EP2097253A1 - Detergent or cleaning agent moulded bodies - Google Patents

Abstract

The invention relates to a detergent or cleaning agent tablet made from a compressed particulate material that has a protrusion on the single-phase upper side thereof, characterised in that it is easier to dissolve in relation to conventional tablets with the same hardness.

Description

 "Detergent tablets"

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 for short as detergent tablets or dishwasher tablets, and to processes for their production.

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. Form-resistant and fracture-resistant molded body can be produced only by relatively high pressing pressures, there is 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 particularly occurs with detergent tablets is the often inadequate stability of these tablets against the stresses of packaging, shipping and handling, i. 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 hits on an approximately 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, which can lead to Kantenbruch- 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, ie transport and handling stability, and easy disintegration of the moldings many approaches have been developed in the prior art. A particular from the pharmacy known and in the field of washing and Detergent tablet extended approach is the incorporation of certain disintegration aids, which facilitate the access of water or swell on access of water or gas evolving or disintegrating in some other form. 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.

Thus, EP 687 464 (Allphamed Arzneimittel-Gesellschaft) describes effervescent tablets comprising at least one active ingredient or combination of active ingredients, at least one binder, optionally excipients such as flavors, dyes, fragrances, plasticizers, bleaching agents and effervescent additives, propylene glycol or glycerol being used as binders, preferably in amounts of from 0.004 to 2.5% by weight. Also claimed are methods of making these effervescent tablets. According to the statements of this document can be produced with the teaching of the invention also a detergent effervescent tablet without the binder used would lead to a loss of carbon dioxide in the effervescent additives.

European Patent Application EP 711 828 (Unilever) describes detergent tablets containing surfactant (s), builder (s) and a polymer which acts as a binding and disintegrating 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 described 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 disclosed, for example, in DE 198 41 146 (Henkel). 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 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 is of particular importance in the solution of the abovementioned problems.

The subject matter of the present invention is a washing or cleaning agent tablet made of pressed particulate material, characterized in that the single-phase upper side has a protrusion.

A tablet according to the invention, hereinafter also referred to as a shaped body, has an upper and a lower side and one or more side surfaces. The underside is the area of the tablets which comes into 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), while polygonal tablets have an equal number of side surfaces in terms of the 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 present application therefore relates to washing or cleaning agent tablets made of compressed particulate material, comprising a lower surface or bottom surface, a single-phase upper side opposite the lower surface or bottom surface, and one or more lateral surface or lateral surface (s) connecting the bottom surface and the upper side. characterized in that the top of the tablet has a protrusion, the bottom surface but no protrusion, in particular no protrusion of the top complementary recess. The top of the molding is single-phase and includes the protrusion, which is why it can therefore not be at the protrusion placed on the tops or embedded in the top core.

In the present application, the term "washing or cleaning agent tablet" refers in particular to those shaped bodies which are suitable for carrying out individual cleaning cycles.Such moldings preferably have a weight between 8 and 30 g, preferably between 10 and 25 g and in particular between 12 and 20 g The volume of the shaped bodies is usually in the range between 5 and 40 ml, preferably between 8 and 30 ml and in particular between 12 and 20 ml. The molded body can be used by means of a dosing aid or by simply introducing it into the interior of a cleaning machine, for example a dishwasher. For example, nets or bags are conceivable as dosing aids, as are devices which automatically deliver the dosing unit into the interior of the cleaning machine at a given time. The group of automatic dosing systems also includes the dosing chambers of automatic dishwashers.

The spatial shape of the moldings is preferably adapted in their dimensions to the dispensing compartment of commercial household washing machines or the dosing chamber of commercially available dishwashers, so that the moldings can be metered directly into the dispensing compartment without dosing aid, where they dissolve during the dispensing operation or from where they are during of the cleaning process are released.

If dosing aids are used, the shaped body in its spatial form is preferably adapted to the dimensions of this dosing aid. Particularly preferred shaped bodies have dimensions in the range of 5 cm × 3 cm × 2 cm, preferably in the range of 4.5 cm × 2.5 cm × 2 cm, particularly preferably in the range of 4 cm × 2 cm, 2 cm.

The top of the tablet is inventively provided with a protrusion. The protrusion on the tablet top corresponds to a depression on the upper punch of the tablet press (see below). According to the invention, the horizontal extent of the protrusion at the level of the tablet surface is greater than its height. In other words, the protrusion in the x, y direction at the level of the tablet top has a greater extent than in the z direction of the tablet height. In tablets preferred according to the invention, the horizontal extent of the protrusion at the level of the tablet surface is 1.5 times to 15 times, preferably 1.5 times to 10 times, more preferably 2 to 8 times the height the protrusion.

According to the invention preferred detergent tablets are characterized in that the protrusion protrudes from a, at least partially plan top. In addition to completely planar upper sides, such "convex or concave upper sides" are also referred to as "planar upper side", provided that these upper sides have no height differences of more than 2 mm, preferably no height differences of more than 1 mm The upper and lower sides are therefore preferably arranged plane-parallel to each other, in particular the planar region of the upper surface surrounding the protrusion extends in a preferred embodiment at least partly, preferably however, completely plane-parallel to the bottom of the tablet. The protrusion located on the upper side is preferably centered on the upper side such that it is completely surrounded by planar areas of the upper side. The minimum width of the planar surface surrounding the protrusion, hereinafter also referred to as "web", is preferably at least 1.5 mm, preferably at least 2 mm. 5 mm, preferably at least 2 mm, are preferred according to the invention Detergent and cleaning agent tablets having a web width above 3 mm, in particular between 3 and 8 mm or 3 and 6 mm are particularly preferred.

