WO2001007244A1 - Tableting presses and pressing method - Google Patents

Abstract

The invention relates to tableting presses which significantly reduce the sticking of the material being pressed to the presses during the tableting process and which are particularly suitable for producing shaped detergent bodies. The inventive tableting presses have projections and recesses on their pressing surfaces, the distance between the projections being between 5 and 200 νm and the height of the projections being between 5 and 100 νm. The use of tableting presses of this type makes long tableting times possible, without cleaning intervals and regardless of the tableting press used, without any negative effects on the individual shaped body.

Description

 .Tabletting punches and pressing methods'

The present invention relates to tabletting punches and a process for the production of moldings, in particular detergent tablets, using such tabletting punches. In particular, the invention relates to a method for producing such shaped articles in large quantities, the weight fluctuations of the tablets and the caking of the stamp on the tabletting stamps being minimized within a series.

The production of molded articles, especially tablets, is a state of the art in the field of pharmacy, in particular. Thanks to its specified dosage, its compactness and the reduced packaging, transport and storage costs due to its high density, the "tablet" offer has also found its way into other areas. Today, tablet technology is used to manufacture many everyday products such as batteries or tea lights, in particular detergent tablets for machine dishwashing and detergent tablets for household laundry of textiles are important.

As with the manufacture of pharmaceutical tablets, problems arise in the production of detergent tablets, which concern the fluctuating weight and thus also the fluctuating hardness of several tablets within a series. Especially for detergent tablets, the dichotomy between hardness and disintegration time is a central problem - on the one hand, the tablets have to be sufficiently stable to be packed after being pressed, transported to the retailer and handled by the consumer, but on the other hand to guarantee washing and Extremely short disintegration times can be achieved in order to prevent residues on textiles or to allow the molded articles to be washed in via the washing-in chamber of household washing machines. In the Large-scale production cannot avoid the fact that the moldings produced differ more or less in their hardness. Since the tablet presses usually used for manufacturing (both eccentric and rotary presses) compress to a predetermined height (corresponding to a constant volume), fluctuations in density of the premix to be pressed and inaccuracies in the metering of the premix lead to weight fluctuations in the finished shaped bodies, which is additionally caused by this can be reinforced that the premixes to be pressed adhere to the tabletting rams during the pressing process. Such caking of stamps leads to weight loss on individual tablets and, moreover, has the effect that flat surfaces can no longer be pressed. The tabletting punches must therefore usually be cleaned at short intervals with each tabletting.

In order to solve such problems in tablet technology, special recipe optimizations or the use of mold release agents are recommended in the prior art. From the technical point of view, it is recommended to provide the punches with plastic inserts or to use machines that allow the punches to rotate. However, all of the solutions mentioned only partially lead to success.

The present invention was based on the object of providing tabletting stamps which significantly reduce the problem of stamp caking when tabletting. In particular, in the production of detergent tablets, a method should be provided which, regardless of the tablet press used, makes it possible to carry out long tableting intervals without a cleaning interval and without negative effects on the individual tablets.

This task is solved by providing tabletting punches with a defined surface structure and using them in tabletting processes.

The invention thus relates to tabletting punches, the pressing surface of which has elevations and depressions, the distance between the elevations being between 5 and 200 μm and the height of the elevations between 5 and 100 μm. The special surface structure of the pressing surfaces leads to significantly minimized caking when tabletting particulate premixes, whereby the nature of the mixture to be tableted plays a subordinate role. The materials from which the press surface or the press die are made are freely selectable and can be adapted to other requirements, for example with regard to strength, weight, tendency to wear, etc. Preferred surface structures show elevations and depressions which have heights and distances within narrower areas. Preferred tabletting punches are characterized in that the distance between the elevations is 6 to 180 μm, preferably 7 to 160 μm, particularly preferably 8 to 140 μm and in particular 10 to 100 μm. Analogous information can be given about the amount of the surveys. In preferred tabletting punches, the height of the elevations is 6 to 90 μm, preferably 7 to 80 μm, particularly preferably 8 to 70 μm and in particular 10 to 50 μm.

Optimally low caking is achieved if the elevations of the surface structures are close enough together to prevent the depressions or depressions between the areas from being touched by particles or ingredients of the premix to be pressed. If the elevations of the surface structures are close together or if the depressions are not deep enough, the surface structure again acts like a closed surface and can be wetted better, which increases the tendency to stick. The aim should therefore be that the increasing the distance between the surveys, the greater their height.

Such surface structures can be produced in a wide variety of ways. For example, it is possible to subject the pressing surface of a prefabricated tabletting die to one of the treatment steps mentioned below in order to produce the desired surface structure. Another possibility is to produce parts of the press stamp separately with the desired surface structure and to subsequently connect them to the rest of the stamp part. The production of disks with the desired surface structures should be mentioned in particular, the disks being applied (for example glued) to tabletting dies after their manufacture and forming the pressing surface. The surface structures according to the invention can be implemented independently of the geometry of the pressing surface, so that flat pressing surfaces with a circular, elliptical, triangular, square, rectangular, square, five, six, seven, eight and polygonal shape, but also with completely irregular shapes such as arrows, plant or animal shapes can be produced. The surface structure of the pressing surfaces according to the invention offers particular advantages in the case of non-planar pressing surfaces, in particular those which have surface structures such as milled or raised lettering, characters, etc. Convex or concave curved pressing surfaces can also be provided according to the invention.

