EP1682649B1 - Tablets resistant to shock loads - Google Patents

Abstract

The invention relates to tablets consisting of pressed particulate washing or cleaning agents and comprising at least two reinforcing grooves on the upper side thereof, the horizontal extension of said grooves on the plane of the tablet surface being longer than the depth thereof. The inventive tablets are characterized by a short disintegration time for a pre-determined hardness and exhibit increased stability in terms of shock loads and falls.

Description

The present invention is in the field of compact moldings having washing and cleaning properties. Such detergent tablets comprise, for example, laundry detergent tablets for washing textiles, automatic dishwashing detergent tablets or hard surface cleaning agents, bleach tablets for use in dishwashers or dishwashers, water softening tablets or patch salt tablets. In particular, the invention relates to detergent tablets which are used for cleaning dishes in a domestic dishwasher and are referred to briefly as detergent tablets or dishwasher tablets.

Detergent tablets are widely described in the art and are becoming increasingly popular with consumers because of their ease of use. Tableted detergents and cleaners have a number of advantages over powdered ones: they are easier to dose and to handle and, due to their compact structure, have advantages in storage and transport. Also in the patent literature washing and cleaning agent tablets are thus described comprehensively. A problem which occurs again and again in the application of washing and cleaning-active moldings is the too low disintegration and dissolution rate of the moldings under conditions of use. Since sufficiently stable, i. Shock-resistant moldings can only be produced by relatively high molding pressures, resulting in a strong compaction of the molding constituents and a consequent delayed disintegration of the molding in the aqueous liquor and thus to a slow release of the active substances in the washing or cleaning process ,

Another problem that occurs especially in detergent tablets, is often insufficient stability of these tablets against the burden of packaging, transport and handling, ie against falling and impact stresses. After pressing, the tablets are fed on conveyor belts of the package, the tablets individually or grouped wrapped with a foil and then packaged in boxes. When filling the tablet meets on a nearly parabolic trajectory from the conveyor belt of the film wrapping machine on the cardboard wall or the previously filled tablets. Here occur in particular in rectangular tablets forces in the longitudinal direction of the tablet, the can lead to edge breakage and Abrieberscheinungen and affect the appearance of the molding or even lead to a complete destruction of the molding structure.

To overcome the dichotomy between hardness, i. Transport and handling stability, and easy disintegration of the moldings, many approaches have been developed in the prior art. An approach known in particular from the pharmaceutical industry and extended to the field of detergent tablets is the incorporation of certain disintegration aids which facilitate the ingress of water or which swell or become gas-evolved or otherwise disintegrate upon the ingress of water. Other proposed solutions from the patent literature describe the compression of premixes of certain particle sizes, the separation of individual ingredients of certain other ingredients and the coating of individual ingredients or the entire molded article with binders.

That's how it describes EP 687 464 (Allphamed Arzneimittel-Gesellschaft ) Effervescent tablets, consisting of at least one active ingredient or combination of active ingredients, at least one binder, excipients such as flavors, dyes, fragrances, plasticizers, bleaching agents and effervescent additives, wherein as a binder propylene glycol or glycerol, preferably in amounts of 0.004 to 2.5 wt. -%, be used. Also claimed are methods of making these effervescent tablets. According to the statements of this document can be prepared with the teaching of the invention, a detergent effervescent tablet without the binder used would lead to a loss of carbon dioxide in the effervescent additives.

The European patent application EP 711 828 (Unilever ) describes detergent tablets which contain surfactant (s), builder (s) and a polymer which acts as a binding and disintegration aid. The binders disclosed in this document should be solid at room temperature and fed to the premix to be compressed as a melt. Preferred binders are the relatively high molecular weight polyethylene glycols.

The use of solid polyethylene glycols is also used in the German patent application DE 197 09 411.2 (Henkel ). This document teaches synergistic effects between the polyethylene glycols and overdried amorphous silicates.

Solutions to the problem of friability or abrasion resistance of detergent tablets are, for example, in the DE 198 41 146 (Henkel ) disclosed. According to the teaching of this document, the addition of non-surfactant, water-soluble, liquid binders to the tableting mixtures has a positive effect on their abrasion behavior.

All solutions have in common is the idea to specifically modify the ingredients or incorporate special ingredients, so that the tablet properties are positively influenced. A recipe-independent approach to the problems mentioned is not disclosed in the prior art.

the German Patent DE 198 60 189 C1 (Henkel KGaA ), an alternative problem solution can be found, according to which the hardness and the disintegration time of washing or cleaning agent tablets can be optimized by the biconvex or biconcave configuration of the upper and lower sides of these tablets.

The present invention was based on the object, washing or cleaning agent tablets provide that are characterized by short disintegration times for a given hardness and thus can be dosed via the dispensing chamber household washing machines. In addition to these requirements, the moldings should have increased stability against shock and impact loads. The corresponding advantages should be achieved regardless of the formulation in order to be able to dispense with expensive pre-assembly steps or the use of expensive tabletting aids only for this purpose.

It has now been found that the surface design of the tablets in the solution of the above problems is of particular importance.

The present invention is a tablet of compressed particulate detergent or cleaning agent having on its upper side at least two reinforcing recesses whose horizontal extent is greater than the depth of the tablet surface level, the reinforcing recesses emanating radially from a common center.

A tablet of the invention has a top and a bottom and one or more side surfaces. The underside is the area of the tablets which comes in contact with the lower punch of the tablet press during the pressing process, while the upper side is the surface which contacts the upper punch of the tablet press. The side surfaces are touched by the walls of the die during the pressing process, with a round or oval tablet having only one side wall (the cylinder jacket surface), whereas polygonal tablets have an equal number of side surfaces in number of corners. Preferred in accordance with the invention are rectangular tablets which have four side surfaces. In the special case of the square tablet, all four side surfaces are the same size, while in tablets with rectangular top and bottom only equal to two side surfaces.

The top of the tablet according to the invention provided with reinforcing recesses, which are hineingeprägt in the top. The depressions on the tablet top correspond to elevations on the tableting punch (see below). According to the invention, the horizontal extent of the reinforcing recesses is greater at the level of the tablet surface than its depth. In other words, the gain pits in the x, y direction on the

Level of the tablet top to a greater extent than in the z-direction of the tablet height. In tablets preferred according to the invention, the horizontal extent of the reinforcing depressions at the level of the tablet surface is 1.01-fold to 5-fold, preferably 1.02-fold to 4-fold, particularly preferably 1.04-fold to 3-fold and more preferably 1.05 to 2 times the depth of the reinforcing pits.

Accordingly, a 5 mm deep reinforcement depression has a length or width of more than 5 mm, wherein in preferred tablets the length or width is 5.05 to 25 mm, preferably 5.5 to 20 mm, particularly preferably 5.2 to 15 mm and in particular 5.25 to 10 mm.

In tablets preferred according to the invention, the depth of the reinforcing recesses is correlated with the height of the tablets in order to further optimize the breakage stability (kink stability) of the tablet. Here, particularly preferred tablets according to the invention are characterized in that the depth of the reinforcing recesses is 0.05 times to 0.5 times, preferably 0.1 times to 0.4 times and in particular 0.15 times to 0 , 3 times the tablet height.

According to the invention, the tablets have at least two reinforcing recesses. Depending on the shape of the reinforcing recesses but also more than two wells can be mounted on the top of the molding. For example, tablets according to the invention are preferred which have at least 3, preferably at least 4, more preferably at least 5, more preferably at least 6, more preferably at least 7, more preferably at least 8, even more preferably at least 9 and in particular at least 10 reinforcing recesses.

The reinforcing recesses can be embossed as straight grooves in the molding surface, but they can also be angled or wavy lines.

The reinforcing recesses radiate from a common center. This arrangement is for example particularly advantageous if the molded body has further recesses, which are used as a cavity or cavity to incorporate therein other ingredients or to insert other tablet ingredients. Such well tablets are currently known in the art as dishwashing agents and can be stabilized by the reinforcing recesses according to the invention. Visually, such an arrangement of the gain pits recalls a sun with the corresponding number of beams, for example four, five, six, seven or eight beams. Of course, the "sun rays" can be formed not only by straight lines, but also by curved or wavy lines.

Regardless of the outer shape of the reinforcing recesses, these preferably have a cross section which is semicircular or semi-elliptical or triangular. The "cross section" of the reinforcing recesses is the vertical section through the tablet, vertical to the respective reinforcing recess. Accordingly, tablets according to the invention are preferred in which the cross-section of the reinforcing recesses is triangular or semicircular.

As already indicated above, the tablet height and the depth of the reinforcing recesses are preferably correlated with each other. In addition to the relative statements mentioned above, absolute details can be made of particularly advantageous embodiments. Preferred tablets according to the invention are characterized in that the height of the tablet is 5 to 25 mm, preferably 7 to 22 mm and in particular 10 to 20 mm. Accordingly, the depth of the reinforcing recesses in preferred tablets according to the invention is 0.5 to 10 mm, preferably 0.75 to 8 mm and in particular 1 to 5 mm. The depth of the reinforcing depressions is the lowest point of the respective reinforcing depressions, for example, in the case of v-shaped reinforcing depressions, the triangular tip.

