DE19961367A1 - Preparation of multi-phase shaped detergent bodies, which can include regions of temperature/pressure-sensitive components, by pressing core shaped bodies and particulate premix - Google Patents

Abstract

New processes for preparation of multi-phase shaped detergent bodies are described. Independent claims are included for: (1) preparation of multi-phase shaped detergent bodies, comprising: (a) production of core shaped bodies which contain the active substance; (b) optional insertion of one or more of the core shaped bodies obtained in (a) into the mould of a tablet press; (c) introduction of at least one particulate premix into the tablet press mould; (d) addition of at least one core shaped body obtained in (a) into the tablet press mould; (e) optional single or multiple repetition of steps (c) and/or (d); and (f) compaction into shaped bodies. Steps (c) and (d) can be carried out in reverse order. In at least one of steps (b), (c), (d) or (f), the upper and/or lower plunger of the tablet press has a non-planar compacting surface; (2) preparation of multi-phase shaped detergent bodies, comprising: (a) production of core shaped bodies which contain the active substance; (b) optional insertion of one or more of the core shaped bodies obtained in (a) into the mould of a tablet press; (c) introduction of at least one particulate premix into the tablet press mould; (d) addition of at least one core shaped body obtained in (a) into the tablet press mould; (e) optional single or multiple repetition of steps (c) and/or (d); (f) compaction into shaped bodies which have at least one cavity; (g) insertion of one or more of the core shaped bodies obtained in (a) into the cavity of the tablet press; and (h) pressing of the core shaped body or bodies into the cavities.

Description

The present invention relates to a novel method for producing molded articles pern, especially of detergent tablets.

Detergent tablets are widely described in the prior art are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents have a number of powdered products Advantages: They are easier to dose and handle and because of their compact structure Advantages in storage and transport. There is therefore one extremely broad state of the art for detergent tablets, which itself is also reflected in an extensive patent literature. The Ent is there early developers of tablet-shaped products came across the idea differently set areas of the molded body certain ingredients only under defined conditions release in the wash or cleaning cycle to improve cleaning success ser. In addition to the core / shell Tablets and ring / core tablets, in particular multilayered molded articles, which are offered today for many areas of washing and cleaning or hygiene become. The optical differentiation of products is also becoming increasingly important tion, so that single-phase and single-color moldings in the field of washing and Cleansing was largely replaced by multi-phase moldings. Common in the market are currently two-layer molded articles with a white and a colored phase or with two differently colored layers. There are also point tablets, ring core tablets, coated tablets, etc., which currently have a rather minor meaning.  

Multi-phase cleaning tablets for the toilet are described, for example, in EP 055 100 (Jeyes Group). This document discloses blocks of toilet cleaners that a molded body from a slowly soluble detergent composition comprise, in which a bleach tablet is embedded. This document immediately reveals different forms of multi-phase moldings. The Her position of the molded body is done according to the teaching of this document either by insertion a compressed bleach tablet in a mold and pour this tablet into the Detergent composition, or by pouring some of the detergent composition into the mold, followed by inserting the pressed bleach Ablette and possibly subsequent pouring together with other cleaning agents settlement.

EP 481 547 (Unilever) also describes multi-phase detergent tablets which to be used for automatic dishwashing. These moldings have the Form of core / shell tablets and are obtained by gradually compressing the loading components manufactured: First, a bleaching agent composition is pressed to a shaped body which in a matrix half-filled with a polymer composition is inserted, which is then filled with further polymer composition and into one provided with a polymer jacket molded bleach is pressed. The procedure is then repeated with an alkaline detergent composition, so that there is a three-phase molded body.

Another way of producing optically differentiated detergents and cleaning agents Shaped body is in the international patent applications WO99 / 06522, WO99 / 27063 and WO99 / 27067 (Procter & Gamble). According to the teaching of these writings a molded body is provided which has a cavity with a solidifying Melt is filled. Alternatively, a powder is filled in and by means of a coating layer attached in the cavity. All three registrations have in common that the Kavi area to be filled should not be pressed, since pressure sensitive In contents should be spared.  

The way described in the prior art to prepare melts into the tablets are placed or which are poured into moldings, includes a thermal loading load of the ingredients in the melts. In addition, the exact dosage requires flu siger to pasty media as well as the subsequent cooling a high technical Effort that depends in part on the composition of the melt Shrinkage when cooling and the resulting detachment of the filling is made. The filling of cavities with powdery ingredients and the fixie Coating is also complex and has similar stability problems is liable. In addition, no specifically controlled different can be used in both methods Hardness of the individual molded body areas can be realized.

If pre-pressed core moldings are added to tablettable premixes, so the areas that lie above or below these cores are the compression process is more compressed, which can lead to delays in solubility. If the solubility of these overpressed areas due to an overall lower pressure to be compensated, there may be too little compression of the molded part che come, above or below which there are no core moldings, which is undesirable reduced handling stability leads.

The conventional tableting of multilayer tablets takes place in the field of Detergent tablets also have their limits if only one layer should have a small proportion of the total molded body. If you fall below a be if the layer thickness was correct, then there is pressing of one adhering to the rest of the molded body Layer increasingly difficult.

The production of kernel coat occasionally used in the pharmaceutical sector Tablets or so-called "Bulleye" tablets is used to manufacture large molded articles not easily adaptable, since problems with the placement of the cores occur. On core that is not inserted exactly in the center disturbs the visual impression of the molded body enormous. The requirements for the placement accuracy of cores therefore increase with the Area of the molded body exponentially.  

The pressing of particulate compositions into cavities of moldings solves the problem of the temperature load of these fillings, but on the other hand can a release delay of this pressed part lead to the addition of release attachment nigern required if there is an accelerated release of the ingredients from this region.

The present invention was based on the object of providing moldings in which both temperature and pressure sensitive ingredients in limited Re gions can be introduced, the demarcated region (s) with regard to their Size should not be limited in terms of the overall molded body. On the one hand, there should be an optical differentiation from conventional two layered tablets can be achieved, on the other hand, the production of the molded body without great technical effort also work safely in large series without the shape Disadvantages in terms of stability or inaccuracies in the dosage would be feared. The procedure to be provided should address the problem of Overpressing the areas that lie above or below inserted core moldings, mi minimize and additionally have the greatest possible flexibility. Especially the her provision of shaped bodies with faster and / or slower soluble areas at high optical differentiation from conventional tablets should be made possible.

It has now been found that the task set mentioned is solved if one before pressed molded body supplies a tablet press and this together with in the Matri ze pre-metered premixed to multiphase tablets, at least at a place in the tabletting machine with a non-flat surface the good to be tabletted.

The invention relates to a method for producing multiphase detergent tablets which comprises the steps

• a) production of core moldings which contain active substance,
• b) optional insertion of one or more core moldings from step a) into a dimension trize a tablet press,  
• c) filling at least one particulate premix into the matrix of the Ta tablet press,
• d) feeding at least one core molding from step a) into the die of the Ta tablet press,
• e) optional repetition of steps c) and / or d) one or more times,
• f) pressing into shaped bodies,

where steps c) and d) are carried out, if appropriate, in interchanged order which may include, wherein in at least one of process steps b), c), d) or f) the upper and / or lower punch of the tablet press has a non-planar pressing surface.

In the first step of the method according to the invention, a shaped body is produced which subsequently - together with a particulate premix - to a multi-phase tablet is pressed. The method according to the invention also allows several to be pressed Core moldings together with one or more particulate premixes, whereby both of the recipe variability as well as of the optical differentiation the resulting molded body creates almost unlimited possibilities.

The method according to the invention is described in more detail below. The term "core molded body "denotes a molded body in the context of the present invention by who can be supplied to the method according to the invention in a targeted manner. From Particle-shaped premix differs on the one hand by this core molding its greater spatial extent compared to the individual particles of the pre mischs and on the other hand in that its placement in the matrix of the tablet press not in an arbitrary manner (i.e. in bulk as the particulate premix), but takes place in a defined and orderly movement.

In the context of the present invention, the term “shaped base body” denotes all Areas of the process end products of the process according to the invention that are not core are molded, d. H. all Be obtained by pressing particulate premixes rich.  

The term "flat" pressing surface denotes surfaces that do not have a significant increase exercises and / or deepenings, with "significant" surveys in size order range up to 500 µm are to be understood. "Non-planar" pressing surfaces are there forth pressing surfaces from which (an) elevation (s) protrude / protrude or into which (a) Protrusion (s) protrude / protrude higher or lower than 500 µm.

For the purposes of the present invention, pressing surfaces are a circumferential elevation have, in order to produce the molded bodies a "chamfered" (beveled) edge lend, flat, since the pressure exerting surface is flat. The well-known use han Standard stamp inlays made of polymers such as Vulkollan®, which are applied to the pressing surfaces be glued, leaves the pressure-exerting surfaces flat, so that this type of stem pel equipment is also plan in the sense of the present invention.

A method according to claim 1, characterized in that the top and / or bottom pel the tablet press does not have a non-planar pressing surface during the entire process che has.

A method according to claim 2, characterized in that as an upper and / or lower stamp a stamp is used which consists of several independently of one another and in parallel is constructed on movable sub-stamps.

In this embodiment of the method according to the invention, each partial stamp is required of the lower and / or upper stamp, of course, a separate stamp path, so one mutually independent mobility of the partial stamp is guaranteed. The rest too parts used in conventional rotary presses for moving the one-piece Ensure stamps, such as pressure rollers and optional pull-down rails are within the scope of the preferred embodiment mentioned in two Executions required.

The division of the lower and / or upper stamp into two independently we Partial stamps can be made in different ways. For example wise conceivable, a square or round stamp in the first case through two half corners  or two triangles and in the latter case to be replaced by two semicircles. this leads to multi-phase tablets in which at least one end face has a dividing line has the optically by using differently colored premixes can be highlighted. The variety of design options are hardly any Set limits so that the above example can be extended to that the dividing line is not a straight line, but a more or less strong and frequent one curved curve. A wide variety of molded articles can be produced in this way.

As the complexity of the pressing surfaces of the two partial punches increases technical problems such as stamp caking, lids, excessive wear, etc. increase sharply, a method according to the invention is preferred in which the upper and / or lower stamp a stamp is used which consists of two independently and is constructed parallel to one another partial stamps, stamps preferred are composed of a central mandrel and a ring stamp surrounding this central mandrel consist.

Here too there are a variety of design options for ring stamps and Middle mandrel. So can with a square die and one adapted to this die Ring stamp with an angular outline of the end face (pressing surface) an angular or a round Middle mandrel are used, leading to different views of the surface of the produced tablets leads. Round or oval tablets with an angular shape are analogous or round insert can be produced. For the reasons mentioned above is a fiction moderate device preferred, in which the center mandrel is an elliptical, circular or has a rectangular face.

In this embodiment, the ring punch surrounding the center mandrel has one also circular hole in which the center mandrel can be freely moved up and down can. This geometry has no influence on the outer plan of the front face of the Die (and thus the ring stamp) - here are still all shape variants possible. However, circular matrices should also be used for aesthetic reasons to prefer. In this special embodiment, the ring stamp has a plan in the form of two concentric circles.  

The following explanations relate only to the preferred embodiment shape with ring stamp and center mandrel, but can be completely analogous to other partial stems transfer skin geometries. Terms such as "ring" and "core" could be replaced by "Left area" and "Right area" or analogs that are known to those skilled in the art.

It is of course also possible to use the press ram with several movable mandrels equip, so that a stamp, for example, from three partial stamps ("ring stamp" with two "holes" and two thorns), or from four partial stamps ("ring stamp" with three "Holes" and three thorns) can be built. With increasing division of the stem However, the requirements for the management of the individual partial stamps are always pel higher, so that, from a procedural point of view, stamps made up of two partial stamps are built, are preferred.

The design of the lower stamp as a ring stamp with a central mandrel can be exact Use centering of core moldings. Ideally, you fit the press surface of the Center mandrels to the base of the core moldings produced in step a). Becomes now the center mandrel of the lower die before carrying out process step b) lowered, the core molding can (with several lowerable center mandrels: the Dosed moldings) precisely. After filling with premix, the middle can mandrel of the lower stamp can be raised again so that the lower stamp is a plane Has pressing surface. Corresponding variants of the method according to the invention, at which the pressing surface of the lower punch in process step b) at least one cavity has are preferred.

In the final pressing, the lower die pressing surface is preferably flat, which is what following ejections relieved. Processes characterized in that the press area of the lower die in process step f) is a preferred embodiment men of the inventive method.

Not only is a premix metered into the matrix of the tablet machine, but also several, so after each filling shoe the surface can be smoothed by lightly pressing  ken with the upper stamp to make a clean phase boundary between the one individual phases composed of different premixes. Each According to the recipe and process design, this step can also be omitted, whereby to take into account that the adhesion between the individual layers is the better, depending the pressure load on the premix filled first is lower. Because of However, optics are preferred in which the particulate premix (s) after each process step c) is / are smoothed by lowering the upper punch.

The above-mentioned explanations for the lower stamp can also be analogously judge the upper stamp. Upper dies can also be used here, the pressing surface of which is at least at times has elevations and / or depressions, again the first described "mandrel stamp" can be used. In particular, in the case above described variant of "smoothing" the intermediate surfaces, methods are preferred, which are characterized in that the pressing surface of the upper punch when lowering has at least one survey.

Regardless of whether one or more premixes are filled and whether one Smoothing between the individual premix additions, methods are preferred, in which the pressing surface of the upper punch in process step f) is flat.

Are lower punches used, the pressing surface at least once in the invention If the process is not straightforward, conventional upper punches can be used result from processes which are characterized in that the pressing surface of the upper stamp is plan throughout the process.

Alternatively, upper punches can also be used in the method according to the invention, that have (an) elevation (s) on the press surface due to the design. In contrast no additional guide rails are required for the punches with a central mandrel Lich, because the "thorn" protrudes permanently from the stamp surface. Such variants of the The method according to the invention, in which the pressing surface of the upper punch during entire method has at least one survey are also preferred.  

The present invention therefore furthermore relates to processes for the production of multiphase detergent tablets, which have the following steps

• a) production of core moldings which contain active substance,
• b) optional insertion of one or more core moldings from step a) into a die a tablet press,
• c) Pouring at least one particulate premix into the tablet matrix tenpress,
• d) optional feeding of one or more core shaped body (s) from step a) into the die ze the tablet press,
• e) optional repetition of steps b) and / or c) one or more times,
• f) pressing to form bodies which have at least one cavity,
• g) feeding the core shaped body (s) from step a) into the cavity (s) of the tablet press,
• h) pressing the core mold body (s) into the cavity (s)

Marked are.

The fact that the upper stamp has at least one elevation, the end ver pressing obtained in step f) moldings which have at least one cavity. This The cavity (s) is / are subsequently filled with a core molding (s) which are in Step h) of the method according to the invention for achieving planar shaped body surfaces is pressed into the cavity (s).

Preferred methods according to the invention are characterized in that the ver pressing in step f) using an upper punch, the embossing element min at least has a pin surrounded by a flat base.

The term "embossing element", which is used in places below, is included synonymous with "press surface" and denotes the part of the press ram, which in Kon rhythm with the material to be tabletted.  

As already mentioned, the pressing forces are directed perpendicular to the flat base. There the flat base represents the lowest height in the profile of the embossing element, is in the given the lowest compression of the material to be pressed. This has the result that lower surface pressures can also be expected in the area of the base area are as in the area of the upwardly curved pin. For these reasons, the mate rial of the base area must not necessarily be incompressible, especially from the printing geometry only normal forces are to be expected. Accordingly, the seizure stamp can be made be designed that the elevation (s) consist of a hard material, while the Base area (i.e., the remaining part that comes into contact with the tabletting mixture the pressing surface from which the protrusion (s) protrudes with soft materials is coated to increase the surface quality of the resulting tablets. Ent speaking processes in which the base of the embossing element can be walked in the pressing operation and the pin or pins are coated incompressible and at least to reduce adhesion are preferred embodiments.

The structure of beds of powdery or fine crystalline substances is true to be considered uniform in relation to larger areas or volumes, in the microbe rich however quite different. Due to this in the micro range different Density ratios become those present on the surface of the base material uniform press forces different resistances of the material to be pressed opposite. This leads to the fact that on the micro-spaced sparks on the Surface different specific pressures and consequently with compressible mate rial of the base element slightly different deformations of the material occur. This phenomenon, referred to here as walking, has its origin from below different normal and transverse forces on the surface of the material, causing the Tendency for material to adhere to the surface of the embossing element in the region of the Base area is prevented or at least largely reduced.