The surface structure according to the invention can subsequently be applied to the stamp or produced on it. It is possible, for example, to apply such surface structures in that correspondingly large particles are adhered to smoother pressing surfaces. Here, in particular, the adhesion of particles, in particular plastic particles, has proven itself. Subsequent application of the surface structures is also easily possible, for example, by gluing appropriate foils or panes. Here the film or disk forms the pressing surface. The surface structures according to the invention can be produced on stamping surfaces, for example by subsequent scribing, embossing or etching, and heated stamping parts or rollers can also be used, which has proven particularly useful in the case of thermoplastic deformable stamping surfaces. The etching can be carried out, for example, by chemical etching or by physical etching, for example ion etching or sandblasting.

In addition to the size and spacing of the elevations, the shape of the elevations can also be specifically varied in the shaping. It is particularly preferred here if the elevations have rounded tips, which are ideally hemispherical.

The materials of the pressing surface can be freely selected according to the invention and thus adapted to other requirements. In view of a particularly large reduction in die caking, it has proven to be preferred to make the pressing surfaces as water-repellent as possible. Here, tabletting punches are particularly preferred in which at least the elevations consist of hydrophobic polymers or durable hydrophobicized materials. In particular, polyolefins, preferably polyethylene or polypropylene, have proven successful as hydrophobic polymers, from which at least the elevations preferably consist. Polyethylenes (PE) are polymers with groupings of the type belonging to the polyolefins

- [CH ₂ -CH ₂ ] -

as a characteristic basic unit of the polymer chain. Polyethylenes are produced by polymerizing ethylene using two fundamentally different methods, the high-pressure and the low-pressure process. The resulting products are accordingly often referred to as high-pressure polyethylene or low-pressure polyethylene; they differ mainly in their degree of branching and, related to this, in their degree of crystallinity and density. Both processes can be carried out as solution polymerization, emulsion polymerization or gas phase polymerization.

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 copolymerization of the ethylene with longer-chain olefins, in particular with butene and octene; the copolymers have the code 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 materials for at least the elevations, it being preferred if the entire pressing surface consists of these materials. Polypropylenes (PP) are thermoplastic polymers of propylene with basic units of the type

- [CH (CH ₃ ) -CH ₂ ] -

Polypropylenes can be prepared by stereospecific polymerization of propylene in the gas phase or in suspension to give highly crystalline isotactic or less crystalline syndiotactic or amorphous atactic polypropylenes. Technically important isotactic polypropylene, in which all methyl groups are located on one side of the polymer chain. Polypropylene is characterized by high hardness, resilience, rigidity and heat resistance and is therefore an ideal material for the surveys within the scope of the present invention.

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

Tableting punches according to the invention, in which at least the elevations consist of a polyolefin, preferably of polyethylene or polypropylene, are preferred.

Further tablet punches preferred in the context of the present invention are characterized in that at least the elevations consist of polyvinylidene fluoride or polytetrafluoroethylene.

Polyvinylidene fluorides, also called PVDF or PVF2 for short, are polymers that can be produced from vinylidene fluoride with the basic unit:

- [CH ₂ -CF ₂ ] - Polyvinylidene fluorides are thermoplastic, easily processable fluoroplastics with high resistance to the effects of temperature and chemicals, but do not achieve PTFE quality in this regard. The degree of crystallinity of the polyvinylidene fluoride depends on its thermal history: rapid cooling of thin molded parts (fo lien) leads to transparent (amorphous), slow cooling (or post-annealing) to highly crystalline products.

Polyvinylidene fluorides are notable for high mechanical strength, rigidity and toughness (even at low temperatures) and, in the context of the present invention, are outstandingly suitable as materials for the elevations on the pressing surfaces or for entire pressing surfaces or pressing dies.

Polytetrafluorethylene are polymers of tetrafluoroethylene with the basic unit:

- [CF ₂ -CF ₂ ] -

which are also referred to with the abbreviation PTFE. Another common name for such polymers is the name Teflon ^® , a trademark of Du Pont for polytetrafluoroethylene (PTFE), developed by RJ Plunkett at Du Pont in 1938, manufactured since 1941 and sold under the trademark since 1943.

Technical polytetrafluoroethylenes have degrees of polymerization of n = approx. 5000-100000, which corresponds to molar masses of approx. 500000-10000000 g / mol. The polymerization of the monomers is initiated by free radicals in the aqueous medium in the absence or presence of stabilizers. In the first case, a dispersion of the polytetrafluoethylenes results in the initial stage of the polymerization, which coagulate in the further course of the reaction. The result is a granulate which, after working up, is ground to the desired particle size. Fine-powdered polytetrafluoroethylene products are obtained when emulsifiers are used in a type of emulsion polymerization as a metastable dispersion that can be easily broken to isolate the polymers. Under suitable conditions, fine-particle stable dispersions with solids contents of 60-65% can also be produced when using ionic surfactants as stabilizers.

