WO2004046287A2

WO2004046287A2 - Portioned products comprising different constituents

Info

Publication number: WO2004046287A2
Application number: PCT/EP2003/012444
Authority: WO
Inventors: Wilfried Rähse; Sandra Hoffmann
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2002-11-15
Filing date: 2003-11-07
Publication date: 2004-06-03
Also published as: WO2004046287A3; AU2003296568A1; AU2003296568A8; DE10253214A1

Abstract

The invention relates to portioned products, which have the advantages of shaped bodies and make it possible to achieve the aesthetic appeal of the color and design of polymer packagings thereby inducing a high acceptance among consumers. These portioned products have a hollow element comprised of at least one solidified melt and have at least one other solid body, whereby the at least one other solid body is located, at least in portions, inside the wall of the hollow element after having been poured therein.

Description

"Portioned agents with different ingredients"

The present invention relates to portioned compositions which consist of different constituents and methods for producing such portioned compositions. The agents according to the invention can be used, for example, in the food, animal feed, cosmetics, crop protection agents or construction industry, a particularly preferred area of application for the agents according to the invention being that of detergents or cleaning agents.

Portioned detergents and cleaning agents are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage. The portioning can be achieved, for example, by converting it into a compact form or by separate packaging. In the former case, tableting has an outstanding role; in the latter case, in the area of detergents or cleaning agents, mainly portions are used which are surrounded by packaging made of water-soluble materials.

Tableted detergents and cleaning agents have a number of advantages over powdered ones: They are easier to dose and handle and, thanks to their compact structure, have advantages during storage and transport. Detergent tablets are consequently also extensively described in the patent literature. A problem that occurs again and again when using shaped articles which are active in washing and cleaning is the insufficient rate of disintegration and dissolution of the shaped articles under conditions of use. Since sufficiently stable, i.e. Shaped and unbreakable moldings can only be produced by relatively high pressure, there is a strong compression of the mold components and a consequent delayed disintegration of the mold in the aqueous liquor and thus to a slow release of the active substances in the washing or cleaning process , The delayed disintegration of the moldings has the further disadvantage that many detergent tablets cannot be washed in via the induction chamber of household washing machines, since the tablets do not disintegrate into secondary particles that are small enough to pass from the induction chamber into the washing drum in a sufficiently rapid time to be washed in.

This dichotomy between hardness (ie manageability) and decay only plays a subordinate role in packaged detergent or cleaning agent portions. Rather, phenomena such as the solubility or disintegration of the packaging come to the fore, while the Packaged detergents or cleaning agents only play a role with their physical properties if a tablet has been packed.

The more recent patent literature discloses in particular packaging made of water-soluble polymers, which are produced by injection molding; Thermoforming or blow molding. These portions have the disadvantage that they dissolve poorly or too slowly under conditions of use, since the water-soluble polymers initially swell and leave a layer of swollen polymer on the contents, which hinders the further dissolution of the active substances.

Solubility advantages are to be expected when using liquid detergents or cleaning agents - however, there are disadvantages in handling such as spilling, sticking to the measuring cup or bottle neck or leakage when dosing directly into the drum. Portioned liquid detergents or liquid cleaning agents require a great deal of technical effort during production and, because of the unstable bags and the associated space or leakage problems, they are only marginally accepted by consumers. In addition, a large part of the manufacturing costs can be attributed to the elaborate packaging, so that the consumer pays more for the same amount of product without gaining additional performance - the portioned meterability must be "bought" by him, so to speak.

Alternative approaches lie in the use of moldings, either as a compact casting or as a cast hollow mold, into which further substances are filled. Here, the casting matrices often have advantageous properties in terms of application technology, so that the packaging is not just ballast. German patent application DE 100 33 827 A1 discloses a detergent, cleaning agent or detergent portion contained in one or more dimensionally stable hollow body (s) with at least one compartment

(a) at least one wash-active, cleaning-active or rinse-active preparation;

(b) at least one at least one preparation according to (a) wholly or partly surrounding enclosure made of a non-pressed material which disintegrates under washing, cleaning or rinsing conditions and gives the hollow body (s) dimensional stability; and

(c) optionally one or more means (s) for compartmentalizing the dimensionally stable hollow body (s).

In this context, DE 100 58 647 A1 discloses a manufacturing process for portioned detergents or cleaning agents, in which an open hollow mold is produced by solidification, then filled with detergents or cleaning agents and then optionally closed. The object of the present invention was to further develop the approaches described above. Portioned agents should be provided, which on the one hand have the advantages of castings, but on the other hand enable the aesthetic stimuli of the coloring and shape design of polymer packaging and thus cause a high level of consumer acceptance. In addition, the possibility of separating active substances should be implemented in a more incompatible manner without having to produce complex multi-chamber systems.

It has now been found that solids can be incorporated into the wall of hollow bodies from solidified melts and provide easily soluble, aesthetically highly appealing bodies.

In a first embodiment, the present invention relates to a portioned agent comprising a hollow mold made from at least one solidified melt and at least one further solid body, the at least one further solid body being at least partially cast into the wall of the hollow mold.

In the context of the present invention, the term “hollow shape” denotes a shape enclosing at least one space, wherein the enclosed space can be filled or can be. In addition to the at least one enclosed space, the hollow shape can have further enclosed spaces and / or spaces that are not completely enclosed. In the context of the present invention, the hollow shape does not have to consist of a uniform wall material, but can also be composed of several different materials.

The inclusion of at least one solid in the wall of the hollow mold is possible, for example, by producing a hollow shell from a solidified melt, which at least partially encloses at least one solid. This hollow shell can then be filled and closed, for example by a melt with a different composition. The two solidified melts together form the hollow form of the agents according to the invention.

Analogously, at least one solid can also be incorporated at least partially into the melt, which closes the hollow shell from solidified melt. Again, the hollow shell made of solidified melt and the solidified melt that forms the “lid” together form the hollow form of the agents according to the invention. In this embodiment, the hollow shell can at least partially enclose at least one solid (then the hollow form contains at least two solids), it can but also be completely free of a solid, because the solid, at least partially enclosed by the sealing melt, is at least partially cast into the wall of the hollow mold. The portioned agents according to the invention comprise a hollow form. This can be a hollow shell, for example, which serves to hold further active substance and can be closed if necessary. However, it is also possible (see above) to produce a hollow shell without inclusion of solid bodies and at least partially embed at least one solid body in a solidifying melt which closes the hollow mold. At least one additional solid body is at least partially cast into the wall of this hollow mold. In the context of the present invention, “solid” means that the body or bodies do not melt at the melting temperature of the melt and do not dissolve in the melt either. When processing into the portioned compositions according to the invention, the melt is therefore before cooling After the melt has cooled, the solids still represent discrete areas of the hollow mold wall, but the entire hollow mold is naturally solid.

All solids or solids that do not melt at the processing temperature of the melt and do not dissolve in the melt can be considered as the solid to be poured in. Only one body can be cast in at least partially as a solid, but it is also possible to pour in several solid, for example many individual granulate, extrudate or powder particles. Further details can be found below.

In the following, one often speaks of portions of detergent or cleaning agent in connection with portioned agents; this does not represent any restriction of the subject matter of the present invention, but only serves to illustrate a particularly preferred area of application of portioned agents according to the invention.

The hollow form of the portioned compositions according to the invention comprises at least one solidified melt. This melt can be a melted pure substance or a mixture of several substances. It is of course possible to mix the individual substances of a multi-substance melt before melting or to produce separate melts which are then combined. Melting from mixtures of substances can e.g. be of advantage if eutectic mixtures are formed which melt significantly lower and thus lower the process costs.

Preferred portioned compositions according to the invention are characterized in that the hollow mold consists of at least one material or material mixture whose melting point is in the range from 40 to 1000 ° C, preferably from 42.5 to 500 ° C, particularly preferably from 45 to 200 ° C and in particular from 50 to 160 ° C. The material of the melt preferably has a high water solubility, for example above 100 g / l, with solubilities above 200 g / l in distilled water at 20 ° C. being particularly preferred.

Such substances come from a wide variety of substance groups. In the context of the present invention, such melts, which consist of the groups of carboxylic acids, carboxylic acid anhydrides, dicarboxylic acids, dicarboxylic acid anhydrides, hydrogen carbonates, hydrogen sulfates, have proven to be particularly suitable as material for the hollow mold.

Polyethylene glycols, polypropylene glycols, sodium acetate trihydrate and / or urea. Portioned agents according to the invention are particularly preferred in which the material of the hollow form contains one or more substances from the groups of carboxylic acids, carboxylic anhydrides, dicarboxylic acids, dicarboxylic anhydrides, hydrogen carbonates, hydrogen sulfates,

Polyethylene glycols, polypropylene glycols, sodium acetate trihydrate and / or urea in amounts of at least 40% by weight, preferably at least 60% by weight and in particular at least 80% by weight, in each case based on the weight of the hollow mold.

A class of substances which is outstandingly suitable as a material for the hollow form are aliphatic and aromatic dicarboxylic acids which can be melted individually, in a mixture with one another or in a mixture with other substances and processed according to the invention. Particularly preferred dicarboxylic acids are summarized in the table below:

Instead of the dicarboxylic acids mentioned or in a mixture with them, the corresponding anhydrides can also be used, which is particularly advantageous in the case of glutaric acid, maleic acid and phthalic acid.

In addition to the dicarboxylic acids, carboxylic acids and their salts are also suitable as materials for the production of the open hollow form. From this class of substances, citric acid and trisodium citrate as well as salicylic acid and glycolic acid have proven to be particularly suitable. It is also particularly advantageous to use fatty acids, preferably those with more than 10 carbon atoms, and their salts as material for the open hollow form. Carboxylic acids which can be used in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (oenanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid etc. The use of fatty acids such as Dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotinic acid) and meltsiacetic acid (9) Hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9tecadienoic acid, 9tecadienoic acid, 9tecadienoic acid, 9tecadienoic acid, linadic acid, 9tecadienoic acid, 9tecadienoic acid ) and 9c, 12c, 15c-octadecatreic acid (linolenic acid) It is preferred not to use the pure species, but rather technical mixtures of the individual acids, as are accessible from fat cleavage. Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C _12, 18% by weight of C _14, 10 wt .-% C _16, 2 wt .-% C ₁₈ , 8 wt .-% C ₁₈ -, 1 wt .-% C _1β -). Palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10l 50 wt .-% _C12, 15 wt .-% Cι _4, 7 wt .-% C _16, 2 wt .-% C ₁₈ , 15 wt% C ₁₈ -, 1 wt% C _i8 ). Tallow fatty acid (approx. 3% by weight C ₁₄ , 26% by weight C ₁₆ , 2% by weight C ₁₆ -, 2% by weight C ₁₇ , 17% by weight C ₁₈ , 44% by weight Cι ₈ -, 3 wt .-% C ₁₈ -, 1 wt .-% C _1β -), hardened tallow fatty acid (about 2 wt .-% C ₁₄ , 28 wt .-% C _1β , 2 wt .-% C _17, 63 wt .-% C _1B, 1 wt .-% C _18), technical grade oleic acid (about 1 wt .-% C _12, 3 wt .-% C _14, 5 wt .-% C _16, 6 wt % C ₁₆ -, 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C ₁₈ -, 10% by weight C ₁₈ -, 0.5% by weight C ₁₈ -), technical palmitin / stearic acid (approx. 1 wt% C ₁₂ , 2 wt% C ₁₄ , 45 wt% C ₁₈ , 2 wt% C ₁₇ , 47 wt% C ₁₈ , 1% by weight C ₁₈ ) and soybean oil fatty acid (approx. 2% by weight C ₁₄ , 15% by weight C ₁₆ , 5% by weight C ₁₈ , 25% by weight C ₁₈ -, 45% by weight % C ₁₈ -, 7% by weight C ₁₈ ).

The above-mentioned carboxylic acids are largely obtained industrially from native fats and oils by hydrolysis. While the alkaline saponification carried out in the past century led directly to the alkali salts (soaps), today is On an industrial scale, only water is used for splitting, which splits the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage. The alkali metal salts of the abovementioned carboxylic acids or carboxylic acid mixtures can also be used for the preparation of the open hollow mold, if appropriate in a mixture with other materials. Salicylic acid and / or acetysalicylic acid or their salts, preferably their alkali metal salts, can also be used, for example.

Other suitable materials that can be processed into open hollow molds via the state of the melt are hydrogen carbonates, in particular the alkali metal hydrogen carbonates, especially sodium and potassium hydrogen carbonate, and the hydrogen sulfates, in particular alkali metal hydrogen sulfates, especially potassium hydrogen sulfate and / or sodium hydrogen sulfate. The eutectic mixture of potassium hydrogen sulfate and sodium hydrogen sulfate has also proven to be particularly suitable, which consists of 60% by weight of NaHS0 ₄ and 40% by weight of KHS0 ₄ .

