DE10253214A1 - Portioned agents with different ingredients - Google Patents

Abstract

Portioned agents, which on the one hand have the advantages of castings, on the other hand enable the aesthetic stimuli of the color and shape design of polymer packaging and thus cause a high level of consumer acceptance, comprise a hollow mold made from at least one solidified melt and at least one further solid, the at least one further solid is at least partially cast into the wall of the hollow mold.

Description

The present invention relates to portioned agents, which consist of different ingredients exist as well as processes for the production of such portioned agents. The agents according to the invention can for example in the food, animal feed, cosmetics, crop protection or construction industries are used, a particularly preferred area of application for the agents according to the invention that is the detergent or cleaning agent.

Portioned washing and cleaning agents are widely described in the prior art and enjoy Consumers are becoming increasingly popular due to the simple dosage. The portioning can be done for example by transfer to achieve a compact shape or by separate packaging. in the the former case, the tableting has an outstanding role, in the latter case, predominantly in the field of detergents or cleaning agents Portions used by packaging made from water-soluble Materials are surrounded.

Tableted washing and cleaning agents have opposite powdery a number of advantages: they are easier to dose and to handle and have advantages due to their compact structure Storage and transportation. In the patent literature too, washing and detergent tablets therefore extensively described. A problem that arises when using washing and cleaning active moldings occurs again and again, is the slow decay and dissolution rate the molded body under conditions of use. Since sufficiently stable, i.e. Shape- and break-resistant moldings only by relatively high compressive pressures can be made there is a strong compression of the molded parts and a consequent delayed Disintegration of the molded body in the aqueous fleet and thus too slow a release of the active substances in the washing or cleaning process. Has delayed disintegration of the molded body furthermore the disadvantage that many detergent tablets do not have the induction bowl Have it washed in by household washing machines as the tablets does not disintegrate into secondary particles that are small in a sufficiently rapid time are enough to get out of the induction bowl washed into the washing drum to become.

This dichotomy between hardness (i.e. Manageability) and disintegration play with packaged detergent or cleaning agent portions only a subordinate role. Rather, phenomena like here occur the solubility or Disintegration of packaging in the foreground, while that packaged detergents or cleaning agents with their physical Properties only play a role if a tablet has been packed.

In the more recent patent literature in particular packaging made from water-soluble polymers, which by injection molding, Thermoforming or blow molding. Have these servings the disadvantage that they dissolve poorly or too slowly under conditions of use because the water-soluble polymers first swell and a layer of swollen polymer on the contents leave behind, which is the further resolution the active substances hindered.

Löslichkeitsvorteile are more fluid when used Detergent or cleaning agent to be expected - exist with this offer form however disadvantages in handling such as spills, Stick to the measuring cup or bottleneck or a leak when dosing directly into the drum. Portioned liquid detergents or liquid Cleaning agents require a great deal of technical effort the manufacture and own because of the unstable bags and thus connected space or Leakage problems are only marginally accepted by consumers. moreover is a big part the manufacturing costs due to the elaborate packaging, so that the Consumer for the same amount of product pays more without an increase in performance get - the portioned dosing must of are virtually "bought" for him.

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. The 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 purgative Preparation;
• (b) at least one at least one preparation according to (a) in its entirety or partially surrounding enclosure from under washing, cleaning or rinsing conditions disintegrable, the hollow body (s) dimensional stability lending, not pressed Material; and
• (c) optionally one or more devices) for compartmentalization of the dimensionally stable hollow body (s).

In this context, the DE 100 58 647 A1 a manufacturing process for portioned Detergent or cleaning agent in which an open hollow mold is produced by solidification, then filled with detergent or cleaning agent and then optionally closed.

The present invention was the Task based on developing the approaches described above. Portioned funds should be provided, which on the one hand have the advantages of castings, on the other hand, the aesthetic Enable stimuli in the color and shape design of polymer packaging and thus cause a high level of consumer acceptance. Next to it Possibilities of Material separation incompatible can be realized without to have to produce complex multi-chamber systems.

It has now been found that solids in the wall of hollow bodies let it work from solidified melts and be easily soluble, aesthetically highly responsive bodies deep.

Object of the present invention is in a first embodiment a portioned agent comprising a hollow form of at least a solidified melt and at least one further solid, wherein the at least one further solid at least partially is cast into the wall of the hollow mold.

Within the scope of the present invention the term "hollow shape" denotes at least one enclosing a room Form, whereby the enclosed space can be filled or can be. In addition to the at least one enclosed space, the hollow shape have other enclosed spaces and / or incompletely enclosed spaces. The hollow shape must be in Framework of the present invention, not from a uniform Wall material exist, but can also be several different Materials.

The inclusion of at least one solid in the wall of the hollow mold is possible, for example, by using a hollow shell is produced from a solidified melt, which at least a solid at least partially encloses. This hollow shell can then filled and sealed, for example, by a differently composed melt become. The two solidified melts together form the hollow shape of the agents according to the invention.

Analogously, at least one solid can also are at least partially incorporated into the melt closes the hollow shell from solidified melt. Again form the hollow shell solidified melt and the solidified melt that forms the "lid" together the hollow form of the agent according to the invention. In this embodiment can the hollow shell at least partially a solid enclose (then contains the hollow form at least two solids), but it can also be completely free of a solid be because of the sealing melt at least partially enclosed solid bodies is at least according to the invention partly cast into the wall of the hollow mold.

The portioned agents according to the invention comprise a hollow shape. This can be a hollow shell, for example, which serve to hold further active substance and, if necessary, closed can be. But it is also possible (see above) to produce a hollow shell without inclusion of solid and at least one solid into a cavity that closes the mold at least partially embed the solidifying melt. In the Wall of this hollow form is at least one other solid at least partially cast in. "Solid" means in Within the scope of the present invention that the body or bodies at the melting temperature of the melt itself does not melt and itself also do not dissolve in the melt. When processing into the portioned compositions according to the invention therefore before cooling Melt as a flowable mass as well as solids. Place after cooling the melt the solids still represent discrete areas of the cavity wall, the entire Hollow shape is naturally firm.

All come as solid bodies to be cast Solids or solids not considered at the processing temperature of the melt melt and do not dissolve in the melt. As a solid can just a body be cast in at least partially, but it is also possible to pour in several solid bodies, for example many individual granulate, extrudate or powder particles. More details see below for this.

Below is related with portioned agents, often from detergent or cleaning agent portions spoken; this does not limit the subject matter of the present invention, but is for illustration only a particularly preferred application of portioned according to the invention Medium.

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. Melt from Sub Punch mixtures can be of advantage, for example, when eutectic mixtures are formed which melt significantly lower and thus lower the process costs.

Preferred portioned according to the invention Means are characterized in that the hollow shape consists of at least consists of a material or mixture of materials whose melting point 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 preferably has the Melt high water solubility on, for example, above 100 g / l, with solubilities above 200 g / l in distilled water at 20 ° C. is particularly preferred are.

Such substances come from a wide variety Groups of substances. Within the scope of the present invention such melts are particularly suitable as material for the hollow mold proven that from the groups of carboxylic acids, carboxylic anhydrides, dicarboxylic acids, dicarboxylic Hydrogen carbonates, hydrogen sulfates, polyethylene glycols, polypropylene glycols Sodium acetate trihydrate and / or urea. Here are portioned according to the invention Means particularly preferred in which the material of the hollow mold one or more substances from the groups of carboxylic acids, carboxylic anhydrides, dicarboxylic acids, dicarboxylic 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 84% by weight, in each case based on the weight of the 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 can mix with them also the corresponding anhydrides are used, which in particular with glutaric acid, maleic and phthalic acid is advantageous.

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), 9t, 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatreic acid (linolenic acid). For reasons of cost, 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 wt .-% _C14, 10 wt .-% C _16, 2 wt .-% _C18, 8 wt .-% _C18 ', 1 wt .-% C _18' '), palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt _12% C, 15 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 15 wt .-% _C18 ', 1 wt .-% C _18' '), tallow ( approx. 3 wt% C ₁₄ , 26 wt% C ₁₆ , 2 wt% C ₁₆ ', 2 wt% C ₁₇ , 17 wt% C ₁₈ , 44 wt% C ₁₈ ', 3 wt% C ₁₈ '', 1 wt% C ₁₈ '''), hardened tallow fatty acid (approx. 2 wt% C ₁₄ , 28 wt% C ₁₆ , 2 wt% C ₁₇ , 63% by weight C ₁₈ , 1% by weight C ₁₈ '), technical oleic acid (approx. 1% by weight C ₁₂ , 3% by weight C ₁₄ , 5% by weight C ₁₆ , 6 wt% C ₁₆ ', 1 wt% C ₁₇ , 2 wt% C ₁₈ , 70 wt% C ₁₈ ', 10 wt% C ₁₈ ', 0.5 wt% % C ₁₈ '''), technical palmitic / stearic acid (about 1 wt .-% C _12, 2 wt .-% C ₁₄ 45 wt .-% C _16, 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 carboxylic acids are technically for the most part from native fats and oils Hydrolysis won. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps) is now used on an industrial scale only water is used for cleavage, which the fats in glycerol and the free fatty acids splits. Industrially processes used are, for example, cleavage in the autoclave or continuous high pressure fission. Also the alkali metal salt of the above carboxylic acids or carboxylic acid mixtures can - if necessary in a mixture with other materials - for the production of the open Use hollow form. Salicylic acid and / or, for example, can also be used acetylsalicylic acid or their salts, preferably their alkali metal salts.

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 NaHSO ₄ and 40% by weight of KHSO 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 ^® ,

As particularly suitable materials for the In the context of the present invention, the sugars, sugar acids and sugar alcohols. These substances are generally not only sufficiently soluble but are also characterized by low costs and good processability out. This is how sugar and sugar derivatives, especially those Mono- and disaccharides and their derivatives, for example in the form process their melts, these melts having good solvent power both for dyes as also for have many washing and cleaning-active substances. From solidification resulting from the solidification of the sugar melts is also characterized by a smooth surface and an advantageous look, like high surface brilliance or transparent appearance.

The group of preferred as the material for the melt in the context of the present application are charged 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 weight fraction of the Isomalt ^® on the total weight of the above-mentioned mixtures is preferably at least 20 wt .-%, particularly preferably at least 40 wt .-%, and especially at least 80 wt .-%.

