CA2311989A1

CA2311989A1 - Compression process for laundry detergent and cleaning product tablets

Info

Publication number: CA2311989A1
Application number: CA 2311989
Authority: CA
Inventors: Hans-Friedrich Kruse; Andreas Lietzmann; Claus-Peter Thiessies; Torsten Wietholz; Dieter Jung
Original assignee: Henkel AG and Co KGaA
Current assignee: Individual
Priority date: 1999-06-19
Filing date: 2000-06-19
Publication date: 2000-12-19
Also published as: AU5680400A; WO2000078910A1

Abstract

Laundry detergent and cleaning product tablets having high mechanical stability to impact, jolting and friction and high active substance contents even in the coating may be produced if at least one punch of a press-punch pair is rotated about its vertical axis during the tableting operation. This avoids further process steps and reduces the costs of producing the tablets.

Description

COMPRESSION PROCESS FOR LAUNDRY DETERGENT AND CLEANING
PRODUCT TABLETS
Field of the Invention The present invention relates to a process for producing laundry detergent and cleaning product tablets and to tablets produced by this process, and to the use thereof. The invention relates in particular to tablets and production processes such as laundry detergent tablets, cleaning product tablets, bleach tablets or water softener tablets and their respective production.
Background of the Invention Laundry detergent and cleaning product tablets have become firmly established alongside liquid and particulate products as commercial forms for compositions of the abovementioned type, since they possess a range of advantages, such as ease of metering, safe handling, high compaction and, as a result, reduced packaging, transport and storage cost, as well as esthetic appeal.
But there are disadvantages as well as these advantages. In many cases, compression to sufficiently stable tablets results in reduced solubility or disintegration rate, which is particularly undesirable in laundry detergent and cleaning product tablets. If, on the other hand, better solubility is sought by only gently compressing the tablets, then problems such as breakage, edge fracture and abrasion occur, which are perceived by the consumer as undesirable.
One solution proposed in response to this in the prior art is to use coated tablets in which a "shell"
envelops the internally situated laundry detergent and cleaning product tablet ("core") and gives it stability.
Coated laundry detergent tablets are described, for example, in European Patent Application EP 716 144 (Unilever). According to the teaching of that document, a coating of water-soluble material is said to reduce tablet friability and abrasion without affecting the solubility. Coating materials specified in that , document are, in particular, film-forming materials such as water-soluble polymers or sugars. The coating is applied in a process downstream of the tableting operation and accounts in terms of weight for a few percent of the finished tablet.
Coated laundry 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 these documents, coatings containing dicarboxylic acids are applied in the form of melts or solutions to precompressed tablets. Here again, the coating, in terms of weight, accounts for a few percent of the finished tablet and requires a separate processing step for its application.
In the cited cases of the prior art, the coating fulfils the function of a protective coat around the tablets produced beforehand, and fulfills no functions in the subsequent washing or cleaning process. Based on the overall weight of the tablets, therefore, the consumer is sold a certain percentage of material free of active substance. Furthermore, the above-described technology necessitates the use of two different process stages: tableting, on the one hand, and coating, on the other. This places an unfavorable burden on the process economics.

Suximnary of the Invention It is an object of the present invention to provide laundry detergent and cleaning product tablets which achieve the advantages of coating tablets without the use of materials that are of no benefit in the washing or cleaning operation. High mechanical stability to impact, jolting and friction, i.e., high fracture resistance and low friability and abrasion tendency, are to be achieved together with high active substance contents even in the coating.
In addition, the intention is to avoid further process steps, in order to reduce the costs of producing the tablets. A further object is to provide a tablet coating which brings the abovementioned advantages without the need for a special coating step following compression.
It has now been found that by means of a special compression process it is possible to produce surface-enhanced laundry detergent and cleaning product tablets whose outer layers have the quality of a conventional coating and exhibit the abovementioned advantages.
The present invention provides a process for producing laundry detergent and cleaning product tablets by compressing one or more particulate laundry detergent and cleaning product compositions in a tableting press.
in which at least one punch of a press-punch pair is rotated about its vertical axis during the tableting operation.
Without wishing to be bound by the theory, the applicant assumes that by virtue of the rotation of at least one punch of a press-punch pair during the tableting operation the tablet surface becomes harder, as a result of friction, than the rest of the tablet.

In this way, even with low pressing forces, a thin, relatively hard layer is produced in the form of a shell on the surface of the tablet, significantly increasing the stability of the tablet and its resistance to abrasion. A particular advantage here is that the relatively hard "shell" consists of the same premix as the rest of the tablet, i.e., it has the same composition. This avoids the use of coating layers free from active substance. At the same time, the coating is produced actually in the course of the pressing operation, obviating the need for downstream coating process steps.
Overall, through the process of the invention, the compressive pressure, which is in any case much lower with laundry detergent and cleaning product tablets than for other tableting mixtures, may be reduced further without the fear of disadvantages in respect of stability during handling or transport. The overall further reduction in compressive pressure leads, advantageously, to even faster-dissolving tablets.
Detailed Description of the Invention In order to achieve a "shell" structure that is as homogeneous as possible around the entire tablet, it is of advantage if not only one press punch of a punch pair rotates but rather upper punch and lower punch each rotate around their vertical axis during the tableting operation. Processes in which both punches of a press-punch pair are case rotated about their vertical axis during the tableting operation are, accordingly, preferred.
The rotation of two punches whose pressing faces are opposite one another may be codirectional or counterdirectional. In addition, the angle of rotation, and with it the rotary speed, of the punches may differ. Although, in accordance with the invention, all six conceivable embodiments (same direction of rotation, upper punch rotates faster/further; same direction of rotation, lower punch rotates faster/further; different direction of rotation, upper punch rotates faster/further; different direction of rotation, lower punch rotates faster/further; same direction of rotation, both punches rotate equally fast/far; opposite direction of rotation, both punches move equally fast/far) lead to success and may be used, process variants in which the punches are rotated in opposite directions have been found to be preferred.
The rotary speed, and the angular amount by which the punches are rotated, may be the same or different. It has been found advantageous to select identical punch speeds for the production of single-phase tablets whereas for the production of multilayer tablets the speed of one punch may be coordinated with the composition of the premix which comes into contact with it. Through variation of the parameters of mixture composition, rotational speed and surface quality of the press punch, the physical properties of the coating layer may be varied in a controlled manner.
The rotation of the tableting punches) may in principle take place at any point in the tableting operation. An appropriate point in time is, for example, a punch rotation when the compressed laundry detergent and cleaning product tablet is ejected from the die and is surface-treated by the punches) in the course of its ejection. Accordingly, processes wherein the rotation of the punches) takes place following compression, in the ejection region of the tableting press, are preferred embodiments.

Particularly suitable points in time at which to form stable coating layers are those in which the punches are pressure-loaded, i.e., for example, during the precompaction of the introduced premix and/or during the final compression leading to the finished laundry detergent and cleaning product tablet. After the particulate premix (the particulate laundry detergent and cleaning product composition) has been introduced, the lower punch may be raised, the upper punch lowered, and uniform distribution of the premix in the die enabled by rotating the punch(es). In this case, the bed of particles is deaerated at the same time, improving the homogeneity of the tablet and its uniform stability in all areas of the tablet. The deaeration of the particle bed permits reduced tablet friability and greater tableting press output. Accordingly, processes wherein the rotation of the press punches) takes place in the filling and/or pressure region of the tableting press, preferably in the filling and pressure region, are preferred.
The abovementioned points in time for rotation of the punches) may be combined with one another as desired.
In this context it is particularly advantageous if the punch (es) is (are) rotated not only at the precompression stage (in the filling region) but also in the main compression stage (in the pressure region) and after the compression stage (in the ejection region). Preferred processes are, therefore, those wherein rotation of the press punches) is carried out at the precompression stage and at the main compression stage and, optionally, after the compression stage.
The disintegration of the tablets may be sharply reduced as a result of an incorrect choice of the point in time for rotation. It has been observed that there is a marked deterioration in the disintegration times if the punches) is (are) rotated at the point in time at which the compressive force is between 40 and 100 of the maximum compressive force. Accordingly, preferred points in time for rotation are those at which the compressive forces at the punch (es) are from 0 to 405 of the maximum compressive force, preferably from 0 to 20~ of the maximum compressive force.
The rotation of the punches can be effected constructionally by means of cams on the punch, the rotation being carried out by way of stop rails on the press. Furthermore, the rotation may also be effected by means of driven plastic rollers which bear on the punches at certain times. It is also possible to provide the punches with a toothed wheel. The rotation is effected by way of toothed rails mounted on the press. The combination of materials for the toothed wheel/toothed rail pairing should preferably be chosen such that in operation the toothed rail is subject to greater wear. It is appropriate, for example, to give the toothed rail a spring mounting in order to build up slowly the acting forces on the tooth faces.
The details above relate, verbally, closely to the production of single-phase tablets from a particulate premix which is a laundry detergent and cleaning product composition. However, the process of the invention is by no means restricted thereto; rather, multiphase tablets as well may be produced with the advantages of the process of the invention. The present invention therefore further provides a process for producing multiphase laundry detergent and cleaning product tablets by compressing a plurality of particulate laundry detergent and cleaning product compositions in a tableting press in which at least one punch of a press-punch pair is rotated about its vertical axis during the tableting operation.