The ridge width can also be defined as a relative variable, regardless of the absolute dimensions of the molded body, wherein according to the invention, in particular those detergent or cleaning agent molded bodies are preferred, whose protrusion from a ridge with a relative ridge width <0.5, preferably <0.4 and in particular < 0.3 is surrounded. The relative web width is a size that is independent of the geometry of the molded body and the geometry of the protrusion and results as a quotient of the web width and the width of the molding. In the case of a rectangular shaped body with a symmetrically arranged rectangular bulge, the web width is constant over the entire web, with a round or ellipsoid bulge the web width varies since the curvature of the protrusion results in an increased distance to the molded body edge. In these cases, the absolute web width is the smallest distance of the trough edge to the edge of the molding. In moldings whose protrusions have a different shape than the molding itself, the web width can have a different value in a longitudinal section through the molded body than in a cross section. This is easily possible in the context of the present invention, as long as the criterion <0.5 is satisfied for each relative web width to be determined. For technical reasons, a limited number of ridge widths are always preferred because symmetrically arranged protrusions exert a significantly higher aesthetic appeal than asymmetrically arranged. Technically advantageous embodiments are, for example, round tablets with a concentrically arranged round protrusion (a single web width), square shaped bodies with a round protrusion whose center is also in the center of the square (a web width), rectangular shaped bodies with a round or elliptical protrusion, which is arranged symmetrically (depending on the embodiment, one or two web widths) and rectangular moldings with a symmetrically arranged rectangular protrusion (depending on the embodiment, one or two web widths).

The upper side of the base tablet may have in its edge region a chamfer, that is to say a bevelled surface, which has been obtained by chamfering or chamfering or chamfering the shaped body edge. This chamfer may for example have an angle of 45 °. If the chamfer is not continuous, it is called a stepped chamfer. If the top has a chamfer, then this chamfer is part of the above-mentioned bar. In such a case, however, the bridge is always wider than the chamfer. Preferred shaped bodies with protrusion have a rectangular shape and have different relative web widths on longitudinal and cross-section. The protrusion here may be circular, elliptical or ellipsoidal or rectangular.

However, it is also possible according to the invention for rectangular shaped bodies to be produced in which the relative web widths on the longitudinal and cross-section are identical. Again, the protrusions may be round, elliptical or ellipsoidal or rectangular.

In the case of the aforementioned rectangular shaped bodies, the identical relative web width on the longitudinal and cross-section means that the absolute web widths differ due to the differences between length and width. The only exception here are the shaped bodies with a square base surface as a special case of a rectangle, in which equal relative widths cause equal absolute widths. In the context of the present invention, the person skilled in the art can choose both the absolute and the relative web widths identical or different, depending on which aesthetic impression he prefers. The selection criterion here is merely that the relative web width at the edge next to the point of the protrusion at each mold body edge is <0.5.

Within the scope of the present invention, it is likewise possible without any problems that the base tablets have a circular shape.

Suitable shapes for the protrusion can be selected by the person skilled in the art depending on the shape of the washing and cleaning agent molding - there are no limits to its formulation freedom, so that octagonal molded bodies with round or square (or other) protrusions are also conceivable. In such moldings then a maximum of eight relative web widths would be considered. Preference is given to quadrangular, circular or elliptical or ellipsoidal protrusions.

Analogous to the definition of a relative web width, a relative height of the protrusion can also be defined, the relative height of the protrusion corresponding to the quotient of the height of the molded body in the area of the protrusion and the height of the molded body in the area of the planar top surrounding the protrusion. Preferred detergent tablets are characterized in that the protrusion has a relative height> 1.05. Detergents and cleaning agent tablets whose protrusion have a relative height above 1, 1, in particular between 1, 1 and 1, 4 or between 1, 1 and 1, 3, are particularly preferred.

The protrusion may be orthorhombic, ie have the shape of a brick, but it may also be in plan view - as already stated - for example, round or elliptical. The shape of the protrusion in the longitudinal or cross section of the molding must not be rectangular. Rather, it is preferred that the protrusion in cross section is in the shape of a triangle However, protrusions, which also in the longitudinal and / or cross-section in the form of a truncated ellipse or a semicircle, are particularly preferred. In other words, in particular those washing and cleaning agent shaped bodies are preferred in which the contour line of the protrusion steadily increases from the edge to the center and has an upwardly curved curvature.

Washing or cleaning agent tablet, characterized in that the protrusion in cross section has the shape of a hemi-ellipsoid or a hemisphere, or the shape of an ellipsoid segment or a segment of a sphere, are preferred according to the invention. Preference is furthermore given to washing or cleaning agent tablets in which the protrusion has cylindrical side walls in cross-section and a convex upper side. In a special embodiment, the protrusion has the shape of a cone or a conical segment.

If the protrusion has an upper side and one or more lateral or lateral surfaces connecting the upper side with the upper side of the molded article, then this lateral surface (s) is preferably not orthogonal on the upper side of the molded article but instead is in the direction of the center of the Prevailing inclined, since such a design, the Ent formability of the molded articles from the press can be significantly improved.

The protrusion preferably covers between 20 and 80%, preferably between 30 and 70% and particularly preferably between 30 and 60% of the upper side of the shaped body.

The washing and cleaning agent tablets according to the invention can be configured as single or multi-phase. Detergent or detergent tablets which have two, three or more phases, preferably two, three or four layers, are preferred according to the invention.

The individual phases of two- or multi-phase tablets are preferably arranged in layers. The proportion by weight of the smallest phase, based on the total tablet, is preferably at least 5% by weight, preferably at least 10% by weight and in particular at least 20% by weight. The proportion by weight of the phase with the highest proportion by weight of the tablet in the case of biphasic tablets is preferably not more than 90% by weight, preferably not more than 80% by weight and in particular between 55 and 70% by weight. In the case of three-phase tablets, the proportion by weight of the phase with the highest proportion by weight of the tablet is preferably not more than 80% by weight, preferably not more than 70% by weight and in particular between 40 and 60% by weight.

The preferred biphasic or multiphase structure of this tablet is preferably for the separation of incompatible ingredients of this dosing unit. As described further below in the description of the H according to the invention first method 11, which is to tablets to be compressed, usually powdery or fine-grained material, if not particularly complex and production hindering precautions are taken for a specific distribution, when filling in the press die about evenly distributed. As a result, the material must be compressed the most 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. Characteristic of preferred detergent tablets according to the invention is consequently a heterogeneous density distribution within the base tablet, wherein the density of the tablet is in the region of the protrusion in the least, while in the area surrounding the protrusion, especially in the edge region of the tablet is significantly higher.