Polytetrafluoethylenes are thermoelastic polymers with high linearity, a relatively high (up to 70%) degree of crystallinity and a melting point of approx. 327 ° C, at which they become glass-like transparent. Polytetrafluoethylenes have an extremely high chemical resistance and can be used in a very wide temperature range (-200 ° to 250 °); they have high thermal resistance (maximum continuous use temperature approx. 260 °). Polytetrafluoroethylenes have only a very low adhesive power, which, in conjunction with the surface structures according to the invention, makes them ideal materials for pressing surfaces or entire pressing dies. For particularly demanding applications in which, for example, high creep resistance and low cold flow are required, polytetrafluoroethylenes can be reinforced by adding glass fibers, carbon fibers, carbon black, molybdenum sulfide or polymers such as polyimides, polyether ketones or polyphenylene sulfides.

In addition to the polyolefins and fluoropolymers, polyamides are preferred materials for the elevations in the context of the present invention. Polyamides are high-molecular compounds that consist of building blocks linked by peptide bonds. With a few exceptions, the synthetic polyamides (PA) are thermoplastic, chain-like polymers with recurring acid amide groups in the main chain. According to the chemical structure, the so-called homopolyamides can be divided into two groups: the aminocarboxylic acid types (AS) and the diamine-dicarboxylic acid types (AA-SS); A denotes amino groups and S carboxy groups. The former are formed from one building block by polycondensation (amino acid) or polymerization (ω-lactam), the latter from two building blocks by polycondensation (diamine and dicarboxylic acid).

The polyamides are coded from unbranched aliphatic building blocks according to the number of carbon atoms. For example, the name PA 6 is the polyamide and ε-aminocaproic acid or ε-caprolactam. PA 12 is a poly (ε-laurine lactam) made from ε-laurine lactam. With type AA-SS, the carbon number of diamine and then that of dicarboxylic acid are mentioned first: PA 66 (polyhexamethylene adipamide) is made from hexamethylene diamine (1,6-hexane diamine) and adipic acid, PA 610 (polyhexamethylene sebacinamide) from 1, 6-hexanediamine and sebacic acid, PA 612 (polyhexamethylene dodecanamide) from 1,6-hexanediamine and dodecanedioic acid. In the context of the present invention, the polyamide types mentioned are preferred materials for the elevations on the surfaces or for the surfaces themselves. Tableting punches preferred according to the invention consist at least of the elevations of a polyamide, preferably of PA 6, PA 12, PA 66, PA 610 or PA 612.

Other preferred materials for the surveys are polyurethanes. Tableting punches in which at least the elevations consist of a polyurethane are also preferred.

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 ^! -O]-

as characteristic basic units of the basic macromolecules, in which R ^{1 stands} for a low-molecular or polymeric diol radical 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 -CH ₂ -C ₆ H ₄ ) or hexamethylene diisocyanate [HMDI, R ² = (CH ₂ ) ₆ ].

The plastics mentioned can be used alone as materials for the surveys, but they can also be provided with coatings or laminations made of metals or other substances. In the context of the present invention, the use of glass fiber-reinforced plastics as a material for pressing surfaces to which the structures mentioned are applied has proven particularly useful. Glass fiber reinforced plastics (GRP) are composite materials made from a combination of a matrix of polymers and glass fibers that act as reinforcements. The glass materials used for fiber reinforcement are present in the GRP as fibers, yarns, rovings (fiberglass strands), nonwovens, fabrics or mats. Suitable polymeric matrix systems for GRP are both thermosets (such as epoxy resins, unsaturated polyester resins, phenol and furan resins), and thermoplastics (such as polyamides, polycarbonates, polyacetals, polyphenylene oxides and sulfides, polypropylenes and styrene copolymers). The weight ratio between reinforcing material and polymer matrix is usually in the range of 10: 90-65: 35, the strength properties of the GRP generally increasing up to an amplifier content of approx. 40% by weight.

The GRP is mainly manufactured in pressing processes; other important manufacturing processes are hand lamination, fiber spraying, continuous impregnation, winding and spinning processes. In many cases, so-called prepregs, glass fiber materials pre-impregnated with resins, are used, which are heat-cured using pressure. Compared to the non-reinforced matrix polymers, the GRP are characterized by increased tensile, bending and compressive strength, impact resistance, dimensional stability and stability against the influence of heat, acids, salts, gases or solvents. In the context of the present invention, glass-fiber-reinforced polyterafluoethylene and glass-fiber-reinforced polyamides have proven particularly useful as materials for the pressing surfaces or tabletting punches. Tableting punches in which at least the elevations consist of a glass fiber reinforced plastic, preferably a glass fiber reinforced polytetrafluoroethylene or polyamide, are therefore preferred.

In the case of the composite materials mentioned, it is possible to produce the surface structures from composite powder or films, but it is also possible to prepare entire tablet punches from the composite materials, which are subsequently provided with the surface structure according to the invention, see above.