Particularly suitable further melt materials can be found in the table below:

As can be seen in the table, sugars are also suitable materials for the melt. Portioned compositions according to the invention are further preferred, which are characterized in that the material of the hollow form contains one or more substances from the group of sugars and / or sugar acids and / or sugar alcohols, preferably from the group of sugars, particularly preferably from the group of Oligosaccharides, oligosaccharide derivatives, monosaccharides, disaccharides, monosaccharide derivatives and disaccharide derivatives and mixtures thereof, in particular from the group consisting of glucose and / or fructose and / or ribose and / or maltose and / or lactose and / or sucrose and / or maltodextrin and / or isomalt ^® ,

Sugar, sugar acids and sugar alcohols have proven to be particularly suitable materials for the melt in the context of the present invention. These substances are generally not only sufficiently soluble, but are also characterized by low costs and good processability. For example, sugar and sugar derivatives, in particular the mono- and disaccharides and their derivatives, can be processed, for example, in the form of their melts, these melts having good solubility both for dyes and for many active washing and cleaning substances. The solid bodies resulting from the solidification of the sugar melts are also distinguished by a smooth surface and an advantageous appearance, such as a high surface brilliance or transparent appearance.

The group of preferred as the material for the melt in the context of the present application include sugar from the group of mono- and disaccharides, and derivatives of mono- and disaccharides in particular glucose, fructose, ribose, maltose, lactose, sucrose, maltodextrin, and isomalt, and mixtures ^® of two, three, four or more mono- and / or disaccharides and / or the derivatives of mono- and / or disaccharides. Mixtures of Isomalt ^® and glucose, Isomalt ^® and lactose, Isomalt ^® and fructose, Isomalt ^® and ribose, Isomalt ^® and maltose, glucose and sucrose, Isomalt ^® and maltodextrin or Isomalt ^® and sucrose are particularly preferred as materials for the melt. The proportion by weight of Isomalt ^{® in} the total weight of the aforementioned mixtures is preferably at least 20% by weight, particularly preferably at least 40% by weight, and in particular at least 80% by weight.

Mixtures of maltodextrin and glucose, maltodextrin and lactose, maltodextrin and fructose, maltodextrin and ribose, maltodextrin and maltose or maltodextrin and sucrose are also particularly preferred as the material for the melt. The proportion by weight of maltodextrin in the total weight of the aforementioned mixtures is preferably at least 20% by weight, particularly preferably at least 40% by weight, and in particular at least 80% by weight.

In the context of the present application, maltodextrin refers to water-soluble carbohydrates (dextrose equivalents, DE 3-20) obtained by enzymatic degradation of starch with a chain length of 5-10 anhydroglucose units and a high proportion of maltose. Maltodextrin are foods to improve theological and. added caloric properties, taste little sweet u. do not tend to retrogradate. Commercial products, for example from Cerestar, are generally offered as spray-dried, free-flowing powders and have a water content of 3 to 5% by weight.

As isomalt ^® in the context of the present application, a mixture of 6-O-α-D-glucopyranosyl-D-sorbitol (1, 6-GPS) and 1-O-α-D-glucopyranosyl-D-mannitol (1, 1 -GPM). In a preferred embodiment, the weight fraction of the 1,6-GPS in the total weight of the mixture is less than 57% by weight. Mixtures of this type can be prepared industrially, for example, by enzymatic rearrangement of sucrose into isomaltose and subsequent catalytic hydrogenation of the isomaltose obtained to form an odorless, colorless and crystalline solid.

In the context of the present application, particularly preferred materials used for the melt are the sugar acids. Sugar acids can be used alone or in combination with other substances such as the above-mentioned sugars in an advantageous manner as part of the active phase, with sugar acids from the group consisting of gluconic acid, galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid and 2-deoxy-ribonic acid being particularly preferred to be favoured. Materials which contain ^{Isomalt® in} addition to the sugar acids mentioned are particularly preferred. The weight fraction of Isomalt ^{® in} the total weight of these mixtures is preferably at least 20% by weight, particularly preferably at least 40% by weight, and in particular at least 80% by weight, mixtures of Isomalt ^® with gluconic acid, Isomalt ^® with galactonic acid, isomalt ^® with mannonic acid, isomalt ^® with Fructonsäure, isomalt ^® with arabinonic acid, xylonic acid with isomalt ^®, isomalt ^® are particularly preferred with ribonic acid and isomalt ^® with 2-deoxy-ribonic acid. A third group of materials which can be used advantageously for the melt are the sugar alcohols, of which mannitol, sorbitol, xylitol, dulcitol and arabitol are preferred in the context of the present application. The sugar alcohols can be used alone or as mixtures with one another or as a mixture with other sugars, sugar derivatives, sugar acids or sugar acid derivatives. Mixtures of sugar alcohols with Isomalt ^® are particularly preferably used, mixtures of Isomalt ^® with mannitol, Isomalt ^® with sorbitol, Isomalt ^® with xylitol, Isomalt ^® with dulcitol and Isomalt ^® with arabitol being particularly preferred. The weight fraction of ^{Isomalt® in} the total weight of these mixtures is preferably at least 20% by weight, particularly preferably at least 40% by weight, and in particular at least 80% by weight.

With a view to improved product aesthetics, preferred portioned agents according to the invention are optically upgraded in that the wall of the hollow mold and the solid body (or the majority of the solid body) which is at least partially cast into the wall appear distinctly differently. This can be achieved, for example, in that the solidified melt is transparent or translucent, or in that the melt is colored.

In a particularly preferred embodiment of portioned compositions according to the invention, the solidified melt is transparent. For the purposes of this invention, transparency is understood to mean that the transmittance within the visible spectrum of light (410 to 800 nm) is greater than 20%, preferably greater than 30%, most preferably greater than 40% and in particular greater than 50%. As soon as a wavelength of the visible spectrum of light has a transmittance greater than 20%, it is to be regarded as transparent in the sense of the invention. Transparent solidified melts improve the overall appearance of agents according to the invention and offer a further possibility of visualizing the solid bodies contained in these solidified melts, which may be present in these transparent walls, for example as crystals or granules or extrudates or tablets etc. (see below), and because of the transparency the at least partially surrounding wall is visible to the consumer. In this way, effects achieved with the compositions can be visualized and thus "explained" to the consumer.

Another possibility to improve the appearance of agents according to the invention is to color the melt. The walls of portioned compositions which are particularly preferred in the context of the present application will accordingly also contain dyes in addition to melt material and solid (s). Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity compared to the other ingredients of the agents and against light and no pronounced substantivity towards dishes or textiles, so as not to stain them.

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

Effect dyes can also be used, for example those which vary their color depending on the viewing angle. Pigments can also be used, and special optical effects can be achieved, for example, by using pearlescent pigments. Pearlescent pigments are gloss pigments that have the shine as an additional property compared to other pigments. They are flat, small, thin platelets with relatively large diameters and smooth surfaces. Their characteristic properties of the flat structure, the high refractive index and the transparency create effects in transparent media as a result of the multiple reflection of light, which are equivalent to the gloss of pearls or mother-of-pearl. They can also achieve metal and similar effects without the disadvantages observed with metals and metal alloys.

All pearlescent pigments consist of thin platelets of the natural mineral mica, which are coated with titanium dioxide and / or iron III oxide. The pearlescent pigments are available in different particle size ranges, whereby the pearlescent or colored gloss can be varied depending on the size of the ponds from silk matt to a glittering sparkle. The outstanding chemical, thermal and mechanical properties of the pearlescent pigments offer universal applications, varnishes, prints, plastics and much more. They give the products a new color quality. The pigments are physiologically safe, environmentally friendly and can also be used in food packaging be used. Diluted acids and alkalis do not attack pearlescent pigments. The pigments are non-flammable and not self-igniting. They do not conduct the electrical current and tolerate temperatures up to approx. 800 ° C, which makes them particularly suitable for incorporation into the melt. Pearlescent pigments are supplied as a dry powder. For special applications, pigments can also be offered as pastes or specially modified.

Interference pigments represent a further class. Interference is the superposition of waves: As with the waves that are created in the water by throwing in two stones, certain waves are amplified during the overlay and others are extinguished or weakened. The waves are amplified whenever Wellenberg meets Wellenberg. Wellenberg auf Wellental results in a weakening or extinction. Classic pearlescent pigments, known under the name Iriodin ^® from Merck KGaA, consist of a mica plate as a carrier. This is encased by a heavy-breaking metal oxide such as titanium dioxide or iron oxide. Depending on the structure of the pigments, different colors result: Silver-white and whitish-colored pearlescent pigments are created by coating with titanium dioxide, reddish-copper by coating with iron oxide. Combining both metal oxides gives gold-yellow pigments. Green pigments can also be produced if titanium dioxide and chromium (3) oxide are used together. In addition to this body color, these pigments also show an interference color.

BASF AG went another way to coat mica and aluminum flakes: iron oxide was applied using a CVD process. Especially in the red and gold range these pigments with the trade name Paliocrom ^{® show} interesting color impressions and with aluminum as a carrier they offer high hiding power.

Consequently, new substrate materials were also searched for. Merck KGaA began developing new synthetic substrate materials at the beginning of the 1990s. The aluminum oxide and silicon dioxide flakes, which aim for different effects, should be mentioned here in particular. In the presence of coated aluminum oxide flakes (Xirallic ^® pigments), coated objects show a lively, sparkling appearance in the paint film, a brilliant sparkling effect not previously observed with finely divided effect pigments. An essential goal in the development of the new Si0 ₂ flakes (Colorstream ^® pigments) was the synthesis of effect pigments, which acquire their unique optical properties through a substrate material of a defined layer thickness. Appropriate combinations of carrier properties and coating result in a variety of new color effects.

The Si0 ₂ flakes are coated with highly refractive materials (e.g. Ti0 ₂ , Fe ₂ 0 ₃ ), in a process comparable to the proven manufacturing process for mica pigments. Thereby highly pigmented effect pigments are created, in which different color impressions are obtained depending on the respective viewing angle (color change). The simultaneous transparency gives the stylist a wide styling potential.

Flex Products and BASF AG offer opaque pigments with color changes. Flex's pigments, which are marketed under the name Chromaflair ^® , have an opaque aluminum layer as the central layer, which is surrounded by a magnesium fluoride layer and a semi-transparent metal layer. All three materials are colorless in themselves, the color is generated by interference and absorption of light. The pigments show a strong, almost abrupt color change and are not transparent due to the opaque metal layer. Color Variable Pigments from BASF (Variocrom ^® ) are multi-layer pigments that contain a reflective substrate such as aluminum or iron oxide platelets), a low-refractive interlayer (Si0 ₂ ) and an outer, selectively reflective layer made of iron oxide. In the pure shade, these pigments show brilliant color effects from bluish red to greenish gold. By combining with classic absorption pigments, color changes can be set in the entire color space.

In the case of readily water-soluble colorants, for example the above-mentioned Basacid ^® green or the above-mentioned Sandolan ^® blue, colorant concentrations in the range from a few 10 ^"2 to 10 ^-3 % by weight are typically selected. In the case of those, in particular, on account of their brilliance preferred, but less readily water-soluble pigment dyes, for example the above-mentioned Pigmosol ^® dyes, the suitable concentration of the colorant in the active phase, on the other hand, is typically a few 10 ^"3 to 10 ^{" 4} % by weight. These colorant concentrations can, in the case of strongly colored parts, which make up only a small proportion of the agents according to the invention, deviate considerably from the values mentioned. If, for example, a tablet is included in the wall, which accounts for only 5% of the total weight of the agents according to the invention, the dye concentration in this tablet can be in the percent or even to reach into the percentage range.

Of course, a non-colored (e.g. white) melt can also be combined with a colored solid that is at least partially cast in the wall.

The solidified melt forms a hollow shape which is suitable for taking up further active substance. (A) solid body is / are at least partially cast into the wall of the hollow mold. It has proven to be advantageous if the wall thickness of the hollow mold is between 0.1 and 6 mm. Portioned agents according to the invention are preferred here, in which the hollow form has wall thicknesses of 100 to 6000 μm, preferably 500 to 5000 μm and in particular 1000 to 4000 μm. The wall of the hollow mold at least partially encloses at least one solid. The wall can enclose a solid at least partially in several ways, which is explained below using the example of the wall of a hollow shell made of solidified melt and a tablet. Of course, the invention is not limited to these explanations by way of example, but rather can be implemented analogously with a plurality of solid bodies, these solid bodies not necessarily having to be tableted (see above). For example, it is possible for the wall of the hollow shell to surround the tablet in such a way that a surface of the tablet is visible on the outer wall (ie the "dome"). For this purpose, the tablet can be placed in the mold for the melt and poured over with melt If the melt is now metered in such a way that it only wets the edge of the tablet and not the surface of the tablet facing away from the mold, the tablet is also visible from the inside. In this case, the tablet is like a "window" in a brickwork of the Enclosed melt. Of course, the melt can also cover the surface of the tablet facing away from the mold.