A tabletting stamp, the embossing element of which is embodied in the form described, is shown in advantageously preventive of adhesion or at least reducing adhesion. With a sol Chen press tool can long tool life and flawless tablets areas can be reached.  

In one embodiment, in which the embossing element of the tabletting die is not on the side should be limited by the base area, and this by a substantially even gene, incompressible marginal strips, are repercussions of the compression ons and deformations on the inner wall of the die on the compressible base area excluded. An outward slope of the edge strip be this advantageously has a clean material distribution in the die and a Stabilization of the tablet structure.

Very special advantages in the production of the tabletting stamp and the stability of the pressing tool are guaranteed in an embodiment in which the stamping element ment consists of several individual parts. Expediently, scope and purpose cut the individual parts to the different materials or material requirements oriented. The individual production of the elipsoid-shaped pin is made of incompressible and on the outer surface at least adhesion-reducing coated material, ei nes plate-shaped element made of walkable material for the base and one annular element made of incompressible material for the edge strip an advantage strict demarcation for the design of the individual parts, which differ because of their different Offers materials.

As described above, the coating of the pin must be hard and resistant at the same time be able to withstand high wing loads, but also friction have reducing or lubricating properties. For this have nickel-containing waiters surface coatings proven to be very suitable, in which the finest PTFE particles (Teflon) are included. These give the coating anti-stick and material guzzling contraceptive properties. As an alternative, an embodiment for the Adhesion-reducing coating has proven itself in the case of the base coating material consists of a nickel-phosphorus alloy instead of nickel.

As a further alternative for surface coating with at least adhesion reducing effect, but also otherwise the requirements for hardness and durability a coating made of graphite containing diamond particles  lasts. The surface of the pin is coated with a graphite layer, which as lubricating or gliding are known, and here as binders to fixies tion of diamond particles, which in turn provide the surface with the required hardness lend. Experiments with these surface coatings of the journal have shown that No material build-up can be observed even when the tools are very long were. Thus, methods are preferred which are characterized in that the at least adhesion-reducing coating of the pin (s) made of Ni-P-PTFE or C- Diamond exists.

Problems can arise when pressing powder mixtures into shaped bodies men, because on the borderline between the semi-ellipsoid and the plastic insert Pul caking can occur. These caking led to flaking along of the trough edge, which is especially the case when pressing colored premixes Impact the appearance of the molded body. Are also with the previously mentioned Materials complicated pin geometries, such as lettering or other For to realize only with high technical effort.

Instead of an at least adhesion-reducing coating of the pin, the pin can can also be made entirely from low-adhesion materials. To do this Proven especially plastics. Another preferred embodiment of the present The present invention therefore provides that the spigot not only be reducing adhesion layers, but is made entirely of adhesion-reducing material. Especially tablet punches are preferred, the pins of which are made of plastic.

The term "plastics" characterizes in the context of the present invention Materials whose essential components consist of such macromolecular organic Compounds exist that are synthetic or by modifying natural products stand. They are in many cases under certain conditions (heat and pressure) meltable and malleable. In principle, plastics are organic polymers and can either according to their physical properties (thermoplastics, thermosets and elasto mere), according to the type of reaction in which they are produced (polymers, polycondensates and  Polyadducts) or according to their chemical nature (polyolefins, polyesters, polyamides, polyu rethane etc.) are classified.

The pin, in the preferred embodiments mentioned gefer made of plastic is done, provides a survey on the embossing within the scope of the present invention element of the tabletting die. The surface on which the pin is applied can also take different forms, with the flat, flat surface up to hemispherical configurations, a multitude of possibilities are conceivable is. In the context of the present invention, it is preferred, on the one hand, that the surface on that the cone sits, plan, d. H. is flat and on the other hand in all directions on the plane protrudes beyond the pin, d. H. that the pin sits on a surface as an elevation and nowhere directly touches the edge of the press tool or forms this edge. Before also the base on which the pin sits is made of plastic, so that tableting stamps are preferred, in which the pin and the flat base Plastic are made.

In the context of the present invention, it is particularly preferred if the mate rial of the pin is harder than that of the base. Methods according to the invention, in which the embossing elements of the upper punches a Zap surrounded by a flat base fen, wherein the base and the pin are made of plastics and the material of the pin is harder than that of the base, are therefore in accordance with the invention prefers.

In the context of the present invention, the term “hardness” is the designation for the resistance which a solid body opposes to the penetration of another body. For example, while the so-called scratch hardness (Mohs hardness) is measured for minerals, other methods of hardness testing have become established in technical terms. Brinell, Rockwell and Vickers processes (especially for steel and other metals) are used most frequently. To determine the Brinell hardness (HB, ball pressure hardness, DIN 50 351), standardized steel or Widia balls with a diameter of 10 mm and a test load P (expressed in N) are pushed into the substances to be tested and the surface O (in mm ² ) of the pressed dome of diameter d. The Bri nell hardness is then given by:

When determining the Rockwell hardness (HR), which is suitable for higher degrees of hardness, either a diamond cone (HRC) or steel balls of different diameters (HRB) are pressed into the material. A diamond pyramid with a surface opening angle of 136 ° is used to determine the Vickers hardness (HV); here too the hardness is defined as the load in relation to the impression surface (N / mm ² ). With this test method, the impressions are very small, so that the hardness can also be determined with very thin layers. This also applies analogously to the Knoop hardness (HK), for the determination of which a diamond pyramid with a rhombic outline is used. When determining the hardness of the impact, the diameter of a ball impression, which was generated by impact with a hand hammer (Poldihammer, scleroscope) or by a tensioned spring, serves as the basis for the calculation. Another, also dynamic, method for determining hardness is the spring-back method. The Shore hardness determined in this way is determined as the rebound hardness for steel by the ball drop test or measured for rubber and other elastomers as resistance to penetration against a truncated cone.

With harder plastics, e.g. B. for hard thermoplastics and especially thermosets, the ball indentation hardness is measured as the quotient of the test force and the surface of the impression a steel ball (5 mm diameter) after 10, 30 or 60 seconds under load.

Very special advantages in the production of the tabletting stamp and the stability of the pressing tool are guaranteed in an embodiment in which the stamping element ment consists of several individual parts. Expediently, scope and purpose cut the individual parts to the different materials or material requirements oriented. So is the one-off production of the elipsoid-shaped cone from the harder art fabric, a plate-shaped element made of the softer plastic, preferably one walkable material, for the base and a ring-shaped element made of incom  pressible material for the edge strips an advantageous delimitation for the design of the individual parts that are offered because of their different materials.

As described above, the pin is made of a harder plastic than that Floor space. Hard plastics in particular meet the requirement profile that the pin must be hard and resistant to high surface loads at the same time others must also have a friction-reducing or lubricating property.

Polyolefins, preferably polyethylene or polypropylene, have proven particularly useful as plastic materials for the journal. Polyethylenes (PE) are polyolefins belonging to polymers with groupings of the type

- [CH ₂ -CH ₂ ] -

as a characteristic basic unit of the polymer chain. Polyethylenes are made by Polyme The ethylene is produced using two fundamentally different methods, the high pressure and the low pressure process. The resulting products will be accordingly frequently referred to as high-pressure polyethylene or low-pressure polyethylene; they differ mainly in their degree of branching and thus ver bound in their degree of crystallinity and their density. Both methods can be used as Lö solution polymerization, emulsion polymerization or gas phase polymerization leads.

The high-pressure process produces branched polyethylenes with low density (approx. 0.915-0.935 g / cm ³ ) and degrees of crystallinity of approx. 40-50%, which are referred to as LDPE types. Products with a higher molecular weight and the resulting improved strength and stretchability are known as HMW-LDPE (HMW = high molecular weight). The pronounced degree of branching of the polyethylenes produced by the high-pressure process can be reduced by copolymerizing ethylene with longer-chain olefins, in particular with butene and octene; the copolymers have the symbol LLD-PE (linear low density polyethylene).

The macromolecules of the polyethylenes from low-pressure processes are largely linear and unbranched. These polyethylenes (HDPE) have degrees of crystallinity of 60-80% and a density of approx. 0.94-0.965 g / cm ³ . They are particularly suitable as cone materials.

Polypropylenes (PP) are thermoplastic polymers of propylene with basic units of the type

- [CH (CH ₃ ) -CH ₂ ] -

Polypropylenes can be obtained by stereospecific polymerization of propylene in the gas phase or in suspension to highly crystalline isotactic or less crystalline syndiotactic or to amorphous atactic polypropylenes. Tech The isotactic polypropylene, in which all methyl groups, is of particular importance are located on one side of the polymer chain. Polypropylene is characterized by high Hardness, resilience, rigidity and heat resistance and is within the present invention thus an ideal cone material.

The mechanical properties of polypropylenes can be improved by Reinforcement with talc, chalk, wood flour or glass fibers, and also the application metallic coatings are possible.

In addition to the polyolefins, polyamides are preferred in the context of the present invention usable cone materials. Polyamides are high molecular weight compounds that are made from building blocks linked by peptide bonds. The synthet. Polyamides (PA) are, with a few exceptions, thermoplastic, chain-like polymers with recurrence acid amide groups in the main chain. Leave after chemical build up the so-called homopolyamides are divided into two groups: the aminocarboxylic acid Types (AS) and the diamine dicarboxylic acid types (AA-SS); denote A amino Groups and S carboxy groups. The former are made from a building block by polycondensation sation (amino acid) or polymerization (ω-lactam), the latter consisting of two building blocks Polycondensation (diamine and dicarboxylic acid) are formed.  

The polyamides are encoded from unbranched aliphatic building blocks according to the An number of carbon atoms. For example, the designation PA 6 is that from ε- Aminocaproic acid or ε-caprolactam and polyamide. PA 12 is a poly (ε- laurin lactam) from ε-laurolactam. In the AA-SS type, the number of carbon is first of diamine and then that of dicarboxylic acid: PA 66 (polyhexamethylene adipina mid) arises from hexamethylenediamine (1,6-hexanediamine) and adipic acid, PA 610 (Po lyhexamethylene sebacinamide) from 1,6-hexanediamine and sebacic acid, PA 612 (polyhexa methylene dodecanamide) from 1,6-hexanediamine and dodecanedioic acid. The mentioned polya mid types are preferred materials for the scope of the present invention Cones.

Polyurethanes (PUR) are polymers (polyadducts) with groupings of the type that are accessible through polyaddition from dihydric and higher alcohols and isocyanates

- [CO-NH-R ² -NH-CO-OR ¹ -O] -

as characteristic basic units of the basic macromolecules, in which R ^{1 stands} for a low-molecular or polymeric diol residue and R ² for an aliphatic or aromatic group. Technically important PUR are made from polyester and / or polyether diols and, for example, from 2,4- or 2,6-toluenediisocyanate (TDI, R ² = C ₆ H ₃ - CH ₃ ), 4,4'-methylene di (phenyl isocyanate) (MDI, R ² = C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) or hexamethylene diisocyanate [HMDI, R ² = (CH ₂ ) ₆ ]. Tableting punches, the pin of which is made of a polyurethane, are also preferred according to the invention.

The plastics mentioned can be used alone as peg materials, they but can also with coatings or laminations made of metals or others Fabrics. Has proven particularly useful in the context of the present invention the use of glass-fiber reinforced plastics as peg material. Glass fiber reinforced Plastics (GRP) are composite materials made from a combination of a matrix Polymers and glass fibers acting as amplifiers. Use that for fiber reinforcement Glass materials are in the GRP as fibers, yarns, rovings (glass fiber strands), Fleeces, fabrics or mats. As polymeric matrix systems for GRP, you are both  plastics (such as epoxy resins, unsaturated polyester resins, phenol and furan resins), as well as thermoplastics (such as polyamides, polycarbonates, polyacetals, Polyphenylene oxides and sulfides, polypropylenes and styrene copolymers) are suitable. The Ge weight ratio between reinforcing material and polymer matrix is usually in the loading range from 10: 90-65: 35, the strength properties of the GRP usually up to an amplifier content of approx. 40% by weight.

The GRP is mainly manufactured in pressing processes; other important ferti hand lamination, fiber spraying, continuous impregnation, winding and Spin process. In many cases, so-called prepregs with resins are used impregnated fiberglass materials, made using heat under pressure be hardened. The GFK stand out compared to the non-reinforced matrix polymers through increased tensile, bending and compressive strength, impact strength, dimensional stability and Stability against the influence of heat, acids, salts, gases or solvents out. In the context of the present invention, glass fiber-reinforced materials in particular have become Proven polytetrafluoroethylene and glass fiber reinforced polyamides as cone materials.

As already mentioned above, an elevation from the surface of the spigot can not only can be realized by inserting a disc, but also by manufacturing a geometrically identical body made of one material. For such geometries plastics are particularly suitable, whereby polyamides have proven particularly useful.

The dimension of the pin can be the dimension of the molded body to be manufactured be fit so that the resulting cavity in the molded body compared to the molded body pervolume has suitable dimensions. For common shaped geometries and sizes it has proven to be advantageous if the cone has a volume of 0.5 to 5 ml before has from 0.6 to 3 ml and in particular from 0.8 to 2 ml. The volume of the Zap fens is to be understood as the volume that the pin as a trough in the molded body embossed. The term cone volume therefore denotes the volume of the "cone head ", where the" stem ", i.e. the elements that attach the elevation to the Ta serve as stamps, not counting. Appropriate procedures where the embossing element has a pin which has a volume of 0.5 to 5 ml, preferably 0.6  up to 3 ml, particularly preferably 0.8 to 2 ml, are preferred embodiments of the inventive method.

The pin or pins preferably protrude clearly from the base of the embossing element out. Methods according to the invention, which are characterized in that the embossing ment has one or more pins, each at least 1 mm, preferably protrude at least 2 mm and in particular at least 3 mm from the base, are preferred.

The liability-preventing or at least liability- or adhesion-reducing effect of the walkable material for base formation has been described above. As already mentioned, it is preferred that the base surface is reversibly deformed material with a hardness of 40 to 99 Shore A according to DIN 53 505. In Versu Chen has been shown that, for example, with the polyurethane material Vulkollan or the PVC material Mipolam very good results could be achieved. About commitment During several thousand pressings, there was no buildup on the base Chen material found.

The dimension of the base area is adapted to the dimension of the molded body to be produced, so that the base and top of the molded body have suitable dimensions compared to the molded body volume. For conventional molded body geometries and sizes, processes have proven to be advantageous in which the base area of the embossing element is 2.5 to 60 cm ² , preferably 5 to 40 cm ² , particularly preferably 7.5 to 20 cm ² .

As already mentioned, the pressing processes can be optimized if the tabletting punch is designed so that the footprint of an incompressible, essentially is evenly bordered. In preferred embodiments of the present ing invention this edge strip lies inside at the level of the base surface and is sloping towards the outside.  

It is used, for example, for the production of moldings for machine dishes preferably rinse that these have a rectangular shape to han in dosing chambers conventional machines can be introduced. Tableting stamp, the base of which che is substantially rectangular and preferably has rounded corners therefore preferred.

The above-mentioned preferred dimensions of base area and spigot can be realized in a stamp used for the manufacture of washing and cleaning medium shaped bodies. In the preferred tablet within the scope of the present invention tierstempel has the essentially rectangular base including border trim have the dimensions of approximately 36 × 26 mm and the ellipsoid of the surrounding one Tenon has approximately the semi-axis lengths of a = 8.3, b = 11.5 and c = 5 mm.

Of course, round detergent tablets with a stamps according to the invention are produced. Another important embodiment The present invention therefore provides that the tabletting stamp is thereby characterized is that the base is essentially round.

It has already been pointed out that very special advantages in the manufacture of the Tabletting stamp and the stability of the pressing tool in one embodiment are guaranteed, in which the embossing element consists of several individual parts, which too can be fixed together. Expediently, the scope and cut of the one parts based on the different materials or material requirements. How already made, the individual production of the elipsoid-shaped pin is in this way from incompressible and at least adhesion-reducing on the outer surface layered material or made of completely reduced-adhesion plastic, one plate shaped element made of walkable material for the base and an annular Element of incompressible material for the edge strip an advantageous border for the design of the individual parts, which differ due to their different materials offers.  

