate premix. Preferred variants of the process according to the invention are therefore characterized in that the or at least one of the premixes to be added additionally contains surfactant-containing granules.

Methods preferred in the context of the present invention therefore comprise the compression of a particulate premix comprising at least one surfactant-containing granulate and at least one admixed powdery component. The granules containing surfactant can be produced by conventional industrial granulation processes such as compacting, extrusion, mixer granulation, pelletization or fluidized bed granulation.

In preferred process variants, the surfactant-containing granules also meet certain particle size criteria. Methods according to the invention are preferred in which the surfactant-containing granules have particle sizes between 100 and 2000 μm, preferably between see 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 μm.

In addition to the active substances (anionic and or nonionic and / or cationic and / or amphoteric surfactants), the surfactant granules preferably also contain carriers which particularly preferably come from the group of builders. Particularly advantageous processes are characterized in that the surfactant-containing granules contain anionic and / or nonionic surfactants and builders and total surfactant contents of at least 10% by weight, preferably at least 15% by weight and in particular at least 20% by weight, based on the granules.

These surface-active substances come from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and because of their range of services.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. As surfactants of the sulfonate type, preference is given to C ₃ -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 1 -C ₈ -monoolefins with an end or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C ₁ -C ₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerin esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production 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 become. Preferred sulfated fatty acid glycerol esters are the sulfate products of saturated fat acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₂ -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁ -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, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The Ci2-Cι ₆ alkyl sulfates and Cι ₂ - Cι alkyl sulfates and C | ₄ -C ₅ alkyl sulfates 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 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 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 Cg.ig 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. Likewise 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.

In the context of the present invention, surfactant granules are preferred which contain 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 10 to 30% by weight of anionic surfactant (s), in each case based on the granules .

When selecting the anionic surfactants, there are no general conditions to be observed that prevent freedom of formulation. Preferred surfactant granules, however, have a soap content which exceeds 0.2% by weight, based on the total weight of the detergent tablets produced. Anionic surfactants to be used with preference are the alkylbenzenesulfonates and fatty alcohol sulfates, with preferred detergent tablets 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s) in each case based on the weight of the detergent tablets.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical has a linear or preferably 2-methyl branching may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues are made 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 preferred. The preferred ethoxylated alcohols include, for example, Ci2-i4 alcohols with 3 EO or 4 EO, C ₉ . _n -Alcohol with 7 EO, Cι ₃ .ι ₅ -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Cι ₂ - ι ₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures from C i ₂ - ₁ 4- alcohol with 3 EO and Cι ₂ -ι ₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application OA-90713533.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides that can be used satisfy the general formula RO (G) _z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is Is a symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.

Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used. The end products of the process according to the invention can preferably contain alkyl polyglycosides, with APG contents of more than 0.2% by weight, based on the total molded body, being preferred. Particularly preferred detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.

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),

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 ^2nd

I.

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 is an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C - alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this 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.

Regardless of whether anionic or nonionic surfactants or mixtures from these classes of surfactants and, if appropriate, amphoteric or cationic surfactants are used in the surfactant granules, methods according to the invention are preferred in which the surfactant content of the surfactant-containing granules is 5 to 60% by weight, preferably 10 is up to 50 wt .-% and in particular 15 to 40 wt .-%, each based on the surfactant granules.

The surfactant granules can be used in the detergent tablets or in individual phases of multi-phase tablets in varying amounts. Processes according to the invention in which the proportion of the surfactant-containing granules in the detergent tablets or in a single phase of the detergent tablets 40 to 95% by weight, preferably 45 to 85% by weight and in particular 55 to 75 % By weight, based in each case on the weight of the detergent tablets, is preferred. From an application point of view, it can be advantageous if certain classes of surfactant are not included in some phases of the detergent tablets or in the entire molded article, ie in all phases. Another important embodiment of the present invention therefore provides that at least one phase of the molded article is free of nonionic surfactants.

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

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

It has been shown that the surfactant content of the premixes to be influenced influences the quality of the coating layer produced by the process according to the invention. The stability of the coating layer improves with increasing surfactant content. It is therefore preferred if the surfactant content of the tableting premix is above 10% by weight and particularly preferably above 15% by weight.

The type of surfactants used also has an influence on the coating layer. At higher nonionic surfactant levels, the disintegration time of the tablets produced deteriorates. Thus, a premix is preferred in which the ratio of nonionic surfactants to anionic surfactants is greater than 2: 1, preferably greater than 3: 1.

On the other hand, it was found, in particular when tableting recipes containing zeolite, that a certain non-ionic surfactant content helped to form the coating layer. is rich. The nonionic surfactant content of such a zeolite-containing tablet is therefore preferably at least 2% by weight, preferably at least 3% by weight.

In addition to the wash-active substances, builders are the most important ingredients in detergents and cleaning agents. The surfactant granules, but also as a component of the premix, can contain all builders commonly used in detergents and cleaning agents, in particular zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - the phosphates. The latter are builders to be used with particular preference in detergent tablets for machine dishwashing.