Alternatively, the melt can also be poured coherently, where it forms a hollow shell. After the excess melt has been poured off, the tablet can be placed in the wall, where it is fixed by the solidifying melt. Here the tablet (in the case of an opaque melt) is only visible from the inside. If a further melt of the same or a different composition is poured into the inside of the hollow shell in this procedure, the tablet is completely surrounded by solidified melts and (in the case of opaque melts) is no longer visible.

As already mentioned, a single solid body can be at least partially enclosed, but it is also possible to enclose a plurality of solid bodies, for example two, three, four, five, six, seven, eight, nine, ten or eleven, at least partially in the wall , Even higher numbers of solid bodies can be included, the size of the solid bodies decreasing with increasing number for geometric reasons. Small solids, most of which are at least partially included in the majority, are powders, granules, extrudates, flakes, pellets, prills, etc. With these solids, particle sizes between 0.4 and 4 mm are preferred.

Within the scope of the present invention, preferably only one, two or three solid bodies are at least partially cast into the wall of the hollow mold. Such solid bodies are preferably bodies which have been produced by means of tableting or (preferably filled) polymer bodies. Portioned agents according to the invention are preferred here, in which the at least one further solid is a tablet and / or a casting and / or an extruded part and / or an injection molded part and / or a gelatin capsule and / or a blow molded part and / or a pouch and / or a deep-drawn part.

In the case of non-tableted solids, portioned agents according to the invention are preferred here, in which the at least one further solid is a hollow body which is filled with a liquid or flowable composition.

The production of powder-filled or liquid-filled hollow bodies (or also empty hollow bodies) by shaping processing is carried out according to the methods customary in the plastics processing industry, with film production and further processing, blow molding and injection molding being preferred in particular. All processes have in common that a plastic granulate is melted with the help of an extruder and fed to shaping tools.

In a preferred embodiment of the present invention, the melt leaving the extruder is blow molded. Blow molding methods suitable according to the invention include extrusion blow molding, coextrusion blow molding, injection stretch blow molding and immersion blowing. The wall thicknesses of the moldings can be produced differently in some areas by means of blow molding, by correspondingly varying the wall thicknesses of the preform, preferably along its vertical axis, preferably by regulating the amount of thermoplastic material, preferably by means of an adjusting spindle when the preform is removed from the extruder nozzle, formed.

The powder-filled or liquid-filled solid can be blow-molded with areas of different outer circumference and constant wall thickness by changing the wall thicknesses of the preform, preferably along its vertical axis, with different thicknesses, preferably by regulating the amount of thermoplastic material by means of an adjusting spindle when the preform is removed from the extruder nozzle.

In this way, different geometrical configurations of the molded body can be blow-molded with and without compartments. In a single work cycle, bottles, balls, Santa Clauses, Easter bunnies or other figures can be blow-molded, which can be filled with agents, then sealed and then removed from the mold.

It is particularly advantageous that the molded body can be embossed and / or decorated in the blow mold during blow molding. By appropriately designing the blow mold, a motif can be transferred to the molded body in mirror image. In this way, the surface of the molded body can be designed practically as desired. For example, it can be used on the molded body Apply information such as calibration marks, application notes, hazard symbols, brands, weight, quantity, expiry date, pictures, etc.

The preform, the shaped body and / or the liquid-tightly closed shaped body can be tubular, spherical or bubble-shaped. A spherical shaped body preferably has a shape factor (= shape factor) of> 0.8, preferably of> 0.82, preferably> 0.85, more preferably> 0.9 and particularly preferably of> 0.95.

The shape factor in the sense of the present invention can be precisely determined using modern particle measurement techniques with digital image processing. A common method is, for example, the Camsizer® system from Retsch Technology or the KeSizer® from Kemira. These methods are based on the fact that the bodies are irradiated with a light source and the shaped bodies are recorded, digitized and processed by computer technology as projection surfaces. The surface curvature is determined by an optical measuring method in which the “shadow cast” of the body to be examined is determined and converted into a corresponding form factor. The basic principle for determining the form factor was described, for example, by Gordon Rittenhouse in “A Visual method of estimating two -dimensional sphericity "in the Journal of Sedimentary Petrology, Vol. 13, No. 2, pages 79-81. The measuring limits of this optical analysis method are 15 μm to 90 mm. Methods for determining the shape factor for larger particles are known to the person skilled in the art. These are usually based on the principles of the aforementioned procedures.

The walls of the solid bodies produced by blow molding have a wall thickness of between 0.05 and 5 mm, preferably between 0.06 and 2 mm, preferably between 0.07 and 1.5 mm, more preferably between 0.08 and 1 , 2 mm, more preferably between 0.09-1 mm and most preferably between 0.1-0.6 mm.

The filling opening of the hollow body after filling can be closed in a liquid-tight manner, preferably by material closure, preferably by means of thermal treatment, particularly preferably by putting on a hot melt. The filling opening or openings of the hollow body can also advantageously be closed in a liquid-tight manner by thermal treatment, preferably by fusing the walls which adjoin the opening, in particular by means of clamping jaws.

It is particularly preferred according to the invention to design the blow molding process as a BFS (blow-fill-seal -) process, so that the moldings produced are still filled and sealed in the blow mold. With this blow mold / filler closure technique, the desired shape is first blown, then filled with the content and then in one operation locked. Here, a tube of plasticized water-soluble plastic material is extruded into an open blow mold, the blow mold is closed and expanded by generating an effective pressure gradient on the tube and applied to the shaping wall of the blow mold to form the container.

In another preferred embodiment of the present invention, the melt of water-soluble polymer blend leaving the extruder is shaped by means of an injection molding process. The injection molding is carried out according to methods known per se at high pressures and temperatures with the steps of closing the mold connected to the extruder for injection molding, injecting the polymer at high temperature and high pressure, cooling the injection-molded molding, opening the mold and removing the molded blank , Further optional steps such as the application of release agents, demolding etc. are known to the person skilled in the art and can be carried out using technology known per se.

The advantages of the method of production by injection molding lie in the sophisticated technology of this method, the high flexibility with regard to the materials that can be used, the possibility of obtaining exactly the desired wall thickness s of the molded part or dimensionally stable hollow body and the possibility of one step with high Reproducibility of producing a dimensionally stable hollow body with one or more integral compartmentalization device (s).

In preferred processes, injection molding is carried out at a pressure of up to 5000 bar, preferably between 2 and 2500 bar, particularly preferably between 5 and 2000 bar, more preferably between 10 and 1500 and in particular between 100 and 1250 bar.

The temperature of the material to be injection molded is preferably above the melting or softening point of the material and thus also depends on the type and composition of the polymer blend. In preferred processes according to the invention, injection molding is carried out at temperatures between 100 and 250 ° C., preferably between 120 and 200 ° C. and in particular between 140 and 180 ° C.

The tools that hold the materials are preferably preheated and have temperatures above room temperature, temperatures between 25 and 60 ° C. and in particular from 35 to 50 ° C. being preferred.

Regardless of the material used for the moldings, but depending on the desired dissolution properties, the thickness of the wall can be varied. The wall should on the one hand, be chosen so thin that a drafty disintegration is achieved and the ingredients are rapidly released into the application liquor, but a certain minimum thickness is also required in order to give the hollow mold the desired stability, in particular shape stability

Preferred wall thicknesses of injection molded articles are in the range from 100 to 5000 μm, preferably from 200 to 3000 μm, particularly preferably from 300 to 2000 μm and in particular

The molded body produced by injection molding regularly does not have closed walls on all sides and is open on at least one of its sides - in the case of a spherical or elliptical body in the region of part of its shell - due to the manufacturing process. The remaining opening becomes into the inside of the molded body (s) compartment (s) or preparation (s) filled in. This also takes place in a manner known per se, for example in the context of manufacturing processes known from the confectionery industry, and procedures which run in several steps are also conceivable. A one-step procedure is particularly then preferred if, in addition to solid preparations, preparations comprising liquid components (dispersions or emulsions, suspensions) or even preparations comprising gaseous components (foams) are to be introduced into moldings

Regardless of the manner in which the at least partially cast-in solid body (s) are produced, he / she can be used for separating active ingredients. In this way, incompatible ingredients can be spatially separated from one another

Further advantages can be achieved in that the wall of the hollow mold and / or the solid (s) are controlled by solubility. Here, a loosening acceleration can be achieved by incorporation of disintegration aids, a solubility delay by the use of loosening agents, for example polymers

For example, the hollow mold (or the at least partially cast-in solid (s)) can contain so-called disintegrants. These substances increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand pressure can be generated by the release of gases. which, for example, allows a tablet or the wall of the solidified melt to disintegrate into smaller particles. Well-known disintegration aids are, for example, carbonate / citric acid systems, but also other organic acids can be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.

Examples of suitable swellable disintegration aids are bentonites or other swellable silicates. Synthetic polymers, in particular the superabsorbers or cross-linked polyvinylpyrrolidone used in the hygiene sector, can also be used.

Polymers based on starch and / or cellulose are used with particular advantage as swellable disintegration aids. These basic substances can be processed alone or as a mixture with other natural and / or synthetic polymers to form swellable disintegrants.

In the simplest case, a cellulose-containing material or pure cellulose can be converted into secondary particles by granulation, compaction or other application of pressure, which swell on contact with water and thus serve as disintegrants. Wood pulp has proven itself as a cellulose-containing material that is accessible by thermal or chemical-thermal processes from wood or wood chips (sawdust, sawmill waste). This cellulose material from the TMP process (thermo-mechanical pulp) or the CTMP process (chemo-thermo-mechanical pulp) can then be compacted by application of pressure, preferably roller-compacted, and converted into particle form. Of course, pure cellulose can also be used completely analogously, although this is more expensive from the raw material basis. Both microcrystalline and amorphous, finely divided cellulose and mixtures thereof can be used here.

Another way is to granulate the cellulose-containing material with the addition of granulating aids. Solutions of synthetic polymers or nonionic surfactants, for example, have proven useful as granulating aids.

In order to avoid residues on textiles washed with the agents according to the invention, the primary fiber length of the cellulose used or of the cellulose in the cellulose-containing material should be less than 200 μm, primary fiber lengths below 100 μm, in particular below 50 μm, being preferred. The secondary particles ideally have a particle size distribution in which more than 90% by weight of the particles have sizes above 200 μm. A certain amount of dust can contribute to an improved storage stability of the tablets produced with it. Fractions of a fine dust fraction of less than 0.1 mm up to 10% by weight, preferably up to 8% by weight, can be present in the disintegrant granules used according to the invention. The finely divided cellulose preferably has bulk densities from 40 g / l to 300 g / l, very particularly preferably from 65 g / l to 170 g / l. If already granulated types are used, their bulk density is higher and, in an advantageous embodiment, can be from 350 g / l to 550 g / l. The bulk densities of the cellulose derivatives are typically in the range from 50 g / l to 1000 g / l, preferably in the range from 100 g / l and 800 g / l.

As already stated, cellulose-based disintegration aids can also be used which contain other active ingredients or auxiliaries in addition to cellulose. Suitable here are, for example, compacted disintegrant granules composed of 60-99% by weight of non-water-soluble, water-swellable cellulose and optionally further modified water-swellable polysaccharide derivatives, 1-40% by weight of at least one polymeric binder in the form of a polymer or copolymer of (meth) acrylic acid and / or their salts, and 0-7% by weight of at least one liquid surfactant which forms water. These disintegrants preferably have a moisture content of 2 to 8% by weight.

The proportion of cellulose in such disintegrant granules is between 60 to 99% by weight, preferably between 60 to 95% by weight. Regenerated celluloses such as viscose can also be used in these explosives. Particularly regenerated celluloses in powder form are characterized by very good water absorption. The viscose powder can be made from cut viscose fiber or by precipitation of the dissolved viscose. Low molecular weight cellulose degraded by electron beam is also suitable, for example, for producing such disintegrant granules.

Furthermore, the swellable disintegration aids contained according to the invention in the washing or cleaning agent tablets can contain water-swellable cellulose derivatives, such as cellulose ethers and cellulose esters and starch or starch derivatives, as well as other swellable polysaccharides and polygalactomannans, for example ionically modified celluloses and starches such as carboxymethyl-modified cellulose and starch, non-ionically modified Starches such as alkoxylated celluloses and starches such as hydroxypropyl and hydroxyethyl starch or hydroxypropyl and hydroxyethyl cellulose and alkyl etherified products such as methyl cellulose as well as mixed modified celluloses and starches from the aforementioned modifications, optionally combined with a modification which leads to crosslinking. Suitable starches are also cold-swelling starches, which are formed by mechanical or degrading reactions on the starch grain. Above all, this includes swelling starches from extruder and drum dryer processes as well as enzymatically, oxidizing or acid-degrading modified products. Chemically derivatized starches preferably contain substituents which are linked to the polysaccharide chains in sufficient numbers by ester and ether groups Starches modified with ionic substituents such as carboxylate, hydroxyalkyl or phosphate groups have proven to be particularly advantageous and are therefore preferred. The use of slightly cross-linked starches has also proven itself to improve the swelling behavior. Alkaline-treated starches can also be used because of their good cold water swellability. In an advantageous embodiment, the combination of cellulose with cellulose derivatives and / or starch and / or starch derivatives has proven itself. The proportions can vary within wide limits, based on the combination the proportion of cellulose derivatives and / or starch and / or starch derivatives is preferably 0.1 to 85% by weight, particularly preferably 5 to 50% by weight.