_ g _ In complete analogy to the remarks above, preferred processes for the production of multiphase tablets as well are those wherein both punches of a press-punch pair are each rotated about their vertical axis during the tableting operation. Also, processes wherein the punches are rotated in opposite directions are preferred embodiments of the process of the invention for producing multiphase tablets.
In this process of the invention, the rotation of the punches may likewise take place at a wide variety of positions and at a wide variety of points in time in the tableting process. In analogy to the above remarks, preference in the production of multiphase tablets is also given to processes wherein the rotation of the press punches) takes place following compression, in the ejection region of the tableting press.
With the production of multiphase tablets as well, of course, the rotation of the press punches) in the filling and/or pressure region of the tableting press, preferably in the filling and pressure region, which was emphasized above as being advantageous, is advantageous.
In preferred processes, therefore, rotation of the press punches) is carried out at the precompression stage of the first premix and at each further precompression stage of further premixes and at the main compression stage of the multiphase tablet, and, optionally, after the compression stage.
In the context of the production of multiphase tablets, the adhesion of the individual phases to one another may be improved by abandoning precompression between the metering steps for the individual premixes. At the same time this avoids the multiple exertion of compressive pressure on the first premix, which is disadvantageous for the solubility of the first phase.
A further embodiment therefore envisages processes of the invention wherein no intermediate compression takes place between the metering steps for the individual premixes.
The press punches used in the process of the invention may possess surface structures of any desired form, although rotation of the punches requires that the punches be circular. To produce simple or multilayer circular (biplanar) tablets it is possible to use punches having planar surfaces, as are known for the conventional tableting processes. In order to produce specially shaped tablets, which may likewise be composed of two or more layers, it is also possible to use punches having elevations or indentations, which may in turn be rotationally symmetric along the longitudinal axis of the punch. For example, it is possible to use a punch in which a cylinder having a relatively small diameter has been applied to a base area of greater diameter. In production, punches of this kind produce tablets having a circular depression which protrudes into the circular tablet. A
corresponding cylindrical depression in the press punch leads to a tablet having the form of two cylinders stacked one atop the other. Normally, the diameter-to-height ratio of such cylinders is more than 1, preferably more than 1.5, and in particular more than 2.
Said modifications may of course be carried out on upper and lower punches, thereby producing either, again, annular tablets (the mounted cylinders meet in the middle of the tablet during the pressing operation and form the continuous hole) or double-depression tablets or tablets having the form of three cylinders stacked atop each other.
The principle depicted above may also be extended to two, three or more successive elevations or indentations on the punch surface. It is also possible to mount rings on the punch surface or mill rings into it, with the resulting tablets having annular indentations or elevations.
One particularly preferred embodiment of the present invention provides for the use of domed punch surfaces.
In this case, one punch can be chosen to be planar while the other punch is convexly or concavely curved.
This results in tablets having a concave indentation or convex elevation on one side while the other side is planar. The last-mentioned tablets, having an upwardly domed "lens-shaped" elevation, may be transported on conventional conveyor belts owing to their smooth undersides and make it possible, for example, to raise the tablets where this is desired. The combination of two convexly or concavely curved punches is likewise 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 it is possible to realize a more or less thick cylindrical "rim" between the domed faces. Also possible, not least, is the combination of a convexly curved lower punch with a concavely curved upper punch (or vice versa), resulting in a tablet having the shape of a watchglass. For a given mass and given diameter, such tablets have a greater height than biplanar tablets.
Of course, fluid transitions between the individual forms mentioned are possible. Another preferred embodiment of tableting punches envisages an annular elevation on the edge of the punch, preferably with a triangular cross section. By means of such punches it is possible to produce tablets having a faceted edge (beveled edges). Here again, there are virtually no limits on the design diversity, so that the faceted edge may also be quadrant-shaped, stepped, multiply curved, etc. in design.
The production of multiphase tablets may result in different design forms. Thus it is possible, depending on the shaping of the press tools, to produce core/jacket or ring-core tablets. Bulleye tablets may also be produced by the pressing technology of the invention. In all embodiments of the press tools it is necessary to ensure that the rotating punches are rotationally symmetric so that when the punch/punches rotate no shifts occur in the structure of the mixture in the die. Since the production of the abovementioned multiphase tablets entails a high level of technical expenditure, it may be advantageous on grounds of process economics to use planar, circular press tools and to produce tablets having a layer construction.
Accordingly, processes wherein the phases have the form of layers are preferred.
The details given below apply independently of whether single-phase, double-layer or multiphase tablets with different structures are being produced. They relate in particular to the operation of rotation in accordance with the invention.
Regarding the direction of rotation of the rotating punch(es), reference may be made to the details given above. The amount by which the punch rotates may likewise be varied within wide limits, all embodiments being possible from the small rotation by a few tenths of a degree through to complete rotation. In view of the time spent by the press punches in the rotational positions, which is short at high throughputs, preference is given to processes wherein the press punches) is (are) rotated by from 0.1 to 90°, preferably by from 0.25 to 45°, and in particular by from 0.5 to 20°, at each rotation.
The amount of rotation of one punch, as already remarked above, is thus not tied to the amount of rotation of the other punch in the punch pair. Entirely analogously, depending on the rotational position, the punch may be rotated by different amounts. For example, it is possible to rotate a punch by five degrees of angle in the filling region, whereas the same punch is rotated by 0.5° in the compression region and by 45° in the ejection region. Of course, the figures mentioned are merely exemplary in nature, and at each rotational position a punch rnay be rotated by any conceivable amount. Rotation may be characterized not only by the angle traveled but also by the intensity of the rotation. This depends, in turn, on the time within which the rotation is completed. In the light of the throughputs of the tableting press, which should advantageously be high, the punch has only a limited time available for the rotation. Processes wherein the rotation of the press punches) is carried out over a period of from 1 to 1000 ms, preferably from 2 to 500 ms, and in particular from 5 to 100 ms, are preferred. In this way, depending on the size of the angle to be traveled, high angular velocities are achieved which lead to the desired friction on the surface of the tablet and to the formation of the coating layer.
In addition to the abovementioned factors of time (travel) and intensity of rotation, the thickness of the coating layer may also be influenced by way of the nature of the press punches, the compressive pressure, and the pressing temperature. Long paths of rotation, rapid rotations, rough punch surfaces, and increased pressing temperatures result in a thicker and thus more stable layer. The roughness of the punch surfaces may be indicated by the extent of the peak-to-valley height, which describes the difference in height between the lowest and the highest point of the punch surface. In accordance with the invention, processes wherein the pressing faces of the press punches have a peak-to-valley height of from 5 to 500 ~,m, preferably from 10 to 250 ~.m, and in particular from 20 to 150 Vim, are preferred.
Preference is likewise given in accordance with the invention to processes wherein compression is conducted at temperatures between 10 and 60°C, preferably between 15 and 50°C, and in particular between 20 and 40°C.
The compressive forces for the process of the invention are preferably within the range from 1 to 50 kN, in particular from 5 to 20 kN, these being the maximum forces (main compressive forces) obtaining at the punches. In accordance with the above-described preferred point in time of rotation of the punches, therefore, the punches) is (are) preferably rotated with compressive forces of from 0.2 to 20 kN, in particular from 1 to 8 kN, obtaining. Such forces lead to different pressures depending on the size of the area over which the force is distributed. In preferred process variants, these pressures are between 50 and 2500 N cm-2, in particular between 100 and 1500 N cm-2, the figure in turn representing the main compressive pressure. In preferred processes of the invention, rotation of the punches takes place with compressive pressures of between 10 and 1000 N cm-z, in particular between 20 and 600 N cm-2.

The process of the invention is used to produce laundry detergent and cleaning product tablets and consists in the compression of one or more particulate laundry detergent and cleaning product compositions.
Advantageous effects of the process end products may be achieved by means of suitable compositions and/or physical parameters of this (these) laundry detergent and cleaning product composition(s). The text below contains details of physical parameters and ingredients of the laundry detergent and cleaning product compositions, which are also referred to in the context of the present invention as "premixes".
For a high density of the resulting tablets it is advantageous if the premix for compression has a relatively high bulk denisity. In particular, processes wherein the particulate laundry detergent and cleaning product compositions) has (have) a bulk density of at least 500 g/l, preferably at least 600 g/1, and in particular at least 700 g/1, are preferred embodiments of the present invention.
It is also possible to give details of the particle size and the particle size distribution of the laundry detergent and cleaning product compositions) for compression. For example, preferred processes are those wherein the particulate laundry detergent and cleaning product compositions) has (have) particle sizes of between 100 and 2000 ~.m, preferably between 200 and 1800 Vim, with particular preference between 400 and 1600 ~,m, and in particular between 600 and 1400 ~,m.
Within the stated particle size ranges as well it is possible to perceive tendencies as to which premixes are particularly suitable. Processes wherein the particulate laundry detergent and cleaning product compositions) comprises/comprise less than 20~ by weight, preferably less than 10~ by weight, and in particular less than 5~ by weight, of particles having a size below 200 ~.m are further preferred in accordance with the invention. Similar details may also be given regarding the upper limit of the particle size distribution. Here, preferred processes are those wherein the particulate laundry detergent. and cleaning product compositions) comprises/comprise less than 20~
by weight, preferably less than 10% by weight, and in particular less than 5~ by weight, of particles having a size above 1600 Vim.
In accordance with the process of the invention, it is possible to produce, for example, laundry detergent tablets with particular preference. Whereas in detergent tablets for machine dishwashing, for example, the fraction of surfactants is small and this surfactant fraction may be entirely absent from bleach tablets or water softener tablets, surfactants are an essential constituent of textile laundry detergents, irrespective of their commercial form. Laundry detergent tablets are normally produced by blending surfactant granules with preparation components and subsequently compressing this particulate premix. In preferred variants of the process of the invention, therefore, the premix, or at least one of the premixes, for compression further comprises one or more types of surfactant-containing granules.
Processes which are preferred in the context of the present invention therefore comprise compressing a particulate premix comprising at least one type of surfactant-containing granules and at least one admixed pulverulent component. The surfactant-containing granules may be produced by customary industrial granulation processes such as compacting, extrusion, mixer granulation, pelletizing, or fluidized bed granulation.
In preferred process variants, the surfactant-s containing granules likewise satisfy defined particle size criteria. For instance, preference is given to processes of the invention wherein the surfactant-containing granules have particle sizes of between 100 and 2000 Vim, preferably between 200 and 1800 Vim, with particular preference between 400 and 1600 ~,m, and in particular between 600 and 1400 Vim.
In addition to the active substances (anionic and/or nonionic and/or cationic and/or amphoteric surfactants), the surfactant granules preferably further comprise carrier materials, which with particular preference come from the group of the builders. Particularly advantageous processes are those wherein the surfactant-containing granules comprise anionic and/or nonionic surfactants and also builders and have 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 the anionic, nonionic, zwitterionic or cationic surfactants, anionic surfactants being distinctly preferred for economic reasons and on account of their performance spectrum.
Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C9_13 alkylbenzenesulfonates, olefinsulfonates, i.e., mixtures of alkenesulfonates and hydroxyalkanesulfonates, and also disulfonates, as are obtained, for example, from Cla-la monoolefins having a terminal or internal double bond by sulfonating with gaseous sulfur trioxide followed by alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates, which are obtained from Clz-le alkanes, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, respectively. Likewise suitable, in addition, are the esters of a-sulfo fatty acids (ester sulfonates), e.g., the a-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are the monoesters, diesters and triesters, and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with from 1 to 3 mol of fatty acid or in the transesterification of triglycerides with from 0.3 to 2 mol of glycerol.
Preferred sulfated fatty acid glycerol esters are the sulfation products of saturated fatty acids having 6 to 22 carbon atoms, examples being those of caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid, or behenic acid.
Preferred alk(en)yl sulfates are the alkali metal salts, and especially the sodium salts, of the sulfuric monoesters of Clz-C18 fatty alcohols, examples being those of coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or of Clo-Czo oxo alcohols, and those rnonoesters of secondary alcohols of these chain lengths. Preference is also given to alk(en)yl sulfates of said chain length which contain a synthetic straight-chain alkyl radical prepared on a petrochemical basis, these sulfates possessing degradation properties similar to those of the corresponding compounds based on fatty-chemical raw materials. From a detergents standpoint, the Clz-Cls alkyl sulfates and Clz-C,,s alkyl sulfates, and also C14-Cls alkyl sulfates, are preferred. In addition, 2, 3-alkyl sulfates, which may for example be prepared in accordance with US Patents 3,234,258 or 5,075,041 and obtained as commercial products from Shell Oil Company under the name DAN~, are suitable anionic surfactants.
Also suitable are the sulfuric monoesters of the straight-chain or branched C,_zl alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C9_11 alcohols containing on average 3.5 mol of ethylene oxide (EO) or Clz-is fatty alcohols containing from 1 to 4 EO. Because of their high foaming behavior they are used in cleaning products only in relatively small amounts, for example, in amounts of from 1 to 5~ by weight.
Further suitable anionic surfactants include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters and which constitute monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates comprise C8_1$ fatty alcohol radicals or mixtures thereof. Especially preferred sulfosuccinates contain a fatty alcohol radical derived from ethoxylated fatty alcohols which themselves represent nonionic surfactants (for description, see below).
Particular preference is given in turn to sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols having a narrowed homolog distribution. Similarly, it is also possible to use alk(en)ylsuccinic acid containing preferably 8 to 18 carbon atoms in the alk(en)yl chain, or salts thereof.

Further suitable anionic surfactants are, in particular, soaps. Suitable soaps include saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and, in particular, mixtures of soaps derived from natural fatty acids, e.g., coconut, palm kernel, or tallow fatty acids.
The anionic surfactants, including the soaps, may be present in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
Preferably, the anionic surfactants are 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, preference is given to surfactant granules which contain from 5 to 50% by weight, preferably from 7.5 yo 40% by weight, and in particular from 10 to 30% by weight, of anionic surfactant(s), based in each case on the granules.
In the selection of the anionic surfactants there are no boundary conditions to be observed which stand in the way of freedom to formulate. Preferred surfactant granules, however, have a soap content which exceeds 0.2% by weight, based on the overall weight of the laundry detergent and cleaning product tablet produced.
Anionic surfactants for use with preference are the alkylbenzenesulfonates and fatty alcohol sulfates, with preferred laundry detergent and cleaning product tablets containing from 2 to 20% by weight, preferably from 2.5 to 15% by weight, and in particular from 5 to 10% by weight, of fatty alcohol sulfate(s), based in each case on the weight of the laundry detergent and cleaning product tablets.

Nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, especially primary, alcohols having preferably 8 to 18 carbon atoms and on average from 1 to 12 mol of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or, preferably, methyl-branched in position 2 and/or may comprise linear and methyl-branched radicals in a mixture, as are commonly present in oxo alcohol radicals. In particular, however, preference is given to alcohol ethoxylates containing linear radicals from alcohols of natural origin having 12 to 18 carbon atoms, e.g., from coconut, palm, tallow fatty or oleyl alcohol and on average from 2 to 8 EO per mole of alcohol. Preferred ethoxylated alcohols include, for example, Clz-14 alcohols containing 3 EO or 4 EO, C9_11 alcohol containing 7 E0, C13-15 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Clz-1$ alcohols containing 3 EO, 5 EO
or 7 EO, and mixtures thereof , such as mixtures of Clz-14 alcohol containing 3 EO and Clz-18 alcohol containing 5 E0. The stated degrees of ethoxylation represent statistical mean values, which for a specific product may be an integer or a fraction. Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NREs). In addition to these nonionic surfactants it is also possible to use fatty alcohols containing more than 12 EO. Examples thereof are tallow fatty alcohol containing 14 EO, 25 EO, 30 EO
or 40 EO.
A further class of nonionic surfactants used with preference, which are used either as sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated, or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as are described, for example, in Japanese Patent Application JP 58/217598, or those prepared preferably by the process described in International Patent Application WO-A-90/13533.
Another class of nonionic surfactants which may be used with advantage are the alkyl polyglycosides (APGs).
Alkyl polyglycosides suitable for use satisfy the general formula RO(G)Z, where R is a linear or branched aliphatic radical, especially an aliphatic radical which is methyl-branched in position 2, which is saturated or unsaturated and has 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol representing a glycose unit having 5 or 6 carbon atoms, preferably 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.
Preference is given to the use of linear alkyl polyglucosides, i.e. alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.
The process end products of the process of the invention may preferably include alkyl polyglycosides, preference being given to APG contents of more than 0.2% by weight, based on the overall tablet.
Particularly preferred laundry detergent and cleaning product tablets contain APGs in amounts of from 0.2 to 10% by weight, preferably from 0.2 to 5% by weight, and in particular from 0.5 to 3% by weight.
Nonionic surfactants of the amine oxide type, examples being N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and of the fatty acid alkanolamide type, may be 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 thereof.
Further suitable surfactants are polyhydroxy fatty acid amides of the formula (I), R-CO-N-[ZJ (I) where RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R1 is hydrogen or an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms, and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and from 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which are customarily obtainable 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 the polyhydroxy fatty acid amides also includes compounds of the formula (II) R j -O-RZ
R-CO-N-[ZJ (II) where R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, preference being given to C1_4 alkyl radicals or phenyl radicals, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of said radical.
[Z] is preferably obtained by reductive amination of a reduced sugar, e.g., glucose, fructose, maltose, lactose, galactose, mannose, or xylose. The N-alkoxy-or N-aryloxy-substituted compounds may then be converted to the desired polyhydroxy fatty acid amides, for example, in accordance with the teaching of International Patent Application TAO-A-95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
Irrespective of whether anionic or nonionic surfactants or mixtures of these classes of surfactant, and also, if desired, amphoteric or cationic surfactants, are used in the surfactant granules, preferred processes of the invention are those wherein the surfactant content of the surfactant-containing granules is from 5 to 60 by weight, preferably from 10 to 50~ by weight, and in particular from 15 to 40~ by weight, based in each case on the surfactant granules.
The surfactant granules may be used in varying amounts in the laundry detergent and cleaning product tablets or in individual phases of multiphase tablets.
Processes of the invention wherein the proportion of the surfactant-containing granules in the laundry detergent and cleaning product tablets, or in an individual phase of the laundry detergent and cleaning product tablet, is from 40 to 95~ by weight, preferably from 45 to 85~ by weight, and in particular from 55 to 75~ by weight, based in each case on the weight of the laundry detergent and cleaning product tablets, are preferred.

From a performance standpoint it may be advantageous if certain classes of surfactant are absent from some phases of the laundry detergent and cleaning product tablets or from the tablet as a whole, i.e., from all phases. A further important embodiment of the present invention therefore envisages that at least one phase of the tablets is free from nonionic surfactants.
Conversely, however, the presence of certain surfactants in individual phases or in the whole tablet, i.e., in all phases, may produce a positive effect. The incorporation of the above-described alkyl polyglycosides has been found advantageous, and so preference is given to laundry detergent and cleaning product tablets in which at least one phase of the tablets comprises alkyl polyglycosides.
Similarly to the case with the nonionic surfactants, the omission of anionic surfactants from phases or all phases may also result in laundry detergent and cleaning product tablets better suited to certain fields of application. In the context of the present invention, therefore, it is also possible to conceive of laundry detergent and cleaning product tablets in which at least one phase of the tablet is free from anionic surfactants.
It has been found.that the surfactant content of the premixes for compression influences the quality of the coating layer produced by the process of the invention.
As the surfactant content increases there is an improvement in the stability of the coating layer. Thus it is preferred for the surfactant content of the tableting premix to be more than 10~ by weight and with particular preference more than 15~ by weight.

The nature of the surfactants used also has an influence on the coating layer. With relatively high proportions of nonionic surfactants, there is an increasing deterioration in the disintegration time of the tablets produced. Thus preference is given to a premix 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, especially in connection with the tableting of formulas containing zeolite, that a certain nonionic surfactant content is useful for the formation of the coating layer. The nonionic surfactant content of a zeolite-containing tablet of this kind is therefore preferably at least 2%
by weight, more preferably at least 3% by weight.
In addition to the wash-active substances, builders are the most important ingredients of laundry detergent and cleaning products. In the surfactant granules, but also as a constituent of the premix, it is possible for all of the builders commonly used in laundry detergents and cleaning products to be present, i.e. in particular zeolites, silicates, carbonates, organic cobuilders, and - where there are no ecological prejudices against their use - phosphates as well. The latter are builders preferred for use in particular in detergent tablets for machine dishwashing.
Suitable crystalline, layered sodium silicates possess the general formula NaMSiX02X+1yH20, where M is sodium or hydrogen, x is a number from 1.9 to 4, y is a number from 0 to 20, and preferred values for x are 2, 3 or 4.
Crystalline phyllosilicates of this kind are described, for example, in European Patent Application EP-A-0 164 514. Preferred crystalline phyllosilicates of the formula indicated are those in which M is sodium and x adopts the value 2 or 3. In particular, both (S
and 8-sodium disilicates Na2SizO5~yH20 are preferred, (3-sodium disilicate, for example, being obtainable by the process described in International Patent Application WO-A-91/08171.
It is also possible to use amorphous sodium silicates having an Na20:Si0z modulus of from 1:2 to 1:3.3, preferably from 1:2 to 1:2.8, and in particular from 1:2 to 1:2 .6, which are dissolution-retarded and have secondary washing properties. The retardation of dissolution relative to conventional amorphous sodium silicates may have been brought about in a variety of ways - for example, by surface treatment, compounding, compacting, or overdrying. In the context of this invention, the term "amorphous" also embraces "X-ray-amorphous". This means that in X-ray diffraction experiments the silicates do not yield the sharp X-ray reflections typical of crystalline substances but instead yield at best one or more maxima of the scattered -radiation, having a width of several degree X

units of the diffraction angle. However, good builder properties may result, even particularly good builder properties, if the silicate particles in electron diffraction experiments yield vague or even sharp diffraction maxima. The interpretation of this is that the product s have microcrystalline regions with a size of from 10 to several hundred nm, values up to max.

50 nm and in particular up to max. 20 nm being preferred. So-called X-ray-amorphous silicates of this kind, which likewise possess retarded dissolution relative to the conventional waterglasses, are described, for example, in German Patent Application DE-A-44 00 024. Particular preference is given to compacted amorphous silicates, compounded amorphous silicates, and overdried X-ray-amorphous silicates.

