DE19934690A1 - Tabletting stamp used for reducing stamp caking in washing and cleaning tablets, has press surface with depressions and protrusions spaced apart - Google Patents

Abstract

A tabletting stamp has a press surface with depressions and also protrusions spaced apart by 5 - 200 mu m and 5 - 100 mu m deep, giving reduced caking. An Independent claim is also included for the production of molded articles by pressing a particulate mixture in a tabletting stamp with protrusions and depressions. The distance between the protrusions being 5 - 200 mu m and height being 5 - 100 mu m.

Description

The present invention relates to tabletting punches and a method for producing them of moldings, in particular of detergent tablets under Ver use of such tabletting stamps. In particular, the invention relates to a method for Manufacture of such moldings in large quantities, the weight fluctuations the tablets and the stamp caking on the tabletting stamps within a series are minimized.

The production of moldings, especially tablets, is particularly in the area of Pharmaceutical state of the art. The offer form "tablet" has due to their specified dosage, their compactness and the due to high density reduced packaging, transport and storage costs also in others Successfully entered areas. With the help of tablet technology today manufactured many everyday products such as batteries or tea lights, with Reini in particular detergent tablets for automatic dishwashing and detergent tablets for the household laundry of textiles is important.

As in the manufacture of pharmaceutical tablets occur in the production of Detergent tablets have problems with the fluctuating weight and with it the fluctuating hardness of several molded parts within a series affect. The dichotomy is particularly important for detergent tablets hardness and disintegration time are a central problem - the moldings must on the one hand be sufficiently stable to be packed, transported to trade and after pressing  To be handled by the consumer, but on the other hand, must guarantee of a washing and cleaning success extremely short disintegration times can be realized in order For example, to prevent residues on textiles or to wash in the molded articles to enable household washing machines via the dispenser. In the Large-scale production can not be avoided that the molded body produced in differentiate their hardness more or less. Because the usually used to manufacture tablet presses used (both eccentric and rotary presses) on one pressing predetermined height (corresponding to a constant volume), lead density fluctuations in the premix to be pressed and inaccuracies in the dosage of the premix to weight fluctuations in the finished molded articles, the additional can be reinforced by the fact that the premixes to be pressed during the pressing process stick to the tablet punches. Such caking leads to one Weight loss on individual tablets and also cause that no pla let more surfaces be pressed. Usually, the tabletting stamp must be included each tablet should therefore be cleaned at short intervals.

To solve such problems of tableting technology, the prior art sp recipe optimization or the use of mold release agents recommended. Of the The technical side of the equipment is recommended to verse the stamp with plastic inserts hen or use machines that allow the punches to rotate. All ge the solutions mentioned only partially lead to success.

The object of the present invention was now to prepare tabletting punches places that significantly reduce the problem of stamp caking when tabletting. In particular, in the manufacture of detergent tablets should a method is provided that is independent of the tablet used tenpresse enables long tableting intervals without cleaning interval and without negati ve effects on the individual molded body.

This task is solved by tabletting punches with defined surfaces structure and used in tableting processes.  

The invention thus relates to tabletting punches, the pressing surface of which are elevations and Has depressions, the distance between the elevations between 5 and 200 µm and the height of the surveys is between 5 and 100 µm.

The special surface structure of the pressing surfaces leads to particle formation during tableting miger premixes to significantly minimized caking, the nature of the tablet tive mixture plays a subordinate role. Even the materials from which the Press surface or the press ram exist, are freely selectable and can meet other requirements rations, for example with regard to strength, weight, tendency to wear etc. be fit. Preferred surface structures show elevations and depressions that Show heights and distances within narrow areas. So are preferred tablets animal stamp characterized in that the distance between the elevations 6 to 180 µm, preferably 7 to 160 µm, particularly preferably 8 to 140 µm and in particular 10 is up to 100 µm. Analogous information can be given about the amount of the surveys. In preferred tabletting stamps, the height of the elevations is 6 to 90 microns, preferably as 7 to 80 microns, particularly preferably 8 to 70 microns and in particular 10 to 50 microns.

Optimally low caking is achieved when the elevations of the surfaces structures are close enough together to be a touch of between the areas lying depressions or depressions due to particles or ingredients of the ver to avoid pressing premix. Are the elevations of the surface structures the surfaces are close together or if the depressions are not deep enough structure again like a closed surface and can be wetted better where due to the tendency to stick. It should therefore be aimed to increase The distance between the surveys should also increase in height.

The production of such surface structures can be done in many different ways consequences. It is possible, for example, the pressing surface of a prefabricated tabletting star pels to undergo one of the treatment steps mentioned below to the ge to produce the desired surface structure. Another option is parts the press ram separately with the desired surface structure and this subsequently connect with the rest of the stamp. Here is the manufacturer in particular  development of panes with the desired surface structures, the Discs applied to tabletting stamps after their manufacture (example be glued) and form the press surface. The surfaces according to the invention structures can be realized regardless of the geometry of the press surface, so that flat pressing surfaces with circular, elliptical, triangular, square, rectangular tall, square, five, six, seven, eight and polygonal shape, but also with complete irregular shapes such as arrows, plant or animal shapes can be produced. Special The surface structure of the pressing surfaces according to the invention does not offer any advantages plan press surfaces, especially those with surface structures such as milled or have raised lettering, characters, etc. Also convex or concave Pressing surfaces can be provided according to the invention.