The subject matter of the present application is therefore also a washing or cleaning agent tablet of compressed particulate material, comprising a top side and a bottom side and at least one side surface connecting the top and bottom sides, characterized in that the tablet matrix has a heterogeneous density distribution in which the density within a phase in at least one to the bottom of the tablet plane-parallel cutting plane from the side edge of the tablet to the center of the tablet decreases.

In a preferred embodiment, the densities of the tablet matrix differ within a phase by at least 0.05 g / cm ³ , preferably by at least 0.1 g / cm ³ and in particular by at least 0.2 g / cm ³ or 0.3 g / cm ³ , wherein the density is higher in the edge area of the tablet than in its center. The average density of the entire tablet phase or of the entire tablet is preferably in the range from 1.0 to 2.8 g / cm ³ , preferably in the range from 1.2 to 2.5 g / cm ³ and in particular in the range of 1, 3 to 2.0 g / cm ³ .

The above-described heterogeneous density distribution within the tablet phases has the advantage that the tablet rank has a sufficient hardness for transport with simultaneously good disintegration properties.

The tablet is manufactured in a predetermined spatial form and predetermined size, as a form of space practically all useful manageable configurations come into consideration. However, in particular cube, cuboid and corresponding space elements with a rectangular base and four planar, orthogonal standing on the base or bottom, flat side surfaces and in particular cylindrical configurations with circular or oval base or bottom are preferred. The protrusion of these single- or multi-phase tablets with heterogeneous density distribution can occupy the entire upper phase, ie extend to the side edge of the tablet, but are preferably surrounded by a planar edge region which is preferably at least partially, but more preferably completely plane-parallel to the underside of the tablet runs.

If the protrusion extends as far as the side edge of the tablet, the upper phase rises from the side edge in the direction of the center of the upper side, preferably curved in the direction of the center of the upper side. The "midpoint" describes the center of the upper side when viewed from this side, and in its simplest embodiment, the upper phase is convex.This curved slope distinguishes tablets according to the invention with the protrusion of tablets with a flat, rather than linear, bevel.

The curvature radius of the arched upper phase is preferably between 0.1 d and 2 d, preferably between 0.2 d and 1, 6 d, preferably between 0.4 d and 1, 2 d, with "d" as the maximum diameter of the underside of arched phase.

In a preferred variant, this convex curvature is flattened in the center of the upper side, wherein the flattened region preferably runs plane-parallel to the undersides of the tablet. The ratio of the maximum diameter of the flattened area to the maximum diameter of the underside of the curved phase is preferably between 0.1 and 0.9, preferably between 0.2 and 0.8 and in particular between 0.4 and 0.7.

Preference is given in particular to those tablets in which the flattened region of the upper side makes up between 10% and 80%, preferably between 12% and 60%, particularly preferably between 15% and 50% of the total surface of the upper side.

Particularly preferred are biphasic, in particular two-layered tablets with the previously described heterogeneous density distribution and a circular underside with a diameter between 30 and 60, preferably between 35 and 55 mm; an orthogonal on the bottom standing flat side surface with a height between 4 and 12, preferably 6 and 10 mm; a curved upper surface adjoining the flat side surface with a radius of curvature between 0.2 d and 1.6 d, preferably between 0.4 d and 1.2 d, with "d" as the diameter of the circular underside, a total height between 15 and 30, preferably between 18 and 25 mm, wherein the curved top is flattened in its center such that a flat surface is formed, which is plane-parallel to the bottom of the tablet and has a surface area, which is between 10 and 80, preferably between 15 and 60, particularly preferably between 20 and 40% of the surface area of the circular underside.

The agents according to the invention described above contain washing or cleaning substances, preferably from the group of builders, surfactants, polymers, bleaches, bleach activators, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.

builders

The builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.

With preferred crystalline layered silicates of general formula NaMSi _x O _{2x + I} ^■ y H ₂ O are used, wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, wherein particularly preferred Values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layered silicates of the formula NaMSi _x O _{2x + 1} ^■ y H ₂ O are sold for example by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ ^.xH ₂ O, kenyaite), Na-SKS-2 (Na ₂ Sh ₄ O ₂₉ ^.xH ₂ O, magadiite), Na-SKS -3 (Na ₂ Si ₈ Oi ₇ ^.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 crystalline layer silicates with the formula NaMSi _x O _{2x + 1} ^■ y H ₂ O, in which x stands for 2 h. In particular, both .beta.- and δ-sodium Na ₂ Si ₂ O ₅ ^■ y H ₂ O, and further in particular Na-SKS-5 ((X-Na ₂ Si ₂ O _5), Na-SKS-7 (.beta. Na ₂ Si ₂ 0 _5, natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ ^■ H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ - 3 H ₂ O, kanemite), Na-SKS-1 1 (t-Na ₂ Si ₂ 0 ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (5-Na ₂ Si ₂ O ₅ ) is preferred.

Washing or cleaning composition preferably contain a weight proportion of crystalline layered silicate of the formula NaMSi _x O _{2x + 1} ^■ y H ₂ O from 0.1 to 20 wt .-%, preferably from 0.2 to 15 wt .-% and in particular of 0.4 to 10 wt .-%, each based on the total weight of these agents.

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 preferably delayed release and have secondary washing properties. The dissolution delay compared to conventional amorphous sodium silicates can be achieved in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying be caused. In the context of this invention, the term "amorphous" is understood to mean 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 , cause.

Alternatively or in combination with the abovementioned amorphous sodium silicates, X-ray amorphous silicates are used whose silicate particles produce fuzzy or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such X-ray amorphous silicates also have a dissolution delay compared to conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

In the context of the present invention, it is preferred that these silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali metal disilicates, be present in detergents or cleaners in amounts of from 3 to 60% by weight, preferably from 8 to 50 Wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the washing or cleaning agent, are included.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of greatest importance in the washing and cleaning agent industry.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to high molecular weight 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.