The shape of the pin protruding from the base can be chosen freely, whereby it has already been mentioned that this shape preferably corresponds to the shape of that in step a) provided core shaped body is aligned. Nevertheless, spherical sections, cones can be used here dies, ellipsoid sections, cuboids, prisms etc. can be realized as a peg geometry. In preferred methods, the outer surface of the pin (s) forms the base of the Embossing element an angle of 90 to 160 °, preferably from 90 ° to 140 ° and in particular special from 100 to 120 °.

It is also preferred if the “bottom” of the trough of the shaped bodies produced in step f) runs parallel to the underside of the tablet. Appropriate procedures, which are characterized by it are characterized in that the pressing surface of the pin (s) parallel to the base of the embossing runs, are advantageous.

As already mentioned, it is advantageous if the core molding (s) a) form in step g) are conclusively insertable into the cavity.

The pressing of the core molding (s) into the cavity is the last step of the method according to the invention, which is followed by the ejection of the molding from the die. The compression pressure when the core moldings are pressed in also depends on the composition of the base moldings and core moldings, but is usually below the compression pressures which are necessary for the compression in step f). Preferred processes are characterized in that the pressing in step h) is carried out at press pressures of 0.1 to 50 kNcm ^-2 , preferably 0.5 to 25 kNcm ^-2 and in particular 1 to 15 kNcm ^-2 .

Depending on the ingredients of the core molding and their desired type The mass of the core molding can vary in part of the overall molding. Here are The method according to the invention is preferred, in which the mass of the core molding a) is more than 0.5 g, preferably more than 1 g and in particular more than 2 g.

Regardless of the mass of the core molding, it is further preferred if it has a certain spatial extent, with methods according to the invention being preferred in which the core molding a) has a base area of at least 50 mm ² , preferably at least 100 mm ² and in particular at least 150 mm ² has.

In the case of core moldings which do not consist of two plane-parallel surfaces which are defined by a man are connected, the definition of a base area does not make sense. Here the end products of preferred method steps a) meet the condition, that the size of the horizontal cut surface satisfies the above values.

In general, core moldings with a point-symmetrical base are preferred, wherein Processes according to the invention are particularly preferred in which the core molding a) has a circular base.

Regardless of the shape of the core molding and regardless of the nature of its manufacturing process (see below), it is preferred if the core molding has a lower density than the entire process end product of the method according to the invention. In absolute values, processes are preferred in which the core molding has a density below 1.4 gcm ^-3 , preferably below 1.2 gcm ^-3 and in particular below 1.0 gcm ^-3 .

The process end product of the process according to the invention contains more than one Molded cores, the information given above preferably applies to all cores molded body individually, d. H. not for the sum of the core moldings, but for everyone individual.

The above information on the mass, geometry and density of the core moldings can also be made for the end products of the process according to the invention, ie the moldings themselves. Here, processes are preferred in which the mass of the entire detergent tablet is 10 to 100 g, preferably 15 to 80 g, particularly preferably 18 to 60 g and in particular 20 to 45 g, while the base area of the end products in preferred processes is chosen so that the detergent tablets have a base area of at least 500 mm ² , preferably of at least 750 mm ² and in particular of at least 1000 mm ² .

With regard to the density, methods according to the invention are preferred in which the entire molded body has a density above 1.1 gcm ^-3 , preferably above 1.2 gcm ^-3 and in particular above 1.4 gcm ^-3 .

It has proven to be advantageous if the premix which is invented in step c) According to the inventive method is filled into the die, certain physical criteria terie is enough. Preferred methods are characterized, for example, in that the Particulate premix in step c) a bulk density of at least 500 g / l before preferably has at least 600 g / l and in particular at least 700 g / l.

The particle size of the premix filled in step c) is also preferably sufficient certain criteria: methods in which the particulate premix in step c) Particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 μm, are preferred according to the invention. Another narrowed particle size in the premixes to be pressed can be used to obtain advantageous shaped bodies properties can be discontinued. In preferred variants for the Ver driving, the particulate premix filled in step c) has a particle size external distribution, in which less than 10% by weight, preferably less than 7.5% by weight and in particular less than 5% by weight of the particles larger than 1600 μm or smaller than Are 200 µm. Narrower particle size distributions are further preferred here. Especially Advantageous process variants are characterized in that the step c) added particulate premix has a particle size distribution in which more than 30% by weight, preferably more than 40% by weight and in particular more than 50 wt .-% of the particles have a particle size between 600 and 1000 microns.

When carrying out the method according to the invention, one is limited to the fact that just filled a particulate premix and later ver to a shaped body is pressed. Rather, process step c) can also be carried out several times in succession -  optionally interrupted by optional process steps d) - carry out so that one produces multilayered shaped bodies in a manner known per se by two or preparing several premixes which are pressed together. Here it can First pre-mixed, lightly pre-pressed to create a smooth and parallel to the Get molded bottom trending top, and after filling the second Premixed to the final molded article. With three or more layers Moldings can be precompressed after each addition of premix conditions before the molding is finally pressed after the addition of the last premix. Of course, in the context of the method according to the invention, it can also be completely an intermediate pressing can be dispensed with, so that only after filling in the last pre mixing or feeding the last core molding, the direct pressing takes place.

The end products of the process according to the invention can be prepared in advance certain spatial shape and predetermined size. Come as a spatial form practically all sensibly manageable configurations, for example the Training as a board, the shape of bars or bars, cubes, cuboids and the like Room elements with flat side surfaces and in particular a cylindrical shape with circular or oval cross-section. This last embodiment covers there in the form of presentation from tablets to compact cylinder pieces with one Ratio of height to diameter above 1.

The molded body produced can assume any geometric shape, in particular special concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahe drale, octahedral, conical, pyramidal, ellipsoid, five, seven and octagonal prismatic and rhombohedral shapes are preferred. Completely irregular too Base areas such as arrow or animal shapes, trees, clouds, etc. can be realized. If the molded article has corners and edges, these are preferably off rounded. As an additional optical differentiation, an embodiment is also blurred preferred corners and chamfered ("chamfered") edges.  

The end products of the process according to the invention are produced by tableting; this method can optionally be used for the production of the core molding. In general, methods of tableting according to the invention are preferred, which are characterized in that the compression in step a) and / or f) at pressures from 1 to 100 kNcm ^-2 , preferably from 1.5 to 50 kNcm ^-2 and in particular from 2 to 25 kNcm ^-2 .

During step f) of the process according to the invention, a mandatory process step is, d. H. the method according to the invention falls into the group of tableting methods the core moldings can also be produced by other processes known to the person skilled in the art. A preferred way to get core moldings is through the ingredients melt and pour into molds where they solidify. This preferred procedure ren, in which the core moldings are produced in step a) by casting always be advantageous to use where the ingredients of the core molding are fusible. Because additional fusible substances can be found with certain fusible substances Accelerating or decelerating effects, this is the manufacturing process ren preferred for the core moldings.

Where the use of meltable matrix substances from material or recipe Prohibited for reasons, sintering is another preferred method of manufacture the core molding. Appropriate processes in which the manufacture of the core mold body in step a) by sintering are also preferred.

If a thermal load on the ingredients of the core molding is avoided other manufacturing processes are recommended. Among these, the Ta bletting an important position, so that methods are preferred, which ge are characterized in that the production of the shaped core body in step a) by Tablettie tion takes place.

Further information on tableting for the production of core moldings in step a) of the inventive method are below in the detailed description of process step f).  

Another preferred production process for the core moldings a) is to provide this in the form of a capsule. Processes characterized by that the core molding is a capsule are also preferred embodiments of the present invention.

Regardless of the way in which the core moldings a) are produced certain substances common in washing or cleaning agents preferably in the core molded articles included. The method according to the invention is not based thereon limits that only one type of core moldings is used, all core moldings contain the same active substance in the same amounts.

Rather, according to the invention, several differently composed cores can also be used Shaped body in steps b) and d) inserted into the die of the tablet press the. Likewise, the placement of differently shaped core moldings is also problem-free possible. Also different core moldings, the same active substance in different Chen amounts (based on the core molding) can be in the fiction Manufacture and use the appropriate procedure.

A special feature occurs in the method according to the invention if only one core molded body is transferred into the die: In the order of the process steps a) -c) -d) -f), a tablet is obtained in which the core molding is at the top of the result Renden molded body is localized. It can be beneficial for certain reasons first transfer a core molding into the empty die and then pre-mix it replenish. This would correspond to a sequence of process steps a) -d) -c) -f), or in principle a method a) -b) -c) -f), in which step d) is dispensed with. Here but Step d) is not carried out optionally, but is mandatory, steps c) and d) of the method according to the invention, if appropriate, in reversed order leads. This results in a shaped body in which the core shaped body is on the lower side of the resulting molded body is localized.  

Regardless of whether only a core molding is transferred to the die or whether Two, three, four or more core moldings are supplied are certain active Substances preferably contained in the core molding (s). So are inventive Processes preferred in which the core molding a) contains surfactant (s) as an ingredient. These substances are described in detail below. Preferred levels of the core molding (s) of surfactant (s) are based on the individual core shape body - at 0.5 to 80% by weight, preferably at 1 to 70% by weight and in particular at 5 up to 60% by weight.

Also methods according to the invention, in which the core molding a) as ingredient En zym (e) contains are preferred according to the invention. These substances also become white described in detail below. Preferred contents of the core molding (s) in ten zym (s) are - based on the individual core moldings - from 0.01 to 50% by weight, preferably 0.1 to 25% by weight and in particular 1 to 15% by weight.

Processes which are characterized in that the core molding a) as an ingredient Bleach and / or bleach activator (s) are also preferred. The Ver Treads of these substance classes are described in detail below. Preferred The bleaching agent content of the core molding (s) is based on the individual Core moldings - at 0.5 to 100 wt .-%, preferably 1 to 90 wt .-% and esp especially at 5 to 80 wt .-%, while preferred levels of bleach activators in the Be range from 0.1 to 70% by weight, preferably from 0.5 to 50% by weight and in particular from 1 up to 25% by weight.

For reasons of acceleration of disengagement, the disintegration of the Accelerate core moldings. Therefore, methods are also preferred in which the Molded core a) as an ingredient disintegration aid and / or gas-forming system me contains. These substances are used in the detailed description of the ingredients described below. Preferred disintegrati contents of the core molding (s) on aids - based on the individual core moldings - 0.1 to 30 wt .-%, preferably 0.5 to 20% by weight and in particular 2.5 to 15% by weight, while Shower systems advantageously in amounts of 1 to 80% by weight, preferably 2.5 to  70 wt .-% and in particular from 5 to 60 wt .-% are used. Particularly preferred is the combination of shower systems with enzymes.

Processes according to the invention in which the core molding a) contains water as an ingredient hardens and / or complexing agents are also preferred. As a water softener for example, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetate (NTA) and related substances, but also ion exchangers and other complexing agents, as they are described in detail below, can be used with preference.

Following process step a), the core moldings can optionally be coated or be treated with encapsulants. Appropriate procedures in which after Production of the core moldings in step a) a coating and / or encapsulation the molded core is preferred.

Regardless of the manufacturing process for the core moldings, these can be taken for granted Lich also take any form, referring to the above statements becomes. A multi-phase configuration of the shaped core body is also in the sense of the present ing invention possible and preferred.

If the core moldings are produced by a casting process, they contain before preferably one or more meltable substance (s) with a melting point above of 30 ° C, preferred methods being characterized in that the in Step a) produced core moldings based on his / her weight at least 30% by weight, preferably at least 37.5% by weight and in particular at least 45% by weight contains meltable substance (s) with a melting point above 30 ° C.

Process in which the core molding (s) contains one or more substances with a Melting range between 30 and 100 ° C, preferably between 40 and 80 ° C and in particular especially between 50 and 75 ° C, contains / are included, are particularly preferred.

To these fusible substances, which in this process variant are in the core moldings are used, there are various requirements, on the one hand the enamel  or solidification behavior, but also the material properties the melt in the solidified state, d. H. in the core moldings. Because the core molded articles must be permanently protected against environmental influences during transport or storage if the fusible substance has a high stability compared to, for example, when Shock loads occurring during transport. So the meltable substance should either have at least partially elastic or at least plastic properties, in order to respond to a shock load caused by elastic or plastic deformation and not to break. The meltable substance should have a melting range (solid tion range) in such a temperature range in which other ingredients the core moldings are not exposed to excessive thermal stress. On the other hand However, the melting range must be sufficiently high to at least slightly increase Temperature still to provide effective protection for active substances used. Invention According to the meltable substances have a melting point above 30 ° C, Ver are preferred in which the core moldings only contain meltable substances Melting points above 40 ° C, preferably above 45 ° C and in particular included above 50 ° C. Particularly preferred core moldings contain as content substance c) one or more substances with a melting range between 30 and 100 ° C, before preferably between 40 and 80 ° C and in particular between 50 and 75 ° C.

It has proven to be advantageous if the meltable substance does not have a sharply defined one Melting point shows how it usually occurs with pure, crystalline substances, but may have a melting range spanning several degrees Celsius.

The meltable substance preferably has a melting range that is between approximately 52.5 ° C and about 80 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the Melting range. The width of the melting range is preferably at least 1 ° C. preferably about 2 to about 3 ° C.

The properties mentioned above are usually fulfilled by so-called waxes. "Waxing" is understood to mean a number of natural or artificially obtained substances, which usually melt above 50 ° C without decomposition and a little above the  Melting point are relatively low viscosity and not stringy. You assign one strongly temperature-dependent consistency and solubility.

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

Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, Rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walrus, lanolin (wool wax), or pretzel fat, Mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as Petrolatum, paraffin waxes or micro waxes.

The chemically modified waxes include hard waxes such as Montanester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes generally include polyalkylene waxes or Understand polyalkylene glycol waxes. Can also be used as a meltable substance Compounds from other classes of substances which meet the requirements mentioned with regard to the Meet softening point. Suitable synthetic compounds have been found for example higher esters of phthalic acid, especially dicyclohexyl phthalate, the is commercially available under the name Unimoll® 66 (Bayer AG). Suitable are also synthetically produced waxes from lower carboxylic acids and fatty alcohols, for example Dimyristyl Tartrate, which is sold under the name Cosmacol® ETLP (Condea) is available.

The meltable substance contained in the core moldings preferably contains a proportion of paraffin wax. That is, at least 10% by weight of the total contained fusible substances, preferably more, consist of paraffin wax. Especially Paraffin wax contents (based on the total amount of meltable Substance) of about 12.5% by weight, about 15% by weight or about 20% by weight, being even higher Fractions of, for example, more than 30% by weight can be particularly preferred. In a  particular embodiment of the invention, the total amount of used meltable substance exclusively from paraffin wax.

Paraffin waxes have a frame compared to the other natural waxes mentioned The present invention has the advantage that in an alkaline Detergent environment no hydrolysis of the waxes takes place (as for example is to be expected in the wax esters), since paraffin wax has no hydrolyzable groups contains.

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

Preferred processes are characterized in that the core molded body (s) have at least one contains / contain at least one paraffin wax with a melting range of 30 ° C to 65 ° C.

The content of the paraffin wax used is preferably at ambient temperature (usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes if possible high. The more solid wax components in a wax at room temperature, the more useful it is within the scope of the present invention. With increasing share of solid wax components increases the resilience of the core moldings to impacts or Rubbing on other surfaces, resulting in longer-lasting protection of the active ingredients leads. High levels of oils or liquid wax components can weaken them lead, whereby pores are opened and the active ingredients mentioned above Be exposed to environmental influences.  

In addition to paraffin, the meltable substance can also contain one or more of the abovementioned Contain waxes or wax-like substances. It should preferably be the fusible one Substance-forming mixture must be such that the core moldings at least are largely insoluble in water. The solubility in water should be at a temperature of about 30 ° C do not exceed about 10 mg / l and are preferably below 5 mg / l.

In any case, the material should preferably have the lowest possible water Solubility, even in water at elevated temperature, to have a temperature-independent release of the active substances as far as possible ver avoid.

The principle described above serves to delay the release of ingredients a certain time in the cleaning cycle and can be particularly advantageous use if in the main wash cycle at a lower temperature (e.g. 55 ° C) is rinsed, so that the active substance from the core moldings only in the final rinse cycle higher temperatures (approx. 70 ° C) is released.