Polymers or copolymers of (meth) acrylic acid or mixtures of such polymers or copolymers are used as binders in preferred disintegration aid granules. The polymers are selected from the group of homopolymers of (meth) acrylic acid, from the group of copolymers with the following monomer components of ethylenically unsaturated dicarboxylic acids and / or their anhydrides and / or ethylenically unsaturated sulfonic acids and / or acrylic esters and / or vinyl esters and / or vinyl ethers or their saponification products and / or crosslinking agents and / or graft bases based on polyhydroxy compounds.

Uncrosslinked polymers or copolymers of (meth) acrylic acid with weight average molecular weights of 5,000 to 70,000 have proven to be particularly suitable. The copolymers are preferably copolymers of (meth) acrylic acid and ethylenically unsaturated dicarboxylic acids or their anhydrides, such as maleic acid or maleic anhydride, which contain, for example, 40 to 90% by weight of (meth) acrylic acid and 60 to 10% by weight of maleic acid or Contain maleic anhydride whose relative molar mass, based on free acids, is between 3,000 and 100,000, preferably 3,000 to 70,000 and very particularly preferably 5,000 to 50,000. Ter- and quattropolymeric polycarboxylates, built up from (meth) acrylic acid, maleic acid and optionally fully or partially saponified vinyl alcohol derivatives, or from (meth) acrylic acid, ethylenically unsaturated sulfonic acids and polyhydroxy units, such as sugar derivatives, have also proven to be very suitable binders from (meth) acrylic acid, maleic acid, vinyl alcohol derivatives and sulfonic acid group-containing monomers.

The polymeric binders are preferably used in the production in the form of their aqueous solutions, but can also be used in the form of finely divided powders. The binder polymers are preferably in partially or fully neutralized form, the salt formation preferably taking place with cations of alkali metals, ammonia and amines or their mixtures. The proportion of the polymers / copolymers in preferred disintegrants is between 1 and 40% by weight, preferably between 1 and 20% by weight, particularly preferably between 5 and 15% by weight. Polymer contents above 15% in the disintegrant lead to harder disintegrant granules, while polymer contents below 1% tend to form soft granules which are less resistant to abrasion.

Suitable polymer binders are also crosslinked polymers made from (meth) acrylic acid. They are preferably used as finely divided powders and preferably have average particle sizes of 0.045 mm to 0.150 mm and are preferably used at 0.1 to 10% by weight. Particles with average particle sizes of more than 0.150 mm also result in good disintegrant granules, but after dissolving the tablets produced with the granules, they lead to swelling bodies which are visually visible as particles and which, for example in the case of textile washes, are deposited on the textile material in a disruptive manner, for example. A particular embodiment of the invention is the combination of soluble poly (meth) acrylate homopolymers and copolymers and the aforementioned finely divided crosslinked polymer particles.

Disintegrant granules that are preferably used contain one or more liquid, gel-forming surfactants selected from the group of nonionic, anionic or amphoteric surfactants, which are present in amounts of up to 7% by weight, preferably up to 3.5% by weight can. If the surfactant content in the disintegrant is too high, in addition to increased abrasion of the tablets produced with it, poor swelling properties will also result.

The nonionic surfactants are described in detail below.

Disintegration aids preferably used according to the invention are notable for their particular swelling kinetics, the expansion not changing linearly as a function of time, but already reaching a very high level after a very short time. The swelling behavior in the first 10 seconds after contact with water is of particular interest. The specific water absorption capacity of preferably used disintegration aids can be determined gravimetrically and is preferably 500 to 2000%

The liquid absorption (also referred to as specific porosity) of preferred disintegrants is in a range from more than 600 ml / kg, preferably from more than 750 ml / kg, in particular in the range from 800 to 1000 ml / kg. Granulated disintegrant granules are first produced by mixing the granulate components using customary mixing methods. For example, mixers from Vomm, Lödige, Schugi, Eirich, Henschel or Fukae can be used. In this first step of mixing and granulating, pre-compounds are produced by agglomeration processes.

In the next step, these pre-compounds are mechanically compressed. Compression using pressure can be done in several ways. The products can be placed between two pressure surfaces in roller compressors, e.g. B. smooth or profiled. The compactate is ejected as a strand. Compaction methods in matrices with punches or cushion rollers result in compact forms such as tablets or briquettes. Roller compactors, extruders, roller or cube presses, but also pelletizing presses can be used as compaction machines.

Compression with pelleting presses has proven to be particularly suitable, granules which can be dried without further comminution being obtained by suitable process control. Suitable pelleting presses are e.g. manufactured by Amandus Kahl and Fitzpatrick.

The coarse, compacted particles are crushed, e.g. Mills, shredders or roller mills are suitable. The shredding can be carried out before or after drying. Preferred water contents of 2-8% by weight, preferably 2.5-7% by weight and particularly preferably 3-5% by weight can be set in the drying process. Common dryers such as Roller dryers (temperatures e.g. from 95 - 120 ° C) or fluid bed dryers (temperatures e.g. from 70 - 100 ° C) are suitable.

Also suitable as swellable disintegration aids are coprocessates which are obtained from polysaccharide material and insoluble disintegrants. The above-mentioned substances from the groups powdered cellulose, microcrystalline cellulose and mixtures thereof are particularly suitable as polysaccharide materials; The insoluble disintegrant used here is in particular insoluble polyacrylic acid monopolymer, insoluble polyacrylamide monopolymer, insoluble polyacrylic acid-polyacrylamide copolymer and mixtures thereof.

The content of the individual components in these disintegrants can vary within wide limits, for example from 1 to 60% by weight of insoluble polyacrylic product disintegrant and 40 to 99% by weight of cellulose. A content of 3 to 60% by weight of insoluble polyacrylic product disintegrant and 40 to 97% by weight of cellulose is preferred. A is even more preferred Content of 5 to 30% by weight insoluble polyacrylic product disintegrant and 70 to 95% by weight cellulose. Optionally, small amounts of further disintegrants, for example various starches, effervescent mixtures, for example of sodium carbonate and sodium hydrogen sulfate, etc., can also be added to this disintegrant, these amounts being compensated for, ie compensated for, by appropriate deductions in the amount of cellulose.

This suitable disintegrant can be obtained by coprocessing a cellulose as defined above with an insoluble disintegrant as defined above by wet or dry compression under pressure. The term "coprocessing" is used here to dry compress e.g. between counter-rotating compacting rollers at pressures of 20-60 kN, preferably 30-50 kN, or wet compaction after the addition of water, by kneading or pressing moist plastic materials through a sieve, a perforated disc or via an extruder and then drying.

As an alternative to this, the wall of the hollow mold (or the at least partially cast-in solid body (s)) can contain substances that lead to a delay in detachment. Polymers in particular should be mentioned here. If the at least partially cast-in solid is a blow molded part, an injection molded part, a pouch, a deep-drawn part or a gelatin capsule, it is usually already delayed in dissolution. The incorporation of additional polymers is not necessary here; instead, the decay accelerators described above can be used if necessary.

In the case of tablets which are at least partially cast in, the incorporation of polymer (s) may be indicated to delay the dissolution.

Preferred polymers useful as dissolving retarders are described below. All of these polymers can also be used as wall materials for at least partially cast-in blow moldings or injection moldings.

The polymers used to delay the solubility can consist of a single material or a blend of different materials. Preferred release retarders are materials from the group (optionally acetalized) polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinyl pyrrolidone, polyethylene oxide, polyethylene glycol, gelatin and / or copolymers and mixtures thereof. In the context of the present invention, polyvinyl alcohols are particularly preferred as water-soluble polymers. "Polyvinyl alcohols" (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure

which in small proportions (approx. 2%) also structural units of the type

contain.

Commercial polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approximately 100 to 2500 (molar masses from approximately 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , therefore still contain a residual content of acetyl groups. The manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax. Polyvinyl alcohol is largely impervious to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allows water vapor to pass through.

Agents preferred in the context of the present invention are characterized in that the solidified melt and / or at least one at least partially enclosed solid body comprises polyvinyl alcohols and / or PVAL copolymers and / or thermoplastic PVAI and / or PVAI copolymer compounds, the degree of hydrolysis 70 thereof is up to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%. Polyvinyl alcohols of a certain molecular weight range are preferably used, agents according to the invention being preferred in which the solidified melt and / or at least one at least partially enclosed solid body comprises polyvinyl alcohols and / or PVAL copolymers whose molecular weight is in the range from 3,500 to 100,000 gmol ^"1 , preferably from 10,000 to 90,000 gmol ^'1 , particularly preferably from 12,000 to 80,000 gmol ^"1 and in particular from 13,000 to 70,000 gmol ^{" 1} .

The degree of polymerization of such preferred polyvinyl alcohols is between approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1890, particularly preferably between approximately 240 to approximately 1680 and in particular between approximately 260 to approximately 1500.

Agents preferred according to the invention are characterized in that the solidified melt and / or at least one at least partially enclosed solid body comprises polyvinyl alcohols and / or PVAL copolymers whose average degree of polymerization is between 80 and 700, preferably between 150 and 400, particularly preferably between 180 and 300 and / or whose molecular weight ratio MG (50%) to MG (90%) is between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6.

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Kuraray Specialties Europe, KSE). Particularly suitable in the context of the present invention, polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88, Mowiol ^® 8-88 and L648, L734, Mowiflex LPTC KSE 221 as well as the ex Compounds of Texas polymer such as Vinex 2034.

Further polyvinyl alcohols which are particularly suitable as dissolving retardants can be found in the table below:

Other polyvinyl alcohols suitable as material for the delay in dissolution are ELVANOL 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX ^® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gθhsenol ^® NK-05, A-300, AH-22, C- 500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (trademark of Nippon Gohsei KK) , ERKOL types from Wacker are also suitable.

A further preferred group of water-soluble polymers which can serve as a release retardant according to the invention are the polyvinylpyrrolidones. These are sold, for example, under the name Luviskoi ^® (BASF). Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (IV)

which are produced by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-radical formers (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer only provides products with low molecular weights. Commercial polyvinylpyrrolidones have molar masses in the range from approx. 2500-750000 g / mol, which are characterized by the K values and, depending on the K value, have glass transition temperatures of 130-175 °. They are presented as white, hygroscopic powders or as aqueous ones. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).

Also suitable are copolymers of vinylpyrrolidone with other monomers, in particular vinylpyrrolidone / Vinylester copolymers, as are marketed, for example under the trademark Luviskoi ^® (BASF). Luviskoi ^® VA 64 and Luviskoi ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.

The vinyl ester polymers are polymers accessible from vinyl esters with the grouping of the formula (V)

as a characteristic basic building block of macromolecules. Of these, the vinyl acetate polymers (R = CH ₃ ) with polyvinyl acetates as by far the most important representatives have the greatest technical importance.

The vinyl esters are polymerized by free radicals using various processes (solution polymerization, suspension polymerization, emulsion polymerization,

Bulk polymerization.). Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (IV) and (V)

Other suitable water-soluble polymers are the polyethylene glycols (polyethylene oxides), which are briefly referred to as PEG. PEG are polymers of ethylene glycol which have the general formula (VI)

H- (0-CH ₂ -CH ₂ ) _n -OH (VI)

are sufficient, where n can have values between 5 and> 100,000.

PEGs are manufactured industrially by anionic ring opening polymerization of ethylene oxide (oxirane), usually in the presence of small amounts of water. Depending on how the reaction is carried out, they have molar masses in the range of approximately 200-5,000,000 g / mol, corresponding to degrees of polymerization of approximately 5 to> 100,000.

The products with molar masses <approx. 25,000 g / mol are liquid at room temperature and are referred to as the actual polyethylene glycols, abbreviation PEG. These short chain PEGs can in particular be other water soluble polymers e.g. Polyvinyl alcohols or cellulose ethers can be added as plasticizers. The polyethylene glycols which can be used according to the invention and are solid at room temperature are referred to as polyethylene oxides, abbreviation PEOX. High molecular weight polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and therefore only show weak glycol properties.

