DE10258584A1 - Portioned detergent or cleaning agent - Google Patents

Abstract

Container for dosing, packaging and storage of active substances with at least three receiving chambers, comprising a base body made of a first wrapping material and at least one web located within the base body and a first sealing surface consisting of a second wrapping material, which seals the base body, characterized in that the container furthermore has a second sealing surface, which together with the web and the base body at least partially delimits at least two receiving chambers, is characterized by high storage and transport stability, in particular with regard to the stability of the sealing seams. Such containers are particularly suitable for separate metering, packaging and storage of mutually incompatible ingredients, preferably liquid or flowable ingredients. By using the webs mentioned, the number of necessary sealing steps can be minimized in the manufacture of these containers.

Description

The present invention resides the area of the portion container for active substances or combinations of active ingredients. In particular, this invention relates to subdivided or compartmentalized containers, ie containers with several receiving chambers, and means comprising these containers and one or more active substances. These funds are suitable, for example for the common dosing of mutually incompatible active substances or combinations of active substances. A preferred field of application of the claimed agents is the field of dosing, packaging, storage, washing and cleaning active Substances such as those used for cleaning textiles, Dishes or hard surfaces be used.

The portioned packaging of active ingredients or drug combinations plays in many areas of applied Chemistry, for example in pharmacy, crop protection, but also play an important role in the area of washing or cleaning agents. Portioning can be time-consuming and labor-intensive Dosing by the user is avoided, as is direct contact of the user with the corresponding active ingredients.

For example, WO 93108095 A1 (Rhone-Poulenc) discloses a bag of water soluble or water-dispersible material, which has two horizontal receiving chambers has and for example for packaging toxic substances suitable is. The bags can be produced by the thermoforming process.

Subject of WO 02185738 A1 (Reckitt Benckisers) are water soluble container with at least two on top of each other arranged receiving troughs. These containers are manufactured by gradually sealing individual foils or prefabricated ones filled Individual compartments to the final container.

WO 02142401 A1 (Procter & Gamble) describes one Method for machine cleaning of dishes claimed, which using a container with several receiving chambers. Point the appropriate containers a horizontal arrangement of the individual receiving chambers on and are formed by sequential bonding of individual foils of the receiving chambers, including individual ones, by deep drawing Shaped, foils can be used.

The manufacture of those cited in the Multi-chamber containers described in documents are made by repeated fill and sealing preformed receptacles or by gluing several separately prefabricated, filled individual chambers. The process products are always characterized by horizontally one above the other placed arrangement of the receiving chambers with horizontally compartmentalizing partitions out. Multi-chamber container, caused by multiple thermal loads or repeated gluing the same container areas sealed, also have an increased tendency to leak, in particular along the sealing seams thus obtained.

The object of the present invention was to avoid the disadvantages described above. In particular, multi-chamber dosing units with at least three Receiving chambers are provided, which due to increased stability of the sealing seams have a reduced tendency to leakage. The making of this Multi-chamber dosing units should be without the pre-assembled pre-glued filled Individual compartments are made and should have a minimal number Have sealing steps. Furthermore, multi-chamber dosing units are provided which have an increased overall stability. So should preferably tilt or twist the individual chambers around a web axis, as is the case in the multi-chamber metering units of the stand technology occurs, is reduced or avoided altogether.

It has now surprisingly been found that at Process for the production of multi-chamber containers the number of sealing steps can be minimized if the basic body of the multi-chamber container at least has a web.

• a) Formgebende Verarbeitung eines ersten Hüllmaterials unter Ausbildung eines oberseitig geöffneten Grundkörpers der Höhe h, umfassend eine die oberseitige Öffnung des Grundkörpers bildende Krempe, sowie mindestens zwei, durch mindestens einen Steg der Höhe h – x getrennte Aufnahmekammern;
• b) Versiegeln der Aufnahmekammer(n) mit einem zweiten Hüllmaterial, wobei die Siegelnaht wenigstens anteilsweise in einer Ebene der Höhe h – x liegt;
• c) Befüllen des verbleibenden Behältervolumens.

A first subject of the present application is therefore a method for producing a container, comprising the steps:

• a) shaping processing of a first wrapping material to form a base body of height h which is open at the top, comprising a brim forming the top opening of the base body and at least two receiving chambers separated by at least one web of height h - x;
• b) sealing the receiving chamber (s) with a second covering material, the sealing seam lying at least partially in a plane of height h-x;
• c) Filling the remaining container volume.

As height h of the manufactured according to the invention body the vertical distance applies within the scope of the present application between a first sealing plane formed by the brim and the lowest point of the receiving chambers formed in step a) of the container according to the invention. Become formed in step a) more than two receiving chambers, so the separating according to the invention Bridges of course the same height h - x and / or different heights h - x and h - x; to have. The analogy is in the latter case in step b) with a second wrapping material at least in part on the respective different web heights h - x; sealed.

The according to the inventive method manufactured containers have at least one web of height h - x. The value "x" stands for a length, which is smaller than "h". Hence x <h. The relative Difference between the values "h" and "x" is preferred Method at least 5%, preferably at least 10%, especially preferably at least 20%, very particularly preferably at least 35% and in particular at least 50%, each based on the amount h. With in other words The relationship the height h - x of the footbridge to the height h of the basic body in a preferred embodiment less than 0.95, preferably less than 0.90, particularly preferred less than 0.80, most preferably less than 0.65 and especially less than 0.50. Methods according to the invention are very particularly preferred, where the height h - x the web between 10 and 95%, preferably between 15 and 85%, particularly preferably between 25 and 75% and in particular between 35 and 60 % the height h of the basic body is. The absolute difference between the values "h" and "x" is in a preferred embodiment of the method according to the invention preferably between 0.1 and 8 cm, particularly preferably between 0.2 and 6 cm, particularly preferably between 0.4 and 5 cm and in particular between 0.5 and 4 cm.

The method according to the invention begins with shaping processing of a first wrapping material. As form-giving Processes for processing the wrapping materials, especially the first wrapping material thermoforming processes, injection molding processes or casting process. As a "deep drawing process" are in the frame referred to such methods in the present application which a first film-like wrapping material after spending over a receiving trough located in a die forming the deep-drawing plane and molding the wrapping material into this receiving trough by the action of pressure and / or vacuum is deformed. The wrapping material can be done before or during molding by exposure to heat and / or solvent and / or conditioning by changes compared to environmental conditions relative humidity and / or temperatures are pretreated. The pressure can be exerted by two parts of a tool, which behave like positive and negative to each other and one between these tools spent film deforming when compressed. Suitable as pressure forces however, the effect of compressed air and / or the dead weight of the film and / or the dead weight of one on top of the Foil spent active ingredient.

With these deep-drawing processes, continue between procedures in which the wrapping material is horizontally into a Forming station and from there in a horizontal manner for filling and / or Sealing and / or separating is carried out and procedure when which the wrapping material has a Continuously rotating die forming roller (optionally optional with an opposite out Male forming roll, which forms the upper punch to the cavities of the Guide die forming roller) guided will distinguish. The first-mentioned process variant of the The flatbed process is both continuous and discontinuous to operate the process variant using a form roller usually takes place continuously.

In the method according to the invention, a web is formed by shaping a first covering material. This web is preferably designed so that it has no contact point with the side wall of the container. In a method preferred according to the invention, the web formed in step a) has no contact point with the side walls of the container. This means that at least one web located in the base body has no such contact points. Of course, the base body cannot have only one web. Preferred base bodies have two, three, four, five or more separate webs which are not in contact with one another. Methods according to the invention are now characterized in that at least one, but preferably all, of the webs formed in step a) has / have no contact points with the peripheral brim. The web can run linearly or non-linearly in the top view ("supervision" in the context of this application refers to the observation of the container with a view orthogonal to the deep-drawing plane). It is preferred in the context of the present application that this web is not linear in the top view Such webs can be designed in all technically feasible forms. Preferred embodiments are described in more detail below:
Preferred methods according to the invention are characterized in that the web formed in step a) has no contact point with the side walls of the container. Such a web is necessarily closed to form two separate receiving chambers, has curvatures and / or corners and includes a surface when viewed from above. This surface enclosed by the web in the top view, that is to say the opening on the top side of a receiving chamber enclosed by such a web, can, just like the surface surrounded in the top view by the self-contained brim, that is, the top opening of the base body, each have technically feasible symmetrical and non-symmetrical shape. If the self-contained web or the self-contained brim has only curvatures and no corners, a circular or oval surface is realized, for example. If the web or brim has opposing curvatures, round or oval surfaces with indentations result (e.g. kidney or peanut shape). If curvatures and corners are combined, surfaces in the form of a drop or an archway can be created, for example. Two, three, four, five, six, seven, eight, or polygonal webs or brims can also be realized and are particularly preferred. In a special embodiment, webs are preferred which have no contact points with the surrounding brim and have no circular shape.

In a further preferred embodiment of the method according to the invention the web has at least one contact point with the side walls of the container on. Container, which have two such contact points are special prefers. Like the self-contained webs described above, can also from one point of the sidewall to another point of the Sidewall trending curvatures and / or have corners. In preferred methods according to the invention the first casing material is shaped in step a) with formation of a web with at least one, preferably two, three, four, five or more corner (s). The one where the two meet in such a corner sections angle of the web is preferably between 1 and 179 °, especially preferably between 45 and 135 °, very particularly preferably between 70 and 110 ° and in particular between 80 and 100 °.

Methods according to the invention are particularly preferred in which the web formed in step a) by shaping processing of a first covering material has at least one, preferably two, three, four, five or more curvatures). The radii of curvature of these curvatures can vary widely. Based on the maximum diameter d _{max of} the area enclosed by the peripheral brim, preferred radii of curvature have values between 0.1 and 5 d _max , preferably between 0.2 and 3 d _max and in particular between 0.3 and 1.5 d _max ,

Of course, one can be in supervision non-linear web also through a forked web be realized. In a preferred variant of the method according to the invention has the trained by the shaping processing in step a) Bridge at least one, preferably two, three, four, five or more crotches on. Forks are preferred three, four or five, however, preferably three or four branches of the non-linear running web meet. Be particularly preferred Bars with a fork and three branches and bars with two crotches and two branches each. In another preferred embodiment becomes a web, which is a contact point with the surrounding brim in a first fork split into two branches, these branches in turn in a second fork to each other guided and the web is then at a second contact point with the circumferential brim runs out. Such a container has three separate receiving chambers.

The width of between each Compartment webs can vary. Preferred methods according to the invention are characterized in that the Web formed in step a) has a width between 0.5 and 15 mm, preferably between 0.6 and 12 mm, particularly preferably between 0.7 and 10 mm, very particularly preferably between 0.8 and 8 mm and in particular between 1.0 and 5.0 mm. Particularly preferred are bridges, which are not over their entire length have constant width.

In a preferred embodiment of the method according to the invention at least one of the receiving chambers is filled after step a). Especially methods according to the invention are preferred, where the top opening of the basic body after filling of the remaining container volume is sealed.

• a) Formgebende Verarbeitung eines ersten Hüllmaterials unter Ausbildung eines oberseitig geöffneten Grundkörpers der Höhe h, umfassend eine die oberseitige Öffnung des Grundkörpers bildende Krempe, sowie mindestens zwei, durch mindestens einen Steg der Höhe h – x getrennte Aufnahmekammern;
• b) Befüllen mindestens einer Aufnahmekammer;
• c) Versiegeln der befüllten Aufnahmekammer(n) mit einem zweiten Hüllmaterial, wobei die Siegelnaht wenigstens anteilsweise in einer Ebene der Höhe h – x liegt;
• d) Befüllen des verbleibenden Behältervolumens;

A preferred subject of the present application is therefore a method for producing a container, comprising the steps:

• a) shaping processing of a first wrapping material to form a base body of height h which is open at the top, comprising a brim forming the top opening of the base body and at least two receiving chambers separated by at least one web of height h - x;
• b) filling at least one receiving chamber;
• c) sealing the filled receiving chamber (s) with a second wrapping material, the sealing seam lying at least partially in a plane of height h - x;
• d) filling the remaining container volume;

• a) Formgebende Verarbeitung eines ersten Hüllmaterials unter Ausbildung eines oberseitig geöffneten Grundkörpers der Höhe h, umfassend eine die oberseitige Öffnung des Grundkörpers bildende Krempe, sowie mindestens zwei, durch mindestens einen Steg der Höhe h – x getrennte Aufnahmekammern;
• b) Versiegeln der Aufnahmekammer(n) mit einem zweiten Hüllmaterial, wobei die Siegelnaht wenigstens anteilsweise in einer Ebene der Höhe h – x liegt;
• c) Befüllen des verbleibenden Behältervolumens;
• d) Versiegeln der oberseitigen Öffnung des Grundkörpers mit einem dritten Hüllmaterial.

Another preferred subject of the present application is also a method for producing a container, comprising the steps:

• a) shaping processing of a first wrapping material to form a base body of height h which is open at the top, comprising a brim forming the top opening of the base body and at least two receiving chambers separated by at least one web of height h - x;
• b) sealing the receiving chamber (s) with a second covering material, the sealing seam lying at least partially in a plane of height h-x;
• c) filling the remaining container volume;
• d) sealing the top opening of the base body with a third covering material.

• a) Formgebende Verarbeitung eines ersten Hüllmaterials unter Ausbildung eines oberseitig geöffneten Grundkörpers der Höhe h, umfassend eine die oberseitige Öffnung des Grundkörpers bildende Krempe, sowie mindestens zwei, durch mindestens einen Steg der Höhe h – x getrennte Aufnahmekammern;
• b) Befüllen mindestens einer Aufnahmekammer;
• c) Versiegeln der befüllten Aufnahmekammer(n) mit einem zweiten Hüllmaterial, wobei die Siegelnaht wenigstens anteilsweise in einer Ebene der Höhe h – x liegt;
• d) Befüllen des verbleibenden Behältervolumens;
• e) Versiegeln der oberseitigen Öffnung des Grundkörpers mit einem dritten Hüllmaterial.

Finally, a particularly preferred subject matter of the present application is a method for producing a container, comprising the steps:

• a) shaping processing of a first wrapping material to form a base body of height h which is open at the top, comprising a brim forming the top opening of the base body and at least two receiving chambers separated by at least one web of height h - x;
• b) filling at least one receiving chamber;
• c) sealing the filled receiving chamber (s) with a second wrapping material, the sealing seam lying at least partially in a plane of height h - x;
• d) filling the remaining container volume;
• e) sealing the top opening of the base body with a third wrapping material.

In steps c) and e) of the method according to the invention become sealing surfaces applied. According to the invention, the sealing in step c) takes place under Formation of another reception chamber, which by the step c) applied sealing surface as well as parts of the body is limited. The sealing surface applied in step c) can one or more sealing seams exhibit. At least one of the sealing seams of this sealing surface preferably runs at least Proportionally along that in the shaping processing of the first shell material formed web. Methods according to the invention are preferred, where the sealing along the web and at least along one of the basic body forming side walls. The sealing layer in step e) is applied in one preferred embodiment completely along one the basic body enclosing encircling brim, which is preferably the top opening of this the body forms. For the sealing in steps c) and e), but especially for sealing in step e) of the preferred according to the invention Prefabricated closure parts, in particular closure parts, are suitable for the method, by injection molding or by compression molding, preferably by compression molding under the previous one and / or simultaneous heating, getting produced. Such prefabricated closure parts can in their design from the planars usually used Clearly distinguish sealing foils. In particular, are preferred Closing parts, which are convex and / or concave, preferably round or rounded arches, exhibit. In a preferred embodiment, these closure parts are wave-like buckles on. In addition to these "organic" forms, of course, too closing parts realizable, which to the outside or have protruding angular bulges on the inside. Will in step e) used a stretchable film for sealing, so can this planar film after sealing by shrinking the with the container provided with the sealing film also bulge outwards. such Shrinkage occurs particularly in deep-drawn containers. The "level" of those in these containers Active substances lie as a result of the shrinkage and the associated Reduction in the volume of the receiving chambers significantly above which is the top opening of the basic body forming brim. The sealing foil is domed outwards.

The top opening of the base body Brim is in a preferred embodiment of the method according to the invention planar. The width of this brim results from the chosen manufacturing process. If a deep-drawing process is used for shaping processing, so the width of the brim is determined by the separation of the base body Cutting or punching from the distance of the cutting lines to the opening of the Body. Is used for shaping processing, preferably during training a prefabricated body, an injection molding process used, this preferably has a circumferential sealing brim; after closing of the basic body with a final sealing surface it is possible Outside die cut next to this injection molded brim, however it will preferred, against the design-technical background of a tolerance and a perfect fit Manufacture of multi-cavity punching tools, to punch through the injection molded rim sealing surface.

In a preferred variant of the inventive method show the sealed seams the sealing surfaces applied in steps c) and e) have no overlaps or overlaps on. For example, it is preferred that the seal of the first sealing surface exclusively along the web and / or along the inside of the side walls of the the body done while the sealing of the second sealing layer only along one the top opening of the basic body forming brim with this body.

A further wrapping material is used for sealing, which can be identical to the first and / or second wrapping material mentioned above. The sealing takes place, for example, by means of a film or a preformed closure part. The materials to be sealed can be welded by the action of heat or glued using adhesive. Solutions are preferably suitable as adhesives medium (e.g.

Water), which the to be glued Areas of wrapping materials superficial dissolve. Solutions of are also preferred as adhesives Shell materials. In addition to (solved) Adhesive systems can but also melt-based adhesives, especially from packaging technology known hot melts may be preferred. The application of the adhesive can for example by spraying and / or by roller application and / or by contacting with capillaries Wetting systems, such as moistened felt, take place.

• – Reaktionen zwischen dem im Behälterinnenraum befindlichen Mitteln und den Hüllmaterialien oder
• – Reaktionen zwischen dem im Behälterinnenraum befindlichen Mitteln und von außen durch das Hüllmaterial in den Behälterinnenraum diffundierten Substanzen (z.B. Wasser) oder
• – Reaktionen der im Behälterinnenraum befindlichen Mittel miteinander oder
• – durch Licht oder Wärme verursachte Zerstzungsreaktionen einzelner im Behälterinnenraum befindlichen Mittel.

In a further preferred preferred variant of the method according to the invention, the seal has a device for pressure equalization between the container interior and the surrounding atmosphere. Such pressure equalization is particularly preferred for those methods according to the invention in which the interior of the container is filled with such liquid or solid active substances which tend to release gas in the course of storage after sealing. Such reactions are usually caused by chemical reactions, in particular

• - Reactions between the agent in the interior of the container and the wrapping materials or
• - Reactions between the agents in the interior of the container and substances (eg water) or diffused from the outside through the shell material into the interior of the container
• - Reactions of the agents in the container interior with one another or
• - Destruction reactions of individual agents inside the container caused by light or heat.

To the active substances, which for Gas release after one of the reactions described tend to count in particular the bleaches described below, for example the Percarbonates and perborates. As a device for pressure equalization within the scope of the present application, in particular valves, preferably however micro holes, prefers micro holes with a diameter between 0.1 and 2 mm, particularly preferred between 0.2 and 1.5 mm and in particular between 0.5 and 1 mm. Farther microchannels are also suitable or the use of permeable wrapping materials. In a particularly preferred embodiment, the closure part and / or container nanoholes with a diameter between 0.1 and 100 μm, preferably between 0.2 and 80 μm and in particular between 0.4 and 60 μm.