To prepare the tablets according to the invention, particulate premixes are compacted in a so-called matrix between two punches to form a solid compressed product. This process, hereinafter referred to as tabletting, is divided into four sections: dosing, compaction, plastic deformation and ejection.

First, the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool. The constant dosage even at high molding throughputs is preferably achieved via a volumetric metering of the premix. As the tableting progresses, the upper punch contacts the pre-mix and continues to descend toward the lower punch. In this compression, the particles of the premix are pressed closer to each other, with the void volume within the filling between the punches decreasing continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molding. Depending on the physical properties of the premix, some of the premix particles are also crushed, and even higher pressures cause sintering of the premix. With increasing pressing speed, so high throughput amounts, the phase of the elastic deformation is shortened more and more, so that the resulting moldings may have more or less large cavities. In the last step of tableting, the finished molded body is pushed out of the die by the lower punch and carried away by subsequent transport means. At this time, only the weight of the shaped body is finally determined because the compacts due to physical processes (re-expansion, crystallographic effects, cooling, etc.) can change their shape and size.

The tabletting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches. In the latter case, not only the upper punch is used to build up pressure, and the lower punch moves during the pressing on the upper punch, while the upper punch presses down. For small production quantities, eccentric tablet presses are preferably used in which the die or punches are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed. The movement of these punches is comparable to the operation of a conventional four-stroke engine. The compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohrungen is extended accordingly. The throughputs of eccentric presses vary depending on the type of a few hundred to a maximum of 3000 tablets per hour.

In eccentric presses, the lower punch is usually not moved during the pressing process. A consequence of this is that the resulting tablet has a hardness gradient, i. harder in the areas closer to the upper punch than in the areas closer to the lower punch.

For larger throughputs, rotary tablet presses are selected in which a larger number of dies are arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are commercially available. Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp. The die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection. At the points where a particularly serious increase or decrease of the stamp is required (filling, compaction, ejection), these curved paths are supported by additional low-pressure pieces, Nierderzugschienen and lifting tracks. The filling of the die via a rigidly arranged supply device, the so-called filling shoe, which is connected to a reservoir for the premix. The pressing pressure on the premix is individually adjustable via the compression paths for upper and lower punches, wherein the pressure build-up is done by the Vorbeirollen the stamp shank heads on adjustable pressure rollers.

Concentric presses can be provided with two Füllschuhen to increase the throughput, with the production of a tablet only a semicircle must be traversed. To produce two-layered and multi-layered shaped bodies, several filling shoes are used arranged one behind the other, without the slightly pressed first layer is ejected before further filling. By suitable process control coat and point tablets can be produced in this way, which have a zwiebelschalenartigen structure, wherein in the case of the point tablets, the top of the core or the core layers is not covered and thus remains visible. Even rotary tablet presses can be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes are used simultaneously for pressing. The throughputs of modern rotary tablet presses amount to over one million moldings per hour.

Of course, the tablets can also in the context of the present invention, multi-phase, in particular multi-layered, ausgestalten. The moldings can be made in a predetermined spatial form and predetermined size. As a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section. This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.

The spatial form of another embodiment of the moldings is adapted in their dimensions of the dispenser of commercial household washing machines or the dosing of commercial dishwashers, so that the moldings can be metered without dosing directly into the dispenser, where they dissolve during the dispensing process, or from where they are released during the cleaning process. Of course, however, it is also possible to use the washing and cleaning agent tablets via dosing aids without problems.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be detected by the measurand of the diametric breaking load. This is determinable $$\sigma =\frac{2P}{\mathit{\pi Dt}}$$

Herein, σ is the diametrical fracture stress (DFS) in Pa, P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article, D is the molded article diameter in meters and t the height of the moldings.

In order to obtain moldings according to the invention, the upper punch of the tablet press used for production must have corresponding elevations on the reinforcing depressions embossed on the later tablet top side. These elevations are preferably made of wear-resistant materials to increase the service life of the Tablettierstempel. In particular, metals and plastics have proven to be suitable.

Another object of vorligenden invention is therefore a process for the preparation of tablets from compressed particulate detergent or cleaner by per se known compression of particulate premixes, wherein for pressing an upper punch is used, which has at least two elevations on its pressing surface for pressing reinforcing recesses , whose horizontal extent at the level of the pressing surface is greater than its height, wherein the elevations radiate from a common center.

The tablet to be pressed, usually powdery or fine-grained material is, if not particularly complicated and the production hindering precautions for a special distribution are taken, evenly distributed when filling in the Preßmatrize. This has the consequence that the material must be most compressed at the points where the profile of the embossing element has the highest elevations. Although the material to be pressed tries to avoid the highest pressure peaks by a movement in the direction of the less highly stressed areas, in the areas of the highest profile elevations also the highest specific surface pressures occur.

If the profile of the embossing element consists of a flat surface, for example the base surface which surrounds the elevations for the reinforcing depressions, the highest surface loads are to be expected at the elevations, and at the summit or the highest point. In the area of the crest, the area has only very small angles of inclination with respect to the base plane. By definition, these angles of inclination increase towards the base of the elevations and are greatest at the transition into the surrounding base area. The pressing force acts perpendicular to the base plane and the surface element in the center of the dome. With increasing distance from this mid-point element, the pressing force is directed to an increasingly inclined surface, so that the pressing force is divided into a correspondingly smaller, perpendicular to the respective surface element force component and in turn directed perpendicular thereto force component. These shear forces act almost tangentially. The force components perpendicular to the normal force are a measure of the shear and abrasion forces acting at the interface between the elevations for the reinforcing recesses and the material to be pressed. Among other things because of this Abrasionskräfte the protrusions for the reinforcing recesses must be made of a very hard, incompressible material.

The adhesion tendency of the material to be pressed on the surface of the press ram is determined inter alia by the specific surface pressures between the material to be pressed and the stamp surface and by the surface structure. If, for example, the surface of the pressing or tableting punch has friction-reducing or lubricating or sliding-promoting properties, this prevents or at least reduces the sticking tendency.

As already mentioned, the pressing forces are directed perpendicular to the flat base. Since the flat base area represents the lowest height in the profile of the embossing element, the lowest compression of the material to be pressed is given in this area. As a result, lower surface pressures are also to be expected in the region of the base surface than in the area of the upwardly curved elevations for the reinforcing recesses. For these reasons, the material of the base must not be incompressible, especially from the Druckgeomentrie only normal forces are to be expected.

Although the structure of beds of powdery or finely crystalline substances is to be regarded as uniform with respect to larger areas or volumes, it is quite different in the microarea. By virtue of these density ratios, which differ in the micro range, different resistances of the material to be pressed are opposed to the uniform pressing forces applied to the surface of the base material. As a result, different specific pressures occur at points spaced from the micro-region on the surface, and consequently, with compressible material of the base-surface element, slightly different deformations of the material occur. This phenomenon, referred to here as walking, results in the creation of different normal and transverse forces on the material surface, whereby the tendency for the adhesion of material to the surface of the embossing element in the region of the base surface is prevented or at least greatly reduced.

A tabletting die, whose embossing element is designed in the described form, is advantageously anti-adhesion or at least adhesion-reducing. With such a pressing tool long tool life and perfect tablet surfaces can be achieved.

In an embodiment in which the embossing element of the tabletting punch is not intended to be laterally delimited by the base surface, and this of a substantially uniform, is surrounded by incompressible edge strips, repercussions of the compression and deformation process on the die inner wall are excluded on the compressible base. An outwardly sloping beveling of the edge strip thereby advantageously results in a clean material distribution in the die and a stabilization of the tablet structure.

Very particular advantages in the production of the tableting die and the stability of the pressing tool are ensured in an embodiment in which the embossing element consists of several individual parts. Appropriately, the scope and cutting of the items are oriented to the different materials or material requirements. Thus, the individual production of the elevations for the reinforcing recesses of incompressible and on the outer surface at least adhesion reducing coated material, a plate-shaped element of walkbarem material for the base and an annular element of incompressible material for the edge strip is an advantageous delimitation for the design of the individual parts that because of their different materials.

As described above, the coating of the elevations for the reinforcing recesses must be both hard and resistant to high surface loads, but on the other hand also have a friction-reducing or lubricating property. For this purpose, nickel-containing surface coatings have proved to be very suitable, in which the finest PTFE particles (Teflon) are included. These give the coating anti-adhesion and material-seizure-preventing properties. Alternatively, an embodiment for the adhesion-reducing coating, in which the base coating material consists of a nickel-phosphorus alloy instead of nickel, has also proved to be suitable.