The surface structure according to the invention can be subsequently applied to the stamp or be generated on it. An application of such surface structures is an example as possible thereby that correspondingly large particles adhere firmly to smoother pressing surfaces be applied. Here in particular has the sticking of particles, in particular Plastic particles, proven. Subsequent application of the surface structures is for example, by gluing appropriate foils or discs possible. Here the film or disk forms the pressing surface. The generation of the fiction Appropriate surface structures on ram surfaces can be created, for example, by weary scratching, embossing or etching, including heated embossing pieces or whale zen can be used, which is particularly in the case of thermoplastic deformable has proven its stamp surfaces. The etching is, for example, by chemical etching or by physical etching, for example ion etching or sandblasting feasible.

In addition to the size and spacing of the elevations, the shape can also vary The form of the surveys can be varied in a targeted manner. It is particularly preferred if the Elevations have rounded tips, which are ideally hemispherical.

According to the invention, the materials of the pressing surface can be freely selected and thus wide ren requirements are adjusted. With a view to a particularly large reduction  the stamp caking has been found to be preferred, the pressing surfaces possible as water-repellent as possible. Tabletting punches are particularly preferred here, where at least the bumps are made of hydrophobic polymers or durable hydrophobic materials.

In particular, polyolefins, preferably polyethylene or polypropylene, have proven to be useful as hydrophobic polymers, of which at least the elevations consist. Polyethylenes (PE) are polymers belonging to the polyolefins with groups of the type

- [CH ₂ -CH ₂ ] -

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

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

The macromolecules of the polyethylenes from low-pressure processes are largely linear and unbranched. These polyethylenes (HDPE) have degrees of crystallinity of 60-80% and a density of approx. 0.94-0.965 g / cm ³ . They are particularly suitable as 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 obtained by stereospecific polymerization of propylene in the gas phase or in suspension to highly crystalline isotactic or less crystalline syndiotactic or to amorphous atactic polypropylenes. Tech The isotactic polypropylene, in which all methyl groups, is of particular importance are located on one side of the polymer chain. Polypropylene is characterized by high Hardness, resilience, rigidity and heat resistance and is within the The present invention is thus an ideal material for the surveys.

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

Tableting stamp according to the invention, in which at least the elevations from a bottom lyolefin, preferably made of polyethylene or polypropylene, are preferred.

Further tabletting punches preferred in the context of the present invention are there characterized in that at least the elevations made of polyvinylidene fluoride or Po lytetrafluoroethylene exist.

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 not PTFE quality. The degree of crystallinity of the polyvinylidene fluoride depends on their thermal history: rapid cooling of thin molded parts (Fo lien) leads to transparent (amorphous), slow cooling (or post-heating) highly crystalline products.

Polyvinylidene fluorides are characterized by high mechanical strength, rigidity and toughness ability even at low temperatures and are within the scope of the present invention excellent as materials for the elevations on the press surfaces or for entire press surfaces or press stamps suitable.

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), which was developed by R. J. Plunkett at Du Pont in 1938 Manufactured in 1941 and sold under the trademark since 1943.

Technical polytetrafluoroethylenes have degrees of polymerization of n = approx. 5000-100000, the molar masses of approx. 500000-10000000 g / mol correspond. The polymerization of the Mo nomeren is initiated radically in the aqueous medium in the absence or presence of Sta bilisators carried out. In the first case results in the initial stage of the polymerization a dispersion of the polytetrafluoethylenes, which coagulate as the reaction proceeds. The result is a granulate which after working up to the desired particle size len. Fine powder polytetrafluoroethylene products are used with Emul gators in a type of emulsion polymerization obtained as a metastable dispersion, the can easily be broken to isolate the polymers. Under suitable conditions are fine-particle stable dispersions when using ionic surfactants as stabilizers Can be produced with solids contents of 60-65%.  

Polytetrafluoethylenes are thermoelastic polymers with high linearity, relatively high (up to 70%) degree of crystallinity and a melting point of approx. 327 ° C, at which it is glassy become transparent. Polytetrafluoethylenes have an extremely high chemical resistance and can be used in a very wide temperature range (-200 ° to 250 °) become; they have high thermal resistance (maximum continuous use temperature approx. 260 °). Polytetrafluoethylene have only a very low adhesive power, what in combination with the surface structures according to the invention to ideal materials s for press surfaces or entire press dies. For particularly demanding users applications where z. B. high creep resistance and low cold flow are required, can polytetrafluoroethylene by admixing glass fibers, carbon fibers, carbon black, Mo lybdenum sulfide or polymers such as polyimides, polyether ketones or polyphenylene sulfide that are reinforced.

In addition to the polyolefins and fluoropolymers, polyamides are within the scope of the present Invention preferably uses materials for the surveys. Are polyamides high molecular weight compounds made up of building blocks linked by peptide bonds consist. With a few exceptions, the synthetic polyamides (PA) are thermoplastic chain-like polymers with recurring acid amide groups in the Main chain. After the chemical structure, the so-called homopolyamides can be in divide 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 made from a 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 encoded from unbranched aliphatic building blocks according to the An number of carbon atoms. For example, the designation PA 6 is that of 6- Aminocaproic acid or ε-caprolactam and polyamide. PA 12 is a poly (ε laurin lactam) from ε-laurolactam. In the AA-SS type, the number of carbon is first of diamine and then that of dicarboxylic acid: PA 66 (polyhexamethylene adipina mid) arises from hexamethylenediamine (1,6-hexanediamine) and adipic acid, PA 610 (Po  lyhexamethylene sebacinamide) from 1,6-hexanediamine and sebacic acid, PA 612 (polyhexa methylene dodecanamide) from 1,6-hexanediamine and dodecanedioic acid. The mentioned polya mid types are preferred materials for the purposes of the present invention Surveys on the surfaces or for the surfaces themselves preferred tablet stamps according to the invention consist at least of the elevations made of a polyamide, preferably PA 6, PA 12, PA 66, PA 610 or PA 612.