In a preferred according to the invention The process becomes at least one water-soluble or water-dispersible shell material used. In a preferred method, the first wrapping material is and / or the second wrapping material and / or the third wrapping material water soluble or water dispersible. Preferably at least two of the shell materials, all three shell materials used are particularly preferably water-soluble or water-dispersible. It may be the case with the envelope materials used deal with identical or different materials. So you can the wrapping materials for example in their thickness and / or their chemical composition differ. In a particularly preferred embodiment of the method according to the invention indicate the shell materials used have an identical chemical composition, differ however in their thickness. For example, the side walls of the the body preferably a higher one Thickness than the sealing layers obtained in step c) and e). In a further preferred embodiment differ the envelope materials used for sealing both in their chemical composition as well as in its thickness from the wrapping material of the basic body. In Particularly preferred methods according to the invention are different shell materials from water soluble or water-dispersible material used, which different dissolution rates exhibit. It is preferred that the in particular Sealing material used wrapping materials in an aqueous medium dissolve faster than the shell materials used to manufacture the base body. The different solubilities can thereby both by a different material thickness, as also caused by different chemical compositions become.

In the method according to the invention are generally all through thermoplastic molding processes such as for example injection molding or deep-drawing processes and / or by melt-based casting processes processable wrapping materials can be used, but the use of water-soluble or water-dispersible packaging materials is preferred. Accordingly, preferred methods according to the invention are characterized that at least one of the wrapping materials used water soluble or is water dispersible.

• a) wasserlöslichen nichtionischen Polymeren aus der Gruppe der a1) Polyvinylpyrrolidone, a2) Vinylpyrrolidon/Vinylester-Copolymere, a3) Celluloseether
• b) wasserlöslichen amphoteren Polymeren aus der Gruppe der b1) Alkylacrylamid/Acrylsäure-Copolymere b2) Alkylacrylamid/Methacrylsäure-Copolymere b3) Alkylacrylamid/Methylmethacrylsäure-Copolymere b4) Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere b5) Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere b6) Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere b7) Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat-Copolymere b8) Copolymere aus b8i) ungesättigten Carbonsäuren b8ii) kationisch derivatisierten ungesättigten Carbonsäuren b8iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren
• c) wasserlöslichen zwitterionischen Polymeren aus der Gruppe der c1) Acrylamidoalkyltrialkylammoniumchlorid/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze c2) Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze c3) Methacroylethylbetain/Methacrylat-Copolymere
• d) wasserlöslichen anionischen Polymeren aus der Gruppe der d1) Vinylacetat/Crotonsäure-Copolymere d2) Vinylpyrrolidon/Vinylacrylat-Copolymere d3) Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere d4) Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen d5) gepfropften und vernetzten Copolymere aus der Copolymerisation von d5i) mindesten einem Monomeren vom nicht-ionischen Typ, d5ii) mindestens einem Monomeren vom ionischen Typ, d5iii) von Polyethylenglycol und d5iv) einem Vernetzter d6) durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltenen Copolymere: d6i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren, d6ii) ungesättigte Carbonsäuren, d6iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe d6ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten Ca_8-18-Alkohols d7) Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester d8) Tetra- und Pentapolymere aus d8i) Crotonsäure oder Allyloxyessigsäure d8ii) Vinylacetat oder Vinylpropionat d8iii) verzweigten Allyl- oder Methallylestern d8iv) Vinylethern, Vinylestern oder geradkettigen Allyl- oder Methallylestern d9) Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinylmethylether, Acrylamid und deren wasserlöslicher Salze d10) Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in α-Stellung verzweigten Monocarbonsäure
• e) wasserlöslichen kationischen Polymeren aus der Gruppe der e1) quaternierten Cellulose-Derivate e2) Polysiloxane mit quaternären Gruppen e3) kationischen Guar-Derivate e4) polymeren Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure e5) Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats e6) Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere e7) quaternierter Polyvinylalkohol e8) unter den INCI-Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 und Polyquaternium 27 angegeben Polymere.

Some particularly preferred water-soluble or water-dispersible coating materials which are suitable both for producing the base body and for sealing it are listed below. The polymers mentioned can be used as the covering material either alone or in combination with one another or in combination with other substances, for example plasticizers or solubilizers.

• a) water-soluble nonionic polymers from the group of a1) polyvinylpyrrolidones, a2) vinyl pyrrolidone / vinyl ester copolymers, a3) cellulose ether
• b) water-soluble amphoteric polymers from the group of b1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkylacrylic acrylamino / methacrylate amide (meth) acrylic acid copolymers b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b7) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers b8) copolymers of b8i) unsaturated carboxylic acids b8ii) cationically derivatized further unsaturated ionic carboxylic acids b8ii) nonionic monomers
• c) water-soluble zwitterionic polymers from the group of c1) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts c2) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts c3) methacroylethylbetaine / methacrylate copolymers
• d) water-soluble anionic polymers from the group of d1) vinyl acetate / crotonic acid copolymers d2) vinyl pyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers d4) graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid alone Mixture copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the non-ionic type, d5ii) at least one monomer of the ionic type, d5iii) of polyethylene glycol and d5iv) a crosslinker d6) copolymers obtained by copolymerizing at least one monomer from each of the three following groups: d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, d6iii) esters of long-chain Carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched Ca _8-18 alcohol d7) terpolymers from crotonic acid, vinyl acetate and an allyl or methallyl ester d8) tetra and pentapolymers from d8i ) Crotonic acid or allyloxyacetic acid d8ii) vinyl acetate or vinyl propionate d8iii) branched allyl or methallyl esters d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters d9) crotonic acid copolymers with one or more monomers from the group consisting of ethylene and vinyl ethers, acrylate, vinylbenzene, acrylate Salts d10) terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position
• e) water-soluble cationic polymers from the group of e1) quaternized cellulose derivatives e2) polysiloxanes with quaternary groups e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) copolymers with quaternary vinyl derivatives of dialkylaminoacrylate and methacrylate e6) vinylpyrrolidone-methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol e8) under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyqua ternium 27 indicated polymers.

Water-soluble polymers in the sense of Invention are those polymers that are at room temperature in water more than 2.5% by weight soluble are.

In the in the method according to the invention used wrapping material it is preferably at least partially a substance from the group (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, Polyethylene oxide, gelatin.

In a preferred process variant comprises at least one envelope material one or more water-soluble) Polymer (s), preferably a material from the group (if appropriate acetalized) polyvinyl alcohol (PVAL), polyvinyl pyrrolidone, polyethylene oxide, Gelatin, cellulose, and their derivatives and their mixtures.

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

enthalten."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 have degrees of hydrolysis of 98-99 and 87-89 mol%, respectively, so they still contain a residual content of acetyl groups. The polyvinyl alcohols are characterized on the part of the manufacturer by specifying the degree of polymerization 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. The coatings are made of polyvinyl alcohol largely impenetrable for Gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but let water vapor pass through.

Within the scope of the present invention it is preferred that in the method according to the invention used wrapping material at least partially comprises a polyvinyl alcohol, the Degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly is preferably 81 to 89 mol% and in particular 82 to 88 mol%. In a preferred embodiment there is that used in the method according to the invention first wrapping material at least 20% by weight, particularly preferably at least 40% by weight, entirely particularly preferably at least 60% by weight and in particular at comprises at least 80% by weight of a polyvinyl alcohol, the 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 as materials for the containers, it being preferred according to the invention that the shell material comprises a polyvinyl alcohol, the molecular weight of which ranges from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly preferably from 12,000 up 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

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (ex Clariant, risen in 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 that are particularly suitable as wrapping material can be found in the table below:

Other polyvinyl alcohols suitable as wrapping material 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).

The water solubility of PVAL can be due to Aftertreatment with aldehydes (acetalization) or ketones (ketalization) changed become. As particularly preferred and pronounced on the basis of it good solubility in cold water Polyvinyl alcohols have been found to be particularly advantageous, those with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof can be acetalized or ketalized. As extremely beneficial The reaction products made of PVAL and starch are to be used.

Furthermore, the water solubility by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, Change borax and so targeted to desired Set values. PVAL films are largely impenetrable for gases like oxygen, nitrogen, helium, hydrogen, carbon dioxide however water vapor will pass through.

Examples of suitable water-soluble PVAL films are the PVAL films available from Syntana Handelsgesellschaft E. Harke GmbH & Co. under the name "SOLUBLON ^® ". Their solubility in water can be adjusted to the degree, and films of this product range are available which are soluble in the aqueous phase in all temperature ranges relevant to the application.

Polyvinylpyrrolidones, abbreviated as PVP, can be described by the following general formula:

PVP are through radical polymerization made from 1-vinylpyrrolidone. Commercial PVP have molecular weights in the range of approx. 2,500 to 750,000 g / mol and are called white, hygroscopic Powder or offered as aqueous solutions.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula H- [O-CH ₂ -CH ₂ ] _n -OH which are produced industrially by base-catalyzed polyaddition of ethylene oxide (oxirane) in systems containing mostly small amounts of water with ethylene glycol as the starting molecule. They have molar masses in the range from approx. 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n from approx. 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.

Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as a water-soluble coating material is extremely widespread, particularly in pharmacy in the form of hard or soft gelatin capsules. Gelatin is found in the form of foils because of its compared to the previous one Because of the high-cost polymers mentioned, they are only used to a limited extent.

Are preferred in the context of the method according to the invention shell materials, which is a polymer from the group starch and starch derivatives, cellulose and Cellulose derivatives, especially methyl cellulose and mixtures thereof include.

Starch is a homoglycan, being the glucose units are α-glycosidic connected are. Strength is made up of two components of different molecular weights: from approx. 20 to 30% straight-chain amylose (MW. approx. 50,000 to 150,000) and 70 to 80% branched chain amylopectin (MW approx. 300,000 to 2,000,000). There are also small amounts of lipids, phosphoric acid and Cations included. While the amylose due to the binding in the 1,4-position long, helical, intertwined Forms chains with about 300 to 1,200 glucose molecules the chain for amylopectin after an average of 25 glucose units through 1,6-binding to a knot-like Formations with about 1,500 to 12,000 molecules of glucose. In addition to pure starch to make water soluble wrappings the detergent, detergent and detergent portions within the scope of the present invention also starch derivatives suitable, which can be obtained by polymer-analogous reactions from starch. Such chemically modified starches include, for example, products from esterifications or etherifications, in which hydroxy hydrogen atoms have been substituted. But also Strengthen, in which the hydroxy groups against functional groups that do not have a Oxygen atoms are replaced, can be used as starch derivatives deploy. The starch derivatives group, for example Alkali strengths, carboxymethyl (CMS), starch ester and ether and amino starches.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, viewed formally, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 500 to 5,000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

Preferred methods according to the invention are characterized in that one of the envelope materials used is transparent or translucent. For example, for injection molding and / or Thermoforming and / or sealing shell material used is preferred transparent. Under transparency is in the sense of this invention understand 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 of light is greater than 20%, it is to be regarded as transparent in the sense of the invention.

Other preferred wrapping materials are colored and / or printed. Particularly preferred colored and / or printed envelope materials are transparent or translucent.

Containers produced according to the invention the production of which was made of transparent covering material, can contain a stabilizing agent. Stabilizing agent in the sense of the invention are materials which are in the receiving chambers and / or the ingredients in a space before decomposition protect or deactivate by exposure to light. As particularly suitable antioxidants, UV absorbers and fluorescent dyes have been proven here.

Particularly suitable stabilizers in the sense of the invention are the antioxidants. In order to prevent undesired changes to the formulations caused by light radiation and thus radical decomposition, the formulations can contain antioxidants. Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants. Further examples are propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long-chain (C8-C22) esters of gallic acid, such as dodecyl gallate. Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives, such as isopropyl citrate, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic acid palmitate, organosulfur compounds, such as the esters of 3,3'-thiodipropionic acid with C _1-18 alkanols, in particular C _10-18 alkanols, metal ion deactivators which are capable of metal ions, such as copper, which catalyze the autooxidation. to complex, such as nitrilotriacetic acid and its derivatives and their mixtures. Antioxidants can be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.

Another class of stabilizers that can preferably be used are the UV absorbers. UV absorbers can improve the lightfastness of the recipe components. These include organic substances (light protection filters) that are able to absorb ultraviolet rays and release the absorbed energy in the form of long-wave radiation, eg heat. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles, such as, for example, the water-soluble benzenesulfonic acid 3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Cibafast ^® H), are also phenyl-substituted acrylates in the 3-position ( Cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid. Of particular importance are biphenyl and especially stilbene derivatives, which are commercially available as Tinosorb ^® FD or Tinosorb ^® FR ex Ciba. 3-Benzylidene camphor or 3-benzylidene norcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor, may be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene); Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropyl benzyl ester, salicylic acid homomethyl ester; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives, such as 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and Octyl Triazone or Dioctyl Butamido Triazone (Uvasorb HEB ^®); Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'methoxy-phenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-benzylidene camphor, such as 4- (2-oxo-3-bornylidene methyl) benzene sulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl, are particularly suitable as typical UV-A filters -4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds. The UV-A and UV-B filters can of course also be used in mixtures. In addition to the soluble substances mentioned, insoluble light-protection pigments, namely finely dispersed, preferably nanoized metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. Silicates (talc), barium sulfate or zinc stearate can be used as salts. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs in some other way from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobicized. Typical examples are coated titanium dioxide, such as titanium dioxide T 805 (Degussa) or Eusolex ^® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferably used.

UV absorbers can be used in amounts of up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight, based in each case on the Total weight of one in a compartment or space contained mixture of substances.

Another preferred one The class of stabilizers are the fluorescent dyes. Count among them the 4,4'-diamino-2,2'-stilbene disulfonic acids 4,4'-distrybiphenlene, Methyl umbelliferones, coumarins, (flavonic acids), 4,4'-dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid, Benzoxazole, Benzisoxazole and Benzimidazole systems and those substituted by heterocycles Pyrene derivatives. The sulfonic acid salts are of particular importance of the diaminostilbene derivatives and polymeric fluorescent substances.

Fluorescent materials can be sourced on the total weight of one in a receiving chamber or space substance mixture present, in amounts of up to 5% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0.5 and in particular from 0.03 to 0.1% by weight.

In a preferred embodiment the aforementioned stabilizers in any mixtures used. The stabilizing agents are based on the total weight one in a receiving chamber or a space Mixture of substances, in amounts of up to 40% by weight, preferably up to 30 % By weight, particularly preferably from 0.01 to 20% by weight, in particular from 0.02 to 5% by weight.

In the process (s) according to the invention used envelope material (ien) it is preferably a water-soluble or water-dispersible Polymer. Is the shaping processing of the water-soluble or water-dispersible polymer by deep drawing, so for this Process preferably used a film. Preferred process variants are characterized in that in step a) of the method according to the invention used film a thickness of 5 to 2000 microns, preferably from 10 to 1000 microns, particularly preferably from 15 to 500 μm, very particularly preferably from 20 to 200 μm and in particular from 25 to 100 μm.

The films used can are single or multi-layer films (laminate films). The Water content of the films is preferably below 10% by weight, particularly preferably below 7% by weight, very particularly preferably below 5% by weight and in particular below 4% by weight.

A particularly preferred method according to the invention is characterized in that the at least two receiving chambers in step b), each with different Means filled become. It is particularly preferred that for the filling in steps b) and d) different means are used, that is, each of the at least three reception chambers with funds, which are in their distinguish chemical or physical properties, be filled. Such means can for example different chemical compositions or have different particle sizes. The funds can change in their composition as well as in their composition and state of matter. As a result, regarding the Physical states the fillable Active substances or combinations of active substances between solid and liquid substances distinguished, being as solids in the context of the present application Active substances and combinations of active substances are summarized, which is a firm, i.e. dimensionally stable, not flowable consistency exhibit. This category includes, for example, substances in solid state, but also dimensionally stable substances such as dimensionally stable Gels and combinations of these substances. Filled bodies are also included a solid outer shell as Solids, regardless of the physical state of the filled in this bodies contained fillers. In a particularly preferred embodiment of the method according to the invention is at least one of the receiving chambers with a gas, preferably Air, filled. The resulting gas-filled Admission Chamber has in the later Application, for example, the function of a buoyancy body or a mechanical buffer.

Within the framework of the present application preferably powder and / or granules and / or Extrudates and / or compactates and / or castings, regardless of whether it is pure substances or mixtures of substances. The mentioned solids can thereby in amorphous and / or crystalline and / or partially crystalline Form. Preferred solids within the scope of the present Invention a water content (for example, can be determined as a loss on drying or according to Karl Fischer) below 7% by weight, preferably below 4.5% by weight, and particularly preferably below 2% by weight. The amorphous and / or crystalline and / or partially crystalline solids can can be used both as a pure substance and as a mixture of substances. The preferred mixtures of substances include in particular made-up compounds Solids in compounded and / or encapsulated and / or coated Shape.

Powder is a general term for one Form of division of solid substances and / or mixtures of substances that one by crushing, that is Grate or crush in the grinding bowl (pulverization), grinding in mills or as a result of atomization or freeze drying. A particularly fine division is often called atomization or micronization; the corresponding powders are called micro powders designated. Preferred powders have a uniform (homogeneous) Mixtures of the solid, finely divided ingredients tend to in the case of mixtures of substances in particular not for separation into Individual components of these mixtures. Within the scope of the present application therefore particularly preferred powders have a particle size distribution in which at least 80% by weight, preferably at least 60% by weight, particularly preferably at least 95% by weight and in particular at least 99% by weight of the powder, based in each case on its total weight, to a maximum of 80%, preferably a maximum of 60% and in particular a maximum 40% deviate from the average particle size of this powder.

There is a rough classification according to the grain size the powder in coarse, fine and Very fine powder common; a more precise classification powdery Bulk goods are made via their bulk density and through sieve analysis. in principle powders of any particle size can be used, preferred powders however, average particle sizes of 40 to 500 microns, preferably from 60 to 400 μm and in particular from 100 to 300 μm on. Methods for determining the average particle size are supported usually on the aforementioned sieve analysis and are described in detail in the prior art.

The unwanted caking of the Powder can be obtained using sprinkling aids or powdering agents to encounter. In a preferred embodiment, the in according to the inventive method powder produced therefore pouring aids or powdering agents, preferably in parts by weight of 0.1 to 4 wt .-%, particularly preferably of 0.2 to 3 wt .-% and in particular from 0.3 to 2 wt .-%, each based on the total weight of the powder. Preferred trickle aids or powdering agents, preferably in finely ground form, Silicates and / or silicon oxide and / or urea.

Powders can be used as particulate mixtures agglomerate through a number of techniques. Each of the in the booth Method known for the agglomeration of particulate mixtures is in principle suitable in those produced according to the invention containers to convert enclosed solids into larger aggregates. in the Within the scope of the present invention preferably used as solids) In addition to the granules, agglomerates are the compactates and extrudates.

Accumulations become granules of granules designated. A granulate is an asymmetrical aggregate from powder particles. Granulation processes are state of the art broadly described. Granules can by wet granulation, by dry granulation or compacting and produced by melt solidification granulation.

The most common pelletizing technology is wet granulation since this technique has the fewest restrictions is subjected and most safely to granules with cheap Properties leads. Moist granulation is carried out by moistening the powder mixtures with solvents and / or solvent mixtures and / or solutions of binders and / or solutions of adhesives and is preferably used in mixers, fluidized beds or spray towers, where said mixer equipped for example with stirring and kneading tools could be. For the However, granulation are also combinations of fluidized beds) and Mixer (s) or combinations of different mixers can be used. The granulation is dependent of the starting material and the desired product properties under the influence of low to high shear forces.