Further materials from which at least the elevations on the pressing surfaces of the pressing dies according to the invention, but preferably the entire pressing surfaces or pressing dies can consist are, for example, silicones or silanized hydrophilic surfaces. Metals are also suitable as materials from which at least the elevations on the pressing surfaces of the pressing dies according to the invention, but preferably the entire pressing surfaces or pressing dies, can be made. In addition to the known steels and stainless steels of the prior art, titanium and titanium alloys, tantalum and tantalum alloys as well as tungsten and tungsten alloys are particularly suitable. In principle, however, all metals are well suited, and the choice of materials can be made with regard to the material to be tabletted. Another object of the present invention is a process for the production of moldings by pressing a particulate premix, in which the tabletting punches used for pressing have elevations and depressions on their pressing surface, the distance between the elevations being between 5 and 200 μm and the height the elevations are between 5 and 100 μm.

As already mentioned in the introduction, significantly reduced stamp caking is achieved regardless of the physical and chemical properties of the premix. The method according to the invention can therefore be used advantageously for all tableting processes. The production of pharmaceutical tablets, the tableting of battery parts, the production of food and animal feed, the tableting of candles and other consumer goods as well as the production of technical tablets such as carbon briquettes, catalysts in tablet form or the like are only examples here. called.

The process according to the invention can be used with particular advantage for tableting “sticky” premixes, such as are tabletted, for example, in the production of compact detergent tablets. Another object of the present invention is therefore a process in which the particulate premix is a detergent or Detergent composition is and the tablets are detergent tablets.

Pressable premixes for detergent tablets have usually at least one surfactant-containing granulate, which is mixed with other detergent or cleaning agent ingredients to form the premix to be pressed and subsequently pressed. In preferred methods according to the invention, particulate premix contains surfactant-containing granules and has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1.

The production of granules containing surfactants is widely described in the prior art. In addition to the conventional granulation and agglomeration processes, which can be carried out in a wide variety of mixing granulators and mixing agglomerators, press agglomeration processes can also be used, for example. The granulation can be carried out in a large number of apparatuses customarily used in the detergent and cleaning agent industry. Both high-intensity mixers ("high-shear mixers") and normal mixers with lower circulation speeds can be used as mixers. Suitable mixers are, for example, Eirich mixer ^® Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi Flexomix ^®, the Fukae ^® FS-G mixers (trade marks of Fukae Powtech, Kogyo Co., Japan), the Lödige ^® FM, KM and CB mixers (trademarks of Lödige Maschinenbau GmbH, Paderborn) or the Drais ^® series T or KT (trademarks of Drais-Werke GmbH, Mannheim). The residence times of the granules in the mixers are in the range of less than 60 seconds, the residence time also being dependent on the circulation speed of the mixer. The dwell times are reduced accordingly the faster the mixer runs. The residence times of the granules in the mixer are preferably less than one minute, preferably less than 15 seconds.

In preferred methods according to the invention, the surfactant granules have particle sizes between 200 and 2000 μm, preferably between 400 and 1800 μm and in particular between 600 and 1400 μm.

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

These surface-active substances come from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and because of their range of services. Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably Cg.ι - alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from Cι- ₈ monoolefins with an end 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, which are for example obtained from _2- Cι ι ₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

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

As alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₀ -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, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₂ -C ₆ alkyl sulfates and C ₁ -C ₅ alkyl sulfates and C ₅ -C ₅ alkyl sulfates are preferred for reasons of washing technology. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants. The sulfuric acid monoesters of the straight-chain or branched C _-2] alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cg.π alcohols with an average of 3.5 moles of ethylene oxide (EO) or Cι _2- ι ₈ fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-i8 fatty alcohol radicals or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

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

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

In the context of the present invention, processes for producing detergent tablets are preferred in which the content of the surfactant granules is high anionic surfactants is 5 to 45% by weight, preferably 10 to 40% by weight and in particular 15 to 35% by weight, in each case based on the weight of the surfactant granules.

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

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue is linear or preferably in 2- Position may be methyl branched or may contain linear and methyl branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, C ₁₂ -14-alcohols with 3 EO or 4 EO, C _9- π alcohol containing 7 EO, _{C] 3-15} - alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C _{] 2-0 8} alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci ₂ - ₁₄ alcohol with 3 EO and

with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

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

Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.

The detergent tablets according to the invention can preferably contain alkyl polyglycosides, with APG contents of more than 0.2% by weight, based on the entire tablet, being preferred. Particularly preferred detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.

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

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I), R ¹

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

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

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

R * -OR ²

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

in which R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^! represents a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ^{2 stands} for a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical with 1 to 8 carbon atoms, where C - alkyl or Phenyl radicals are preferred and [Z] stands for a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example, after the teaching of international application WO-A-95/07331 can be converted into the desired polyhydroxyfatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

In detergent tablets which can preferably be produced in the context of the present invention, the nonionic surfactant content of the surfactant granules is 1 to 15% by weight, preferably 2.5 to 10% by weight and in particular 5 to 7.5% by weight. , each based on the weight of the surfactant granules.