The finely crystalline, synthetic zeolite used, containing bound water, is preferably zeolite A
and/or P. A particularly preferred zeolite P is Zeolite MAP~ (commercial product from Crosfield). Also suitable, however, are zeolite X and also mixtures of A, X and/or P. A product available commercially and able to be used with preference in the context of the present invention, for example, is a cocrystallizate of zeolite X and zeolite A (approximately 80~ by weight zeolite X), which is sold by CONDEA Augusta S.p.A.
under the brand name VEGOBOND AX~ and may be described by the formula nNa20~ (1-n) KZO~A12O3~ (2-2 . 5) Si02~ (3 .5-5.5) H20.
The zeolite may be used either as a builder in a granular compound or as a kind of "powdering" for the entire mixture intended for compression, it being common to utilize both methods for incorporating the zeolite into the premix. Suitable zeolites have an average particle size of less than 10 ~m (volume distribution; measurement method: Coulter counter) and contain preferably from 18 to 22~ by weight, in particular from 20 to 22~ by weight, of bound water.
Of course, the widely known phosphates may also be used as builder substances provided such a use is not to be avoided on ecological grounds. Among the large number of commercially available phosphates, the alkali metal phosphates, with particular preference being given to pentasodium and pentapotassium triphosphate (sodium and potassium tripolyphosphate, respectively), possess the greatest importance in the laundry detergent and cleaning product industry.
Alkali metal phosphates is the collective term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, among which meta-phosphoric acids (HP03) n and orthophosphoric acid H3P04, in addition to higher-molecular-mass representatives, may be distinguished. The phosphates combine a number of advantages: they act as alkali carriers, prevent limescale deposits on machine components, and lime incrustations on fabrics, and additionally contribute to cleaning performance.
Sodium dihydrogen phosphate, NaH2P04, exists as the dehydrate (density 1.91 g cm-3, melting point 60°) and as the monohydrate (density 2.04 g cm-3). Both salts are white powders of very ready solubility in water which lose the water of crystallization on heating and undergo conversion at 200°C into the weakly acidic diphosphate (disodium dihydrogen diphosphate, Na2H2P20~) and at the higher temperature into sodium trimetaphosphate (Na3P309) and Maddrell's salt (see below). NaH2P04 reacts acidically; it is formed if phosphoric acid is adjusted to a pH of 4.5 using sodium hydroxide solution and the slurry is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium diphosphate, PDP), KH2PO4, is a white salt with a density of 2.33 g cm-3, has a melting point of 253° [decomposition with formation of potassium polyphosphate (KP03)X], and is readily soluble in water.
Disodium hydrogen phosphate (secondary sodium phosphate), Na2HP04, is a colorless, crystalline salt which is very readily soluble in water. It exists in anhydrous form and with 2 mol (density 2.066 g cm~3, water loss at 95° ) , 7 mol (density 1. 68 g cm-3, melting point 48° with loss of 5 H20), and 12 mol of water (density 1.52 g cm-3, melting point 35° with loss of 5 H20), becomes anhydrous at 100°, and if heated more severely undergoes transition to the diphosphate Na4P20~. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with sodium carbonate solution using phenolphthalein as indicator.
Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K2HP04, is an amorphous white salt which is readily soluble in water.
Trisodium phosphate, tertiary sodium phosphate, Na3P04, exists as colorless crystals which as the dodecahydrate have a density of 1.62 g cm-3 and a melting point of 73-76°C (decomposition), as the decahydrate (corresponding to 19-20% P205) have a melting point of 100°C, and in anhydrous form (corresponding to 39-40%
P205) have a density of 2.536 g cm-3. Trisodium phosphate is readily soluble in water, with an alkaline reaction, and is prepared by evaporative concentration of a solution of precisely 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K3P04, is a white, deliquescent, granular powder of density 2.56 g cm-3, has a melting point of 1340°, and is readily soluble in water with an alkaline reaction. It is produced, for example, when Thomas slag is heated with charcoal and potassium sulfate. Despite the relatively high price, the more readily soluble and therefore highly active potassium phosphates are frequently preferred in the cleaning products industry over corresponding sodium compounds.
Tetrasodium diphosphate (sodium pyrophosphate), Na4P20~, exists in anhydrous form (density 2.534 g cm 3, melting point 988°, 880° also reported) and as the decahydrate (density 1.815-1.836 g cm-3, melting point 94° with loss of water). Both substances are colorless crystals which dissolve in water with an alkaline reaction. Na4P20~ is formed when disodium phosphate is heated at > 200° or by reacting phosphoric acid with sodium carbonate in stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and water hardeners and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate) , ICøP20~, exists in the form of the trihydrate and is a colorless, hygroscopic powder of density 2.33 g cm-3 which is soluble in water, the pH of the 1% strength solution at 25° being 10.4.
Condensation of NaH2P04 or of KH2P04 gives rise to higher-molecular-mass sodium and potassium phosphates, among which it is possible to distinguish cyclic representatives, the sodium and potassium metaphos-phates, and catenated types, the sodium and potassium polyphosphates. For the latter in particular a large number of names are in use: fused or calcined phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are referred to collectively as condensed phosphates.
The industrially important pentasodium triphosphate, Na5P301o (sodium tripolyphosphate), is a nonhygroscopic, white, water-soluble salt which is anhydrous or crystallizes with 6 Hz0 and has the general formula Na4- [P (O) (ONa) -O] n-Na where n - 3 . About 17 g of the anhydrous salt dissolve in 100 g of water at room temperature, at 60° about 20 g, at 100° around 32 g;
after heating the solution at 100° for two hours, about 8% orthophosphate and 15% diphosphate are produced by hydrolysis. For the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in stoichiometric ratio and the solution is dewatered by spraying. In a similar way to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves numerous insoluble metal compounds (including lime soaps, etc). Pentapotassium triphosphate, K5P301o (potassium tripolyphosphate), is commercialized, for example, in the form of a 50~ strength by weight solution (> 23~ P205, 25~ K20) . The potassium polyphosphates find broad application in the laundry detergents and cleaning products industry. There also exist sodium potassium tripolyphosphates, which may likewise be used for the purposes of the present invention. These are formed, for example, when sodium trimetaphosphate is hydrolyzed with KOH:
(NaP03) 3 + 2 KOH ~ Na3K2P301o + H20 They can be used in accordance with the invention in precisely the same way as sodium tripolyphospate, 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 tripolyphospate, may also be used in accordance with the invention.
Organic cobuilders which may be used in the laundry detergent and cleaning product tablets of the invention are, in particular, polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below), and phosphonates. These classes of substance are described below.
Organic builder substances which may be used are, for example, the polycarboxylic acids, usable in the form of their sodium salts, the term polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. Examples of these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, malefic acid, fumaric acid, sugar acids, amino carboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable on ecological grounds, and also mixtures thereof. Preferred salts are the salts of the polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, and mixtures thereof.
The acids per se may also be used. In addition to their builder effect, the acids typically also possess the property of an acidifying component and thus also serve to establish a lower and milder pH of laundry detergents or cleaning products. In this context, mention may be made in particular of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any desired mixtures thereof.
Also suitable as builders are polymeric poly-carboxylates; these are, for example, the alkali metal salts of polyacrylic acid or of polymethacrylic acid, examples being those having a relative molecular mass of from 500 to 70,000 g/mol.
The molecular masses reported for polymeric poly-carboxylates, for the purposes of this document, are weight-average molecular masses, Mw, of the respective acid form, determined basically by means of gel permeation chromatography (GPC) using a W detector.
The measurement was made against an external polyacrylic acid standard, which owing to its structural similarity to the polymers under investigation provides realistic molecular weight values. These figures differ markedly from the molecular weight values obtained using poly-styrenesulfonic acids as the standard. The molecular masses measured against polystyrenesulfonic acids are generally much higher than the molecular masses reported in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular mass of from 2000 to 20,000 g/mol. Owing to their superior solubility, preference in this group may be given in turn to the short-chain polyacrylates, which have molecular masses of from 2000 to 10,000 g/mol, and with particular preference from 3000 to 5000 g/mol.
Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with malefic acid. Copolymers which have been found particularly suitable are those of acrylic acid with malefic acid which contain from 50 to 90~ by weight acrylic acid and from 50 to 10°~ by weight malefic acid. Their relative molecular mass, based on free acids, is generally from 2000 to 70,000 g/mol, preferably from 20,000 to 50,000 g/mol, and in particular from 30,000 to 40,000 g/mol.
The (co)polymeric polycarboxylates can be used either as powders or as aqueous solutions. The (co)polymeric polycarboxylate content of the compositions is preferably from 0.5 to 20~ by weight, in particular from 3 to 10~ by weight.
In order to improve the solubility in water, the polymers may also contain allyl sulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, for example, as monomers.
Particular preference is also given to biodegradable polymers comprising more than two different monomer units, examples being those comprising, as monomers, salts of acrylic acid and of malefic acid, and also vinyl alcohol or vinyl alcohol derivatives, or those comprising, as monomers, salts of acrylic acid and of 2-alkylallylsulfonic acid, and also sugar derivatives.
Further preferred copolymers are those described in German Patent Applications DE-A-43 03 320 and DE-A-44 17 734, whose monomers are preferably acrolein and acrylic acid/acrylic acid salts, and, respectively, acrolein and vinyl acetate.
Similarly, further preferred builder substances that may be mentioned include polymeric amino dicarboxylic acids, their salts or their precursor substances.
Particular preference is given to polyaspartic acids and their salts and derivatives, which are disclosed in German Patent Application DE-A-195 40 086 to have not only cobuilder properties but also a bleach-stabilizing action.
Further suitable builder substances are polyacetals, which may be obtained by reacting dialdehydes with polyol carboxylic acids having 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and/or glucoheptonic acid.
Further suitable organic builder substances are dextrins, examples being oligomers and polymers of carbohydrates, which may be obtained by partial hydrolysis of starches. The hydrolysis can be conducted by customary processes; for example, acid-catalyzed or enzyme-catalyzed processes. The hydrolysis products preferably have average molecular masses in the range from 400 to 500, 000 g/mol . Preference is given here to a polysaccharide having a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, DE being a common measure of the reducing effect of a polysaccharide in comparison to dextrose, which possesses a DE of 100. It is possible to use both maltodextrins having a DE of between 3 and 20 and dried glucose syrups having a DE of between 20 and 37, and also so-called yellow dextrins and white dextrins having higher molecular masses, in the range from 2000 to 30,000 g/mol.
The oxidized derivatives of such dextrins comprise their products of reaction with oxidizing agents which are able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function.
Oxidized dextrins of this kind, and processes for preparing them, 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 and from 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. Likewise suitable is an oxidized oligosaccharide in accordance with German Patent Application DE-A-196 00 018. A product oxidized at C6 of the saccharide ring may be particularly advantageous.
Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are also further suitable cobuilders. Ethylenediamine N,N'-disuccinate (EDDS) is used preferably in the form of its sodium or magnesium salts. Further preference in this context is given to glycerol disuccinates and glycerol trisuccinates as well. Suitable use amounts in formulations containing zeolite and/or silicate are from 3 to 15~ by weight.
Examples of further useful organic cobuilders are acetylated hydroxy carboxylic acids and their salts, which may also be present in lactone form and which contain at least 4 carbon atoms, at least one hydroxyl group, and not more than two acid groups. Such cobuilders are described, for example, in International Patent Application WO 95/20029.
A further class of substance having cobuilder properties is represented by the phosphonates. The phosphonates in question are, in particular, hydroxyalkane- and aminoalkanephosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphos-phonate (HEDP) is of particular importance as a cobuilder. It is used preferably as the sodium salt, the disodium salt being neutral and the tetrasodium salt giving an alkaline (pH 9) reaction. Suitable aminoalkanephosphonates are preferably ethylenediamine-tetramethylenephosphonate (EDTMP), diethylenetriamine-pentamethylenephosphonate (DTPMP), and their higher homologs. They are used preferably in the form of the neutrally reacting sodium salts, e.g., as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP. As a builder in this case, preference is given to using HEDP from the class of the phosphonates. Furthermore, the aminoalkanephosphonates possess a pronounced heavy metal binding capacity.
Accordingly, and especially if the compositions also contain bleach, it may be preferred to use aminoalkanephosphonates, expecially DTPMP, or to use mixtures of said phosphonates.
Furthermore, all compounds capable of forming complexes with alkaline earth metal ions may 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. In turn, the amount of builders used is dependent on the intended use, so that bleach tablets may contain higher amounts of builders (for example, between 20 and 70% by weight, preferably between 25 and 65% by weight, and in particular between 30 and 55% by weight) than, say, laundry detergent tablets (usually from 10 to 50% by weight, preferably from 12.5 to 45% by weight, and in particular between 17.5 and 37.5% by weight). In detergent tablets for machine dishwashing, even higher builder contents may be present, for example, from 40 to 95% by weight, preferably from 50 to 90% by weight, and in particular from 60 to 85% by weight. Water softener tablets may even consist of builders to the extent of 100% by weight.
In order to facilitate the disintegration of highly compacted tablets, it is possible to incorporate disintegration aids, known as tablet disintegrants, into the tablets in order to reduce the disintegration times. Tablet disintegrants, or disintegration accelerators, are understood in accordance with Rompp (9th Edition, Vol. 6, p. 4440) and Voigt "Lehrbuch der pharmazeutischen Technologie" [Textbook of pharmaceutical technology] (6th Edition, 1987, pp.
182-184) to be auxiliaries which ensure the rapid disintegration of tablets in water or gastric fluid and the release of the drugs in absorbable form.
These substances increase in volume on ingress of water, with the possibility on the one hand of an increase in the intrinsic volume (swelling) and on the other hand, by way of the release of gases, of the generation of a pressure which causes the tablets to disintegrate into smaller particles. Examples of established disintegration aids are carbonate/citric acid systems, with the use of other organic acids also being possible. Examples of swelling disintegration aids are synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers and/or modified natural substances such as cellulose and starch and their derivatives, alginates, or casein derivatives.
Preferred laundry detergent and cleaning product tablets contain from 0.5 to 10% by weight, preferably from 3 to 7% by weight, and in particular from 4 to 6%
by weight, of one or more disintegration aids, based in each case on the tablet weight.
Preferred disintegrants used in the context of the present invention are cellulose-based disintegrants and so preferred laundry detergent and cleaning product tablets comprise a cellulose-based disintegrant of this kind in amounts from 0.5 to 10% by weight, preferably from 3 to 7% by weight, and in particular from 4 to 6%
by weight. Pure cellulose has the formal empirical composition (C6H1o05) n and, considered formally, is a (3-1,4-polyacetal of cellobiose, which itself is constructed of two molecules of glucose. Suitable celluloses consist of from about 500 to 5000 glucose unit s and, accordingly, have average molecular masses of from 50,000 to 500,000. Cellulose-based disintegrants which can be used also include, in the context of the present invention, cellulose derivatives obtainable by polymer-analogous reactions from cellulose. Such chemically modified celluloses include, for example, products of esterifications and etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxy groups have been replaced by functional groups not attached by an oxygen atom may also be used as cellulose derivatives. The group of the cellulose derivatives embraces, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and cellulose ethers and aminocelluloses. Said cellulose derivatives are preferably not used alone as cellulose-based disintegrants but instead are used in a mixture with cellulose The cellulose derivative content of these mixtures is preferably less than 50~
by weight, with particular preference less than 20~ by weight, based on the cellulose-based disintegrant. The particularly preferred cellulose-based disintegrant used is pure cellulose, free from cellulose derivatives.
The cellulose used as disintegration aid is preferably not used in finely divided form but instead is converted into a coarser form, for example, by granulation or compaction, before being admixed to the premixes intended for compression. Laundry detergent and cleaning product tablets comprising disintegrants in granular or optionally cogranulated form are described in German Patent Applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in International Patent Application W098/40463 (Henkel). These documents also provide further details on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle sizes of such disintegrants are usually above 200 Vim, preferably between 300 and 1600 ~m to the extent of at least 90~ by weight, and in particular between 400 and 1200 ~m to the extent of at least 90~
by weight. The abovementioned, relatively coarse disintegration aids based on cellulose, and those described in more detail in the cited documents, are preferred for use as disintegration aids in the context of the present invention and are available commercially, for example, under the designation Arbocel~ TF-30-HG from the company Rettenmaier.