The granulation takes place in one spray tower so can as starting materials, for example, melting (melt solidification) or, preferably aqueous, slurries (Spray drying) solid substances are used, which are at the top of a Sprayed tower in a defined droplet size, solidify or dry in free fall and as at the bottom of the tower Granules accumulate. Melt solidification is generally suitable especially for shaping low-melting materials in the area the melting temperature are stable (e.g. urea, ammonium nitrate u. various formulations such as enzyme concentrates, pharmaceuticals etc.), the corresponding granules are also referred to as prills. Spray drying will especially for the production of detergents or detergent components used.

Others described in the prior art Agglomeration techniques are extruder or perforated roll granulation those optionally with granulating liquid staggered powder mixtures when pressing through perforated disks (extrusion) or plastically deformed on perforated rollers. The products of Extruder granulation is also called extrudate.

Compactas can be, for example through dry granulation techniques such as tableting or roller compaction produce. Compacting in tablet presses means that or multi-phase tablets or briquettes. To count the multi-phase tablets in addition to the multi-layer or sandwich tablets, for example the coated tablets and the point tablets (bull-eye tablets). The briquettes can just like the slugs produced in compacting rollers after the compacting through opposing Spiked rollers are crushed or struck by sieves.

As castings are within the scope of the present Registration refers to solid substance particles caused by solidification and / or crystallization from melts or solutions. The solidification and / or crystallization preferably takes place in prefabricated ones Matrices. The castings released from the matrices after solidification can be in the Connection each according to the size of the die and intended use of the casting in their original Size or optionally after comminution as solids in the water-soluble according to the invention containers be used.

As a matrix material for the above mentioned solids, but especially for castings, which are caused by solidification are produced, meltable substances are particularly suitable from the group of fats and / or triglycerides and / or fatty acids and / or Fatty alcohols and / or waxes and / or parrafins.

Fats) or triglycerides) is the Term for Compounds of glycerol in which the three hydroxy groups of Glycerins through carboxylic acids are esterified. Of course Occurring fats are triglycerides, which are usually different fatty acids in the same glycerin molecule contain. By saponification of the fats and subsequent esterification or reaction with acyl chlorides are also synthetic triglycerides, in which only one fatty acid bound, accessible (e.g. tripalmitin, triolein or tristearin). Natural and / or synthetic fats and / or mixtures of the two are used as matrix material or matrix component for Cast body or one of the other solids mentioned in the context of the present Invention preferred.

Aliphatic saturated or unsaturated, carboxylic acids with branched or unbranched carbon chain are referred to as fatty acids in the present application. A large number of production methods exist for the production of the fatty acids. While the lower fatty acids are mostly based on oxidative processes based on alcohols and / or aldehydes as well as aliphatic or acyclic hydrocarbons, the higher homologues are mostly still most easily accessible today by saponification of natural fats. Due to advances in transgenic plants are now almost unlimited possibilities to vary the fatty acid spectrum in the storage fats of oil plants. In the context of the present invention, preferred fatty acids have a melting point which allows these fats to be processed as a material or as a component of a casting. Fatty acids which have a melting point above 25 ° C. have proven particularly advantageous. Preferred matrix materials and / or constituents are therefore capric acid and / or undecanoic acid and / or lauric acid and / or tridecanoic acid and / or myristic acid and / or pentadecanoic acid and / or palmitic acid and / or margaric acid and / or stearic acid and / or nonadecanoic acid and / or arachic acid and / or erucic acid and / or elaeosteraric acid. But also fatty acids with a melting point below 25 ° C can be used as a component of the matrix for castings or other solids mentioned above.

Fatty alcohol is a collective term for the by reducing the triglycerides, fatty acids or fatty acid esters available linear, saturated or unsaturated primary Alcohols with 6 to 22 carbon atoms. The fatty alcohols can be found in dependence saturated by the manufacturing process or unsaturated his. Myristyl alcohol and / or 1-pentadecanol and / or cetyl alcohol and / or 1-heptadecanl and / or stearyl alcohol and / or erucyl alcohol and / or 1-nonadecanol and / or arachidyl alcohol and / or 1-heneicosanol and / or Behenyl alcohol and / or erucyl alcohol and / or brassidyl alcohol are preferred components of the matrix of castings or other of the produced according to the invention containers enclosed solids.

It has also proven to be beneficial proven if the enclosed in the containers produced according to the invention Solids, especially the preferably enclosed casting, as Matrix material waxes included. Preferred waxes have a melting range that is between about 45 ° C and about 75 ° C. This means in the present case that the Melting range occurs within the specified temperature interval and does not denote the width of the melting range. Grow with Such a melting range are dimensionally stable at room temperature however melt at for the machine dishwashing typical temperatures from 30 ° C to 90 ° C and are therefore easier to disperse water at these temperatures.

"Growing" is a series of natural or artificial understood substances that usually melt above 40 ° C without decomposition and a little above the melting point, relatively low viscosity and not are stringy. They have a strongly temperature-dependent consistency and solubility on.

They are divided according to their origin Wax in three groups, the natural waxes, chemically modified Waxes and synthetic waxes.

Natural waxes include, for example vegetable waxes such as candelilla wax, carnauba wax, Japanese wax, Esparto grass wax, cork wax, guaruma wax, rice germ oil wax, Sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walrus, lanolin (wool wax), or uropygial fat, Mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

To the chemically modified waxes counting for example hard waxes such as Montanester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material which meet the stated softening point requirements can also be used as meltable or softenable substances for the masses hardening by cooling. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ^® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ^® ETLP (Condea). Conversely, synthetic or semi-synthetic esters from lower alcohols with fatty acids from native sources can also be used. Tegin ^® 90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances. Shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used according to the invention as a matrix material in solids, preferably in castings.

The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating of the present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ^® (Pamentier & Co).

In a further preferred embodiment, one or more of the solids enclosed in the containers produced according to the invention, but preferably a cast body produced by melt solidification, predominantly contains paraffin wax (Panafine) as the matrix material. The means that at least 50% by weight of the total meltable or softenable substances contained, preferably more, consist of paraffin wax. Paraffin wax contents (based on the total weight of the matrix materials) of approximately 60% by weight, approximately 70% by weight or approximately 80% by weight are particularly suitable, with even higher proportions of, for example, more than 90% by weight being particularly preferred , In a particular embodiment of the invention, the entire material of one or more of the solids filled into the containers produced according to the invention consists of paraffin wax.

Paraffin waxes point towards the other named, natural Grow in the context of the present invention, the advantage that at one Use of the manufactured according to the invention container as a dosing unit for Detergents and cleaning agents in an alkaline cleaning agent environment there is no hydrolysis of the waxes (such as in wax is expected), since paraffin wax is not hydrolyzable Contains groups.

Paraffin waxes consist mainly of Alkanes and low proportions of iso- and cycloalkanes. The one to be used according to the invention Paraffin preferably has essentially no constituents a melting point of more than 70 ° C, particularly preferably of more than 60 ° C on.

Preferred solids, in particular Cast body included at least one paraffin wax as matrix material and / or matrix component with a melting range of 40 ° C up to 60 ° C.

The content of the used is preferably Paraffin wax at ambient temperature (usually about 10 up to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible. The more solid wax components are present in a wax at room temperature, the more useful it is within the scope of the present invention.

Other beneficial ingredients the matrix of solids, especially castings, are wax alcohols, ie fatty alcohols with approx. 24–36 Carbon atoms, the main component in the form of wax esters of higher molecular fatty acids (wax acids) many natural Are waxes. Exemplary for preferred wax alcohols here are lignoceryl alcohol, ceryl alcohol, Myricyl alcohol or melissyl alcohol called.

Dimensionally stable gels are another solid particularly preferred in the context of the present invention. The term "dimensionally stable" denotes Gels which have inherent dimensional stability, which enables them under usual Conditions of manufacture, storage, transportation and Handling by the consumer a stable against breakage, not to take disintegrating spatial form, whereby this spatial form under the conditions mentioned, also over a longer period of time, preferably 4 Weeks, particularly preferably 8 weeks and in particular 32 weeks, not changed, this means under the usual Conditions of manufacture, storage, transportation and Handling by the consumer in the conditions related to the manufacture spatial-geometric Form persists, that is, for example, does not melt or when exposed to an external under the conditions of manufacture, storage, transport and handling usual Force in this spatial-geometric Shape returns.

To achieve the desired dimensional stability, the gels with good product properties (solubility, washing and cleaning performance, stability of the gel), it is within the scope of the present invention preferred, as a thickener one or more substances from the Group agar-agar, carrageenan, tragacanth, gum arabic, alginates, Pectins, polyoses, guar flour, locust bean gum, starch, dextrins, Gelatin, casein, carboxymethyl cellulose, core meal ether, polyacrylic u. Polymethacrylic compound, vinyl polymers, polycarboxylic acids, polyethers, Polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonite, Zeolites and silicas contain, where it has proven to be particularly advantageous if the gels are these or one of the following thickeners in amounts between 0.2 and 10% by weight, preferably between 0.3 and 7 wt .-% and particularly preferably between 0.4 and 4 wt .-% based on the total weight of the molded body contain.

Natural polymers, which are used as thickeners in the context of the present invention are, for example, agar agar, carrageenan, Tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, Locust bean gum, starch, Dextrins, gelatin and casein.

Modified natural products come from especially from the group of modified starches and celluloses, exemplary here are carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and -propyl cellulose and core meal ether called.

A large group of thickeners that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes. Thickeners from these classes of substances are widely available commercially and are sold, for example, under the trade names Acolol ^® -820 (methacrylic acid (stearyl alcohol-20-E0) ester-acrylic acid copolymer, 30% strength in water, Rohm & Haas), Dapral ^® -GT-282- S (alkyl polyglycol ether, Akzo), Deuterol ^® polymer 11 (dicarboxylic acid copolymer, Schönes GmbH), Deuteron ^® -XG (anionic heteropolysaccharide based on (3-D-glucose, D-manose, D-glucuronic acid, Schönes GmbH) , Deuteron ^® -XN (non-ionic polysaccharide, Schönes GmbH), Dicnlan ^® -thickener-0 (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA ^® -81 and EMA ^® -91 (Ethylene-maleic anhydride copolymer, Monsanto), thickener-QR-1001 (polyurethane emulsion, 19–21% in water / diglycol ether, Rohm & Haas), Mirox ^® -AM (anionic acrylic acid-acrylic acid ester copolymer dispersion, 25% ig in Wasser, Stockhausen), SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo ^® -S (high molecular polysaccharide, stabilized with formaldehyde, Shell) and Shellflo ^® -XA (xanthan biopolymer, stabilized with formaldehyde, Shell) offered.

Due to their manufacturing process as well to optimize their release behavior preferred gels contain various solvents, whereby gels with regard to their product properties as particularly advantageous have proven to be water and / or one or more water miscible solvent in amounts of 5 to 70% by weight, preferably 10 to 65% by weight and particularly preferably contain from 15 to 60% by weight.

It has been particularly advantageous also proved to be when the water-miscible solvent was one or more Substances from the group of the group ethanol, n- or i-propanol, n- or sec- or tert-butanol, glycol, propane or butanediol, glycerin, Diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, Ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, Diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, Di-isopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene-glycol-t-butyl ether contain.

Further preferably in those produced according to the invention containers encapsulated solids are the capsules. "Capsule" is a term for a commonly used Packaging form in different sized, possibly colored envelopes made of gelatin, wax, or wafer material solid, semi-solid or liquid substances contains. Most frequently the gelatin capsules (made of hard or soft gelatin) are used.

In a special embodiment of the present invention has one, more, or all of those produced in the invention container filled Solids, for example one, several or all of them container filled Powder and / or granules) and / or extrudate (s) and / or compact (s) and / or Cast body and / or dimensionally stable) and / or capsule (s), a coating (coating) on. Such a coating can serve different purposes. On the one hand, a coating, for example, can cause an undesirable Contact of active substances contained in the solids which are sensitive to hydrolysis or oxidation, with the outside air or other solids enclosed in the water-soluble container according to the invention be avoided. On the other hand, a coating can also an advantageous visual effect can be achieved.

As ingredients for the reception chambers are suitable for the liquids and solids mentioned above. With solids, a distinction is made between powders, granules, extrudates, Compacts, castings as well distinguishable stable gels. Liquids are considered in the scope this application in addition to low-viscosity, flowable liquids or flowable gels also flowable dispersions, for example emulsions or suspensions. Considered flowable Active substances or combinations of active substances if they have no inherent dimensional stability, which enables them under usual Conditions of manufacture, storage, transportation and Handling by the consumer a non-disintegrating spatial form to take, this spatial form under the conditions mentioned also about longer Time, preferably 4 weeks, particularly preferably 8 weeks and in particular 32 weeks, unchanged, this means under the usual Conditions of manufacture, storage, transportation and Handling by the consumer in the conditions related to the manufacture spatial-geometric shape persists, that is, does not melt. The determination of fluidity refers in particular to those customary for storage and transportation Conditions, in particular at temperatures below 50 ° C., are preferred below 40 ° C. As liquids therefore, in particular, active ingredients or combinations of active ingredients apply with a melting point below 25 ° C, preferably below 20 ° C, particularly preferably below 15 ° C.

The table below describes preferred process variations for carrying out the process according to the invention while filling two receiving chambers in step b) (receiving chambers 1 and 2) and a further receiving chamber in step d) (receiving chamber 3). The filling of the receiving chambers 1 and 2 in step b) of the method according to the invention can take place simultaneously or at different times.

Within the scope of the present application are particularly preferred methods according to the invention characterized that at least a receiving chamber with a liquid, at least one additional receiving chamber is filled with a solid. Methods according to the invention in which a Receiving chamber with a liquid, another receiving chamber with a solid and a third Receiving chamber is filled with a melt.

The deep-drawn containers can be simultaneously with or after being removed from the receiving troughs the die, for example, by cutting or punching become. The cutting or punching takes place in the area the wrapping material foil, which after deep drawing is not within the receiving trough rather, in addition to the receiving trough on the level (plan) Top of the die. The one so isolated container consequently has a brim which is at an angle from the through the wrapping material formed receiving chambers protrudes outwards and the openings encloses these receiving chambers at least partially. The in supervision from the self-contained brim area, the is called the entire top sealing surface that according to the inventive method manufactured containers, can be any technically feasible symmetrical or non-symmetrical form exhibit. The total length the brim, that is the top circumference of the containers produced according to the invention is preferably between 1 and 75 cm, particularly preferably between 2 and 60 cm, entirely particularly preferably between 4 and 40 cm and in particular between 5 and 20 cm.

Another subject of this application is therefore a container the height h from a first wrapping material, comprising at least three receiving chambers as well as a circumferential h a brim forming a first sealing plane, characterized in that that the container at least one seal from a second wrapping material along a sealing seam has, which is not in the formed by the peripheral brim Seal level runs.

Containers according to the invention are particularly preferred characterized in that the Sealing seam, which is not in the formed by the all-round brim Seal level runs at least partially along a web located in the container Height h - x runs.

The height h of the container according to the invention applies within the scope of the present application the vertical distance between the first sealing level formed by the brim and the deepest Point of the container according to the invention.

The containers according to the invention have at least one Footbridge of height h - x on. The value "x" stands for a length, which is smaller than "h". Hence x <h. The relative Difference between the values "h" and "x" is in preferred ones containers at least 5%, preferably at least 10%, particularly preferred at least 20%, very particularly preferably at least 35% and in particular at least 50%, each based on the amount h. In other words, the ratio is Height h - x of the Bridges to height h of the basic body in a preferred embodiment less than 0.95, preferably less than 0.90, particularly preferred less than 0.80, most preferably less than 0.65 and especially less than 0.50. Containers according to the invention are very particularly preferred which the height h - x the web between 10 and 95%, preferably between 15 and 85%, particularly preferably between 25 and 75% and in particular between 35 and 60% of the amount h of the basic body is. The absolute difference between the containers preferably between 0.1 and 8 cm, particularly preferably between 0.2 and 6 cm, particularly preferably between 0.4 and 5 cm and in particular between 0.5 and 4 cm.

The containers according to the invention are shaped by Processing from a first wrapping material receive. Suitable shaping processes are, for example Thermoforming, injection molding or casting process. The containers according to the invention act it is therefore preferably deep-drawn containers, injection-molded containers or cast containers. As a "deep-drawn Containers "are in the frame the present application designates such containers, which a first film-like wrapping material after placing this material in a deep-drawing level forming cavity and molding of the shell material into this receiving trough by the action of pressure and / or vacuum be preserved. The wrapping material can be done before or during molding by exposure to heat and / or solvent be pretreated. The pressure can be divided into two parts Tools that are like positive and negative to each other behave and watch a film between these tools press together deform. As pressure forces however, the action of compressed air and / or that is also suitable Dead weight of the film and / or the dead weight of one on the top the active substance. Following the deep drawing process can the deformed shell material by the action of selected ones relative humidity and / or temperature can be conditioned.

In these deep-drawing processes, it is also possible to distinguish between processes in which the wrapping material is guided horizontally into a forming station and from there in a horizontal manner for filling and / or sealing and / or separating, and processes in which the wrapping material has a continuously rotating die differentiate between the forming roller (optionally with a counter-rotating male molding roller, which guides the shaping upper punches to the cavities of the female molding roller). The first-mentioned process variant of the flatbed process is to be operated both continuously and discontinuously; the process variant using a shaping roller is generally carried out continuously.

The deep-drawn containers can be simultaneously with or after being removed from the receiving troughs the die, for example, by cutting or punching become. The cutting or punching takes place in the area the wrapping material foil, which after deep drawing is not within the receiving trough rather, in addition to the receiving trough on the level (plan) Top of the die. The one so isolated container consequently has a brim which is at an angle from the through the wrapping material formed receiving chambers protrudes outwards and the openings encloses these receiving chambers at least partially. The in supervision from the self-contained brim area, the is called the entire top sealing surface container according to the invention, any technically feasible symmetrical or non-symmetrical shape exhibit. The total length the brim, that is the top circumference of the container according to the invention is preferably between 1 and 75 cm, particularly preferably between 2 and 60 cm, very particularly preferably between 4 and 40 cm and in particular between 5 and 20 cm.

In a preferred embodiment of the containers according to the invention, the sealing seam, which does not run along the circumferential brim, runs at least partially along a web of height h-x located in the container. This web can run linearly or non-linearly in the top view ("supervision" in the context of this application refers to the observation of the container with a direction orthogonal to the deep-drawing plane). It is preferred in the context of the present application that this web is not linear in the top view Such webs can be designed in all technically feasible forms. Preferred embodiments are described in more detail below:
Preferred containers according to the invention are characterized in that the web has no contact point with the side walls of the container. Such a web is necessarily closed to form two separate receiving chambers, has curvatures and / or corners and includes a surface when viewed from above. This surface enclosed by the web when viewed from above, that is to say the opening on the top side of one of the receiving chambers, can have any technically feasible symmetrical or non-symmetrical shape, just like the previously described area surrounded by the closed brim when viewed from above. If the self-contained web or the self-contained brim has only curvatures and no corners, a circular or oval surface is realized, for example. If the web or brim has opposing curvatures, round or oval surfaces with indentations result (e.g. kidney or peanut shape). If curvatures and corners are combined, surfaces in the form of a drop or an archway can be created, for example. Two, three, four, five, six, seven, eight, or polygonal webs or brims can also be realized and are particularly preferred. In a special embodiment, webs are preferred which have no contact points with the surrounding brim and have no circular shape.