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

As a maltodextrin be in the frame of the present application obtained by enzymatic degradation of starch water-soluble Carbohydrates (dextrose equivalents, DE 3-20) with a chain length of 5-10 anhydroglucose units and a high proportion of maltose designated. Maltodextrin is used to improve foods rheological and added caloric properties, taste only a little sweet u. tend not for retrogradation. Commercial products, for example the company Cerestar are usually spray-dried as free-flowing powders offered and have a water content of 3 to 5 wt .-%.

As isomalt ^® is within the scope 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 proportion 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, alone or in combination with other substances, such as the above-mentioned sugars, can advantageously be used as a component 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-deoxyribonic acid being particularly preferred , 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 are preferred portioned according to the invention Visually upgraded means that the wall of the hollow form and the solid (at least partially cast into the wall (or the majority of solids) stand out clearly differently. This can be done, for example realize that solidified melt is transparent or translucent, or that the melt colored becomes.

In a particularly preferred embodiment portioned according to the invention The solidified melt is transparent. Under transparency is to be understood in the sense of this invention that the permeability within the visible spectrum of light (410 to 800 nm) larger than 20%, preferably greater than 30%, extremely preferred larger than 40% and especially larger than Is 50%. As soon as a wavelength of the visible spectrum a permeability of light larger 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 another option the visualization of the solidified melts Solid, which in these transparent walls, for example as crystals or Granules or extrudates or tablets etc. may be present (see below), and due to the transparency of it, at least in part surrounding wall for are visible to consumers. In this way, the Compositions visualize effects achieved and thus "explain" 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 to the other ingredients of the compositions and to light, and none Embossed substantivity towards tableware 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). Which as a commercial product ^® for example as Basacid Green 970 from BASF, Ludwigshafen, and mixtures thereof with suitable blue dyes. Other colorants include Pigmosol ^® Blue 6900 (CI 74160), Pigmosol ^® Green 8730 (CI 74260), Basonyl ^® Red 545 FL (CI 45170), Sandolan ^® Rhodamine EB400 (CI 45100), Basacid ^® Yellow 094 (CI 47005), Sicovit ^® Patentblau 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol ^® Blau GLW (CAS 12219-32-8, CI Acidblue 221 )), Nylosan ^® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan ^® Blue (CI Acid Blue 182, CAS 12219-26-0).

Effect dyes can also be used, for example those that vary in color depending on the viewing angle. Pigments can also are used, with special optical effects for example can be achieved by using pearlescent pigments. pearlescent are luster pigments that compare the luster as an additional property to have other pigments. They are flat, small, thin plates with relatively large Diameters and smooth surfaces. Their characteristic properties of the flat structure, the high Refractive index and transparency generate in transparent media as Follow the multiple reflection of light effects that reflect the sheen of Equal pearls or mother-of-pearl. Also metal and the like Effects can be achieved with them without affecting metals and metal alloys give observed disadvantages.

All pearlescent pigments consist of thin Tile of the natural Minerals mica coated with titanium dioxide and / or ferric oxide are. The pearlescent pigments are available in different particle size ranges, the pearlescent or colored sheen depending on the size of the ponds of satin matt can be varied to a glittering sparkle. The excellent chemical, thermal and mechanical properties of the pearlescent pigments offer universal applications, Varnishes, prints, plastics and much more. You give the products a new color quality. The pigments are physiologically harmless, environmentally friendly and can can also be used in food packaging. Diluted acids and Alkali do not attack pearlescent pigments. The pigments are not flammable and not self-igniting. They do not conduct the electrical current and tolerate temperatures up to approx. 800 ° C, what they are for incorporation into the melts is particularly predestined. pearlescent are supplied as dry powder. Pigments can be used for special applications can also be offered as an incline 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 SiO 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 SiO ₂ flakes are processed using high-index materials (e.g. TiO ₂ , Fe ₂ O ₃ ) in one process comparable to the proven manufacturing process for mica pigments, coated. This creates strongly angle-dependent effect pigments, 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 (SiO 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.

For highly soluble dyes, for example, the above-mentioned Basacid ^® Green or the above-mentioned Sandolan Blue ^®, are typically selected dye concentrations in the range of a few 10 ^-2 to 10 ^-3 wt .-%. In the due to their brilliance, particularly preferred, but are less readily water-soluble Pigmenffarbstoffen, including the above-mentioned Pigmosol ^® ATTO-dyes, the appropriate concentration of the colorant is in the active phase, however, is typically a few 10 ^-3 to 10 ^-4 wt .-%. In the case of strongly colored parts which make up only a small proportion of the agents according to the invention, these colorant concentrations can deviate considerably from the values mentioned. If, for example, a tablet is enclosed 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 reach into the parts per thousand or even into the percentage range.

Of course, one cannot either colored (e.g. white) Melt with a colored Solid that is at least partially poured into the wall is present, can be combined.

The solidified melt forms one Hollow form, which is suitable for taking up additional active substance. In the wall of the hollow mold there is (are) at least some solid bodies cast. It has proven to be advantageous if the wall thickness of the Hollow shape is between 0.1 and 6 mm. Here are portioned according to the invention Means preferred, in which the hollow shape wall thicknesses of 100 to 6000 microns, preferably from 500 to 5000 μm and in particular from 1000 to 4000 μm.

The wall of the hollow mold encloses at least a solid at least partially. The wall can be a solid enclose at least partially in several ways, as shown below using the example the wall of a hollow shell made of solidified melt and a tablet explained becomes. Of course the invention is not based on these exemplary explanations limited, but can be analog with several solids realize this solid do not have to be tableted (see above). So is for example it is possible that the Wall of the hollow shell encloses the tablet so that a surface of the tablet on the outer wall (i.e. the "dome") is visible can put the tablet in the mold for the Melt inserted and poured over with melt. If the Melt is now metered so that it only the tablet edge and does not wet the surface of the tablet facing away from the mold the tablet is also visible from the inside. The tablet is in this Fall like a "window" in a brick wall surrounded by the melt. Of course, the melt can too the surface facing away from the shape cover the tablet.

Alternatively, the melt can also coherent be poured where it forms a hollow shell. After pouring off excess melt the tablet can be pushed into the wall, where it is from the solidifying melt is fixed. Here is the tablet (at opaque melt) only visible from the inside. Is at this procedure a further melt of the same or one other composition poured into the inside of the hollow shell, so the tablet is complete surrounded by solidified melts and (in the case of opaque melts) not visible anymore.

As already mentioned, a single solid can at least partially included, but it is also possible to include one Variety of solids, for example two, three, four, five, six, seven, eight, nine, to enclose ten or eleven at least partially in the wall. Also even higher Number of solids are included, being for geometric reasons the size of the solid with increasing number decreases. Small solid bodies, mostly in the majority at least partly included are powders, granules, Extrudates, dandruff, pellets, prills, etc. With these solids are Particle sizes between 0.4 and 4 mm 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 solids are preferably. around bodies which have been produced by means of tableting or around (preferably filled) polymer bodies. Portioned agents according to the invention are preferred here, in which the at least one further solid body is a tablet and / or a casting and / or an extrusion and / or an injection molded part and / or a gelatin capsule and / or a blow molded part and / or a pouch ("pouch") and / or a deep-drawn part.

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

The production of powder or liquid-filled hollow bodies (or even unfilled Hollow bodies) Shaping processing takes place according to that in plastics processing Industry usual Process, in particular film production and further processing, blow molding and injection molding are preferred. All procedures has in common that a Plastic granules are melted using an extruder and shaping tools supplied becomes.

In a preferred embodiment In the present invention, the melt leaving the extruder blow molded. Suitable according to the invention Blow molding processes include extrusion blow molding, coextrusion blow molding, Injection stretch blow molding and plunge blowing. Leave the wall thickness of the moldings produce different areas by blow molding, by looking at the wall thicknesses the preform, preferably along its vertical axis, accordingly different thicknesses, preferably by regulation the amount of thermoplastic material, preferably by means of a Adjusting spindle forms when the preform is removed from the extruder nozzle.

The powder or liquid-filled solid can one with areas of different outer perimeter and more consistent Wall thickness blow molding by changing the wall thicknesses of the preform, preferably along. its vertical axis, accordingly different thicknesses, preferably by regulation the amount of thermoplastic material using an adjusting spindle when the preform is removed from the extruder nozzle.

In this way, different geometric configurations of the molded body with and without compartments blow molding. In a single cycle, bottles can be Balls, Santa Clauses, Easter bunnies or other figures blow molds that are filled with funds can, subsequently sealed and then demolded.

It is particularly advantageous that the moldings emboss and / or decorate in the blow mold during blow molding. By appropriate design of the blow mold, a motif can be mirrored transferred to the molded body. That way the surface of the shaped body design practically any. For example, the molded body Information such as calibration marks, application notes, hazard symbols, Brands, weight, filling quantity, Apply expiry date, pictures, etc.

The preform, the molded body and / or the liquid-tight closed molded body can be tubular, spherical or bubble-shaped. Has a spherical shaped body preferably a shape factor of> 0.8, preferably of> 0.82, preferably> 0.85, more preferably> 0.9 and particularly preferred from> 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 by means of blow molding manufactured solid have a, wall thickness from between 0.05 - 5 mm, preferably from between 0.06-2 mm, preferably from between 0.07-1.5 mm, more preferably from between 0.08-1.2 mm, more preferably from between 0.09 - 1 mm and most preferably between 0.1-0.6 mm.

The filling opening of the hollow body after the slope let yourself liquid-tight, preferably by material closure, preferably by means of thermal Treatment, particularly preferably by applying a melt blob, close. The filling opening or openings of the hollow body can also be advantageously by thermal treatment, preferably by fusing the walls adjacent to the opening, in particular by means of clamping jaws, liquid-tight close.

It is particularly preferred according to the invention to design the blow molding process as a BFS (blow-fall 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 closed in one operation. Here, a tube is plasticized water-soluble plastic material is extruded into an open blow mold, the blow mold is closed and expanded by generating a pressure gradient effective on the hose and applied to the shaping wall of the blow mold to form the container.

In another preferred embodiment In the present invention, the melt leaving the extruder from water soluble Polymer blend processed using a injection molding process. Injection molding takes place according to known procedures at high pressures and Temperatures with the steps of closing the to the extruder Spritrgießen connected form, injection of the polymer at high temperature and high pressure, cooling of the injection molded molding, opening the Shape and remove the molded blank. Other optional steps such as the application of release agents, demolding etc. Known in the art and can be carried out according to technology known per se.