Other preferred materials for the surveys are polyurethanes. Tabletting stamp, where at least the elevations consist of a polyurethane are also be prefers.

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

- [CO-NH-R ² -NH-CO-OR ¹ -O] -

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

The plastics mentioned can be used alone as materials for the surveys , but they can also be coated or laminated with metals or other fabrics. Has proven particularly useful in the context of the present the invention the use of glass fiber reinforced plastics as a material for pressing surfaces, to which the structures mentioned are applied. Glass fiber reinforced plastics (GRP) are composite materials made from a combination of a matrix of polymers and glass fibers acting as amplifiers. The Glasma used for fiber reinforcement Materials are in the GRP as fibers, yarns, rovings (fiberglass strands), nonwovens, fabrics be or mats in front. As polymeric matrix systems for GRP, both thermosets (such as  for example epoxy resins, unsaturated polyester resins, phenol u. Furan resins), as well Thermoplastics (such as polyamides, polycarbonates, polyacetals, polyphenylene oxides and sulfides, polypropylenes and styrene copolymers) are suitable. The weight ratio nis between the reinforcing material and the polymer matrix is usually in the range of 10: 90-65: 35, the strength properties of the GRP usually up to a ver increase the starch content by approx. 40% by weight.

The GRP is mainly manufactured in pressing processes; other important ferti hand lamination, fiber spraying, continuous impregnation, winding and Spin process. In many cases, so-called prepregs with resins from v Rim-impregnated fiberglass materials, made using heat under pressure be hardened. The GFK stand out compared to the non-reinforced matrix polymers through increased tensile, bending and compressive strength, impact strength, dimensional stability and Stability against the influence of heat, acids, salts, gases or solvents out. In the context of the present invention, glass fiber-reinforced materials in particular have become Polyterafluoethylene and glass fiber reinforced polyamides as materials for the pressing surfaces or tablet stamp proven. Tableting stamp, in which at least the elevations made of a glass fiber reinforced plastic, preferably a glass fiber reinforced poly tetrafluoroethylene or polyamide, are therefore preferred.

With the composite materials mentioned, it is possible to make the surface structures from Ver to produce powdered material or foils, but also whole tableting systems pel are prepared from the composite materials, which are subsequently with the Invention surface structure, see above.

Other materials from which at least the elevations on the pressing surfaces of the inventions Press die according to the invention, but preferably the entire press surface or press die pel are, for example, silicones or silanized hydrophilic surfaces. Metals are also considered as materials from which at least the elevations on the press surface Chen the press ram according to the invention, but preferably the entire press surfaces or press ram can be suitable. In addition to the well-known steels and stainless steels of the prior art, in particular titanium and titanium alloys, tantalum  and tantalum alloys as well as tungsten and tungsten alloys. In principle are each but all metals are well suited, the choice of materials taking into account the Good to be tabletted can be taken.

Another object of the present invention is a method for producing Shaped bodies by pressing a particulate premix in which the ver Pressing tabletting stamps on their pressing surface elevations and depressions have, the distance between the elevations between 5 and 200 microns and the The height of the surveys is between 5 and 100 µm.

As already mentioned in the introduction, regardless of the physical and chemi properties of the premix significantly reduced stamp caking. The method according to the invention is therefore advantageous for all tabletting processes to apply. The production of pharmaceutical Ta is just an example bletten, the tableting of battery parts, the production of food and animal feed means, the tableting of candles and other consumer goods as well as the production of technical tablets such as coal briquettes, catalysts in tablet form or the like.

The method for tableting according to the invention can be used with particular advantage Use "sticky" premixes, such as those used to make them more compact Detergent tablets are tabletted. Another subject of The present invention is therefore a process in which the particulate premix is a detergent or cleaning agent composition and the tablets are washing or Detergent tablets are.

Compressible premixes for detergent tablets contain more commonly as at least one surfactant-containing granules, which with further washing or cleaning medium ingredients mixed to the premix to be pressed and then ver is pressed. In preferred methods according to the invention contains particulate pre mixed surfactant-containing granulate (s) and has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.  

The production of granules containing surfactants is widely described in the prior art. Next the conventional granulation and agglomeration processes, which come in a wide variety of Mixing granulators and mixing agglomerators can be carried out, for example wise also press agglomeration process can be used.

The granulation can be found in a wide variety of industries in the detergent and cleaning agent industries usually used apparatus can be carried out. You can use it as a mixer Both high-intensity mixers ("high-sliear mixer") and normal mixers with gerin lower rotational speeds can be used. Suitable mixers are, for example se Eirich® mixer series R or RV (trademark of the machine factory Gustav Ei rich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixer (trademark of Fu kae Powtech, Kogyo Co., Japan), the Lödige® FM, KM and CB mixers (trademark Lödige Maschinenbau GmbH, Paderborn) or the Drais® series T or K-T (goods trademark of Drais-Werke GmbH, Mannheim). The residence times of the granules in the Mi shears are in the range of less than 60 seconds, the residence time also of depends on the speed of the mixer. Here the dwell time is reduced the faster the mixer runs. The residence times are preferably Granules in the mixer under one minute, preferably under 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 a carrier fe, which particularly preferably come from the group of builders. Particularly advantageous Adhesive processes are characterized in that the surfactant-containing granules are anionic and / or nonionic surfactants and builders and total surfactant content of at least 10% by weight, preferably at least 15% by weight and in particular at least at least 20% by weight.  