In a further preferred embodiment of the container according to the invention the web has at least one contact point with the side walls of the container having. Container, which have two such contact points are special prefers. Furthermore, such containers are particularly preferred, the side walls have protuberances in the contact area with the web (s), the on the inside of the container surface of these protuberances with the top of the web (s) preferably a smooth, preferably planar surface form. The transition of the web (s)) to the side wall in these preferred embodiments therefore no corner and is special for creating one Seal seam suitable. Like the previously described self-contained Webs, can also from one point of the sidewall to another point of the Sidewall extending webs curvatures and / or Have corners. Preferred container are characterized in that the Bridge at least one, preferably two, three, four, five or has more corner (s). The one through the two in such a corner intersecting sections angle of the web is preferably between 1 and 179 °, especially preferably between 45 and 135 °, very particularly preferably between 70 and 110 ° and in particular between 80 and 100 °.

In a further embodiment, preferred containers according to the invention are characterized in that the web has at least one, preferably two, three, four, five or more curvatures). The radii of curvature of these curvatures can vary widely. Relative to the maximum diameter d _{max of} the opening enclosed by the peripheral brim, preferred radii of curvature have values between 0.1 and 5 d _max , preferably between 0.2 and 3 d _max and in particular between 0.3 and 1.5 d _max ,

Of course, a bridge can also be realized by a forked bridge. A preferred container according to the invention is accordingly characterized in that the web has at least one, preferably two, three, four, five or more forkings. Forks are preferred at de NEN three, four or five, but preferably three or four branches of the non-linear web meet. Webs with one fork and three branches and webs with two forks and two branches each are particularly preferred. In a further preferred embodiment, a web, which has a contact point with the peripheral brim, is split into two branches in a first fork, these branches in turn being guided to one another in a second fork and the web then at a second contact point with the peripheral brim expires. Such a container has three separate receiving chambers.

The width of between each Compartment webs can vary. Preferred containers according to the invention are characterized in that the Bridge width between 0.5 and 15 mm, preferably between 0.6 and 12 mm, particularly preferably between 0.7 and 10 mm, very particularly preferably between 0.8 and 8 mm and in particular between 1.0 and Has 5.0 mm. Bars that do not have theirs are particularly preferred whole length have constant width.

The admission chambers can be any have technically feasible form. Spherical dome-shaped, cylindrical or cubic chambers are particularly preferred. Preferred admission chambers have at least one edge and one corner, receiving chambers with two, three, four, five, six, seven, eight nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty or more edges or two, three, four, five, six, seven, eight nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty or more corners are also feasible and preferred according to the invention. Further realizable and in alternative embodiments of the means according to the invention preferred receiving chambers have a dome-shaped structure. The side walls of the Receiving chambers are preferably planar. Spatially opposite side walls can be arranged both parallel and not parallel to each other. The footprint the receiving chambers can be convex, concave or planar, whereby with consideration to the later one filling of the space or spaces between the receiving chambers planar base areas are preferred. The footprint itself can be designed as a circle, but can also have corners. base areas with a corner (teardrop shape), two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty or more corners are preferred in the context of the present application. The transition the base area to the side wall or walls or the transition of the side walls into each other in preferred embodiments of this application designed in a rounded shape. The reception chambers accordingly point outward no pointed or sharp, but rather rounded edges.

A preferred container according to the invention draws is characterized in that the base areas of the receiving chambers are planar.

The dimensions and volume more preferred container will primarily focus on the later application of the resulting container orientate. Preferred according to the invention container have a total volume of the receiving chambers between 0.1 and 1000 mL, preferably between 1 and 100 mL, particularly preferably between 2 and 50 mL, very particularly preferably between 4 and 30 mL and especially between 5 and 25 mL. Preferred according to the invention By means of at least two receiving chambers with the same spatial Shape as well as an identical volume. In another preferred embodiment the at least two receiving chambers present in the container have different ones Volume, taking the ratio these volumes preferably between 25: 1 and 1.05: 1, preferably is between 20: 1 and 2: 1 and in particular between 15: 1 and 4: 1. at preferred means, the container has two receiving chambers different Volume, with the volume of the smaller receiving chamber at least 2%, preferably at least 5%, particularly preferably at least 10% and in particular at least 20%, 30%, 40%, 50%, 60%, 65 %, 70%, 75% or 80% of the volume of the larger receiving chamber is. The Volume of the individual chambers is preferably between 0.05 and 900 mL, particularly preferred between 0.1 and 90 mL, very particularly preferably between 0.5 and 40 mL and especially between 1.0 and 25 mL.

In a preferred embodiment the containers according to the invention have receiving chambers different depths. It does not necessarily exist a direct connection with the chamber depth and the chamber volume. So can in a container with two receiving chambers, the receiving chamber with the smaller chamber depth quite the larger chamber volume have while the receiving chamber with the greater chamber depth has a smaller volume. Also the two or more chambers have the same volume despite different chamber depths. However, a container is preferred in the context of the present application which the receiving chamber with the smaller chamber depth also compared to the other receiving chamber (s) a smaller one Has volume, with respect to the absolute volumes and the volume ratios reference is made to the above information.

Containers preferred according to the invention comprise receiving chambers with, apart from the procedural necessity, mostly slight and preferably between 0.5 ° and 5 ° formed demolding angle, essentially vertically sloping side walls and / or web walls. However, containers in which at least one receiving chamber has at least one inclined side wall and / or web wall are particularly preferred. In such receiving chambers, the angle which lies between the side wall and / or the web wall and an imaginary seal which closes the receiving chamber is accordingly less than 90 °. Of course, this angle can vary for the different side walls and / or web walls of an individual receiving chamber. If the receiving chamber has only a single side wall (cylinder-like receiving chambers), even a single side wall can have different angles with the corresponding shaping of the deep-drawing troughs used in deep-drawing. Preference is given to receiving chambers in which the said angle is between 30 and 90 °, preferably between 35 and 89 °, particularly preferably between 40 and 88 ° and in particular between 45 and 87 °.

The admission chambers can continue Have gradations. The corresponding, preferred containers have Receiving chambers without flat side walls and / or web walls, rather they have side walls, which are separated by steps or curvatures Marked are. The number of curvatures can vary preferred container according to the invention are where the number of steps and / or curvatures in one or more receiving chamber (s) per chamber a maximum of 10, preferably between 1 and 9, particularly preferably between 1 and 8, very particularly is preferably between 2 and 7 and in particular between 2 and 6. The Steps or curvatures can all around in the receiving troughs or only on individual ones sidewalls and / or web walls be trained. The course of the steps or curvatures is preferably horizontal. Steps and / or curvatures with a screw thread similar up or down however, indicative courses are also feasible and for certain Areas of application preferred.

The "volume" of the receiving chambers is in the frame this registration the filling volume designated, which when filling the chambers or spaces with a liquid without overflow this liquid on the preferably planar sealing edges.

According to the invention, preferred sealants have container prefabricated closure parts, especially closure parts, by injection molding or by compression molding, preferably by compression molding under the previous one and / or simultaneous heating, are made on. Such prefabricated closure parts can in their design from the planars usually used Clearly distinguish sealing foils. In particular, are preferred Closing parts, which are convex and / or concave, preferably round or rounded arches, exhibit. In a preferred embodiment, these closure parts are wave-like buckles on. In addition to these "organic" forms, of course, too closing parts realizable, which to the outside or have protruding angular bulges on the inside. Used as a sealing unit a stretchable film is used, so this planar film can after sealing by shrinking the with the sealing film provided container also to the outside bulge. such Shrinkage occurs particularly in deep-drawn containers. The "level" of those in these containers Active substances lie as a result of the shrinkage and the associated reduction of the volume of the receiving chambers clearly above the top opening of the the body forming brim. The sealing foil is domed outwards. such container are particularly preferred in the context of the present application.

• – Reaktionen zwischen dem im Behälterinnenraum befindlichen Aktivsubstanzen und den Hüllmaterialien oder
• – Reaktionen zwischen dem im Behälterinnenraum befindlichen Aktivsubstanzen und von außen durch das Hüllmaterial in den Behälterinnenraum diffundierten Substanzen (z.B. Wasser) oder
• – Reaktionen der im Behälterinnenraum befindlichen Aktivsubstanzen miteinander oder
• – durch Licht oder Wärme verursachte Zerstzungsreaktionen einzelner im Behälterinnenraum befindlichen Aktivsubstanzen.

Particularly preferred containers according to the invention have a device in the seal for pressure compensation between the container interior and the surrounding atmosphere. Such pressure equalization is particularly preferred for those containers according to the invention in which the container interior is filled with such liquid or solid active substances which tend to release gas in the course of storage after sealing. Chemical reactions, in particular, are usually the cause of such gas release

• - Reactions between the active substances in the interior of the container and the casing materials or
• - Reactions between the active substances in the interior of the container and substances (eg water) or diffused from outside through the shell material into the interior of the container
• - Reactions of the active substances in the interior of the container with one another or
• - Destruction reactions of individual active substances in the interior of the container caused by light or heat.

The active substances which tend to release gas after one of the reactions described include in particular the bleaching agents described below, for example the percarbonates and perborates. Valves, but preferably microholes, preferably microholes with a diameter between 0.1 and 2 mm, particularly preferably between 0.2 and 1.5 mm and in particular between 0.5 and 1 mm are used as devices for pressure compensation in the context of the present application designated. Microchannels or the use of permeable covering materials are also suitable. In a particularly preferred embodiment, the closure part and / or container have nano holes with a diameter water between 0.1 and 100 μm, preferably between 0.2 and 80 μm and in particular between 0.4 and 60 μm.

• a) wasserlöslichen nichtionischen Polymeren aus der Gruppe der a1) Polyvinylpyrrolidone, a2) VinylpyrrolidonNinylester-Copolymere, a3) Celluloseether
• b) wasserlöslichen amphoteren Polymeren aus der Gruppe der b1) Alkylacrylamid/Acrylsäure-Copolymere b2) Alkylacrylamid/Methacrylsäure-Copolymere b3) Alkylacrylamid/Methylmethacrylsäure-Copolymere b4) Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere b5) Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere b6) Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere b7) Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat-Copolymere b8) Copolymere aus b8i) ungesättigten Carbonsäuren b8ii) kationisch derivatisierten ungesättigten Carbonsäuren b8iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren
• c) wasserlöslichen zwitterionischen Polymeren aus der Gruppe der c1) Acrylamidoalkyltrialkylammoniumchlorid/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze c2) Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze c3) Methacroylethylbetain/Methacrylat-Copolymere
• d) wasserlöslichen anionischen Polymeren aus der Gruppe der d1) Vinylacetat/Crotonsäure-Copolymere d2) Vinylpyrrolidon/Vinylacrylat-Copolymere d3) Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere d4) Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen d5) gepfropften und vernetzten Copolymere aus der Copolymerisation von d5i) mindesten einem Monomeren vom nicht-ionischen Typ, d5ii) mindestens einem Monomeren vom ionischen Typ, d5iii) von Polyethylenglycol und d5iv) einem Vernetzter d6) durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltenen Copolymere: d6i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren, d6ii) ungesättigte Carbonsäuren, d6iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe d6ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols d7) Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester d8) Tetra- und Pentapolymere aus d8i) Crotonsäure oder Allyloxyessigsäure d8ii) Vinylacetat oder Vinylpropionat d8iii) verzweigten Allyl- oder Methallylestern d8iv) Vinylethern, Vinylestern oder geradkettigen Allyl- oder Methallylestern d9) Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinylmethylether, Acrylamid und deren wasserlöslicher Salze d10) Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in α-Stellung verzweigten Monocarbonsäure
• e) wasserlöslichen kationischen Polymeren aus der Gruppe der e1) quaternierten Cellulose-Derivate e2) Polysiloxane mit quaternären Gruppen e3) kationischen Guar-Derivate e4) polymeren Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure e5) Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats e6) Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere e7) quaternierter Polyvinylalkohol e8) unter den INCI-Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 und Polyquaternium 27 angegeben Polymere.

Containers preferred according to the invention comprise at least one water-soluble or water-dispersible polymer. Some particularly preferred water-soluble or water-dispersible coating materials, which are suitable both as coating material, are listed below:

• a) water-soluble nonionic polymers from the group of a1) polyvinylpyrrolidones, a2) vinylpyrrolidone / vinyl ester copolymers, a3) cellulose ethers
• b) water-soluble amphoteric polymers from the group of b1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkylacrylic acrylamino / methacrylate amide (meth) acrylic acid copolymers b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b7) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers b8) copolymers of b8i) unsaturated carboxylic acids b8ii) cationically derivatized further unsaturated ionic carboxylic acids b8ii) nonionic monomers
• c) water-soluble zwitterionic polymers from the group of c1) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts c2) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts c3) methacroylethylbetaine / methacrylate copolymers
• d) water-soluble anionic polymers from the group of d1) vinyl acetate / crotonic acid copolymers d2) vinyl pyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers d4) graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid alone Mixture copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the non-ionic type, d5ii) at least one monomer of the ionic type, d5iii) of polyethylene glycol and d5iv) a crosslinker d6) copolymers obtained by copolymerizing at least one monomer from each of the three following groups: d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, d6iii) esters of long-chain Carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol d7) terpolymers from crotonic acid, vinyl acetate and an allyl or methallyl ester d8) tetra and pentapolymers from d8i ) Crotonic acid or allyloxyacetic acid d8ii) vinyl acetate or vinyl propionate d8iii) branched allyl or methallyl esters d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters d9) crotonic acid copolymers with one or more monomers from the group consisting of ethylene and vinyl ethers, acrylate, vinylbenzene, acrylate Salts d10) terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position
• e) water-soluble cationic polymers from the group of e1) quaternized cellulose derivatives e2) polysiloxanes with quaternary groups e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate e6) vinylpyrrolidone-methoimidazolinium chloride copolymers e7) quaternium polyvinyl, INCI-quaternized polyvinyl 17, Polyquaternium 18 and Polyquaternium 27 indicated polymers.

Water-soluble polymers in the sense of Invention are those polymers that are at room temperature in water more than 2.5% by weight soluble are.

Preferred wrapping materials preferably include at least partially a substance from the group (acetalized) Polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin.

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

enthalten."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 have degrees of hydrolysis of 98-99 and 87-89 mol%, respectively, so they still contain a residual content of acetyl groups. The polyvinyl alcohols are characterized on the part of the manufacturer by specifying the degree of polymerization 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. The coatings are made of polyvinyl alcohol largely impenetrable for Gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but let water vapor pass through.

Within the scope of the present invention it is preferred that a at least container according to the invention a wrapping material which has at least partially a polyvinyl alcohol comprises whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol% is. In a preferred embodiment there is at least one envelope material used for at least 20 % By weight, particularly preferably at least 40% by weight, very particularly preferably at least 60% by weight and in particular at least 80% by weight from a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and is in particular 82 to 88 mol%. It can be both around the first wrapping material act which the side walls of the receiving chambers and the spaces, as well as that second wrapping material, which is used as a sealing material. Preferably there is the entire envelope material used at least 20% by weight, particularly preferably at least 40% by weight, very particularly preferably at least 60% by weight and in particular to at least 80 wt .-% of a polyvinyl alcohol, the 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 as the coating materials, it being preferred according to the invention that the coating material comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly preferably from 12,000 to 80,000 gmol ^-1 and especially 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

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (ex Clariant, risen in 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 that are particularly suitable as wrapping material can be found in the table below:

Other polyvinyl alcohols suitable as wrapping material 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).

The water solubility of PVAL can be due to Aftertreatment with aldehydes (acetalization) or ketones (ketalization) changed become. As particularly preferred and pronounced on the basis of it good solubility in cold water Polyvinyl alcohols have been found to be particularly advantageous, those with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof can be acetalized or ketalized. As extremely beneficial The reaction products made of PVAL and starch are to be used.

Furthermore, the water solubility by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, Change borax and so targeted to desired Set values. PVAL films are largely impenetrable for gases like oxygen, nitrogen, helium, hydrogen, carbon dioxide however water vapor will pass through.

Examples of suitable water-soluble PVAL films are the PVAL films available from Syntana Handelsgesellschaft E. Harke GmbH & Co. under the name "SOLUBLON ^® ". Their solubility in water can be adjusted to the degree, and films of this product range are available which are soluble in the aqueous phase in all temperature ranges relevant to the application.

Polyvinylpyrrolidones, abbreviated as PVP, can be described by the following general formula:

PVP are through radical polymerization made from 1-vinylpyrrolidone. Commercial PVP have molecular weights in the range of approx. 2,500 to 750,000 g / mol and are called white, hygroscopic Powder or offered as aqueous solutions.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula H- [O-CH ₂ -CH ₂ ] _n -OH which are produced industrially by base-catalyzed polyaddition of ethylene oxide (oxirane) in systems containing mostly small amounts of water with ethylene glycol as the starting molecule. They have molar masses in the range from approx. 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n from approx. 5 to> 100,000. po ethylene oxides have an extremely low concentration of reactive hydroxyl end groups and only show weak glycol properties.

Gelatin is a polypeptide (molecular weight: approx.15,000 to> 250,000 g / mol), mainly by hydrolysis of the skin and bones obtained from animals containing collagen under acidic or alkaline conditions becomes. The amino acid composition The gelatin largely corresponds to that of the collagen from which it is made and varies depending on its provenance. The use of gelatin as a water-soluble coating material is particularly important extremely wide 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.

Are preferred within the scope of the present Invention of envelope materials, which is a polymer from the group starch and starch derivatives, cellulose and Cellulose derivatives, especially methyl cellulose and mixtures thereof include.

Starch is a homoglycan, being the glucose units are α-glycosidic connected are. Strength is made up of two components of different molecular weights: from approx. 20 to 30% straight-chain amylose (MW. approx. 50,000 to 150,000) and 70 to 80% branched chain amylopectin (MW approx. 300,000 to 2,000,000). There are also small amounts of lipids, phosphoric acid and Cations included. While the amylose due to the binding in the 1,4-position long, helical, intertwined Forms chains with about 300 to 1,200 glucose molecules the chain for amylopectin after an average of 25 glucose units through 1,6-binding to a knot-like Formations with about 1,500 to 12,000 molecules of glucose. In addition to pure starch to make water soluble wrappings the detergent, detergent and detergent portions within the scope of the present invention also starch derivatives suitable, which can be obtained by polymer-analogous reactions from starch. Such chemically modified starches include, for example, products from esterifications or etherifications, in which hydroxy hydrogen atoms have been substituted. But also Strengthen, in which the hydroxy groups against functional groups that do not have a Oxygen atoms are replaced, can be used as starch derivatives deploy. The group of starch derivatives, for example Alkali strengths, carboxymethyl (CMS), starch ester and ether and amino starches.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, viewed formally, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 500 to 5,000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

In preferred containers according to the invention at least one of the wrapping materials transparent or translucent. The shell material used is preferred transparent. Under transparency is in the sense of this invention understand 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.

Preferred containers have colored and / or printed wrapping materials on. Particularly preferred containers are characterized by colored and / or printed transparent or translucent covering materials out.