The advantages of the procedure manufacturing by injection molding lie in the mature technology of this procedure, the high flexibility in terms of the materials that can be used, the ability to have exactly the desired wall thickness s To obtain shaped or dimensionally stable hollow body and the possibility of a dimensionally stable in one step with high reproducibility hollow body with one or more integral compartmentalization device (s) manufacture.

In preferred methods, a pressure 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 injection molded.

The temperature of the material that 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 methods according to the invention is at temperatures between 100 and 250 ° C, preferably between 120 and 200 ° C and especially injection molded between 140 and 180 ° C.

The tools, the materials record, are preferably preheated and have temperatures above room temperature, with temperatures between 25 and 60 ° C and especially from 35 to 50 ° C are preferred.

Regardless of the material used for the Moldings, but dependent of the ones you want dissolution properties the thickness of the wall can be varied. The wall should be chosen so thin on the one hand that a speedy resolution or disintegration is achieved and the ingredients quickly into the application fleet released, but a certain minimum thickness is also required, the desired shape around the hollow shape Stability, especially dimensional stability, to rent.

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 from 500 to 1500 μm.

Regularly, the one produced by injection molding moldings not closed walls on all sides and is on at least one of its sides - at a spherical one or elliptical body in the area of part of its shell - open due to manufacturing. Through the remaining opening is / are in the compartment (s) formed inside the molded body (s) one or preparations). This also happens in a way known per se, for example within the confectionery industry known manufacturing processes; in several steps are also conceivable current procedures. A one step process is particularly preferred if in addition to solid preparations liquid components comprehensive preparations (dispersions or emulsions, suspensions) or even gaseous Formulations comprising components (foams) introduced should be.

Whichever way the solid or at least partially cast-in solid can, can he / she can be used for material separation. This way you can interact with each other incompatible Ingredients spatially from each other be separated.

This can have further advantages be achieved that the Wall of the hollow mold and / or the solid body (s) are solubility-controlled. This can accelerate the release can be achieved by incorporating disintegration aids, a solubility delay due to the use of release delays, for example of polymers.

The hollow shape (or the at least partially cast-in solid (s) so-called disintegrants contain. These substances enlarge Water ingress their volume, whereby on the one hand the own volume increases (swelling), on the other hand also about the release of gases can generate a pressure that, for example a tablet or the wall from the solidified melt into smaller ones Particles disintegrate. Well-known Disintegration aids include carbonate / citric acid systems, taking other organic acids can be used. Swelling disintegration aids are, for example, synthetic Polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or modified natural products like cellulose and starch and their derivatives, alginates or casein derivatives.

Examples of swellable disintegration aids are bentonites or other swellable Si likate into consideration. Synthetic polymers, in particular the superabsorbents or cross-linked polyvinylpynolidone used in the hygiene sector, can also be used.

With particular advantage as swellable Disintegration aid polymers based on starch and / or Cellulose used. These basic substances can be used alone or in a mixture with more natural and / or synthetic polymers to swellable disintegrants are processed.

In the simplest case, a cellulosic Material or pure cellulose through granulation, compacting or other application of pressure can be converted into secondary particles, which on contact swell with water and serve as an explosive. As a cellulosic Material wood pulp has proven itself, by thermal or chemical-thermal processes from wood or wood chips (Sawdust, sawmill waste) is accessible. This cellulose material from the TMP process (thermo mechanical pulp) or the CTMP (chemo-thermo mechanical pulp) process can then be used Application of pressure compacted, preferably roller compacted and be converted into particle form. Of course let yourself completely similarly also use pure cellulose, but from the raw material base is more expensive. Here you can both microcrystalline and amorphous fine cellulose and Mixtures of the same can be used.

Another way is that Cellulosic material with the addition of granulation aids to granulate. As pelletizers, for example solutions synthetic polymers or non-ionic surfactants.

For residues on with the agents of the invention To avoid washed textiles, the primary fiber length should be the used cellulose or the cellulose in the cellulose-containing material are less than 200 μm, with primary fiber lengths below 100 μm, especially below 50 μm are preferred. The secondary particles ideally have a particle size distribution where more than 90% by weight of the particle sizes above of 200 μm to have. A certain amount of dust can improve the storage stability of the products manufactured with it Tablets contribute. Fractions of a fine dust fraction of smaller 0.1 mm up to 10 wt.%, Preferably up to 8 wt.% Can in the used according to the invention Disintegrant granules are present.

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, lies whose bulk density is higher and can be in an advantageous embodiment 350 g / l to 550 g / l. The bulk weights of the cellulose derivatives are typically in the range from 50 g / l to 1000 g / l, preferably in Range of 100 g / l and 800 g / l.

As already stated, leave also use cellulose-based disintegration aids, which contain other active ingredients or auxiliaries besides cellulose. For example, compacted disintegrant granules are suitable from 60 - 99 % By weight not water-soluble, water-swellable cellulose and optionally other modified ones water-swellable polysaccharide derivatives, 1 - 40% by weight at least one polymeric binder in the form of a polymer or copolymer the (meth) acrylic acid and / or their salts, and 0-7 % By weight of at least one liquid, with water-forming surfactants. 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 which have been modified with ionic substituents such as carboxylate, hydroxyalkyl or phosphate groups have proven to be particularly advantageous and are therefore preferred. To improve the swelling behavior, the use of slightly starched starches has also proven itself. 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 preferably 0.1 to 85% by weight, particularly preferably 5 to 50% by weight.

As a binder in preferred disintegration aid granules become polymers or copolymers of (meth) acrylic acid or mixtures of such Polymers or copolymers used. The polymers are selected from the group of homopolymers of (meth) acrylic acid, from the group of copolymers with the following monomer components 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.

Have proven to be particularly suitable uncrosslinked polymers or copolymers of (meth) acrylic acid, with weight-average ones Molecular weights of 5,000 to 70,000 proven. For the copolymers it is preferably copolymers of (meth) acrylic acid and ethylenically unsaturated dicarboxylic acids or their anhydrides, such as maleic acid or maleic anhydride, which, for example, 40 to 90% by weight (meth) acrylic acid and 60 to 10% by weight maleic acid or maleic anhydride contain, whose relative molar mass, based on free acids, between 3,000 and 100,000, preferably 3,000 to 70,000 and very particularly is preferably 5,000 to 50,000. Ter- and quattropolymers have also proven to be suitable binders Proven 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, or such (Meth) acrylic acid, maleic acid, Vinyl alcohol derivatives and monomers containing sulfonic acid groups.

The polymeric binders will preferably used in the production in the form of their aqueous solutions, but can can also be used in the form of fine powder. The binder polymers are preferably in partially or fully neutralized form, whereby salt formation preferably with cations of alkali metals, ammonia and amines, or their mixtures.

The percentage of polymers / copolymers in preferred disintegrants, between 1 and 40% by weight is preferred 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 that less abrasion resistant are.

Suitable polymer binders are also cross-linked polymers made from (meth) acrylic acid. They are preferred as finely divided powders are used and preferably have average particle sizes of 0.045 mm to 0.150 mm and are preferably 0.1 to 10% by weight used. Particles with average particle sizes over 0.150 mm also result good disintegrant granules but after dissolving of tablets made with the granules too visually as particles visible source bodies, which, for example, is clearly visible in the case of textile washes the textile in disruptive Deposit way. A special embodiment of the invention provides the combination of soluble Poly (meth) acrylate homo- and copolymers and the aforementioned finely divided crosslinked polymer particles.

Included as another ingredient preferably used disintegrant granules one or more liquid, with Water-gelling surfactants selected from the group of non-ionic, anionic or amphoteric surfactants, in amounts up to 7% by weight, preferably up to 3.5 wt .-% can be present. If the surfactant content in the explosive is too high, in addition to increased abrasion the tablets made with it also have poorer swelling properties. The nonionic surfactants are described in detail below.

Disintegration aids preferably used according to the invention are characterized by a special swelling kinetics, whereby the expansion depending does not change linearly over time, but reached a very high level after a very short time. The swelling behavior in the first is of particular interest 10 seconds after touch with water. The specific water absorption capacity is preferably used Disintegration aids can be determined gravimetrically and is preferably 500 to 2000% The fluid intake (also called specific porosity preferred) explosive is in a range of over 600 ml / kg, preferably of over 750 ml / kg, especially in the range 800 to 1000 ml / kg.

The production of granulated disintegrant granules is done first by mixing the granulate components with conventional mixing methods. For example can Mixers from Vomm, Lödige, Schugi, Eirich, Henschel or Fukae can be used. With this The first step in mixing and granulating are pre-compounds produced by agglomeration processes.

The next step will be these Precompounds mechanically compressed. Compacting using of pressure can be done in different ways. The products can be between two printing areas in Roll compressors, e.g. B. smooth or profiled. The emission of the The compact is made as a strand. Compression methods in matrices with stamps or pillow rollers result in compact forms such as tablets or briquettes. Roll compactors, extruders, Roller or cube presses, but also pelletizing presses are used.

Compression with pelleting presses has proven to be particularly suitable, with a ge suitable process control granules are obtained which can be dried without further comminution. Suitable pelletizing presses are manufactured, for example, by Amandus Kahl and Fitrpatrick.

The coarse, compacted particles are crushed, e.g. mills, Schnitzler or roller mills are suitable. The shredding can be done before or after drying carried out become. Can in the drying process preferred water content of 2 - 8 % By weight, preferably 2.5-7 % By weight and particularly preferably 3-5% by weight. Therefor are common Dryers such as Roller dryer (temperatures e.g. from 95 - 120 ° C) or fluid bed dryer (Temperatures e.g. from 70 - 100 ° C).

As a swellable disintegration aid coprocessates which are made of polysaccharide material are also suitable and insoluble Explosives are obtained. As polysaccharide materials are here the above-mentioned substances from the groups powdered cellulose, microcrystalline cellulose and mixtures thereof are particularly suitable; as insoluble Disintegrants come here in particular insoluble polyacrylic acid monopolymer, insoluble Polyacrylamide Monopolymerisat, insoluble Polyacrylic acid polyacrylamide copolymer and mixtures thereof.