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

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 delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term "amoφh" is also understood to mean "roentgenamoφh". This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties. if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be integrated in such a way that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous 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 context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ O ^• (ln) K ₂ 0 'Al ₂ O ₃ ^' (2 - 2.5) SiO ₂ ^' (3.5 - 5.5) H ₂ O

can be described. The zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be used, usually both ways of incohering the zeolite into the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

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. Among the large number of commercially available phosphates, the alkali metal phosphates have particular preference for pentasodium or pentapotassium tri- phosphate (sodium or potassium tripolyphosphate) is of the greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPθ ₃ ) _n and orthophosphoric acid H ₃ PO4 in addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.

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

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly ^"3 , water loss at 95 °), 7 mol. (Density 1.68 gladly ^{" 3} , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 ^"3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more. Disodium hydrogenphosphate is lost by neutralizing phosphoric acid with soda solution Using phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water. Trisodium phosphate, tertiary sodium phosphate, Na _? Pθ4, are colorless crystals that like a dodecahydrate a density of 1.62 ^"" and a melting point of 73-76 ° C (decomposition), as a decahydrate (corresponding to 19-20% P ₂ O ₅ ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 ^"3. Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or three-base potassium phosphate), K ₃ PO4, is a white, deliquescent, granular powder with a density of 2.56 ^"" , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It occurs, for example, when heated of Thomas slag with coal and potassium sulfate Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate),

exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 like ^{" 3} , melting point 94 ° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na PO ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K4P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 ^"3 , which is soluble in water, with the pH of the 1% solution 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO4 produces higher mol. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates. The technically important pentasodium triphosphate, Na P ₃ Oιo (sodium tripolyphosphate), is an anhydrous or 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. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH - »Na ₃ K ₂ P3θ, o + H ₂ O

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

Organic cobuilders that can be used in the detergent tablets according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below. Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid. Maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

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

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

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

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

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

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

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

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

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect. Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

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

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 known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as 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. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediaminisisuccinate, are further suitable cobuilders. Ethylenediamine-N, N ^'- disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts. Also preferred in this context are glycine disuccinates and glycine disuccinates. Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as a sodium salt, the dinate salt being neutral and the tetrasodium salt being alkaline (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g. B. as Hexanatπumsalz the EDTMP or as Hepta- and Octa-Natnumsalz the DTPMP, used. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth ions can be used as cobuilders.

The amount of builder is usually between 10 and 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight. Again, the amount of builders used is dependent on the intended use, so that bleach tablets can have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular re between 30 and 55% by weight), for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 to 45% by weight and in particular between 17.5 and 37.5% by weight). Detergent tablets for machine dishwashing may contain even higher levels of builders, for example 40 to 95% by weight, preferably 50 to 90% by weight and in particular 60 to 85% by weight. Water softener tablets can even consist of 100% by weight of builders.

In order to facilitate the disintegration of highly compressed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology ^' ' (6th edition, 1987, p. 182-184), tablet disintegrants or disintegration accelerators are understood to be auxiliaries which are quick to use Disintegration of tablets in water or gastric juice and release of the pharmaceuticals in an absorbable form.

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

Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the molded article weight.

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

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

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

Processes preferred in the context of the present invention are characterized in that the or at least one of the premixes to be treated is a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight. %, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the premix.

Also with the disintegration aid (s), special effects can result from the partial or complete omission of such substances from individual phases of multi-phase molded bodies. For example, it is preferred to produce multi-phase, in particular multi-layer, molded bodies, the individual phases of which contain a disintegrant in different amounts. In this way, active substances can be released from one phase in a controlled manner, for example accelerated or delayed, which results in advantages in terms of application technology.

In addition to the constituents mentioned surfactant, builder and disintegration aid, the detergent tablets according to the invention can be used in other Detergents and cleaning agents contain the usual ingredients from the group of bleaching agents, bleach activators, disintegration aids, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-deposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and produce H ₂ O ₂ in water. "Sodium percarbonate" is a non-specific term for sodium carbonate peroxohydrates, which strictly speaking are not "percarbonates" (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate. The merchandise has the average composition 2 Na ₂ CO ₃ -3 H ₂ O ₂ and is therefore not peroxy carbonate. Sodium percarbonate often forms a white, water-soluble powder with a density of 2.14 ^"3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.

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

The industrial production of sodium percarbonate is mainly produced by precipitation from an aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg ⁺ ions). The precipitated salt, which still contains 5 to 12% by weight of mother liquor, is then filtered off and dried at 90 ° C. in fluid bed dryers. The bulk density of the finished product can vary between 800 and 1200 g / 1 depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating processes and materials used for coating are widely described in the patent literature. In principle, all commercially available percarbonate types can be used according to the invention are used, such as those offered by Solvay Interox, Degussa, Kemira or Akzo.