As a further cellulose-based disintegrant or as a constituent of this component, it is possible to use microcrystalline cellulose. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack only the amorphous regions (approximately 30% of the total cellulose mass) of the celluloses and break them up completely but leave the crystalline regions (approximately 70%) intact. Subsequent deaggregation of the microfine celluloses resulting from the hydrolysis yields the microcrystalline celluloses, which have primary particle sizes of approximately 5 ~m and can be compacted, for example, to granules having an average particle size of 200 Vim.
Processes which are preferred in the context of the present invention are those wherein the premix or at least one of the premixes for compression comprises a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight, and in particular from 4 to 6% by weight, based in each case on the premix.
With the disintegration aids) as well, particular effects may result from the complete or partial absence of such substances from individual phases of multiphase tablets. Thus it is preferred, for example, to produce multiphase tablets, especially multilayer tablets, whose individual phases contain a disintegrant in different amounts. In this way, active substances may be released from one phase in a controlled - for example, accelerated or retarded - manner, giving rise to performance advantages.

In addition to the abovementioned constituents, surfactant, builder and disintegration aid, the laundry detergent and cleaning product tablets of the invention may further comprise further customary laundry detergent and cleaning product ingredients from the group consisting of bleaches, bleach activators, disintegration aids, enzymes, pH standardizers, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors, and corrosion inhibitors.
Among the compounds used as bleaches which yield HzOz in water, particular importance is possessed by sodium percarbonate. This "sodium percarbonate" is an unspecifically used designation for sodium carbonate peroxohydrates, which strictly speaking are not "percarbonates" (i.e., salts of percarbonic acid) but are instead hydrogen peroxide adducts onto sodium carbonate. The commercial product has the average composition 2 Na2C03~3 H202 and thus is not a peroxy-carbonate. Sodium percarbonate forms a white, water-soluble powder of density 2.14 g cm-3 which readily breaks down into sodium carbonate and into oxygen which has a bleaching and oxidizing action.
Sodium carbonate peroxohydrate was first obtained in 1899 by precipitation with ethanol from a solution of sodium carbonate in hydrogen peroxide, but was erroneously regarded as a peroxycarbonate. Only in 1909 was the compound recognized to be a hydrogen peroxide addition compound; nevertheless, the historical designation "sodium percarbonate" has become established in the art.
Industrially, sodium percarbonate is produced pre-dominantly by precipitation from aqueous solution (known as the wet process). In this process, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by means of salting agents (predominantly sodium chloride), crystallizing auxiliaries (for example, polyphosphates, polyacrylates), and stabilizers (for example, Mg2+ ions). The precipitated salt, which still contains from 5 to 12~ by weight of mother liquor, is subsequently centrifuged aff and dried in fluid bed driers at 90°C. Depending on production process, the bulk density of the finished product may vary between 800 and 1200 g/1. In general, the percarbonate is stabilized by means of an additional coating. Coating processes and substances used for coating have been described widely in the patent literature. In principle, it is possible in accordance with the invention to use all commercially customary types of percarbonate, as offered, for example, by Solvay Interox, Degussa, Kemira or Akzo.
Further bleaches which may be used are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates, and H2O2-donating peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoper acid or diperdodecanedioic acid. With the use of bleaches, as well, it is possible to dispense with the use of surfactants and/or builders:
straight bleach tablets may be prepared. If such bleach tablets are for laundry use, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of the other ingredients of the tablet. If preparing detergent or bleach tablets for machine dishwashing, bleaches from the group of organic bleaches may also be used. Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide, for example. Further typical organic bleaches are the peroxy acids, particular examples being the alkyl peroxy acids and the aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxy-benzoic acids, but it is also possible to use peroxy-a-naphthoic acid and magnesium monoperphthalate, (b) aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, s-phthalimidoperoxy caproic acid [phthaloiminoperoxy-hexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamido-persuccinates, and (c) aliphatic and araliphatic peroxy dicarboxylic acids, such as 1,12-diperoxydecane-dicarboxylic acid, 1,9-diperoxyazelaic acid, diperoxy-sebacic acid, diperoxybrassylic acid, the diperoxy-phthalic acids, 2-decyldiperoxybutane-1,4-dioic acid and N,N-terephthaloyldi(6-aminopercaproic acid).
Bleaches used in tablets for machine dishwashing may also be substances which release chlorine or bromine.
Suitable chlorine- or bromine-releasing materials include, for example, heterocyclic N-bromoamides and N-chloroamides, examples being trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and/or dichloroisocyanuric acid (DICA) and/or salts thereof with cations such as potassium and sodium.
Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin, are likewise suitable.
In order to achieve an improved bleaching action when washing or cleaning at temperatures of 60°C and below, it is possible to incorporate bleach activators. Bleach activators, which boost the action of the bleaches, are for example compounds containing one or more N-acyl and/or O-acyl groups, such as substances from the class of the anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetylethylene-diamine (TAED), tetraacetylmethylene-diamine (TAMD), and tetraacetylhexylenediamine (TAHD), and also pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxo hexahydro-1,3,5-triazine (DADHT), and isatoic anhydride (ISA) .
Bleach activators which may be used are compounds which under perhydrolysis conditions give rise to aliphatic peroxo carboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or substituted or unsubstituted perbenzoic acid. Suitable substances are those which carry 0-acyl and/or N-acyl groups of the stated number of carbon atoms, and/or substituted or unsubstituted benzoyl groups. Preference is given to polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexa-hydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acyl imides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydro-furan, N-methylmorpholiniumacetonitrile methyl sulfate (MMA), and the enol esters known from German Patent Applications DE 196 16 693 and DE 196 16 767, and also acetylated sorbitol and mannitol and/or mixtures thereof (SORMAN), acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetyl-fructose, tetraacetylxylose and octaacetyllactose, and acetylated, optionally N-alkylated glucamine and gluconolactone, and/or N-acylated lactams, for example, N-benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams are likewise used with preference. Combinations of conventional bleach activators may also be used.
In addition to the conventional bleach activators, or instead of them, it is also possible to incorporate what are known as bleaching catalysts. These substances are bleach-boosting transition metal salts or transition metal complexes such as, for example, Mn-, Fe-, Co-, Ru- or Mo-salen complexes or -carbonyl complexes. Other bleaching catalysts which can be used include Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands, and also Co-, Fe-, Cu- and Ru-ammine complexes.
Preference is given to the use of bleach activators from the group of polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acyl imides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), N-methylmorpholiniumacetonitrile methyl sulfate (MMA), preferably in amounts of up to 10~ by weight, in particular from 0.1~ by weight to 8~ by weight, more particularly from 2 to 8~ by weight, and with particular preference from 2 to 6~ by weight, based on the overall composition.
Bleach-boosting transition metal complexes, especially those with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and/or Ru, preferably selected from the group of manganese and/or cobalt salts and/or complexes, with particular preference from cobalt ammine complexes, cobalt acetato complexes, cobalt carbonyl complexes, the chlorides of cobalt or manganese, and manganese sulfate, are used in customary amounts, preferably in an amount of up to 5~ by weight, in particular from 0.0025 by weight to 1~ by weight, and with particular preference from 0.01 by weight to 0.25 by weight, based in each case on the overall composition. In specific cases, however, it is also possible to use a greater amount of bleach activator.
On account of their oxidizing action, it is advantageous to separate the bleaches from other ingredients, for which purpose processes of the invention for producing multiphase tablets are particularly suitable. Processes where one of the premixes for compression comprises bleaches while another premix comprises bleach activators are preferred.
It may also be advantageous to separate the bleaches from other ingredients. Processes for producing multiphase tablets where one of the premixes for compression comprises bleaches while another premix comprises enzymes are likewise preferred. Suitable enzymes in this context include in particular those from the classes of the hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases, and mixtures of said enzymes. In the laundry, all of these hydrolases contribute to removing stains, such as proteinaceous, fatty or starchy marks and instances of graying. Cellulases and other glycosyl hydrolases may additionally contribute, by removing pilling and microfibrils, to color retention and to enhancing the softness of the textile. For bleaching and/or to inhibit color transfer, it is also possible to use oxidoreductases. Especially suitable enzymatic active substances are those obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Coprinus cinereus and Humicola insolens, and also from genetically modified variants thereof. Preference is given to the _ 4~ _ use of proteases of the subtilisin type, and especially to proteases obtained from Bacillus lentus. Of particular interest in this context are enzyme mixtures, examples being those of protease and amylase or protease and lipase or lipolytic enzymes, or of protease and cellulase or of cellulase and lipase or lipolytic enzymes, or of protease, amylase and lipase or lipolytic enzymes, or protease, lipase or lipolytic enzymes and cellulase, but especially protease and/or lipase-containing mixtures or mixtures with lipolytic enzymes. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proven suitable in some cases. The suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases, and pectinases. Cellulases used are preferably cellobiohydrolases, endoglucanases and endoglucosidases, also known as cellobiases, and/or mixtures thereof. Since different cellulase types differ in their CMCase and Avicelase activities, the desired activities may be established by means of tailored mixtures of the cellulases.
In detergent tablets for machine dishwashing, of course, different enzymes are used in order to take account of the different substrates treated and the different types of stain. Suitable enzymes in this case include in particular those from the classes of the hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases, and mixtures of said enzymes. All of these hydrolases contribute to removing stains, such as proteinaceous, fatty or starchy marks. For bleaching, it is also possible to use oxidoreductases. Especially suitable enzymatic active substances are those obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Coprinus cinereus and Humicola insolens, and also from genetically modified variants thereof. Preference is given to the use of proteases of the subtilisin type, and especially to proteases obtained from Bacillus lentus. Of particular interest in this context are enzyme mixtures, examples being those 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 lipolytic enzymes. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proven suitable in some cases.
The suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases, and pectinases.
The enzymes may be adsorbed on carrier substances or embedded in coating substances in order to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules may be, for example, from about 0.1 to 5~ by weight, preferably from 0.5 to about 4.5~ by weight, based in each case on the premix (es) .
The premixes for compression may likewise have incorporated into them corrosion inhibitors for protecting the ware or the machine, with special importance in the field of machine dishwashing being possessed, in particular, by silver protectants. The known substances of the prior art may be used. In general it is possible to use, in particular, silver protectants selected from the group consisting of triazoles, benzotriazoles, bisbenzotriazoles, amino-triazoles, alkylaminotriazoles, and transition metal salts or transition metal complexes. Particular preference is given to the use of benzotriazole and/or alkylaminotriazole. Frequently encountered in cleaning formulations, furthermore, are agents containing active chlorine, which may significantly reduce corrosion of the silver surface. In chlorine-free cleaners, use is made in particular of oxygen-containing and nitrogen-containing organic redox-active compounds, such as divalent and trivalent phenols, e.g., hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol, and derivatives of these classes of compound. Inorganic compounds in the form of salts and complexes, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, also find frequent application. Preference is given in this context to the transition metal salts selected from the group consisting of manganese and/or cobalt salts and/or complexes, with particular preference being given to cobalt ammine complexes, cobalt acetato complexes, cobalt carbonyl complexes, the chlorides of cobalt or of manganese and manganese sulfate. Similarly, zinc compounds may be used to prevent corrosion on the ware.
Where corrosion inhibitors are used in multiphase tablets, it is preferred to separate them from the bleaches. Processes where one of the premixes for compression comprises bleaches while another premix comprises corrosion inhibitors are, accordingly, preferred.
Further ingredients which may be a constituent of one or more premixes in the context of the process of the invention are, for example, dyes, optical brighteners, fragrances, soil release compounds, soil repellants, antioxidants, fluorescers, foam inhibitors, silicone oils, liquid paraffins, color transfer inhibitors, graying inhibitors, detergency boosters, etc.
In order to enhance the esthetic appeal of the laundry detergent and cleaning product tablets of the invention, they may be colored, in whole or in part, with appropriate dyes. Preferred dyes, whose selection presents no difficulty whatsoever to the skilled worker, possess a high level of storage stability and insensitivity to the other ingredients of the compositions, and to light, and possess no pronounced affinity for the substrates treated, such as textile fibers or tableware pieces, for example, so as not to stain them.
Preference for use in laundry detergent tablets of the invention is given to all colorants which may be oxidatively destroyed in the washing process, and also mixtures thereof with appropriate blue dyes, known as bluing agents. It has proven advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples include anionic colorants, e.g., anionic nitroso dyes. One possible colorant is, for example, naphthol green (Colour Index (CI) Part l: Acid Green 1;

Part 2: 10020), which is obtainable as a c ommercial product, for example, as Basacid~ Green 970 from BASF, Ludwigshafen, and also mixtures thereof with suitable blue dyes. Further colorants employed are Pigmasol~

Blue 6900 (CI 74160), Pigmasol~ Green 8730 (CI
74260), Basonyl~ Red 545 FL (CI 45170), Sandolan~ Rhodamine EB400 (CI 45100), Basacid~ Yellow 094 (CI 47005), Sicovit~ Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acid Blue 183), Pigment Blue 15 (CI

74160), Supranol~ Blue GLW (CAS 12219-32-8, CI Acid Blue 221)), Nylosan~ Yellow N-7GL SGR (CAS 61 814-57-1, CI Acid Yellow 218) and/or Sandolari Blue (CI Acid Blue 182, CAS 12219-26-0).