The content of each component in these explosives can vary within wide limits, for example from 1 to 60% by weight insoluble polyacrylic product disintegrant and 40 to 99% by weight cellulose. A content of 3 to is preferred 60% by weight insoluble Polyacrylprodukt-explosive and 40 to 97% by weight cellulose. A salary is more preferred from 5 to 30% by weight insoluble Polyacrylic product disintegrant and 70 to 95 wt .-% cellulose. Optional can this disintegrant still contains small amounts of other disintegrants, for example various strengths, Shower mixes e.g. from sodium carbonate and sodium hydrogen sulfate, etc. are added, these amounts by appropriate deductions at the Balanced amount of cellulose i.e. be compensated.

This suitable disintegrant can by coprocessing a cellulose as defined above with a insoluble as defined above Disintegrant by damp or dry compression under pressure be preserved. Under the term "coprocessing" is a dry compression e.g. between opposing Compacting rollers at pressures from 20-60 kN, preferably from 30-50 kN, or wet compaction after adding water, by kneading or pressing wet plastic Masses through a sieve, a perforated disc or via an extruder and final Understand drying.

Alternatively, the wall the hollow shape (or the at least partially cast-in) Solids) Contain substances that lead to a delay in dissolving. Here polymers should be mentioned in particular. If at least partially cast solid a blow molded part, an injection molded part, a pouch, a deep-drawn part or is a gelatin capsule, it is usually already delayed in dissolving. The Incorporation of additional Polymers are not necessary here; use the decay accelerators described above become.

With at least partially cast in Tablets can incorporate polymer (s) to delay dissolution, however be indexed.

Below are preferred as Release delay can be used Polymers described. All of these Polymers are also used as wall materials for at least partially cast-in Blow mold or injection molded body can be used.

The ones used to delay solubility Polymers can from a single material or a blend of different materials consist. Preferred release delays 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.

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten.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, the as white-yellowish Powder or granules with degrees of polymerization in the range of approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol) are offered are, have degrees of hydrolysis of 98-99 and 87-89 mol% so there is still a residual content of acetyl groups. Be characterized the polyvinyl alcohols from the manufacturer by specifying the Degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

Polyvinyl alcohols are dependent on Degree of hydrolysis soluble in water and a few strongly polar organic solvents (Formamide, dimethylformamide, dimethyl sulfoxide); from (chlorinated) They do not attack hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility can be achieved by post-treatment with aldehydes (acetalization) Complexing with Ni or Cu salts or by treatment with dichromates, boric acid or reduce borax. Polyvinyl alcohol is largely impenetrable for gases such as Oxygen, nitrogen, helium, hydrogen, carbon dioxide, however, leaves Pass water vapor through.

Within the scope of the present invention preferred means are characterized in that the solidified Melt and / or at least one at least partially enclosed solid Polyvinyl alcohols and / or PVAL copolymers and / or thermoplastic PVAI and / or PVAI copolymer compounds, whose Degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferred 81 to 89 mol% and in particular 82 to 88 mol%.

Polyvinyl alcohols of a certain molecular weight range are preferably used, with 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 about 200 to about 2100, preferably between approximately 220 to about 1890, more preferably between about 240 to about 1680 and especially between about 260 to about 1500th

Agents preferred according to the invention are thereby characterized that the the solidified melt and / or at least one at least partially enclosed solid Polyvinyl alcohols and / or PVAL copolymers, their average Degree of polymerization between 80 and 700, preferably between 150 and 400, particularly preferably between 180 to 300 and / or their molecular weight ratio MG (50%) to MG (90%) 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:

Further as a material for the release delay suitable polyvinyl alcohols 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.), Gohsenol ^® 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.

die durch radikalische Polymerisation von 1-Vinylpyrrolidon nach Verfahren der Lösungs- oder Suspensionspolymerisation unter Einsatz von Radikalbildnern (Peroxide, Azo-Verbindungen) als Initiatoren hergestellt werden. Die ionische Polymerisation des Monomeren liefert nur Produkte mit niedrigen Molmassen. Handelsübliche Polyvinylpyrrolidone haben Molmassen im Bereich von ca.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 Luviskol ^® (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 molecular weights in the range of approx.

2500-750000 g / mol, which over the Specification of the K values and - depending on the K value - glass transition temperatures from 130-175 °. They are called white, hygroscopic powder or as aqueous. Solutions offered. Polyvinyl pyrrolidones 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 Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.

als charakteristischem Grundbaustein der Makromoleküle. Von diesen haben die Vinylacetat-Polymere (R = CH₃) mit Polyvinylacetaten als mit Abstand wichtigsten Vertretern die größte technische Bedeutung.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 are by far the most important technical representatives.

Polymerization of vinyl esters takes place radically according to different 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- (O-CH ₂ -CH ₂ ) _n -OH (VI) are sufficient, where n can have values between 5 and> 100,000.

PEGs are manufactured technically by anionic ring opening polymerization of ethylene oxide (oxirane) mostly in the presence of small amounts of water. You have depending on the reaction Molar masses in the range of approx. 200-5,000,000 g / mol, corresponding to degrees of polymerization from approx. 5 to> 100 000th

The products with molar masses <approx. 25,000 g / mol are liquid at room temperature become sore as the actual polyethylene glycols, abbreviation PEG, designated. These short chain PEGs can in particular be other water soluble Polymers, e.g. Polyvinyl alcohols or cellulose ethers as plasticizers be added. The usable according to the invention at room temperature Solid polyethylene glycols are called polyethylene oxides, short marks Peox; designated. High molecular weight polyethylene oxides are extremely low Concentration of reactive hydroxy end groups and therefore only show still weak glycol properties.

According to the invention, gelatin is also suitable as a release retarder, these preferably used together with other polymers becomes. Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol) that primarily by hydrolysis of the contained in animal skin and bones Collagen is obtained under acidic or alkaline conditions. The amino acid composition of the Gelatin largely corresponds to that of the collagen from which it is obtained was and varies depending of its provenance. The use of gelatin as a water soluble shell material is extremely wide, especially in pharmacy in the form of hard or soft gelatin capsules common. Gelatin is found in the form of foils because of their comparison only low for the above-mentioned high-cost polymers Use.

Further water-soluble polymers which are suitable according to the invention as dissolving retardants are next described below:
- cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and methylhydroxypropyl cellulose, such as are for example sold under the trademark Culminal® ^® and Benecel ^® (AQUALON).

in R für H oder einen Alkyl-, Alkenyl-, Alkinyl-, Aryl- oder Alkylarylrest steht. In bevorzugten Produkten steht mindestens ein R in Formel (III) für -CH₂CH₂CH₂-OH oder -CH₂CH₂-OH. Celluloseether werden technisch durch Veretherung von Alkalicellulose (z.B. mit Ethylenoxid) hergestellt. Celluloseether werden charakterisiert über den durchschnittlichen Substitutionsgrad DS bzw. den molaren Substitutionsgrad MS, die angeben, wieviele Hydroxy-Gruppen einer Anhydroglucose-Einheit der Cellulose mit dem Veretherungsreagens reagiert haben bzw. wieviel mol des Veretherungsreagens im Durchschnitt an eine Anhydroglucose-Einheit angelagert wurden. Hydroxyethylcellulosen sind ab einem DS von ca. 0,6 bzw. einem MS von ca. 1 wasserlöslich. Handelsübliche Hydroxyethyl- bzw. Hydroxypropylcellulosen haben Substitutionsgrade im Bereich von 0,85-1,35 (DS) bzw. 1,5-3 (MS). Hydroxyethyl- und -propylcellulosen werden als gelblich-weiße, geruch- und geschmacklose Pulver in stark unterschiedlichen Polymerisationsgraden vermarktet. Hydroxyethyl- und -propylcellulosen sind in kaltem und heißem Wasser sowie in einigen (wasserhaltigen) organischen Lösungsmitteln löslich; in den meisten (wasserfreien) organischen Lösungsmitteln dagegen unlöslich; ihre wäßrigen Lösungen sind relativ unempfindlich gegenüber Änderungen des pH-Werts oder Elektrolyt-Zusatz.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 ₂ 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. Commercial 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 varying degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water as well as in some (water-containing) organic solvents; insoluble in most (anhydrous) 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 SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - Contain COO ^- or -SO ₃ ^- groups, and summarize those polymers which contain -COOH or SO 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. Also preferred amphopolymers are composed of unsaturated carboxylic acids (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (e.g. acrylamidopropyl-trimethyl-ammonium chloride) and optionally other ionic or non-ionic monomers, such as 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 those available under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL) octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.

Water-soluble anionic suitable according to the invention Polymers are u. 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)
• - vinylpyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF): A preferred poymer 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 as a mixture with other copolymerizable compounds, can be used on polyalkylene glycols obtained by hot polymerization in a homogeneous phase by adding the polyalkylene glycols to the monomers ren of the vinyl ester, 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
  
  are sufficient, where n can take values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetrapropylene glycol, ie 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 a non-ionic type monomer,  ii) at least one Ionic type monomers,  iii) of polyethylene glycol and  iv) a networked  The polyethylene glycol used has a Molecular weight between 200 and several million, preferably between 300 and 30,000.  The non-ionic monomers can be of very different types and among these are the following 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 equally be of very different types, among them especially preferably crotonic acid, allyloxyacetic, Vinyl acetic acid, maleic acid, Acrylic acid and methacrylic acid are contained in the graft polamers. Are preferred as crosslinkers Ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, Tetraallyloxyethane and polyallylsucrose with 2 to 5 allyl groups per molecule Saccharin.  The grafted and cross-linked described above Copolymers are preferably formed from: i) 5 to 85% by weight at least one non-ionic type monomer,  ii) 3 to 80% by weight of at least one ionic type monomer,  iii) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and iv) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinker by the ratio the total weights of i), ii) and iii) is formed.
• - 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 carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol. Short-chain carboxylic acids or alcohols are to be understood as those having 1 to 8 carbon atoms, the carbon chains of these compounds being optionally by double-bonded hetero groups such as - O-, -NH-, -S can be interrupted.
• 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:
  
  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 C _1-6 alkyl radical and the sum of the 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% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17% by weight .-% Allyl- or Methallyletsre of formula VII.
• - tetra and pentapolymers i) crotonic acid or allyloxyacetic acid ii) Vinyl acetate or vinyl propionate iii) branched allyl or methallyl iv) vinyl ethers, vinyl esters or straight-chain Ally1 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 made of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic branched in the ⧠ position Monocarboxylic acid.

Further polymers, preferably according to the invention as dissolving retarders are cationic polymers. Among the cationic polymers are the permanently cationic polymers are preferred. As "permanent become cationic " according to the invention such Polymers referred to independently have a cationic group of pH. These are in the Rule polymers that are a quaternary Contain nitrogen atom, for example in the form of an ammonium group.

• – quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat^® und Polymer JR^® im Handel erhältlich sind. Die Verbindungen Celquat^® N 100, Celquat^® L 200 und Polymer JR^®400 sind bevorzugte quatemierte Cellulose-Derivate.
• – Polysiloxane mit quaternären Gruppen, wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trimethylsilylamodimethicon), Dow Corning^® 929 Emulsion (enthaltend ein hydroxyl-amino-modifiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM-55067 (Hersteller: Wacker) sowie Abil^®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt; diquatemäre Polydime- thylsiloxane, Quaternium-80),
• – Kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosmedia^®Guar und Jaguar^® vertiebenen Produkte,
• – Polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat^®100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat^®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere.
• – Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminomethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat^®734 und Gafquat^®755 im Handel erhältlich.
• – Vinylpyrrolidon-Methoimidazoniumchlorid-Copolymere, wie sie unter der Bezeichnung Luviquat^® angeboten werden.
• – quaternierter Polyvinylalkohol sowie die unter den Bezeichnungen
• – Polyquaternium 2,
• – Polyquaternium 17,
• – Polyquaternium 18 und
• – Polyquaternium 27

bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette. Die genannten Polymere sind dabei nach der sogenannten INCI-Nomenklatur bezeichnet, wobei sich detaillierte Angaben im CTFA International Cosmetic Ingredient Dictionary and Handbook, 5^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, finden, auf die hier ausdrücklich Bezug genommen wird.Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^® . The compounds Celquat ^® N 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 ^Corning® 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; diquaternary polydimethylsiloxane, Quaternium-80),
• Cationic guar derivatives, such as in particular the products marketed under the trade names Cosmedia ^® Guar and Jaguar ^® ,
• - Polymers dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products commercially available under the names Merquat ^® 100 (poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers.
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755.
• - Vinylpyrrolidone-methoimidazonium chloride copolymers, as are offered under the name Luviquat ^® .
• - Quaternized polyvinyl alcohol and those under the names
• - polyquaternium 2,
• - polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27

known polymers with quaternary nitrogen atoms in the main polymer 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; especially 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) at least partially cast in may 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 form can be optional before filling be coated with suitable agents. You can do that too only parts of the hollow mold can be provided with a coating, for example, around the hollow form before the attack due to incompatible ingredients of the later filling protect. Of course only the at least partially cast-in solid can also be suitable be coated. A coating is preferred - if them at all carried out will - but only on the filled one and closed hollow body applied. In principle, however, after every intermediate manufacturing step, a coating step can be connected, it is also possible only parts of the surface, inside and outside, to coat.

The hollow molds with at least one be at least partially cast into the wall preferably filled with further active substance. Here are portioned according to the invention Means preferred in which the hollow form additionally a further preparation, preferably a particulate Preparation and in particular a particulate detergent or cleaning agent composition, contains.

Particularly preferred portions according to the invention are, for example, from a solidified melt with a cast solid (preferably a tablet) and a particulate filling (powder, Granulate, extrudate).

Following the filling can the open mold is closed. This is with liquid or pasty fillings necessary to prevent the filling from leaking before use prevent. For fillings, which remain firmly in the mold, can be closed No form if desired is. A closing can also in such cases out of aesthetic establish be displayed.

The optional closing of the Hollow form can be done in different ways. For molded articles with Bunghole can do this, for example, by inserting a suitable one Partially closed. Open hollow forms in the form of hollow bodies without Undercuts can closed with foils or after filling with other material for the Poured over the hollow form become. The optional closing with foils is described below.

The film covering the opening (s) closes the hollow mold (s), gets to the surface the hollow form applied and firmly connected to what for example by gluing, partial melting or by chemical reaction can take place. It is possible to apply the film to all surfaces of the Hollow shape (not just over the opening) apply and bond firmly with it, so that the film a coating, a "coating" of the entire molded body. Preferred laundry detergents according to the invention and detergent portions are characterized, however, that the Do not film the entire molded body encloses.

For reasons of process economy and the aesthetic It is impressively preferred that the Film is only applied in such a way that it fulfills a function, i.e. closing the hollow shape serves.

The sealing film can of course also a laminate of several differently composed foils be about different compositions of individual film layers can open the Hollow mold at certain times in the washing and cleaning cycle be released.

Preferred film materials are the polymers known from the prior art. Here can be on the above statements referred to the solubility retarders be because all polymers mentioned there also as film materials for an optional close the hollow shape are suitable.

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

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

When incorporating liquid, gel or more pasty Active substances or mixtures of active substances must have the composition of the hollow body and the film on the filling be matched to premature destruction of the film or loss of active substance through the hollow body to avoid through. This is when solid substances are incorporated into the cavity only to a minor extent (chemical incompatibility) required so that in preferred manufacturing process, the washing filled into the hollow mold or detergent composition in particulate form, preferably in powder, granular, extruded, pelleted, prilled, flaked 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 to enable the filled particles or liquids to move within the hollow mold. Particularly when filling with regularly shaped larger particles, attractive optical effects can be achieved realize. 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 shape, the density of the hollow body, the density of the active substance (s) in the hollow form and the degree of filling the proportion of the further active substance (s) in the Make up different proportions of the overall molded body. Here are manufactured according to the invention Detergent or cleaning agent portions preferred, in which the weight ratio of Hollow body too the contained in the space enclosed by the film and the hollow body Active substance (s) 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1 aged. at the weight ratio defined above is the relationship 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.

Through suitable packaging of hollow body and film material can be the time; to which the contained in the hollow body Substances are released, predetermined. For example the film can be instantly soluble, so that the in active substance contained in the hollow mold right at the beginning of the washing dosed into the washing or cleaning liquor becomes. Alternatively, the film can be so poorly soluble that first the molded body disbanded and the active substance contained in the hollow mold is released.

Depending on this release mechanism can be molded articles, for example realize in which the active substance contained in the mold solved in the cleaning liquor is present before the components of the hollow body are dissolved or after this happened. On the one hand, detergent tablets are preferred, which are characterized in that in the by the Foil and the hollow body contained active substance dissolves faster than that Hollow body. But also detergent tablets, in which the in contained in the space enclosed by the film and the hollow body Active substance dissolves more slowly than the hollow body, are preferred embodiments of the present invention.

As an alternative to closing with a slide can the filled hollow body also by applying a melt, solution, emulsion or dispersion the above-mentioned film materials, at least in part, be closed. This forms, at least in part, closes Layer from the melt, solution, Emulsion or dispersion by cooling or evaporation of the Solvent, i.e. the sealing "foil" is placed on the hollow mold generated. This alternative can be especially with complete filled Apply cavity molds while only partially filled Hollow forms expediently be closed in a different way, provided that you value the "flexibility" of the content , for example as a special purchase incentive. In special cases it prefers a occlusive Layer in the form of a very thin film or skin train in order to fix an otherwise possibly only temporarily movable filling to favor; this can be preferred for leakage-free transport and / or before collapsing in a double frame mold one in the manufacturing process individual stations still incompletely generated, hollow body according to the invention.

Of course, the hollow body can also so that they connected to another filled hollow body and can be closed in this way. Such bodies are shapes assembled from two half-shells without undercuts, which is an equatorial plane have. The latter does not have to must be arranged centrally, but can also, for example in the upper or lower third, fourth, fifth, etc. This approach will be easier if the hollow body Have flange parts. Alternatively, the liability of the molded parts to each other just about the boundary edges of the opening areas are made.

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 size and number the at least partially cast in solid and depending of the presence and size of an opening in the solidified melt can have different proportions on the total surface the portions according to the invention exhibit.

Here are portioned according to the invention Means preferred in which the outer surface of the hollow mold is at least 50%, preferably at least 60%, particularly preferably at least 70% and in particular at least 80% of the surface of the agent.

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 that the hollow varies form on the total mass of agents according to the invention. 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 different ingredients of washing or cleaning agents contain. You can the different areas such as the at least partially enclosed solids, individual regions of the / the at least partially included Solid) (with multiphase solids), Melt or individual melt regions as well as fillings for the separation of incompatible Ingredients are used.

The main ingredients that in the portions according to the invention may be included are described below.

The detergent or cleaning agent portions according to the invention preferably contain surfactant (s), anionic, nonionic, cationic and / or amphoteric surfactants can be used. Prefers are mixtures from a technical point of view for textile detergents from anionic and nonionic surfactants, the proportion of anionic surfactants may be larger should be considered the proportion of nonionic surfactants. The total surfactant content the detergent or cleaning agent portions are preferably below 30 wt .-%, based on the total agent. Nonionic surfactants have already been described above as optional plasticizers for the wrapper. The same substances can also be used in the portions as wash-active Use substances so that on the above statements can be referred.

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 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferred nonionic surfactants, either as the sole nonionic Surfactant or used 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.

Also non-ionic surfactants of the type the amine oxides, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can 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 from that.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen A1kyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula below,

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.

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

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 an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this remainder.

[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 more preferred for textile washing washing machine according to the invention or detergent portions of nonionic surfactants is 5 to 20% by weight, preferably 7 to 15% by weight and in particular 9 to 14 % By weight, based in each case on the total composition.

In automatic dishwashing detergents are preferably low-foaming non-ionic surfactants used.

In conjunction with the surfactants mentioned can anionic, cationic and / or amphoteric surfactants are also used be, because of their foam behavior in machine Dishwashing detergents only are of secondary importance and mostly only in quantities below of 10% by weight, mostly even below 5% by weight, for example from 0.01 to 2.5% by weight, based in each case on the agent. In contrast, these surfactants are of significantly greater importance in detergents. The washing according to the invention or portions of detergent thus also anionic, cationic and / or as a surfactant component contain amphoteric surfactants.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1–6-A1kyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8–28-Alky1- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.The agents according to the invention can contain, for example, cationic compounds of the formulas I, II or III as cationic active substances:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl, or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl 1 or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

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

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Among fatty acid glycerol esters are the mono-, di- and triesters and their mixtures to understand how they in the manufacture by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerin be preserved. Preferred sulfonated fatty acid glycerol esters are included the sulfonation products of saturated fatty acids with 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 _12-18 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 similar to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

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

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

Other anionic surfactants especially soaps. Saturated and unsaturated Fatty acid soaps, like the salts of lauric acid, myristic, Palmfinsäure, Stearic acid, (hydrogenated) erucic and behenic acid and especially from natural ones fatty acids, z. B. coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.