Containers according to the invention can consist of a single or several different wrapping materials consist. In a preferred embodiment, a container according to the invention comprises at least two different wrapping materials, preferably two different water-soluble or water-dispersible Polymers that have different dissolution rates.

Containers according to the invention are particularly suitable Way of portioning, packaging and dosing and safe Transport of active substances or mixtures of active substances. Another The subject of the present application is therefore an agent a container according to the invention and at least one active substance.

Preferred agents include active substance or mixtures of active substances from the fields of pharmaceuticals, cosmetics, Feed, crop protection or fertilizer, Adhesives, food and / or personal care products, preferably however, washing and cleaning active substances. A particularly preferred one agent according to the invention is therefore characterized in that it is an active substance the group of agricultural chemicals, cosmetics or detergents and cleaning agents includes.

Preferred active substances or mixtures of active substances from the field of cosmetics are in particular hair test agents, Hair restorers and hair dyes. The preferred personal care product counting in addition to the hair washing and care products, the pre-treatment agents, Hairdressing aids and course rinses. Active substances from the area of bath additives such as for example bath salts or bath tablets but also shower, foam or cream baths.

A particularly preferred agent according to the invention is characterized in that two different active substances separately from each other in different Containment chambers, that is, at least two containment chambers contain different active substances.

The active substances can both in their composition and in their composition and state of matter. As a result, regarding the Physical states of the fillable active ingredients or combinations of active substances between solid and liquid agents distinguished, being as solids in the context of the present application Active substances and combinations of active substances are summarized, which is a fixed, that is dimensionally stable, non-flowable consistency exhibit. For example, substances fall into this category in the solid state, but also dimensionally stable substances such as dimensionally stable gels and combinations of these substances. Farther are filled body with a solid outer shell as Solids, regardless of the physical state of the filled in this bodies contained fillers. In a particularly preferred embodiment of the method according to the invention is at least one of the receiving chambers with a gas, preferably Air, filled. The resulting gas-filled Admission Chamber has in the later Application, for example, the function of a buoyancy body or a mechanical buffer.

Within the framework of the present application preferably powder and / or granules and / or Extrudates and / or compactates and / or castings, regardless of whether it is pure substances or mixtures of substances. The mentioned solids can thereby in amorphous and / or crystalline and / or partially crystalline Form. Preferred solids within the scope of the present Invention a water content (for example, can be determined as a loss on drying or according to Karl Fischer) below 7% by weight, preferably below 4.5% by weight, and particularly preferably below 2% by weight. The amorphous and / or crystalline and / or partially crystalline solids can can be used both as a pure substance and as a mixture of substances. The preferred mixtures of substances include in particular made-up compounds Solids in compounded and / or encapsulated and / or coated Shape.

Powder is a general term for one Form of division of solid substances and / or mixtures of substances that one by crushing, that is Grate or crush in the grinding bowl (pulverization), grinding in mills or as a result of atomization or freeze drying. A particularly fine division is often called atomization or micronization; the corresponding powders are called micro powders designated. Preferred powders have a uniform (homogeneous) Mixtures of the solid, finely divided ingredients tend to in the case of mixtures of substances in particular not for separation into Individual components of these mixtures. Within the scope of the present application therefore particularly preferred powders have a particle size distribution in which at least 80% by weight, preferably at least 60% by weight, particularly preferably at least 95% by weight and in particular at least 99% by weight of the powder, based in each case on its total weight, to a maximum of 80%, preferably a maximum of 60% and in particular a maximum 40% deviate from the average particle size of this powder.

There is a rough classification according to the grain size the powder in coarse, fine and Very fine powder common; a more precise classification pulvertörmiger Bulk goods are made via their bulk density and through sieve analysis. in principle powders of any particle size can be used, preferred powders however, average particle sizes of 40 to 500 microns, preferably from 60 to 400 μm and in particular from 100 to 300 μm on. Methods for determining the average particle size are supported usually on the aforementioned sieve analysis and are described in detail in the prior art.

The unwanted caking of the Powder can be obtained using sprinkling aids or powdering agents to encounter. In a preferred embodiment, the powders contain therefore pouring aids or powdering agents, preferably in parts by weight from 0.1 to 4% by weight, particularly preferably from 0.2 to 3% by weight and in particular from 0.3 to 2% by weight, each based on the total weight of the powder. Preferred trickle aids or powdering agents, preferably in finely ground form, Silicates and / or silicon oxide and / or urea.

Powders can be used as particulate mixtures agglomerate through a number of techniques. Each of the in the booth Method known for the agglomeration of particulate mixtures is in principle suitable in those produced according to the invention containers to convert enclosed solids into larger aggregates. in the Within the scope of the present invention preferably used as solids) In addition to the granules, agglomerates are the compactates and extrudates.

Accumulations of granules are referred to as granules. A granulate is an asymmetrical aggregate of powder particles. Granulation processes are widely described in the prior art. Granules can by wet granulation, by dry granulation or compacting and can be produced by melt solidification granulation.

The most common pelletizing technology is wet granulation since this technique has the fewest restrictions is subjected and most safely to granules with cheap Properties leads. Moist granulation is carried out by moistening the powder mixtures with solvents and / or solvent mixtures and / or solutions of binders and / or solutions of adhesives and is preferably used in mixers, fluidized beds or spray towers, where said mixer equipped for example with stirring and kneading tools could be. For the However, granulation are also combinations of fluidized beds) and Mixer (s) or combinations of different mixers can be used. The granulation is dependent of the starting material and the desired product properties under the influence of low to high shear forces.

The granulation takes place in one spray tower so can as starting materials, for example, melting (melt solidification) or, preferably aqueous, slurries (Spray drying) solid substances are used, which are at the top of a Sprayed tower in a defined droplet size, solidify or dry in free fall and as at the bottom of the tower Granules accumulate. Melt solidification is generally suitable especially for shaping low-melting materials in the area the melting temperature are stable (e.g. urea, ammonium nitrate u. various formulations such as enzyme concentrates, pharmaceuticals etc.), the corresponding granules are also referred to as prills. Spray drying will especially for the production of detergents or detergent components used.

Others described in the prior art Agglomeration techniques are extruder or perforated roll granulation those optionally with granulating liquid staggered powder mixtures when pressing through perforated disks (extrusion) or plastically deformed on perforated rollers. The products of Extruder granulation is also called extrudate.

Compactas can be, for example through dry granulation techniques such as tableting or roller compaction produce. Compacting in tablet presses means that or multi-phase tablets or briquettes. To count the multi-phase tablets in addition to the multi-layer or sandwich tablets, for example the coated tablets and the point tablets (bull-eye tablets). The briquettes can just like the slugs produced in compacting rollers after the compacting through opposing Spiked rollers are crushed or struck by sieves.

As castings are within the scope of the present Registration refers to solid substance particles caused by solidification and / or crystallization from melts or solutions. The solidification and / or crystallization preferably takes place in prefabricated ones Matrices. The castings released from the matrices after solidification can be in the Connection each according to the size of the die and intended use of the casting in their original Size or optionally after comminution as solids in the water-soluble according to the invention containers be used.

As a matrix material for the above mentioned solids, but especially for castings, which are caused by solidification are produced, meltable substances are particularly suitable from the group of fats and / or triglycerides and / or fatty acids and / or Fatty alcohols and / or waxes and / or parrafins.

Fats) or triglycerides) is the Term for Compounds of glycerol in which the three hydroxy groups of Glycerins through carboxylic acids are esterified. Of course Occurring fats are triglycerides, which are usually different fatty acids in the same glycerin molecule contain. By saponification of the fats and subsequent esterification or reaction with acyl chlorides are also synthetic triglycerides, in which only one fatty acid bound, accessible (e.g. tripalmitin, triolein or tristearin). Natural and / or synthetic fats and / or mixtures of the two are used as matrix material or matrix component for Cast body or one of the other solids mentioned in the context of the present Preferred ending.

Aliphatic saturated or unsaturated, carboxylic acids with branched or unbranched carbon chain are referred to as fatty acids in the present application. A large number of production methods exist for the production of the fatty acids. While the lower fatty acids are mostly based on oxidative processes based on alcohols and / or aldehydes as well as aliphatic or acyclic hydrocarbons, the higher homologues are mostly still most easily accessible today by saponification of natural fats. Advances in the field of transgenic plants mean that there are almost unlimited possibilities for varying the fatty acid spectrum in the storage fats of oil plants. In the context of the present invention, preferred fatty acids have a melting point which allows these fats to be processed as a material or as a component of a casting. Fatty acids which have a melting point above 25 ° C. have proven particularly advantageous. Preferred matrix materials and / or constituents are therefore capric acid and / or undecanoic acid and / or lauric acid and / or tridecanoic acid and / or myristic acid and / or pentadecanoic acid and / or palmitic acid and / or margaric acid and / or stearic acid and / or nonadecanoic acid and / or arachic acid and / or erucic acid and / or elaeosteraric acid. But fatty acids with a melting point below 25 ° C can also survive part of the matrix can be used for castings or other solids mentioned above.

Fatty alcohol is a collective term for the by reducing the triglycerides, fatty acids or fatty acid esters available linear, saturated or unsaturated primary Alcohols with 6 to 22 carbon atoms. The fatty alcohols can be found in dependence saturated by the manufacturing process or unsaturated his. Myristyl alcohol and / or 1-pentadecanol and / or cetyl alcohol and / or 1-heptadecanl and / or stearyl alcohol and / or erucyl alcohol and / or 1-nonadecanol and / or arachidyl alcohol and / or 1-heneicosanol and / or Behenyl alcohol and / or erucyl alcohol and / or brassidyl alcohol are preferred components of the matrix of castings or other of the produced according to the invention containers enclosed solids.

It has also proven to be beneficial proven if the solids included in the agents according to the invention, in particular the preferably encased casting bodies, waxes as matrix material contain. Preferred waxes have a melting range, the between about 45 ° C and about 75 ° C lies. This means in the present case that the Melting range occurs within the specified temperature interval and does not denote the width of the melting range. Grow with Such a melting range are dimensionally stable at room temperature however melt at for the machine dishwashing typical temperatures from 30 ° C to 90 ° C and are therefore easier to disperse water at these temperatures.

"Growing" is a series of natural or artificial understood substances that usually melt above 40 ° C without decomposition and a little above the melting point, relatively low viscosity and not are stringy. They have a strongly temperature-dependent consistency and solubility on.

They are divided according to their origin Wax in three groups, the natural waxes, chemically modified Waxes and synthetic waxes.

Natural waxes include, for example vegetable waxes such as candelilla wax, carnauba wax, Japanese wax, Esparto grass wax, cork wax, guaruma wax, rice germ oil wax, Sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walrus, lanolin (wool wax), or uropygial fat, Mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

To the chemically modified waxes counting for example hard waxes such as Montanester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. As fusible or softenable substances for the masses that harden by cooling, compounds from other classes of material that meet the requirements with regard to the softening point can also be used. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ^® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ^® ETLP (Condea). Conversely, synthetic or semi-synthetic esters from lower alcohols with fatty acids from native sources can also be used. Tegin ^® 90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances. Shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used according to the invention as a matrix material in solids, preferably in castings.

The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating of the present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowa ^® (Pamentier & Co).

In a further preferred embodiment contains / contain one or more of the solids included in the agents according to the invention, but preferably a cast body produced by melt solidification, predominantly Share of paraffin wax (Panafine) as matrix material. That means that at least 50 % By weight of the total meltable or softenable substances contained, preferably more, consist of paraffin wax. Paraffin wax contents are particularly suitable (based on the total weight of the matrix materials) of about 60 % By weight, approximately 70% by weight or approximately 80% by weight, with even higher proportions of for example, more than 90% by weight are particularly preferred. In a special embodiment the invention consists of the entire material material of one or more in the agents according to the invention included Paraffin wax solids.

Paraffin waxes have the advantage over the other natural waxes mentioned in the context of the present invention that, when the containers produced according to the invention are used as a metering unit for detergents and cleaning agents, no hydrolysis in an alkaline cleaning agent environment the waxes take place (as is to be expected, for example, in the wax testers), since paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of Alkanes, as well as low proportions of iso- and cycloalkanes. The to be used according to the invention Paraffin preferably has essentially no constituents a melting point of more than 70 ° C, particularly preferably of more than 60 ° C on.

Preferred solids, in particular Cast body included at least one paraffin wax as matrix material and / or matrix component with a melting range of 40 ° C up to 60 ° C.

The content of the used is preferably Paraffin wax at ambient temperature (usually about 10 up to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible. The more solid wax components are present in a wax at room temperature, the more useful it is within the scope of the present invention.

Other beneficial ingredients the matrix of solids, especially castings, are wax alcohols, ie fatty alcohols with approx. 24–36 Carbon atoms, the main component in the form of wax esters of high molecular weight fatty acids (wax acids) many natural Are waxes. Exemplary for preferred wax alcohols here are lignoceryl alcohol, ceryl alcohol, Myricyl alcohol or melissyl alcohol called.

Dimensionally stable gels are another solid particularly preferred in the context of the present invention. The term "dimensionally stable" denotes Gels which have inherent dimensional stability, which enables them under usual Conditions of manufacture, storage, transportation and Handling by the consumer a stable against breakage, not to take disintegrating spatial form, whereby this spatial form under the conditions mentioned, also over a longer period of time, preferably 4 Weeks, particularly preferably 8 weeks and in particular 32 weeks, not changed, this means under the usual Conditions of manufacture, storage, transportation and Handling by the consumer in the conditions related to the manufacture spatial-geometric Form persists, that is, for example, does not melt or when exposed to an external under the conditions of manufacture, storage, transport and handling usual Force in this spatial-geometric Shape returns.

To achieve the desired dimensional stability, the gels with good product properties (solubility, washing and cleaning performance, stability of the gel), it is within the scope of the present invention preferred, as a thickener one or more substances from the Group agar-agar, carrageenan, tragacanth, gum arabic, alginates, Pectins, polyoses, guar flour, locust bean gum, starch, dextrins, Gelatin, casein, carboxymethyl cellulose, core meal ether, polyacrylic u. Polymethacrylic compound, vinyl polymers, polycarboxylic acids, polyethers, Polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonite, Zeolites and silicas contain, where it has proven to be particularly advantageous if the gels are these or one of the following thickeners in amounts between 0.2 and 10% by weight, preferably between 0.3 and 7 wt .-% and particularly preferably between 0.4 and 4 wt .-% based on the total weight of the molded body contain.

Natural polymers, which are used as thickeners in the context of the present invention are, for example, agar agar, carrageenan, Tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, Locust bean gum, starch, Dextrins, gelatin and casein.

Modified natural products come from especially from the group of modified starches and celluloses, exemplary here are carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and -propyl cellulose and core meal ether called.

A large group of thickeners that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes. Thickeners from these classes of substances are commercially available and are marketed, for example, under the trade names Acolol ^® -820 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral®-GT-282- S (alkyl polyglycol ether, Akzo), Deuterol ^® polymer 11 (dicarboxylic acid copolymer, Schönes GmbH), Deuteron ^® -XG (anionic heteropolysaccharide based on β-D-glucose, D-manose, D-glucuronic acid, Schönes GmbH), Deuteron ^® -XN (non-ionic polysaccharide, Schönes GmbH), Dicrylan ^® -thickener-O (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA ^® -81 and EMA ^® -91 (ethylene-maleic anhydride copolymer , Monsanto), thickener-QR-1001 (polyurethane emulsion, 19–21% in water / diglycol ether, Rohm & Haas), Mirox ^® -AM (anionic acrylic acid-acrylic ester copolymer dispersion, 25% in water, Stockhausen) , SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo ^® -S (high molecular weight P olysaccharide, stabilized with formaldehyde, Shell) and Shellflo ^® -XA (xanthan biopolymer, stabilized with formaldehyde, Shell).

Due to their manufacturing process and to optimize their dissolving behavior, preferred gels contain various solvents, gels having proven particularly advantageous in terms of their product properties, the water and / or one or more water-miscible solvents in amounts of 5 to 70% by weight, preferably from 10 to 65% by weight and particularly preferably from 15 to 60 % By weight.

It has been particularly advantageous also proved to be when the water-miscible solvent was one or more Substances from the group of the group ethanol, n- or i-propanol, n- or sec- or tert-butanol, glycol, propane or butanediol, glycerin, Diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, Ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, Diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, Di-isopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether contain.

Further preferred in agents according to the invention Solids used are the capsules. "Capsule" is a term for a commonly used Packaging form in different sized, possibly colored envelopes made of gelatin, wax, or wafer material solid, semi-solid or liquid substances contains. Most frequently the gelatin capsules (made of hard or soft gelatin) are used.

In a special embodiment of the present invention has one, more, or all in the means according to the invention Solids used, for example one, several or all in these containers filled Powder and / or granules) and / or extrudate (s) and / or compactate (s) and / or cast body and / or dimensionally stable) gel (s) and / or capsule (s), a coating (coating) on. Such a coating can serve different purposes. On the one hand, a coating, for example, can cause an undesirable Contact of hydrolysis or oxidation sensitive contained in the solids Active substances, with the outside air or other solids enclosed in the water-soluble container according to the invention be avoided. On the other hand, a coating can also an advantageous visual effect can be achieved.

As ingredients for the reception chambers are suitable for the liquids and solids mentioned above. With solids, a distinction is made between powders, granules, extrudates, Compacts, castings as well distinguishable stable gels. Liquids are considered in the scope this application in addition to low-viscosity, flowable liquids or flowable gels also flowable dispersions, for example emulsions or suspensions. Considered flowable Active substances or combinations of active substances if they have no inherent dimensional stability, which enables them under usual Conditions of manufacture, storage, transportation and Handling by the consumer a non-disintegrating spatial form to take, this spatial form under the conditions mentioned also about longer Time, preferably 4 weeks, particularly preferably 8 weeks and in particular 32 weeks, unchanged, this means under the usual Conditions of manufacture, storage, transportation and Handling by the consumer in the conditions related to the manufacture spatial-geometric shape persists, that is, does not melt. The determination of fluidity refers in particular to those customary for storage and transportation Conditions, in particular at temperatures below 50 ° C., are preferred below 40 ° C. As liquids therefore, in particular, active ingredients or combinations of active ingredients apply with a melting point below 25 ° C, preferably below 20 ° C, particularly preferably below 15 ° C.

The following table shows the preferred agent according to the invention filled with three Admission chambers listed. The one with liquid, Fill powder or granules Receiving chambers preferably have a seal. For those with compactates, extrudates, castings or dimensionally stable gels filled Sealing chambers are optional, but are preferred.

Within the scope of the present application Particularly preferred agents are characterized in that at least a receiving chamber a liquid Contains active substance. Other particularly preferred agents are characterized in that at least a receiving chamber contains a solid active substance. Especially preferred in the context of the present invention, however, is that at least a receiving chamber of the agent according to the invention with a liquid, at least one further receiving chamber with a solid, preferably filled with a powder is.

Another preferred embodiment has three receiving chambers, one of which contains a liquid, a second receiving chamber with a powder and a third receiving chamber is filled with a solidified melt.

As disclosed above, the transparent container according to the invention or translucent wrapping materials include. Preferred according to the invention Means which are at least partially a transparent covering material can have therefore contain stabilizing agents. Stabilizing agent in The meaning of the ending are materials that are in the receiving chambers and / or the ingredients located in an intermediate space Protect decomposition or deactivation by exposure to light. As Antioxidants, UV absorbers and Fluorescent dyes proved.