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

The surfactant granules can be used in the detergent tablets or in individual phases of multiphase tablets in varying amounts. Detergent tablets produced according to the invention, in which the proportion of the surfactant-containing granules in the detergent tablets or in a single phase of the detergent tablets 40 to 95% by weight, preferably 45 to 85% by weight and in particular 55 up to 75% by weight, based in each case on the weight of the shaped body, is preferred. Such methods according to the invention are characterized in that the surfactant granules are mixed with further processing components to form a compressible premix which contains 40 to 95% by weight, preferably 45 to 85% by weight and in particular 55 to 75% by weight, of the surfactant granules ,

From an application point of view, it can be advantageous if certain surfactant classes are not contained in some phases of the detergent tablets or in the entire tablet, ie in all phases. Another important embodiment The present invention therefore provides that at least one phase of the shaped body is free from nonionic surfactants.

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

Similar to nonionic surfactants, the omission of anionic surfactants from individual or all phases can result in detergent tablets which are more suitable for certain areas of application. For this reason, detergent tablets in which at least one phase of the tablet is free from anionic surfactants are also conceivable within the scope of the present invention.

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

All salts of orthosilicic acid Si (OH) ₄ and their condensation products are suitable as silicates. For the sake of clarity, the silicates are often not formulated like the other salts, but are formally broken down into oxides. Although the silicates can have very different structures, they are based on the following simple construction principle: each Si atom is always surrounded by four O atoms, and only the different combinations of these SiO units provide the individual silicate classes. The first main type are silicates with independent, "discrete" anions such as orthosilicates with the anion [SiO ⁴ ] ^2- (so-called nesosilicates or "island silicates"), or di- or trisilicates (so-called sorosilicates or group silicates) ), or Cyclosilicates (ring silicates), in which the [SiO ₄ ] tetrahedra are arranged in rings. So-called inosilicates (chain and ribbon silicates) are known as the second main type. In these the [SiO ₄ ] tetrahedra are linked together to form chains, ie to one-dimensionally unlimited structures that are practically polymers of the anion [SiO] ^{2 ~} . This includes the large number of metasilicates. Combining two chains creates double chains or bands with the anion [SL i] ^6- . Phyllosilicates (leaf and layered silicates) are the third main type. In these silicates, the [SiO] tetrahedra are each linked in one plane; they form layer lattices and are polymers of the anion [Si ₄ Oιo]. The fourth main type are the tectosilicates (framework silicates), in which the chaining of the [SiO ₄ ] tetrahedra continues in all three spatial directions. These are practically polymers of SiO ₂ .

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

Amorphous sodium silicates with a 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 in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “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 ones X-rays having 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 as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

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

nNa ₂ O ^• (ln) K ₂ 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 granular compound and can also be used for a kind of "powdering" of the entire mixture to be pressed, both ways being usually used to incorporate the zeolite into the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. Among the large number of commercially available phosphates, the alkali Lime metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) are of the greatest importance in the detergent and cleaning agent industry.

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

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

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

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 like ^{* 3} , melting point 94 ° with loss of water) In the case of substances, colorless crystals are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed when disodium phosphate is heated to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying. The decahydrate complexes heavy metal -Salt and hardness agent and therefore reduces the hardness of water. Potassium diphosphate (potassium pyrophosphate), KΛO7, exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 ^"3 , which is soluble in water, the pH of the 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 differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates. The technically important pentasodium triphosphate, Na ₅ P ₃ Oιo (sodium tripolyphosphate), is an anhydrous or 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] n- Well with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ Oιo (potassium tripolyphosphate), for example in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) on the market. 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 _{] 0} + H ₂ O

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

In addition to the builders described above, the surfactant granules can also contain polymers, so-called cobuilders. These can also be part of the premix without being present in the surfactant granulate. An important class of polymers with cobuilder properties are the polymeric polycarboxylates. Such (co) polymeric polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol. In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

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

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

To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers. Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers , Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers. Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspagic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Polycarboxylates / polycarboxylic acids, dextrins, other organic cobuilders (see below) and phosphonates can be used in particular in the detergent tablets according to the invention as further organic cobuilders. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

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

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

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0472 042 and EP-A-0 542 496 and international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediaminisisuccinate, are further suitable cobuilders. Ethylenediamine-N, N ^'- disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate. Further usable organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. 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. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

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

The amount of builder is usually between 10 and 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight. Again, the amount of builders used depends on the intended use. It has been shown that excessive amounts of carbonates in the surfactant granules can be problematic in certain formulations, which is why it is advantageous in such formulations not to introduce the carbonates into the detergent tablets via the surfactant granules, but rather as part of the premix, provided that their use is desired. In such formulations, the production of detergent tablets is preferred in which the content of the surfactant granules in sodium and / or Potassium carbonate is below 15% by weight, preferably below 10% by weight and in particular below 5% by weight, in each case based on the weight of the surfactant granules.