According to the invention, gelatin is also further suitable as a dissolving retardant, which is preferably used together with other polymers. Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is primarily produced by hydrolysis of the skin and Bones from collagen contained in animals is obtained under acidic or alkaline conditions. The amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as a water-soluble coating material is extremely widespread, particularly in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.

Further water-soluble polymers suitable according to the invention as dissolving retardants are described below:

Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and

Methyl hydroxypropyl cellulose, such as those sold under the trademarks Culminal ^® and Benecel ^® (AQUALON). Cellulose ethers can be described by the general formula (VI)

in R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products at least one R in formula (III) is -CH ₂ CH CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of cellulose have reacted with the etherification reagent or how many moles of etherification reagent have been attached to an anhydroglucose unit on average. Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercially available hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish white, odorless and tasteless powders in widely differing degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition. Other polymers suitable according to the invention are water-soluble amphopolymers. Ampho-polymers are amphoteric polymers, ie polymers that contain both free amino groups and free -COOH or S0 ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - Contain COO ^" - or -S0 ₃ ^" groups, and summarized those polymers which contain -COOH or S0 ₃ H groups and quaternary ammonium groups. An example of the present invention amphopolymer suitable is that available under the name Amphomer ^® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (1, 1, 3,3- tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Methacrylic acid and its simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (eg acrylic and methacrylic acid), catalytically derivatized unsaturated carboxylic acids (eg acrylamidopropyl-trimethyl-ammonium chloride) and optionally further ionic or non-ionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art can be seen. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat ^® 2001 N, are particularly preferred amphopolymers according to the invention. Other suitable amphoteric polymers are, for example, / 2-hydroxypropyl methacrylate copolymers of the octylacrylamide / methyl tert-butylaminoethyl methacrylate available under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL).

Suitable water-soluble anionic polymers according to the invention include a .:

Vinyl acetate / crotonic acid copolymers, such as are commercially available for example under the names Resyn ^® (National Starch), Luviset ^® (BASF) and Gafset ^® (GAF). In addition to monomer units of the abovementioned formula (II), these polymers also have monomer units of the general formula (VII):

[-CH (CH ₃ ) -CH (COOH) -] _n (VII)

VinylpyrrolidonΛ / inylacrylate copolymers, available for example under the trademark Luviflex ^® (BASF). A preferred polymer is that available under the name Luviflex VBM-35 ^® (BASF) vinylpyrrolidone / acrylate terpolymers.

Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, which are sold, for example, under the name Ultrahold ^® strong (BASF). Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols

Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture with other copolymerizable compounds on polyalkylene glycols, are obtained by polymerization in the heat in a homogeneous phase by the polyalkylene glycols being converted into the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid In the presence of radical formers. Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as esters of acrylic acid or methacrylic acid, those which are used with low molecular weight aliphatic alcohols, in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl 1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are available.

Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula IX

H- (0-CH-CH ₂ ) _n -OH (IX)

I CH ₃

are sufficient, where n can take values between 1 (propylene glycol) and several thousand. Technically important here are in particular di-, tri- and tetrapropylene glycol, i.e. the representatives with n = 2, 3 and 4 in formula VI.

In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used. grafted and crosslinked copolymers from the copolymerization of i) at least one monomer of the non-ionic type, ii) at least one monomer of the ionic type, iii) of polyethylene glycol and iv) a crosslinker

The polyethylene glycol used has a molecular weight between 200 and more

Millions, preferably between 300 and 30,000.

The non-ionic monomers can be of very different types and among these the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, Allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether,

Stearyl vinyl ether and 1-hexene.

The non-ionic monomers can likewise be of very different types, of which crotonic acid, allyloxyacetic acid,

Vinyl acetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the graft polymers.

Ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucrose with 2 to 5 allyl groups per molecule of saccharin are preferably used as crosslinkers.

The grafted and crosslinked copolymers described above are preferably formed from: i) 5 to 85% by weight of at least one monomer of the nonionic type, ii) 3 to 80% by weight of at least one monomer of the ionic type, iii) 2 to 50% by weight, preferably 5 to 30% by weight of polyethylene glycol and iv) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii) is. copolymers obtained by copolymerization of at least one monomer of each of the following three groups: i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or

Esters of short-chain saturated alcohols and unsaturated carboxylic acids, ii) unsaturated carboxylic acids, iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the

Group ii) carboxylic acids with saturated or unsaturated, straight-chain or branched C ₈ . ₁₈ -Alcohol Short-chain carboxylic acids or alcohols are to be understood as meaning those having 1 to 8 carbon atoms, it being possible for the carbon chains of these compounds to be interrupted by double-bonded hetero groups such as -O-, -NH-, -S_.

Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester These terpolymers contain monomer units of the general formulas (IV) and (VI) (see above) and monomer units of one or more allyl or methallyesters of the formula X:

R ¹ R ^J

R -CC (0) -0-CH ₂ - C = CH ₂ (X)

I CH ₃ wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated straight-chain or branched Ci-β-alkyl radical and the sum of

Carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2.

The above-mentioned terpolymers preferably result from the

Copolymerization of 7 to 12 wt .-% crotonic acid, 65 to 86 wt .-%, preferably 71 to 83 wt .-% vinyl acetate and 8 to 20 wt .-%, preferably 10 to 17 wt .-% allyl or

Methallyletsre of formula VII.

Tetra- and pentapolymers from i) crotonic acid or allyloxyacetic acid ii) vinyl acetate or vinyl propionate iii) branched allyl or methallyl esters iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters

Crotonic acid copolymers with one or more monomers from the group consisting of ethylene,

Vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts

Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic in

D-position branched monocarboxylic acid.

Cationic polymers are further polymers which are preferred according to the invention as dissolution retardants. The permanent cationic polymers are preferred among the cationic polymers. According to the invention, polymers which have a cationic group irrespective of the pH value are referred to as “permanently cationic”. These are generally polymers which contain a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic polymers are, for example, quaternized cellulose Derivatives as are commercially available under the names Celquat ^® and Polymer JR ^® The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives.

Polysiloxanes with quaternary groups, such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow ^Coming® 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; di-quaternary polydimethylsiloxane, Quaternium-80),

Cationic guar derivatives, such as in particular the products sold under the trade names Cosmedia ^® Guar and Jaguar ^® ,

Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The under the names Merquat ^® 100 (poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyl diallylammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers.

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as, for example, vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755.

Vinylpyrrolidone methoimidazolinium chloride copolymers such as those sold under the name Luviquat ^®, quaternized polyvinyl alcohol, as well as those known under the designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 polymers having quaternary nitrogen atoms in the polymer main chain. The polymers mentioned are named according to the so-called INCI nomenclature, with detailed information in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, to which express reference is made here becomes.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers. Cationic cellulose derivatives, in particular the commercial product Polymer ^® JR 400, are very particularly preferred cationic polymers.

In addition to release retarders or accelerators, the wall of the hollow mold and / or the solid body (s) cast at least in part can also contain elasticity or stability sensors. Preferred stabilizers are, for example, the already mentioned polyethylene or propylene glycols, which have proven particularly useful when using urea as the material for the solidifying melt. Other stabilizers are fibers, for example cellulose fibers.

The hollow mold can optionally be coated with suitable agents before filling. Only parts of the hollow mold can also be provided with a coating, for example in order to protect the hollow mold from attack by incompatible constituents of the subsequent filling. Of course, only the at least partially cast-in solid can also be suitably coated. A coating is preferably - if it is carried out at all - but only applied to the filled and closed hollow body. In principle, however, a coating step can be connected as desired after each intermediate production step, it also being possible to coat only partial areas of the surface, inside and outside.

The hollow molds with at least one solid body which is at least partially cast into the wall are preferably filled with further active substance. Portioned compositions according to the invention are preferred here, in which the hollow form additionally contains a further preparation, preferably a particulate preparation and in particular a particulate detergent or cleaning agent composition.

Portions according to the invention which are particularly preferred are provided, for example, from a solidified melt with a cast-in solid (preferably a tablet) and a particulate filling (powder, granules, extrudate).

After filling, the open hollow mold can be closed. This is necessary for liquid or pasty fillings to prevent the filling from escaping before use. In the case of fillings that remain firmly in the hollow mold, the mold may not be closed if desired. Closure can also be indicated in such cases for aesthetic reasons.

The optional closing of the hollow form can be done in different ways. In the case of moldings with a bung hole, this can be closed, for example, by inserting a suitable part. Open hollow molds in the form of hollow bodies without undercuts can be closed with foils or poured over with additional material for the hollow mold after filling. The optional sealing with foils is described below.

The film, which closes the opening (s) of the hollow mold (s), is applied to the surface of the hollow mold and bonded to it, which can be done, for example, by gluing, partial melting or by chemical reaction. It is possible to apply the film to all surfaces of the hollow mold (that is to say not only via the opening) and to bond it firmly with it so that the film forms a coating, a “coating” of the entire molded body. Preferred detergent and cleaning agent portions according to the invention however, characterized in that the film does not enclose the entire molded body. For reasons of process economy and the aesthetic impression, it is preferred that the film is applied only in such a way that it fulfills a function, ie serves to close the hollow mold.

The sealing film can of course also be a laminate of several differently composed films, the opening of the hollow mold can be released at certain times in the washing and cleaning cycle by means of different compositions of individual film layers.

Preferred film materials are the polymers known from the prior art. Here, reference can be made to the above explanations regarding the solubility retarders, since all of the polymers mentioned there are also suitable as film materials for an optional closing of the hollow mold.

Regardless of the chemical composition of the film, films are preferred which have a thickness of 1 to 150 μm, preferably 2 to 100 μm, particularly preferably 5 to 75 μm and in particular 10 to 50 μm.

Due to the division into a hollow mold consisting of at least two components and at least one filling, a filled portion according to the invention comprises three areas in which different ingredients are contained or different release mechanisms and release kinetics can be realized. The active substance contained in the hollow form can assume any physical state or any form of presentation. Preferred detergent or cleaning agent portions contain the further active substance in liquid, gel-like, pasty or solid form.

When incorporating liquid, gel-like or pasty active substances or active substance mixtures, the composition of the hollow body and the film must be matched to the filling in order to avoid premature destruction of the film or loss of active substance through the hollow body. This is only necessary to a lesser extent (chemical incompatibility) when solid substances are incorporated into the hollow mold, so that in preferred manufacturing processes the detergent or cleaning agent composition filled into the hollow mold is in particulate form, preferably in powdered, granular, extruded, pelleted, prilled, flaked form or in tablet form.

The hollow mold closed by the film can be completely filled with further active substance. However, it is also possible to fill the hollow mold only partially before closing, in order in this way to move the filled particles or liquids within to allow the hollow shape. Particularly when filling with regularly shaped larger particles, attractive optical effects can be achieved. Detergent or cleaning agent portions produced according to the invention are preferred in which the volume ratio of the space enclosed by the film and the hollow body to the active substance contained in this space is 1: 1 to 100: 1, preferably 1.1: 1 to 50: 1, is particularly preferably 1.2: 1 to 25: 1 and in particular 1.3: 1 to 10: 1. In this terminology, a volume ratio of 1: 1 means that the cavity is completely filled.

Depending on the size of the hollow mold, the density of the hollow body, the density of the active substance (s) in the hollow mold and the degree of filling of the hollow mold, the proportion of the further active substance (s) in the hollow mold can make up different proportions of the overall molded body. Detergent or cleaning agent portions produced according to the invention are preferred in which the weight ratio of hollow body to the active substance (s) contained in the space enclosed by the film and the hollow body is 1: 1 to 100: 1, preferably 2: 1 to 80: 1, is particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1. The weight ratio defined above is the ratio of the mass of the unfilled hollow body to the mass of the filling. The mass of the film is not taken into account in this calculation.

The time at which the substances contained in the hollow body are released can be predetermined by suitable packaging of the hollow body and film material. For example, the film can be instantly soluble, so that the active substance contained in the hollow form is dosed into the washing or cleaning liquor right at the beginning of the washing or cleaning cycle. As an alternative to this, the film can be so poorly soluble that only the molded body is dissolved and the active substance contained in the hollow mold is thereby released.

Depending on this release mechanism, it is possible, for example, to produce moldings in which the active substance contained in the hollow mold is present in the cleaning liquor before the components of the hollow body are dissolved or after this has happened. On the one hand, detergent tablets are preferred, which are characterized in that the active substance contained in the space enclosed by the film and the hollow body dissolves faster than the hollow body. However, detergent tablets in which the active substance contained in the space enclosed by the film and the hollow body dissolves more slowly than the hollow body are also preferred embodiments of the present invention. As an alternative to sealing with a film, the filled hollow bodies can also be closed, at least in part, by applying a melt, solution, emulsion or dispersion of the film materials mentioned above. The at least partially occluding layer is formed from the melt, solution, emulsion or dispersion by cooling or evaporation of the solvent, ie the occluding “film” is produced on the hollow mold. This alternative can be used in particular in the case of completely filled hollow molds while only partially filled hollow forms are expediently closed in a different way, provided that a "mobility" of the content is important, for example as a special incentive to buy. In special cases, it is preferred to form a sealing layer in the form of a very thin film or skin in order to favor a possibly only temporary fixing of an otherwise movable filling; this can be, for example, preferably for leakage-free transport and / or prior to possible collapsing in a double-frame mold form of a hollow body according to the invention which is still incompletely produced in the manufacturing process after individual stations.