Particularly suitable stabilizers in the sense of the invention are the antioxidants. In order to prevent undesired changes to the formulations caused by light radiation and thus radical decomposition, the formulations can contain antioxidants. Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants. Further examples are propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long-chain (C8-C22) esters of gallic acid, such as dodecyl gallate. Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives, such as isopropyl citrate, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic acid palmitate, organosulfur compounds, such as the esters of 3,3'-thiodipropionic acid with C _1-18 alkanols, in particular C _10-18 alkanols, metal ion deactivators which are capable of metal ions, such as copper, which catalyze the autooxidation. to complex, such as nitrilotriacetic acid and its derivatives and their mixtures. Antioxidants can be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.

Another class of stabilizers that can preferably be used are the UV absorbers. UV absorbers can improve the lightfastness of the formulation components. These include organic substances (light protection filters) that are able to absorb ultraviolet rays and release the absorbed energy in the form of long-wave radiation, eg heat. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles, such as, for example, the water-soluble benzenesulfonic acid 3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Cibafast ^® H), are also phenyl-substituted acrylates in the 3-position ( Cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid. Of particular importance are biphenyl and especially stilbene derivatives, which are commercially available as Tinosorb ^® FD or Tinosorb ^® FR ex Ciba. 3-Benzylidene camphor or 3-benzylidene norcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor, may be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene); Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropyl benzyl ester, salicylic acid homomethyl ester; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives, such as 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and Octyl Triazone or Dioctyl Butamido Triazone (Uvasorb HEB ^®); Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'methoxy-phenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-benzylidene camphor, such as 4- (2-oxo-3-bornylidene methyl) benzene sulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane, such as, for example, are particularly suitable as typical UV-A filters 1- (4'-tert-Butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds. The UV-A and UV-B filters can of course also be used in mixtures. In addition to the soluble substances mentioned, insoluble light-protection pigments, namely finely dispersed, preferably nanoized metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. Silicates (talc), barium sulfate or zinc stearate can be used as salts. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs in some other way from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobicized. Typical examples are coated titanium dioxide, such as titanium dioxide T 805 (Degussa) or Eusolex ^® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferably used.

UV absorbers can be used in amounts of up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight, based in each case on the Total weight of one in a compartment or space contained mixture of substances.

Another preferred one The class of stabilizers are the fluorescent dyes. Count among them the 4,4'-diamino-2,2'-stilbene disulfonic acids 4,4'-distrylbiphenlene, Methyl umbelliferones, coumarins, (flavonic acids), dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic imides, Benzoxazole, Benzisoxazole and Benzimidazole systems and those substituted by heterocycles Pyrene derivatives. The sulfonic acid salts are of particular importance of the diaminostilbene derivatives, as well as polymeric fluorescent substances.

Fluorescent materials can be sourced on the total weight of one in a receiving chamber or space substance mixture present, in amounts of up to 5% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0.5 and in particular from 0.03 to 0.1% by weight.

In a preferred embodiment the aforementioned stabilizers in any mixtures used. The stabilizing agents are based on the total weight a substance mixture located in a receiving chamber, in Amounts up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20% by weight, in particular from 0.02 to 5% by weight.

At least two of the admission chambers are containers according to the invention sealed. All of the receiving chambers of a container according to the invention are preferably sealed. The first mentioned above and second wrapping material it can be the same but also different materials. However, it is particularly preferred if the first and second shell material for example in their chemical composition or in their Distinguish thickness and have different dissolution rates.

The dissolution behavior of containers and closing part can except due to the chemical composition of the shell materials used for example, can also be influenced by the thickness of the container walls or the closure parts. Preferred container are characterized in the context of the present application, that the from the first wrapping material existing side walls the receiving chambers a thickness of 5 to 2000 microns, preferably from 10 to 1000 microns, particularly preferably from 15 to 500 μm, very particularly preferably from 20 to 200 μm and in particular from 25 to Has / have 100 μm. The second wrapping material used for sealing preferably has a thickness of 5 to 100 μm, particularly preferably from 6 to 80 μm and in particular from 7 to 50 μm on. It is particularly preferred that the container and sealing material be different Have thickness, such containers are advantageous whose Sealing material have a smaller wall thickness compared to the associated containers.

Preferred shell materials are water soluble or water-dispersible. Within the scope of the present application therefore agents according to the invention preferred which is at least one water-soluble or water-dispersible shell material exhibit. Such agents according to the invention are particularly preferred, where the shell materials used a water soluble or water-dispersible polymer.

In a preferred embodiment comprise the agents according to the invention Active substances or active substance mixtures from the fields of pharmaceuticals, Cosmetics, animal feed, crop protection or fertilizers, adhesives, food and / or personal care products, but preferably from the field of active washing and cleaning Substances.

Preferred active substances or active substance mixtures from the field of cosmetics are, in particular, hair setting agents, hair shaping agents and hair colorants. In addition to the hair washing and hair care products, the preferred personal care products also include the pretreatment products and hairdressing aids medium as well as course rinses. Active substances from the area of bath additives, such as bath salts or bath tablets, but also shower, foam or cream baths, are also preferred.

Particularly preferred agents according to the invention are characterized in that at least a receiving chamber and / or at least one space with one Detergent or cleaning agent filled is. Preferably, all of the receiving chambers are active in washing or cleaning Substances filled. Washing and cleaning-active substances are particularly preferred from the group of bleaching agents, bleach activators, polymers, builders, Surfactants, enzymes, disintegration aids, electrolytes, pH adjusting agents, fragrances, Perfume carriers, dyes, Hydrotropes, foam inhibitors, anti-redeposition agents, optical Brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, Dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Corrosion inhibitors, antistatic agents, phobias and impregnants, Swelling and sliding solid, non-aqueous solvents, fabric softener, protein hydrolyzate, as well as UV absorbers.

Bleaching agents and bleach activators can be included in the agents according to the invention as important components of detergents and cleaning agents. Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Detergent tablets for automatic dishwashing can also contain bleaches from the group of organic bleaches. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peioxy-α-naphthoic acid and magnesium monoper phthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthaloxyhexanoic acid ( PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacinic acid, diperoxydoxybutyldiperoxydoxybutylacid, , 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Are the agents of the invention as automatic dishwashing detergent used so can these bleach activators contain to when cleaning at temperatures of 60 ° C and below to achieve an improved bleaching effect. As bleach activators can 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 that are O- and / or are suitable N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

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

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

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

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

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

The surfactants come in particular the anionic surfactants in acid form, aqueous solutions or Pastes of neutralized anionic surfactants, non-ionic surfactants and / or cationic surfactants or amphoteric surfactants. Dependent on of the choice of the surfactant (s) used are surfactant-containing agents according to the invention for example in the removal of grease or oil contamination can be used, their field of application from textile cleaning to to remove oil spills in nature is enough. Within the scope of the present application Granules preferred, which have a surfactant content of 1 to 70 wt .-%, particularly preferably from 2 to 60% by weight, particularly preferably from 4 to 50% by weight, based in each case on the total weight of the compositions.

In addition to the ingredients mentioned Bleaching agents and bleach activators are builders other important ingredients of detergents. Preferred agents according to the invention can all usually contain builders used in cleaning agents, in particular So zeolites, silicates, carbonates, organic cobuilders and - where no ecological There are prejudices against their use - including phosphates. The above builders can of course can also be used in surfactant-free compressed products.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M 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 dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide Venniaschen 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 that can be used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which was developed by CONDEA Augusta SpA under the Brand name VEGOBOND AX ^{® is} distributed and through the formula nNa ₂ O · (1-n) K ₂ O · Al ₂ O ₃ · (2 - 2.5) SiO ₂ · (3.5 - 5.5) H ₂ O can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, there is also a stake of the well-known phosphates possible as builder substances, provided that such use is not avoided for ecological reasons should be. The sodium salts of the orthophosphates are particularly suitable, the pyrophosphates and especially the tripolyphosphates.

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

Sodium dihydrogen phosphate, NaHP ₂ O ₄ , disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ and by condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ arise higher mol. 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, as well as the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) are further within the scope of the present Registration with advantage used builders.

Usable organic builders are, for example, those in the form of their alkali and especially sodium salts usable polycarboxylic acids, like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, Sugar acids, amino carboxylic acids, nitrilotriacetic (NTA), provided that such use is not 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.

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, with the meaning of this ending preferably the alkali carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate can be used.

Are the agents of the invention with automatic dishwashing used, are water-soluble Builder preferred as they work on dishes and hard surfaces tend to be less likely to form insoluble residues. Usual builder are the low molecular weight polycarboxylic acids and their salts, the homopolymers and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and silicates. Prefers are used to manufacture tablets for machine dishwashing trisodium citrate and / or Pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class the disilicates and / or metasilicates used. Particularly preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate. A builder system is also particularly preferred, which is a mixture of tripolyphosphate and sodium carbonate and sodium disilicate contains.

As organic cobuilders, in the cleaning agents in the context of the present invention in particular Polycarboxylates / polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used become. These classes of substances are described below.

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 this is 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, methylglycine, 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 of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.

Polymers are also used as builders Suitable polycarboxylates, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The 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 1000 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 1200 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 will be detailed in the following described.

• i) ungesättigten Carbonsäuren
• ii) Sulfonsäuregruppen-haltigen Monomeren
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

enthalten.However, it is also possible to provide agents according to the invention which, as so-called “3-in-1” products, combine the conventional cleaners, rinse aids and a salt replacement function. For this purpose, automatic dishwashing agents according to the invention are preferred which additionally comprise 0.1 to 70% by weight of copolymers

• i) unsaturated carboxylic acids
• ii) Monomers containing sulfonic acid groups
• iii) optionally further ionic or nonionic monomers

contain.

These copolymers cause the Such items treated dishes in subsequent cleaning operations clearly become cleaner than dishes that have been washed using conventional means.

As an additional positive effect occurs a shortening the drying time of the dishes treated with the detergent on, i.e. the consumer can after the cleaning program the dishes earlier Take out of the machine and use again. Under drying time is part of the teaching of the invention in general the literal meaning understood, that is, the time that passes until one in a dishwasher treated dish surface has dried, but especially the time that passes until 90% one with a detergent or rinse aid in concentrated or diluted form treated surface is dried.

In the context of the present invention, unsaturated carboxylic acids of the formula I are preferred as the monomer R ¹ (R ² ) C = C (R ³ ) COOH (I), in which R ¹ to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

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

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

Preferred among these monomers are those of the formulas IIa, IIb and / or IIc, H ₂ C = CH-X-SO ₃ H (IIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (IIb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (IIc), in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ CH ₃ ) in formula IIa), 2-acrylamido-2-propanesulfonic acid (X = -C ( O) NH-C (CH ₃ ) ₂ in formula IIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-C (CH ₃ ) ₂ CH ₂ - in formula IIa), 2-methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-C (CH ₃ ) ₂ CH ₂ - in formula IIb), 3-methacrylamido-2-hydroxy-propanesulfonic acid (X = -C ( O) NH-CH ₂ CH (OH) CH ₂ - in formula IIb), allylsulfonic acid (X = CH ₂ in formula IIa), methallylsulfonic acid (X = CH ₂ in formula IIb), allyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula IIa), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula XIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid (X = CH ₂ in formula IIb), styrenesulfonic acid (X = C ₆ H ₄ in formula IIa), vinylsulfonic acid (X not present in formula IIa), 3-acrylamido-propanesulfonic acid (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in For mel IIa), 3-methacrylamido-propanesulfonic acid (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula IIb), sulfomethacrylamide (X = -C (O) NH- in formula IIb), sulfomethyl methacrylamide (X = -C (O) NH-CH ₂ - in formula IIb) and water-soluble salts of the acids mentioned.

As another ionic or non-ionic Monomers are particularly suitable ethylenically unsaturated compounds. Preferably is the content of those used according to the invention Polymers on monomers of group iii) less than 20% by weight, based on the Polymer. Polymers to be used with particular preference only exist from monomers of groups i) and ii).

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

besonders bevorzugt.In summary, copolymers are made of

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

particularly preferred.

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

Particularly preferred copolymers consist of

• i) one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and / or maleic acid
• ii) one or more monomers of the formulas IIa, IIb and / or IIc containing sulfonic acid groups: H ₂ C = CH-X-SO ₃ H (IIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (IIb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (II), in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ )
• iii) optionally further ionic or nonionic monomers.

The copolymers, which are contained in the medium can the monomers from groups i) and ii) and, if appropriate, iii) Contained in varying amounts, with all representatives from the group i) with all Representatives from group ii) and all representatives from the Group iii) can be combined. Especially preferred polymers have certain structural units that are described below.

For example, agents according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula III - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (III), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are produced by copolymerizing acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have structural units of the formula IV - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (IV), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Completely analogously, acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Agents according to the invention which contain one or more copolymers which have structural units of the formula V - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (V), contain, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are also preferred, a preferred embodiment of the present invention, just as preferred are agents which are characterized in that they contain one or more copolymers which have structural units of the formula VI - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (VI), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) -, are preferred.

Instead of or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly preferred monomer from group i). In this way, preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers, the structural units of the formula VII - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VII) , in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) -, are preferred and to agents which are characterized in that they contain one or more copolymers, the structural units of the formula VIII - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _P - (VIII), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In summary, automatic dishwashing agents according to the invention are preferred which contain, as ingredient b), one or more copolymers which have structural units of the formulas III and / or IV and / or V and / or VI and / or VII and / or VIII - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (III), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (IV), - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (V), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _P - (VI), - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VII), - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (VIII), contain, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In the polymers, the sulfonic acid are wholly or partly in neutralized form, i.e. that the acid Hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and in particular can be exchanged for sodium ions. Appropriate means, which are characterized in that the sulfonic acid flu Partially or fully neutralized in the copolymer are preferred according to the invention.

The monomer distribution of the in the agents according to the invention copolymers used at Copolymers containing only monomers from groups i) and ii), preferably in each case 5 to 95% by weight i) or ii), particularly preferably 50 to 90% by weight of monomer from group i) and 10 to 50% by weight of monomer from group ii), each based on the polymer.

Such are special with terpolymers preferred, the 20 to 85 wt .-% monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) included.

The molar mass of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the intended use. Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

The content of one or more Copolymers in the agents according to the invention can vary depending on the application and the desired product performance, preferred machine according to the invention Dishwashing liquid are characterized in that they the copolymer (s) in amounts of 0.25 to 50% by weight, preferably from 0.5 to 35% by weight, particularly preferably from 0.75 to 20% by weight and in particular contain from 1 to 15% by weight.

As already mentioned further above, it is particularly preferred to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers in the agents according to the invention. The polyacrylates were described in detail above. Combinations of the above-described copolymers containing sulfonic acid groups with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons, are particularly preferred. Such polyacrylates are commercially available under the trade names Sokalan ^® PA15 or Sokalan ^® PA25 (BASF).

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 100,000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 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.

To improve water solubility can the polymers also allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as Contain monomer.

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.

As anionic surfactants in acid form are preferred one or more substances from the group of carboxylic acids, the Schwefelsäurehalbester and the sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and of alkylarylsulfonic acids, used. In order to have sufficient surface-active properties, the compounds mentioned should have long-chain hydrocarbon residues feature, thus have at least 6 carbon atoms in the alkyl or alkenyl radical. Usually are the C chain distributions the anionic surfactants in the range from 6 to 40, preferably 8 to 30 and in particular 12 to 22 carbon atoms.

Carboxylic acids, which are used as soaps in detergents and cleaning agents in the form of their alkali metal salts, are technically largely obtained from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps), only water is used on an industrial scale to split the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in car claws or continuous high-pressure cleavage. Carboxylic acids which can be used as an anionic surfactant in acid form in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. The preferred compound in the context of the present compound is 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), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), triacidic acid (melotinic acid), triacidic acid (melotonic acid), and melonic acid unsaturated species 9c-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-octadecenoic acid) (9c -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 can be obtained from fat cleavage. Such mixtures are, for example, coscos oil fatty acid (approx. 6% by weight C ₈ ; 6% by weight C ₁₀ , 48% by weight C ₁₂ , 18% by weight C ₁₄ , 10% by weight C ₁₆ , 2% by weight .-% _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% by weight of C ₁₄ , 26% by weight of C ₁₆ , 2 wt% C ₁₆ , 2 wt% C _{16 '} , 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 wt% C ₁₈ , 1 wt% C _{18 '),} technical grade oleic acid (about 1 wt .-% C _12, 3 wt .-% C _14, 5 wt .-% C _16, 6 wt .-% C _16', 1 wt .-% C _17, 2 % By weight C ₁₈ , 70% by weight C _{18 '} , 10% by weight C _18'' , 0.5% by weight C _18''' ), technical palmitin / stearic acid (approx. 1% by weight % C _12, 2 wt .-% C ₁₄ 45 wt .-% C _16, 2 wt .-% C ₁₇ 47 wt .-% C _18: 1 wt .-% C _{18 ')} and soybean oil fatty acid (ca. 2 wt% C ₁₄ , 15 wt% C ₁₆ , 5 wt% C ₁₈ , 25 wt% C _{18 '} , 45 wt% C _18'' , 7 wt% C _{18 '''} ).

Sulfuric acid semiesters of longer-chain alcohols are also anionic surfactants in their acid form and can be used in the context of the present invention. Their alkali metal, in particular sodium salts, the fatty alcohol sulfates, are commercially available from fatty alcohols which are reacted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to give the alkyl sulfuric acids concerned and are subsequently neutralized. The fatty alcohols are obtained from the fatty acids or fatty acid mixtures concerned by high-pressure hydrogenation of the fatty acid methyl esters. In terms of quantity, the most important industrial process for the production of fatty alkyl sulfuric acids is the sulfonation of the alcohols with SO ₃ / air mixtures in special cascade, falling film or tube bundle reactors.

Another class of anionic surfactant acids that used according to the invention are the alkyl ether sulfuric acids, their salts, the alkyl ether sulfates, compared to the alkyl sulfates by a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts). Alkyl become like the alkyl sulfuric acids synthesized from fatty alcohols, which with ethylene oxide to the concerned Fatty alcohol ethoxylates are implemented. Instead of ethylene oxide propylene oxide can also be used. The subsequent sulfonation with gaseous Sulfur trioxide in short-term sulfonation reactors yields over 98% on the relevant alkyl ether sulfuric acids.

Alkanesulfonic acids and olefin sulfonic acids are also in the context of the present invention as anionic surfactants in acid form used. alkanesulfonic can the sulfonic acid group terminal bound (primary alkane sulfonic acids) or contain along the C chain (secondary alkanesulfonic acids), where only the secondary ones alkanesulfonic have commercial importance. These are by sulfochlorination or Sulfoxidation of linear hydrocarbons produced. In sulfochlorination according to Reed, n-paraffins with sulfur dioxide and chlorine under irradiation with UV light corresponding sulfochlorides implemented in the hydrolysis with alkalis directly deliver the alkanesulfonates, when reacting with water the alkanesulfonic acids. Because in the sulfochlorination, di- and polysulfochlorides as well as chlorinated hydrocarbons can occur as by-products of the radical reaction the reaction usually only carried out up to degrees of implementation of 30% and then canceled.