These surface-active substances come from the group of anionic, non-ionic , zwitterionic or cationic surfactants, anionic surfactants from eco mix reasons and because of their range of services are clearly preferred.

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

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

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

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

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

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

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

Within the scope of the present invention are processes for the production of washing and Preferred detergent tablets in which the content of the surfactant granules anionic surfactants 5 to 45% by weight, preferably 10 to 40% by weight and in particular 15 to 35 wt .-%, based in each case on the weight of the surfactant granules.

When choosing the anionic surfactants, there is no question of freedom of formulation framework conditions in the way. However, preferred surfactant granules have one Soap content of 0.2% by weight based on the total weight of the manufactured Detergent tablets, exceeds. Anionic to be used with preference Surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, preferred ones Detergent tablets 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10 wt .-% fatty alcohol sulfate (s), each based on the Ge importance 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 on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol residue is linear or preferably in the 2-position May be methyl branched or may contain linear and methyl branched radicals in the mixture, as are usually present in oxoalko radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C ₁₃ - ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and _C12-18 alcohol containing 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferred nonionic surfactants, which are used either as allei some nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and pro poxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described, for example, in Japanese Pa tentanmeldung JP 58/217598 are described or which are preferably according to the in the international patent application WO-A-90/13533 become.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides which 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 the symbol which stands for a glycosyl 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, are preferably used in de the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

The detergent tablets according to the invention can preferably Al Contain kylpolyglycoside, with APG contents over 0.2 wt .-%, based on the entire molded body, are preferred. Particularly preferred washing and cleaning agents molded articles contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5 % By weight and in particular from 0.5 to 3% by weight.

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

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

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

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

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

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

In washing and cleaning products which can preferably be produced within the scope of the present invention Non-ionic tensi is the content of the surfactant granules in detergent tablets 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 of these Classes of surfactants and, if applicable, amphoteric or cationic surfactants in the surfactant granule lat are used, are manufacturing processes according to the invention for washing or cleaning Preferred shaped tablets, in which the surfactant content of the surfactant-containing granules 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight, each based on the surfactant granules.

The surfactant granules can be in the detergent tablets or individually NEN phases of multi-phase moldings are used in varying amounts. According to the invention Manufactured detergent tablets, in which the proportion of the surfactant-containing granules on the detergent tablets or on a single phase of the detergent tablet 40 to 95% by weight, preferably 45 to 85% by weight and in particular 55 to 75% by weight, in each case based on the weight of the shaped body is preferred. Such method according to the invention Ren are characterized in that the surfactant granules with further processing com components is mixed into 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 contains.  

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

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

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

In addition to the washing-active substances, builders are the most important ingredients of Detergents and cleaning agents. In the surfactant granules, but also as part of the Premixes can all be used in washing and cleaning agents Builders may be included, in particular thus zeolites, silicates, carbonates, organic Cobuilder and - where there are no ecological prejudices against their use - also that Phosphates. The latter are in particular in detergent tablets for the machine Dishwashers are preferred builders.

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 ₄ units provide the individual silicate classes.

The first main type is formed by 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 combined to form chains, ie to form one-dimensionally unlimited structures that are practically polymers of the anion [SiO ₃ ] ^2- . This includes the large number of metasilicates. Combining two chains creates double chains or ribbons with the anion [Si ₄ O ₁₁ ] ^6- _. Phyllosilicates (leaf and layered silicates) are the third main type. In these silicates, the [SiO ₄ ] tetrahedra are each linked in one plane; they form layer lattices and are polymers of the anion [Si ₄ O ₁₀ ] ^4- . 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 + 1} . 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 disilicates are Na ₂ Si ₂ O ₅ . yH ₂ O is preferred, wherein β-sodium disilicate can be obtained, for example, by the process 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 and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted in such a way that the products have microcrystalline ranges of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a release delay compared to the conventional water glass glasses, are described for example in German patent application DE-A-44 00 024. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.

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

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

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

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

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

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

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

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

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

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

All higher sodium and potassium phosphates are called condensed phos called phate.

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

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

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

In addition to the builders described above, the surfactant granules can also Contain polymers, so-called cobuilders. These can also be part of the pre be mixed without being present in the surfactant granulate. An important class of polymers with The polymeric polycarboxylates are co-builder properties. Such (co) polymeric poly  Carboxylates are, for example, the alkali metal salts of polyacrylic acid or poly methacrylic acid, for example those with a molecular weight of 500 to 70000 g / mol.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _W , 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 Have 2000 to 20,000 g / mol. Because of their superior solubility, the This group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.

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

To improve water solubility, the polymers can also allylsulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer Biodegradable polymers of more than two are particularly preferred various monomer units, for example those which are salts of the monomers Acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or the  as monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar Derivatives included.

Further preferred copolymers are those which are described in German patent applications DE- A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate. Exactly so as further preferred builder substances are polymeric aminodicarboxylic acids, the To name salts or their precursors. Polyaspa are particularly preferred Ragic acids or their salts and derivatives, of which in the German patent application DE-A-195 40 086 discloses that, in addition to cobuilder properties, it is also bleached have a stabilizing effect.

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

As further organic cobuilders in the washing and cleaning agents according to the invention moldings, in particular polycarboxylates / polycarboxylic acids, dextrins, white tere organic cobuilders (see below) and phosphonates can be used. This Substance classes are described below.