Technically particularly important phosphates are the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate). The sodium potassium tripolyphosphates are preferably used according to the invention. If phosphates are used as detergents or cleaning agents in the context of the present application, preferred agents comprise these phosphate (s), preferably alkali metal phosphate (s), more preferably pentasodium or pentapotassium triphosphate (sodium or pentasodium) Potassium tripolyphosphate), in amounts of 5 to 80 wt .-%, preferably from 15 to 75 wt .-% and in particular from 20 to 70 wt .-%, each based on the weight of the detergent or cleaning agent.

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 alkali 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. Because of their low chemical compatibility with the other ingredients of detergents or cleaners compared with other builders, the alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 wt .-% and in particular below 2 wt .-%, each based on the total weight of the detergent or cleaning agent used. Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.

Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 2 to 50 wt .-%, preferably from 5 to 40 wt .-% and in particular from 7.5 to 30 wt .-%, each based on the weight of the washing or cleaning agent. Particular preference is given to compositions which, based on the weight of the washing or cleaning agent, contain less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and in particular less than 9% by weight of carbonate ( e) and / or bicarbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.

Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. 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, as well as mixtures of these. In addition to their builder effect, the free acids also typically 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 of 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.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of detergents or cleaning agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight and in particular from 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 salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,

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

Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference.

Particularly preferred as sulfonic acid-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 are as unsaturated monomer carboxylic acids of the formula

R ¹ (R ² ) C = C (R ³ ) COOH

in which 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, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -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 above formula 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 are those of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

in which 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 chain branched mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH, or by -COOH or -COOR ⁴ , where 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 ), - - with n = O 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

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

HO ₃ SX (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H

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 - (CHz) _n - with n = O to 4, -C00- (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, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate , 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids.

Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds. The content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers to be used consist only of monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH and monomers of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H.

In summary, copolymers of i) unsaturated carboxylic acids of the formula R ¹ (R ² ) C =C (R ³ ) COOH 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, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, ii) sulfonic acid group-containing monomers of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H 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 selected is selected from - (CH ₂ ), - with n = O 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 ) - iii) optionally further ionogenic or nonio nogenen monomers particularly preferred.

Further particularly preferred copolymers consist of i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid ii) one or more sulfonic acid group-containing monomers of the formulas:

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

HO ₃ SX (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H

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 J _n - with n = O to 4, -C00- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) - iii) optionally further ionogenic or non-ionogenic 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, copolymers which are structural units of the formula are preferred

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CHs) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred. The corresponding copolymers contain the structural units of the formula

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

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 substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein O- (CH ₂ ) _n - where n = 0 to 4, -O- (C ₆ H ₄ ) -, -NH- C (CHs) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , 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, copolymers which are structural units of the formula

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

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -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 particularly preferred, just as preferred as copolymers, the structural units of the formula

- [CH ₂ -C (CH ₃ ) COOHL- [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _P -

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CHs) 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 gives way to inventively preferred copolymers, the structural units of the formula

- [HOOCCH-CHCOOH- [CH ₂ -CHC (O) -Y-SO ₃ H] _P -

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. Also preferred according to the invention are copolymers which contain structural units of the formula

- [HOOCCH-CHCOOH- [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _P -

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CHs) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In summary, such copolymers are preferred according to the invention, the structural units of the formulas

- [CH ₂ -CHCOOH- [CH ₂ -CHC (O) -Y-SO ₃ H] _P -

- [CH ₂ -C (CH ₃ ) COOHL- [CH ₂ -CHC (O) -Y-SO ₃ H] _P -

- [CH ₂ -CHCOOH- [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _P -

- [CH ₂ -C (CH ₃ ) COOHL- [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _P - - [HOOCCH-CHCOOH- [CH ₂ -CHC (O) -Y -SO ₃ H] _P - - [HOOCCH-CHCOOH- [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _P -

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y for -O- (CH ₂ ) _n - with n = O to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CHs) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In the polymers, the sulfonic acid groups can be completely or partially in neutralized form, ie the acidic acid of the sulfonic acid group can be present in some or all of the sulfonic acid groups. acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular against sodium ions. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.

The monomer distribution of the copolymers preferably used 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 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 molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred washing or cleaning agents are characterized in that the copolymers have molar masses 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} .

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts.

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

Further suitable organic builder substances are dextrins, 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 ethylenediaminedisuccinate, are also suitable co-builders. Ethylenediamine-N, ^{N'-disuccinate} (EDDS) is preferably used in form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are from 3 to 15 wt .-%.

The machine dishwashing detergents according to the invention particularly preferably comprise methylglycinediacetic acid or a salt of methylglycinediacetic acid, the weight fraction of methylglycinediacetic acid or of the salt of methylglycinediacetic acid preferably being between 0.5 and 15% by weight, preferably between 0.5 and 10% by weight. and in particular between 0.5 and 6 wt .-% is.

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.

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

surfactants

The group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is 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 an arbitrary 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 1 to 4 carbon atoms in the alkyl chain.

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.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula

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

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

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 oxy-alkyl radical having 1 to 8 carbon atoms, wherein C-ι_ ₄ alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of 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 prepared by reaction with fatty acid methyl esters in Presence of an alkoxide can be converted as a catalyst into the desired polyhydroxy fatty acid amides.

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, washing or cleaning agents, in particular automatic dishwashing detergents, contain 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 an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue 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 moles of EO per mole of alcohol are preferred. Preferred ethoxylated alcohols include, for example, _C12 - ₁₄ - alcohols with 3 EO or 4 EO, C ₉ n-alcohol with 7 EO, C-ms alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C ₂ - ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci ₂ - ₁₄ -alcohol with 3 EO and C- | ₂ - ₁₈ -alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

With particular preference, ethoxylated nonionic surfactants which are from C ₆ - ₂ o-monohydroxyalkanols or C ₆ . _20- alkylphenols or C ₁₆ . ₂₀ fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol were obtained used. A particularly preferred nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C-ι ₆ - ₂ o alcohol), preferably obtained a d ₈ 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 ranks ethoxylates" are particularly preferred.