Another process for making alkanesulfonic acids is sulfoxidation, in the case of n-paraffins under irradiation with UV light with sulfur dioxide and oxygen be implemented. This radical reaction occurs successively Alkylsulfonyl radicals that add oxygen to the alkylpersulfonyl radicals continue to respond. The reaction with unreacted paraffin provides an alkyl radical and the alkyl persulfonic acid, which are converted into an alkyl peroxysulfonyl radical and a hydroxyl radical breaks down. The reaction of the two radicals with unreacted paraffin provides the alkyl sulfonic acids or water, which reacts with alkyl persulfonic acid and sulfur dioxide to form sulfuric acid. To the yield of the two end products alkyl sulfonic acid and Sulfuric acid if possible To keep high and suppress side reactions, this reaction is usually only carried out up to degrees of implementation of 1% and then terminated.

Olefin sulfonates are becoming technical by reaction of α-olefins made with sulfur trioxide. Intermediate hermaphrodites form which cyclize into so-called sultons. Under suitable conditions (alkaline or acidic hydrolysis) these sultones react to hydroxylalkanesulfonic acids or alkensulfonic acids both also as anionic surfactant acids can be used.

Alkylbenzenesulfonates as powerful Anionic surfactants have been around since the 1930s known. At that time, monochlorination of kogasin fractions and subsequent ones Friedel-Crafts alkylation alkylbenzenes made with oleum sulfonated and neutralized with sodium hydroxide solution. beginning of fifties Years have passed to the production of alkylbenzenesulfonates propylene branched α-dodecylene tetramerized and the product over a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride converted to tetrapropylene benzene, the following sulfonated and neutralized. This economic opportunity the production of tetrapropylene benzene sulfonates (TPS) led to Breakthrough of this class of surfactants, which subsequently the soaps as the main surfactant displaced in detergents and cleaning agents.

Because of the lack of biological Degradability of TPS resulted in the need for new alkylbenzenesulfonates to be presented, which are characterized by improved ecological behavior. These requirements are met by linear alkyl benzene sulfonates, which today almost exclusively alkylbenzenesulfonates produced and with the abbreviation ABS or LAS can be used.

Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which in turn are accessible from linear olefins. For this purpose, petroleum fractions with molecular sieves are separated on an industrial scale into the n-paraffins of the desired purity and dehydrated to the n-olefins, both α- and i-olefins result. The resulting olefins are then reacted with benzene in the presence of acidic catalysts to give the alkylbenzenes, the choice of Friedel-Crafts catalyst having an influence on the isomer distribution of the linear alkylbenzenes formed: When using aluminum trichloride, the content of the 2-phenyl isomers is in the mixture with the 3, 4, 5 and other isomers at approx. 30% by weight, on the other hand, if hydrogen fluoride is used as a catalyst, the 2-phenyl isomer content can be reduced to approx. 20% by weight , Finally, the sulfonation of linear alkylbenzenes is now possible on a large industrial scale with oleum, sulfuric acid or gaseous sulfur trioxide, the latter being by far the most important. For the sulfonation, special film or tube bundle reactors are used which deliver a 97% by weight alkylbenzenesulfonic acid (ABSS) as product, which can be used as anionic surfactant acid in the context of the present invention.

in der die Summe aus x und y üblicherweise zwischen 5 und 13 liegt. Erfindungsgemäß bevorzugt als Aniontensid in Säureform sind C_8-16-, vorzugsweise C_9-13-Alkylbenzolsulfonsäuren. Es ist im Rahmen der vorliegenden Erfindung weiterhin bevorzugt, C_8-16-, vorzugsweise C_9-13-Alkybenzolsulfonsäuren einzusetzen, die sich von Alkylbenzolen ableiten, welche einen Tetralingehalt unter 5 Gew.-%, bezogen auf das Alkylbenzol, aufweisen. Weiterhin bevorzugt ist es, Alkylbenzolsulfonsäuren zu verwenden, deren Alkylbenzole nach dem HF-Verfahren hergestellt wurden, so daß die eingesetzten C_8-16-, vorzugsweise C_9-13-Alkybenzolsulfonsäuren einen Gehalt an 2-Phenyl-Isomer unter 22 Gew.-%, bezogen auf die Alkylbenzolsulfonsäure, aufweisen.By choosing the neutralizing agent, a wide variety of salts, ie alkylbenzenesulfonates, can be obtained from the ABSS. For reasons of economy, it is preferred to prepare and use the alkali metal salts and, among them, the sodium salts of the ABSS. These can be described by the general formula IX:

in which the sum of x and y is usually between 5 and 13. According to the invention, preferred as the anionic surfactant in acid form are C _8-16 -, preferably C _9-13 -alkylbenzenesulfonic acids. In the context of the present invention, it is further preferred to use C _8-16 , preferably C _9-13 alkylbenzenesulfonic acids which are derived from alkylbenzenes which have a tetralin content below 5% by weight, based on the alkylbenzene. It is further preferred to use alkylbenzenesulfonic acids whose alkylbenzenes have been prepared by the HF process, so that the C _8-16 -, preferably C _9-13- alkylbenzenesulfonic acids used have a 2-phenyl isomer content of less than 22% by weight. , based on the alkylbenzenesulfonic acid.

The anionic surfactants mentioned above in its acid form can used alone or in a mixture with one another. But it is also possible and preferred that the Anionic surfactant in acid form before adding to the substrate (s)) further, preferably acidic, ingredients of detergents and cleaning agents in amounts from 0.1 to 40% by weight, preferably from 1 to 15% by weight and in particular from 2 to 10% by weight, in each case based on the weight the mixture to be reacted.

Suitable as acidic reactants in the context of the present invention, in addition to the "surfactant acids", the abovementioned ones fatty acids, phosphonic, polymer acids or partially neutralized polymer acids as well as "builder acids" and "complex builder acids" (details later in the text) alone as well as in any mixtures. As ingredients of laundry and cleaning agents are particularly suitable for acidic washing and cleaning agent ingredients, for example phosphonic acids, which in neutralized form (phosphonates) as incrustation inhibitors Are components of many detergents and cleaning agents. The use of (partially neutralized) polymer acids such as polyacrylic acids, is possible according to the invention. It is but also possible acid-stable Mix ingredients with the anionic surfactant acid. Bid here For example, so-called small components, which otherwise would have to be added in complex further steps, ie For example, optical brighteners, dyes, etc., in individual cases acid stability is to be checked.

Of course it is also possible that Use anionic surfactants partially or fully neutralized. These salts can then as a solution, Suspension or emulsion are present in the granulating liquid, but also as a solid be part of the solid bed. As cations for such Anionic surfactants are available in addition to the alkali metals (in particular here according to claim and K salts) ammonium and mono-, di- or triethanolalkonium ions on. Instead of mono-, di- or triethanolamine you can also the analog representatives of mono-, di- or trimethanolamine or those of the higher alkanolamines Alcohols quaternized and present as a cation.

Cationic surfactants can also be used with advantage as active substances. The delivery form of the cationic surfactant can be added directly to the mixer, or it can be sprayed onto the solid carrier in the form of a liquid to pasty form of cationic surfactant. Such cationic surfactant preparation forms can be prepared, for example, by mixing commercially available cationic surfactants with auxiliaries such as nonionic surfactants, polyethylene glycols or polyols. Also lower alcohols like ethanol and isopropanol can be used, the amount of such lower alcohols in the liquid cationic surfactant preparation form should be below 10% by weight for the reasons mentioned above.

Suitable cationic surfactants for the agents according to the invention all usual Substances are considered, cationic surfactants with fabric softening Effect are clearly preferred.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- 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 one or more cationic, fabric softening agents of the formulas X, XI or XII as cationic active substances with fabric softening effect:

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 or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

In preferred embodiments of the present invention the solids) additionally Nonionic surfactants) as an active substance.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 mol ethylene oxide (EO) per mol alcohol, in which the alcohol radical can be linearly or preferably 2-branched methyl or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mol alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃; -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.In the context of the present invention, weakly foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants. Among these, surfactants with EO-AO-EO-AO blocks are preferred, one to ten EO or AO groups being bonded to one another before a block follows from the other groups. Agents according to the invention which contain surfactants of the general formula XIV as nonionic (s) surfactants are preferred here

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

The preferred nonionic surfactants of the formula XIV can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethyl or alkylene oxide. The radical R ¹ in the above formula XIV can vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is generally not shown, the linear radicals being from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol are preferred. Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or, in the mixture, methyl-branched or linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, compositions according to the invention are preferred in which R ¹ in formula XIV for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit. However, other alkylene oxides in which R ² or R ³ are selected independently of one another from -CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are also suitable. Preferred agents are characterized in that R ² or R ³ for a radical -CH ₃ , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.

In summary, nonionic surfactants which have a C _9-15 alkyl radical with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, are particularly preferred for use in the agents according to the invention.

The specified C chain lengths as well Degrees of ethoxylation or degrees of alkoxylation are statistical Mean values for a special product can be an integer or a fractional number can. Due to the manufacturing process, there are commercial products for the above Formulas are usually not from an individual representative, but rather from mixtures, whereby both for the C chain lengths as also for the degrees of ethoxylation or degrees of alkoxylation mean values and resulting in fractional numbers.

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 esters.

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 Alkyl- 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 XV,

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 propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula XVI,

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 oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this remainder.

[Z] is preferably by reductive Obtained amination of a reduced sugar, for example glucose, Fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy substituted compounds can then by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

It is special for many applications preferred if the ratio from anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably is between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2. Prefers are containers according to the invention which Surfactant (s), preferably anionic (s) and / or nonionic surfactant (s), in amounts of 5 to 80% by weight, preferably 7.5 to 70% by weight, particularly preferably from 10 to 60% by weight and in particular from 12.5 up to 50 wt .-%, each based on the weight of the enclosed Solids.

As already mentioned, the use of surfactants in cleaning agents for automatic dishwashing is preferably limited to the use of nonionic surfactants in small amounts. If the containers according to the invention are intended to enclose such agents, these agents preferably contain only certain nonionic surfactants, which are described below. Usually only weakly foaming nonionic surfactants are used as surfactants in automatic dishwashing detergents. By contrast, representatives from the groups of anionic, cationic or amphoteric surfactants are of lesser importance. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 mol ethylene oxide (EO) per mol alcohol, in which the alcohol radical can be linearly or preferably 2-branched methyl or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mol alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In particular with water-soluble according to the invention containers for the Portioning, packaging and dosing of cleaning agents for mechanical Wash the dishes it is preferred that this contain a nonionic surfactant that has a melting point above Has room temperature, preferably a nonionic surfactant a melting point above 20 ° C. Nonionic to be used with preference Surfactants have melting points above 25 ° C, particularly preferably to be used nonionic surfactants have melting points between 25 and 60 ° C, in particular between 26.6 and 43.3 ° C.

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

Preferred than at room temperature fixed nonionic surfactants come from the groups of alkoxylated Nonionic surfactants, especially ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control out.

In a preferred embodiment The present invention is the nonionic surfactant with a Melting point above room temperature an ethoxylated nonionic surfactant, that from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferred at least 15 moles, especially at least 20 moles of ethylene oxide per MoI alcohol or alkylphenol has emerged.

A particularly preferred nonionic surfactant which is solid at room temperature is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol ethylene oxide , Among these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

The nonionic surfactant that is solid at room temperature preferably has additional Propylene oxide units in the molecule. Such PO units preferably make up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or Alkylphenols additionally Have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules makes preferably more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight such non-ionic surfactants.

Further particularly preferably to be used Contains nonionic surfactants with melting points above room temperature 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.

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

Another preferred surfactant can be represented by the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ] describe in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1, 5 and y represents a value of at least 15.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

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

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above the formula have values of k = 1 and j = 1, so that the above formula becomes R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 represents} H and x assumes values from 6 to 15.

Preferred agents according to the invention, which are used as automatic dishwashing detergents in addition to the surfactants mentioned to improve the rinse aid result furthermore amphoteric or cationic polymers.

Agents according to the invention can contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all the enzymes established in the prior art for these purposes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are accordingly preferred. Agents ^according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5 percent by weight based on active protein. The protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-bichinolyl-4,4'-dicarboxylic acid) or the biuret method.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and that which can no longer be assigned to the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. The variants listed under the name BLAP ^{® are} derived from the protease from Bacillus lentus DSM 5483.

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

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

Furthermore are for this Purpose of the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948); are as well Fusion products of the molecules mentioned can be used.

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

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

Agents according to the invention can, especially if they for the Treatment of textiles are thought to contain cellulases, each by purpose as pure enzymes, as enzyme preparations or in the form of Mixtures in which the individual components are advantageously complement in terms of their various performance aspects. To count these performance aspects especially contributions for primary washing performance, for secondary washing performance of the agent (anti-redeposition effect or graying inhibition) and finish (tissue effect), up to the exertion of a "stone washed" effect.

A useful fungal, endoglucanase (EG) -rich cellulase preparation or its further developments are offered by the Novozymes company under the trade name Celluzyme ^® . The products Endolase ^® and Carezyme ^® , also available from Novozymes, are based on the 50 kD-EG and the 43 kD-EG from H. insolens DSM 1800. Other possible commercial products from this company are Cellusoft ^® and Renozyme ^® . The 20 kD EG cellulase from Melanocaipus, which is available from AB Enzymes, Finland, under the trade names Ecostone ^® and Biotouch ^® , can also be used. Other commercial products from AB Enzymes are Econase ^® and Ecopulp ^® . Another suitable cellulase from Bacillus sp. CBS 670.93 is available from Genencor under the trade name Puradax ^® . Other commercial products from Genencor are "Genencor detergent cellulase L" and IndiAge ^® Neutra.

Agents according to the invention can contain further enzymes, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, United States. The obtained from B. subtilis β-glucanase is available under the name Cereflo ^® from Novozymes., To increase the bleaching action, inventive washing or cleaning agent oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, like halo-, chloro- , Bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases). Suitable commercial products are Denilite ^® 1 and 2 from Novozymes. Advantageously, organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of greatly different redox potentials between the oxidizing enzymes and the soiling.

The agents according to the invention the enzymes used are either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or according to known biotechnological processes produced by suitable microorganisms, such as transgenic Expression hosts of the genera Bacillus or filamentous fungi.

Purification of the concerned Enzymes are conveniently made by themselves established processes, for example via precipitation, sedimentation, concentration, Filtration of the liquid Phases, microfiltration, ultrafiltration, exposure to chemicals, Deodorization or suitable combinations of these steps.

Agents according to the invention can Enzymes are added in any form established according to the prior art become. This includes for example by granulation, extrusion or lyophilization obtained solid preparations or, especially with liquid or gel-shaped Means, solutions the enzymes, advantageously if possible concentrated, low in water and / or mixed with stabilizers.

Alternatively, the enzymes can be used for both the solid for as well the liquid Dosage form are encapsulated, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural polymer or in the form of capsules, for example those in which the enzymes as in enclosed in a solidified or in the core-shell type, in which an enzyme-containing core with a water, air and / or Chemical-impermeable Protective layer covered is. Additional active ingredients, for example stabilizers; Emulsifiers, pigments, bleaching or Dyes are applied. Such capsules are after known methods, for example by shaking or Roll granulation or applied in fluid-bed processes. Are advantageous granules of this type, for example by applying polymeric film formers, low dust and storage stable due to the coating.

It is also possible to have two or assemble several enzymes so that a single Granulate multiple enzyme activities having.

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

A group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, Borax, boric acids, boronic acids or their salts or esters, including primarily derivatives with aromatic groups, such as ortho, meta or para substituted phenylboronic, or their salts or esters. Furthermore, peptide aldehydes, this means Suitable oligopeptides with reduced C-terminus. As a peptide Protease inhibitors include ovomucoid and leupeptin mention; an additional Option is the formation of fusion proteins from proteases and peptide inhibitors.

Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and their mixtures, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End group-capped fatty acid amide alkoxylates can also be used as stabilizers.

Lower aliphatic alcohols but above all polyols, such as glycerol, ethylene glycol, Propylene glycol or sorbitol are other frequently used enzyme stabilizers. Furthermore protects also di-glycerol phosphate against denaturation by physical Influences. Calcium salts, such as calcium acetate, are also used or calcium formate and magnesium salts.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or, such as cellulose ethers, acrylic polymers and / or polyamides, stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polymers containing polyamine-N-oxide act simultaneously as enzyme stabilizers and as color transfer inhibitors. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkyl polyglycosides can also stabilize the enzymatic components of the agent according to the invention and even increase their performance. Crosslinked N-containing compounds fulfill a double function as soil release agents and as enzyme stabilizers.

Reducing agents and antioxidants such as sodium sulfate or reducing sugars increase the stability of the enzymes across from oxidative decay.

Combinations of are preferred Stabilizers used, for example from polyols, boric acid and / or Borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing Salt. The effect of peptide-aldehyde stabilizers can by the combination with boric acid and / or boric acid derivatives and polyols increased and according to the additional Use of divalent cations, such as calcium ions further strengthened become.

Is particularly preferred in the frame of the present invention the use of liquid enzyme formulations. Here are agents according to the invention preferred that in addition Enzymes and / or enzyme preparations, preferably solid and / or liquid Protease preparations and / or amylase preparations, in amounts of 1 to 5% by weight, preferably from 1.5 to 4.5 and in particular from 2 to 4% by weight, in each case based on the entire average.

To decay the optional into the agents according to the invention included To facilitate solids such as tablets or granules, can these compressed disintegration aids, so-called tablet disintegrants, contain. Under tablet disintegrants or disintegrators according to Römpp (9. Edition, Vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184) Excipients understood for the rapid disintegration of tablets in water or gastric juice and for the release of the pharmaceuticals in a resorbable form.

These substances, also because of their Effect called "explosive" medium increase with water ingress their volume, on the one hand increasing their own volume (swelling), on the other hand also about the Release of gases creates a pressure on the tablet can disintegrate into smaller particles. 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 substances such as cellulose and starch and their derivatives, alginates or casein derivatives. All of the above Disintegration aids can be used according to the invention.

As a preferred disintegration aid become disintegration aids within the scope of the present invention based on cellulose, preferably in granular, co-granulated or compact form, used.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, viewed formally, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which are obtained from cellulose by polymer-analogous reactions are available. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

The cellulose derivatives mentioned are preferably not alone as a cellulose-based disintegrant used, but used in a mixture with cellulose. The salary these mixtures of cellulose derivatives are preferably below 50 % By weight, particularly preferably below 20% by weight, based on the Disintegrant based on cellulose. Is particularly preferred pure cellulose is used as disintegrant based on cellulose, which is free of cellulose derivatives. As another disintegrant Cellulose based or as a component of this component can be microcrystalline Cellulose can be used. This microcrystalline cellulose will by partial hydrolysis of celluloses under such conditions receive only the amorphous areas (approx. 30% of the total cellulose mass) the celluloses attack and completely dissolve the crystalline areas (approx. 70%) but leave it undamaged. A subsequent disaggregation of the microfine celluloses produced by hydrolysis the microcrystalline celluloses, which have primary particle sizes of approx. 5 μm and compactable, for example, into granules with an average particle size of 200 μm are.

In addition to or instead of disintegration aids cellulose-based the agents according to the invention a gas-releasing system from organic acids and carbonates / bicarbonates contain.

The solid mono-, oligo- and polycarboxylic acids, for example, can be used as organic acids which release carbon dioxide from the carbonates / bicarbonates in aqueous solution. 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. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).

The acids mentioned do not have to be stoichiometric to the carbonates or hydrogen carbonates contained in the compressed products be used.

One within the scope of the present invention preferred detergent and cleaning agent compressed additionally contains Effervescent system.