However, the principle mentioned can also be reversed in that the active ingredient (s) released from the material, not released, but accelerated. This can be seen in easily achieved by the fact that, as fusible substances, but releasing accelerators are used so that the solidified melt is not slowly solves, but quickly. In contrast to the bad described above water-soluble dissolution retarders, preferred dissolution accelerators are readily water-soluble. The The solubility of the dissolving accelerator can be made even clear by certain additives be increased, for example by incorporating easily soluble salts or Shower systems. Such accelerated meltable substances (with or without additives of other solubility improvers) lead to a rapid release of the enclosed active substances at the beginning of the cleaning cycle.

As a release accelerator, i.e. fusible substances for the accelerated release of the Active substances from the core moldings are particularly suitable for the above mentioned synthetic waxes from the group of polyethylene glycols and polypropylene glycol  cole, so that preferred core moldings have at least one substance from the group of polyes contain ethylene glycols (PEG) and / or polypropylene glycols (PPG).

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

H- (O-CH ₂ -CH ₂ ) _n -OH (I)

are sufficient, where n can have values between 1 (ethylene glycol) and over 100,000. Decisive in evaluating whether a polyethylene glycol can be used according to the invention is the physical state of the PEG at, d. H. the melting point of the PEG must be above of 50 ° C, so that the monomer (ethylene glycol) and the lower oligomers with n = 2 to approx. 10 cannot be used because they have a melting point below 30 ° C point. The higher molecular weight polyethylene glycols are polymolecular, i.e. H. they be consist of collectives of macromolecules with different molecular weights. For Po There are various nomenclatures in polyethylene glycols that lead to confusion can. The specification of the average relative molecular weight in the Connection to the indication "PEG", so that "PEG 200" is a polyethylene glycol with a relati Characterized ven molecular weight from about 190 to about 210. According to this nomenclature Within the scope of the present invention, the technically customary polyethylene glycols PEG 1550, PEG 3000, PEG 4000 and PEG 6000 are preferred.

A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and a number follows the hyphen directly, which corresponds to the number n in the above formula I. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) according to the invention, for example, PEG-32, PEG-40, PEG-55, PEG 60, PEG-75, PEG-100, PEG-150 and PEG-180 can preferably be used according to the invention.

Polyethylene glycols are commercially available, for example, under the trade names Carbowax® PEG 540 (Union Carbide), Emkapol® 6000 (ICI Americas), Lipoxol® 3000  MED (HÜLS America), Polyglycol® E-3350 (Dow Chemical), Lutrol® E4000 (BASF) and the corresponding trade name with higher numbers.

Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the general formula II

are sufficient, where n values can be between 1 (propylene glycol) and approx. 1000. Similar Lich, as with the PEG described above, it comes to the assessment whether a poly propylene glycol can be used according to the invention on the physical state of the PPG, d. H. the melting point of the PPG must be above 30 ° C so that the monomer (propy lenglycol) and the lower oligomers with n = 2 to approx. 10 cannot be used since they have a melting point below 30 ° C.

In addition to the PEG and which can preferably be used as solution-accelerated meltable substances Of course, PPGs can also be used with other substances, provided that they are sufficiently high Have water solubility and have a melting point above 30 ° C.

The core moldings produced and used in the process according to the invention can NEN - in the production on the condition of the melt - preferably other active and / or auxiliaries from the groups of dyes, fragrances, anti-settling agents, sweat agents, anti-floating agents, thixotropic agents and dispersing agents in quantities from 0 to 10% by weight, preferably from 0.25 to 7.5% by weight, particularly preferably from 0.5 to 5 wt .-% and in particular from 0.75 to 2.5 wt .-%, contain. While color and fragrances as usual ingredients of detergents or cleaning agents below are described, the ingredients for the invention by casting Core moldings produced are specific, described below.  

At exceptionally low temperatures, for example at temperatures below 0 ° C, the core moldings could break under impact or friction. To stability at such low temperatures can improve the meltable substances optionally additives are added. Suitable additives must be completely with let the melted wax mix, d 99999 00070 552 001000280000000200012000285919988800040 0002019961367 00004 99880 Substances do not change significantly, the elasticity of the core molded body at depth Improve temperatures, the permeability of the core moldings to water or moisture in general and must not increase the viscosity of the melt increase to the extent that processing becomes difficult or even impossible. Suitable Additives that increase the brittleness of a material that is essentially paraffin Lowering at low temperatures are, for example, EVA copolymers, hydrogenated resin Acid methyl ester, polyethylene or copolymers of ethyl acrylate and 2-ethylhexyl acrylate.

It may also be advantageous to add further additives to the meltable substance, for example to prematurely separate the mixture in the state of the melt prevent. The anti-settling agents that can be used for this purpose, which are also known as floating agents are from the prior art, for example from the varnish and printing manufacturing, known. In order to transition from the plastic solidification area to the Solid sedimentation phenomena and concentration gradient of the substances ver avoid, there are, for example, surface-active substances, dis pergified waxes, montmorillonite, organically modified bentonite, (hydrogenated) castor oil oil derivatives, soy lecithin, ethyl cellulose, low molecular weight polyamides, metal stearates, cal cium soaps or hydrophobicized silicas. Other substances that have the effects mentioned cause come from the groups of anti-floating agents and thixotropic agents and can be used chemically as silicone oils (dimethylpolysiloxanes, methylphenylpolysiloxanes, Polyether-modified methylalkylpolysiloxanes), oligomeric titanates and silanes, polyami ne, salts of long-chain polyamines and polycarboxylic acids, amine / amide-functional Polyester or amine / amide-functional polyacrylates are referred to.

Additives from the classes of substances mentioned are commercially extremely diverse available. Commercial products that are advantageous in the context of the method according to the invention Aerosil® 200 (pyrogenic pebbles  acid, Degussa), Bentone® SD-1, SD-2, 34, 52 and 57 (Bentonite, Rheox), Bentone® SD-3, 27 and 38 (hectorite, Rheox), Tixogel® EZ 100 or VP-A (organically modified Smec tit, Südchemie), Tixogel® VG, VP and VZ (montmorillonite loaded with QAV, Südche mie), Disperbyk® 161 (block copolymer, Byk-Chemie), Borchigen® ND (sulfo-free er ion exchanger, Borchers), Ser-Ad® FA 601 (servo), brine (aromatic Ethoxylate, ICI), Surfynol® types (Air Products), Tamol® and Triton® types (Rohm & Haas), Texaphor®963, 3241 and 3250 (polymers, Henkel), Rilanit® types (Hen kel), Thixcin E and R (castor oil derivatives, Rheox), Thixatrol® ST and GST (castor oil Derivatives, Rheox), Thixatrol® SR, SR 100, TSR and TSR 100 (polyamide polymers, Rheox), Thixatrol® 289 (polyester polymer, Rheox) and the various M-P-A® Types X, 60-X, 1078-X, 2000-X and 60-MS (organic compounds, Rheox).

The tools mentioned can be in the core moldings depending on the material used and active substance can be used in varying amounts. Usual concentration of use tions for the aforementioned anti-settling, anti-floating, thioxotropic and Dispersants are in the range from 0.5 to 8.0% by weight, preferably between 1.0 and 5.0 wt .-%, and particularly preferably between 1.5 and 3.0 wt .-%, each based on the total amount of meltable substance and active substances.

Particularly preferred emulsifiers in the context of the present invention are polyglycerol esters, in particular esters of fatty acids with polyglycerols. These preferred polyglycerol esters can be described by the general formula III

in which R ¹ in each glycerol unit is independently H or a fatty acyl radical having 8 to 22 carbon atoms, preferably having 12 to 18 carbon atoms, and n is a number between 2 and 15, preferably between 3 and 10.

These polyglycerol esters are known in particular with degrees of polymerization n = 2, 3, 4, 6 and 10 and are commercially available. As materials of the type mentioned can also be found in cosmetic formulations widespread, some of these substances are classified in the INCI nomenclature (CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 199. This The standard cosmetic work contains, for example, information on the keywords POLYGLYCERYL-3-BEESWAX, POLYGLYCERYL-3-CETYL ETHER, POLYGLYCERYL-4-COCOATE, POLYGLYCERYL-10-DECALINOLEATE, POLY GLYCERYL-10-DECAOLEATE, POLYGLYLECYL -DIISOSTEARATE, POLYGLYCERYL-3-DIISOSTEARATE, POLY GLYCERYL-10-DIISOSTEARATE, POLYGLYCERYL-2-DIOLEATE, POLY GLYCERYL-3-DIOLEATE, POLYGLYCERYL-6-DIOLEATE, POLYGLYCERYLATE-10- DIOLEATE - DISTEARATE, POLYGLYCERYL-10-DISTEARATE, POLYGLYCERYL-10 HEPTAOLEATE, POLYGYLCERYL-12-HYDROXYSTEARATE, POLYGLYCERYL- 10-HEPTASTEARATE, POLYGLYCERYL-6-HEXAOLEARATE, POLYGLYCAREL LYGLYCERYL-4-ISOSTEARATE, POLYGLYCERYL-6-ISOSTEARATE, POLYGLYCERYL-10-LAURATE, POLY GLYCERYLMETHACRYLATE, POLYGLYCERYL-10-MYRISTATE, POLYGLYCERYL-2-OLEATE, POLYGLYLELEATE-3-POLYGLYLE , POLYGLYCERYL-8-OLEATE, POLYGLYCERYL-10-OLEATE, POLYGLYCERYL-6-PENTAOLEATE, POLYGLYCERYL-10-PENTAOLEATE, POLYGLYCERYL-6-PENTASTEARATE, POLYGLYCERYL-10-PENTASTEARATELATEQUATE LATE POLYGLYCERYL-2-STEARATE, POLYGLYCERYL-3-STEARATE, POLYGLYCERYL-4-STEARATE, POLYGLYCERYL-8-STEARATE, POLYGLYCERYL-10-STEARATE, POLY GLYCERYL-2-TETRAISOSTEARATE, POLYGLYETERYLYLETRY-10-TYPE -2-TRIISOSTEARATE, POLYGLYCERYL-10-TRIOLEATE, POLYGLYCERYL-6-TRISTEARATE. The commercially available products from different manufacturers, which are classified under the abovementioned keywords in the work mentioned, can advantageously be used as emulsifiers in process step b) according to the invention.

Another group of emulsifiers which can be used in the core moldings are substituted silicones which carry side chains reacted with ethylene or propylene oxide. Such polyoxyalkylene siloxanes can be described by the general formula IV

in which each radical R ¹ independently of one another for -CH ₃ or a polyoxyethylene or propylene group - [CH (R ² ) -CH ₂ -O] _x H group, R ² for H or -CH ₃ , x for one Number between 1 and 100, preferably between 2 and 20 and in particular less than 10, and n indicates the degree of polymerization of the silicone.

Optionally, the polyoxyalkylenesiloxanes mentioned can also be attached to the free OH groups of the Polyoxyethylene or polyoxypropylene side chains are etherified or esterified. The Unetherified and unesterified polymer from dimethylsiloxane with polyoxyethylene and / or In the INCI nomenclature, polyoxypropylene is called DIMETHICONE COPOLYOL designated and is under the trade names Abil® B (Goldschmidt), Alkasil® (Rhône- Poulenc), Silwet® (Union Carbide) or Belsil® DMC 6031 commercially available.

The DIMETHICONE COPOLYOL ACETATE esterified with acetic acid (for example Belsil® DMC 6032, -33 and -35, Wacker) and the DIMETHICONE COPOLYOL BUTYL ETHERS (e.g. KF352A, Shin Etsu) are also considered within the scope of the present invention Emulsifiers can be used.  

The same applies to emulsifiers as to meltable substances and the rest Ingredients that can be used over a wide range. Usually, emulsifiers of the type mentioned make up 1 to 25% by weight, preferably 2 to 20% by weight and in particular 5 to 10% by weight of the weight of the Detergent component.

As already mentioned above, the ingredients can be selected appropriately Core shaped bodies specifically vary the physical and chemical properties. Who for example, only ingredients used at the melting temperature of the Mixture are liquid, so it is easy to produce single-phase mixtures characterized by special storage stability even in the molten state. The addition of solids, such as color pigments or substances with higher enamel score, automatically leads to two-phase mixtures, but also one out excellent storage stability and an extremely low tendency to separate.

Regardless of the composition of the process according to the invention in step a) Rens produced core moldings are preferred such core moldings by a Melting point between 50 and 80 ° C, preferably between 52.5 and 75 ° C and esp are specially marked between 55 and 65 ° C.

The processing of the state of the melt in step a) is, however, according to the invention not the casting, d. H. pouring and solidifying into molds, bound. One can According to the invention, melts can also be converted into core moldings by melting ze processed by suitable methods to particulate material and these particles subsequently pressed into core moldings. Methods according to the invention, in which the Production of the core shaped body by converting a melt into particulate Material and subsequent pressing are therefore further preferred designs Forms of the present invention.

When using fusible substances as ingredients of the core moldings, parti cone-shaped preparations are prepared by methods known per se, which in  Within the scope of the present invention is preferred. The following are particularly useful Beating, pastilling or scaling.

The Ver preferably to be used according to the invention for the production of compressible particles driving, which is briefly referred to as prilling, involves the production of granular bodies meltable substances, with the melt from the respective ingredients at the top a tower is sprayed in a defined droplet size, freezes and freezes the prills at the bottom of the tower accumulate as granules.

In general, all gases can be used as the cold gas stream, the Temperature of the gas is below the melting temperature of the melt. Long time To avoid falling stretches, cooled gases are often used, for example with frozen air or even with liquid nitrogen that is injected into the spray towers.

The grain size of the resulting prills can be varied by the choice of droplet size particle sizes in the range from 0.5 to 2 mm, preferably around 1 mm.

A preferred process variant according to the invention therefore provides that for the production the core molded body a) a melt is pressed and subsequently pressed.

An alternative method of twisting is pastilling. Another embodiment The present invention therefore sees a method for producing a sub-step position of pelletized detergent components, in which you melt on dosed chilled pastilles.

Pastilling involves metering the melt from the respective ingredients a (cooled) belt or rotating, inclined plate that is below the temperature Have melting temperature of the melt and preferably below room temperature be cooled. Here too, process variants can be carried out in which the pastilles are frozen. However, measures must be taken to prevent this condensing be hit by humidity.  

The pastillation provides larger particles, the sizes between technically common processes rule 2 and 10 mm, preferably between 3 and 6 mm.

Another preferred method variant is therefore characterized in that Production of the core moldings a) pastillized a melt and subsequently pressed becomes.

As an even more economical variant for the production of particulate cleaning agents components of the above-mentioned composition from melts can be used Cooling rollers. Another sub-step of the present invention is therefore a method for the production of particulate detergent components, in which one Applying or spraying the melt onto a chill roll, scraping off the solidified melt and crushed if necessary. The use of chill rolls enables a problem-free Setting the desired particle size range, which is also un can be below 1 mm, for example 200 to 700 µm.

The latter process step, which is characterized in that for the production the core molding a) a melt is shed and subsequently pressed, is flat if part of a preferred process variant.

The procedural detour of the production of prills, pastilles or flakes and the subsequent pressing to form shaped bodies can be used in a targeted manner to achieve the To control the decay characteristics of the core moldings and thereby the controlled release set to achieve an increase in ingredients.

In the case of core moldings which are produced in the manner mentioned, targeted Air inclusions are provided, whereby the grain structure of the finished core molding is loosened and this when the temperature rises in the washing or cleaning cycle better disintegrates into its components. Another preferred method according to the invention therefore provides that core moldings a) are made with air pockets, which  at most 0.8 times, preferably at most 0.75 times and in particular at most have 0.7 times the mass of a melting body with the same volume and formulation.

Through the production of particles from the melt and the subsequent pressing are obtained in this way, which are characterized by a lower density to draw. The incorporation of air pockets is procedural, for example controllable by the choice of grain size and particle size distribution. So it happened shown that premixes with low pourability and low bulk density be can preferably be pressed into "air-rich" core moldings. This can still be too are additionally reinforced by the fact that the prills, pastilles or flakes to be pressed have the narrowest possible, preferably monomodal, particle size distribution. Par Articles that are not spherical are particularly preferred in this process variant to be pressed into "airy" core moldings.