As a further alternative for the surface coating with at least adhesion-reducing effect, but which otherwise meets the requirements of hardness and resistance, a coating of diamond particles containing graphite has proven itself. In this case, the surface of the pin is coated with a graphite layer, which are known as lubricating or slide-promoting, and here also serves as a binder for fixing diamond particles, which in turn give the surface the required hardness. Experiments with these surface coatings of the elevations for the reinforcing recesses have shown that even with very long service lives of the tools no material adherences were observed. It is therefore preferred that the at least adhesion-reducing coating consists essentially of carbon.

The adhesion-preventing or at least adhesion or adhesion-reducing effect of the walkable material for the formation of the base has been described above. In Experiments have shown that very good results could be achieved, for example, with the polyuretane material Vulkollan or the PVC material Mipolam. Over use times of several thousand pressures, no adhesion to the base material was found.

As an alternative to metals, which may need to be coated, it is also possible to use plastics as materials for the elevations in the upper punch which characterize the reinforcing recesses. By producing the elevations of plastic materials can be produced Tablettierstempel that also realize complicated geometries.

The term "plastics" in the context of the present invention characterizes materials whose essential constituents consist of such macromolecular organic compounds which are formed synthetically or by modification of natural products. In many cases they are meltable and malleable under certain conditions (heat and pressure). Plastics are therefore in principle organic polymers and can either by their physical properties (thermoplastics, thermosets and elastomers), by the nature of the reaction of their preparation (polymers, polycondensates and polyadducts) or by their chemical nature (polyolefins, polyesters, polyamides, poly-urethanes etc.).

The elevations in the upper punch, which characterize the reinforcing recesses, represent elevations on the embossing element of the tableting punch in the context of the present invention. The surface on which the elevations in the upper punch, which emboss the reinforcing depressions, are applied, can also assume different shapes, from the flat, flat surface to hemispherical configurations a variety of ways is conceivable. In the context of the present invention, on the one hand, it is preferred that the surface on which the elevations in the upper punch, which emboss the reinforcing recesses, sit, plane, i. is just.

Preferably, the base on which the elevations in the upper punch, which shape the reinforcing recesses sitting, made of plastic, so that Tablettierstempel are preferred in which the elevations in the upper punch, which shape the reinforcing recesses and the flat base are made of plastic.

It is particularly preferred in the context of the present invention, when the material of the elevations in the upper punch, which characterize the reinforcing recesses, is harder than that of the base surface.

The term "hardness" is in the context of the present invention, the term for the resistance that opposes a solid body to the penetration of another body. While, for example, for minerals the so-called scratch hardness (hardness to Mohs) is measured, technically different methods for hardness testing have prevailed. Brinell, Rockwell and Vickers methods (especially for steel and other metals) are most commonly used. To determine the Brinell hardness (HB, ball hardness, DIN 50351) standardized steel or Widia balls with 10 mm diameter and a test load P (in terms of N) pressed bumplessly in the substances to be tested and the surface O (in mm ² ) of indented dome of diameter d determined. The Brinell hardness is then given by: $$\mathit{HB}=\frac{P}{O}=\frac{1}{9.817\mathit{\pi }}\cdot \frac{2P}{D\cdot \left(D-\sqrt{D^2-d^2}\right)}$$

In the determination of the Rockwell hardness (HR) suitable for higher degrees of hardness, either a diamond cone (HRC) or steel balls of different diameters (HRB) are pressed into the material. When determining the Vickers hardness (HV), a diamond pyramid with an area opening angle of 136 ° is used; Here, too, the hardness is defined as the load in relation to the impression surface (N / mm ² ). In this test method, the impressions are very small, so that one can also determine the hardness of very thin layers. Similarly, this also applies to the Knoop hardness (HK), in the determination of which a diamond pyramid with a rhombic ground plan is used. In the determination of impact hardness, the diameter of a ball impression, which was generated by impact with the hand hammer (Poldihammer, scleroscope) or by a tensioned spring, serves as a basis for calculation. Another dynamic method of determining hardness is the return method. The Shore hardness determined in this way is determined in the case of steel by the ball impact test as rebound hardness or, in the case of rubber and other elastomers, as penetration resistance against a truncated cone.
For harder plastics, eg for hard thermoplastics and especially for thermosets, the ball hardness is measured as the quotient of the test load and the surface of the impression of a steel ball (5 mm diameter) after 10, 30 or 60 seconds under load.

As described above, the elevations in the upper punch, which characterize the reinforcing recesses, consist of a harder plastic than the base. Hard plastics in particular meet the requirement profile, the elevations in the upper punch, which characterize the reinforcing recesses, at the same time be hard and resistant to high surface loads, but on the other hand must also have a friction-reducing or lubricating property.

As plastic materials for the elevations in the upper punch, which characterize the reinforcing recesses, in particular polyolefins, preferably polyethylene or polypropylene, have proven themselves. Polyethylene (PE) are polymers belonging to the polyolefins with groupings of the type

- [CH ₂ -CH ₂ ] -

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

When high-pressure method branched low-density polyethylenes fall at (about .915 to .935 g / cm ³⁾ and crystallinity of about 40-50%, which is referred to as LDPE types. Products with a higher molecular weight and the resulting improved strength and ductility have the abbreviation HMW-LDPE (HMW = high molecular weight). By copolymerizing the ethylene with longer-chain olefins, in particular with butene and octene, the pronounced degree of branching of the polyethylenes produced in the high-pressure process can be reduced; the copolymers have the abbreviation LLD-PE (linear low density polyethylene).

The macromolecules of the polyethylenes from low-pressure process are largely linear and unbranched. These polyethylenes (HDPE) have degrees of crystallinity of 60-80% and a density of about 0.94-0.965 g / cm ³ . They are particularly suitable as Mmaterialien for the elevations in the upper punch, which shape the reinforcing recesses.

Polypropylene (PP) are thermoplastic polymers of propylene with repeat units of the type

- [CH (CH ₃ ) -CH ₂ ] -

Polypropylenes can be prepared by stereospecific polymerization of propylene in the gas phase or in suspension to give highly crystalline isotactic or less crystalline syndiotactic or amorphous atactic polypropylenes, respectively. Of particular technical importance is the isotactic polypropylene, in which all methyl groups are located on one side of the polymer chain. Polypropylene is characterized by high hardness, resilience, stiffness and heat resistance and is in the context of the present invention thus a ideal material for the elevations in the upper punch, which characterize the reinforcing recesses.

An improvement in the mechanical properties of the polypropylenes is achieved by reinforcement with talc, chalk, wood flour or glass fibers, and also the application of metallic coatings is possible.

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

The polyamides are coded from unbranched aliphatic building blocks according to the number of carbon atoms. For example, the term PA 6 is the polyamide composed of ε-aminocaproic acid or ε-caprolactam, and PA 12 is a poly (ε-laurolactam) from ε-laurolactam. The AA-SS type first mentions the carbon number of the diamine and then the dicarboxylic acid: PA 66 (polyhexamethylene adipamide) is formed from hexamethylenediamine (1,6-hexanediamine) and adipic acid, PA 610 (polyhexamethylene sebacinamide) from 1,6-hexanediamine and Sebacic acid, PA 612 (polyhexamethylenedodecanamide) from 1,6-hexanediamine and dodecanedioic acid. The polyamide types mentioned are preferred materials for the elevations in the upper punch which emboss the reinforcing recesses.

Polyurethanes (PUR) are polymers (polyadducts) which can be obtained by polyaddition from dihydric and higher alcohols and isocyanates with groupings of the type

- [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 weight or polymeric diol residue and R ^{2 stands} for an aliphatic or aromatic group. Technically important PUR are made of polyester and / or Polyether diols and, for example, 2,4- and 2,6-toluene diisocyanate (TDI, R ² = C ₆ H ₃ -CH ₃ ), 4,4'-methylenedi (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 elevations in the upper punch, which characterize the reinforcing recesses, but they can also be provided with coatings or laminations of metals or other materials. Has proven particularly useful in the context of the present invention, the use of glass fiber reinforced plastics as a material for the elevations in the upper punch, which shape the reinforcing recesses. Glass reinforced plastics (GRP) are composites of a combination of a matrix of polymers and glass fibers acting as amplifiers. The glass materials used for fiber reinforcement are present in the GRP as fibers, yarns, rovings (glass fiber strands), nonwovens, fabrics or mats. As polymeric matrix systems for GRP, both thermosets (such as, for example, epoxy resins, unsaturated polyester resins, phenolic and furan resins) and thermoplastics (such as, for example, polyamides, polycarbonates, polyacetals, polyphenylene oxides and sulfides, polypropylenes and styrene copolymers) are suitable. The weight ratio between the reinforcing material and the polymer matrix is usually in the range from 10:90 to 65:35, with the strength properties of the GRP generally increasing to an amplifier content of about 40% by weight.