Of course, the hollow bodies can also be produced in such a way that they can be connected to another filled hollow body and closed in this way. Such bodies are composed of two half-shells without undercuts and have an equatorial plane. The latter does not necessarily have to be arranged in the center, but can, for example, also be in the upper or lower third, fourth, fifth, etc. This procedure is made easier if the hollow bodies have flange parts. Alternatively, the molded parts can only adhere to one another via the boundary edges of the opening surfaces.

Particularly preferred portioned agent of the invention are characterized in that the hollow mold is closed, wherein solidified melts, preferably translucent or transparent solidified melts and particularly solidified melts of isomalt ^® are preferred.

Depending on the size and number of the at least partially cast-in solid bodies and depending on the presence and size of an opening in the hollow mold, the solidified melt can have different proportions of the total surface area of the portions according to the invention.

Portioned compositions according to the invention are preferred in which the outer surface of the hollow mold accounts for at least 50%, preferably at least 60%, particularly preferably at least 70% and in particular at least 80% of the surface of the composition. The hollow mold can be produced from materials which have a function in the later application medium of the agents according to the invention. For reasons of aesthetics or product safety, however, it may also be necessary for the hollow form to contain or consist of substances which have no effect in the later application medium. Depending on this, the mass fraction which the hollow form makes up of the total mass of agents according to the invention varies. Portioned agents are preferred in which the ratio of the masses of unfilled hollow mold (including cast-in parts) and content is in the range from 10: 1 to 1: 1000, preferably from 2: 1 to 1: 100, particularly preferably from 1: 1 to 1:50 and in particular from 1: 5 to 1:25.

Depending on the desired application, the portions according to the invention can contain different detergent or cleaning agent ingredients. The various areas such as the at least partially enclosed solid (s), individual regions of the at least partially enclosed solid (s) (in the case of multiphase solid bodies), melt or individual melting regions and fillings can be used to separate incompatible ingredients.

The most important ingredients that can be contained in the portions according to the invention are described below.

The detergent or cleaning agent portions according to the invention preferably contain surfactant (s), it being possible to use anionic, nonionic, cationic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants in textile detergents, the proportion of anionic surfactants being greater than the proportion of nonionic surfactants. The total surfactant content of the detergent or cleaning agent portions is preferably below 30% by weight, based on the total agent. Nonionic surfactants have already been described above as optional plasticizers for the coating. The same substances can also be used in the portions as detergent substances, so that reference can be made to the above statements.

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

Another class of preferably used nonionic surfactants, which are 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 with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.

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

Other suitable surfactants are polyhydroxy fatty acid amides of the formula below,

R ¹

R-CO-N- [Z]

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The 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 following formula,

R ¹ -0-R ²

I

R-CO-N- [Z]

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

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

The content of non-ionic surfactants in preferred detergent or cleaning agent portions according to the invention which are suitable for textile washing is 5 to 20% by weight, preferably 7 to 15% by weight and in particular 9 to 14% by weight, in each case based on the total agent.

Low-foaming nonionic surfactants are preferably used in automatic dishwashing detergents.

Anionic, cationic and / or amphoteric surfactants can also be used in conjunction with the surfactants mentioned, these being of only minor importance because of their foaming behavior in automatic dishwashing detergents and mostly only in amounts below 10% by weight, mostly even below 5% by weight .-%, for example from 0.01 to 2.5 wt .-%, each based on the agent. In contrast, these surfactants are of significantly greater importance in detergents. The detergent or cleaning agent portions according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as the surfactant component.

The agents according to the invention can contain, for example, cationic compounds of the formulas I, II or III as cationic active substances: R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (I)

(CH ₂ ) _n -TR

R ¹

R>ι'- MN (" ⁺ ) .- (CH ₂ ) _n -CH-CH ₂ (II)

R ¹ TT

R ² R ²

R ¹

I

R ³ -N ⁽⁺⁾ - (CH ₂ ) _π -TR ² (III)

I

R ⁴

wherein each R ^{1 group is} independently selected from de-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 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.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C ₉ -C ₃ -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C ₁₂ . ₁₈ -monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration. Alkanesulfonates which are derived from C ₁₂ are also suitable. ₁₈ -alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters are also the same of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

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

The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred from a washing-technical point of view. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 mol of ethylene oxide. ₂ ι alcohols, such as 2-methyl-branched C ₉ . _ι Alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ -ι ₈ fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

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

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

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

The anionic surfactant content of preferred textile detergents according to the invention is 5 to 25% by weight, preferably 7 to 22% by weight and in particular 10 to 20% by weight, in each case based on the total composition. Cleaning agents according to the invention for machine dishwashing are preferably free from anionic surfactants.

In the context of the present invention, preferred agents additionally contain one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating agents, swelling and sliding agents and UV absorbers.

The builders that can be contained in the agents according to the invention include, in particular, phosphates, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

The use of the generally known phosphates as builder substances is possible according to the invention, provided that such use should not be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry. Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric acid H ₃ PÖ _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ P0 ₄ , exists as a dihydrate (density 1, 91 like ^"3 , melting point 60 °) and as a monohydrate (density 2.04 like ^{" 3} ). Both salts are white powders, which are very easily soluble in water, lose the water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ 0 ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O _g ) and Maddrell's salt (see below). NaH ₂ P0 _{4 is} acidic; it arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ P0 ₄ , is a white salt with a density of 2.33 ^'3 , has a melting point of 253 ° [decomposes to form potassium polyphosphate (KP0 ₃ ) J and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HP0 ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly ^"3 , water loss at 95 °), 7 mol. (Density 1, 68 gladly ^'3 , melting point 48 ° with loss of 5 H ₂ Ö) and 12 mol. Water ( Density 1, 52 like ^"3 , melting point 35 ° with loss of 5 H ₂ 0), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ 0 ₇ when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HP0 ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PÖ ₄ , are colorless crystals that like a dodecahydrate a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as a decahydrate (corresponding to 19-20% P ₂ 0 ₅ ) have a melting point of 100 ° C. and, in anhydrous form (corresponding to 39-40% P ₂ 0 ₅ ), a density of 2.536 ^{″ 3} . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or three-base potassium phosphate), K ₃ P0 ₄ , is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction Heating of Thomas slag with coal and potassium sulfate Despite the higher price in the detergent industry, the more soluble ones are therefore highly effective, potassium phosphates often preferred over corresponding sodium compounds.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ 0 ₇ , exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1, 836 like ^{" 3} , melting point 94 ° with water loss). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ 0 ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ 0 ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33, preferably ³ , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ P0 ₄ or the KH ₂ P0 ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (0) (ONa) -0] _n that crystallizes with 6 H ₂ 0 -Na with n = 3. About 17 g of the salt of water free of water of crystallization dissolve in 100 g of water at room temperature, about 20 g at 60 ° and around 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (> 23% P ₂ 0 ₅ , 25% K ₂ 0). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaP0 ₃ ) ₃ + 2 KOH -> Na ₃ K ₂ P ₃ O ₁₀ + H ₂ 0 According to the invention, these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O ^ _* , H ₂ 0, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ 0 ₅ yH ₂ 0 are preferred.

Amorphous sodium silicates with a module Na ₂ 0: Si0 ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula nNa _z O ^• (1-n) K ₂ 0 'AI ₂ Ö ₃ ^■ (2 - 2.5) Si0 ₂ ^■ (3.5 - 5.5) H ₂ 0

can be described. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production. In the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C 5 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Other important builders are in particular the carbonates, citrates and silicates. Trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicates and / or metasilicates are preferably used.

Alkali carriers can be present as further constituents. Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the abovementioned substances are considered to be alkali carriers, alkali metal carbonates, in particular sodium carbonate, in particular sodium bicarbonate or sodium sesquicarbonate being used for the purposes of this invention.

A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred.

A builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.

In addition, other ingredients may be present, washing, rinsing or cleaning agents according to the invention being preferred which additionally contain one or more substances from the group of the acidifying agents, chelate complexing agents or the deposit-inhibiting polymers.

Both inorganic acids and organic acids are suitable as acidifiers, provided that these are compatible with the other ingredients. The solid mono-, oligo- and polycarboxylic acids can be used in particular for reasons of consumer protection and handling safety. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. The anhydrides of these acids can also be used as acidifying agents, in particular maleic anhydride and succinic anhydride are commercially available. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).

Another possible group of ingredients are the chelating agents. Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination point on a central atom, i. H. is at least "bidentate". In this case, normally elongated compounds are closed to form rings by complex formation via an ion. The number of ligands bound depends on the coordination number of the central ion.

Common chelate complexing agents preferred in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Complex-forming polymers, that is to say polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and generally react with suitable metal atoms to form chelate complexes, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or can belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.

Complexing groups (ligands) of conventional complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3-dicarbonyl - And crown ether residues with z. T. very specific Activities against ions of different metals. The base polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities by polymer-analogous conversions.

In the context of the present invention, particular preference is given to detergent or cleaning agent portions which contain one or more chelate complexing agents from the groups of

(i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, (ii) nitrogen-containing mono- or polycarboxylic acids,

(iii) geminal diphosphonic acids,

(iv) aminophosphonic acids,

(v) phosphonopolycarboxylic acids,

(vi) cyclodextrins

in amounts above 0.1% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight, in each case based on the weight of the By means of, included.

All complexing agents of the prior art can be used in the context of the present invention. These can belong to different chemical groups. The following are preferably used individually or in a mixture:

a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid, b) nitrogen-containing mono- or polycarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 3-nitridodiacetic acid, nitridodiacetic acid , N-di- (β-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA), c) geminal diphosphonic acids such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), their higher homologues with up to 8 carbon atoms and derivatives thereof containing hydroxyl or amino groups, and 1-aminoethane-1, 1-diphosphonic acid, their higher homologues with up to 8 carbon atoms as well as derivatives thereof containing hydroxyl or amino groups, d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methy lenphosphonic acid) or nitrilotri (methylenephosphonic acid), e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1, 2,4-tricarboxylic acid and f) cyclodextrins.

In the context of this patent application, polycarboxylic acids a) are understood to mean carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl groups and the hydroxyl groups contained in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. At the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali, ammonium or alkylammonium salts, in particular sodium salts, are preferred. Deposit-inhibiting polymers can also be contained in the agents according to the invention. These substances, which can have different chemical structures, originate, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, polymers with molecular weights below 15,000 daltons being preferred.

Deposit-inhibiting polymers can also have cobuilder properties. Organic cobuilders which can be used in the dishwasher detergents according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

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

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

Polymeric polycarboxylates are also suitable as builders or scale inhibitors; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

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

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 500 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1000 to 4000 g / mol, can in turn be preferred from this group.

Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention. The copolymers containing sulfonic acid groups are described in detail below.

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

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

Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers , Further preferred copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred which, in addition to cobuilder properties, also have a bleach-stabilizing effect.

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

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

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders. Ethylenediamine-N, N ^'- disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). As Aminoalkane phosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition to the substances from the classes of substances mentioned, the agents according to the invention can contain further usual ingredients of detergents, dishwashing detergents or cleaning agents, bleaching agents, bleach activators, enzymes, silver protection agents, colorants and fragrances being particularly important. These substances are described below.

Among the compounds which serve as bleaching agents and supply H ₂ 0 ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ 0 ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the detergent tablets. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU) are preferred , N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, especially triacetin, and triacetin diacetoxy-2,5-dihydrofuran.

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

Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxireductases can also be used to bleach or inhibit the transfer of color. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.12 to about 2% by weight.

Detergent portions according to the invention for machine dishwashing can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents in particular being particularly important in the area of machine dishwashing. The known substances of the prior art can be used. Generally can especially silver protection agents selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the transition metal salts or complexes are used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

A wide number of different salts can be used as electrolytes from the group of inorganic salts. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl ₂ in the agents according to the invention is preferred. The proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.

In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or bases can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 5% by weight of the total formulation.

Foam inhibitors that can be used in the agents according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials. Suitable anti-deposition agents, which are also made up according to the invention and are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether and the polymers of phthalic acid and / or terephthalic acid or their derivatives, in particular polymers, known from the prior art Ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of the phthalic acid and terephthalic acid polymers are particularly preferred.