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

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

Within the scope of the present invention also contain preferred agents 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, anti-redeposition agents, optical brighteners, graying inhibitors, run-in preventers, anti-crease agents, Color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating, Swelling and sliding resistant agents as well as UV absorbers.

As builders in the agents according to the invention may be included are in particular phosphates, silicates, aluminum silicates (in particular Zeolites), carbonates, salts of organic di- and polycarboxylic acids as well To name mixtures of these substances.

The use of the well-known Phosphates as builder substances are possible according to the invention, provided that such use is not avoided for ecological reasons should be. Among the variety of commercially available The alkali metal phosphates have particular preference for phosphates of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) of greatest importance in the detergent and cleaning agent industry.

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

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

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

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

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

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

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. In 100 g of water about 17 g of the crystal water-free salt dissolve at room temperature, about 20 g at 60 ° and about 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 O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

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

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are: Preferred crystalline sheet 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 O ₅ .yH ₂ O are preferred.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are delayed in release and have secondary rapid properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compaction 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 (approx. 80% by weight zeolite X ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula n Na ₂ O · (1-n) K ₂ O · Al ₂ O ₃ · (2–2.5) SiO ₂ · (3.5–5.5) H ₂ O can be described. The zeolite can be used 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 minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C _12-18 fatty alcohols with 2 to 5 ethylene oxide groups, C _12-14 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: counter 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. Prefers become trisodium citrate and / or pentasodium tripolyphosphate and / or Sodium carbonate and / or sodium bicarbonate and / or gluconate and / or silicate builders from the class of disilicates and / or metasilicates used.

Alkali carriers can be present as further constituents his. As an alkali carrier apply alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, Alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the aforementioned substances, wherein for the purposes of this invention preferably the alkali carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate can be used.

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

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

In addition, other ingredients be present, washing, rinsing or cleaning agents according to the invention are preferred that additionally one or more substances from the group of acidifying agents, Contain chelating 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, maleic anhydride and succinic anhydride in particular being commercially available. Organic sulfonic acids such as amidosulfonic acid can also be used. Commercially available and also preferred as an acidifying agent in the context of the present invention Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight) can be used.

Another possible group of ingredients represent the chelating agents. Chelating agents are Substances that form cyclic compounds with metal ions, where a single ligand has more than one coordination site at one Central atom occupied, d. H. is at least "bidentate". In this case, normally elongated connections 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 and in the context of Preferred chelate complex images are present invention polyoxycarboxylic, Polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Also complex-forming polymers, i.e. polymers that are either in the Main chain itself or sideways contribute to this functional groups that can act as ligands and with suitable metal atoms, usually with the formation of chelate complexes react, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can come from only one macromolecule or belong to different polymer chains. The latter leads to Cross-linking of the material, unless the complex-forming polymers already before covalent bonds were cross-linked.

Complexing groups (ligands) more common complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, Guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cycl.) Polyamino, mercapto, 1,3-dicarbonyl and crown ether residues with z. T. very specific Activities towards ions different metals. Many base polymers are also commercially available important complex-forming polymers are polystyrene, polyacrylates, Polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethylene imines. Even natural Polymers such as cellulose, starch or chitin are complex-forming polymers. In addition, this provided with further ligand functionalities by polymer-analogous conversions become.

• (i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
• (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,
• (iii) geminalen Diphosphonsäuren,
• (iv) Aminophosphonsäuren,
• (v) Phosphonopolycarbonsäuren,
• (vi) Cyclodextrine

in Mengen oberhalb von 0,1 Gew.-%, vorzugsweise oberhalb von 0,5 Gew.-%, besonders bevorzugt oberhalb von 1 Gew.-% und insbesondere oberhalb von 2,5 Gew.%, jeweils bezogen auf das Gewicht des Mittels, enthalten.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 composition , contain.

Within the scope of the present invention can all complexing agents of the prior art are used. This can belong to different chemical groups. Preferably be single or used in a mixture:

• a) polycarboxylic acids in which the sum of 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, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, 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) geminate diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), whose higher homologues with up to 8 carbon atoms as well as those containing hydroxyl or amino groups Derivatives thereof and 1-aminoethane-1,1-diphosphonic acid, the higher Homologs with up to 8 carbon atoms as well as those containing hydroxyl or amino groups Derivatives thereof,
• d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic 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, carboxylic acids a) are also understood as meaning 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 required according to the invention solutions, these complex bilgeers are at least partially available 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 metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

Deposit-inhibiting polymers can also in the agents according to the invention be included. These substances that are chemically different could be come, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, with polymers with Molar masses below 15,000 daltons are preferred.

Deposit-inhibiting polymers can also Have cobuilder properties. As organic cobuilders, in the machine according to the invention dishwashing detergents in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are as follows described.

Usable organic builders are, for example, those that can be used in the form of their sodium salts polycarboxylic being under polycarboxylic acids such carboxylic acids can be understood that 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), unless such use for ecological reasons objectionable, and mixtures of these. Preferred salts are the salts of polycarboxylic acids like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used become. The acids In addition to their builder effect, they typically also have the property an acidifying component and thus also serve to set a lower and milder one pH value of detergents or cleaning agents. In particular, here are citric acid, Succinic acid, glutaric, adipic acid, gluconic and to name any mixtures of these.

As a builder or base inhibitor polymeric polycarboxylates are also suitable, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight from 500 to 70000 g / mol.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w 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 molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

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

Are particularly preferred in the agents according to the invention both polyacrylates and copolymers of unsaturated Carboxylic acids, Containing sulfonic acid Monomers and optionally other ionic or nonionic Monomers used. The copolymers containing sulfonic acid groups detailed below described.

Copolymers are also suitable Polycarboxylates, especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been particularly suitable maleic proven to contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative molecular mass, 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 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.

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

Are also preferred as others Builder substances polymeric aminodicarboxylic acids, their salts or their precursors to call. Polyaspartic acids or their salts and derivatives, which in addition to cobuilder properties have a bleach-stabilizing effect.

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

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 according to the usual for example acid or enzyme-catalyzed processes. Preferably acts are hydrolysis products with average molecular weights in the range from 400 to 500000 g / mol. There is a polysaccharide with one Dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, are preferred, where DE is a common one Measure of the reducing Effect of a polysaccharide compared to dextrose, which a DE of 100 has. Both maltodextrins can be used 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.

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.

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

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which optionally also in lactone form and which at least 4 carbon atoms and at least one hydroxyl group and maximum two acid groups included., Another class of substances with cobuilder properties represent the phosphonates. These are in particular Hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9) reacts. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Homologues in question. They are preferably in the form of neutral reactions Sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta- and octa sodium salt the DTPMP. As a builder, the class becomes the Phosphonates preferably used HEDP. The aminoalkane phosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the agent also bleach contain, be preferred, aminoalkanephosphonates, in particular DTPMP, to use, or to use mixtures of the phosphonates mentioned.

In addition to the fabrics from the mentioned substance classes the agents according to the invention more usual Ingredients of washing, rinsing or contain cleaning agents, in particular bleaching agents, bleach activators, Enzymes, silver preservatives, colors and fragrances are important. These substances are described below.

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

To when washing at temperatures of 60 ° C and among them to achieve an improved bleaching effect, bleach activators can be incorporated into the detergent tablets. Can be used as bleach activators Compounds containing aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid result can be used. Substances containing the O- and / or N-acyl groups of the abovementioned are suitable Number of carbon atoms and / or optionally substituted benzoyl groups wear. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-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, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with stick Tripod ligands containing substances as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

In particular, there are enzymes from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or others Glycosyl hydrolases and mixtures of the enzymes mentioned in question. All these hydrolases wear in the wash for removing stains such as protein, fat or starchy Stains and graying. Cellulases and other glycosyl hydrolases can about that by removing pilling and microfibrils for color retention and increase contribute to the softness of the textile. For bleaching or for inhibition the color transfer can oxireductases can also be used. Are particularly well suited from bacterial strains or Mushrooms such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens obtained enzymatic agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus ientus are used. There are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytically active enzymes or Protease and cellulase or from cellulase and lipase or lipolytic acting enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic Enzymes and cellulase, but especially protease and / or lipase-containing Mixtures or mixtures with lipolytically active enzymes of of special interest. Examples of such lipolytically active Enzymes are the well-known cutinases. Also peroxidases or oxidases have in some cases proven suitable. Suitable amylases include in particular α-amylases, Iso-amylases, pullulanases and pectinases. As cellulases preferably cellobiohydrolases, endoglucanases and R-glucosidases, which are also called cello bias, or mixtures of these used. Since different types of cellulase differ by their CMCase and avicelase activities can distinguish the desired activities are set by targeted mixtures of the cellulases become.

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

Servings of detergent according to the invention for the machine dishwashing can to protect the dishes or the machine contain corrosion inhibitors, especially Silver protective agents in the field of automatic dishwashing have special meaning. The known substances can be used the state of the art. In general, silver protection agents in particular selected from the group of triazoles, benzotriazoles, bisbenzotriazoles; the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. To be used particularly preferably are benzotriazole and / or alkylaminotriazole. One finds in cleaner formulations about that out often agents containing active chlorine, which clearly corrode the silver surface can reduce. Chlorine-free cleaners especially contain oxygen and nitrogenous ones organic redox-active compounds, such as di- and trihydric phenols, z. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Prefers here are the transition metal salts, the selected are from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Likewise can Zinc compounds are used to prevent corrosion on the wash ware become.

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 manufacturing 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.

The pH of the agents according to the invention in the desired Bringing range, the use of pH adjusting agents can be indicated his. All of them can be used here known acids or lyes, provided that their use does not result from application technology or ecological establish or for reasons of consumer protection. Usually exceeds the amount of these adjusting agents is not 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 known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalate laten or anionically and / or nonionically modified derivatives of these. Of these, the sulfonated derivatives of the phthalic acid and terephthalic acid polymers are particularly preferred.