Further bleaching agents which can be used are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid 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, irrespective of which other ingredients are contained in the moldings. If cleaning tablets or bleach tablets for machine dishwashing are manufactured, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monophosphate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthaloxyhexanoic acid (ε-phthaloxyhexanoic acid) . 1, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

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

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

In order to achieve an improved bleaching effect when washing or cleaning at temperatures of 60 ° C and below, bleach activators can be incorporated. Bleach activators which support the action of the bleaching agents are, for example, compounds which contain one or more N- or O-acyl groups, such as substances from the class of anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD) and tetraacetylhexylenediamine (TAHD), but also pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxo-hexahydro-l, 3,5-triazine (DADHT) and isatoic acid anhydride (ISA).

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic 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 number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran, n-methyl-Moφholinium acetonitrile-methyl sulfate (MMA), and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767 as well as acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives , in particular pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose as well as acetylated, optionally N-alkylated Gl ucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams 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, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

Bleach activators from the group of multiply acylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (N-) or iso-NOBs iso , n-Methyl-Moφholinium-Acetonitril-Methylsulfat (MMA), preferably in amounts up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferred 2 to 6 wt .-% based on the total agent used.

Bleach-boosting transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular 0.0025% by weight .-% to 1 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 processes according to the invention are particularly suitable for the production of multi-phase molded articles. Procedures in which one of the advantages to be addressed Mixtures containing bleach while another premix contains bleach activators are preferred.

The separation of the bleaching agents from other ingredients can also be advantageous. Processes for the production of multi-phase molded articles, in which one of the premixes to be treated contains bleaching agents, while another premix contains enzymes, are also preferred. Suitable enzymes are in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxidoductases can also be used to bleach or inhibit the transfer of color. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types are characterized by their CMCase and avicelase Differentiate activities, the desired activities can be set by targeted mixtures of the cellulases.

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

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

Corrosion inhibitors can also be incorporated into the premixes to be protected in order to protect the items to be washed or the machine, silver protection agents being particularly important in the field of automatic dishwashing. The known substances of the prior art can be used. In general, Sil- Protective agents selected from the group consisting of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Benzotriazole and or alkylaminotriazole are particularly preferably to be used. In addition, active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetaf) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

If anticorrosive agents are used in multi-phase molded articles, it is preferred to separate them from the bleaching agents. Processes in which one of the premixes to be contained contains bleaching agents while another premix contains anticorrosive agents are therefore preferred.

Further ingredients that can be part of one or more premixes in the process according to the invention are, for example, dyes, optical brighteners, fragrances, soil-release compounds, soil repellents, antioxidants, fluorescent agents, foam inhibitors, silicone and or paraffin oils, color transfer inhibitors, Graying inhibitors, detergent boosters etc.

In order to improve the aesthetic impression of the detergent tablets according to the invention, they can be colored in whole or in part with suitable dyes. Preferred dyes, the selection of which does not pose any difficulty for the person skilled in the art, have a long shelf life and are insensitive to the other ingredients of the compositions and to light and have no pronounced substantivity against over the treated substrates such as textile fibers or tableware to avoid staining them.

Preferred for use in detergent tablets according to the invention are all colorants which can be oxidatively destroyed in the washing process, and also mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. For example, anionic colorants, for example anionic nitroso dyes, are suitable. A possible colorant is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which is available as a commercial product, for example as Basacid Green 970 from BASF, Ludwigshafen, and mixtures of these suitable blue dyes. Other colorants include 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 ^® Patentblau 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol ^® Blau 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 noted that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the washing or cleaning

® agents. In the case of colorants which are readily water-soluble, e.g. the above-mentioned basacid

Green or the Sandolan blue also mentioned above, colorant concentrations in the range from a few 10 ^"2 to 10 ^{" 3} % by weight are typically chosen. In those that are particularly preferred due to their brilliance, but are less water-soluble In contrast, pigment dyes, for example the pigmosol dyes mentioned above, the suitable concentration of the colorant in washing or cleaning agents is typically a few 10 ^"3 to 10 ^{" 4} % by weight.

The laundry detergent and cleaning product tablets produced by the process according to the invention can contain one or more optical brighteners. These fabrics, which are also called "whiteners", are used in modern laundry detergents because even freshly washed and bleached white laundry has a slight yellow tinge. Optical brighteners are organic dyes that convert part of the invisible UV radiation from sunlight into longer-wave blue light. The emission of this blue light complements the "gap" in the light reflected by the textile, so that a textile treated with an optical brightener appears whiter and brighter to the eye. Since the action mechanism of brighteners presupposes that they are drawn onto the fibers, a distinction is made depending on the "dyed" fibers, for example brighteners for cotton, polyamide or polyester fibers. The commercially available brighteners suitable for incoφoration in detergents essentially include five structural groups: the stilbene, the diphenylstilbene, the coumarin-quinoline, the diphenylpyrazoline group and the group of the combination of benzoxazole or benzimidazole with conjugated systems. An overview of common brighteners can be found, for example, in G. Jakobi, A. Löhr "Detergents and Textile Washing", VCH-Verlag, Weinheim, 1987, pages 94 to 100. Suitable are e.g. Salts of 4,4'-bis [(4-anilino-6-moφholino-s-triazin-2-yl) amino] -stilbene-2,2'-disulfonic acid or compounds of the same structure which instead of the Moφholino group have a diethanolamino group , a methylamino 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.