In addition to the surfactant and builder components mentioned, the detergent tablets produced according to the invention and thus the premixes to be pressed can also contain one or more substances from the group of disintegration auxiliaries, bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes , Foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors. In the following information on the individual substances, they are described in part as a component of the premix and in part as a component of the detergent tablets produced from this premix.

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

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

The industrial production of sodium percarbonate is mainly produced by precipitation from an aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg ²⁺ ions). The precipitated salt, which still contains 5 to 12% by weight of mother liquor, is then filtered off and dried in fluidized bed dryers at 90.degree. The bulk density of the finished product can vary between 800 and 1200 g / 1 depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating processes and materials used for coating are widely described in the patent literature. In principle, according to the invention, all commercially available percarbonate types can be used, such as those offered by the companies Solvay Interox, Degussa, Kemira or Akzo.

Further bleaching agents that can be used are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and HO ₂ -supplying acidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, irrespective of which other ingredients are contained in the molded articles. If cleaning tablets or bleach tablets for machine dishwashing are manufactured, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoxy acid perooxyperaproic acid (ε-phthalimidoperoxy-capoic acid) )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxybriperyl acid Acids, 2-decyldiperoxybutane-l, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

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

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

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

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-Moφholinium-acetonitrile-methyl sulfate (MMA), and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767 and acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylactamylactamylactamylactamylactamylamylamylamylamylactamylamylamylactamylamylamylamylactamylamylamylactamylactylamylamylactamylamylactamylamylamylactyl and lactam, for example. Hydrophilically substituted acylacetals and acyllactams are also preferably used. Combinations of conventional bleach activators can also be used.

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

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

Bleach-enhancing transition metal complexes, in particular 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 are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular 0.0025% by weight .-% to 1 wt .-% and loading particularly preferably from 0.01% by weight to 0.25% by weight, based in each case on the total agent. But in special cases, more bleach activator can be used.

Because of their oxidizing effect, it is advantageous to separate the bleaching agents from other ingredients, for which multi-phase moldings are particularly suitable. Detergent or shaped articles in which one of the phases of the shaped article contains bleaching agents while another phase contains bleach activators are preferred.

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

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

The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, approximately 0.1 to 5% by weight, preferably 0.5 to approximately 4.5% by weight, in each case based on the premix (s). Corrosion inhibitors can also be incorporated into the washing or cleaning agent molded articles to protect the items to be washed or the machine, silver protection agents being particularly important in the field of automatic dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

If anti-corrosive agents are used in multi-phase moldings, it is preferred to separate them from the bleaching agents. Detergent tablets, in which one phase contains bleaching agent while another phase contains anti-corrosion agents, are therefore preferred.

Further ingredients which can be part of the detergent tablets in the context of the present invention are, for example, dyes, optical brighteners, fragrances, soil-release compounds, soil repellents, antioxidants, fluorescent agents, foam inhibitors, silicone and / or paraffin oils, color transfer inhibitors. ren, graying inhibitors, detergent boosters, etc. In order to improve the aesthetic impression of the detergent tablets according to the invention, they can be wholly or partially colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substance to the treated substrates, such as textile fibers or dishes, in order not to stain them.

Preferred for use in detergent tablets produced according to the invention are all colorants which can be oxidatively destroyed in the washing process, and also mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. For example, anionic colorants, for example anionic nitroso dyes, are suitable. A possible colorant is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which is available as a commercial product, for example as Basacid Green 970 from BASF, Ludwigshafen, and mixtures thereof suitable blue dyes. Other colorants include Pigmosol ^® Blue 6900 (CI 74160), Pigmosol ^® Green 8730 (CI 74260), Basonyl ^® Red 545 FL (CI 45170), Sandolan ^® Rhodamine EB400 (CI 45100), Basacid ^® Yellow 094 (CI 47005), Sicovit ^® Patentblau 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol ^® Blau GLW (CAS 12219-32-8, CI Acidblue 221 )), Nylosan ^® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan ^® Blue (CI Acid Blue 182, CAS 12219-26-0).

When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the washing or cleaning supply convey. In the case of colorants which are readily water-soluble, for example the above-mentioned basacid

® green or the above-mentioned Sandolan blue, colorant concentrations are typically selected in the range from a few 10 ^" to 10 ^" % by weight. In the case of those which are particularly preferred on the basis of their brilliance, but less water-soluble

Pigment dyes, e.g. the Pigmosol dyes mentioned above, is the most suitable

Concentration of the colorant in detergents or cleaning agents, on the other hand, is typically around 10 ^"3 to 10 ^{" 4} % by weight.