Optical brighteners (so-called "whiteners") can according to the invention as a textile detergent made up compositions according to the invention can be added to the graying and yellowing of the treated Eliminate textiles. These substances pull on the fiber and cause a brightening and feigned bleaching effect by they invisible ultraviolet radiation into visible longer wrinkled Convert light, being the ultraviolet absorbed from sunlight Light as a slightly bluish Fluorescence is emitted and with the yellow tone of the grayed or yellowed laundry pure white results. Suitable compounds come from the substance classes, for example 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenylene, Methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid, Benzoxazole, benzisoxazole and benzimidazole systems as well as by Heterocycle-substituted pyrene derivatives. The optical brighteners are common in amounts between 0.05 and 0.3% by weight, based on the finished product Means used.

Graying inhibitors have that Task, the detached from the fiber Keep dirt suspended in the fleet and keep it moving to prevent the dirt. For this purpose, water-soluble colloids are usually more organic Suitable in nature, for example glue, gelatin, salts of ether sulfonic acids Strength or the cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water soluble, polyamides containing acidic groups are suitable for this purpose. Farther can be soluble Starch preparations and other than the above starch products use, e.g. degraded starch, aldehyde starches, etc. Polyvinyl pyrrolidone is also useful. However, are preferred 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 their mixtures in amounts of 0.1 to 5% by weight, based on the composition, used

The agents according to the invention can - also with further additional benefits. Here are for example for inventive as a textile detergent made-up agents color transfer inhibitors Compositions, agents with "anti-gray formula", agents with ironing relief, Agents with special fragrance release, agents with improved dirt release or Prevention of pollution, antibacterial agents, UV protection agents, color refreshing agents, etc. can be formulated. Some examples will be explained below: Because textile fabrics, in particular from rayon, rayon, cotton and mixtures thereof, able to wrinkle, because the individual fibers prevent bending, kinking. Pressing and squeezing Crosswise to the fiber direction, the agents according to the invention can be synthetic Anti-crease included. These include, for example, synthetic Products based on fatty acids, Fettsäureestern. fatty acid amides, -alkyl esters, -alkylolamides or fatty alcohols, mostly with Ethylene oxide are implemented, or products based on lecithin or modified phosphoric acid ester.

To fight microorganisms can the agents according to the invention contain antimicrobial agents. A distinction is made here depending on the antimicrobial spectrum and mechanism of action between Bacteriostatics and bactericides, fungistats and fungicides etc. Important substances from these groups are, for example, benzalkonium chlorides, Alkylarlyl sulfonates, halophenols and phenol mercuric acetate, wherein in the inventive means also entirely these connections can be dispensed with.

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 surfactants 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 the previous one.

The antimicrobial active ingredient can be selected from ethanol, n-propanol, i-propahol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerin, 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-choorphenyl) -N- (3,4-dichlorophenyl) urea, N, N '- (1,10-decanediyldi) 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 ₁ , N ₁ -methyldiguanido-N ₅ , N ₅ ') -hexanedihydrochloride, 1,6-di- (N ₁ , N ₁ ' -o-chlorophenyldiguanido-N ₅ , N ₅ ') -hexane-dihydrochloride, 1,6-di- (N ₁ , N ₁ ' - 2,6-dichlorophenyldiguanido-N ₅ , N ₅ ') hexane-dihydrochloride, 1,6-di- [N ₁ , N ₁ ' -beta- (p-methoxyphenyl) diguanido-N ₅ , N ₅ '] -hexanes- 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- (N ₁ , N ₁ '-phenyldiguanido-N ₅ , N ₅ ') -di-n-propylether-dihydrochloride, ome ga: omega'-di- (N ₁ , N ₁ '-p-chlorophenyldiguanido-N ₅ , N ₅ ') -di-n-propylether-tetrahydrochloride, 1,6-di- (N ₁ , N ₁ '-2 , 4-dichlorophenyldiguanido-N ₅ , N ₅ ') hexane-tetrahydrochloride, 1,6-di- (N ₁ , N ₁ ' -p-methylphenyldiguanido-N ₅ , N ₅ ') hexane-dihydrochloride, 1,6-di - (N ₁ , N ₁ '-2,4,5-trichlorophenyldiguanido-N ₅ , N ₅ ') hexane-tetrahydrochloride, 1,6-di- [N ₁ , N ₁ '-alpha- (p-chlorophenyl) ethyldiguanido -N ₅ , N ₅ '] hexane-dihydrochloride, omega: omega-di- (N ₁ , N ₁ ' -p-chlorophenyldiguanido-N ₅ , N ₅ ') m-xylene-dihydrochloride, 1,12-di- ( N _1, N ₁ '-pchlorophenyldiguanido-N _5, N _5') dodecane dihydrochloride, 1,10-di- (N _1, N ₁ '-phenyldiguanido-N _5, N _5') - decane tetrahydrochloride, 1, 12-Di- (N ₁ , N ₁ '-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- (ptolyl biguanide ), Ethylene bis (3,5-dimethylphenylb iguanide), ethylene bis (p-tert-amylphenyl biguanide), ethylene bis (nonylphenyl biguanide), ethylene bis (phenyl biguanide), ethylene bis (N-butylphenyl biguanide), ethylene bis (2,5-diethoxyphenyl biguanide) ), Ethylene bis (2,4-dimethylphenyl biguanide), ethylene bis (odiphenyl biguanide), ethylene bis (mixed amyl naphthyl biguanide), N-butyl ethylene bis (phenyl biguanide), trimethylene bis (o-tolyl biguanide), N-Buty1-trimethyl-bis- (phenyl biguanide) and the corresponding salts such as acetates, gluconates, hydrochlorides, hydrobromides, citrates, bisulfites, fluorides, polymaleates, N-cocosalkyl sarcosinates, phosphates, hypophosphites, perfluorooctanoates, silicates, sorbates, malteylates, salicylates , Tartrates, fumarates, ethylenediaminetetraacetates, iminodiacetates, cinnamates, thiocyanates, arginates, pyromellitates, tetracarboxybutyrates, benzoates, glutarates, monofluorophosphates, perfluoropropionates and any mixtures thereof. 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 agent of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent 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 ₁ -C ⁴ ₂₂ alkyl radicals, C ₇ -C ₂₈ aralkyl radicals or heterocyclic radicals, where two or, in the case of an aromatic bond, as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, for example a pyridinium or imidazolinium compound, and represent X-halide ions , Sulfate ions, hydroxide ions or similar anions. For an optimal antimicrobial effect, at least one of the residues preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.

QAV are due to the implementation of tertiary amines with alkylating agents, e.g. 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 succeed particularly easy, also the quaternization of tertiary amines with two long residues and a methyl group can be created using Methyl chloride can be carried out under mild conditions. Amines over three have long alkyl radicals or hydroxy-substituted alkyl1 radicals not very reactive and are preferably quaternized with dimethyl sulfate.

Suitable QAC are, for example, benzalkonium chloride (N-alky1-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-timethyl-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), dioctyldimethylammoniumchloric, 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 ₁₈ -alkyl radicals, in particular C ₁₂ -C ₁₄ -alkyl-benzyl-dimethylammonium 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 ins Special from 0.01 to 0.2 wt .-% used.

To unwanted, due to exposure to oxygen and other oxidative processes caused changes in the agents and / or To prevent the treated textiles, the agents can have antioxidants contain. This class of compounds includes, for example, substituted ones Phenols, hydroquinones, pyrocatechols and aromatic amines as well organic sulfides, polysulfides, dithiocarbamates, phosphites and Phosphonates.

An increased wearing comfort can the additional Use of antstatics result, the agents according to the invention additionally enclosed become. Antistatic agents increase the Surface conductivity and enable thus an improved drainage formed charges. External antistatic agents are usually substances with at least one hydrophilic molecular ligand and give on the surfaces a more or less hygroscopic film. These are mostly surface-active Antistatic agents can be broken down into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphoric (phosphoric acid esters) and divide 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 Finishing effect is achieved.

To improve water absorption, the Rewettability of the treated textiles and for relief of ironing of the treated textiles can in the agents according to the invention, for example Silicone derivatives are used. These also improve that rinse 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 one to five Have carbon atoms and are partially or completely fluorinated. preferred Silicones are polydimethylsiloxanes, which may be derivatized could be and then are amino-functional or quaternized or Si-OH-, Si-H- and / or have Si-Cl bonds. The viscosities of the preferred silicones are at 25 ° C in the range between 100 and 100,000 centistokes, with the silicones in amounts between 0.2 and 5% by weight, based on the total agent can be used.

Finally, the agents according to the invention also contain UV absorbers that attach to the treated textiles and lightfastness of the fibers improve. Connections that you want Have properties are, for example, those due to non-radiation Deactivating active compounds and derivatives of benzophenone with substituents in 2- and / or 4-position. Substituted benzotriazoles are also in 3-position phenyl-substituted acrylates (cinnamic acid derivatives), if appropriate with cyano groups in the 2-position, salicylates, organic Ni complexes as well as natural substances such as umbelliferone and the body's own urocanoic acid.

Another subject 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 foil sealing and / or Thermoforming;
• ii) production of a hollow shell by solidification under at least partial inclusion of the Solid produced in step i).

Optionally, those produced according to the invention Filled molds and be locked. Processes according to the invention are preferred here in those following Step ii) the following steps are carried out:

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

As mentioned at the beginning, hollow shells can also be produced which are not solids contain. These hollow shells are filled with a solidifying one Closed melt, which at least one molded body at least partially encloses, this also leads to hollow shapes according to the invention, which in their Wall at least one solid enclose at least partially.

• i) Herstellung mindestens eines Festkörpers, vorzugsweise durch Tablettierung und/oder Gießen und/oder Strangpressen und/oder Spritzgießen und/oder Blasformen und/oder Verkapseln und/oder Foliensiegeln und/oder Tiefziehen;
• ii) Bereitstellung einer (befüllten) Hohlschale und Verschließen dieser Hohlschale durch Übergießen mit mindestens einer Schmelze und Erstarren unter mindestens anteilsweisem Einschluß des in Schritt i) hergestellten Festkörpers

umfaßt.Another object of the present invention is therefore a process for the production of 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 sealing of this hollow shell by pouring over it with at least one melt and solidifying with at least partially including the solid body produced in step i)

includes.

It has already been stated above that both Process variants according to the invention can be combined with each other. In this way, agents according to the invention are obtained, which has at least two solid bodies in the wall of the hollow mold partially include. Of course can with these means both the two wall materials as well the at least two solids be composed the same or different. Preferred according to the invention Variants of the latter method are therefore characterized in that that the or when repeating according to step (v) at least one step iv) the wear of the hollow shell by pouring over at least one melt and solidify at least partially Inclusion of a other solid includes.