Fragrances are added to the agents according to the invention in order to improve the aesthetic impression of the products and, in addition to the performance of the product, provide the consumer with a visually and sensorially "typical and distinctive" product put. 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 glycinate phenyl-, Allylcyclohexylpropionat, Styrallylpropionat and benzyl are benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethyl-thylbenzyl carbinylacetat, phenylethyl acetate, Linalyl benzoate, benzyl formate, ethyl methyl. The ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the jonones, oc-isomethyl ionone and methyl cedryl ketone , to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and Teφineol, to the hydrocarbons mainly belong the Teφene like 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, patchouli, 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 fragrance content of the detergent tablets according to the invention is usually up to 2% by weight of the total formulation. The fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

In addition, the detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty is, which has already been 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 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 ethers, as well as the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

Foam inhibitors that can be used in the agents produced according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof in amounts of 0.1 to 5% by weight, based on the composition, are preferably used

Since textile fabrics, in particular rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers prevent bending and kinking. If pressing and squeezing across the grain are sensitive, the agents produced according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylol amides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

To combat microorganisms, the agents produced according to the invention can contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungiostatics and fungicides etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halogenophenols and phenol mercuriacetate, although these compounds can be dispensed with entirely.

In order to prevent undesirable changes in the agents and / or the treated textiles caused by the action of oxygen and other oxidative processes, the agents can contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

Increased wearing comfort can result from the additional use of antistatic agents, which are additionally added to the agents produced according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. External antistatic agents are described, for example, in patent applications FR 1,156,513, GB 873 214 and GB 839 407. The lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed here are suitable as antistatic agents for textiles or as an additive to detergents, an additional finishing effect being achieved. To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, for example silicone derivatives can be used in the agents produced according to the invention. These additionally improve the rinsing behavior of the agents due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 centistokes, the silicones being used in amounts between 0.2 and 5% by weight, based on the total agent.

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

With all of the above-mentioned ingredients, advantageous properties can result from separating them from other ingredients or assembling them together with certain other ingredients. In the case of multi-phase molded bodies, the individual phases can also have a different content of the same ingredient, as a result of which advantages can be achieved. Methods in which at least two of the premixes to be treated 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 phase, but to the re- The relative amount, based on the phase weight, therefore represents a% by weight, based on the individual phase.

Another object of the present invention is the use of tablet presses, in which at least one punch of a pair of press punches is rotated about its vertical axis during the tabletting process, for the production of detergent tablets. In the use according to the invention, all advantageous embodiments described above for the method according to the invention are likewise preferred mutatis mutandis. To avoid redundancies, reference is made to the information above.

The process according to the invention provides, as process end products, detergent tablets which have a novel and advantageous structure. These are laundry detergent and cleaning agent tablets which, with a uniform composition, consist of a core and a shell surrounding this core. Such washing and cleaning agent shaped bodies have not been described in the prior art. The invention therefore furthermore relates to detergent tablets made from compressed, particulate detergents and cleaning agents which consist of a core and a shell surrounding this core, which have the same composition, the shell being harder than the core.

Due to the formation of the "shell" in the method according to the invention, the shell has a higher hardness than the core it protects. At the same time, the shell also has a higher density, so that detergent tablets made of compressed, particulate detergent and cleaning agent , which consist of a core and a shell surrounding this core, which have the same composition, the shell having a higher density than the core, are also an object of the present invention.

The principle according to the invention of the coated molded article, in which the casing and core have the same composition, but are characterized by different physical parameters, can not only be applied to single-phase detergent and cleaning agent forms. Apply body. If, for example, two-layer molded bodies are produced from two premixes with different compositions, the process according to the invention provides two-layer detergent and cleaning agent molded bodies which have two different layers pressed onto one another and a shell (“shell”) surrounding them, the shell surrounding the first layer being has the same composition as the first layer and the shell that surrounds the second layer, has the same composition as the second layer, the two “shells” result overall in the harder or denser shell that encloses the molded body and gives it its advantageous properties .

Another object of the present invention are thus also multi-phase detergent shaped bodies made of compressed, particulate detergent and cleaning agent compositions which consist of a multi-phase core and a multi-phase shell surrounding this multi-phase core, the individual phases of which have the same composition as the phases whose Cover the surface, the shell being harder than the core.

Completely analogous to the above explanations are also multi-phase detergent tablets made of compressed, particulate detergent and cleaning agent compositions which consist of a multi-phase core and a multi-phase shell surrounding this multi-phase core, the individual phases of which have the same composition as the phases, the surface of which they cover, the shell having a higher density than the core, a further object of the present invention.