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

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

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

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 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.

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

Other useful organic cobuilders are, for example, acetylated hydroxycarbon acids or their salts, which may optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and maxi contain two acid groups. Such cobuilders are used, for example, in the inter national patent application WO 95/20029.

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

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

The amount of builder is usually between 10 and 70 wt .-%, preferably as between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%. How therefore the amount of builders used depends on the intended use. It has It has been shown that excessive amounts of carbonates in the surfactant granules in certain Recipes can be problematic, which is why it is advantageous in such recipes the carbonates do not go into the detergent or cleaning agent form via the surfactant granules  body, but as part of the premix, provided their use is ge wishes. Such formulations involve the manufacture of washing and cleaning agents telformkörper preferred, in which the content of the surfactant granules of sodium and / or Potassium carbonate below 15% by weight, preferably below 10% by weight and in particular below 5% by weight, based in each case on the weight of the surfactant granules.

In addition to the constituents mentioned surfactant and builder, they can be used according to the invention produced detergent tablets and thus the to be pressed Premixes continue to be one or more substances from the group of disintegrations auxiliaries, bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, antiredepositions medium, optical brighteners, graying inhibitors, color transfer inhibitors and Corrosion inhibitors included. The following information on the individual sub These are punched partly as part of the premix, partly as part the detergent tablets made from this premix be wrote.

Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and produce H ₂ O ₂ in water. "Sodium percarbonate" is a non-specific term for sodium carbonate peroxohydrates, which strictly speaking are not "percarbonates" (ie salts of percarbonic acid) but are 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 forms a white, water-soluble powder with a density of 2.14 gcm ^-3 that easily disintegrates into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first made in 1899 by precipitation with ethanol from a Obtained solution of sodium carbonate in hydrogen peroxide, but mistakenly as peroxy viewed carbonate. It was not until 1909 that the compound was Addition compound recognized, nevertheless the historical designation "sodium per carbonate "prevailed in practice.  

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

Further bleaching agents which can be used are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium ses quicarbonate is preferred, regardless of what other ingredients are contained in the moldings. If cleaning tablets or bleach tablets for machine dishwashing are manufactured, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) 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 peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoxy acid panoic acid (Pε) )], o-Carboxybenzamidoperoxycapronsäure, N- nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic acid, the Diperoxyphthal acids, 2-decyldiperoxybutane-1 , 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or. Can also be used as bleaching agents in moldings for automatic dishwashing Bromine-releasing substances are used. Among the appropriate chlorine or bromine releasing materials come for example heterocyclic N-bromine 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.

To be a better choice when washing or cleaning at temperatures of 60 ° C and below To achieve the greatest bleaching effect, bleach activators can be added to the premix position of the detergent tablets are incorporated. Bleaching stock Examples of compounds which support the action of the bleaching agents are compounds, which contain one or more N- or O-acyl groups, such as substances from the class the anhydrides, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine (TAED), tetraacetylmethylene diamine (TAMD) and tetraa cetylhexylenediamine (TAHD), but also pentaacetylglucose (PAG), 1,5-diacetyl-2,2- dioxohexahydro-1,3,5-triazine (DADHT) and isatoic anhydride (ISA).

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

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

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

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

Because of their oxidizing effect, it is advantageous to remove the bleaching agents from other contents to separate substances, for which multiphase moldings are particularly suitable. Washing or Detergent tablets, in which one of the phases of the tablet contains bleach holds 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 containing enzymes are also preferred. In particular come as enzymes those from the classes of hydrolases such as proteases, esterases, lipases or lipoly table-acting enzymes, amylases, cellulases or other glycosyl hydrolases and Ge mix the enzymes mentioned in question. All of these hydrolases contribute to the laundry Removal of stains such as stains containing protein, fat or starch and Graying at. Cellulases and other glycosyl hydrolases can also be used by removing pilling and microfibrils for color retention and enhancement contribute to the softness of the textile. For bleaching or to inhibit color transfer can also be used oxidoreductases. Bacts are particularly suitable strain or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus gri seus, Coprinus Cinereus and Humicola insolens and from their genetically modified enzymatic active ingredients obtained in ten variants. Proteases are preferably from Subtilisin type and in particular proteases derived from Bacillus lentus set. Enzyme mixtures, for example of protease and amylase or Protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, Amylase and lipase or lipolytic enzymes or protease, lipase or li poly-acting enzymes and cellulase, but especially protease and / or Lipa  Se-containing mixtures or mixtures with lipolytic enzymes from beson their interest. Examples of such lipolytically active enzymes are the known ones Cutinases. Peroxidases or oxidases have also proven suitable in some cases grasslands. Suitable amylases include in particular alpha-amylases, iso-amylases, Pullulanases and pectinases. Cellobiohydrolases are preferably used as cellulases, Endoglucanases and glucosidases, which are also called cellobiases, or mixtures gene used from these. Since different types of cellulase differ by their CMCase and Avicelase activities can be distinguished by targeted mixtures of the cellulases the desired activities are set.