The gas-developing shower system consists in the agents according to the invention in addition to the above-mentioned organic acids from carbonates and / or Bicarbonates. The representatives of this substance class are from cost reasons the alkali metal salts are clearly preferred. For the alkali metal carbonates The hydrogen and sodium carbonates are the sodium and potassium salts for cost reasons across from clearly preferred to the other salts. Of course you don't have to the relevant pure alkali metal carbonates or bicarbonates be used; rather can Mixtures of different carbonates and hydrogen carbonates are preferred his.

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

To determine the pH of solutions of the water-soluble according to the invention container 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 reasons or for reasons of consumer protection. Usually exceeds the amount of these adjusting agents is not 1% by weight of the total formulation.

In the context of the present invention, individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexyl benzylatepylpionate, allyl cyclohexyl propyl pionate. The ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, ∝-isomethylionone and methyl cedryl ketone , the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures such as those obtained from plant sources are available, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The general description of the usable perfumes (see above) generally represents the different classes of substances of fragrances. In order to be perceptible, a fragrance must be volatile, being in addition to the nature of the functional groups and the structure the molecular weight also plays an important role in the chemical compound plays. Most fragrance substances have molecular weights of up to around 200 Dalton while Molar masses of 300 daltons and above rather an exception. Because of the different volatility changed by fragrances the smell of one composed of several fragrances perfumes or fragrance during of evaporation, whereby the odor impressions in "top note" (top note), "heart or middle note" (middle note or body) and "base note" (end note or dry out) divided. Because the smell perception to a large extent also on the gen intensity is based, the top note of a perfume or fragrance is not alone from volatile Connections while the base note for the most part from less volatile, i.e. non-stick fragrances. When composing perfumes can be easier volatile Fragrances are bound to certain fixatives, for example, which prevents it from evaporating too quickly. The following Classification of the fragrances in "lighter is volatile "or" adhesive "fragrances so about the smell impression and above, whether the corresponding fragrance is perceived as a top or heart note nothing is said.

By a suitable selection of the mentioned fragrances or perfume oils can both the smell of the water-soluble containers according to the invention or those enclosed in them Solids (product scent) and, after the cleaning and care process, in addition for example the scent of laundry affected become. Due to their design, especially due to the in the outer wall openings, are water-soluble containers according to the invention in Compared to complete sealed containers particularly suitable even when using smaller amounts of fragrance to ensure a distinctive product fragrance, with this Purpose, especially volatile fragrances, while to achieve a sufficient laundry fragrance, the use of more adhesive Fragrance is advantageous. Adhesive fragrances in the frame of the present invention can be used, for example the essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, bergamot oil, champaca flower oil, noble fir oil, noble pine cone oil, elemi oil, eucalyptus oil, fennel oil, spruce pine oil, galbanum oil, geranium oil, ginger grass oil, guajun oil oil, guajun oil oil, guajun oil oil, guajun oil oil, guajun oil oil, guajun oil oil, guajun oil oil, guajak oil oil, guajak oil oil, guajak oil oil, guajak oil oil, guajak oil oil, guajak oil oil, guajak oil oil, guajun oil oil, guajak oil oil, guajak oil oil, guajak oil oil, guajun oil oil, guajun oil oil, guajun oil oil, guajak oil oil, guajak oil oil, guajun oil oil, guajun oil oil, guajun oil oil, guajun oil oil, guajak oil since oil Kajeput oil, calamus oil, chamomile oil, camphor oil, Kanaga oil, cardamom oil, cassia oil, pine needle oil, copaiva balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, mandarin oil, lemon balm oil, musk oil, ner oil oil, nut oil oil, nut oil oil, nut oil oil, ner oil oil, nut oil oil, nut oil oil, ner oil oil, nut oil oil, oil oil oil Origanum oil, palmarosa oil, patchouli oil, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, allspice oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery oil, spik oil, star anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper oil, juniper oil, juniper oil, juniper oil Ylang oil, hyssop oil, cinnamon oil, Cinnamon leaf oil, lemon oil, lemon oil as well Cypress oil. But also the higher boiling ones or solid fragrances natural or synthetic origin in the context of the present invention as adhesive fragrances or Fragrance mixtures, i.e. fragrances, are used. To this Count connections the following compounds and mixtures of these: Ambrettolide, α-amyl cinnamaldehyde, Anethole, anisaldehyde, anis alcohol, anisole, anthranilic acid methyl ester, Acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, Benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerianate, Borneol, bornyl acetate, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, Eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, Geranyl acetate, geranyl formate, heliotropin, heptincarboxylic acid methyl ester, Heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, Indole, iron, isoeugenol, isoeugenol methyl ether, isosafrol, jasmon, Camphor, karvakrol, karvon, p-cresol methyl ether, Coumarin, p-methoxyacetophenone, methyl-n-amylketone, methylanthranilic acid methyl ester, p-methylacetophenone, methylchavicol, p-methylquinoline, methyl-β-naphthyl ketone, Methyl-n-nonylacetaldehyde, methyl-n-nonyl ketone, muscon, β-naphthol ethyl ether, β-naphthol methyl ether, Nerol, nitrobenzene, n-nonylaldehyde, nony alcohol, n-octylaldehyde, p-oxy-acetophenone, Pentadecanolide, β-phenylethyl alcohol, Phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegon, safrole, salicylic acid isoamyl ester, methyl salicylate, Salicylsäurehexylester, Salicylsäurecyclohexylester, Santalol, Skatol, Terpineol, Thymen, Thymol, γ-undelactone, Vanilin, Veratrumaldehyde, Cinnamaldehyde, cimate alcohol, cinnamic acid, cinnamate, Zimtsäurebenzylester. To the more volatile fragrances counting especially the low-boiling fragrances natural or synthetic origin, used alone or in mixtures can be. examples for more volatile Fragrance substances are alkyisothiocyanates (alkyl mustards), butanedione, limonene, linalool, Linate acetate and propionate, menthol, menthone, methyl-n-heptenone, Phellandrene, phenylacetaldehyde, terpinylacetate, citral, citronellal.

In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art prepared, have a high storage stability and insensitivity to the other ingredients of the agent and to light. If the containers according to the invention contain detergents and cleaning agents for textile cleaning, the dyes used should furthermore have no pronounced substantivity towards textile fibers in order not to stain them.

As a hydrotrope or solubilizer are substances that are present in others because of their presence a certain solvent practically insoluble Compounds in this solvent soluble or make emulsifiable (solubilization). There are solution mediators with the slightly soluble Substance is a molecular compound and those that work through micell formation. One can also say that only solution brokers a so-called latent solvent lend its solvency. With water as (latent) solvent one speaks instead of solution brokers mostly from hydrotropes, in certain cases better from emulsifiers.

Foam inhibitors which can be used in the agents according to the invention include soaps, oils, fats, paraffins or silicone oils, which can optionally be applied to carrier materials. Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the aforementioned materials. Agents preferred in the context of the present application contain paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are structured according to the scheme (R ₂ SiO) x and are also referred to as silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids with a molecular weight between 1000-150,000, and viscosities between 10 u. 1,000,000 mPas.

Suitable anti-redeposition agents, which 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 wt .-% and of hydroxypropyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether and the polymers of phthalic acid and / or known from the prior art terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.

Optical brighteners (so-called "white tones") can agents 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 in visible long-wave 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'-distyryl-biphenylene, Methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid, Benzoxazole, Benzisoxazole and Benzimidazole systems and the pyrene derivatives substituted by heterocycles.

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 the water-soluble salts of polymeric carboric acids, glue, Gelatin, salts of ether sulfonic acids of 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 etc. Polyvinyl pyrrolidone is also useful. As graying inhibitors cellulose ethers such as carboxymethyl cellulose (sodium salt) can also be used, Methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures.

Because textile fabrics, especially from Rayon, rayon, cotton and their blends, for wrinkling can, because the individual fibers prevent bending, kinking. Pressing and squeezing The agents according to the invention can be sensitive across the grain contain synthetic anti-crease agents. These include, for example synthetic products based on fatty acids, fatty acid esters. 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. One in particular textile finishing Suitable care and substance is the cottonseed oil, which for example by pressing out the brown, cleaned cotton seeds and refining with about 10% sodium hydroxide or by extraction made with hexane at 60-70 ° C can be. Such cotton oils contain 40 to 55 wt .-% linoleic acid, 16 to 26 wt .-% oleic acid and 20 to 26% by weight palmitic acid. More on fiber smoothing and fiber care particularly preferred agents are the glycerides, in particular the monoglycerides of fatty acids such as glycerol monooleate or glycerol monostearate.

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

To unwanted, due to exposure to oxygen and other oxidative processes caused changes in the washing and To prevent cleaning agents and / or the treated textiles, can the agents according to the invention Contain antioxidants. This connection class includes, for example substituted phenols, hydroquinones, pyrocatechols and aromatic Amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

An increased wearing comfort can the additional Use of antistatic agents 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 active on the Giens area 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 also as antistatic for Textiles or as an additive to detergents, with an additional Finishing effect is achieved.

Phobia and impregnation processes are used to finish Textiles with substances that prevent the deposition of dirt or make it easier to wash out.

Preferred waterproofing and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum u. Zirconium salts, organic silicates, Silicones, polyacrylic acid esters with perfluorinated alcohol component or with perfluorinated acyl or sulfonyl radical-coupled, polymerizable compounds. Also Antistatic agents can be included. The dirt-repellent finish with phobing and impregnating agents is often classified as an easy-care kit. The intrusion the impregnating agent in the form of solutions or emulsions of the active substances concerned can be added by adding Wetting agents that reduce the surface tension are facilitated. On Another area of application of phobing and impregnating agents is water-repellent equipment of textile goods, tents, tarpaulins, leather etc., in contrast to that the tissue pores are not closed to make them waterproof, the fabric therefore remains breathable (hydrophobic). The one for waterproofing coat the water repellant used Textiles, leather, paper, wood etc. with a very thin layer hydrophobic groups, such as longer ones Alkyl chains or siloxane groups. Suitable water repellents are z. B. paraffins, waxes, metal soaps, etc. with additives Aluminum or zirconium salts, quaternary ammonium compounds with long chain alkyl residues, urea derivatives, fatty acid modified Melamine resins, chromium complex salts, silicones, organic tin compounds and glutardialdehyde and perfluorinated compounds. The hydrophobized Feel materials does not look greasy; still pearls - similar to greased water droplets them off without wetting. So z. B. silicone-impregnated Textiles a soft touch u. are water u. stain-resistant; Stains from ink, wine, fruit juices and the like are easier to remove.

The non-aqueous solvents contained in the agents according to the invention can be used counting especially the organic solvents, Only the most important of which can be listed here: alcohols (methanol, ethanol, Propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, Diethylene glycol), ether u. Glycol ether (diethyl ether, dibutyl ether, Anisole, dioxane, tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ether), Ketones (acetone, butanone, cyclohexanone), esters (acetic acid esters, Glycol esters), amides and the like. a. Nitrogen compounds (dimethylformamide, Pyridine, N-methylpyrrolidone, Acetonitrile), sulfur compounds (carbon disulfide, dimethyl sulfoxide, Sulfolan), nitro compounds (nitrobenzene), halogenated hydrocarbons (Dichloromethane, chloroform, carbon tetrachloride, tri, carbon tetrachloride, 1,2-dichloroethane, chlorofluorocarbons), hydrocarbons (gasolines, Petroleum ether, cyclohexane, methylcyclohexane, decalin, terpene solvent, Benzene, toluene, xylenes). Alternatively, instead of the pure solvent also their mixtures, which, for example, have different solution properties solvent advantageously combine, be used. Such and in Particularly preferred solvent mixture within the scope of the present application is, for example, white spirit, suitable for chemical cleaning Mixture of different hydrocarbons, preferably with one C12 to C14 hydrocarbon content above 60% by weight, particularly preferably above 80% by weight and in particular above 90% by weight, each based on the total weight of the mixture, preferably with a boiling range of 81 to 110 ° C.

To care for the textiles and to improve the textile properties such as a softer "handle" (finish) and reduced electrostatic charging (increased wearing comfort), the agents according to the invention can contain fabric softeners. The active ingredients in fabric softener formulations are "esterquats", quaternary ammonium compounds with two hydrophobic residues, such as, for example, disteraryldimethylammonium chloride, which, however, due to its insufficient biodegradability, is increasingly being replaced by quaternary ammonium compounds, which have ester groups as predetermined breaking points in their hydrophobic residues contain the biodegradation. Such "esterquats" with improved biodegradability can be obtained, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products with alkylating agents in a manner known per se. Dimethylolethylene urea is also suitable as a finish.

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. Other preferred silicones are the polyalkylene oxide modified polysiloxanes, i.e. polysiloxanes, which have, for example, polyethylene glycols and the polyalkylene oxide-modified Dimethylpolysiloxanes.

Protein hydrolyzates are on the ground their fiber care effect further within the scope of the present Invention preferred active substances in the field of washing and Cleaning supplies. Protein hydrolyzates are product mixtures that are created by acidic, basic or enzymatically catalyzed breakdown of proteins (proteins) become. According to the invention, protein hydrolyzates both vegetable and animal origin can be used. Animal protein hydrolyzates are, for example, elastin, collagen, Keratin, silk and milk protein protein hydrolyzates, too may be in the form of salts. Preferred according to the invention is the use of protein hydrolyzates of plant origin, z. B. soy, almond, rice, pea, potato and wheat protein hydrolyzates. Although the use of the protein hydrolyzates as such is preferred where appropriate, amino acid mixtures obtained otherwise or single amino acids such as arginine, lysine, histidine or pyrroglutamic acid become. Also possible is the use of derivatives of protein hydrolyzates, for example in the form of their fatty acid condensation products.

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 the 2- and / or 4-position. Furthermore, too substituted benzotriazoles, in the 3-position phenyl substituted acrylates (Cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes as well as natural substances such as umbelliferone and the body's own urocanic suitable.

Detergents for automatic dishwashing may contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents and glass corrosion inhibitors in particular being particularly important in the field of automatic dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate, as well as the manganese complexes
[Me-TACN) Mn ^IV (m-0) ₃ Mn ^IV (Me-TACN)] ²⁺ (PF ₆ ^- ) ₂ ,
[Me-McTACN) Mn ^IV (m-0) ₃ Mn ^IV (Me-McTACN)] ²⁺ (PF ₆ ^- ) ₂ ,
[Me-TACN) Mn ^III (m-0) (m-OAc) ₂ Mn ^III (Me-TACN)] ²⁺ (PF ₆ ^- ) ₂ and
[Me-McTACN) Mn ^III (m-0) (m-OAc) ₂ Mn ^III (Me-McTACN)] ²⁺ (PF ₆ ^- ) ₂ , where Me-TACN is 1,4,7-trimethyl-1, 4,7-triazacyclononane and Me-McTACN stands for 1,2,4,7-tetramethyl-1,4,7-triazacyclononane. Zinc compounds can also be used to prevent corrosion on the wash ware.

Within the scope of the present invention it is preferred, in addition at least one silver protection agent selected from the group of triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the Alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole, in amounts from 0.001 to 1% by weight, preferably from 0.01 to 0.5 % By weight and in particular from 0.05 to 0.25% by weight, in each case based the total weight of the solids enclosed in the water-soluble containers according to the invention, use.

In addition to the aforementioned silver protection agents can agents according to the invention one or more substances to reduce glass corrosion contain. Within the scope of the present application, in particular additions of zinc and / or inorganic and / or organic zinc salts and / or silicates, for example the layered crystalline sodium disilicate SKS 6 from Clariant GmbH, and / or water-soluble glasses, for example glasses, which a mass loss of at least 0.5 mg below that in DIN ISO 719 specified conditions to reduce glass corrosion prefers. Particularly preferred agents contain at least one Zinc salt of an organic acid, preferably selected from from the group zinc oleate, zinc stearate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate.

Claims (27)

A method of making a container comprising the steps: a) Shaping processing of a first wrapping material with the formation of a body open at the top Height h, comprising an opening on the top of the basic body forming brim, as well as at least two, by at least one web the height h - x separate reception chambers; b) sealing the receiving chamber (s) with a second wrapping material, the sealing seam at least partially in one plane of the Height h - x; c) fill of the remaining container volume. A method according to claim 1, characterized in that the shaping processing of the first wrapping material by injection molding or by Thermoforming takes place. Method according to one of claims 1 or 2, characterized in that that the Web has no contact point with the side walls of the container. Method according to one of claims 1 to 3, characterized in that that the Bridge at least one contact point with the side walls of the container having. Method according to one of claims 1 to 4, characterized in that that the Bridge at least one, preferably two, three, four, five or has more corner (s). Method according to one of claims 1 to 5, characterized in that that the Bridge at least one, preferably two, three, four, five or has more bifurcations. Method according to one of claims 1 to 6, characterized in that that the Bridge at least one, preferably two, three, four, five or more curvatures) having. Method according to one of claims 1 to 7, characterized in that that the Bridge width between 0.5 and 15 mm, preferably between 0.6 and 12 mm, particularly preferably between 0.7 and 10 mm, very particularly preferably between 0.8 and 8 mm and in particular between 1.0 and Has 5.0 mm. Method according to one of claims 1 to 8, characterized in that that at least one of the wrapping materials used water soluble or is water dispersible. Method according to one of claims 1 to 11, characterized in that one of the wrapping materials used is transparent or translucent. Method according to one of claims 1 to 12, characterized in that one of the wrapping materials used from a water soluble or water-dispersible polymer. container the height h from a first wrapping material, comprising at least three receiving chambers as well as a circumferential h a brim forming a first sealing plane, characterized in that that the container at least one seal from a second wrapping material along a sealing seam has, which is not in the formed by the peripheral brim Seal level runs. container according to claim 13, characterized in that the sealing seam, which not runs in the sealing plane formed by the circumferential brim, at least partly along a web located in the container Height h - x runs. Container according to one of claims 12 or 13, characterized in that the web has no contact point with the side walls of the container. container according to one of the claims 12 to 14, characterized in that the web has at least one contact point with the side walls of the container having. container according to one of the claims 12 to 15, characterized in that the web has at least one, preferably two, three, four, five or more corners. container according to one of the claims 12 to 16, characterized in that the web has at least one, preferably two, three, four, five or has more bifurcations. container according to one of the claims 12 to 17, characterized in that the web has at least one, preferably two, three, four, five or more curvatures) having. container according to one of the claims 12 to 18, characterized in that the web has a width between 0.5 and 15 mm, preferably between 0.6 and 12 mm, particularly preferred between 0.7 and 10 mm, very particularly preferably between 0.8 and 8 mm and in particular between 1.0 and 5.0 mm. container according to one of the claims 12 to 19, characterized in that at least one of the envelope materials water soluble or is water dispersible. container according to one of the claims 12 to 20, characterized in that at least one of the envelope materials is transparent or translucent. container according to one of the claims 12 to 21, characterized in that at least one of the envelope materials a water soluble or water-dispersible polymer. container according to one of the claims 12 to 22, characterized in that the casing materials made of water-soluble or water-dispersible material and different dissolution rates exhibit. Means comprising a container according to any one of claims 12 to 23 and at least one active substance. Agent according to claim 24, characterized in that it an active ingredient from the group of agricultural chemicals, cosmetics or detergents and cleaning agents. Agent according to one of claims 25 or 25, characterized in that that at least two receiving chambers contain different active substances. Agent according to one of claims 24 to 26, characterized in that that at least a receiving chamber a liquid Contains active substance.