Another embodiment of the present invention provides that the core shape body is only delayed, which is why the disintegration of the core molded body in its Components should be avoided if possible. There are procedures for this are characterized in that core moldings a) are produced without significant air inclusions which are at least 0.8 times, preferably at least 0.85 times and in particular at least 0.9 times the mass of an identical volume and recipe Have melting body, preferred.

Such moldings can also be converted into particles and by melting produce subsequent pressing. It is preferred here if the material to be pressed Particle mixture has the highest possible bulk density and good flow properties. Uniform particle shapes (ideally spherical) and wide particle size distribution lungs are preferred for the production of poorly soluble core moldings.

Preferred core moldings have a content of meltable substances. The composition of particularly preferred core moldings can be described in more detail. In particularly preferred methods according to the invention, at least one core molding a) has the following composition

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above from 30 ° C,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries.

Alternatively, particularly preferred processes are also characterized in that at least one shaped core body a) has the following composition:

• A) 10 to 90% by weight of surfactant (s),
• B) 10 to 90% by weight of fat (s),
• C) 0 to 70 wt .-% meltable substance (s) with a melting point above from 30 ° C,
• D) 0 to 15% by weight of further active ingredients and / or auxiliaries.

These quantity ranges can also be further expanded for extremely preferred core moldings enclose. In particular, methods are preferred in which the shaped core body a) as ingredient i) or I) 15 to 80, preferably 20 to 70, particularly preferably 25 to 60 and in particular contains 30 to 50% by weight of surfactant (s).

Also processes in which the core molding a) as ingredient ii) or III) 15 to 85, preferably 20 to 80, particularly preferably 25 to 75 and in particular 30 to 70% by weight contains fusible substance (s) are preferred process variants.

Last but not least, methods are also preferred in which the core molding a) has the content Substance iii) in amounts of 0.15 to 12.5, preferably 0.2 to 10, particularly preferably contains from 0.25 to 7.5 and in particular from 0.3 to 5% by weight.

Active substances contained in the core molding particularly preferably originate from the Group of surfactants. Preferred detergent tablets contain white then one or more surfactant (s). Anionic, nonionic, cationic and / or amphoteric surfactants or mixtures thereof are used. Mixtures are preferred for detergent tablets from an application point of view  made of anionic and non-ionic surfactants and non-ionic for detergent tablets tensides. The total surfactant content of the moldings (based on the end of the process product of the method according to the invention) is 5 in the case of detergent tablets up to 60% by weight, based on the weight of the shaped body, surfactant contents above 15% by weight are preferred, while detergent tablets for automatic dishwashing preferably contain less than 5% by weight of surfactant (s).

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C _12-18 monoolefins having a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids is suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under fatty acid glyce The mono-, di- and triesters as well as their mixtures are to be understood as Rinestern, as in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Before pulled sulfated fatty acid glycerol esters are the sulfonation products of saturated fat acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Ca. pric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

The alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ -Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

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

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

Soaps are particularly suitable as further anionic surfactants. Are suitable 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 from natural Fatty acids, e.g. B. coconut, palm kernel or tallow fatty acids, derived soap mixtures.  

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

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol residue is linear or preferably in the 2-position May be methyl branched or may contain linear and methyl branched radicals in the mixture, as are usually present in oxoalko radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Another class of preferred nonionic surfactants, which are used either as allei some nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and pro poxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester.

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

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

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

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

in the R for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ¹ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ² for a linear, branched or cyclic alkyl radical or is an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy substituted compounds can then be reacted with fatty acid methyl esters in the presence of an alkoxide as catalyst in the desired Polyhydroxy fatty acid amides are transferred.

In the context of the present invention, methods are preferred in which the core molded body a) as ingredient i) or I) anionic (s) and / or nonionic (s) surfactant (s), preferably non-ionic surfactant (s), with application technology advantages from certain proportions in which the individual surfactant classes are used will result.

Methods according to the invention in which the core or cores are particularly preferred Moldings contain a nonionic surfactant that has a melting point above room temperature. Accordingly, preferred methods are characterized in that the core molding a) as ingredient i) or I) nonionic surfactant (s) with a Melting point above 20 ° C, preferably above 25 ° C, particularly preferred between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, contains.

Suitable nonionic surfactants, the melting or softening points in the above Temperature range are, for example, low-foaming nonionic ten side, which can be solid or highly viscous at room temperature. Will be at room temperature  rature highly viscous nonionic surfactants used, it is preferred that these have a viscosity above half of 20 Pa.s, preferably above 35 Pa.s and in particular above 40 Pa.s exhibit. Also non-ionic surfactants, which have a waxy consistency at room temperature, are preferred.

Preferred nonionic surfactants to be used as solid at room temperature originate from the group pen of the alkoxylated nonionic surfactants, especially the ethoxylated primary alcohols and Mixtures of these surfactants with structurally more complex surfactants such as Po lyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, this is nonionic Surfactants with a melting point above room temperature an ethoxylated nonionic surfactant, that from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 C- Atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has gone.

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

Accordingly, particularly preferred methods according to the invention are characterized in that the core molded body a) as ingredient i) or I) ethoxylated nonionic surfactant (s), the / the C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 - fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Such PO units preferably make up to 25% by weight, in particular  more preferably up to 20% by weight and in particular up to 15% by weight of the total moles mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene Have polyoxypropylene block copolymer units. The alcohol or alkylphenol part such nonionic surfactant molecules preferably make up more than 30% by weight, especially be preferably more than 50% by weight and in particular more than 70% by weight of the total molma such nonionic surfactants. Preferred methods are characterized in that the Core moldings a) as ingredient i) or I) ethoxylated and propoxylated nonionic surfactants contain, in which the propylene oxide units in the molecule up to 25 wt .-%, preferred up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nich make up ionic surfactant.

Other nonionic surfactants to be used with particular preference with melting points above Room temperature contain 40 to 70% of a polyoxypropy len / polyoxyethylene / polyoxypropylene block polymer blends, the 75 wt .-% of a vice returned block copolymers of polyoxyethylene and polyoxypropylene with 17 moles of ethyl lenoxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of Po lyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles Ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.

Nonionic surfactants, which can be used with particular preference, are from for example under the name Poly Tergent® SLF-18 from Olin Chemicals true.

A further preferred method according to the invention is characterized in that the core molding a) as ingredient i) or I) nonionic surfactants of the formula

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

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

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

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

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

As described above, each R ³ in the above formula can be different if x ≧ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, when x is 3, the R ³ group can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which can be joined together in any order, for example (EO ) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO ) (PO) (PO). The value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa.

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

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

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particular preference is given to surfactants in which the radicals R ¹ and R ^{2 have} 9 to 14 C atoms, R ³ stands for H and x assumes values from 6 to 15.

If the last-mentioned statements are summarized, processes according to the invention are preferred in which the core shaped body a) as ingredient i) or I) end-capped poly (oxyalkylated) nonionic surfactants of the formula

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

contains in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl , n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type

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

in which x for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18 stands, are particularly preferred.

In the process according to the invention, the core moldings a) can contain further ingredients hold, with methods are preferred in which the core molding a) as an ingredient II) 12.5 to 85, preferably 15 to 80, particularly preferably 17.5 to 75 and in particular Contains 20 to 70 wt .-% fatty substances.  

In the context of this application, fatty substances are used at normal temperature (20 ° C) liquid to solid substances from the group of fatty alcohols, fatty acids and fatty acids derivatives, especially the fatty acid esters, understood. Implementation products from Fettalko fetching with alkylene oxides as well as the salts of fatty acids count within the scope of the present registration for surfactants (see above) and are not fatty substances in the sense of the Er finding. According to the invention, preferred fatty substances are fatty alcohols and fatty alcohols Hol mixtures, fatty acids and fatty acid mixtures, fatty acid esters with alkanols or diols or use polyols, fatty acid amides, fatty amines etc.

Preferred methods are characterized in that the core molding a) as Ingredient II) one or more substances from the groups of fatty alcohols, the fatty acids and contains the fatty acid ester.

Examples of fatty alcohols are the alcohols 1-hexanol (capro alcohol), 1-heptanol (enant alcohol), 1-octanol (capryl alcohol), 1-nonanol (pelargon alcohol), 1-decanol (capric alcohol), 1, which are accessible from native fats and oils -Undecanol, 10-undecen- 1-ol, 1-dodecanol (lauryl alcohol), 1-tridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (cetyl alcohol), 1-heptadecanol, 1-octadecanol (stearyl alcohol) ), 9-cis-octadecen-1-ol (oleyl alcohol), 9-trans-octadecen-1-ol (erucyl alcohol), 9-cis-octadecen-1,12-diol (ricinol alcohol), all-cis-9.12 -Octadecadien-1-ol (linoleyl alcohol), all-cis-9,12,15-octadecatrien-1-ol (linolenyl alcohol), 1-nonadecanol, 1-eicosanol (arachidyl alcohol), 9-cis-eicosen-1-ol (Gadoleyl alcohol), 5,8,11,14-eicosatetraen-1-ol, 1-heneicosanol, 1-docosanol (behenyl alcohol), 1-3-cis-docosen-1-ol (erucyl alcohol), 1-3- trans- Docosen-1-ol (brassidyl alcohol) and mixtures of these alcohols are used. According to the invention, Guerbet alcohols and oxo alcohols, for example C _13-15 oxo alcohols or mixtures of C _12-18 alcohols with C _12-14 alcohols, can also be used without difficulty as fatty substances. However, alcohol mixtures can of course also be used, for example those such as the C _16-18 alcohols prepared by Ziegler ethylene polymerization. Specific examples of alcohols which can be used as component b) are the above-mentioned alcohols and lauryl alcohol, pal mityl and stearyl alcohol and mixtures thereof.

In particularly preferred processes according to the invention, the core molding a) contains, as ingredient II), one or more C _10-30 fatty alcohols, preferably C _12-24 fatty alcohols, with particular preference for 1-hexadecanol, 1-octadecanol, 9-cis-octadecen-1 -ol, all-cis-9,12-octadecadien-1-ol, all-cis-9,12,15-octadecatrien-1-ol, 1-docosanol and mixtures thereof.

Fatty acids can also be used as fatty substances. Technically, most of these are obtained from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps), today only water is used on an industrial scale that splits the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage. Carboxylic acids which can be used as fatty substances in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid etc. The use of is preferred in the context of the present compound Fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetra cosanoic acid (lignoceric acid), hexacosanoic acid (tricotonic acid) and melissinic acid (cerotic acid) the unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidinic acid), 9c, 12c-octadectanoic acid, 9c Octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c octadecatreic acid (linolenic acid re). Of course, tridecanoic acid, pentadecanoic acid, margaric acid, nonadecanoic acid, erucic acid, elaeostearic acid and arachidonic acid can also be used. For reasons of cost, it is preferred not to use the pure species, but rather technical mixtures of the individual acids, as are accessible from fat cleavage. Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% _C14, 10 wt .-% C _16, 2 wt .-% _C18, 8 wt .-% _{C18 ',} 1 wt .-% C _18'), palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt .-% C _12, 15 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 15 wt .-% _{C18 ',} 1 wt .-% C _{18 "),} tallow fatty acid (ca. 3 wt% C ₁₄ , 26 wt% C ₁₆ , 2 wt% C _{16 '} , 2 wt% C ₁₇ , 17 wt% C ₁₈ , 44 wt% C _18' , 3% by weight C _{18 "} , 1% by weight C _{18 '''} ), hardened tallow fatty acid (approx. 2% by weight C ₁₄ , 28% by weight C ₁₆ , 2% by weight C ₁₇ , wt .-% C _18: 1 wt .-% C _{18 '),} technical grade oleic acid (about 1 wt .-% C _12, 3 wt .-% C _14, 5 wt .-% C _16, 6 parts by weight % C ₁₆ , 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C _{18 '} , 10% by weight C _{18 "} , 0.5% by weight C _18''' ), technical palmitin / stearic acid (approx. 1 wt% C ₁₂ , 2 wt% C ₁₄ , 45 wt% C ₁₆ , 2 wt% C ₁₇ , 47 wt% C ₁₈ , 1 wt% C _{18 '} ) and soybean oil fatty acid (approx. 2 wt% C ₁₄ , 15 wt .-% C _16, 5 wt .-% C _18, 25 wt .-% C _{18 ',} 45 wt .-% C _{18 ",} 7 wt .-% C _18''').

The esters of fatty acids with alkanols, diols or polyo can be used as fatty acid esters Use len, with fatty acid polyol esters being preferred. Com. As fatty acid polyol ester Men mono- or diesters of fatty acids with certain polyols into consideration. The fatty acid Ren, which are esterified with the polyols are preferably saturated or unsaturated Fatty acids with 12 to 18 carbon atoms, for example lauric acid, myristic acid, palmitin acid or stearic acid, preferably the technically obtained mixtures of the fatty acid ren are used, for example those derived from coconut, palm kernel or tallow fat acid mixtures. In particular acids or mixtures of acids with 16 to 18 C Atoms such as tallow fatty acid are for esterification with the polyvalent Al suitable for alcohol. As polyols, who are esterified with the above-mentioned fatty acids in the context of the present invention, sorbitol, trimethylolpropane, Neopentyl glycol, ethylene glycol, polyethylene glycols, glycerin and polyglycerols in Be dress.

Preferred embodiments of the present invention provide that as the polyol, the is esterified with fatty acid (s), glycerin is used. Accordingly, fiction Moderate detergent components are preferred that contain one or more as ingredient b) Contain fatty substances from the group of fatty alcohols and fatty acid glycerides. Especially preferred detergent components contain as component b) a fatty substance the group of fatty alcohols and fatty acid monoglycerides. Examples of such preferred Fat substances used are glycerol monostearic acid esters or glycerol monopalmitic acid esters.  

Process in which the core molding a) as ingredient ii) or III) one or more Substances with a melting range between 30 and 100 ° C, preferably between 40 and 80 ° C and in particular between 50 and 75 ° C, are particularly inventive prefers. The corresponding substance classes have been described in detail above. Methods which are characterized in that the Molded core a) as ingredient ii) or III) at least one paraffin wax with a Contains melting range from 30 ° C to 65 ° C.

In the case of release-accelerated core moldings, methods according to the invention are preferred in which the core molding a) as ingredient ii) or III) consists of at least one substance the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) contains. The representatives of these substance classes were also described in detail above.

The preferred core moldings can contain additional active ingredients and other ingredients Contain auxiliaries. Processes characterized in that the core molding a) as ingredient iv) or IV) further active substances and / or auxiliary substances from the groups of Dyes, fragrances, anti-settling agents, floating agents, anti-floating agents, Thixotro Piermittel and dispersing aids in amounts of 0 to 10 wt .-%, preferably of 0.25 to 7.5% by weight, particularly preferably from 0.5 to 5% by weight and in particular of 0.75 to 2.5 wt .-%, are preferred.

Regardless of the ingredients used and the manufacturing process of the core shape Bodies are preferred according to the invention, in which the core molded body a) egg NEN melting point between 50 and 80 ° C, preferably between 52.5 and 75 ° C and ins especially between 55 and 65 ° C.

As already mentioned several times, several core moldings as well as several Premixes are pressed into the end products of the process according to the invention by the step e) of the method according to the invention - the optional repetition steps c) and d) - is carried out. Regardless of whether the base molding is or is multi-phase and regardless of the number of ent in the process end products  Holding core moldings are preferred in which the weight ratio of entire molded body to the sum of the masses of all the core contained in the molded body Shaped bodies in the range from 1: 1 to 100: 1, preferably from 2: 1 to 80: 1, especially before is from 3: 1 to 50: 1 and in particular from 4: 1 to 30: 1.

Special optical differentiation options are available if at least one Molded core is visible from the outside. Corresponding methods according to the invention, the are characterized in that the surface of at least one shaped core body of is visible from the outside and that the sum of all visible surfaces of all in the molded body contained core moldings 1 to 80%, preferably 5 to 65%, particularly preferably 10 accounts for up to 50% and in particular 15 to 40% of the total surface of the molded body, are preferred.

Analogous statements can also be made about the volumes of the core shape body (s) compared to the total volume of the end product of the process become. Methods are preferred in which the volume of all ent in the molded body core moldings 1 to 60%, preferably 2.5 to 50%, particularly preferably 5 accounts for up to 40% and in particular 7.5 to 30% of the total volume of the shaped body.