Also in the detergent tablets according to the invention, all advantageous embodiments described above for the method according to the invention are likewise preferred mutatis mutandis. To avoid redundancies, reference is made to the information above. In particular with regard to the ingredients, their proportions in the entire molded body, their distribution over individual phases, their proportions in individual phases, etc., what has been said above applies analogously. Since the impact and rubbing load on detergent tablets is particularly high on the base surfaces, it is advantageous to protect these surfaces against abrasion or breakage. Detergent molded articles in which the shell has a thickness on the round sides of the molded article of 5 to 2000 μm, preferably 10 to 1500 μm and in particular 25 to 1000 μm, are preferred according to the invention. In particularly preferred washing and cleaning agent shaped bodies, the sizes mentioned also apply to the annular side surface of the shaped body.

Since the "shell" contributes to the stability of the tablet, the compressive forces can be further reduced, which on the one hand improves the process economy (see above), but on the other hand also has a positive influence on the solubility and disintegration times of the detergent tablets. In this way, for the in The core enclosed in the shell has to accept lower strengths which would otherwise be too fragile and unacceptable. In the case of preferred detergent tablets, the core has a diametrical breaking strength of less than 30 kPa, preferably less than 25 kPa, particularly preferably less than 20 kPa and in particular less than 15 kPa.

At the same time, the shell preferably has a high hardness, which according to the invention is always above the hardness of the core. In particularly preferred detergent tablets, the casing has a diametrical breaking strength of more than 20 kPa, preferably more than 25 kPa, particularly preferably more than 30 kPa and in particular more than 35 kPa.

It is also possible to provide information about preferred densities of the shell or core. Detergent tablets, in which the core has a density of more than 600 g / 1, preferably more than 750 g / 1 and in particular more than 900 g / 1, and detergent tablets, in which the shell has a density of more than 1000 g / 1, preferably of more than 1050 g / 1, particularly preferably of more than 1100 g / 1 and in particular of more than 1 150 g / 1, are preferred according to the invention. The process according to the invention can, by suitable selection of the process parameters such as pressing force, pressing time, direction of rotation, rotation speed, rotation intensity, composition of the premix, pressing temperature, etc., produce thicker or thinner coatings as desired. In particularly preferred detergent tablets, the core and shell are present in a weight ratio of 250: 1 to 1: 1, preferably from 100: 1 to 5: 1 and in particular from 50: 1 to 10: 1.

The detergent tablets according to the invention can be packed after manufacture, the use of certain packaging systems having proven particularly useful. Another aspect of the present invention is a combination of (a) washing and cleaning agent shaped body (s) according to the invention and a packaging system containing the washing and cleaning agent shaped body (s), the packaging system having a moisture vapor permeability rate of 0.1

• y -y g / m / day to less than 20 g / m / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.

According to the invention, the packaging system of the combination of detergent and molded body (s) and packaging system has a moisture vapor permeability rate of 0.1 g / m / day to less than 20 g / m / day when the packaging system is at 23 ° C. and a relative Equilibrium moisture of 85% is stored. The specified temperature and humidity conditions are the test conditions that are mentioned in the DIN standard 53122, whereby according to DIN 53122 minimal deviations are permitted (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor permeability rate of a given packaging system or material can be determined by further standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m- 45 ("Water Vapor Permeability of Sheet Materials at high temperature an Humidity"). The measuring principle of current methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container being closed at the top with the material to be tested. From the surface of the container that is mixed with the material to be tested is closed (permeation surface), the weight gain of calcium chloride and the exposure time can be compared to the moisture vapor permeability rate

24. .0000. , g / m ² / 24b

A v

calculate, where A is the area of the material to be tested in cm ^" , x is the weight gain of calcium chloride in g and y is the exposure time in h.

The relative equilibrium humidity, often referred to as “relative air humidity”, is 85% at 23 ° C. when measuring the moisture vapor permeability rate within the scope of the present invention. The capacity of air for water vapor increases with temperature up to a respective maximum content, the so-called saturation content, and is given in g / m ^3. For example, 1 m ^{3 of} air at 17 ° is saturated with 14.4 g of water vapor, at a temperature of 11 ° there is already saturation with 10 g of water vapor Percentage expressed ratio of the actual water vapor content to the saturation content corresponding to the prevailing temperature, eg if air contains 17 ° 12 g / m ³ water vapor, then the relative air humidity = (12 / 14.4) T00 = 83 If this air is cooled, then the saturation (100% RH) is reached at the so-called dew point (in the example: 14 °), ie at further cooling, a precipitate is formed in the form of fog (dew). Hygrometers and psychometers are used for the quantitative determination of moisture.

The relative equilibrium humidity of 85% at 23 ° C can be set to +/- 2% RH, for example in laboratory chambers with moisture control, depending on the device type. Even over saturated solutions of certain salts, constant and well-defined relative air humidities form in closed systems at a given temperature, which are based on the phase equilibrium between the partial pressure of the water, the saturated solution and the soil. The combinations of detergent tablets and packaging system according to the invention can of course in turn be packaged in secondary packaging, for example cardboard boxes or trays, with no further requirements being placed on the secondary packaging. The secondary packaging is therefore possible, but not necessary.