In detergent tablets for automatic dishwashing, there are naturally others re enzymes used to treat the different substrates and pollution tongues to take into account. Here especially come from the classes of Hy drolases such as proteases, esterases, lipases or lipolytic enzymes, Amyla sen, glycosyl hydrolases and mixtures of the enzymes mentioned. All this hy drolasen help remove soiling such as protein, fat or starchy Stains on. Oxidoreductases can also be used for bleaching. Especially are particularly suitable from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well their genetically modified variants obtained enzymatic active ingredients. Before Proteases of the subtilisin type and in particular proteases derived from Ba cillus lentus are used. There are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytically active enzymes or pro tease, lipase or lipolytic enzymes, but especially protease and / or Mixtures containing lipase or mixtures with lipolytically active enzymes from be special interest. Examples of such lipolytic enzymes are known ten cutinases. Peroxidases or oxidases have also been found to be suitable in some cases proven. Suitable amylases include in particular alpha-amylases, iso- Amylases, pullulanases and pectinases.

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

Corrosion inhibitors can also be used to protect the dishes or the machine the detergent tablets are incorporated, with in the area of automatic dishwashing silver protection agents have a special meaning. A The known substances of the prior art can be used. Generally can before all silver protection agent selected from the group of triazoles, benzotriazoles, Bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salt ze or complexes are used. Benzotria are particularly preferred zole and / or alkylaminotriazole. One also finds in cleaner formulations agents containing active chlorine, which significantly reduce the corroding of the silver surface can. Chlorine-free cleaners especially contain oxygen and nitrogenous ones organic redox-active compounds, such as di- and trihydric phenols, e.g. B. Hydro quinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or Derivatives of these classes of compounds. Also salt and complex inorganic compound such as salts of the metals Mn, Ti, Zr, Hf; V, Co and Ce are often used. The transition metal salts which are selected from the group of Manganese and / or cobalt salts and / or complexes, particularly preferably the Cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, chlorides of cobalt or manganese and manganese sulfate. You can also Zinc compounds are used to prevent corrosion on the wash ware.

If corrosion protection agents are used in multi-phase moldings, it is before moves to separate them from the bleach. Detergent tablets, where one phase contains bleach, while another phase contains corrosion protection contains agents are therefore preferred.

Other ingredients that are part of the washing or detergent tablets, for example dyes, optical Brighteners, fragrances, soil release compounds, soil repellents, antioxidants, fluorescence  lubricants, foam inhibitors, silicone and / or paraffin oils, color transfer inhibitor ren, graying inhibitors, detergent boosters, etc.

To the aesthetic impression of the washing and cleaning products produced according to the invention To improve moldings, they can be wholly or partly with suitable color fabrics are dyed. Preferred dyes, the selection of which none of the expert Difficulties have a high storage stability and insensitivity to about the other ingredients of the agents and against light and no pronounced sub Stativity towards the treated substrates such as textile fibers or Ge cut parts so as not to stain them.

Are preferred for use in detergent tablets produced according to the invention all colorants that can be oxidatively destroyed in the washing process as well as mixtures the same with suitable blue dyes, so-called blue toners. It has proven to be beneficial proven to use colorants in water or at room temperature in liquid organic substances are soluble. For example, anionic colorants are suitable, e.g. B. anionic nitroso dyes. A possible colorant is, for example Naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which is available as a trade product, for example, available as Basacid® Green 970 from BASF, Ludwigshafen is, and mixtures of these with suitable blue dyes. As another colorant come 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® Patent Blue 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. Generally speaking, 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 detergents or cleaning agents varies. In the case of readily water-soluble colorants, e.g. B. the above-mentioned Basacid® green or the above-mentioned Sandolan® blue, coloring agent concentrations are typically selected in the range of a few 10 ^-2 to 10 ^-3 wt .-%. In the preferred because of their brilliance, but less water-soluble pigment dyes, for. B. the above-mentioned Pigmosol® dyes, the suitable concentration of the colorant in detergents or cleaning agents, however, is typically some 10 ^-3 to 10 ^-4 wt .-%.

The premixes to be compressed according to the invention can contain one or more opti contain brighteners. These substances, which are also called "whiteners", are used in modern detergents, since even freshly washed and bleached white Laundry has a slight yellow tinge. Optical brighteners are organic dyes, which part of the invisible UV radiation from sunlight into longer-wave blue Convert light. The emission of this blue light complements the "gap" in the textile reflected light, so that a textile treated with an optical brightener knows the eye appears bigger and brighter. Because the mechanism of action of brighteners is their pulling up on the fibers, one differentiates depending on the "dyed" fibers for example white brightener for cotton, polyamide or polyester fibers. The commercially available for Incorporating brighteners suitable for detergents are essentially five Structure groups. The stilbene, the diphenyl stilbene, the cumann-quinoline, the diphe nylpyrazoline group and the group combining benzoxazole or benzimidazole with conjugated systems. An overview of common brighteners is, for example, in G. Jakobi, A. Löhr "Detergents and Textile Washing"; VCH publishing house, Weinheim, 1987, Sei 94 to 100 to find. Are suitable for. B. Salts of 4,4'-bis [(4-anilino-6-morpholino-s triazin-2-yl) amino] -stilbene-2,2'-disulfonic acid or compounds of the same structure, which instead of the morpholino group is a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, a brightener of the substituted diphenylstyryl type may be present, e.g. B. 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) diphenyl. Mixtures of the aforementioned brighteners can be used.