Finally, preferred methods are characterized in that the height of the in Step a) produced moldings 10 to 50%, preferably 15 to 45%, particularly be preferably 20 to 40% and in particular 25 to 35% of the total height of the shaped body makes.

The core molding (s) and the premix (s) are preferably optically below colored divisible. In addition to the optical differentiation, application technology Advantages through different solubilities of the different shaped body areas aims to be. Methods according to the invention are preferred in which at least a core molding loosens faster than the base molding. The reverse is also true ren preferred, in which at least one molded core dissolves more slowly than the base molded body. By incorporating certain components, on the one hand, solubility the core molding can be accelerated in a targeted manner, on the other hand, the release can be  Coordinated ingredients from the core molded body for advantages in washing and cleaning lead process. Ingredients that are preferably localized at least in part in the core molding are, for example, the disintegration aids described below, Surfactants, enzymes, soil-release polymers, builders, bleaches, bleach activators, Bleaching catalysts, optical brighteners, silver protection agents, etc.

The preferred ingredients of the process end products of the inventive method.

Preferred detergent and cleaning agent form in the context of the present invention Bodies contain builders in amounts of 1 to 100 wt .-%, preferably from 5 to 95% by weight, particularly preferably from 10 to 90% by weight and in particular from 20 to 85 wt .-%, each based on the weight of the entire molded body.

In the laundry detergent and cleaning product tablets produced according to the invention all builders commonly used in detergents and cleaning agents be especially zeolites, silicates, carbonates, organic cobuilders and - where none There are ecological prejudices against their use - including phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .y H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x is 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .y H ₂ O are preferred.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted in such a way that the products have microcrystalline ranges of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdry X-ray amorphous silicates.

In the context of the present invention preferably according to the inventive method Ren manufactured detergent tablets are characterized in that that they contain silicate (s), preferably alkali silicates, particularly preferably crystalline or amor phe alkali disilicates, in amounts of 10 to 60% by weight, preferably 15 to 50% by weight and in particular from 20 to 40% by weight, in each case based on the weight of the mold body, included.

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

n Na ₂ O. (1-n) K ₂ O. Al ₂ O _3. (2-2.5) SiO _2. (3.5-5.5) H ₂ O

can be described. The zeolite can be used both as a builder in a granule Ren compound used, as well as a kind of "powdering" of the whole to be pressed Send mixture are used, usually both ways of incorporation  of the zeolite can be used in the premix. Suitable zeolites have a medium one Particle size of less than 10 µm (volume distribution; measurement method: Coulter Coun ter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight bound water.

It goes without saying that the generally known phosphates are also used as buildersub punching possible, provided that such use is not avoided for ecological reasons should be. Among the large number of commercially available phosphates, the Alka limetal phosphates with particular preference for pentasodium or pentapotassium tri phosphate (sodium or potassium tripolyphosphate) in detergents and cleaning agents Industry the most important.

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

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

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to the diphosphate Na ₄ P ₂ O ₇ when heated to a greater extent. Disodium hydrogen phosphate is produced by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

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

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

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] that crystallizes with 6 H ₂ O. _n -Na with n = 3. In 100 g of water about 17 g dissolve at room temperature, at 20 ° approx. 20 g, at 100 ° around 32 g of the salt free of water; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O.

According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of sodium tripolyphos phate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tri Polyphosphate and sodium potassium tripolyphosphate can be used according to the invention.  

Processes preferred in the context of the present invention are characterized thereby net that the end products of the process phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 20 to 80% by weight, preferably 25 to 75% by weight and in particular from 30 to 70% by weight, in each case based on the weight of the basic shape body, included.

Alkali carriers can be present as further constituents. The following are considered to be alkali carriers for example alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, the alkali silicates mentioned, alkali metals silicates, and mixtures of the aforesaid substances, whereby in the sense of this invention adds the alkali carbonates, especially sodium carbonate, sodium hydrogen carbonate or Sodium sesquicarbonate can be used. A builder system is particularly preferred holding a mixture of tripolyphosphate and sodium carbonate. Also special a builder system containing a mixture of tripolyphosphate and natri is preferred umcarbonate and sodium disilicate.

In particularly preferred processes, the process end product contains carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably natri umcarbonate, in amounts of 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular from 10 to 30% by weight, in each case based on the weight of the end product.

Organic cobuilders which can be used in the washing and ri Detergent tablets, in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These substance classes will follow described below.

Usable organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, with such carboxylic acids under polycarboxylic acids can be understood that carry more than one acid function. For example, these are Citro  Nenoic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one such use is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adi Pinic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of the sen.

The acids themselves can also be used. The acids have besides their buil the effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

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

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

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

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As a special copolymers of acrylic acid with maleic acid, 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative mole Cooling mass, based on free acids, is generally from 2000 to 70,000 g / mol preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

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

Biodegradable polymers of more than two ver. Are also particularly preferred different monomer units, for example those that act as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain.

Further preferred copolymers are those which preferably contain acrolein as monomers and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Polyas are particularly preferred Paraginic acids or their salts and derivatives, which in addition to cobuilder properties have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are produced by the implementation of Dial dehyden with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl have groups that can be obtained. Preferred polyacetals are from Dialde  hyden such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme lysed procedures are carried out. It is preferably hydrolysis pro Products with average molecular weights in the range of 400 to 500,000 g / mol. There is a poly saccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glu can be used cosesirupe with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molar masses in the range from 2000 to 30000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenedia mindisuccinate are other suitable cobuilders. Here, ethylenediamine-N, N'- disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and Gly are also preferred in this context cerintrisuccinate. Suitable amounts are in zeolite and / or silicate salts gene formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarbon acids or their salts, which may optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and maxi contain two acid groups.  

Another class of substances with cobuilder properties are the phosphonates it is in particular hydroxyalkane or aminoalkanephosphonates. Under the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) from of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Ho mologist in question. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP, used. HEDP is preferred as a builder from the phosphonate class turns. The aminoalkanephosphonates also have a pronounced heavy metal bin de assets. Accordingly, it can, especially if the agent also ent bleach hold, be preferred to use aminoalkane phosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.

In addition, all compounds that are capable of complexing with alkaline earth train ions as cobuilders.

The amount of builder is usually between 10 and 70 wt .-%, preferably as between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%. How therefore the amount of builders used depends on the intended use, so that Bleach tablets may have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular re between 30 and 55 wt .-%), for example detergent tablets (usually 10 to 50 wt .-%, preferably 12.5 to 45 wt .-% and in particular between 17.5 and 37.5% by weight).

In preferred processes, the detergent and cleaning agent forms produced contain body still one or more surfactant (s). Anionic, nonionic, katio African and / or amphoteric surfactants or mixtures of these are used become. From an application point of view, detergent tablets Mi are preferred mixtures of anionic and nonionic surfactants and for detergent tablets  nonionic surfactants. The total surfactant content of the moldings is - as already mentioned - In the case of detergent tablets at 5 to 60 wt .-%, based on the shaped body important, with surfactant contents above 15% by weight being preferred, while detergents Abletten for machine dishwashing preferably under 5 wt .-% surfactant (s) ent hold.

Within the scope of the present invention are for the production of detergent tablets Processes preferred in which anionic (s) and nonionic (s) surfactant (s) in the core Shaped body and / or in the particulate premix, where used manure-related advantages from certain proportions in which the individual Surfactant classes can be used, may result.

For example, methods are particularly preferred in which the ratio of Anionic surfactant (s) to nonionic surfactant (s) in the end products of the process between 10: 1 and 1:10, is preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2. Be Processes are also preferred in which the detergent tablets Ten sid (s), preferably anionic (s) and / or nonionic (s) surfactant (s), in amounts of 5 up to 40% by weight, preferably from 7.5 to 35% by weight, particularly preferably from 10 to 30 wt .-% and in particular from 12.5 to 25 wt .-%, each based on the molded body weight, included.

From an application point of view, it can be advantageous if certain classes of surfactants in some phases of the detergent tablets or in their entirety body, d. H. in all phases, are not included. Another important embodiment The present invention therefore provides that at least one phase of the shaped body is free of non-ionic surfactants.

Conversely, the content of individual phases or the entire form can also be used body, d. H. all phases, certain surfactants have a positive effect. The The introduction of the alkyl polyglycosides described above has been found to be advantageous have shown, so that detergent tablets are preferred, in which mind least one phase of the shaped body contains alkyl polyglycosides.  

Similar to the nonionic surfactants can also be left out of anioni tensides from individual or all phases of detergent tablets result that are more suitable for certain areas of application. It is therefore in Within the scope of the present invention, detergent tablets are also produced adjustable, in which at least one phase of the moldings is free from anionic surfactants is.

As already mentioned, the use of surfactants in cleaning detergents for machine dishwashing is preferably limited to the use of nonionic surfactants in small amounts. In the context of the present invention preferably detergent tablets which can be produced as detergent tablets are characterized in that the sum of all the particulate premixes used Ge total surfactant contents below 5% by weight, preferably below 4% by weight, particularly preferably below 3 % By weight and in particular below 2% by weight, each based on the weight of all premixes. Usually only weakly foaming nonionic surfactants are used as surfactants in machine dishwashing detergents. By contrast, representatives from the groups of anionic, cationic or amphoteric ten-side are of lesser importance. With particular preference, the detergent tablets according to the invention for machine dishwashing contain nonionic surfactants, in particular nonionic surfactants from the group of alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In order to facilitate the disintegration of highly compressed moldings, it is possible to disintegrate on aids, so-called tablet disintegrants, in the process according to the invention to reduce disintegration times. Under tablet disintegrants or disintegrants are accelerated according to Römpp (9th edition, Vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology "(6th edition, 1987, pp. 182-184) understood auxiliary substances that for the rapid disintegration of tablets in water or gastric juice and for the release of the pharmaceuticals in a resorbable form.

These substances, which are also referred to as "explosives" due to their effect, ver increase their volume when water enters, and on the one hand increases their own volume (Swelling), on the other hand, a pressure can be generated via the release of gases which can break the tablet into smaller particles. Well-known disintegration aid medium are, for example, carbonate / citric acid systems, but also other organic ones Acids can be used. Swelling disintegration aids are, for example synthetic polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or mo differentiated natural substances such as cellulose and starch and their derivatives, alginates or casein Derivatives.

Preferred detergent tablets contain 0.5 to 10% by weight preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disinfectants Gration aids, each based on the weight of the molded body. Contains only the base molded disintegration aids, the information given relates only to the weight of the base molding.  

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

The cellulose used as disintegration aid is preferably not finely divided form, but before mixing into the premixes to be pressed converted into a coarser form, for example granulated or compacted. Washing and Detergent tablets, the disintegrant in granular or optionally cogranu Contained form, are in the German patent applications DE 197 09 991 (Ste fan Herzog) and DE 197 10 254 (Henkel) and the international patent application WO98 / 40463 (Henkel). These writings are also more detailed information on the Her position of granulated, compacted or cogranulated cellulose disintegrants  men. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 µm and in particular to at least 90% by weight between 400 and 1200 µm. The above and in the writings cited described coarser disintegration aids on cellulose In the context of the present invention, bases are preferred as disintegration aids used and commercially, for example under the name Arbocel® TF-30-HG by available from Rettenmaier.

As a further disintegrant based on cellulose or as part of this compo microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions that only attack the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses and dissolve completely, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine cellulo produced by the hydrolysis sen supplies the microcrystalline celluloses, which have primary particle sizes of approx. 5 µm sen and, for example, to granules with an average particle size of 200 microns are pactable.

Processes preferred in the context of the present invention are characterized thereby net that the detergent tablets produced with them additionally a Disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 up to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, each based on the weight of the molded part.

The detergent tablets produced according to the invention can be in addition, a gas-evolving gas in both the base molding and the core molding Shower system included. The gas-developing shower system can consist of a single sub punch exist, which releases a gas on contact with water. Among these connections Magnesium peroxide should be mentioned in particular, which is oxygen when in contact with water releases. Usually, however, the gas-releasing bubble system itself consists of at least two components that react with one another to form gas. While here  a variety of systems is conceivable and executable, for example nitrogen, acid Release substance or hydrogen, that will in the washing and Bubble system used detergent tablets based on both economic and also choose based on ecological considerations. Preferred shower systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidification detergent, which is suitable from the alkali metal salts in aqueous solution carbon dioxide release.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium are salts are clearly preferred over the other salts for cost reasons. Self ver the pure alkali metal carbonates or -hydrogen carbonates are used; rather, mixtures of different car bonates and hydrogen carbonates may be preferred for washing technology reasons.

In preferred laundry detergent and cleaning product tablets 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular special 3 to 10 wt .-% of an acidifying agent, based in each case on the total Shaped body used.

As an acidifying agent that releases carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal bisulfates, alkali metal dihy drug phosphates and other inorganic salts can be used. However, are preferred organic acidifiers are used, with citric acid being particularly preferred added acidifier. However, the other fixed ones can also be used in particular Mono-, oligo- and polycarboxylic acids. Wine is preferred from this group acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid like polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid are also a settable. Commercially available and as an acidifying agent in the context of the present Sokalan® DCS (trademark of BASF) is also preferably used according to the invention Mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adi pinic acid (max. 33% by weight).  

Preferred process end products in the context of the present invention Detergent tablets, which are used as acidifiers in the shower system a substance from the group of organic di-, tri- and oligocarboxylic acids or Mixtures of these are used.

In addition to the ingredients mentioned builder, surfactant and disintegration aid, NEN the detergent tablets produced according to the invention further in Detergents and cleaning agents usual ingredients from the group of bleaching agents, Bleach activators, dyes, fragrances, optical brighteners, enzymes, foam inhibitors ren, silicone oils, anti-redeposition agents, graying inhibitors, color transfer inhibitors gates and corrosion inhibitors included.

Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and produce H ₂ O ₂ in water. Further usable bleaching agents are, for example, sodium perborate tetrahydrate and the sodium perborate monohydrate, peroxypyro phosphates, citrate perhydrates and H ₂ O ₂ -supplying acidic salts or peracids, such as per benzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimoxyhexanoic acid (peroxyiminoperacid acid) PAP)], o-carboxybenzamido peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacassyl acid, diperoxy acid, diperoxy acid -1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

As a bleach in the detergent tablets according to the invention for the Automatic dishwashing can also use chlorine or bromine-releasing substances become. Come under the appropriate chlorine or bromine releasing materials for example heterocyclic N-bromo- and N-chloramides, for example Trichloroisocyanuric acid, tribromo isocyanuric acid, dibromo isocyanuric acid and / or Dichloroisocyanuric acid (DICA) and / or its salts with cations such as potassium and sodium into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

The bleaches are usually used in machine dishwashing detergents in amounts of 1 up to 30% by weight, preferably from 2.5 to 20% by weight and in particular from 5 to 15% by weight, each based on the agent used. In the context of the present invention the proportions mentioned are based on the weight of the base molding.

Bleach activators that support the action of the bleach can also be be part of the base molding. Known bleach activators are compounds that contain one or more N- or O-acyl groups, such as substances from the class of Anhydrides, the esters, the imides and the acylated imidazoles or oximes. examples are Tetraacetylethylenediamine TAED, Tetraacetylmethylenediamine TAMD and Tetraacetylhe xylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexa hydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

As bleach activators can be compounds that are under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms and / or optionally substituted perbenzoic acid are used become. Substances which contain O- and / or N-acyl groups of the C- Bear atomic number and / or optionally substituted benzoyl groups. Are preferred multiple acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSJ), acylated phenol sulfonates,  in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), and those from the German Patent applications DE 196 16 693 and DE 196 16 767 known enol esters as well acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, especially pentaacetyl glucose (PAG), pentaacetyl fructose Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated Glucamine and gluconolactone, and / or N-acylated lactams, for example N- Benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams also preferably used. Combinations of conventional bleach activators can be used. The bleach activators are made in machine Dishwashing agents usually in amounts of 0.1 to 20 wt .-%, preferably 0.25 up to 15% by weight and in particular from 1 to 10% by weight, in each case based on the composition, used. In the context of the present invention, the aforementioned relate Quantities based on the weight of the base molding.

In addition to the conventional bleach activators or in their place, too so-called bleach catalysts are used in the process according to the invention. At these substances are bleach-enhancing transition metal salts or over transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N- containing tripod ligands and Co, Fe, Cu and Ru amine complexes are bleached catalysts can be used.