Optical brighteners (so-called "whiteners") can be added to the agents according to the invention made up as textile detergents in order to eliminate graying and yellowing of the treated textiles. These substances absorb onto the fiber and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible light of longer wavelength converter, wherein the absorbed from sunlight ultraviolet light is radiated as pale bluish fluorescence and produces the yellow shade of the grayed or yellowed laundry pure white. Suitable compounds originate for example from the substance classes of the 4,4 ^'diamino-2,2 ^'- stilbenedisulfonic (flavonic), ^{4,4'-biphenylene} -Distyryl, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole, benzisoxazole, and benzimidazole systems, and pyrene derivatives substituted by heterocycles the op. Table brighteners are usually used in amounts between 0.05 and 0.3% by weight, based on the finished agent.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used in amounts of 0.1 to 5% by weight, based on the composition

The agents according to the invention can also be provided with further additional benefits. For example, for agents made up according to the invention as textile detergents, there are color-transfer-inhibiting compositions, agents with “anti-gray formula”, agents with ironing relief, agents with special fragrance release, agents with improved dirt detachment or prevention of re-soiling, antibacterial agents, UV protection agents, color-refreshing agents etc. Some examples are explained below: Since textile fabrics, in particular made from rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers prevent bending and kinking. If pressing and squeezing across the grain are sensitive, the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

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

Suitable antimicrobial agents are preferably selected from the groups of alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazolines , Phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1, 2-dibromo-2,4-dicyanobutane, iodo-2-propyl-butyl-carbamate, iodine, iodophores, peroxo compounds, halogen compounds and any mixtures of the above.

The antimicrobial active ingredient can be selected from ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholine- acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylene-bis- (6-bromo-4-chlorophenol), 4,4'-dichloro-2'-hydroxydiphenyl ether (dichlosan), 2.4 , 4'-trichloro-2'-hydroxydiphenyl ether (trichlosan), chlorhexidine, N- (4-chlorophenyl) - N- (3,4-dichlorophenyl) urea, N, N '- (1.10-decane-diyldi-1- pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4-chlorophenyl) -3,12-diimino-2,4,11, 13-tetraaza-tetradecanediimidamide, glucoprotamines, antimicrobial surface-active quaternary compounds, guanidines including the bi- and polyguanidines, such as 1,6-bis- (2-ethylhexyl-biguanido-hexane) dihydrochloride, 1,6-di- (N ₁ , N ₁ '-phenyldiguanido- N ₅ , N ₅ ') -hexane-tetrahydochloride, 1, 6-di- (N ₁ , N ₁ ' - phenyl-N ^ N methyldiguanido-Ns .Ns'Hiexan-dihydrochloride, l ^ -OHN ^ N ^ -o-chlorophenyldiguanido- N ₅ , N ₅ ') -hexane-dihydrochloride, 1, 6-di- (Nι, N ₁ ' -2,6-dichlorophenyldiguanido- N ₅ , N ₅ ') hexane dihydrochloride, 1, 6-di- [N ₁ , Nι'-beta- (p-methoxyphenyl) diguanido-N ₅ , N ₅ '] hexane dihydrochloride, 1, 6-di - (N ₁ , N ₁ '-alpha-methyl-.beta.-phenyldiguanido-N ₅ , N ₅ ') -hexane-dihydrochloride, 1, 6-di- (N ₁ , N ₁ '-p-nitrophenyldiguanido-N ₅ , N ₅ ') hexane dihydrochloride, omega: omega-di- (

phenyldiguanido-N ₅ , N ₅ ') -di-n-propylether-dihydrochloride, omegaOmega'-DHNi.Ni'-p-chlorophenyldiguanido-N ₅ , N ₅ ') -di-n-propylether-tetrahydrochloride, I

dichlorophenyldiguanido-N ₅ , N ₅ ') hexane-tetrahydrochloride, l .δ-Di ^ N _L N-i'-p-methylphenyldiguanido-N ₅ , N ₅ ') hexane-dihydrochloride, l .ö-DKN ^ N ^ Aδ -trichlorophenyldiguanido-Ns.N ^ hexanetrahydrochloride, 1, 6-Di- [N ₁ , Nι'-alpha- (p-chlorophenyl) ethyldiguanido-N ₅ , N ₅ '] hexanedihydrochloride, omegaOmega-D NLN ^ - p-chlorophenyldiguanido-Ns.Ns'Jm-xylene-dihydrochloride, l. ^ - DKNi.Ni'-p-chlorophenyldiguanido-Ns.Ns ') dodecane-dihydrochloride, 1, 10-Di- (N ₁ , N ₁ ' - phenyldiguanido-N ₅ , N ₅ ') -decane-tetrahydrochloride, l. ^ - DK _L N ^ -phenyldiguanido-N ₅ , N ₅ ') dodecane-tetrahydrochloride, 1, 6-di- (N ₁ , N ₁ '- o-chlorophenyldiguanido-N ₅ , N ₅ ') hexane-dihydrochloride, 1,6-di- (N ₁ , N ₁ ' -o-chlorophenyldiguanido-N ₅ , N ₅ ') hexane-tetrahydrochloride, ethylene-bis- (1 -tolyl biguanide), ethylene bis (p-tolyl biguanide), ethylene bis (3,5-dimethylphenyl biguanide), ethylene bis (p-tert-amylphenyl biguanide), ethylene bis (nonylphenyl biguanide), ethylene bis- (phenylbiguanid), ethylene-bis- (N-butylphenylbiguanid) , Ethylene bis (2,5-diethoxyphenyl biguanide), ethylene bis (2,4-dimethylphenyl biguanide), ethylene bis (o-diphenyl biguanide), ethylene bis (mixed amyl naphthyl biguanide), N-butyl ethylene bis- (phenyl biguanide), trimethylene bis (o-tolyl biguanide), N-butyl trimethyl bis (phenyl biguanide) and the corresponding salts such as acetates, gluconates, hydrochlorides, hydrobromides, citrates, bisulfites, fluorides, polymaleates, N-cocoalkyl sarcosinates, phosphites , Hypophosphites, perfluorooctanoates, silicates, sorbates, salicylates, maleates, tartrates, fumarates, ethylenediaminetetraacetates, iminodiacetates, cinnamates, thiocyanates, arginates, pyromellitates, tetracarboxybutyrates, benzoates, glutarates, perofluorophosphate, and mixtures of any of these. Halogenated xylene and cresol derivatives, such as p-chlorometacresol or p-chloro-meta-xylene, and natural antimicrobial active ingredients of vegetable origin (for example from spices or herbs), animal and microbial origin are also suitable. Preferably antimicrobial surface-active quaternary compounds, a natural antimicrobial active ingredient of plant origin and / or a natural antimicrobial active ingredient of animal origin, most preferably at least one natural antimicrobial active ingredient of plant origin from the group comprising caffeine, theobromine and theophylline and essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial active ingredient of animal origin from the group comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound with an ammonium, sulfonium, phosphonium, iodonium - Or arsonium group, peroxo compounds and chlorine compounds are used. Substances of microbial origin, so-called bacteriocins, can also be used.

The quaternary ammonium compounds (QAV) suitable as antimicrobial active ingredients have the general formula (R ¹ ) (R ² ) (R ³ ) (R ⁴ ) N ⁺ X ^" , in which R ¹ to R ^{4 are} identical or different C C ₂₂ alkyl residues, C ₇ -C ₂₈ aralkyl residues or heterocyclic residues, where two or, in the case of an aromatic integration, as in pyridine, even three residues together with the nitrogen atom form the heterocycle, for example a pyridinium or imidazolinium compound, and X ^" Halide ions, sulfate ions, hydroxide ions or similar anions For optimum antimicrobial activity, at least one of the radicals preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.

QAV are by reacting tertiary amines with alkylating agents such as Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide can be produced. The alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly easy, and the quaternization of tertiary amines with two long radicals and one methyl group can also be carried out with the aid of methyl chloride under mild conditions. Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are not very reactive and are preferably quaternized with dimethyl sulfate.

Suitable QAV are, for example, benzalkonium chloride (N-alkyl-N, N-dimethyl-benzyl-ammonium chloride, CAS No. 8001-54-5), benzalkon B (m, p-dichlorobenzyl-dimethyl-C12-alkylammonium chloride, CAS No. 58390-78-6), benzoxonium chloride (benzyl-dodecyl-bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No. 57 -09-0), benzetonium chloride (N, N-dimethyl-N- [2- [2- [p- (1, 1, 3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54-0), dialkyldimethylammonium chloride such as di-n-decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3 ), Dioctyl-dimethyl-ammoniumchloric, 1-cetylpyridinium chloride (CAS No. 123-03-5) and thiazoline iodide (CAS No. 15764-48-1) and their mixtures. Particularly preferred QAV are the benzalkonium chlorides with C ₈ -C _1B- alkyl radicals, in particular C ₁₂ -C ₁₄ -alkyl-benzyl-dimethyl-ammonium chloride.

Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ^® ex Lonza, Marquat® ^® ex Mason, Variquat ^® ex Witco / Sherex and Hyamine ^® ex Lonza and as Bardac ^® ex Lonza. Other commercially obtainable antimicrobial agents are N- (3-chloroallyl) hexaminium chloride such as Dowicide and Dowicil ^® ^® ex Dow, benzethonium chloride such as Hyamine ^® 1622 ex Rohm & Haas, methylbenzethonium as Hyamine ^® 10X ex Rohm & Haas, cetylpyridinium chloride such as Cepacol ex Merrell Labs ,

The antimicrobial active ingredients are preferably used in amounts of from 0.0001% by weight to 1% by weight, preferably from 0.001% by weight to 0.8% by weight, particularly preferably from 0.005% by weight to 0.3 % By weight and in particular from 0.01 to 0.2% by weight. In order to prevent undesirable changes in the agents and / or the treated textiles caused by the action of oxygen and other oxidative processes, the agents can contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

An increased wearing comfort can result from the additional use of antstatics, which are additionally added to the agents according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable as antistatic agents for textiles or as an additive to detergents, with an additional softening effect.

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

Finally, the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are also suitable. Another object of the present invention is a process for the production of portioned agents, in particular washing or cleaning agents, comprising the steps:

i) production of at least one solid, preferably by tableting and / or casting and / or extrusion and / or injection molding and / or blow molding and / or encapsulation and / or film sealing and / or deep drawing; ii) Production of a hollow shell by solidification under at least partial

Inclusion of the solid body produced in step i).

The hollow molds produced according to the invention can optionally be filled and sealed. Methods according to the invention are preferred here, in which the following steps are carried out after step ii):

iii) filling the hollow shell with at least one agent, preferably with at least one washing or cleaning agent; iv) closing the hollow shell to form an at least partially closed hollow mold v) optionally repeating steps iii) and iv).

As mentioned at the beginning, hollow shells can also be produced which do not contain any solids. If these hollow shells are filled and sealed with a solidifying melt which at least partially encloses at least one shaped body, hollow shapes according to the invention are also obtained which at least partially enclose at least one solid body in their walls.

Another object of the present invention is therefore a method for producing portioned agents, in particular washing or cleaning agents, which comprises the steps:

i) production of at least one solid, preferably by tableting and / or casting and / or extrusion and / or injection molding and / or blow molding and / or encapsulation and / or film sealing and / or deep drawing; ii) Provision of a (filled) hollow shell and closing of this hollow shell

Pour over with at least one melt and solidify with at least partially including the solid body produced in step i). It has already been stated above that the two method variants according to the invention can be combined with one another. In this way, agents according to the invention are obtained which at least partially enclose at least two solid bodies in the wall of the hollow mold. Of course, with these agents, both the two wall materials and the at least two solid bodies can have the same or different compositions. Variants of the last-mentioned method which are preferred according to the invention are therefore characterized in that the or, when repeated in step (v), comprises at least one step iv) the sealing of the hollow shell by pouring over at least one melt and solidification with at least partial inclusion of a further solid.

As already mentioned above, the hollow molds can be provided with at least one solid body which is at least partially cast in and / or the filled and closed hollow molds can be additionally provided with a coating with at least one solid body which is at least partially cast in. Methods according to the invention are preferred here, in which a coating layer is applied to the portioned agent following the closing of the hollow shell.

Completely analogous to the above statements regarding the agents according to the invention, methods according to the invention are also preferred in which the hollow shell produced or provided in step ii) has wall thicknesses of 100 to 6000 μm, preferably 120 to 4000 μm, particularly preferably 150 to 3000 μm and in particular from 200 to 2500 μm, wall thicknesses below 2000 μm being preferred.

The hollow shell or shape in step ii) can be produced using different techniques. In the simplest case, a flowable mixture is poured into an appropriate mold, left to harden there and then removed from the mold. A disadvantage here is the design of the shape, since the desired wall thicknesses of the hollow bodies formed do not allow complicated geometries to be filled quickly.