With particular preference further combinations of one or more Taigfettalkoholen be used with 20 to 30 EO and silicone defoamers.

Particular preference is given to nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) (e) having a melting point above 20 ⁰ C, preferably above 25 ° C, more preferably between 25 and 6O ⁰ C and particular between 26.6 and 43.3 ° C, is / are particularly preferred , 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 nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Also, nonionic surfactants having waxy consistency at room temperature are preferred depending on their purpose.

Nonionic surfactants from the group of alkoxylated alcohols, more preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-Niotenside, are also used with particular preference.

The nonionic surfactant solid at room temperature preferably 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 content of such nonionic surfactant molecules preferably makes up 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 agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.

Preferably used surfactants come from the groups of 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 characterized by good foam control.

Further 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 Wt .-% of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane contains.

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. point. 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. Here are nonionic surfactants of the general formula

Ri-O- (CH ₂ -CH ₂ -O) - (CH ₂ -CHO) - (CH ₂ -CH ₂ -O) - (CH ₂ -CHO) -H

R2 R3

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 stand for integers from 1 to 6.

The preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula 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 unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C 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 usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions, preference is given to nonionic surfactants in which R ¹ in the above formula 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. Preference is given to using nonionic surfactants of the above formula in which R ² or R ^{3 is} a radical -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another are values of 1 or 2.

In summary, particular preference is given to nonionic surfactants which have a C ₉ . ₁₅ alkyl 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. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference. Surfactants of the general formula R ¹ -CH (OH) CH ₂ θ- (AO) _w - (AO) _x - (A "O) _y - (A '" O) _z -R ² in which R ¹ and R ² independently represent a linear or branched, saturated or mono- or polyunsaturated C _2-4 o alkyl or alkenyl radical; A, A ', A "and A" are independently of one another a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ - CH ₂ - CH ₂ , -CH ₂ -CH (CHs) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

Particularly preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1, 5 and y is a value of at least 15.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are most preferred.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ P] _x [CH ₂ J _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, 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 R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^2. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, ali- phatic 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 selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is R ¹ O [CH ₂ CH (R ³ ) O] _X CH ₂ CH (OH) CH ₂ OR ² simplified. In the latter 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.

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 first H 11 methods, commercial products of the formulas mentioned mostly do not consist of an individual representative but of mixtures, which means that average values and, consequently, fractional numbers can result for both the C chain lengths and for the degrees of ethoxylation or degrees of alkoxylation.

Of course, the aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants. Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,

If anionic surfactants are used as a constituent of automatic dishwasher detergents, their content, based on the total weight of the compositions, is preferably less than 4% by weight, preferably less than 2% by weight and most preferably less than 1% by weight. Machine dishwashing detergents which do not contain anionic surfactants are particularly preferred.

Instead of the surfactants mentioned or in conjunction with them, it is also possible to use cationic and / or amphoteric surfactants.

As cationic active substances, for example, cationic compounds of the following formulas can be used:

Ri

Ri-N- (CH _{2) n} -T-R 2 (CH _{2) n} -T-R2

wherein each group R ^{1 is} independently selected from C-. ₆ alkyl, alkenyl or hydroxyalkyl groups; each R ² group is independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

In automatic dishwashing detergents, the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. %. Automatic dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred.

polymers

The group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. Generally in Detergents or cleaning agents in addition to nonionic polymers and cationic, anionic and amphoteric polymers used.

"Cationic polymers" for the purposes of the present invention are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride Copolymers, the quaternized polyvinyl alcohols or the polymers listed under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

For the purposes of the present invention, "amphoteric polymers" further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.

Preferred washing or cleaning agents, in particular preferred automatic dishwashing agents, are characterized in that they contain a polymer a) which has monomer units of the formula R ¹ R ² C =CR ³ R ⁴ in which each R ¹ , R ² , R ⁴ radical ³ , R ^{4 is} independently selected from hydrogen, derivatized hydroxy group, C- | ₃ o linear or branched alkyl groups, aryl, aryl substituted Ci _-30 linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group with one positive charge in the partial range of the pH range of 2 to 11, or salts thereof, with the proviso that at least one radical R ¹ , R ² , R ³ , R ^{4 is} a heteroatomic organic group having at least one positive charge without charged nitrogen, at least is a quaternized N atom or at least one amino group having a positive charge. In the context of the present application, particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula

in which R ¹ and R ⁴ are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ^{3 are} independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X represents a counterion, preferably a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula are selected from -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 , and - (CH ₂ CH ₂ -O) _n H.

Very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ¹ and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer unit of the formula

H ₂ C = C H- (CH ₂ ) -N (CH ₃ ) ₂ - (CH ₂ ) -CH = CH ₂ X ^"

in the case of X = chloride, they are also referred to as DADMAC (diallyldimethylammonium chloride).

Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula

R1 HC = CR2-C (O) -NH- (CH ₂₎ -N ⁺ R3R4R5

X ^" in the R ¹ , R ² , R ³ , R ⁴ and R ^{5 are} independently of one another a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from 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 , and - (CH ₂ CH ₂ -O) _{n is} H and x is an integer between 1 and 6.

In the context of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ^{1 is} H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula

H ₂ C = C (C Hs) -C (O) -NH- (CH ₂ ) _X -N (CH ₃ ) ₃

X ^"

in the case of X = chloride also referred to as MAPTAC (Methyacrylamidopropyl trimethylammonium chloride).

According to the invention, preference is given to using polymers which contain diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.

The aforementioned amphoteric polymers have not only cationic groups but also anionic groups or monomer units. Such anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and their derivatives, the allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.

Preferred amphoteric polymers which can be used are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers which cationically derivatized alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Preferred zwitterionic polymers are from the group of acrylamidoalkyltri alkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers. Also preferred are amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride.