Packaging systems preferred in the context of the present invention have a moisture vapor permeability rate of 0.5 g / m ² / day to less than 15 g / m ² / day.

Depending on the embodiment of the invention, the packaging system of the combination according to the invention encloses one or more detergent tablets. It is preferred according to the invention either to design a shaped body in such a way that it comprises an application unit of the detergent and cleaning agent, and to individually package this shaped body, or to pack the number of shaped bodies in a packaging unit, which in total comprises one application unit. With a nominal dosage of 80 g of detergent and cleaning agent, it is therefore possible according to the invention to produce and individually pack an 80 g heavy detergent and cleaning agent molded article, but it is also possible according to the invention to pack two 40 g heavy detergent and cleaning agent shaped articles in one package to arrive at a combination according to the invention. This principle can of course be expanded so that, according to the invention, combinations can also contain three, four, five or even more detergent tablets in one packaging unit. Of course, two or more molded bodies in a packaging can have different compositions. In this way it is possible to spatially separate certain components from one another, for example in order to avoid stability problems.

The packaging system of the combination according to the invention can consist of a wide variety of materials and can take on any external shape. For economic reasons and for reasons of easier processing, packaging systems are preferred in which the packaging material is light in weight, easy to process and inexpensive. In combinations preferred according to the invention the packaging system from a sack or bag made of single-layer or laminated paper and / or plastic film.

The detergent tablets can be unsorted, i.e. as a loose fill, be filled into a bag made of the materials mentioned. However, for aesthetic reasons and for sorting the combinations in secondary packaging, it is preferable to fill the detergent and cleaning agent shaped articles individually or in groups in sacks or bags. For individual application units of the detergent tablets that are in a sack or bag, the term "flow pack" has become common in technology. Such "flow packs" can then - again preferably sorted - be optionally packed in repackaging, which the compact offer form of the molded body underlines.

The sacks or bags made of single-layer or laminated paper or plastic film, which are preferably to be used as a packaging system, can be designed in a wide variety of ways, for example as a blown-up bag without a central seam or as a bag with a central seam, which is sealed by heat (hot fusion), adhesives or adhesive tapes become. Single-layer bag or sack materials are the known papers, which can optionally be impregnated, and plastic films, which can optionally be co-extruded. Plastic films which can be used as a packaging system in the context of the present invention are given, for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Düsseldorf 1988, page 193. Figure 111 shown there also provides clues for water vapor permeability of the materials mentioned.

Combinations which are particularly preferred in the context of the present invention contain, as packaging system, a sack or bag made of single-layer or laminated plastic film with a thickness of 10 to 200 μm, preferably 20 to 100 μm and in particular 25 to 50 μm.

Although it is possible, in addition to the films or papers mentioned, wax-coated papers in the form of cardboard boxes as packaging systems for washing and cleaning To use medium-shaped bodies, it is preferred in the context of the present invention if the packaging system does not comprise boxes made of wax-coated paper. In the context of the present invention, the term “packaging system” always characterizes the primary packaging of the molded articles, ie the packaging that is in direct contact with the inside of the molded article surface. No requirements are placed on an optional secondary vacuum, so that all common materials and systems can be used here.

As already mentioned above, the detergent tablets of the combination according to the invention contain further ingredients of detergents in varying amounts, depending on their intended use. Regardless of the intended use of the molded article, it is preferred according to the invention that the washing and cleaning agent molded article or articles have a relative equilibrium moisture content of less than 30% at 35 ° C.

The relative equilibrium moisture content of the detergent tablets can be determined using standard methods, with the following procedure being chosen within the scope of the present investigations: A water-impermeable 1-liter container with a lid, which has a closable opening for introducing samples, was used filled with a total of 300 g detergent tablets and kept at a constant 23 ° C for 24 h to ensure a uniform temperature of the vessel and substance. The water vapor pressure in the space above the molded bodies can then be determined using a hygrometer (Hygrotest 6100, Testoterm Ltd., England). The water vapor pressure is now measured every 10 minutes until two successive values show no deviation (equilibrium moisture). The above Hygrometer allows a direct display of the recorded values in% relative humidity.

Also preferred are embodiments of the combination according to the invention in which the packaging system is designed to be resealable. Combinations in which the packaging system has a microperforation can also be preferably implemented according to the invention. Another object of the present invention is a washing method for washing textiles in a household washing machine, which is characterized in that one or more inventive detergent and detergent tablets are placed in the washing-up chamber of the washing machine and a washing program is run, in the course of which the molded body (s) are washed in.

However, the molded body or bodies do not have to be dosed via the dispenser, but can also be added directly to the washing drum. Both a metering aid, for example a mains metering device, can be used here, but the shaped bodies can also be added directly to the laundry in the drum without a metering aid. A washing method for washing textiles in a household washing machine, in which one or more detergent shaped articles according to the invention are inserted into the washing drum of the washing machine with or without metering aid and a washing program is run, in the course of which the shaped article (s) are dissolved is therefore also an object of the present invention.