Alternatively, the solidifying mixture can be filled into a mold that is designed only as a cavity. If you let the mixture solidify there, you would get a compact body, not a hollow shell. Appropriate process management and selection of the materials (on the one hand the melts, on the other hand the die form), for example with regard to their heat capacity and conductivity, can ensure that the mixture first solidifies on the wall of the mold. If you turn the mold over after a certain time t, the excess mixture flows off and leaves a lining of the mold, which itself is one Represents hollow shell that can be removed from the mold after complete solidification. As already mentioned, the filling can also take place before demolding; filling during the solidification process is also possible.

Preferred embodiments of the present invention are therefore methods in which an open die form is filled with the flowable shell material in step ii) and the excess mass is emptied after a time t between 0 and 5 minutes.

As an alternative to completely filling the mold and pouring excess mixture, the mold can only be partially filled. In these cases, the mixture is pressed with a suitable stamp against the wall of the die, where it solidifies to form a hollow body. This process variant represents a kind of intermediate form between the "pouring technique" and the casting technique in negative forms of the hollow body. Corresponding processes in which in step ii) an open die mold is filled with the flowable shell material and the material is pressed onto the walls by an optionally cooled stamp The mold is thus also preferred, and a hollow mold is thus produced. A particularly advantageous feature of this method, which is also referred to as the “cold stamp method”, is the possibility of producing large quantities with a precisely defined wall thickness of the hollow body. In addition, the process is largely insensitive to fluctuating flow properties and can also be used with higher-viscosity mixtures.

The methods described above are particularly suitable for producing hollow bodies which have a shape without undercuts, i.e. have the shape of a "shell", i.e. an opening area which corresponds to the largest horizontal cross-sectional area. These "shells" can be filled and optionally closed.

With regard to the shape of the shells, the person skilled in the art has no limits in the selection. All hollow bodies can be produced, from the hemisphere to square ("cardboard-like") shells to complicated structures with a pronounced surface structure (e.g. in the form of nut shells or animal shapes).

However, according to the invention it is also possible to produce hollow bodies which have only a small opening and later to fill the resulting hollow shape through this small “bunghole”. Corresponding processes are usually carried out on an industrial scale with closable double shapes which are sufficient for wall lining in the desired thickness A lot of solidifying mixture is filled and moved in all spatial directions, and all shapes are possible, from spheres to egg shapes to complicated hollow structures such as animal shapes, company logos, etc. Another preferred one An embodiment of the present invention therefore provides a method in which in step ii) a closable double mold is filled with the later solidifying mass and is moved for a time t between 0 and 5 minutes.

The hollow shells or hollow molds can also be produced with multilayer walls by applying a further melt (which preferably has a different composition from the first melt) to the first wall following the first filling of the molding tools and the removal of the melt which has not yet solidified , The process steps described above are therefore repeated again, which can also be carried out several times in order to produce three-, four-, five-, six- or multi-layer walls.

In the context of the present invention, preferred variants of the processes described above are characterized in that a multi-layer hollow shell is produced by repeating the process step with a differently composed melt.

As already mentioned, another hollow mold can also be used to close the hollow mold. Methods according to the invention are preferred here in which the hollow mold has flange parts and is closed in step iv) by a positive connection and / or non-positive connection and / or adhesive bonding and / or welding with a further hollow mold.

A complete manufacturing process is explained below by way of example. In a first preliminary stage, the molded shell material is melted in a storage container and tempered to the required casting temperature, which can optionally be pre-crystallized. The melt is then fed to the dosing stations via heated and / or insulated line systems; in parallel, the individual molds are preheated or cooled to the desired temperature.

The liquid melt is metered into the mold troughs in a casting machine, these being filled up to the upper die edge. As a rule, several identical molds run past the casting machine and are filled. After leaving the casting machine (or moving past the dosing head), the filled molds are either fed to a cooling section or moved or "parked" until the melt begins to solidify from the outside. This is essential for the later wall thickness of the molded shell to be formed among other things, the substance-dependent cooling time. After the specified time has elapsed, the mold is turned from top to bottom or turned upside down, so that the not yet solidified and excess melt mass runs out of the mold into a ready-made collection reservoir for recycling into the process. Depending on the material system, and in particular in the case of slowly solidifying melts, no completely solidified shell is yet formed at the time of emptying, so that mainly the adhesion to the casting mold ensures that the melt mass remains in the mold. The adhesive shell formation can be supported by an eccentric movement of the mold, the centrifugal forces evenly transporting the still flowing melt to the mold surface and ensuring the formation of a shell with a uniform wall thickness. Degassing the melt by vibrating the mold may also be necessary.

Depending on where the at least partially cast-in solid (s) should be located, the corresponding solid is placed in the unfilled form before filling with melt (solid later visible from the outside) or later on the inside of the wall placed in the not yet hardened melt (later only translucent or visible with a transparent melt).

After this, the formation of the shell can be completed by cooling. Shell remnants protruding over the edge of the casting mold can be cut off, whereby knives or thermal rollers can be used.

The formed shell is then filled and the filling is later cooled, if necessary. Depending on the desired type of sealing, the mold is filled completely or only partially. To seal the mold, a sealing barrier layer can be applied (especially in the case of liquid fillings), which consists of a substance which has a lower melting point than the shell material and can be sprayed well. The mold can then be firmly closed by filling the mold shell provided with the filling with the melt for the shell material. The mold can be vibrated again during the solidification time for uniform lid formation and for the necessary degassing. The solidification to the finished molded body can also be promoted here by passing through a cooling section.

Finally, the moldings are removed from the mold in a mold emptying station. For this purpose, the mold is turned from top to bottom so that the molded body formed can fall down onto a conveyor belt or be put down. This demolding step can be supported by twisting / twisting the mold and / or by striking the back and / or by demolding / cleaning stamp. As already mentioned, the moldings produced according to the invention can be produced in any shape and size and combine a high aesthetic appeal with great technical flexibility and the possibility of realizing various product advantages such as, for example, controlled-release concepts.

Some of the agents according to the invention are shown in the figures. Show:

1 shows a hollow mold (half-shell) made of solidified urea melt, in which a tablet was poured. The hollow mold with cast-in tablet was then filled with two particulate compositions (extrudate and powder in two different colors red and blue) and another (transparent) isomalt melt was poured over it. Another tablet was incorporated into the transparent melt for optical enhancement.

Figure 2 shows an agent analogous to Figure 1, wherein a liquid-filled gelatin capsule was inserted into the transparent melt.

The agents according to the invention are particularly suitable as washing or cleaning agents. Another object of the present invention is therefore the use of the agents according to the invention as washing or cleaning agents. Methods for washing textiles in a household washing machine are particularly preferred here, in which one or more portioned agents according to the invention are introduced into the washing-up chamber of the washing machine and a washing program is run.

Drum dosing is of course also possible. Methods according to the invention for washing textiles in a household washing machine are preferred here, in which one or more portioned agents according to the invention are introduced into the drum of the washing machine and a washing program is run.

The portions according to the invention are also suitable for cleaning dishes in household dishwashers. Methods according to the invention for cleaning dishes in a domestic dishwasher are preferred here, in which one or more portioned agents according to the invention are introduced into the dishwasher and a cleaning program is run.

Claims

claims:

1. Portioned composition comprising a hollow mold made of at least one solidified melt and at least one further solid, characterized in that the at least one further solid is at least partially cast into the wall of the hollow mold.

2. Portioned agent according to claim 1, characterized in that the hollow mold consists of at least one material or material mixture whose melting point is in the range from 40 to 1000 ° C, preferably from 42.5 to 500 ° C, particularly preferably from 45 to 200 ° C and in particular from 50 to 160 ° C.

3. Portioned agent according to one of claims 1 or 2, characterized in that the material of the hollow form one or more substances from the groups of carboxylic acids, carboxylic anhydrides, dicarboxylic acids, dicarboxylic anhydrides, hydrogen carbonates, hydrogen sulfates, polyethylene glycols, polypropylene glycols, sodium acetate trihydrate and / or urea in amounts of at least 40% by weight, preferably at least 60% by weight and in particular at least 80% by weight, in each case based on the weight of the hollow mold.

4. portioned agent according to one of claims 1 to 3, characterized in that the material of the hollow form one or more substances from the group of sugars and / or sugar acids and / or sugar alcohols, preferably from the group of sugars, particularly preferably from the group the oligosaccharides, oligosaccharide derivatives, monosaccharides, disaccharides, monosaccharide derivatives and disaccharide derivatives and mixtures thereof, in particular from the group consisting of glucose and / or fructose and / or ribose and / or maltose and / or lactose and / or sucrose and / or maltodextrin and / or isomalt ^® includes.

5. Portioned agent according to one of claims 1 to 4, characterized in that the hollow shape has wall thicknesses of 100 to 6000 microns, preferably from 500 to 5000 microns and in particular from 1000 to 4000 microns.

6. Portioned agent according to one of claims 1 to 5, characterized in that the at least one further solid is a tablet and / or a casting and / or an extruded part and / or an injection molded part and / or a gelatin capsule and / or a blow molded part and / or is a pouch and / or a deep-drawn part.

7. portioned agent according to one of claims 1 to 6, characterized in that the at least one further solid is a hollow body which is filled with a liquid or flowable composition.

8. Portioned agent according to one of claims 1 to 7, characterized in that the hollow form additionally contains a further preparation, preferably a particulate preparation and in particular a particulate detergent or cleaning composition.

Portioned 9. Composition according to one of claims 1 to 8, characterized in that the hollow mold is closed, wherein solidified melts, preferably translucent or transparent solidified melts and particularly solidified melts of isomalt ^® are preferred.

10. Portioned agent according to one of claims 1 to 9, characterized in that the outer surface of the hollow mold accounts for at least 50%, preferably at least 60%, particularly preferably at least 70% and in particular at least 80% of the surface of the agent.

11. Portioned agent according to one of claims 1 to 10, characterized in that the ratio of the masses of unfilled hollow mold (including cast parts) and content in the range from 10: 1 to 1: 1000, preferably from 2: 1 to 1: 100 , particularly preferably from 1: 1 to 1:50 and in particular from 1: 5 to 1:25.

12. A process for the production of portioned agents, in particular washing or cleaning agents, comprising the steps:

Inclusion of the solid body produced in step i).

13. A method for producing portioned agents, in particular washing or cleaning agents, comprising the steps: iii) production of at least one solid, preferably by tableting and / or casting and / or extrusion and / or injection molding and / or blow molding and / or encapsulation and / or film sealing and / or deep drawing; iv) Providing a (filled) hollow shell and closing this hollow shell

Pour over with at least one melt and solidify with at least partially including the solid body produced in step i).

14. The method according to claim 12, characterized in that the following steps are carried out after step ii):

iii) filling the hollow shell with at least one agent, preferably with at least one washing or cleaning agent; iv) closing the hollow shell to form an at least partially closed hollow shape, v) optionally repeating steps iii) and iv).

15. The method according to claim 14, characterized in that the or at repetition according to step (v) comprises at least one step iv) the closing of the hollow shell by pouring with at least one melt and solidification with at least partially including another solid.

16. The method according to any one of claims 12 to 15, characterized in that subsequent to one or more of the process steps i) and / or ii) and / or iii) and / or iv) and / or v) a coating layer on the process product of the respective step is applied.

17. Vaa 12 to 16, characterized in that a coating layer is applied to the portioned agent following the closing of the hollow shell.

18. The method according to any one of claims 12 to 16, characterized in that the hollow shell produced or provided in step ii) wall thicknesses of 100 to 6000 microns, preferably from 120 to 4000 microns, particularly preferably from 150 to 3000 microns and in particular from 200 to 2500 microns, with wall thicknesses below 2000 microns are preferred.

19. The method according to any one of claims 12 or 14 to 18, characterized in that in step ii) an open die form is filled with the flowable shell material and the excess mass is emptied after a time t between 0 and 5 minutes.

20. The method according to any one of claims 12 or 14 to 18, characterized in that in step ii) an open die mold is filled with the flowable shell material and the material is pressed against the walls of the mold by an optionally cooled stamp, thus producing a hollow mold becomes.

21. The method according to any one of claims 12 or 14 to 18, characterized in that in step i) a closable double mold is filled with the later solidifying mass and is moved for a time t between 0 and 5 minutes.

22. The method according to any one of claims 19 to 21, characterized in that a multilayer hollow shell is produced by repeating the process step with a differently composed melt.

23. The method according to any one of claims 12 to 19, characterized in that the hollow form has flange parts and is closed in step iv) by a positive fit and / or non-positive fit and / or adhesive bonding and / or welding with a further hollow form.

24. A method for washing textiles in a household washing machine, characterized in that one or more portioned agents according to one or more of claims 1 to 11 are introduced into the washing-in chamber of the washing machine and a washing program is run.

25. A method for washing textiles in a household washing machine, characterized in that one or more portioned agents according to one or more of claims 1 to 11 are introduced into the drum of the washing machine and a washing program is run.

26. A method for cleaning dishes in a household dishwasher, characterized in that one or more portioned agents according to one or more of claims 1 to 11 are introduced into the dishwasher and a cleaning program is run.