Particularly preferred amphoteric polymers are selected from the group consisting of the methacrylamidoalkyltri-alkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethy1-diallyl ammonium chloride / alkyl - (meth) acrylic acid copolymers and their alkali metal and ammonium salts.

Particular preference is given to amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyldiallylammonium chloride / - Alkyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts.

In a particularly preferred embodiment of the present invention, the polymers are present in prefabricated form. For the preparation of the polymers, inter alia, the encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers; the encapsulation of the polymers by means of water-insoluble, meltable coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ⁰ C; the co-granulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing- or cleaning-active substances, more preferably from the group of builders or cobuilders.

Detergents or cleaning agents contain the aforementioned cationic and / or amphoteric polymers preferably in amounts of between 0.01 and 10 wt .-%, each based on the total weight of the detergent or cleaning agent. In the context of the present application, however, preference is given to those detergents or cleaners in which the weight fraction of the cationic and / or amphoteric polymers is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4 wt .-%, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing agent is.

bleach

The bleaching agents are a particularly preferred washing or cleaning substance. Among the compounds which serve as bleaches and deliver H ₂ O ₂ in water are sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate special meaning. Further bleaches that can be used are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which yield H ₂ O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Furthermore, bleaching agents from the group of organic bleaching agents can also be used. 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 [Phthaliminoperoxyhexanoic acid (PAP )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, 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).

As a bleaching agent and chlorine or bromine releasing substances can be used. Examples of suitable chlorine or bromine-releasing materials are 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. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

According to the invention, washing or cleaning agents, in particular automatic dishwashing agents, are preferred which contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15% by weight % Bleach, preferably sodium percarbonate.

The active oxygen content of the washing or cleaning agents, in particular the automatic dishwashing agents, in each case based on the total weight of the composition, preferably between 0.4 and 10 wt .-%, particularly preferably between 0.5 and 8 wt .-% and in particular between 0.6 and 5 wt .-%. Particularly preferred compositions have an active oxygen content above 0.3 wt .-%, preferably above 0.7 wt .-%, more preferably above 0.8 wt .-% and in particular above 1, 0 wt .-% to. Bleach activators

Bleach activators are used in detergents or cleaners, for example, to achieve an improved bleaching effect when cleaning at temperatures of 60 ⁰ 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, n-methyl-morpholinium-acetonitrile-methylsulfate (MMA) and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl-fructose, tetraacetylxylose and octaacetyllactose as well as acetylated , optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprol actam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used.

These bleach activators are preferably used in amounts of up to 10% by weight, in particular

0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-%, each based on the total weight of the bleach activator-containing agents used.

Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula

R i I ₊ R ₂ -N- (CH ₂ ) -CN X ^"

R3

in which R ¹ is -H, -CH _3, a C ₂ - ₂₄ alkyl or alkenyl group, 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 Ci_ ₂₄ alkyl group, or represents a substituted alkyl or alkenylaryl radical having a Ci_ 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 with n = 1, 2, 3, 4, 5 or 6 and X is an anion.

Particularly preferred 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 , wherein R ⁴ additionally also -H may be and X is an anion, 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 from the group of these substances turn the cationic Nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" in which X ^{" represents} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is particularly preferred.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be used. 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.

Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammin ) Complexes, 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 weight of the bleach activator-containing agents used. In special cases, however, more bleach activator can also be used.

It is particularly preferred to use complexes of manganese in the oxidation state II, IM, IV or IV, which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which Have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-Triazacyclononan (TACN), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN ) and / or 2-methyl-1, 4,7-triazacyclononane (Me / TACN). Suitable manganese complexes are, for example, [Mn ¹ " ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (CIO ₄ ) 2, [Mn '"Mn' ^v (pO) ₂ (p-OAc) ₁ ( TACN) ₂ ] (BPh ₄ ) ₂ , [Mn ^IV 4 (μ-O) ₆ (TACN) ₄ ] (Clθ4) 4, [Mn ^ μ-OMμ-OAcMMe-TACNJzKCIO ^, [Mn ¹¹¹ Mn ¹ ^ pO) ₁ (P-OAc) ₂ (Me-TACN) _2] (ClO _{4) 3,} [Mn ^'v ₂ (pO) ₃ (Me-TACN) _2] (PF _{6) 2} and [Mn' ^v ₂ (pO) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (OAc = OC (O) CH ₃ ).

enzymes

To increase the washing or cleaning performance of detergents or cleaners enzymes can be used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases 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 or cleaning agents, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 × 10 ^-6 to 5 wt .-% 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 of these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from β. amyloliquefaciens, from β. stearothermophilus, from Aspergillus niger and A. oryzae, as well as improved for use in detergents and cleaners further developments of the aforementioned amylases. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from β. agaradherens (DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting 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. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.

Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. 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 can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing 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 several enzyme activities. A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

Preferred are one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, in amounts of 0.1 to 5 wt .-%, preferably from 0.2 to 4.5 wt .-% and in particular from 0.4 to 4 wt .-%, each based on the total enzyme-containing agent used.

Glass corrosion inhibitors

Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes.

The spectrum of the invention preferred zinc salts, preferably organic acids, particularly 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 below 0.01 have mg / l, to those salts which have 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 ⁰ C. water temperature). The first group of zinc salts includes, for example, the zinc nitrate, the zinc oleate and the zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

With particular preference is used as the glass corrosion inhibitor at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and Zinkeitrat used. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

In the context of the present invention, the content of zinc salt in detergents or cleaners is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight. , or the content of zinc in oxidized form (calculated as Zn ²⁺ ) between 0.01 to 1 wt .-%, preferably between 0.02 to 0.5 wt .-% and in particular between 0.04 to 0.2 wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.

corrosion inhibitors

Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, it is possible above all to use silver protectants selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. According to the invention, preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts, these substances being particularly preferably present in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2 Wt .-%, particularly preferably 0.01 to 0.04 wt .-% are 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 and 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, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds used. 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 (ammin) 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, redox-active substances can be used. 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, IM, IV, V or VI are present. 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, for example oxide, sulfate, nitrate, fluoride, but also organic anions such as stearate.