The premixes to be invented may contain one or more optical brighteners. These fabrics, which are also called "whiteners", are used in modern laundry detergents because even freshly washed and bleached white laundry has a slight yellow tinge. Optical brighteners are organic dyes that convert part of the invisible UV radiation from sunlight into longer-wave blue light. The emission of this blue light complements the "gap" in the light reflected by the textile, so that a textile treated with an optical brightener appears whiter and brighter to the eye. Since the action mechanism of brighteners presupposes that they are drawn onto the fibers, a distinction is made depending on the "dyed" fibers, for example brighteners for cotton, polyamide or polyester fibers. The commercially available brighteners suitable for incoφoration in detergents essentially comprise five structural groups: the stilbene, the diphenylstilbene, the coumarin-quinoline, the diphenylpyrazoline group and the group of combinations of benzoxazole or benzimidazole with conjugated systems. An overview of common brighteners can be found, for example, in G. Jakobi, A. Löhr "Detergents and Textile Washing", VCH-Verlag, Weinheim, 1987, pages 94 to 100. Suitable are for example salts of ^4,4'-bis [(4-anilino-6-moφholino-s-triazine-2-yl) amino] stilbene-2,2'-disulfonic acid or compounds of similar composition which, instead of Moφholino- Grappe carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brighteners can also be used. Fragrances are added to the agents according to the invention in order to improve the aesthetic impression of the products and, in addition to the performance of the product, to provide the consumer with a visually and sensorially "typical and distinctive" product. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are glycinate phenyl-, Allylcyclohexylpropionat, Styrallylpropionat and benzyl are benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethyl-thylbenzyl carbinylacetat, phenylethyl acetate, Linalyl benzoate, benzyl formate, ethyl methyl. The ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the ionones, o - isomethyl ionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and teφineol, the hydrocarbons mainly include the teφenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citms, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrance content of the detergent tablets according to the invention is usually up to 2% by weight of the total formulation. The fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries. In addition, the detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case on the nonionic Cellulose ethers, as well as the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

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

Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used in amounts of 0.1 to 5% by weight, based on the detergent Since textile fabrics, in particular rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers prevent bending and kinking. If pressing and squeezing across the grain are sensitive, the agents produced according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

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

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

Increased wearing comfort can result from the additional use of antistatic agents, which are additionally added to the agents according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. External antistatic agents are, for example, in patent applications FR 1,156,513, GB 873 214 and GB 839 407. The lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed here are suitable as antistatic agents for textiles or as an additive to detergents, an additional finishing effect being achieved.

To improve the water absorption capacity, the rewettability of the treated textiles and to ease the ironing of the treated textiles, for example silicone derivatives can be used in the premixes to be processed according to the invention. These additionally improve the rinsing behavior of the agents due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, poly-dialkyl- or alkylarylsiloxanes, in which the alkyl groups have one to five carbon atoms and are partially or completely fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 centistokes, the silicones being used in amounts between 0.2 and 5% by weight, based on the total agent.

Finally, the premixes and the agents produced therefrom can also contain UV absorbers, which absorb onto the treated textiles and improve the lightfastness of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone with substituents in the 2- and / or 4-position which are active by radiationless deactivation. Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are also suitable.

With all of the above-mentioned ingredients, advantageous properties can result from separating them from other ingredients or assembling them together with certain other ingredients. In the case of multi-phase moldings, the individual phases can also have a different content of the same ingredient, as a result of which advantages can be achieved. Detergent or shaped body, in which at least two phases contain the same active ingredient in different amounts are preferred. As already explained, the term “different amount” does not refer to the absolute amount of the ingredient in the phase, but to the relative amount, based on the phase weight, and therefore represents a% by weight, based on the individual phase, represents.

In order to facilitate the disintegration of highly compressed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology ^'1 " (6th edition, 1987, p. 182-184), tablet disintegrants or disintegration accelerators are understood as auxiliary substances which are suitable for ensure the rapid disintegration of tablets in water or gastric juice and the release of pharmaceuticals in an absorbable form.

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

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

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred washing and cleaning agent shaped bodies such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 up to 6% by weight contain. Pure cellulose has the formal Bmttozusammensetzung (C _Ö H _IO O _S, and, formally, is a beta-l, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of ca. 500 to 5000 Glucose units and consequently have average molar masses 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 esterification or Processes in which hydroxyl hydrogen atoms have been substituted, but also celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound by an oxygen atom, can be used as cellulose derivatives. Derivatives fall, for example, alkali celluloses, carboxymethyl cell ulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free from cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.

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

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

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

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

Another object of the present invention is the use of tabletting punches which have elevations and depressions on their pressing surface, the Distance between the elevations between 5 and 200 microns and the height of the elevations between 5 and 100 microns, to reduce stamp caking.

Regardless of the product to be tabletted, i.e. in the manufacture of tablets in the fields of pharmacy, food technology, battery technology or consumer goods production, the use of press punches with the surface structures mentioned leads to significantly reduced die build-up.

In particular in the case of highly adhesive premixes, the use of the tabletting punches according to the invention clearly shows and unexpected advantages. Such premixes can in particular be detergent or cleaning agent compositions, so that the use of tabletting punches which have elevations and depressions on their pressing surface, the distance between the elevations being between 5 and 200 μm and the height of the elevations being between 5 and 100 μm Production of laundry detergent or cleaning agent molded articles is a further object of the present invention.