Bleach activators from the group of multi-acylated alkylene are preferred diamines, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N- Nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile- Methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-%, bezo on the entire medium.  

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

Processes which are characterized in that in step c) bleaching agents from the group the oxygen or halogen bleach, especially the chlorine bleach, among be Particular preference for sodium perborate and sodium percarbonate, in amounts from 2 to 25% by weight, preferably from 5 to 20% by weight and in particular from 10 to 15% by weight, each based on the weight of the premix, are invented According to the preferred embodiment of the present invention.

It is also preferred that the base molding and / or the core molding be bleached activators included. Processes in which the premix in step c) bleach activators from the groups of multiply acylated alkylenediamines, in particular tetraacetylethyl lendiamine (TAED), the N-acylimide, especially N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS) and n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), in Amounts from 0.25 to 15% by weight, preferably from 0.5 to 10% by weight and in particular from 1 to 5% by weight, based in each case on the weight of the base molding also preferred.

The detergent tablets produced according to the invention can in particular in Basic molded body to protect the wash ware or the machine corrosion inhibitors contain, especially silver protection agents in the field of machine dishwashing  lens have a special meaning. The known substances of Stan can be used of technology. In general, silver protection agents can be selected from the group pe of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylamines notriazoles and the transition metal salts or complexes are used. Especially benzotriazole and / or alkylaminotriazole are preferred. One finds in Rei niger formulations also often active chlorine-containing agents that corrode significantly reduce the silver surface. In chlorine-free cleaners, Oxygen and nitrogen-containing organic redox-active compounds, such as two and trihydric phenols, e.g. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid right, phloroglucin, pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds, such as salts of the metals Mn, 28385 00070 552 001000280000000200012000285912827400040 0002019961367 00004 28266 Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts, the are selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the Cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulphide fats. Zinc compounds can also be used to prevent corrosion on the wash ware be set.

In methods preferred in the context of the present invention, silver protection medium from the group of triazoles, benzotriazoles, bisbenzotriazoles, Ami notriazole, the alkylaminotriazole and the transition metal salts or complexes, esp preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.01 to 5% by weight, preferably from 0.05 to 4% by weight and in particular from 0.5 to 3% by weight, in each case based on the weight of the end product of the process.

Of course, the core molding can also contain silver protection agents, the Basic molded body either also contains silver protection or free of such Ver ties is.

In addition to the ingredients mentioned above, there are other substance classes Incorporation in detergents and cleaning agents. Methods are preferred in which in step c) one or more substances from the groups of the enzymes, Korrosi  onsinhibitors, deposit inhibitors, cobuilders, colors and / or fragrances in total from 6 to 30% by weight, preferably from 7.5 to 25% by weight and in particular from 10 to 20 wt .-%, each based on the weight of the end product, who used the.

Enzymes in particular come from the hydrolase classes such as the protea sen, esterases, lipases or lipolytically acting enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal stains such as protein, fat or starchy stains. For Bleach can also be used with oxidoreductases. Are particularly well suited Bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and from their genetically modified adorned variants obtained enzymatic agents. Proteases are preferred of the subtilisin type and in particular proteases obtained from Bacillus lentus, used. Enzyme mixtures, for example of protease and amylase or Protease and lipase or lipolytic enzymes or from protease, amylase and Lipase or lipolytic enzymes or protease, lipase or lipolytic we enzymes, but especially protease and / or lipase-containing mixtures or Mixtures with lipolytically active enzymes of particular interest. examples for Such lipolytic enzymes are the well-known cutinases. Peroxidases too or oxidases have been found to be suitable in some cases. To the appropriate ones Amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectina sen.

The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5% by weight. Reini preferred in the context of the present invention shaped tablets are characterized in that the base tablet protease and / or contains amylase.  

Dyes and fragrances can be used in the washing or cleaning agents produced according to the invention moldings both in the base molding and in the core molding to improve the aesthetic impression of the resulting products and the consumer in addition to the performance a visually and sensory "typical and un interchangeable "product. As perfume oils or fragrances can individual fragrance compounds, e.g. B. the synthetic products of the ester type, Ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Smell Compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p- tert-Butylcyclohexylacetate, Linalylacetat, Dimethylbenzylcarbinylacetat, Phenylethylace tat, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example, benzylethyl ether, to the aldehydes z. B. the linear alkanals with 8-18 C atoms, Citral, Citronel lal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeo nal, to the ketones z. B. the Jonone, α-isomethylionone and methylcedryl ketone to the Alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and ter pineol, the hydrocarbons mainly include terpenes such as limonene and Pinene. However, mixtures of different odoriferous substances are preferably used create an appealing fragrance together. Such perfume oils can also be natural che fragrance mixtures contain, as they are accessible from plant sources, for. B. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Are also suitable Muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden flower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be used directly in the washing and cleaning agents produced according to the invention agents are incorporated, but it may also be advantageous to apply the fragrances Apply carriers that increase and adhere the perfume to the laundry a slower fragrance release ensures a long-lasting fragrance of the textiles. As such Carrier materials have proven themselves, for example, cyclodextrins, the Cyclodex trin-perfume complexes can also be coated with other auxiliaries nen.  

In order to give the aesthetic impression of the washing or cleaning products produced according to the invention to improve moldings, these (or parts thereof) with suitable Dyes are colored. Preferred dyes, the selection of the expert kei difficult, have a high storage stability and insensitivity compared to the other ingredients of the agents and against light and no pronounced Substantivity towards the substrates to be treated with the agents such as textiles, Glass, ceramics or plastic dishes so as not to stain them.

The molded articles are produced in step f) in the process according to the invention. by pressing into tablets, using conventional methods can be. To produce the shaped bodies, the premix, which is at least one Molded core contains, in a so-called die between two stamps to one solid compressed compacted. This process, hereinafter referred to briefly as tableting is divided into four sections: dosage, compression (elastic ver molding), plastic deformation and ejection.

First the premix and the core molding (s) are introduced into the die, where the filling quantity and thus the weight and shape of the molded body formed determined by the position of the lower punch and the shape of the eating tool the. The constant dosing of premixes even with high moldings rates are preferably achieved by volumetric metering of the premix. in the As the tableting continues, the upper punch touches the premix and lowers it further towards the lower stamp. With this compression, the particles of the premix pressed closer together, the void volume within the Filling between the stamps decreases continuously. From a certain position of the The upper stamp (and thus from a certain pressure on the premix) begins plastic deformation, in which the particles flow together and it to form the Shaped body comes. Depending on the physical properties of the premix also some of the premixed particles are crushed and it comes at even higher pressures to sinter the premix. With increasing press speed, i.e. high Throughput quantities, the phase of elastic deformation is shortened more and more, so that the resulting shaped bodies can have more or less large cavities.  

In the last step of tableting, the finished molded article is made using the lower stamp pressed out of the die and wegbe by subsequent transport devices promotes. At this time, only the weight of the molded body is finally fixed sets because the compacts due to physical processes (stretching, crystallographic Effects, cooling etc.) can still change their shape and size.

Tableting takes place in commercially available tablet presses, which are basically or double stamps can be equipped. In the latter case, not only the waiter stamp used to build up pressure, also the lower stamp moves during the Pressing process towards the upper punch, while the upper punch presses down. For Small production quantities are preferably used with eccentric tablet presses which the one or more stamps are attached to an eccentric, which in turn on one Axis is mounted with a certain rotational speed. The movement of this Press ram is comparable to the way a conventional four-stroke engine works. The Ver pressing can be done with one upper and one lower stamp, but several can also be used re stamp on an eccentric disk, the number of die holes gen is expanded accordingly. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected, in which on a so-called called matrix table a larger number of matrices is arranged in a circle. The The number of matrices varies between 6 and 55, depending on the model, with larger matrices also are commercially available. Each die on the die table is a top and bottom stamp assigned, again the pressing pressure active only by the upper or lower stamp, but can also be built up by both stamps. The matrix table and the Stamps move around a common vertical axis, the stamp with the help of rail-like cam tracks during the circulation in the positions for Be filling, compression, plastic deformation and discharge. On the stel len, where a particularly serious raising or lowering the stamp is necessary (filling, compacting, ejecting), these cam tracks are replaced by additional che low-pressure pieces, pull-down rails and lifting tracks supported. The filling The matrix is developed via a rigidly arranged feed device, the so-called  Filling shoe, which is connected to a reservoir for the premix. The press pressure on the premix is individual via the press paths for upper and lower punches adjustable, the pressure build-up by rolling the stamp shaft heads past ver adjustable pressure rollers happens.

Rotary presses can also use two filling shoes to increase throughput hen be, with only one semicircle to manufacture a tablet that must. Several fillers are used to produce two- and multi-layer moldings shoes arranged one behind the other without the slightly pressed first layer in front of the further filling is ejected. Appropriate litigation leads to this se also coated and dot tablets can be produced, which have an onion-shell-like structure have, whereby in the case of the point tablets the top of the core or the core layers is not covered and therefore remains visible. Rotary tablet presses are also included Single or multiple tools can be equipped, so that, for example, an outer circle with 50 and an inner circle with 35 holes simultaneously used for pressing the. The throughputs of modern rotary tablet presses are over a million forms body per hour.

When tableting with rotary presses, it has proven to be advantageous to carry out tableting with the smallest possible fluctuations in the weight of the tablet. The fluctuations in hardness of the tablet can also be reduced in this way. Small fluctuations in weight can be achieved in the following ways:

• - Use of plastic inserts with small thickness tolerances
• - Low number of revolutions of the rotor
• - Big filling shoes
• - Matching the filler paddle speed to the speed of the rotor
• - Filling shoe with constant powder height
• - Decoupling of filling shoe and powder feed.

To reduce the build-up of stamps, all of them can be used in technology known non-stick coatings. Plastic coatings are particularly advantageous,  Plastic inlays or plastic stamps. Rotating stamps also have an advantage proven, whereby the upper and lower stamps are rotatable if possible should. In the case of rotating stamps, a plastic insert is generally not required become. The stamp surfaces should be electropolished here.

It was also shown that long pressing times are advantageous. These can be printed rails, several pressure rollers or low rotor speeds. Since the Fluctuations in the hardness of the tablet are caused by the fluctuations in the pressing forces systems should be used that limit the pressing force. Here elasti cal stamps, pneumatic compensators or resilient elements in the force path be set. The pressure roller can also be designed to be resilient.

Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers are, for example Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Li verpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Me diopharm Kamnik (SI). The hydraulic double is particularly suitable HPF 630 printing press from LAEIS, D. Tableting tools are, for example, from the company Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber & Söhne GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers are e.g. B. the Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

The moldings can - as already mentioned above - in a predetermined space shape and predetermined size are manufactured. Practically everyone comes as a spatial form reasonably manageable configurations, for example the training as Blackboard, the shape of bars or bars, cubes, cuboids and corresponding room elements flat side surfaces and in particular cylindrical configurations with a circle  shaped or oval cross section. This last embodiment covers the darbie form from tablets to compact cylinder pieces with a ratio of Height to diameter above 1.

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

Here σ stands for diametral fracture stress (DFS) in Pa, P is the force in N which leads to the pressure exerted on the molded body, which is the Breakage of the shaped body causes, D is the shaped body diameter in meters and t is the Height of the molded body.

The molded articles produced according to the invention can be wholly or partly with a loading layering. Procedures in which an optional post-treatment in the bring a coating layer on the molded body surface (s) in which the core molded body, or in the application of a coating layer on the entire mold body consists are preferred according to the invention.

The detergent tablets produced according to the invention can be packaged after production, the use of certain packaging systems having proven particularly useful since these packaging systems increase the storage stability of the ingredients. The present invention therefore furthermore relates to a combination of (a) shaped detergent and cleaning product body (s) and a packaging system containing the detergent or cleaning product molding, the packaging system having a moisture vapor transmission rate of 0.1 g / m ² / Day to less than 20 g / m ² / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.

The packaging system of the combination of detergent tablets and packaging system has a moisture vapor transmission rate of 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system is at 23 ° C and a relative equilibrium humidity of 85% is stored. The specified temperature and humidity conditions are the test conditions that are mentioned in the DIN standard 53 122, whereby according to DIN 53 122 minimal deviations are permitted (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor permeability rate of a given packaging system or material can be determined according to further standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at high temperature an Humidity"). The measuring principle of current methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container being closed at the top with the material to be tested. From the surface of the container, which is closed with the material to be tested (permeation surface), the increase in weight of calcium chloride and the exposure time, the moisture vapor transmission rate can be determined

calculate, where A is the area of the material to be tested in cm ² , x is the weight gain of calcium chloride in g and y is the exposure time in h.

The relative equilibrium humidity, often referred to as "relative humidity", is 85% at 23 ° C. when measuring the moisture vapor transmission rate within the scope of the present invention. The absorption capacity of air for water vapor increases with temperature up to a respective maximum content, the so-called saturation content, and is given in g / m ³ . For example, 1 m ^{3 of} air at 17 ° is saturated with 14.4 g of water vapor; at a temperature of 11 ° there is already saturation with 10 g of water vapor. The relative humidity is the ratio of the actual water vapor content to the saturation content corresponding to the prevailing temperature. For example, if air contains 17 ° 12 g / m ³ water vapor, then the relative humidity = (12 / 14.4) .100 = 83%. If you cool this air, then the saturation (100% r.L.) is reached at the so-called dew point (in the example: 14 °), ie, if it cools further, a precipitate is formed in the form of mist (dew). Hygrometers and psy chrometers are used for the quantitative determination of moisture.

The relative equilibrium humidity of 85% at 23 ° C can be found, for example, in La Borehouses with humidity control depending on the device type to ± 2% r. Adjust L. exactly. Even over saturated solutions of certain salts form in closed systems constant and well-defined relative humidity at a given temperature, that on the phase equilibrium between partial pressure of water, saturated solution and soil body are based.

The combinations of detergent tablets and Packaging system can of course in turn in secondary packaging for example, cardboard boxes or trays, are packed, with the secondary packaging no further requirements have to be made. The secondary packaging is that if possible, but not necessary.

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

Depending on the embodiment, the packaging system of the combination according to the invention encloses the invention one or more detergent tablets. It is preferred according to the invention either to design a shaped body such that it comprises an application unit of the detergent and cleaning agent, and this form body to be packed individually, or the number of shaped bodies in one packaging unit to pack, which in total comprises an application unit. With a target dosage of According to the invention, 80 g of detergent and cleaning agent is possible to sweat an 80 g to produce and to individually package detergent tablets, it is but also possible according to the invention, two washing and cleaning agents each weighing 40 g  Packing the shaped body in a packaging to form a Kombinati according to the invention to get on. This principle can of course be expanded, so that fiction three, four, five or even more detergents and cleaning agents according to combinations can contain molded articles in a packaging unit. Of course, two can or more moldings in one package have different compositions sen. In this way it is possible to spatially separate certain components separate, for example to avoid stability problems.

The packaging system of the combination according to the invention can differ from the materials and take on any external shape. From economic For reasons of and for reasons of easier processability, however, there are packaging systems Steme preferred, in which the packaging material is light in weight, easily process and is inexpensive. In combinations preferred according to the invention the packaging system consists of a sack or pouch made of single-layer or laminated Paper and / or plastic film.

The detergent tablets can be unsorted, i. H. as loose bulk tion, be filled into a bag made of the materials mentioned. But it is from aesthetic table reasons and for sorting the combinations in secondary packaging moves, the detergent tablets individually or in several sorted in Fill sacks or bags. For individual application units for washing and cleaning molded article, which are in a sack or pouch, has in Tech nik the term "flow pack" naturalized. Such "flow packs" can then - again preferably sorted - optionally packed in outer packaging, what the compact Offer form of the molded body underlines.

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

Combinations particularly preferred within the scope of the present invention as a packaging system, a sack or bag made of single-layer or laminated art material film with a thickness of 10 to 200 microns, preferably from 20 to 100 microns and esp special from 25 to 50 µm.

Although it is possible, wax-coated in addition to the films or papers mentioned Papers in the form of cardboard boxes as a packaging system for washing and cleaning to use medium shaped bodies, it is preferred in the context of the present invention if the packaging system does not include boxes made of wax-coated paper. The The term “packaging system” in the context of the present invention always the primary packaging of the moldings, d. H. the packaging that is on the inside is in direct contact with the molded body surface. To an optional secondary pack No requirements are made, so that all common materials and Systems can be used.