As mentioned above, detergent tablets for automatic dishwashing can also be produced by the method according to the invention. Accordingly, there is a cleaning method for cleaning dishes in a dishwasher, which is characterized in that one or more detergent form bodies according to the invention are placed in the dosing chamber of the dishwasher and a washing program can be run, in the course of which the dosing chamber opens and the or the shaped body are resolved, another object of the present invention.

In the cleaning process according to the invention, too, the metering chamber can be dispensed with and the molded article (s) according to the invention can be inserted, for example, into the cutlery basket. Of course, the use of a dosing aid, for example a basket, which is attached to the wash cabinet, is also possible without any problems. Accordingly, there is a cleaning method for cleaning dishes in a dishwasher, in which one or more detergent tablets according to the invention, with or without metering aid, are placed in the dishwasher's washing compartment inserted and a rinsing program can run, in the course of which the molded body or bodies are dissolved, a further object of the present invention.

Claims

Claims:

1. A process for the production of washing and cleaning agent shaped bodies by pressing one or more particulate washing and cleaning agent compositions in a tablet press, characterized in that at least one punch of a pair of pressing dies is rotated about its vertical axis during the tabletting process.

2. The method according to claim 1, characterized in that in each case both punches of a pair of press punches are rotated about their vertical axis during the tabletting process.

3. The method according to claim 2, characterized in that the rotation of the stamp takes place in opposite directions.

4. The method according to any one of claims 1 to 3, characterized in that the rotation of the press ram (s) takes place after the Veφressung in the discharge area of the tablet press.

5. The method according to any one of claims 1 to 3, characterized in that the rotation of the press ram (s) in the filling and / or pressure area of the tablet press, preferably in the filling and pressure area, takes place.

6. The method according to any one of claims 1 to 5, characterized in that a rotation of the press ram (s) in the Vorveφressung and in the Hauptveφressung and optionally after the Veφressung takes place.

7. A process for the production of multi-phase detergent and cleaning agent shaped bodies by compressing several particulate detergent and cleaning agent compositions in a tablet press, characterized in that at least one punch of a pair of press punches is rotated about its vertical axis during the tableting process.

8. The method according to claim 7, characterized in that both punches of a pair of press punches are rotated about their vertical axis during the tabletting process.

9. The method according to claim 8, characterized in that the rotation of the stamp takes place in opposite directions.

10. The method according to any one of claims 7 to 9, characterized in that the rotation of the press ram (s) takes place after the Veφressung in the discharge area of the tablet press.

11. The method according to any one of claims 7 to 10, characterized in that the rotation of the press ram (s) in the filling and / or pressure area of the tablet press, preferably takes place in the filling and pressure area.

12. The method according to any one of claims 7 to 11, characterized in that a rotation of the press ram (s) in the Vorveφressung the first premix and with each further Vorveφressung further premixes and in the Hauptveφressung the multi-phase molded body and optionally after the Veφressung .

13. The method according to any one of claims 7 to 12, characterized in that no Zwischenveφressung takes place between the metering steps for the individual premixes.

14. The method according to any one of claims 7 to 13, characterized in that the phases have the form of layers.

15. The method according to any one of claims 1 to 14, characterized in that the press ram (s) are rotated by 0.1 to 90 °, preferably by 0.25 to 45 ° and in particular by 0.5 to 20 ° with each turning operation.

16. The method according to any one of claims 1 to 15, characterized in that the rotation of the press ram (s) over a period of 1 to 1000 ms, preferably from 2 to 500 ms and in particular from 5 to 100 ms.

17. The method according to any one of claims 1 to 16, characterized in that the pressing surfaces of the ram have a roughness of 5 to 500 microns, preferably from 10 to 250 microns and in particular from 20 to 150 microns.

18. The method according to any one of claims 1 to 17, characterized in that the pressing is carried out at temperatures between 10 and 60 ° C, preferably between 15 and 50 ° C and in particular between 20 and 40 ° C.

19. The method according to any one of claims 1 to 18, characterized in that the particulate detergent composition has (s) a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1 .

20. The method according to any one of claims 1 to 19, characterized in that the particulate detergent and cleaning composition (s) particle sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, particularly preferably between 400 and 1600 microns and in particular between 600 and 1400 μm.

21. The method according to any one of claims 1 to 20, characterized in that the particulate detergent and cleaning composition (s) less than 20 wt .-%, preferably less than 10 wt .-% and in particular less than 5 % By weight of particles with a size below 200 μm.

22. The method according to any one of claims 1 to 21, characterized in that the particulate detergent and cleaning composition (s) less than 20 wt .-%, preferably less than 10 wt .-% o and in particular less than 5% by weight of particles with a size above 1600 μm.

23. The method according to any one of claims 1 to 22, characterized in that the or at least one of the premixes to be added additionally contains surfactant-containing granules).