Examples:

To produce a tabletting stamp E1 according to the invention, a tabletting stamp made of polytetrafluoethylene (PTFE) was sprayed with spray adhesive and coated with Teflon powder (average particle size: 11 μm). Another tabletting punch E2 according to the invention was obtained by uniformly heating the pressing surface of a tabletting punch made of polyvinylidene fluoride (PVDF) with a warm air device to the thermoplastic state. A sieve fabric was then pressed onto the pressing surface and removed again. As a result, elevations of 21 μm average height were formed at an average distance of 38 μm. As a comparative example V, an untreated tabletting punch made of PTFE was used.

The stamps El, E2 and V were installed as upper stamps in a Korsch eccentric press, where they were used to manufacture detergent tablets.

For this purpose, a surfactant-containing granulate (for composition, see Table 1) was produced by granulation in a 130-liter ploughshare mixer from Lödige, which was used as the basis for a particulate premix. Following the granulation, the granules were dried in a fluidized bed apparatus from Glatt at a supply air temperature of 60 ° C. over a period of 30 minutes. After drying, fine particles <0.4 mm and coarse particles> 1.6 mm were screened off. The premix was prepared by mixing the surfactant-containing granules with bleach, bleach activator and other processing components. The premix was then pressed into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g) in the Korsch eccentric press equipped with the stamps E1, E2 and V. The composition of the premix to be used (and thus the molded body) is shown in Table 2. Table 1: Composition of the surfactant granules [% by weight]

Table 2: Composition of the premix [% by weight]:

The upper stamps E1, E2 and V were weighed at the beginning of the test and after the production of 10 detergent tablets each with a diametrical yield strength of approx. 30 N. The weight of the stamp caking could be calculated directly from the difference between the measured values. The results of the tests are shown in Table 3: Table 3: Weight of the caking [g]:

It can be clearly seen that the stamp caking can be significantly reduced by the stamp according to the invention with a defined surface structure.

Claims

claims:

1. tabletting stamp, characterized in that its pressing surface has elevations and depressions, the distance between the elevations between 5 and 200 microns and the height of the elevations between 5 and 100 microns.

2. tabletting stamp according to claim 1, characterized in that the distance between the elevations is 6 to 180 microns, preferably 7 to 160 microns, particularly preferably 8 to 140 microns and in particular 10 to 100 microns.

3. tabletting stamp according to one of claims 1 or 2, characterized in that the height of the elevations is 6 to 90 microns, preferably 7 to 80 microns, particularly preferably 8 to 70 microns and in particular 10 to 50 microns.

4. tableting stamp according to one of claims 1 to 4, characterized in that at least the elevations consist of hydrophobic polymers or durable hydrophobic materials.

5. tabletting stamp according to one of claims 1 to 5, characterized in that at least the elevations consist of a polyolefin, preferably of polyethylene or polypropylene.

6. tabletting stamp according to one of claims 1 to 5, characterized in that at least the elevations consist of polyvinylidene fluoride or polytetrafluoroethylene.

7. tabletting stamp according to one of claims 1 to 5, characterized in that at least the elevations consist of a polyamide, preferably PA 6, PA 12, PA 66, PA 610 or PA 612.

8. tabletting stamp according to one of claims 1 to 5, characterized in that at least the elevations consist of a polyurethane.

9. tabletting punch according to one of claims 1 to 5, characterized in that at least the elevations consist of a glass fiber reinforced plastic, preferably a glass fiber reinforced polytetrafluoroethylene or polyamide.

10. A process for the production of molded articles by pressing a particulate premix, characterized in that the tabletting punches used for pressing have elevations and depressions on their pressing surface, the distance between the elevations being between 5 and 200 μm and the height of the elevations being between 5 and 100 μm.

11. The method according to Anspmch 10, characterized in that the particulate premix is a detergent or cleaning agent composition and the molded articles are washing or cleaning agent molded articles.

12. The method according to Anspmch 11, characterized in that the particulate premix contains surfactant-containing granules (s) and has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1.

13. The method according to Anspmch 12, characterized in that the surfactant-containing granules have particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 μm.

14. The method according to any one of claims 12 or 13, characterized in that the surfactant-containing granules contains anionic and / or nonionic surfactants and builders and total surfactant contents of at least 10 wt .-%, preferably at least 15 wt .-% and in particular at least 20 % By weight.

15. The method according to any one of claims 12 to 14, characterized in that the surfactant granules with further processing components to a pressable Vorge is mixed, which contains 40 to 95% by weight, preferably 45 to 85% by weight and in particular 55 to 75% by weight, of the surfactant granules.

16. The method according to any one of claims 11 to 15, characterized in that the premix to be veφress further one or more substances from the group of disintegration aids, bleaching agents, bleach activators, enzymes, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, Contains silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

17. The method according to any one of claims 11 to 16, characterized in that the particulate premix is a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the premix.

18. Use of tabletting punches which have elevations and depressions on their pressing surface, the distance between the elevations being between 5 and 200 μm and the height of the elevations being between 5 and 100 μm, in order to reduce stamp caking.

19. Use of tabletting punches which have elevations and depressions on their pressing surface, the distance between the elevations being between 5 and 200 μm and the height of the elevations between 5 and 100 μm, for the production of detergent tablets.