As already mentioned above, the detergent tablets contain molded articles the combination according to the invention, depending on its intended use, further content fabrics of washing and cleaning agents in varying amounts. Regardless of the ver application of the shaped body, it is preferred according to the invention that the or Detergent tablets have a relative equilibrium moisture content of less than 30% at 35 ° C.

The relative equilibrium moisture content of the detergent tablets can are determined according to common methods, whereby within the scope of the present The following procedure was chosen for investigations: Liter jar with a lid, which has a closable opening for insertion  of samples, was washed with a total of 300 g of detergent tablets filled with pern and kept at a constant 23 ° C for 24 h in order to maintain a constant temperature of Ensure vessel and substance. The water vapor pressure in the room over the form can then use a hygrometer (Hygrotest 6100, Testoterm Ltd., England) be true. The water vapor pressure is now measured every 10 minutes until two successive values show no deviation (equilibrium moisture). The above Hygrometer allows a direct display of the recorded values in% relative humidity action.

Embodiments of the combination according to the invention are also preferred which the packaging system is designed to be resealable. Also combinations, where the packaging system has a microperforation, can be fiction according to implement with preference.

Claims (76)

1. A method for producing multi-phase detergent tablets comprising the steps

• a) production of core moldings which contain active substance,
• b) optional insertion of one or more core moldings from step a) into a die of a tablet press,
• c) filling at least one particulate premix into the die of the tablet press,
• d) feeding at least one core molding from step a) into the die of the tablet press,
• e) optional repetition of steps c) and / or d) one or more times,
• f) pressing into shaped bodies,

wherein steps c) and d) can optionally be carried out in reversed order, characterized in that in at least one of the steps b), c), d) or f) the upper and / or lower punch of the tablet press is a non-planar one Has pressing surface. 2. The method according to claim 1, characterized in that the upper and / or lower Do not stamp the tablet press a non-planar throughout the procedure Has pressing surface. 3. The method according to claim 2, characterized in that as the upper and / or lower stamp a stamp is used which consists of several independently and partial stamps movable parallel to one another is constructed. 4. The method according to any one of claims 2 or 3, characterized in that as the top and / or lower stamp a stamp is used which consists of two independently is constructed different and parallel to each other partial stamps, stamps are preferred which enclose a central mandrel and a central mandrel pass the ring stamp.   5. The method according to any one of claims 2 to 4, characterized in that the pressing surface surface of the lower punch in method step b) has at least one cavity. 6. The method according to any one of claims 2 to 5, characterized in that the pressing surface surface of the lower stamp in process step f) is plan. 7. The method according to any one of claims 2 to 6, characterized in that the Particulate premix (s) after each process step c) by lowering of the upper stamp are smoothed. 8. The method according to claim 7, characterized in that the pressing surface of the upper stamp has at least one elevation when lowering. 9. The method according to any one of claims 1 to 8, characterized in that the pressing surface surface of the upper die in process step f) is plan. 10. The method according to any one of claims 1 to 9, characterized in that the pressing surface surface of the upper die is flat throughout the process. 11. The method according to any one of claims 1 to 9, characterized in that the pressing surface che of the upper stamp during the entire procedure at least one survey having. 12. The method for producing multiphase detergent tablets characterized by the steps

• a) production of core moldings which contain active substance,
• b) optional insertion of one or more core moldings from step a) into a die of a tablet press,
• c) filling at least one particulate premix into the die of the tablet press,
• d) optional feeding of one or more core shaped body (s) from step a) into the die of the tablet press,
• e) optional repetition of steps b) and / or c) one or more times,
• f) pressing to form bodies which have at least one cavity,
• g) feeding the core shaped body (s) from step a) into the cavity (s) of the tablet press,
• h) pressing the core mold body (s) into the cavity (s).

13. The method according to claim 12, characterized in that the pressing in step f) using an upper stamp, the embossing element of at least one of has a peg surrounded by a flat base. 14. The method according to claim 13, characterized in that the base of the embossing elements walkable in the press and the pin or pins incompressible and at least is coated to reduce adhesion. 15. The method according to claim 14, characterized in that the at least adhesive reducing coating of the pin (s) made of Ni-P-PTFE or C-diamond stands. 16. The method according to any one of claims 13 to 15, characterized in that the pre Geelement has a pin that has a volume of 0.5 to 5 ml, preferably 0.6 to 3 ml, particularly preferably 0.8 to 2 ml. 17. The method according to any one of claims 13 to 16, characterized in that the pre ge element has one or more pins, each at least 1 mm in front preferably at least 2 mm and in particular at least 3 mm from the base stick out. 18. The method according to any one of claims 13 to 17, characterized in that the base area of the embossing element is 2.5 to 60 cm ² , preferably 5 to 40 cm ² , particularly preferably 7.5 to 20 cm ² . 19. The method according to any one of claims 13 to 18, characterized in that the / Shell surface of the pin (s) to the base of the embossing element at an angle of 90 to 160 °, preferably from 90 ° to 140 ° and in particular from 100 to 120 ° det. 20. The method according to any one of claims 13 to 19, characterized in that the press area of the pin (s) runs parallel to the base of the embossing element. 21. The method according to any one of claims 12 to 20, characterized in that the / Core moldings a) can be inserted in the cavity in a form-fitting manner in step g). 22. The method according to any one of claims 12 to 21, characterized in that the pressing in step h) at pressures from 0.1 to 50 kNcm ^-2 , preferably from 0.5 to 25 kNcm ^-2 and in particular from 1 to 15 kNcm ^-2 takes place. 23. The method according to any one of claims 1 to 22, characterized in that the mass of the core molding a) more than 0.5 g, preferably more than 1 g and in particular is more than 2 g. 24. The method according to any one of claims 1 to 23, characterized in that the core molded body a) has a base area of at least 50 mm ² , preferably of at least 100 mm ² and in particular of at least 150 mm ² . 25. The method according to any one of claims 1 to 3, characterized in that the core molded body a) has a circular base. 26. The method according to any one of claims 1 to 4, characterized in that the core molding has a density below 1.4 gcm ^-3 , preferably below 1.2 gcm ^-3 and in particular below 1.0 gcm ^-3 . 27. The method according to any one of claims 1 to 5, the mass of the total washing or Detergent tablets 10 to 100 g, preferably 15 to 80 g, especially before is 18 to 60 g and in particular 20 to 45 g. 28. The method according to any one of claims 1 to 6, characterized in that the detergent tablets have a base area of at least 500 mm ² , preferably of at least 750 mm ² and in particular of at least 1000 mm ² . 29. The method according to any one of claims 1 to 7, characterized in that the entire molded body has a density above 1.1 gcm ^-3 , preferably above 1.2 gcm ^-3 and in particular above 1.4 gcm ^-3 . 30. The method according to any one of claims 1 to 8, characterized in that the part Chen-shaped premix in step c) before a bulk density of at least 500 g / l preferably has at least 600 g / l and in particular at least 700 g / l. 31. The method according to any one of claims 1 to 9, characterized in that the part Chen-shaped premix in step c) particle sizes between 100 and 2000 µm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 µm and in particular between 600 and 1400 µm. 32. The method according to any one of claims 1 to 10, characterized in that the compression in step a) and / or e) at pressures from 1 to 100 kNcm ^-2 , preferably from 1.5 to 50 kNcm ^-2 and in particular from 2 to 25 kNcm ^-2 . 33. The method according to any one of claims 1 to 11, characterized in that the Her position of the core moldings in step a) by casting. 34. The method according to any one of claims 1 to 11, characterized in that the Her position of the core moldings in step a) by sintering.   35. The method according to any one of claims 1 to 11, characterized in that the Her position of the core moldings in step a) is carried out by tableting. 36. The method according to any one of claims 1 to 11, characterized in that the core molded body is a capsule. 37. The method according to any one of claims 1 to 15, characterized in that the core molded body a) contains surfactant (s) as an ingredient. 38. The method according to any one of claims 1 to 16, characterized in that the core molded body a) contains enzyme (e) as ingredient. 39. The method according to any one of claims 1 to 17, characterized in that the core molded body a) contains bleach and / or bleach activator (s) as an ingredient. 40. The method according to any one of claims 1 to 18, characterized in that the core molded body a) as an ingredient disintegration aid and / or gas-generating systems contains. 41. The method according to any one of claims 1 to 19, characterized in that the core Shaped body a) contains water softener and / or complexing agent as an ingredient. 42. The method according to any one of claims 1 to 20, characterized in that according to the Production of the core moldings in step a) a coating and / or encapsulation development of the core moldings takes place. 43. The method according to any one of claims 1 to 21, characterized in that the / in Step a) produced core moldings based on his / her weight at least 30% by weight, preferably at least 37.5% by weight and in particular at least 45% by weight meltable substance (s) with a melting point above 30 ° C ent holds / included.   44. The method according to claim 22, characterized in that the / the shaped core body one or more substances with a melting range between 30 and 100 ° C preferably between 40 and 80 ° C and in particular between 50 and 75 ° C, ent holds / included. 45. The method according to any one of claims 22 or 23, characterized in that the Core moldings at least one paraffin wax with a melting range of 30 ° C. contains up to 65 ° C. 46. The method according to any one of claims 22 to 24, characterized in that the Her position of the core moldings by converting a melt into particulate Material and subsequent pressing takes place. 47. The method according to claim 25, characterized in that for the production of the core Shaped body a) a melt is shed and then pressed. 48. The method according to claim 25, characterized in that for the production of the core Shaped body a) a melt is pelletized and subsequently pressed. 49. The method according to claim 25, characterized in that for the production of the core Shaped body a) a melt is pressed and subsequently pressed. 50. The method according to any one of claims 22 to 28, characterized in that the core molded articles a) are produced with air inclusions which are at most 0.8 times, preferably at most 0.75 times and in particular at most 0.7 times that Have the mass of a melting body with the same volume and formulation. 51. The method according to any one of claims 22 to 28, characterized in that the core molded articles a) are produced without significant air inclusions, which at least 0.8 times, preferably at least 0.85 times and in particular at least 0.9 times the mass of a melting body with the same volume and formulation Zen.   52. The method according to any one of claims 1 to 30, characterized in that at least one core shaped body a) has the following composition:

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C.,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries.

53. The method according to any one of claims 1 to 30, characterized in that at least one core shaped body a) has the following composition:

• A) 10 to 90% by weight of surfactant (s),
• B) 10 to 90% by weight of fat (s),
• C) 0 to 70% by weight of meltable substance (s) with a melting point above 30 ° C.,
• D) 0 to 15% by weight of further active ingredients and / or auxiliaries.

54. The method according to any one of claims 31 or 32, characterized in that the Core moldings a) as ingredient i) or I) 15 to 80, preferably 20 to 70, in particular which preferably contains 25 to 60 and in particular 30 to 50% by weight of surfactant (s). 55. The method according to any one of claims 31 to 33, characterized in that the Molded core a) as ingredient ii) or III) 15 to 85, preferably 20 to 80, be particularly preferably 25 to 75 and in particular 30 to 70% by weight of meltable sub punch (s) contains. 56. The method according to any one of claims 31 or 33 to 34, characterized in that the core shaped body a) the ingredient iii) in amounts of 0.15 to 12.5, preferably from 0.2 to 10, particularly preferably from 0.25 to 7.5 and in particular from 0.3 to Contains 5 wt .-%.   57. The method according to any one of claims 31 to 35, characterized in that the Shaped core body a) as ingredient i) or I) anionic and / or nonionic (s) Contains surfactant (s), preferably nonionic surfactant (s). 58. The method according to any one of claims 31 to 36, characterized in that the Core moldings a) as ingredient i) or I) nonionic surfactant (s) with a Melting point above 20 ° C, preferably above 25 ° C, especially before trains between 25 and 60 ° C and in particular between 26, 6 and 43.3 ° C, contains. 59. The method according to any one of claims 31 to 37, characterized in that the core molding a) as ingredient i) or I) ethoxylated (s) nonionic surfactant (s), the / which from C _6-20 monohydroxyalkanols or C _{6- 20} -alkylphenols or C _16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol was obtained. 60. The method according to any one of claims 31 to 38, characterized in that the Core moldings a) as ingredient i) or I) ethoxylated and propoxylated nonionic surfactants contain, in which the propylene oxide units in the molecule up to 25 wt .-% before Adds up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant contains. 61. The method according to any one of claims 31 to 39, characterized in that the core molding a) as ingredient i) or I) nonionic surfactants of the formula
R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ]
contains, in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1.5 and y stands for a value of at least 15. 62. The method according to any one of claims 31 to 39, characterized in that the core molding a) as ingredient i) or I) end-capped poly (oxyalkylated) nonionic surfactants of the formula
R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²
contains, in which R ¹ and R ² stand for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R ^{3 stands} for H or a methyl, ethyl, n-propyl, iso- Propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type
R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²
in which x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred. 63. The method according to any one of claims 32 to 41, characterized in that the Core moldings a) as ingredient II) 12.5 to 85, preferably 15 to 80, particularly preferably contains 17.5 to 75 and in particular 20 to 70% by weight of fat (s). 64. The method according to any one of claims 32 to 42, characterized in that the Molded core a) as ingredient II) one or more substances from the groups of Fatty alcohols containing fatty acids and fatty acid esters. 65. The method according to any one of claims 32 to 43, characterized in that the core molding a) as ingredient II) one or more C _10-30 fatty alcohols, preferably C _12-24 fatty alcohols, with particular preference for 1-hexadecanol, 1st Octadecanol, 9-cis-octadecen-1-ol, all-cis-9,12-octadecadien-1-ol, all-cis-9,12,15-octadecatrien-1-ol, 1-docosanol and mixtures thereof, contains. 66. The method according to any one of claims 31 to 44, characterized in that the Molded core a) as ingredient ii) or III) one or more substances with one Melting range between 30 and 100 ° C, preferably between 40 and 80 ° C and ins especially between 50 and 75 ° C. 67. The method according to any one of claims 31 to 45, characterized in that the Molded core a) as ingredient ii) or III) at least one paraffin wax with egg contains a melting range from 30 ° C to 65 ° C. 68. The method according to any one of claims 31 to 46, characterized in that the Core moldings a) as ingredient ii) or III) at least one substance from the group which contains polyethylene glycols (PEG) and / or polypropylene glycols (PPG). 69. The method according to any one of claims 31 to 47, characterized in that the Shaped core body a) as ingredient iv) or IV) further active ingredients and / or auxiliary substances the groups of dyes, fragrances, anti-settling agents, suspending agents, anti-salts Floating agents, thixotropic agents and dispersing agents in amounts from 0 to 10% by weight, preferably from 0.25 to 7.5% by weight, particularly preferably from 0.5 to 5 wt .-% and in particular from 0.75 to 2.5 wt .-%, contains. 70. The method according to any one of claims 31 to 48, characterized in that the Molded core a) has a melting point between 50 and 80 ° C, preferably between has 52.5 and 75 ° C and in particular between 55 and 65 ° C. 71. The method according to any one of claims 1 to 49, characterized in that the Ge Weight ratio of the entire molded body to the sum of the masses of all in the mold core moldings contained in the range from 1: 1 to 100: 1, preferably from 2: 1 to 80: 1, particularly preferably from 3: 1 to 50: 1 and in particular from 4: 1 to 30: 1 lies. 72. The method according to any one of claims 1 to 71, characterized in that the sum me of all visible surfaces of all core moldings 1 to  80%, preferably 5 to 65%, particularly preferably 10 to 50% and in particular 15 accounts for up to 40% of the total surface of the molded body. 73. The method according to any one of claims 1 to 72, characterized in that the Vo lumens of all core moldings contained in the molded body 1 to 60%, preferably 2.5 up to 50%, particularly preferably 5 to 40% and in particular 7.5 to 30% of the total volume of the molded body. 74. The method according to any one of claims 1 to 73, characterized in that the height 10 to 50%, preferably 15 to 45%, of the moldings produced in step a) particularly preferably 20 to 40% and in particular 25 to 35% of the total height of the Molded body. 75. The method according to any one of claims 1 to 51, characterized in that min at least a core molding loosens faster than the base molding. 76. The method according to any one of claims 1 to 52, characterized in that min at least a core molding loosens more slowly than the base molding.