24. The method according to claim 23, characterized in that the surfactant-containing granules contain anionic and / or nonionic surfactants and builders and total surfactant contents of at least 10% by weight, preferably at least 15% by weight and in particular at least 20% by weight. %, based on the granules.

25. The method according to any one of claims 1 to 24, characterized in that the or at least one of the premixes to be veφressing additionally one or more substances from the group of bleaching agents, bleach activators, disintegration aids, enzymes, pH adjusting agents, fragrances, perfume carriers, fluorescent agents , Dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

26. The method according to any one of claims 1 to 25, characterized in that the or at least one of the premixes to be veφressende a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 % By weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the premix.

27. The method according to any one of claims 7 to 26, characterized in that one of the premixes to be veφress contains bleaching agents, while another premix contains bleach activators.

28. The method according to any one of claims 1 to 27, characterized in that one of the premixes to be contained contains bleaching agents, while another premix contains enzymes.

29. The method according to any one of claims 1 to 28, characterized in that one of the premixes to be contained contains bleaching agents, while another premix contains corrosion protection agents.

30. The method according to any one of claims 1 to 29, characterized in that at least two of the premixes to be veφressen contain the same active ingredient in different amounts.

31. Use of tablet presses in which at least one punch of a pair of press punches is rotated about its vertical axis during the tabletting process for the production of detergent tablets.

32. Washing and cleaning agent molded body made of compressed, particulate washing and cleaning agent, characterized in that it consists of a core and a shell surrounding this core, which have the same composition, the shell being harder than the core.

33. Detergent and shaped body made of compressed, particulate detergent and cleaning agent, characterized in that it consists of a core and a shell surrounding this core, which have the same composition, the shell having a higher density than the core.

34. Multi-phase detergent and shaped body made of compacted, particulate detergent and cleaning agent compositions, characterized in that it consists of a multi-phase core and a multi-phase shell surrounding this multi-phase core, the individual phases of which have the same composition as the phases whose surface they cover , the shell being harder than the core.

35. Mehφhasiger shaped detergent and cleaning agent from compressed, particulate detergent and cleaning agent compositions, characterized in that it consists of a multi-phase core and a multi-phase core surrounding this there is a multi-phase shell, the individual phases of which have the same composition as the phases whose surface they cover, the shell having a higher density than the core.

36. Detergent and molded article according to one of claims 32 to 35, characterized in that the shell on the round sides of the molded article has a thickness of 5 to 2000 microns, preferably from 10 to 1500 microns and in particular from 25 to 1000 microns.

37. Detergent and molded article according to one of claims 32 to 36, characterized in that the core has a diametrical breaking strength of less than 30 kPa, preferably less than 25 kPa, particularly preferably less than 20 kPa and in particular less than 15 kPa having.

38. Detergent and molded article according to one of claims 32 to 37, characterized in that the casing has a diametrical breaking strength of more than 20 kPa, preferably more than 25 kPa, particularly preferably more than 30 kPa and in particular more than 35 kPa having.

39. Detergent and molded article according to one of claims 32 to 38, characterized in that the core has a density of more than 600 g / 1, preferably more than 750 g / 1 and in particular more than 900 g / 1.

40. Detergent and molded article according to one of claims 32 to 39, characterized in that the casing has a density of more than 1000 g / 1, preferably more than 1050 g / 1, particularly preferably more than 1100 g / 1 and in particular of more than 1150 g / 1.

41. Detergent and molded article according to one of claims 32 to 40, characterized in that the core and casing in a weight ratio of 250: 1 to 1: 1, preferably from 100: 1 to 5: 1 and in particular from 50: 1 to 10: 1 are available.

42. Detergent and molded article according to one of claims 32 to 41, characterized in that at least one molded article side is convexly curved.

43. Detergent and molded article according to one of claims 32 to 42, characterized in that at least one molded article side is concavely curved.

44. Detergent and molded article according to one of claims 32 to 43, characterized in that one side of the molded body is convex and the opposite side of the molded body is concavely curved.

45. washing process for washing textiles in a household washing machine, characterized in that one or more detergent and shaped articles according to one of claims 32 to 44 are placed in the washing-up chamber of the washing machine and a washing program is run, in the course of which the shaped body or bodies be washed in.

46. Washing method for washing textiles in a household washing machine, characterized in that one or more detergents and cleaners forrnköφer inserted according to one of claims 32 to 44 with or without dosing aid in the washing drum of the washing machine and a washing program can run in its Course of the molded body or be resolved.

47. Cleaning method for cleaning dishes in a dishwasher, characterized in that one or more washing and cleaning agent shaped bodies according to one of claims 32 to 44 are placed in the dosing chamber of the dishwasher and a washing program can be run, in the course of which the dosing chamber opens and the shaped body or bodies are dissolved.

48. Cleaning method for cleaning dishes in a dishwasher, characterized in that one or more washing and cleaning agent shaped articles according to one of claims 32 to 44 with or without dosing aid in the dishwasher put the dishwasher in and run a washing program, in the course of which the molded body or bodies are dissolved.