The manufacture of the GRP is predominantly in compression molding; Further important manufacturing processes are hand lamination, fiber spraying, continuous impregnation, winding and spin coating processes. In many cases, one starts from so-called prepregs, preimpregnated with fiberglass fiber materials, which are cured under application of pressure in the heat. The GFK are distinguished from the non-reinforced matrix polymers by increased tensile, flexural and compressive strength, impact strength, dimensional stability and stability to the influence of heat, acids, salts, gases or solvents. In the context of the present invention, in particular glass-fiber-reinforced polyterafluoroethylene and glass-fiber-reinforced polyamides have proven to be the materials of the elevations in the upper punch which characterize the reinforcing recesses.

Also suitable as material for the base are plastics that are softer than the plastics used for the construction of the elevations in the upper punch, which characterize the reinforcing recesses. Of course, these plastics can come from the same or from different groups, as long as the condition of hardness or softness is met. The preferably adhesion-preventing or at least adhesion or adhesion-reducing effect of the walkable material for the formation of the base area has been described above. Experiments have shown that, for example, with the polyurethane material Vulkollan or the PVC material Mipolam very good results could be achieved. Over use times of several thousand pressures, no adhesion to the base material was found.

The process according to the invention makes it possible to produce moldings of the most varied compositions, the process according to the invention in particular minimizing the problems in the production and use of detergent tablets for machine dishwashing. These detergent tablets usually contain only minor amounts of surfactants.
Detergent tablets are usually prepared by blending surfactant granules with conditioning components and then compressing this particulate premix. Preferred variants of the process according to the invention are therefore characterized in that the particulate premix contains surfactant-containing granules (e) 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.

In the context of the present invention, preferred methods therefore include the compression of a particulate premix of at least one surfactant-containing granules and at least one admixed pulverulent component. The preparation of the surfactant-containing granules can be carried out by conventional industrial granulation processes such as compaction, extrusion, mixer granulation, pelleting or fluidized bed granulation.
The surfactant-containing granules satisfies certain particle size criteria in preferred process variants. Thus, preference is given to processes according to the invention in which the surfactant-containing granules have particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, more preferably between 400 and 1600 μm and in particular between 600 and 1400 μm.

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

These surfactants come from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic surfactants are clearly preferred for economic reasons and because of their power spectrum.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

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

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which, for example, according to the U.S. Patents 3,234,258 or 5,075,041 are manufactured and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

Also, the sulfuric monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight-chain or branched C _7-21 alcohols, such as 2-methyl-branched C _9-11 alcohols having an average of 3.5 Mole of ethylene oxide (EO) or C _12-18 fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the 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 of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

As further anionic surfactants are particularly soaps into consideration. Suitable are 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, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
The anionic surfactants including the soaps may 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 present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

In the context of the present invention, preference is given to surfactant granules containing from 5 to 50% by weight, preferably from 7.5 to 40% by weight and in particular from 10 to 30% by weight of anionic surfactant (s), in each case based on the granules ,

In the selection of anionic surfactants that are used, the freedom from formulation no obstacle to be observed in the way. However, preferred surfactant granules have a content of soap which exceeds 0.2% by weight, based on the total weight of the detergent tablets prepared in step d). Preferred anionic surfactants to be used are the alkylbenzenesulfonates and fatty alcohol sulfates, with preferred detergent tablets having from 2 to 20% by weight, preferably from 2.5 to 15% by weight and in particular from 5 to 10% by weight of fatty alcohol sulfate (e), in each case based on the weight of the detergent tablets.

When the tablets according to the invention are formulated as automatic dishwashing agents, they preferably contain only minor amounts of anionic surfactants, but mainly nonionic surfactants.

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

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

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

Further suitable surfactants are polyhydroxy fatty acid amides of the formula

wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 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.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder Propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having from 1 to 8 carbon atoms, with 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 be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, the machine dishwashing detergents according to the invention contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. 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 radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. 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.

Particular preference is given to compositions according to the invention which comprise a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred dishwashing detergents are characterized in that they contain nonionic surfactant (s) having a melting point above 20 ° C., preferably above 25 ° C., more preferably between 25 and 60 ° C. and in particular between 26.6 and 43, 3 ° C, included.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as Polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also distinguished by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.

A particularly preferred solid at ambient temperature, non-ionic surfactant is derived from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide , Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred dishwashing agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic Surfactants are included.

More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. -% one Block copolymers of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergen ^® SLF-18 from Olin Chemicals.

A further preferred dishwashing detergent according to the invention contains nonionic surfactants of the formula (VI)

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

in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.

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

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

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

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

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

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

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

Summarizing the latter statements, dishwashing agents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula

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

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type

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

in which x is from 1 to 30, preferably from 1 to 20 and especially from 6 to 18, are particularly preferred.

In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Machine dishwashing agents according to the invention which contain surfactants of the general formula VII as nonionic surfactant (s) are preferred here

R ^{1 is} -O- (CH ₂ -CH ₂ -O) _w - (CH ₂ -CH (R ² ) -O) _x - (CH ₂ -CH ₂ -O) _y - (CH ₂ -CH (R ³ ) -O) _z -H (VII)

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently of one another are integers from 1 to 6.

The preferred nonionic surfactants of formula VII can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in formula X above may vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually undisplayed, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, automatic dishwasher detergents according to the invention are preferred in which R ¹ in formula VII is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from - CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are suitable. Preferred automatic dishwashing agents are characterized in that R ² and R ³ are each a residue -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.

In summary, nonionic surfactants having a C _9-15 alkyl radical having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units are particularly preferred for use in the inventive compositions. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

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

R ¹ O [CH ₂ CH (R ³ ) O] _x R ² (VIII)

in which R ^{1 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{2 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably between 1 and have 5 hydroxy groups and are preferably further functionalized with an ether group, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2- Butyl radical, x for values between 1 and 40.

In particularly preferred nonionic surfactants of the above formula (XIII), R ^{3 is} H. In the resulting end-capped poly (oxyalkylated) nonionic surfactants of the formula (IX)

R ¹ O [CH ₂ CH ₂ O] _x R ² (IX)

In particular those nonionic surfactants are preferred in which R ^{1 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, R ^{2 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and x stands for values between 1 and 40.

In particular, those end-capped poly (oxyalkylated) nonionic surfactants are preferred, which according to the formula (X)

R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² (X)

in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical with 1 have up to 30 carbon atoms R ² , which is a monohydroxylated intermediate group - CH ₂ CH (OH) - adjacent. In this formula, x stands for values between 1 and 40. Such end-capped poly (oxyalkylated) nonionic surfactants can be prepared, for example, by reacting a terminal epoxide of the formula R ² CH (O) CH ₂ with an ethoxylated alcohol of the formula R ¹ O [CH ₂ CH ₂ O] _x-1 CH ₂ CH ₂ OH.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.

Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). Usable Alkypolyglycoside meet the general formula RO (G) _z , in which R is a linear or branched, especially in the 2-position methyl branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.

Preference is given to using linear alkyl polyglucosides, that is to say alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

The surfactant granules may preferably contain alkylpolyglycosides, with contents of APG of more than 0.2% by weight, based on the total molding, being preferred. Particularly preferred detergent tablets contain APG in amounts of from 0.2 to 10% by weight, preferably from 0.2 to 5% by weight and in particular from 0.5 to 3% by weight.
Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

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

The surfactant granules can be used in the detergent tablets in varying amounts. Processes according to the invention in which the proportion of surfactant-containing granules in the washing and cleaning agent tablets is 40 to 95% by weight, preferably 45% to 85 wt .-% and in particular 55 to 75 wt .-%, each based on the weight of the detergent tablets, are thereby preferred. As already mentioned above, automatic dishwashing detergent tablets usually contain only small quantities of surfactants, so that the above information does not apply to this class of detergent tablets.

In addition to the washing-active substances, builders are the most important ingredients of detergents and cleaners. In the surfactant granules, or where no Tensidgranulate be used as part of the premix all commonly used in detergents and cleaning agents builders may be included, especially zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates.

Suitable crystalline layered sodium silicates 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 2, 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification 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 do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a dissolution delay compared with the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

Detergents and cleaning agents which are preferred in the context of the present invention are characterized in that these silicates (e), preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali disilicates, are present in amounts of from 10 to 60% by weight, preferably from 15 to 50% by weight. % and in particular from 20 to 40 wt .-%, each based on the weight of the washing or cleaning agent.

If the agents according to the invention are used as automatic dishwasher detergents, these compositions preferably contain at least one crystalline layered silicate of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22 , preferably from 1.9 to 4, and y is a number from 0 to 33. The crystalline layer-form silicates of the formula (1) are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS, for example Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na -SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ . xH ₂ O, Makatite).

Particularly suitable for the purposes of the present invention are agents which contain crystalline layered silicates of the formula (1) in which x is 2. Of these, especially Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3H ₂ O, kanemite), Na-SKS-11 (t-Na ₂ Si ₂ O ₅₎ and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ). An overview of crystalline sheet silicates can be found, for example, in the article published on pages 805-808 in "Soaps Oils-Fette-Wachse, 116 Volume, No. 20/1990".