Fragrances are added to the agents according to the invention in order to maintain an aesthetic appearance to improve product pressure and consumer in addition to product performance a visually and sensorially "typical and distinctive" product is available put. As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and Koh type Hydrogen oils are used. Fragrance compounds of the ester type are e.g. B. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dime thylbenzyl carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate; Ethylethyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the Ethers include, for example, benzyl ethyl ether, the aldehydes e.g. B. the linear Alka nale with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, α- Isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, are hydrocarbons mainly the terpenes such as limes and pinene. However, Wed are preferred uses different fragrances, which together make an appealing Generate fragrance. Such perfume oils can also contain natural fragrance mixtures ten, as they are accessible from plant sources, e.g. B. Pine, Citrus, Jasmine, Pat chouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Ka millen 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 content of the washing and cleaning agents produced according to the invention is usually moldings of fragrances up to 2% by weight of the total formulation. The Fragrances can be incorporated directly into the agents according to the invention, it can but it can also be advantageous to apply the fragrances to carriers that limit the adhesion of Par reinforce foams on the laundry and through a slower fragrance release for langan maintain the fragrance of the textiles. Such carrier materials have, for example  se Cyclodextrins proven, the Cyclodextrin-Parflim complexes additionally with other auxiliaries can be coated.

In addition, the detergent tablets can also ent components hold, which positively influence the oil and fat washability from textiles (so-called called soil repellents). This effect is particularly evident when a textile is dirty is already several times with a detergent according to the invention, this Contains oil and fat-dissolving component, was washed. Among the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methylhydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15 wt .-%, each bezo gene on the nonionic cellulose ether, as well as those known from the prior art Polymers of phthalic acid and / or terephthalic acid or their derivatives, in particular special polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Especially be of these, the sulfonated derivatives of phthalic and terephthalic acids are preferred re-polymers.

As foam inhibitors that can be used in the agents according to the invention, For example, soaps, paraffins or silicone oils come into consideration, which if necessary can be applied to carrier materials.

Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acid Ren starch or cellulose or salts of acidic sulfuric acid esters of cellulose or strength. Water-soluble polyamides containing acidic groups are also suitable for the suitable purpose. Soluble starch preparations and others other than that can also be used Use the above starch products, e.g. B. degraded starch, aldehyde starches, etc. Polyvinyl pyrrolidone can also be used. However, cellulose ethers such as Carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixtures  ther such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxy methyl cellulose and mixtures thereof in amounts of 0.1 to 5 wt .-%, based on the Means used.

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

To combat microorganisms, the agents according to the invention can be antimicro bielle contain active ingredients. A distinction is made here depending on the antimicrobial spectrum and mechanism of action between bacteriostatics and bactericides, fungiostatics and Fungicides, etc. Important substances from these groups are, for example, benzalkonium chloride, alkylarlyl sulfonates, halophenols and phenol mercuric acetate, whereby also complete Lich these connections can be dispensed with.

To unwanted, caused by oxygen and other oxidative processes Prevent changes to the agents and / or the treated textiles which contain antioxidants. This connection class includes, for example substituted phenols, hydroquinones, pyrocatechols and aromatic amines and or ganic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

An increased 14328 00070 552 001000280000000200012000285911421700040 0002019934690 00004 14209 comfort can result from the additional use of antistatic agents ren, which are additionally added to the agents according to the invention. Enlarge antistatic agents ß improve the surface conductivity and thus enable an improved drainage det charges. External antistatic agents are usually substances with at least one hydrophilic molecular ligands and give a more or less hy on the surfaces wholesale copy film. These mostly surface-active antistatic agents can be put in stick  containing substances (amines, amides, quaternary ammonium compounds), containing phosphorus (Phos divide phosphoric acid ester) 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) dimethyl disclosed here Benzylammonium chlorides are suitable as antistatic agents for textiles or as additives Detergents, with an additional finishing effect.

To improve the water absorption capacity, the rewettability of the behan Delten textiles and to facilitate ironing of the treated textiles can in the premixes to be processed according to the invention, for example silicone derivatives be set. These also improve the rinsing behavior of the agents through 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 sen and are partially or completely fluorinated. Preferred silicones are polydimethylsiloxanes, which may be derivatized and then amino functional or quaternized are or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the be preferred silicones are between 100 and 100,000 centistokes at 25 ° C, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total tel can be used.

Finally, the premixes and the agents made from them can also UV Contain absorbers, which absorb on the treated textiles and the light resistance of the fibers improve. Compounds that have these desired properties are, for example, the compounds which are effective through radiationless deactivation and Derivatives of benzophenone with substituents in the 2- and / or 4-position. Furthermore are also substituted benzotriazoles, in the 3-position phenyl substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni Complexes and natural substances such as umbelliferone and the body's own urocanoic acid are suitable net.

All of the ingredients mentioned above can have advantageous properties result in separating them from other ingredients or combining them with certain others  To assemble ingredients together. In the case of multi-phase moldings, the individual phases also have a different content of the same ingredient sen, whereby advantages can be achieved. Detergent tablets, in which at least two phases ent the same active ingredient in different amounts hold are preferred. The term "different amount" refers to how already explained, not on the absolute amount of the ingredient in the phase, but on the relative amount, based on the phase weight, therefore represents a% by weight reference to the individual phase.

In order to facilitate the disintegration of highly compressed moldings, it is possible to disintegrate on aids, so-called tablet disintegrants, to incorporate them into the disintegration to shorten times. Under tablet disintegrants or disintegrators according to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical Technologie "(6th edition, 1987, pp. 182-184) understood auxiliary substances that are necessary for the rapid Disintegration of tablets in water or gastric juice and for the release of the pharmaceuticals in provide resorbable form.

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

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

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

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

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

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

The disintegration aid (s) can also have special effects from the partial or complete omission of such substances from individual phases more multi-phase Moldings result. So it is preferred, for example, multiphase, in particular to produce multilayered molded articles, the individual phases of which are disintegrated contained in different amounts. In this way, active ingredients from a Phase controlled, for example accelerated or retarded, released from what there are application-related advantages.  