As already mentioned above, the Hollow molds with at least one partially cast in solid and / or the filled ones and closed molds with at least one at least partially cast solid additionally be provided with a coating. Here are methods according to the invention preferred where following the closing a coating layer is applied to the portioned agent in the hollow shell becomes.

Completely analogous to the above statements in terms of of the agents according to the invention are also methods according to the invention preferred, in which the one produced or provided in step ii) Hollow shell wall thickness from 100 to 6000 μm, preferably from 120 to 4000 μm, particularly preferably from 150 to 3000 μm and in particular from 200 to 2500 μm has, with wall thicknesses less than 2000 μm are again preferred.

The manufacture of the hollow shell or -form in step ii) can be done with different techniques. in the The simplest case is a flowable mixture filled into an appropriate form, left to harden there and subsequently removed from the mold. The disadvantage here is the design of the shape, because the desired wall thickness the resulting hollow body a quick filling complicated geometries.

Alternatively, the solidifying mixture filled in a mold that are just called a cavity is trained. Would if you let the mixture solidify there, you would get a compact one Body, no hollow shell. Through appropriate process management and selection of materials (on the one hand the melting, on the other hand the die shape) for example in terms of their heat capacity and conductivity can be guaranteed be that the Mix first solidified on the wall of the mold. If you turn it Form after a certain time t, the excess mixture flows off and leaves one Lining the form, which itself is a hollow shell, the after complete Solidification can be removed from the mold. As already mentioned, the filling can also take place before demolding; also filling during the solidification process is possible.

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

As an alternative to filling the Mold and pouring excess mixture can the die shape is only partially filled become. In these cases the mixture is stamped with a suitable stamp pressed against the wall of the die, where it solidifies into a hollow body. This variant of the method effectively represents an intermediate form the "pouring technique" and the casting technique in negative forms of the hollow body Corresponding procedures in which an open Die shape with the flowable shell material filled and the material by a, if necessary, cooled stamp on the walls of the Form crowded and thus a hollow mold is produced, are therefore also preferred. Particularly advantageous in this procedure, which is also referred to as the "cold stamp method", is the possibility also large quantities with precisely defined wall thickness the hollow body manufacture. In addition, the process is largely insensitive to fluctuating flow properties and also with higher viscous Mixtures applicable.

The procedures described above are particularly suitable for producing hollow bodies which have a Have a shape without undercuts, i.e. they have the shape of a "shell", i.e. an opening area which the largest horizontal Cross sectional area equivalent. These "bowls" can be filled and optionally be closed.

Regarding the shape of the shells There are no limits to the expert's choice. Of the Hemisphere over angular ("cardboard-like") shells up to to complex structures with a pronounced surface structure (e.g. in form of nutshells or animal forms) are all hollow body produced.

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

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

Within the scope of the present invention are preferred variants of the methods described above characterized in that a Multi-layer hollow shell is produced by the process step is repeated with a differently composed melt.

As mentioned earlier, can be used to close the Hollow mold also serve another hollow mold. Here are methods according to the invention preferred, in which the hollow shape has flange parts and in step iv) by positive locking and / or Adhesion and / or Gluing and / or welding is closed with another 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 on the needed Casting temperature tempered, where appropriate can be pre-crystallized in a targeted manner. The Melt is then over heated and / or insulated pipe systems to the dosing stations supplied; in parallel, the individual molds are brought to the desired temperature preheated or cooled.

The liquid melt is in a casting machine dosed into the mold troughs, up to the upper edge of the die filled become. As a rule, several identical molds run on the casting machine over and are filled. After leaving the casting machine (or driving past the dosing head) the filled forms either a cooling section fed in or moved or "parked" until the melt solidifies from the outside starts. Essential for the later Wall thickness The molded shell to be formed is, among other things, the substance-dependent cooling time.

After the specified time if the shape is turned from top to bottom or turned upside down, so that the not yet solidified and excess melt mass from the mold into a waiting collection reservoir for return to the process expires. ever according to material system and especially in the case of slowly solidifying melts is not yet a completely solidified shell at the time of emptying trained so that mainly the adhesion on the mold for the Remains of the melt mass in the form ensures. The adhesive shell formation can be supported by an eccentric movement of the form taking the centrifugal forces the still flowing Melt evenly to the mold surface transport and for the formation of a shell with uniform wall thickness. Degassing of the melt by vibration of the mold may also be possible to be necessary.

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

According to this, the training of Shell by cooling completed become. If necessary, about the edge of the mold protrudes Shell remnants can can be cut off using knives or thermal rollers can reach.

The molded shell will then filled and the filling later cooled if necessary. Depending on the desired type of closing, the shape becomes complete or only partially filled. To close a sealing barrier layer can be applied to the mold (especially with liquid Fillings) which consists of a substance that has a lower melting point has than the shell material and can be sprayed well. The tight closing the form can then be filled by filling the Mold shell with the melt for the shell material. For equal lid formation and any degassing that may be required during the solidification period Form in turn vibrated. The solidification to finished moldings can also be promoted here by passing through a cooling section.

Finally, the moldings in removed from a mold emptying station. To do this, the shape is from top to bottom turned down so that the formed bodies can fall down onto a conveyor belt or be put down. This demolding step can be done by twisting / twisting the mold and / or by punch on the back and / or by Defformungs- / Putzer stamp supports become.

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

1 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.

2 an agent analog 1 , a liquid-filled gelatin capsule being inserted into the transparent melt.

The agents according to the invention are particularly suitable as a washing or cleaning agent. Another subject of the present The invention is therefore the use of the agents according to the invention as a washing or cleaning agent. Here are particular procedures preferred for washing textiles in a household washing machine, in which one or more portioned agents according to the invention in the bleach dispenser brings in the washing machine and runs a washing program.

Drum dosing is also a matter of course possible. Here are the inventive methods for Washing clothes in a household washing machine is preferred, in which one or more portioned agents according to the invention in the Brings in the washing machine drum and run a washing program leaves.

The portions according to the invention are also suitable for cleaning dishes in a domestic dishwasher. Here are methods according to the invention for cleaning dishes in a household dishwasher preferred in which one or more portioned according to the invention Agent in the dishwasher brings in and runs a cleaning program.

Claims (26)

Portioned agent, 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. 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, especially preferably from 45 to 200 ° C and in particular from 50 to 160 ° C, lies. 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, dicarboxylic acids, dicarboxylic 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 wt .-%, based in each case on the weight of the hollow mold. 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 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 ^® . Portioned agent according to one of claims 1 to 4, characterized in that the Hollow form wall thicknesses from 100 to 6000 μm, preferably from 500 to 5000 μm and in particular from 1000 to 4000 μm. Portioned agent according to one of claims 1 to 5, characterized in that the at least one other solid a tablet and / or a casting and / or an extrusion 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 is. Portioned agent according to one of claims 1 to 6, characterized in that the at least one other solid a hollow body is that with a liquid or flowable composition is filled. Portioned agent according to one of claims 1 to 7, characterized in that the Hollow shape in addition a further preparation, preferably a particulate preparation and especially a particulate Detergent or cleaning composition. Portioned agent according to any 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. Portioned agent according to one of claims 1 'to 9, characterized in that that the Outer surface of the Hollow mold at least 50%, preferably at least 60%, especially preferably at least 70% and in particular at least 80% of the surface of the By means of. Portioned agent according to one of claims 1 to 10, characterized in that the Ratio of Masses of unfilled Hollow shape (including cast parts) and content in the area 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. 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 pouring and / or extrusion and / or injection molding and / or blow molding and / or Encapsulation and / or foil sealing and / or deep drawing;  ii) Production of a hollow shell by solidification under at least partial Inclusion of the Solid produced in step i). Process for the preparation before portioned means, in particular washing or cleaning agents, comprising the steps:  iii) Production of at least one solid, preferably by tableting and / or pouring and / or extrusion and / or injection molding and / or blow molding and / or Encapsulation and / or foil sealing and / or deep drawing;  iv) Provision of a (filled) Hollow shell and closing this hollow shell by pouring over at least one melt and solidify at least partially Inclusion of the Solid produced in step i). A method according to claim 12, characterized in that in Connection to Step ü) carried out the following steps become:  iii) filling the hollow shell with at least one agent, preferably with at least one a detergent or cleaning agent; iv) closing the Hollow shell to form an at least partially closed Mold,  v) repeating steps iii) if necessary and iv). A method according to claim 14, characterized in that the or when repeating according to step (v) at least one step iv) closing the hollow shell by pouring over at least one melt and solidify at least partially Inclusion of a other solid includes. Method according to one of claims 12 to 15, characterized in that that in Connection to one or more of 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. Vaa 12 to 16, characterized in that following the close a coating layer is applied to the portioned agent in the hollow shell becomes. Method according to one of claims 12 to 16, characterized in that that the. in step ii) manufactured or provided hollow shell wall thicknesses of 100 to 6000 μm, preferably from 120 to 4000 μm, particularly preferably from 150 to 3000 μm and in particular from 200 to 2500 μm has, with wall thicknesses below 2000 μm are again preferred. Method according to one of claims 12 or 14 to 18, characterized characterized in that in Step ii) filled an open die form with the flowable shell material and after a time t between 0 and 5 minutes, the excess mass is emptied. Method according to one of claims 12 or 14 to 18, characterized characterized in that in Step ii) filled an open die form with the flowable shell material and the material by a, if necessary, cooled stamp on the walls of the Form crowded and so a hollow mold is produced. Method according to one of claims 12 or 14 to 18, characterized characterized in that in Step i) a closable Double form with the later solidified mass filled and during a time t between 0 and 5 minutes. Method according to one of claims 19 to 21, characterized in that that a multilayer cave shell is produced by the process step with a different composite melt is repeated. Method according to one of claims 12 to 19, characterized in that that the Has Hohlfom flange parts and in step iv) by positive locking and / or Adhesion and / or Gluing and / or welding is closed with another hollow mold. Process for washing textiles in a household washing machine, characterized in that one one or more portioned agents according to one or more of claims 1 to 11 into the dispenser brings in the washing machine and runs a washing program. Process for washing textiles in a household washing machine, characterized in that one one or more portioned agents according to one or more of claims 1 to 11 into the drum of the washing machine and a washing program expires. Process for cleaning dishes in a domestic dishwasher, characterized in that one one or more portioned agents according to one or more of claims 1 to 11 in the dishwasher brings in and runs a cleaning program.