In the context of the present application, preferred automatic dishwashing detergents or dishwashing assistants have a weight fraction of the crystalline layered silicate of the formula (I) of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular from 0, 4 to 10 wt .-%, each based on the total weight of these agents on. Particular preference is given to those automatic dishwashing detergents which have a total silicate content of less than 7% by weight, preferably less than 6% by weight, preferably less than 5% by weight, more preferably less than 4% by weight, most preferably less than 3% by weight. % and in particular less than 2.5 wt .-%, wherein it is in this silicate, based on the total weight of the silicate contained, preferably at least 70 wt .-%, preferably at least 80 wt .-% and in particular at least 90 wt .-% of silicate of the general formula NaMSi _x O _{2x + 1} · y H ₂ O is.

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. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa 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 granular compound, as well as to a kind of "powdering" of the entire mixture to be pressed, wherein usually both ways for incorporating the zeolite are used in the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

If desired, in addition to the amount of P and / or X type zeolite introduced by the surfactant granules, additional zeolite may be incorporated into the premix by adding zeolite as a conditioning component. The finely crystalline, synthetic and bound water-containing zeolite used is preferably a zeolite of type A, P, X or Y. However, zeolite X and mixtures of A, X and / or P are also suitable. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. This applies in particular to the use of agents according to the invention as automatic dishwasher detergents, which is particularly preferred in the context of the present application. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

Alkalimetallphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids in which metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to high molecular weight Can distinguish representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the 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 powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid 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), pass. NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium phosphate, KDP), KH ₂ PO ₄ , is a white salt of 2.33 gcm ^-3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of 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 readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate 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 under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents 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 being 1% Solution at 25 ° 10.4.

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The industrially important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is a water-free or with 6 H ₂ O crystallizing a non-hygroscopic white water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

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

These are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; also mixtures of sodium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

Agents preferred in the context of the present invention are characterized in that these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of from 5 to 80% by weight, preferably from 15 to 75% by weight, in particular from 20 to 70% by weight, based in each case on the weight of the washing or cleaning agent.

Particular preference is given to those compositions according to the invention in which the weight ratio of potassium tripolyphosphate present in the composition to sodium tripolyphosphate is more than 1: 1, preferably more than 2: 1, preferably more than 5: 1, more preferably more than 10: 1 and in particular more than 20: 1. Particular preference is given to those agents according to the invention which contain exclusively potassium tripolyphosphate.

Further builders are the alkali carriers. Suitable alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention. Particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate. Also particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.

Particularly preferred detergents and cleaning agents contain carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonates, more preferably sodium carbonate, in amounts of from 2 to 50% by weight, preferably from 5 to 40% by weight and in particular 7.5 to 30 wt .-%, each based on the weight of the detergent or cleaning agent.

As organic cobuilders, it is possible in particular to use polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates in the detergents and cleaners according to the invention. These classes of substances are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning such carboxylic acids which carry more than one acidity function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

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

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

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

Polyacrylates are, for example, under the names Versicol ^® E5, Versicol ^® E7 and Versicol ^® E9 (trademark of Allied Colloids), Narlex ^® LD 30 and Narlex ^® LD 34 (trademark of National Adhesives), Acrysol ^® LMW-10, Acrysol ^® LMW 20, Acrysol ^® LMW-45 and Acrysol ^® A1-N (trademark of Rohm & Haas), and Sokalan ^® PA-20, Sokalan ^® PA-40, Sokalan ^® PA 70 and Sokalan ^® PA-110 (trademark of BASF) available in the stores. Ethylene / maleic acid copolymers are sold under the name EMA ^® (trademark of Monsanto), methyl vinyl ether / maleic acid copolymers under the name Gantrez ^® AN 119 (trademark of GAF Corp.) and acrylic acid / maleic acid copolymers under the name Sokalan ^® CP5 and Sokalan ^® CP7 (trademark of BASF). Acrylic phosphinates are as DKW ^® - available (trademark of National Adhesives) or Belperse ^® grades (trademark of Ciba-Geigy). In combination with the polymers mentioned or as the sole grayness inhibitor, it is also possible to use graft copolymers which are obtained by grafting polyalkylene oxides having molecular weights of between 2000 and 100 000 with vinyl acetate. The acetate groups may optionally be saponified up to 15%. Polymers of this type are available under the name Sokalan ^® HP22 (trademark of BASF) in the trade.

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

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers the salts of acrylic acid and maleic acid and also vinyl alcohol or vinyl alcohol derivatives or the salts of acrylic acid and 2-alkylallyl sulfonic acid as monomers. Derivatives included.

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

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particularly preferred are polyaspartic acids or their salts and.

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

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 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.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Ethylenediamine tetramethylene phosphonates are preferably used as aminoalkane phosphonates (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as co-builders.

Detergents or cleaning agents according to the invention may furthermore contain washing or cleaning-active polymers. The group of these polymers includes, for example, the rinse aid polymers and / or polymers which are effective as softeners. Detergents or cleaning agents which are preferred according to the invention are characterized in that, based on their total weight, they contain 0.1 to 50% by weight, preferably between 0.2 and 40% by weight, more preferably between 0.4 and 35% by weight .-% and in particular between 0.6 and 31 wt .-% of a polymer, preferably at least one polymer from the group of cationic, anionic or amphoteric polymers.

Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference in the compositions according to the invention.

Particularly preferred as Suldonsäuregruppen-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.

In the context of the present invention, unsaturated carboxylic acids of the formula XI are preferred as the monomer,

R ¹ (R ² ) C = C (R ³ ) COOH (XI),

in the R ¹ to R ³ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or for -COOH or - COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the formula XI are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H, R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) is preferred.

In the sulfonic acid-containing monomers, those of the formula XII are preferred,

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XII),

in the R ⁵ to R ⁷ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas XIIa, XIIb and / or XIIIc,

H ₂ C = CH-X-SO ₃ H (XIIa),

H ₁ C = C (CH ₃ ) -X-SO ₃ H (XIIb),

HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XIIc),

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ CH ₃ ) in formula XIIa), 2-acrylamido-2-propanesulfonic acid (X = -C ( O) NH-C (CH ₃ ) ₂ in formula XIIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula XIIa), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula XIIb), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C (O) NH- CH ₂ CH (OH) CH ₂ - in formula XIIb) allyl sulfonic acid (X = CH ₂ in formula XIIa), methallyl sulfonic acid (X = CH ₂ in formula XIIb), Allyloxybenzoisulfonsäure (X = -CH ₂ -O-C ₆ H ₄ - in formula XIIa), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula XIIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid (X = CH ₂ in formula XIIb), styrenesulfonic acid (X = C ₆ H ₄ in formula XIIa), vinylsulfonic acid (X not present in formula XIIa), 3-sulfopropyl acrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula Xlla), 3-sulfopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula XIIb), sulfomethacrylamide (X = - C (O) NH- in formula XIIb), sulfomethylmethacrylamide (X = -C (O) NH-CH ₂ - in formula XIIb) and water-soluble salts of said acids.

Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. The content of the monomers used according to the invention to monomers of group iii) is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers to be used consist only of monomers of groups i) and ii).

1. i) ungesättigten Carbonsäuren der Formel XI.
   
           R¹(R²)C=C(R³)COOH     (XI),
   
   in der R¹ bis R³ unabhängig voneinander für -H -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder - COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder - COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
2. ii) Sulfonsäuregruppen-haltigen Monomeren der Formel XII
   
           R⁵(R⁶)C=C(R⁷)-X-SO₃H     (XII),
   
   in der R⁵ bis R⁷ unabhängig voneinander für -H -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder - COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder - COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
3. iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren
   besonders bevorzugte Inhaltsstoffe der erfindungsgemäßen Wasch- oder Reinigungsmittelzusammensetzungen.

In summary, copolymers are made of

1. i) unsaturated carboxylic acids of the formula XI.
   
   R ¹ (R ² ) C = C (R ³ ) COOH (XI),
   
   in the R ¹ to R ³ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
2. ii) sulfonic acid group-containing monomers of the formula XII
   
   R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XII),
   
   in the R ⁵ to R ⁷ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional Spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -
3. iii) optionally further ionic or nonionic monomers
   particularly preferred ingredients of the washing or cleaning compositions of the invention.

1. i) einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
2. ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln Xlla, Xllb und/oder Xllc:
   
           H₂C=CH-X-SO₃H     (XIIa),
   
           H₂C=C(CH₃)-X-SO₃H     (XIIb),
   
           HO₃S-X-(R⁷)C=C(R⁷)-X-SO₃H     (XIIc),
   
   in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus-(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
3. iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren.

Particularly preferred copolymers consist of

1. i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid
2. ii) one or more sulfonic acid group-containing monomers of the formulas XIIa, XIIb and / or XIIIc:
   
   H ₂ C = CH-X-SO ₃ H (XIIa),
   
   H ₂ C = C (CH ₃ ) -X-SO ₃ H (XIIb),
   
   HO ₃ SX- (R ⁷ ) C = C (R ⁷ ) -X-SO ₃ H (XIIc),
   
   in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -
3. iii) optionally further ionic or nonionic monomers.

The copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii). Particularly preferred polymers have certain structural units, which are described below.

For example, laundry detergent or detergent compositions of the invention are preferred, which are characterized in that they contain one or more copolymers, the structural units of the formula XIII

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIII)

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. When the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use in the washing or cleaning composition according to the invention is also preferred and characterized in that the preferred detergent or cleaner compositions comprise one or more copolymers containing structural units of the formula XIV

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIV),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, washing or cleaning agent compositions according to the invention which contain one or more copolymers which are structural units of the formula XV

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XV),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are preferred, also a preferred embodiment of the present invention, as well as washing or Detergent compositions are preferred, which are characterized in that they contain one or more copolymers, the structural units of the formula XVI

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XVI),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This results in inventively preferred detergent compositions which are characterized in that they contain one or more copolymers which contain structural units of the formula XVII

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XVII),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred and to detergent or cleaning compositions, which are characterized in that they contain one or more copolymers, the structural units of the formula XVIII

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (XVIII),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In summary, washing or cleaning agent compositions according to the invention which contain one or more copolymers which contain structural units of the formulas XIII and / or XIV and / or XV and / or XVI and / or XVII and / or XVIII are preferred

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIII)

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIV),

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XV),

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XVI),

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XVII),

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (XVIII),

in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. Corresponding detergent or cleaning agent compositions which are characterized in that the sulfonic acid groups are present in the copolymer partially or fully neutralized are preferred according to the invention.

The monomer distribution of the copolymers used in the detergent or cleaning compositions according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90 % By weight of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.

In the case of terpolymers, particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,

The molecular weight of the above-described sulfo-copolymers used in the detergent or cleaner compositions of the present invention can be varied to tailor the properties of the polymers to the desired end use. Preferred washing or cleaning compositions are characterized in that the Copolymers have molecular weights of 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

1. i) Ungesättigten Carbonsäuren
2. ii) Sulfonsäuregruppen-haltigen Monomeren
3. iii) Gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren, enthalten.

Particularly preferred detergents or cleaners according to the invention are characterized in that they contain at least one polymer containing sulfonic acid groups, preferably a copolymer

1. i) Unsaturated carboxylic acids
2. ii) sulfonic acid group-containing monomers
3. iii) optionally further ionic or nonionic monomers.

Preferred agents according to the invention, which are used as automatic dishwasher detergents, may further contain amphoteric or cationic polymers to improve the rinse-off result. These particularly preferred polymers are characterized by having at least one positive charge. Such polymers are preferably water-soluble or water-dispersible, that is, they have a solubility in water at 25 ° C above 10 mg / ml. In the context of the present application, particularly preferred detergents or cleaners are characterized in that they contain at least one polymer with a molecular weight above 2000, which has at least one positive charge.

Particularly preferred cationic or amphoteric polymers contain at least one ethylenically unsaturated monomer unit of the general formula

R ¹ (R ² ) C = C (R ³ ) R ⁴

in the R ¹ to R ⁴ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above, a heteroatomic group having at least one positively charged group, a quaternized nitrogen atom or at least one amine group with a positive charge in the pH range between 2 and 11 or -COOH or -COOR ⁵ , wherein R ^{5 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Examples of the above-mentioned (unpolymersized) monomer units are diallylamine, methyldiallylamine, dimethyldimethylammonium salts, acrylamidopropyl (trimethyl) ammonium salts (R ¹ , R ² , and R ³ , = H, R ⁴ = C (O) NH (CH ₂ ) ₂ N ⁺ ( CH ₃ ) ₃ X), methacrylamidopropyl (trimethyl) ammonium salts (R ¹ and R ² = H, R ³ = CH ₃ H, R ⁴ = C (O) NH (CH ₂ ) ₂ N ⁺ (CH ₃ ) ₃ X) ,

Particularly preferred as part of the amphoteric polymers are unsaturated carboxylic acids of the general formula

R ¹ (R ² ) C = C (R ³ ) COOH

used in which R ¹ to R ^{3 are} independently -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with - NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is - COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred amphoteric polymers contain as monomer units derivatives of diallylamine, in particular dimethyldiallylammonium salt and / or methacrylamidopropyl (trimethyl) ammonium salt, preferably in the form of the chloride, bromide, iodide, hydroxide, phosphate, sulfate, hydrosulfate, ethylsulfate, methylsulfate, mesylate, tosylate, formate or acetate in combination with monomer units from the group of ethylenically unsaturated carboxylic acids.

Before the particulate premix is compressed into detergent tablets, the premix can be "powdered" with finely divided surface treatment agents. This may be advantageous for the nature and physical properties of both the premix (storage, compression) and the finished detergent tablets. Fine particulate powdering agents are well known in the art, with mostly zeolites, silicates or other inorganic salts are used. Preferably, however, the premix is "powdered" with finely divided zeolite, with faujasite-type zeolites being preferred. In the context of the present invention, the term "faujasite-type zeolite" denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 (cf. Donald W. Breck: "Zeolite Molecular Sieves," John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92 ). In addition to zeolite X, it is thus also possible to use zeolite Y and faujasite and also mixtures of these compounds, the pure zeolite X being preferred.
Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which need not necessarily belong to the zeolite structure group 4, can be used as a powdering agent, it being advantageous if at least 50 wt .-% of the powdery powder of a zeolite of faujasite Type persist.

In the context of the present invention, preference is given to detergent tablets which consist of a particulate premix containing granular components and subsequently admixed pulverulent substances, the one or more subsequently admixed pulverulent components comprising a faujasite-type zeolite having particle sizes of less than 100 μm, preferably below 10 μm and in particular below 5 μm and makes up at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be tabletted.

According to the invention, detergent tablets and detergent tablets which additionally contain a disintegration assistant are preferred. Also inventive method in which the premix additionally 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 wt .-% and in particular from 4 to 6 wt .-%, each based on the weight of the premix contains, are preferred. In addition to the constituents surfactant, builder and disintegration assistant, or in their place, in the process according to the invention, the particulate premixes to be compressed additionally comprise one or more substances from the group of bleaches, bleach activators, enzymes, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, Foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, dye transfer inhibitors and corrosion inhibitors.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Cleaning agents according to the invention may also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)] , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, Diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

As bleaching agents in the dispersions of the invention it is also possible to use chlorine or bromine-releasing substances. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

Preferred dispersions according to the invention contain bleaching agents in amounts of from 1 to 40% by weight, preferably from 2.5 to 30% by weight and in particular from 5 to 20% by weight, in each case based on the total dispersion.

If the agents according to the invention are used as automatic dishwashing detergents, they may furthermore contain bleach activators as dispersed substances in order to achieve an improved bleaching effect on cleaning at temperatures of 60 ° C. and below. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH. -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist.Other bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitrile of the formula

in the R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C _1-24 -alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH. -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion.

enthalten, in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁶ = -CH₃ und insbesondere R⁴ = R⁵ = R⁶ = -CH₃ gilt und Verbindungen der Formeln (CH₃)₃N⁽⁺⁾CH₂-CN X^-, (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^- , (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂-CN X^-, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂-CN X^-, oder (HO-CH₂-CH₂)₃N⁽⁺⁾CH₂-CN X^- besonders bevorzugt sind, wobei aus der Gruppe dieser Substanzen wiederum das kationische Nitril der Formel (CH₃)₃N⁽⁺⁾CH₂-CN X^-, in welcher X^- für ein Anion steht, das aus der Gruppe Chlorid, Bromid, Iodid, Hydrogensulfat, Methosulfat, p-Toluolsulfonat (Tosylat) oder Xylolsulfonat ausgewählt ist, besonders bevorzugt wird.In particularly preferred inventive agents is a cationic nitrile of the formula

in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , where R ^{4 can} additionally also be -H and X is an anion, where preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ^{( +)} CH ₂ -CN X ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH (CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{- are} particularly preferred, wherein in turn from the group of these substances the cationic nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , in which X ^{- is} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate is particularly preferred.

As bleach activators it is also possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyvalent Alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium acetonitrile-methyl sulfate (MMA) and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG ), Pentaacetylfruktose, tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used. The bleach activators are usually used in automatic dishwashing detergents in amounts of from 0.1 to 20% by weight, preferably from 0.25 to 15% by weight and in particular from 1 to 10% by weight, based in each case on the composition.

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

If, in addition to the nitrile quats, further bleach activators are to be used, preference is given to bleach activators from the group of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (US Pat. N- or iso-NOBS), n-methyl-morpholinium acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, especially 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the total weight of the dispersion used.

Bleach-enhancing transition metal complexes, in particular having 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 the cobalt (ammine) Complexes of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in conventional amounts, preferably in an amount up to 5 wt .-%, in particular of 0.0025 wt % to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in special cases, more bleach activator can be used.