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- di-phosphonate], 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 , as well as their Mixtures such that the metal salts and / or metal complexes 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, with particular preference be used.

The inorganic redox-active substances, in particular metal salts or metal complexes are preferably coated, i. completely coated with a water-proof material which is easily 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.

The metal salts and / or metal complexes mentioned are contained in cleaning agents, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, each based on the total agent.

disintegration aid

In order to facilitate the disintegration of preformed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these compositions in order to shorten the disintegration times. By tablet disintegrants or disintegrants are meant excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients.

These substances, which are also referred to as "explosives" due to their effect, increase their volume upon ingress of water, on the one hand increasing the intrinsic volume (swelling), and on the other hand creating a pressure via the release of gases which can break the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyisocyanates. vinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preference is given to using disintegration aids in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration aid-containing agent.

Preferred disintegrating agents are cellulosic disintegrating agents, so that preferred washing or cleaning agents comprise such cellulose-based disintegrants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. % contain. Pure cellulose has the formal gross composition (C ₆ H ₁₀ Os) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and accordingly have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.

The cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns.

As a further disintegrating agent based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact. A subsequent disaggregation of micro-crystalline celluloses produced by the hydrolysis provide the microcrystalline celluloses which have primary particle sizes of about 5 microns and, for example, compactable into granules with an average particle size of 200 microns.

Preferred disintegration aids, preferably a cellulose-based disintegration assistant, preferably in granular, cogranulated or compacted form, are present in the desintegration agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight in particular from 4 to 6% by weight, in each case based on the total weight of the disinfectant-containing agent.

Furthermore, according to the invention, gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries. The gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water. Among these compounds, mention should be made in particular of magnesium peroxide, which liberates oxygen on contact with water. Usually, however, the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas. While a variety of systems are conceivable and executable here, which release, for example, nitrogen, oxygen or hydrogen, the bubble system used in detergents and cleaners can be selected both on the basis of economic and environmental considerations. Preferred effervescent systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.

As Acidifizierungsmittel which release carbon dioxide from the alkali metal salts in aqueous solution, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred.

fragrances

As perfume oils or fragrances, individual fragrance compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons, can be used in the context of the present invention. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as those available from vegetable sources, such as pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note", "middle note" or "body note" ) and "base note" (end note or dry out). Since odor perception is also largely based on the odor intensity, the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note consists for the most part of less volatile, ie adherent fragrances. For example, in the composition of perfumes, more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly. In the subsequent classification of the fragrances in "more volatile" or "adherent" fragrances so nothing about the olfactory impression and whether the corresponding fragrance is perceived as a head or middle note, nothing said.

The fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.

dyes

Preferred dyes, the selection of which presents no difficulty for 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 the substrates to be treated with the dye-containing agents, such as textiles, glass, ceramics or plastic crockery do not stain them.

When choosing the colorant, it must be taken into account that the colorants have a high storage stability and insensitivity to light. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, colorant concentrations in the range of a few 10 ^-2 to 10 ³ % by weight are typically selected. In the due to their brilliance particularly preferred, but less readily water-soluble pigment dyes the appropriate concentration of the colorant in detergents, however, typically at some 10 ³ to 10 ^{~ 4} wt .-%.

Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable are, for example, anionic colorants, e.g. anionic nitrosofarads.

For the manufacturability, in particular the releasability of detergent tablets according to the invention, it has proved to be advantageous that the tablet contains a polymer compound or an enzyme granulate. Detergent or detergent tablets which contain a polymer compound or an enzyme granulate in the base plate are therefore preferred according to the invention for this reason.

The preparation of washing or cleaning agent tablets preferably takes place in a manner known to those skilled in the art by compressing particulate starting substances. To prepare the tablets, the premix is compressed in a so-called matrix between two punches to form a solid compressed product. This process, hereinafter referred to as tableting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection. The tabletting is preferably carried out on so-called round rotor presses.

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

Use of plastic inserts with small thickness tolerances

Low number of revolutions of the rotor

Big filling shoes

Tuning of the filling paddle speed to the speed of the rotor

Filling shoe with constant powder height

Decoupling of filling shoe and powder template

To reduce Stempelanbackungen offer all known from the art anti-adhesive coatings. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotary punches have also proved to be advantageous, wherein, if possible, upper and lower punches should be rotatable. With rotating stamps can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished.

In the context of the present invention, preferred methods are characterized in that the pressing takes place at pressing pressures of 0.01 to 50 kNcnrf ² , preferably of 0.1 to 40 kNcnrf ² and in particular of 1 to 25 kNcnrf ² .

A further subject of the present application is therefore a process for the preparation of a detergent tablet, comprising the steps of: a) introducing a first particulate composition into the matrix of a tablet press; b) pressing the first particulate composition by means of a press ram having on its pressing surface at least one trough.

Concentric presses can be provided to increase the throughput with two filling shoes, which only a semicircle must be run through to produce a tablet.

As mentioned above, the tablets in the context of the present invention can also be multi-phase, in particular multi-layered. 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.

To produce two-layered and multi-layered shaped bodies, several filling shoes are arranged one after the other without the slightly pressed-on first layer being 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 holes 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.

Corresponding process variants, characterized in that the following further steps are carried out following step b) of the process according to the invention: c) introducing a second particulate composition into the matrix of a tablet press; d) Pressing the second particulate composition by means of a press ram having at least one depression on its pressing surface is preferred according to the invention.

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

2P σ = πDt

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.

Another object of the present 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 on its pressing surface at least one trough, the horizontal extent is greater at the level of the pressing surface than the depth and is suitable for pressing Vorwölbungen.

The tablets to be pressed, usually powdery or fine-grained material is, if not particularly complex and the production hindering precautions for a special distribution are taken when evenly distributed during filling in the press die. As a result, the material must be compressed the most 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.