Another object of the present invention is the use of tablets tierstempel, which have elevations and depressions on their pressing surface, the Distance between the surveys between 5 and 200 µm and the height of the surveys is between 5 and 100 µm, to reduce the build-up of stamps.

Regardless of the good to be tabletted, i.e. when producing tablets on the Fields of pharmacy, food technology, battery technology or con The manufacture of bulk goods leads to the use of press punches with the surfaces mentioned structures to significantly reduce stamp build-up.

In particular in the case of highly adhesive premixes, the use of the inventive compositions shows Tablet stamp clear and unexpected benefits. Such premixes can in particular be special detergent or cleaning agent compositions, so that the use of tabletting dies, which have elevations and depressions on their pressing surface, the distance between the surveys between 5 and 200 microns and the height of the Elevations between 5 and 100 microns, for the production of washing or cleaning medium shaped bodies is another object of the present invention.  

Examples

A tableting star was used to produce a tabletting die E1 according to the invention pel made of polytetrafluoethylene (PTFE) sprayed with spray adhesive and with Teflon powder (medium Particle size: 11 µm) coated. Another tabletting stamp E2 according to the invention was obtained by pressing the surface of a tablet made of polyvinylidene fluoride (PVDF) with a warm air device even in the thermoplastic state was warmed. Then a screen mesh was pressed onto the pressing surface and again away. As a result, elevations of 21 µm in average height were formed in an average Distance of 38 µm. An untreated tabletting punch was used as comparative example V. made of PTFE.

The stamps E1, E2 and V were inserted as upper stamps in a Korsch eccentric press builds where they were used to manufacture detergent tablets.

This was done by granulation in a 130-liter ploughshare mixer from Lödige a surfactant-containing granulate (composition see Table 1), which is the basis was used for a particulate premix. Following the granulation the granulate was in a fluidized bed apparatus from Glatt at a supply air temperature dried at 60 ° C over a period of 30 minutes. After drying the fine particles <0.4 mm and coarse particles <1.6 mm sieved. The premix was de by mixing the surfactant-containing granules with bleach, bleach activator and further processing components manufactured. The premix was then in the the stamps E1, E2 and V equipped Korsch eccentric press to tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g) pressed. The composition of the pressed send premix (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 used at the beginning of the test and after manufacture of 10 detergent tablets with a diametrical breaking strength of approx. 30 N weighed. The weight of the stamp build-up could be determined from the difference of the measured values Calculate gene directly. The results of the tests are shown in Table 3:  

Table 3

Caking weight [g]

It can be clearly seen that the die caking is due to the inventive Have stamps with a defined surface structure significantly reduced.

Claims (19)

1. tabletting stamp, characterized in that its pressing surface has elevations and recesses, 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 6 to 180 microns, preferably 7 to 160 microns, particularly preferred 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 6 to 90 μm, preferably 7 to 80 μm, particularly preferably 8 is up to 70 microns and in particular 10 to 50 microns. 4. tabletting stamp according to one of claims 1 to 4, characterized in that at least the elevations made of hydrophobic polymers or durable hydrophobized Materials exist. 5. tabletting stamp according to one of claims 1 to 5, characterized in that at least the elevations from a polyolefin, preferably from polyethylene or Polypropylene. 6. tabletting stamp according to one of claims 1 to 5, characterized in that at least the best of polyvinylidene fluoride or polytetrafluoroethylene hen. 7. tabletting stamp according to one of claims 1 to 5, characterized in that at least the elevations from a polyamide, preferably from 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 stamp according to one of claims 1 to 5, characterized in that at least the elevations from a glass fiber reinforced plastic, preferably a glass fiber reinforced polytetrafluoroethylene or polyamide. 10. Process for the production of moldings by pressing a particulate Premix, characterized in that the tablet used for pressing have animal stamps on their pressing surface elevations and depressions, the Distance between the surveys between 5 and 200 microns and the height of the heights exercises is between 5 and 100 µm. 11. The method according to claim 10, characterized in that the particulate pre mixture is a detergent or cleaning agent composition and the moldings Detergent tablets are. 12. The method according to claim 11, characterized in that the particulate pre contains mixed surfactant-containing granules and a bulk density of at least 500 g / l, preferably has at least 600 g / l and in particular at least 700 g / l. 13. The method according to claim 12, characterized in that the surfactant-containing granules 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 Granules containing surfactants, anionic and / or nonionic surfactants and builders contains and total surfactant contents of at least 10 wt .-%, preferably at least at least 15% by weight and in particular at least 20% by weight. 15. The method according to any one of claims 12 to 14, characterized in that the Ten Sidgranulat with further processing components to a pressable pre  is mixed, which is 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 compressing premix 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, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color over contains wear inhibitors and corrosion inhibitors. 17. The method according to any one of claims 11 to 16, characterized in that the part Chen-shaped premix a disintegration aid, preferably a disintegra tion aids based on cellulose, preferably in granular, co-granulated or grain-compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7 % By weight and in particular from 4 to 6% by weight, in each case based on the premix, contains. 18. Use of tabletting stamps, the elevations and Vertie on their pressing surface fung, the distance between the elevations between 5 and 200 microns and the height of the bumps is between 5 and 100 µm to reduce Stamp cakes. 19. Use of tabletting stamps, the elevations and Vertie on their pressing surface fung, the distance between the elevations between 5 and 200 microns and the height of the elevations is between 5 and 100 µm, for the production of Detergent tablets.