Another important criterion for the evaluation of a machine dishwashing detergent, apart from its cleaning performance, is the visual appearance of the dry dishes after cleaning. Possibly occurring calcium carbonate deposits on dishes or in the For example, machine interiors can impair customer satisfaction and thus have a causal influence on the economic success of such a cleaning agent. Another long-standing problem with automatic dishwashing is the corrosion of glassware, which can usually manifest itself by the appearance of turbidity, streaks and scratches, but also by iridescence of the glass surface. The observed effects are based essentially on two processes, the leakage of alkali and alkaline earth ions from the glass in conjunction with hydrolysis of the silicate network, on the other hand in a deposition of silicate compounds on the glass surface.
The stated problems can be solved with the dispersions according to the invention if certain glass corrosion inhibitors are incorporated into the compositions in addition to the abovementioned mandatory and optionally optional ingredients. Preferred agents according to the invention therefore furthermore comprise glass corrosion protection agents, preferably from the group of magnesium and / or zinc salts and / or magnesium and / or zinc complexes.

A preferred class of compounds that can be added to the compositions of the invention to prevent glass corrosion are insoluble zinc salts. These can accumulate on the glass surface during the dishwashing process, preventing the dissolution of metal ions from the glass network and the hydrolysis of the silicates. In addition, these insoluble zinc salts also prevent the deposition of silicate on the glass surface, so that the glass is protected from the consequences described above.

Insoluble zinc salts in the context of this preferred embodiment are zinc salts which have a solubility of a maximum of 10 grams of zinc salt per liter of water at 20 ° C. Examples of particularly preferred insoluble zinc salts according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn ₂ (OH) ₂ CO ₃ ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn ₃ (PO ₄ ) ₂ ), and zinc pyrophosphate (Zn ₂ (P ₂ O ₇ )).

The zinc compounds mentioned are preferably employed in the compositions according to the invention in amounts which have a content of the agents of zinc ions of between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and in particular between 0.2 and 1.0 wt .-%, each based on the agent effect. The exact content of the agents on the zinc salt or zinc salts is of course dependent on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration should be in the inventive compositions.

Since the insoluble zinc salts remain largely unchanged during the Geschirreinigungsvorgangs, the particle size of the salts is a criterion to be observed, so that the salts do not adhere to glassware or machine parts. Here are liquid aqueous according to the invention automatic dishwasher detergents are preferred in which the insoluble zinc salts have a particle size below 1.7 millimeters.

If the maximum particle size of the insoluble zinc salts is below 1.7 mm, insoluble residues in the dishwasher are not to be feared. Preferably, the insoluble zinc salt has an average particle size which is significantly below this value in order to further minimize the risk of insoluble residues, for example an average particle size of less than 250 μm. Again, this is even more true the less the zinc salt is soluble. In addition, the glass corrosion inhibiting effectiveness increases with decreasing particle size. For very poorly soluble zinc salts, the average particle size is preferably below 100 microns. For still less soluble salts, it may be even lower; For example, average particle sizes below 100 μm are preferred for the very poorly soluble zinc oxide.

Another preferred class of compounds are magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid. The effect of this is that even with repeated use, the surfaces of glassware do not change corrosively, in particular, no turbidity, streaks or scratches, but also iridescence of the glass surfaces are not caused.

Although, according to the invention, all magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids may be included in the claimed compositions, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids are derived from the Groups of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred. Within these groups, the acids mentioned below are again preferred in the context of the present invention:

From the group of unbranched saturated or unsaturated monocarboxylic acids: methanoic acid (formic acid), ethanoic acid (acetic acid), propionic acid (propionic acid), pentanoic acid (valeric acid), hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), Decanoic acid (capric acid), undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid) , Hexacosanoic acid (cerotic acid), triacotanoic acid (melissinic acid), 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t octadecenoic acid (petroselidic acid), 9c octadecenoic acid (oleic acid), 9t octadecenoic acid (elaidic acid), 9c, 12c octadecadienoic acid (linoleic acid), 9t, 12t octadecadienoic acid (linolaidic acid), and 9c, 12c, 15c octadecranic acid (linolenic acid).

From the group of branched saturated or unsaturated monocarboxylic acids: 2-methylpentanoic acid, 2-ethylhexanoic acid, 2-propylheptanoic acid, 2-butyloctanoic acid, 2-pentylnonanoic acid, 2-hexyldecanoic acid, 2-heptylundecanoic acid, 2-octyldodecanoic acid, 2-nonyltridecanoic acid, 2-decyltetradecanoic acid, 2-undecylpentadecanoic acid, 2-dodecylhexadecanoic acid, 2-tridecylheptadecanoic acid, 2-tetradecyloctadecanoic acid, 2-pentadecylnonadecanoic acid, 2-hexadecyleicosanoic acid, 2-heptadecylheneicosanoic acid.

From the group of unbranched saturated or unsaturated di- or tricarboxylic acids: propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid ( Sebacic acid), 2c-butenedioic acid (maleic acid), 2t-butenedioic acid (fumaric acid), 2-butynedicarboxylic acid (acetylenedicarboxylic acid).

From the group of aromatic mono-, di- and tricarboxylic acids: benzoic acid, 2-carboxybenzoic acid (phthalic acid), 3-carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid (terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid), 3,5-dicarboxybenzoic acid (Trimesionsäure).

From the group of sugar acids: galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, 2-deoxy-ribonic acid, alginic acid.

From the group of hydroxy acids: hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), malic acid (malic acid), 2,3-dihydroxybutanedioic acid (tartaric acid), 2-hydroxy-1,2,3-propanetricarboxylic acid (citric acid), ascorbic acid, 2 Hydroxybenzoic acid (salicylic acid), 3,4,5-trihydroxybenzoic acid (gallic acid).

From the group of oxo acids: 2-oxopropionic acid (pyruvic acid), 4-oxo-pentanoic acid (levulinic acid).

From the group of amino acids: alanine, valine, leucine, isoleucine, proline, tryptophan, phenylalanine, methionine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, lysine, arginine, histidine.

From the group of polymeric carboxylic acids: polyacrylic acid, polymethacrylic acid, alkylacrylamide / acrylic acid copolymers, alkylacrylamide / methacrylic acid copolymers, alkylacrylamide / methylmethacrylic acid copolymers, copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers.

The spectrum of the inventively preferred zinc salts of organic acids, preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / L, preferably below 10 mg / L, in particular have no solubility, to such salts having a solubility in water above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate:

In a further preferred embodiment of the present invention, the dispersions according to the invention comprise at least one zinc salt, but no magnesium salt of an organic acid, which is preferably at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt selected from zinc stearate, zinc oleate, zinc gluconate, zinc acetate , Zinc lactate and / or zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

An agent preferred in the context of the present invention contains zinc salt in amounts of from 0.1 to 5% by weight, preferably from 0.2 to 4% by weight and in particular from 0.4 to 3% by weight, or zinc in oxidized form (calculated as Zn ²⁺ ) in amounts of from 0.01 to 1% by weight, preferably from 0.02 to 0.5% by weight and in particular from 0.04 to 0.2% by weight , in each case based on the total weight of the dispersion.

If the tablets according to the invention are used as dishwashing detergents, then these detergents may contain corrosion inhibitors for the protection of the items to be washed or the machine, silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. Examples which may be mentioned of the 3-amino-5-alkyl-1,2,4-triazoles which are preferably used according to the invention include: 5-propyl, -butyl, -pentyl, -heptyl, -octyl-, Nonyl, decyl, indodecyl, dodecyl, isononyl, versatic-10-acid alkyl, -Phenyl, -p-tolyl, - (4-tert-butylphenyl) -, - (4-methoxyphenyl) -, - (2-, -3-, 4-pyridyl) -, - (2-thienyl) -, - (5-Methyl-2-furyl) -, - (5-oxo-2-pyrrolidinyl) -, 3-amino-1,2,4-triazole. In dishwashing agents, the alkylamino-1,2,4-triazoles or their physiologically tolerated salts in a concentration of 0.001 to 10 wt .-%, preferably 0.0025 to 2 wt .-%, particularly preferably 0.01 to 0.04 wt .-% used. Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid. Especially effective are 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-versatic-10-alkyl-3-amino-1,2,4-triazoles and mixtures of these substances.

In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

Instead of or in addition to the silver protectants described above, for example the benzotriazoles, it is possible to use redox-active substances in the compositions according to the invention. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, wherein the metals preferably in one of the oxidation states II, III , IV, V or VI.

The metal salts or metal complexes used should be at least partially soluble in water. The counterions suitable for salt formation comprise all customary mono-, di- or tri-positively negatively charged inorganic anions, eg. As oxide, sulfate, nitrate, fluoride, but also organic anions such. Stearate.

Metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and optionally additionally one or more of the abovementioned anions. The central atom is one of the above-mentioned metals in one of the abovementioned oxidation states. The ligands are neutral molecules or anions that are mono- or polydentate; the term "Ligands" within the meaning of the invention is, for example, in " Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507 If, in a metal complex, the charge of the central atom and the charge of the ligand (s) are not zero, either one or more of the abovementioned anions or one or more, depending on whether there is a cationic or an anionic charge surplus Cations, for example sodium, potassium and ammonium ions, for charge balance Suitable complexing agents are, for example, citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.

The well-known in chemistry definition for "oxidation state" is eg in " Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1991, page 3168 "reproduced.

Particularly preferred metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ and mixtures thereof. so that preferred automatic dishwasher detergents according to the invention are characterized in that the metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1-diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CosO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ .

In these metal salts or metal complexes are generally commercially available substances that can be used for the purpose of silver corrosion protection without prior purification in the compositions of the invention. Thus, for example, the mixture of pentavalent and tetravalent vanadium (V ₂ O ₅ , VO ₂ , V ₂ O ₄ ) known from the SO ₃ preparation (contact method) is suitable, as is the case by diluting a Ti (SO ₄ ) ₂ - Solution resulting titanyl sulfate, TiOSO ₄ .

The inorganic redox-active substances, in particular metal salts or metal complexes are preferably coated, ie completely coated with a waterproof material which is readily soluble in the cleaning temperatures, in order to prevent their premature decomposition or oxidation during storage. Preferred coating materials, which are applied by known methods, such as Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids. In this case, the coating material solid at room temperature is applied in a molten state to the material to be coated, for example by finely divided material to be coated in a continuous stream by a likewise continuously generated Spray zone of the molten coating material is thrown. The melting point must be chosen so that the coating material easily dissolves or melts during the silver treatment. The melting point should ideally be in the range between 45 ° C and 65 ° C and preferably in the range 50 ° C to 60 ° C.

The metal salts and / or metal complexes mentioned are in the agents, in particular automatic dishwashing agents, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, based on the total weight of Contain funds.

Agents according to the invention may contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all enzymes established for this purpose in the prior art. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Agents ^according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5 percent by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg in a developed form under the trade names Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP ^® variants are derived.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, that under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ^® and protease P ^® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents and cleaners. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and variants derived from the α-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes.

Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae, which are. Another commercial product is, for example, the amylase ^LT® .

Compositions according to the invention may contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^®, Lipolase Ultra ^®, LipoPrime® ^®, Lipozyme® ^® and Lipex ^®. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens . Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. ^Lipase® , Lipase ^AP® , Lipase M- ^AP® and Lipase ^{AML® are} available. From the company Genencor, for example, the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii . Other important commercial products are the originally marketed by Gist-Brocades preparations M1 Lipase ^® and Lipomax® ^® and sold by the company Meito Sangyo KK, Japan under the name Mentioned Lipase MY-30 ^® , Lipase OF ^® and Lipase PL ^® marketed enzymes, and the product Lumafast ^® from Genencor.

Compositions of the invention may contain other enzymes, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 L from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, USA , The obtained from B. subtilis β-glucanase is available under the name Cereflo ^® from Novozymes.

To increase the bleaching effect, detergent and cleaner compositions of the invention may be oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain. Suitable commercial products Denilite® ^® 1 and 2 from Novozymes should be mentioned. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

The enzymes used in agents of the invention are either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or filamentous fungi.

The purification of the relevant enzymes is conveniently carried out by conventional methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps. The agents of the invention may be added to the enzymes in any form known in the art. These include, for example, obtained by granulation, extrusion or lyophilization solid preparations or, in particular in liquid or Gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

Furthermore, it is possible to assemble two or more enzymes together so that a single granule has multiple enzyme activities.

A protein and / or enzyme contained in an agent according to the invention can be protected against damage, for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, in particular during storage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Compositions according to the invention may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

One group of stabilizers are reversible protease inhibitors. Frequently, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are used, including in particular derivatives with aromatic groups, such as ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters. As peptidic protease inhibitors are, inter alia, ovomucoid and leupeptin to mention; An additional option is the formation of fusion proteins from proteases and peptide inhibitors.

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders are additionally capable of stabilizing a contained enzyme.

Lower aliphatic alcohols, but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers. Also used are calcium salts, such as calcium acetate or calcium formate, and magnesium salts.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polyamine N-oxide containing polymers act as enzyme stabilizers. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and even increase their performance. Crosslinked N-containing compounds also act as enzyme stabilizers.

Reducing agents and antioxidants increase the stability of the enzymes to oxidative degradation. A sulfur-containing reducing agent is, for example, sodium sulfite.

Preferably, combinatons of stabilizers are used, for example of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The effect of peptide-aldehyde stabilizers is enhanced by the combination with boric acid and / or boric acid derivatives and polyols and further enhanced by the additional use of divalent cations, such as calcium ions.

Preferred tablets according to the invention are characterized in that they additionally contain one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, in amounts of from 0.1 to 5% by weight, preferably from 0.2 to 4.5 and in particular from 0.4 to 4 wt .-%, each based on the total agent included.

Agents preferred according to the invention are characterized in that they contain, based on their total weight, at least 20% by weight, preferably at least 30% by weight, particularly preferably at least 40% by weight and in particular at least 50% by weight of builders and / or bleaching agents and / or bleach activators and / or washing or cleaning-active polymers and / or glass corrosion inhibitors and / or silver protectants and / or enzymes. Particularly preferred compositions according to the invention consist of at least 90% by weight, preferably at least 92% by weight, preferably at least 94% by weight, especially preferably at least 96% by weight, more preferably at least 98% by weight and most preferably at least 99.5% by weight, exclusively of builders and / or bleaches and / or bleach activators and / or washing or cleaning-active polymers and / or glass corrosion inhibitors and / or silver protectants and / or enzymes.

Particular preference is given to washing or cleaning agents according to the invention which, based on their total weight, are between 0.04 and 18% by weight, preferably between 0.08 and 16% by weight and in particular between 0.2 and 14% by weight. one or more substances from the group of silver protectants, glass protectants or enzymes.

In addition, the detergent tablets may also contain components which positively influence the oil and grease washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent prepared according to the invention, which contains this oil and fat dissolving component. The preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxy-propylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

The shaped bodies may contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed compounds which, instead of the morpholino group, a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl). Mixtures of the aforementioned brightener can be used.

Dyes and fragrances are added to the detergent tablets prepared according to the invention in order to improve the aesthetic impression of the products and to provide the consumer with a visual and sensory "typical and unmistakable" product in addition to the softness performance. As perfume oils or fragrances can individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, α-isomethylionone and Methylcedrylketon to the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood. The content of the detergent tablets and detergent tablets produced according to the invention is usually less than 0.01% by weight of dyes, while fragrances may account for up to 2% by weight of the total formulation.

The fragrances can be incorporated directly into the compositions prepared according to the invention, but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the laundry and provide a slower fragrance release for long-lasting fragrance of the textiles. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.

In order to improve the aesthetic impression of the compositions according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to textile fibers so as not to stain them.

Claims (8)

1. A tablet of compressed particulate washing or cleaning composition, characterized in that it has, on its upper side, at least two reinforcement depressions whose horizontal dimension at the level of the tablet surface is greater than their depth, the reinforcing depressions starting from a common center in a radiating manner.
2. The tablet as claimed in claim 1, characterized in that the horizontal dimension of the reinforcement depressions at the level of the tablet surface is from 1.01 times to 5 times, preferably from 1.02 times to 4 times, more preferably from 1.04 times to 3 times and in particular from 1.05 times to 2 times the depth of the reinforcement depressions.
3. The tablet as claimed in one of claims 1 and 2, characterized in that the depth of the reinforcement depressions is from 0.05 times to 0.5 times, preferably from 0.1 times to 0.4 times and in particular from 0.15 times to 0.3 times the tablet height.
4. The tablet as claimed in one of claims 1 to 3, characterized in that it has at least 3, preferably at least 4, particularly preferably at least 5, more preferably at least 6, more preferably at least 7, more preferably at least 8, more preferably at least 9 and in particular at least 10 reinforcement depressions.
5. The tablet as claimed in one of claims 1 to 4, characterized in that the cross section of the reinforcement depressions is triangular or semicircular.
6. The tablet as claimed in one of claims 1 to 9, characterized in that the height of the tablet is from 5 to 25 mm, preferably from 7 to 22 mm and in particular from 10 to 20 mm.
7. The tablet as claimed in one of claims 1 to 6, characterized in that the depth of the reinforcement depressions is from 0.5 to 10 mm, preferably from 0.75 to 8 mm and in particular from 1 to 5 mm.
8. A process for producing tablets of compressed particulate washing or cleaning composition, characterized in that the compression is effected by using an upper punch which has, on its pressing surface, at least two elevations for pressing of reinforcement depressions, whose horizontal dimension at the level of the pressing surface is greater than their height, the reinforcing depressions starting from a common center in a radiating manner.