In the context of the choice of colorant it must be ensured that the colorants do not have too great an affinity for the textile surfaces, and in particular for synthetic fibers. At the same time, it must also be borne in mind when choosing suitable colorants that colorants have differing stabilities to oxidation. The general rule is that water-insoluble colorants are more stable to oxidation than water-soluble colorants.
Depending on the solubility and thus on the oxidation sensitivity too, the concentration of the colorant in the laundry detergent or cleaning products varies. In the case of readily water-soluble colorants, e.g., the abovementioned Basacid~ Green or the likewise above-mentioned Sandolari Blue, colorant concentrations typically chosen are in the range of several 10-Z to 10-3% by weight. In the case of the pigment dyes, which are particularly preferred on account of their brightness but are less readily soluble in water - for example, the abovementioned Pigmasol~ dyes - the appropriate concentration of the colorant in the laundry detergent or cleaning products, in contrast, is typically from several 10-3 to 10-q% by weight .
The laundry detergent and cleaning product tablets produced by the process of the invention may comprise one or more optical brighteners. These substances, which are also called "whiteners", are used in modern laundry detergents because even freshly washed and bleached white laundry has a slight yellow cast.
Optical brighteners are organic dyes which convert a part of the invisible UV radiation of sunlight into longer-wave blue light. The emission of this blue light fills the "gap" in the light reflected by the textile, so that a textile treated with optical brightener appears whiter and lighter to the eye. Since the mechanism of action of brighteners necessitates that they go onto the fibers, a distinction is made in accordance with the fibers to be "dyed" between, for example, brighteners for cotton, nylon, or polyester fibers. The commercially customary brighteners suitable for incorporation into laundry detergents belong primarily to five structural groups: the stilbene group, the diphenylstilbene group, the coumarin-quinoline group, the diphenylpyrazoline group, and the group involving combination of benzoxazole or benzimidazole with conjugated systems. An overview of current brighteners can be found, for example, in G.
Jakobi, A. Lohr, ~Detergenta and Textile Washings, VCH-Verlag, Weinheim, 1987, pages 94 to 100. Examples of suitable brighteners are salts of 4,4'-bis[(4-anilino-6-morpholino-s-triazin-2-yl)amino]stilbene-2,2'-disul-fonic acid or compounds of similar structure which instead of the morphilino group carry a diethanolamino group, a methylamino group, an anilino group, or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyryl type may be present, examples being the alkali metal salts of 4,4'-bis(2-sulfostyryl)biphenyl, 4,4'-bis(4-chloro-3-sulfostyryl)-biphenyl, or 4-(4-chlorostyryl)-4'-(2-sulfo-styryl)biphenyl. Mixtures of the abovementioned brighteners may also be used.
Fragrances are added to the compositions of the invention in order to enhance the esthetic appeal of the products and to provide the consumer with not only the performance of the product but also a visually and sensorially "typical and unmistakeable" product. As perfume oils and/or fragrances it is possible to use individual odorant compounds, examples being the synthetic products of the ester, ether, aldehyde, ketone, alcohol, and hydrocarbon types. Odorant compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butyl-cyclohexyl acetate, linalyl acetate, dimethyl-benzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allyl cyclohexylpropionate, styrallyl propionate, and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals having 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal;
the ketones include, for example, the ionones, a,-isomethylionone and methyl cedryl ketone; the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol, and terpineol;
the hydrocarbons include primarily the terpenes such as limonene and pinene. Preference, however, is given to the use of mixtures of different odorants, which together produce an appealing fragrance note. Such perfume oils may also contain natural odorant mixtures, as obtainable from plant sources, examples being pine oil, citrus oil, jasmine oil, patchouli oil, rose oil or ylang-ylang oil. Likewise suitable are clary sage oil, camomile oil, clove oil, balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniperberry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, and also orange blossom oil, neroliol, orange peel oil, and sandalwood oil.
The fragrance content of the laundry detergent and cleaning product tablets prepared in accordance with the invention is usually up to 2~ by weight of the overall formulation. The fragrances may be incorporated directly into the compositions of the invention;
alternatively, it may be advantageous to apply the fragrances to carriers which intensify the adhesion of the perfume on the laundry and, by means of slower fragrance release, ensure long-lasting fragrance of the textiles. Materials which have become established as such carriers are, for example, cyclodextrins, it being possible in addition for the cyclodextrin-perfume complexes to be additionally coated with further auxiliaries.

In addition, the laundry detergent and cleaning product tablets may also comprise components which have a positive influence on the ease with which oil and grease are washed off from textiles (these components being known as soil repellants). This effect becomes particularly marked when a textile is soiled that has already been laundered previously a number of times with a detergent of the invention comprising this oil-and fat-dissolving component. The preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose having a methoxy group content of from 15 to 30% by weight and a hydroxypropyl group content of from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and also the prior art polymers of phthalic acid and/or terephthalic acid, and/or derivatives thereof, especially polymers of ethylene terephthalates and/or polyethylene glycol terephthalates or anionically and/or nonionically modified derivatives thereof. Of these, particular preference is given to the sulfonated derivatives of phthalic acid polymers and of terephthalic acid polymers.
Foam inhibitors which may be used in the compositions produced in accordance with the invention are suitably, for example, soaps, paraffins or silicone oils, which may if desired have been applied to carrier materials.
Graying inhibitors have the function of keeping the dirt detached from the fiber in suspension in the liquor and so preventing the redeposition of the dirt.
Suitable for this purpose are water-soluble colloids, usually organic in nature, examples being the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ethersulfonic acids of starch or of cellulose, or salts of acidic sulfuric esters of cellulose or of starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Furthermore, soluble starch preparations and starch products other than those mentioned above may be used, examples being degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone may also be used.
Preference, however, is given to the use of cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose, and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethyl-cellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the compositions.
Since sheetlike textile structures, especially those of filament rayon, viscose rayon, cotton and blends thereof, may tend to crease, because the individual fibers are susceptible to bending, buckling, compressing and pinching transverse to the fiber direction, the compositions produced in accordance with the invention may comprise synthetic crease control agents. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty acid alkylol esters, fatty acid alkylolamides, or fatty alcohols, which are usually reacted with ethylene oxide, or else products based on lecithin or on modified phosphoric esters.
In order to combat microorganisms, the compositions produced in accordance with the invention may comprise antimicrobial active substances. In this context a distinction is made, depending on antimicrobial spectrum and mechanism of action, between bacteriostats and bactericides, fungiostats and fungicides, etc.
Examples of important substances from these groups are benzalkonium chlorides, alkylarylsulfonates, halo-phenols, and phenylmercuric acetate, it also being possible to do without these compounds entirely.
In order to prevent unwanted changes to the compositions and/or the treated textiles as a result of oxygen exposure and other oxidative processes, the compositions may comprise antioxidants. This class of compound includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines, and also organic sulfides, polysulfides, dithiocarbamates, phosphates, and phosphonates.
Increased wear comfort may result from the additional use of antistats which are further added to the compositions produced in accordance with the invention.
Antistats increase the surface conductivity and thus enable better dissipation of charges that are formed.
External antistats are generally substances having at least one hydrophilic molecule ligand, and provide a more or less hygroscopic film on the surfaces. These antistats, which are usually surface-active, may be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric esters), and sulfur-containing (alkyl-sulfonates, alkyl sulfates) antistats. External antistats 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 antistats for textiles and as additives to laundry detergents, in which case, additionally, a hand effect is obtained.
In order to improve the water absorption capacity, the rewettability of the treated textiles, and to facilitate ironing of the treated textiles, silicone derivatives, for example, may be used in the compositions produced in accordance with the invention.

These derivatives additionally improve the rinse-out behavior of the compositions, by virtue of their foam inhibiting properties. Examples of preferred silicone derivatives are polydialkylsiloxanes or alkylaryl-siloxanes where the alkyl groups have one to five carbon atoms and are totally or partially fluorinated.
Preferred silicones are polydimethylsiloxanes, which may if desired have been derivatized and in that case are amino-functional or quaternized, or have Si-OH, Si-H and/or Si-C1 bonds. The viscosities of the preferred silicones at 25°C are in the range between 100 and 100,000 centistokes, it being possible to use the silicones in amounts of between 0.2 and 5~ by weight, based on the overall composition.
Finally, the compositions produced in accordance with the invention may also comprise W absorbers, which attach to the treated textiles and improve the light stability of the fibers. Compounds which have these desired properties are, for example, the compounds which are active via radiationless deactivation, and derivatives of benzophenone having substituents in positions) 2 and/or 4. Also suitable are substituted benzotriazoles, acrylates which are phenyl-substituted in position 3 (cinnamic acid derivatives), with or without cyano groups in position 2, salicylates, organic Ni complexes, and also natural substances such as umbelliferone and the endogenous urocanic acid.
In the case of all of the abovementioned ingredients, advantageous properties may result from separating them from other ingredients and/or compounding them together with certain other ingredients. In the case of multiphase tablets, the individual phases may also differ in the amount at which they contain the same ingredient, as a result of which advantages may be obtained. Processes wherein at least two of the premixes for compression comprise the same active substance in different amounts are preferred. The term "different amount" relates in this case, as already explained, not to the absolute amount of the ingredient in the phase but rather to the relative amount, based on the phase weight; in other words, it is a percentage by weight, based on the individual phase.
The present invention further provides for the use of tableting presses where at least one punch of a press-punch pair is rotated about its vertical axis during the tableting operation to produce laundry detergent and cleaning product tablets. In the case of use in accordance with the invention, all advantageous embodiments described earlier on above for the process of the invention are, mutatis mutandis, likewise preferred. In order to avoid redundancy, reference is made here to the details given above.
As process end products, the process of the invention provides laundry detergent and cleaning product tablets which possess a new and advantageous structure. These are laundry detergent and cleaning product tablets which, with a uniform composition, consist of a core and of a shell surrounding said core. Laundry detergent and cleaning product tablets of this kind have not been previously described in the prior art. The invention therefore further provides laundry detergent and cleaning product tablets comprising compacted, particulate laundry detergent and cleaning product, which comprise a core and a shell surrounding said core which have the same composition, the shell being harder than the core.
As a result of the formation of the shell in the process of the invention, the shell has a hardness greater than that possessed by the core it protects. At the same time the shell also has a greater density;
accordingly, the present invention likewise provides laundry detergent and cleaning product tablets comprising compacted, particulate laundry detergents and cleaning products, which comprise a core and a shell surrounding said core which have the same composition, the shell having a greater density than the core.
The principle in accordance with the invention of the enveloped tablet in which shell and core have the same composition but characteristically have different physical parameters may be applied not only to single-phase laundry detergent and cleaning product tablets.
If, for example, two-layer tablets are produced from two premixes differing in composition, the process of the invention produces two-layer laundry detergent and cleaning product tablets which have two different layers, pressed onto one another, and a shell surrounding them, the shell surrounding the first layer having the same composition as the first layer, and the shell surrounding the second layer having the same composition as the second layer. Together, these two shells produce the harder and/or denser shell which encases the tablet and gives it its advantageous properties.
The present invention therefore additionally provides multiphase laundry detergent and cleaning product tablets comprising compacted, particulate laundry detergent and cleaning product compositions, which comprise a multiphase core and a multiphase shell surrounding said multiphase core, the individual phases of which have the same composition as the phases whose surface they cover, the shell being harder than the core.