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. The coating of the base of the embossing element should therefore at the same time be 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 proven 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 proven to be useful. Preferred methods according to the invention are characterized in that the pressing surface of the press ram is coated to reduce adhesion.

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 buildup was observed. It is therefore preferred that the at least adhesion-reducing coating consists essentially of carbon.

In a further preferred embodiment, the pressing surface of the press ram is at least partially made of plastic, preferably a polyamide.

For the design of the embossing element of the upper punch arise in terms of

Execution of base and trough three alternatives:

Base and trough are made of the same material;

Base and trough are made of different materials, wherein the material used for the production of the base material has a higher hardness and lower Walkbar- speed than the material used for the production of the trough, this variant being particularly advantageous in terms of durability and the embossing elements has proved;

Base and trough are made of different materials, wherein the material used for the production of the base material has a lower hardness and higher Walkbar- speed than the material used for the production of the trough, this variant, especially in relation to the dissolution behavior of the resulting detergent tablets has proved advantageous

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 In the case of minerals the so-called scratch hardness (hardness according 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:

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 you 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.

For the production of pressing surfaces with particular high hardness metals are particularly suitable, which is why processes in which the pressing surface of the press ram is at least partially made of metal, according to the invention are preferred.

As a walkable material for the formation of the base has been described above. Experiments have shown that very good results could be achieved, for example, with the polyurethane material Vulkollan or the PVC material Mipolam. Over use times of several thousand pressures, no adhesion to the base material was found. To produce the preferred tablet forms described at the beginning, the embossing elements of the upper punches in preferred process variants have a geometry corresponding to these embodiments. Thus, preferred methods according to the invention are characterized in that the trough in the pressing surface of the ram is surrounded on all sides by a web with a minimum width of 1, 5 mm, preferably at least 2 mm, wherein the web surrounding the trough in the pressing surface of the press ram on all sides preferably a relative web width <0.5.

The trough in the pressing surface of the ram preferably surrounded by a flat base and in preferred embodiments has in cross-section the shape of a halo ellipsoid or a hemisphere, or the shape of an ellipsoidal segment or a spherical segment or cylindrical side walls and a concave bottom surface formed in a particularly preferred embodiment in cross-section at least partially conical.

Claims

claims

A process for the preparation of a detergent tablet comprising the steps of: a) introducing a first particulate composition into the matrix of a tablet press; b) pressing the first particulate composition by means of a press ram having on its pressing surface at least one trough.

2. The method according to claim 1, characterized in that following step b), the following further steps are carried out: c) introducing a second particulate composition in the mold of a tablet press; d) pressing the second particulate composition by means of a press ram having on its pressing surface at least one trough.

3. The method according to any one of the preceding claims, characterized in that the pressing surface of the press ram is at least partially made of plastic, preferably a polyamide.

4. The method according to any one of the preceding claims, characterized in that the pressing surface of the press ram is at least partially made of metal.

5. The method according to any one of the preceding claims, characterized in that the pressing surface of the press ram is coated adhesion-reducing.

6. The method according to any one of the preceding claims, characterized in that the trough in the pressing surface of the press ram in cross section has the shape of a half ellipsoid or a hemisphere, or the shape of an ellipsoidal segment or a spherical segment.

7.Verfahren according to any one of the preceding claims, characterized in that the trough in the pressing surface of the press ram in cross-section cylindrical side walls and a concave bottom surface.

8. The method according to any one of the preceding claims, characterized in that the trough is at least partially conical in the pressing surface.

9. The method according to any one of the preceding claims, characterized in that the trough is surrounded in the pressing surface of the press ram of a flat base.

10. The method according to any one of the preceding claims, characterized in that the trough in the pressing surface of the press ram is surrounded on all sides by a web with a minimum width of 1, 5 mm, preferably of 2 mm.

11. The method according to any one of the preceding claims, characterized in that the trough in the pressing surface of the press ram is surrounded on all sides by a web with a relative web width <0.4.

12. washing or cleaning agent tablet of compressed particulate material, characterized in that the single-phase top has a protrusion.

13. washing or cleaning agent tablet according to one of the preceding claims, characterized in that the washing or cleaning agent tablet has two, three or more phases, preferably two, three or more layers.

14. washing or cleaning agent tablet according to any one of the preceding claims, characterized in that the protrusion in cross section has the shape of a hemi-ellipsoid or a hemisphere, or the shape of an ellipsoidal segment or a segment of a sphere.

15. washing or cleaning agent tablet according to claim 12, characterized in that the protrusion in cross section has cylindrical side walls and a convex upper side.

16. washing or cleaning agent tablet according to one of the preceding claims, characterized in that the protrusion has the shape of a cone or a cone segment.

17. washing or cleaning agent tablet according to one of the preceding claims, characterized in that the protrusion protrudes from a flat top.

18 washing or cleaning agent tablet according to one of the preceding claims, characterized in that the protrusion is surrounded by a web with a minimum width of 1, 5 mm, preferably 2 mm.

19. washing or cleaning agent tablet according to one of the preceding claims, characterized in that the protrusion is surrounded by a web with a relative web width <0.5.

20. washing or cleaning agent tablet, characterized in that the protrusion has a relative height> 1, 05.

21. Washing or cleaning agent tablets according to one of the preceding claims, characterized in that the base tablet contains a polymer compound or an enzyme granules.

22. washing or cleaning agent tablet of compressed particulate material, comprising a top and a bottom and at least one connecting the top and bottom side surface, characterized in that the tablets matrix has a heterogeneous density distribution, wherein the density within a phase in at least one to the underside of the tablet is plane-parallel cutting plane from the side edge of the tablet to the center of the tablet decreases.

23. Washing or cleaning agent tablet according to claim 22, characterized in that the density of the tablet matrix within a phase at the side edge of the tablet by at least 0.05 g / cm ³ , preferably by at least 0.1 g / cm ³ and in particular by at least 0 , 2 g / cm ^{3 is} higher than in the center of the tablet.