Entirely in analogy to the above remarks, the present invention additionally provides multiphase laundry detergent and cleaning product tablets comprising compacted, particulate laundry detergent and cleaning product compositions, which comprise a multiphase core and a multiphase shell surrounding said multiphase core, the individual phases of which have the same composition as the phases whose surface they cover, the shell having a greater density than the core.
With the laundry detergent and cleaning product tablets of the invention, as well, all of the advantageous embodiments described earlier on above for the process of the invention are, mutatis mutandis, likewise preferred. In order to avoid redundancy, reference is made here to the details above. Especially in respect of the ingredients, their proportions in the tablet as a whole, their distribution between individual phases, their proportions in the individual phases, etc., the comments made above apply analogously.
Since the impact and frictional stressing of laundry detergent and cleaning product tablets is particularly high on the bases, it is of advantage to protect these areas in particular against abrasion or fracture.
Laundry detergent and cleaning product tablets where the shell on the round sides of the tablet has a thickness of from 5 to 2000 ~.m, preferably from 10 to 1500 Vim, and in particular from 25 to 1000 Vim, are preferred in accordance with the invention. In particularly preferred laundry detergent and cleaning product tablets, the sizes specified also apply to the annular side face of the tablets.
Since the shell contributes to the stability of the tablet, the compression forces may be reduced further, which on the one hand improves the process economics (see above) and on the other hand also has a positive influence on the solubilities and disintegration times of the laundry detergent and cleaning product tablets.
Thus lower strengths may be accepted for the core enclosed in the shell, which would otherwise be too fragile and unacceptable. In the case of preferred laundry detergent and cleaning product tablets, the core has a diametral fracture strength of less than 30 kPa, preferably of less than 25 kPa, with particular preference of less than 20 kPa, and in particular of less than 15 kPa.
At the same time, the shell preferably has a high hardness which in accordance with the invention is always greater than the hardness of the core. In particularly preferred laundry detergent and cleaning product tablets the shell has a diametral fracture strength of more than 20 kPa, preferably of more than kPa, with particular preference of more than 30 kPa, 20 and in particular of more than 35 kPa.
It is. also possible to give details of preferred densities of shell and core, respectively. Laundry detergent and cleaning product tablets where the core 25 has a density of more than 600 g/1, preferably more than 750 g/1, and in particular more than 900 g/l, and laundry detergent and cleaning product tablets where the shell has a density of more than 1000 g/1, preferably of more than 1050 g/1, with particular preference of more than 1100 g/1 and in particular of more than 1150 g/1, are preferred in accordance with the invention.
Through an appropriate choice of the process parameters such as compressive force, compressing time, direction of rotation, speed of rotation, intensity of rotation, premix composition, compressing temperature, etc., the process of the invention is able to produce thicker or thinner sheaths as desired. In particularly preferred laundry detergent and cleaning product tablets, core and shell are in a weight ratio of from 250:1 to 1:1, preferably from 100:1 to 5:1, and in particular from 50:1 to 10:1.
Following production, the laundry detergent and cleaning product tablets of the invention may be packed, the use of certain packaging systems having proven particularly useful. A further aspect of the present invention is a combination of (a) laundry detergent and/or cleaning product tablets) of the invention and a packaging system containing the laundry detergent and/or cleaning product tablet(s), said packaging system having a moisture vapor transmission rate of from 0.1 g/mz/day to less than 20 g/m2/day if said packaging system is stored at 23°C and a relative equilibrium humidity of 85~.
The packaging system of the combination of laundry detergent and cleaning product tablets) and packaging system has, in accordance with the invention, a moisture vapor transmission rate of from 0.1 g/m2/day to less than 20 g/m2/day when said packaging system is stored at 23°C and a relative equilibrium humidity of 85~. These temperature and humidity conditions are the test conditions specified in DIN Standard 53122, which allows minimal deviations (23 t 1°C, 85 ~ 2~ relative humidity). The moisture vapor transmission rate of a given packaging system or material may be determined in accordance with further standard methods and is also described, for example, in ASTM Standard E-96-53T
("Test for measuring water vapor transmission of materials in sheet form") and in TAPPI Standard T464 m-45 ("Water vapor permeability of sheet materials at high temperature and humidity"). The measurement principle of common techniques is based on the water uptake of anhydrous calcium chloride which is stored in a container in the appropriate atmosphere, the container being closed at the top face with the material to be tested. From the surface area of the container closed with the material to be tested (permeation area), the weight gain of the calcium chloride, and the exposure time, the moisture vapor transmission rate may be calculated as follows:
~,R~ 24~I0000 _ x ~g~m~ ~24jr~
A ly where A is the area of the material to be tested in cm2, x is the weight gain of the calcium chloride in g, and y is the exposure time in h.
The relative equilibrium humidity, often referred to as "relative atmospheric humidity", is 85~ at 23°C when the moisture vapor transmission rate is measured in the context of the present invention. The ability of air to accommodate water vapor increases with temperature up to a particular maximum content, the so-called saturation content, and is specified in g/m3. For example, 1 m3 of air at 17° is saturated with 14.4 g of water vapor; at a temperature of 11°, saturation is rcarhar~ W;rr ;»~t 1o a of water vapor. The relative atmospheric humidity is the ratio, expressed as a percentage, of the actual water vapor content to the saturation content at the prevailing temperature. If, for example, air at 17° contains 12 g/m3 water vapor, then the relative atmospheric humidity (RH) -(12/14.4)~100 = 83~. If this air is cooled, then saturation (100 RH) is reached at what is known as the dew point (in the example: 14°), i.e., on further cooling a precipitate is formed in the form of mist (dew). The humidity is determined quantitatively using hygrometers and psychrometers.
The relative equilibrium humidity of 85% at 23°C can be established precisely, for example, in laboratory chambers with humidity control, to +/-2% RH depending on the type of apparatus. In addition, constant and well-defined relative atmospheric humidifies are formed in closed systems at a given temperature over saturated solutions of certain salts, these humidifies deriving from the phase equilibrium between water partial pressure, saturated solution, and sediment.
The combinations of the invention, comprising laundry detergent and cleaning product tablets and packaging system, may of course in turn be packaged in secondary packaging, examples being cardboard packaging systems or trays, there being no need to impose further requirements on the secondary packaging. The secondary packaging, accordingly, is possible but not necessary.
Packaging systems which are preferred in the context of the present invention have a moisture vapor transmission rate of from 0.5 g/m2/day to less than 15 g/mz/day.
Depending on the embodiment of the invention, the packaging system of the combination of the invention contains one or more laundry detergent and cleaning product tablets. In accordance with the invention it is preferred either to design a tablet such that it comprises one application unit of the laundry detergent and cleaning product, and to package this tablet individually, or to pack into one packaging unit the number of tablets which totals one application unit. In the case of an intended dose of 80 g of laundry detergent and cleaning product, therefore, it is possible in accordance with the invention to produce and package individually one laundry detergent and cleaning product tablet weighing 80 g, but in accordance with the invention it is also possible to package two laundry detergent and cleaning product tablets each weighing 40 g into one pack in order to arrive at a combination in accordance with the invention. This principle can of course be extended, so that, in accordance with the invention, combinations may also comprise three, four, five or even more laundry detergent and cleaning product tablets in one packaging unit. Of course, two or more tablets in a pack may have different compositions. In this way it is possible to separate certain components spatially from one another in order, for example, to avoid stability problems.
The packaging system of the combination of the invention may consist of a very wide variety of materials and may adopt any desired external forms. For reasons of economy and of greater ease of processing, however, preference is given to packaging systems in which the packaging material has a low weight, is easy to process, and is inexpensive. In combinations which are preferred in accordance with the invention, the packaging system consists of a bag or pouch of single-layer or laminated paper and/or polymer film.
The laundry detergent and cleaning product tablets may be filled unsorted, i.e., as a loose heap, into a pouch made of said materials. On esthetic grounds and for the purpose of sorting the combinations into secondary packaging, however, it is preferred to fill the laundry detergent and cleaning product tablets individually, or sorted into groups of two or more, into bags or pouches. For individual application units of the laundry detergent and cleaning product tablets which are located in a bag or pouch, a term which has become established in the art is that of the "flow pack". Flow packs of this kind may optionally then be packaged -preferably sorted in turn - into outer packaging, which underscores the compact form of the tablet.
The single-layer or laminated paper or polymer film bags or pouches preferred for use as packaging systems may be designed in a very wide variety of ways: for example, as inflated pouches without a center seam or as pouches with a center seam which are sealed by means of heat, adhesives, or adhesive tapes. Single-layer pouch and bag materials include the known papers, which may if appropriate be impregnated, and also polymer films, which may if appropriate be coextruded. Polymer films that can be used as a packaging system in the context of the present invention are specified, for example, in Hans Domininghaus, "Die Kunststoffe and ihre Eigenschaften", 3rd edition, VDI Verlag, Diisseldorf, 1988, page 193. Figure 111 shown therein also gives indications of the water vapor permeability of the materials mentioned.
Combinations which are particularly preferred in the context of the present invention comprise as packaging system a bag or pouch of single-layer or laminated polymer film having a thickness of from 10 to 200 Vim, preferably from 20 to 100 Vim, and in particular from 25 to 50 ~tm.
Although it is possible in addition to the abovementioned films and papers to use wax-coated papers in the form of cardboard packaging as a packaging system for the laundry detergent and cleaning product tablets, it is preferred in the context of the present invention for the packaging system not to comprise any cardboard boxes made of wax-coated paper.

In the context of the present invention, the term "packaging system" always relates to the primary packaging of the tablets, i.e., to the packaging whose inner face is in direct contact with the tablet surface. No requirements whatsoever are imposed on any optional secondary packaging, so that all customary materials and systems can be used in this case.
As already mentioned earlier on above, the laundry detergent and cleaning product tablets of the combination of the invention comprise further ingredients of laundry detergents and cleaning products, in varying amounts, depending on their intended use. Independently of the intended use of the tablets, it is preferred in accordance with the invention for the laundry detergent and cleaning product tablets) to have a relative equilibrium humidity of less than 30~ at 35°C.
The relative equilibrium humidity of the laundry detergent and cleaning product tablets may be determined in accordance with common methods, the following procedure having been chosen in the context of the present investigations: a water-impermeable 1 liter vessel with a lid which has a closable opening for the introduction of samples was filled with a total of 300 g of laundry detergent and cleaning product tablets and held at a constant 23°C for 24 h in order to ensure a uniform temperature of vessel and substance. The water vapor pressure in the space above the tablets can then be determined using a hygrometer (Hygrotest 6100, Testoterm Limited, UK). The water vapor pressure is then measured every 10 minutes until two succeeding values show no deviation (equilibrium humidity). The abovementioned hygrometer permits direct display of the recorded values in ~ relative humidity.

Likewise preferred are embodiments of the combination of the invention wherein the packaging system is of resealable configuration. Combinations wherein the packaging system has a microperforation may also be realized advantageously in accordance with the invention.
The present invention additionally provides a method of washing textiles in a domestic washing machine, which comprises placing one or more tablets of the invention in the dispenser drawer of the washing machine and running a wash program in the course of which the tablet or tablets is or are rinsed in.
The tablet or tablets need not, however, be metered via the dispenser drawer but instead may also be placed directly in the wash drum. In this case, firstly, a dosing aid - for example, a dosing net - may be used;
alternatively, the tablets may be placed directly on 20, the laundry in the drum without a dosing aid. The present invention therefore likewise provides a method of washing textiles in a domestic washing machine, which comprises placing one or more detergent tablets of the invention, with or without a dosing aid, in the wash drum of the washing machine and running a wash program in the course of which the tablet or tablets is or are dissolved.
As mentioned earlier on above, detergent tablets for machine dishwashing may also be produced by the process of the invention. Accordingly, the present invention additionally provides a method of cleaning tableware and kitchenware in a dishwashing machine, which comprises placing one or more detergent tablets of the invention in the dispensing cup of the dishwasher and running a wash program in the course of which the dispensing cup opens and the tablet or tablets is or are dissolved.
With the dishwashing method of the invention as well it is possible to do without the dosing cup and to place the tablet or tablets of the invention in, for example, the cutlery basket. Here again, of course, the use of a dosing aid, for example, a basket insert which is placed in the washing compartment, is possible without problems. Accordingly, the present invention further provides a method of cleaning tableware and kitchenware in a dishwashing machine, which comprises placing one or more detergent tablets of the invention, with or without a dosing aid, in the washing compartment of the dishwasher and running a wash program in the course of which the tablet or tablets is or are dissolved.
The invention may be varied in any number of ways as would be apparent to a person skilled in the art and all obvious equivalents and the like are meant to fall within the scope of this description and claims. The description is meant to serve as a guide to interpret the claims and not to limit them unnecessarily.

Claims

1. A process for producing laundry detergent and cleaning product tablets by compressing one or more particulate laundry detergent and cleaning product compositions in a tableting press, wherein at least one punch of a press-punch pair is rotated about its vertical axis during the tableting operation.

2. The process as claimed in claim 1, wherein both punches of a press-punch pair are each rotated about their vertical axis during the tableting operation.

3. The process as claimed in claim 2, wherein the punches are rotated in opposite directions.

4. The process as claimed in any of claims 1 to 3, wherein the rotation of the press punch(es) takes place following compression, in the ejection region of the tableting press.

5. The process as claimed in any of claims 1 to 3, wherein the rotation of the press punch(es) takes place in the filling and/or pressure region of the tableting press, preferably in the filling and pressure region.

6. The process as claimed in any of claims 1 to 5, wherein rotation of the press punch(es) is carried out at the precompression stage and at the main compression stage and, optionally, after the compression stage.

7. A process for producing multiphase laundry detergent and cleaning product tablets by compressing a plurality of particulate laundry detergent and cleaning product compositions in a tableting press, wherein at least one punch of a press-punch pair is rotated about its vertical axis during the tableting operation.

8. The process as claimed in claim 7, wherein both punches of a press-punch pair are each rotated about their vertical axis during the tableting operation.

9. The process as claimed in claim 8, wherein the punches are rotated in opposite directions.

10. The process as claimed in any of claims 7 to 9, wherein the rotation of the press punch(es) takes place following compression, in the ejection region of the tableting press.

11. The process as claimed in any of claims 7 to 10, wherein the rotation of the press punch(es) takes place in the filling and/or pressure region of the tableting press, preferably in the filling and pressure region.

12. The process as claimed in claim 11 wherein the rotation takes place in the filling and pressure region.

13. The process as claimed in any of claims 7 to 11, wherein rotation of the press punch(es) is carried out at the precompression stage of the first premix and at each further precompression stage of further premixes and at the main compression stage of the multiphase tablet and, optionally, after the compression stage.

14. The process as claimed in any of claims 7 to 13, wherein no intermediate compression takes place between the metering steps for the individual premixes.

15. The process as claimed in any of claims 7 to 14, wherein the phases have the form of layers.

16. The process as claimed in any of claims 1 to 15, wherein the press punch(es) is (are) rotated by from 0.1 to 90°, at each rotation.

17. The process as claimed in any of claims 1 to 16, wherein the press punch(es) is (are) rotated by from 0.25 to 45°, at each rotation.

18. The process as claimed in any of claims 1 to 17, wherein the press punch(es) is (are) rotated by from 0.5 to 20°, at each rotation.

19. The process as claimed in any of claims 1 to 18, wherein the rotation of the press punch(es) is carried out over a period of from 1 to 1000 ms.

20. The process as claimed in any of claims 1 to 19, wherein the rotation of the press punch(es) is carried out over a period of from 2 to 500 ms.

21. The process as claimed in any of claims 1 to 20, wherein the rotation of the press punch(es) is carried out over a period of from 5 to 100 ms.

22. The process as claimed in any of claims 1 to 21, wherein the pressing faces of the press punches have a peak-to-valley height of from 5 to 500 µm.

23. The process as claimed in any of claims 1 to 22, wherein the pressing faces of the press punches have a peak-to-valley height of from 10 to 250 µm.

24. The process as claimed in any of claims 1 to 23, wherein the pressing faces of the press punches have a peak-to-valley height of from 20 to 150 µm.

25. The process as claimed in any of claims 1 to 24, wherein compression is conducted at temperatures between 10 and 60°C.

26. The process as claimed in any of claims 1 to 25, wherein compression is conducted at temperatures between 15 and 50°C.

27. The process as claimed in any of claims 1 to 26, wherein compression is conducted at temperatures between 20 and 40°C.

28. The process as claimed in any of claims 1 to 27, wherein the particulate laundry detergent and cleaning product composition(s) has (have) a bulk density of at least 500 g/l.

29. The process as claimed in claim 28, wherein the bulk density is at least 600 g/l.

30. The process as claimed in claim 28, wherein the bulk density is at least 700 g/1.

31. The process as claimed in any of claims 1 to 30, wherein the particulate laundry detergent and cleaning product composition(s) has (have) particle sizes of between 100 and 2000 µm.

32. The process as claimed in claims 31, wherein the particle sizes are between 200 and 1800 µm.

33. The process as claimed in claim 31, wherein the particle sizes are between 400 and 1600 µm.

34. The process as claimed claim 31, wherein the particle sizes are between 600 and 1400 µm.

35. The process as claimed in any of claims 1 to 34, wherein the particulate laundry detergent and cleaning product composition(s) comprises/comprise less than 20% by weight of particles having a size below 200 µm.

36. The process as claimed in claim 35, wherein the particles having a size below 200 µm is less than 10% by weight.

37. The process as claimed in claim 35, wherein the particles having a size below 200 µm is less than 5% by weight.

38. The process as claimed in any of claims 1 to 37, wherein the particulate laundry detergent and cleaning product composition(s) comprises/comprise less than 20% by weight particles having a size above 1600 µm.

39. The process as claimed in claim 38, wherein the particles having a size above 1600 µm comprise less than 10% by weight.

40. The process as claimed in claim 38, wherein the particles having a size above 1600 µm comprise less than 5% by weight.

41. The process as claimed in any of claims 1 to 40, wherein the premix or at least one of the premixes for compression further comprises one or more types of surfactant-containing granules.

42. The process as claimed in claim 41, wherein the surfactant-containing granules comprise anionic and/or nonionic surfactants and also builders and have total surfactant contents of at least 10% by weight, based on the granules.

43. The process as claimed in claim 42, wherein the contents are at least 15% by weight.

44. The process as claimed in claim 42, wherein the contents are at least 20% by weight.

45. The process as claimed in any of claims 1 to 44, wherein the premix or at least one of the premixes for compression further comprises one or more substances from the group consisting of bleaches, bleach activators, disintegration aids, enzymes, pH standardizers, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors, and corrosion inhibitors.

46. The process as claimed in any of claims 1 to 45, wherein the premix or at least one of the premixes for compression comprises a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, based in each case on the premix.

47. The process as claimed in claim 46, wherein the amount is from 3 to 7% by weight.

48. The process as claimed in claim 46, wherein the amount is from 4 to 6% by weight.

49. The process as claimed in any of claims 7 to 48, wherein one of the premixes for compression comprises bleaches while another premix comprises bleach activators.

50. The process as claimed in any of claims 1 to 49, wherein one of the premixes for compression comprises bleaches while another premix comprises enzymes.

51. The process as claimed in any of claims 1 to 50, wherein one of the premixes for compression comprises bleaches while another premix comprises corrosion inhibitors.

52. The process as claimed in any of claims 1 to 51, wherein at least two of the premixes for compression comprise the same active substance in different amounts.

53. The use of tableting presses where at least one punch of a press-punch pair is rotated about its vertical axis during the tableting operation to produce laundry detergent and cleaning product tablets.

54. A laundry detergent or cleaning product tablet comprising compacted, particulate laundry detergent or cleaning product, which comprises a core and a shell surrounding said core which have the same composition, the shell being harder than the core.

55. A laundry detergent or cleaning product tablet comprising compacted, particulate laundry detergent or cleaning product, which comprises a core and a shell surrounding said core which have the same composition, the shell having a greater density than the core.

56. A multiphase laundry detergent or cleaning product tablet comprising compacted, particulate laundry detergent or cleaning product composition, which comprises a multiphase core and a multiphase shell surrounding said multiphase core, the individual phases of which have the same composition as the phases whose surface they cover, the shell being harder than the core.

57. A multiphase laundry detergent or cleaning product tablet comprising compacted, particulate laundry detergent or cleaning product composition, which comprises a multiphase core and a multiphase shell surrounding said multiphase core, the individual phases of which have the same composition as the phases whose surface they cover, the shell having a greater density than the core.

58. The laundry detergent or cleaning product tablet as claimed in any of claims 54 to 57, wherein the shell on the round sides of the tablet has a thickness of from 5 to 2000 µm.

59. The tablet as claimed in claim 58 having a thickness of from 5 to 200 µm.

60. The tablet as claimed in claim 58 having a thickness of from 25 to 1000 µm.

61. The laundry detergent or cleaning product tablet as claimed in any of claims 54 to 60, wherein the core has a diametral fracture strength of less than 30 kPa.

62. The tablet as claimed in claim 61, wherein the strength is less than 25 kPa.

63. The tablet as claimed in claim 61, wherein the strength is less than 20 kPa.

64. The tablet as claimed in claim 61, wherein the strength is less than 15 kPa.

65. The laundry detergent or cleaning product tablet as claimed in any of claims 54 to 64, wherein the shell has a diametral fracture strength of more than 20 kPa.

66. The tablet as claimed in claim 65, wherein the strength is less than 25 kPa.

67. The tablet as claimed in claim 65, wherein the strength is less than 30 kPa.

68. The tablet as claimed in claim 65, wherein the strength is less than 35 kPa.

69. The laundry detergent or cleaning product tablet as claimed in any of claims 54 to 68, wherein the core has a density of more than 600 g/l.

70. The tablet as claimed in claim 69, wherein the core has a density of more than 750 g/l.

71. The tablet as claimed in claim 69, wherein the core has a density of more than 900 g/l.

72. The laundry detergent or cleaning product tablet as claimed in any of claims 54 to 71, wherein the shell has a density of more than 1000 g/l, preferably of more than 1050 g/l.

73. The tablet as claimed in claim 72, wherein the density is more than 1100 g/l.

74. The tablet as claimed in claim 72, wherein the density is more than 1150 g/l.

75. The laundry detergent or cleaning product tablet as claimed in any of claims 54 to 74, wherein core and shell are in a weight ratio of from 250: 1 to 1:1.

76. The tablet as claimed in claim 75, wherein the weight ratio is from 100:1 to 5:1.

77. The tablet as claimed in claim 75, wherein the weight ratio is from 50:1 to 10:1.

78. The laundry detergent or cleaning product tablet as claimed in any of claims 54 to 78, wherein at least one tablet side is convexly curved.

79. The laundry detergent or cleaning product tablet as claimed in any of claims 54 to 78, wherein at least one tablet side is concavely curved.

80. The laundry detergent or cleaning product tablet as claimed in any of claims 54 to 79, wherein one tablet side is convexly curved and the opposite tablet side is concavely curved.

81. A method of washing textiles in a domestic washing machine, which comprises placing one or more detergent tablets as claimed in any of claims 54 to 80 in the dispenser drawer of the washing machine and running a wash program in the course of which the tablet or tablets is or are rinsed in.

82. A method of washing textiles in a domestic washing machine, which comprises placing one or more detergent tablets as claimed in any of claims 54 to 80, with or without a dosing aid, in the wash drum of the washing machine and running a wash program in the course of which the tablet or tablets is or are dissolved.

83. A method of cleaning tableware and kitchenware in a dishwashing machine, which comprises placing one or more detergent tablets as claimed in any of claims 54 to 80 in the dispensing cup of the dishwasher and running a wash program in the course of which the dispensing cup opens and the tablet or tablets is or are dissolved.

84. A method of cleaning tableware and kitchenware in a dishwashing machine, which comprises placing one or more detergent tablets as claimed in any of claims 54 to 80, with or without a dosing aid, in the washing compartment of the dishwasher and running a wash program in the course of which the tablet or tablets is or are dissolved.