DE10310932A1 - Portioned detergent or cleaning agent - Google Patents

Abstract

Deep-drawing processes using deep-drawing dies with lowerable sections, preferably lowerable punches and / or lowerable webs, are suitable for the production of volume-optimized containers. The resulting filled containers are characterized by a low proportion of packaging.

Description

The present invention resides the field of portion packaging for active substances or combinations of active substances. In particular, this invention relates to divided or compartmentalized Packaging, that is Packaging with several receiving chambers, for common dosing more incompatible with each other Active substances or combinations of active substances as well as processes for the production of this packaging. A preferred application of the claimed Means and processes are in the field of washing or cleaning agents, like for example for used for cleaning textiles, dishes or hard surfaces become.

The portioned packaging of active ingredients or drug combinations plays in many areas of applied Chemistry, for example in pharmacy, but crop protection 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 93/08095 A1 (Rhone-Poulenc) discloses a bag of water soluble or water-dispersible material, which has two receiving chambers has and for example for packaging toxic substances suitable is. The bags can be produced by the thermoforming process.

WO 02/42401 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.

Subject of WO 02/85738 A1 (Reckitt Benckisers) are water soluble container with at least two receiving troughs. These containers are manufactured by gradually sealing individual foils or prefabricated ones Individual compartments to the final container.

WO 02/85736 A1 (Reckitt Benckiser) describes water soluble container with at least two receiving chambers. The receiving chambers can by Injection molding or Thermoforming are made, and are designed so that the closed chambers by folding in a mirror image arrangement fold up.

The products of the state of the art described packaging method, in particular the disclosed injection molding are characterized by a high proportion of packaging materials out. In general, the proportion of packaging materials in thermoformed or injection molded packaging due to the used for the partitions Materials with the number of each contained in this packaging separate reception chambers. Because especially from the stand the deep-drawing process known in the art, the separation of the receiving chambers is achieved through the use of webs or stamps a film to be deformed is drawn, the result Products usually have a "loss volume" that corresponds to the volume corresponds to this web or stamp and the space between forms the separate receiving chambers. Such "loss volumes" reduce the stability of the packaged Final product.

The object of the present invention was to avoid the disadvantages described above. In particular, the packaging proportion per dosing unit should be one Multi-chamber container reduced and the containers received despite reduced Material use mechanically stable. Farther the loss volume of these containers should be reduced.

The present application discloses now a process for packaging active ingredients or combinations of active ingredients, which face each other the methods disclosed in the prior art by a reduced Consumption of packaging materials, optimized use of space the packaging body and an increased Stiffness and transport or Shelf life of the resulting container distinguished.

It has now been found that the solve the aforementioned tasks leave if a thermoforming process for packaging active ingredients is used, in which a part of the the mold containing the deep-drawing troughs is lowered.

• a) Tiefziehen eines ersten Hüllmaterials in die Tiefziehmulde einer Matrize unter Ausbildung mindestens einer Aufnahmekammer;
• b) Absenken eines Teils der Matrize und erneutes Tiefziehen unter Vergrößerung mindestens einer der in Schritt a) gebildeten Aufnahmekammer und/oder unter Bildung mindestens einer weiteren Aufnahmekammer.

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

• a) deep-drawing a first wrapping material into the deep-drawing trough of a die, forming at least one receiving chamber;
• b) lowering a part of the die and deep drawing again, enlarging at least one of the receiving chambers formed in step a) and / or forming at least one further receiving chamber.

The containers produced by the method according to the invention can be used both after the first deep-drawing step and after the second deep-drawing step, which in connection with the lowering of a part of the Die is filled, the filling of the receiving chamber after the first deep-drawing step, in particular for the production of multiphase fillings or compartmentalized containers (containers with separate receiving chambers) has proven to be particularly advantageous.

A preferred method according to the invention is therefore characterized in that at least one of the receiving chambers before and / or after lowering a part of the die is filled.

• a) Tiefziehen eines ersten Hüllmaterials in die Tiefziehmulde einer Matrize unter Ausbildung mindestens einer Aufnahmekammer;
• b) Befüllen mindestens einer der in Schritt a) gebildeten Aufnahmekammern;
• c) Absenken eines Teils der Matrize und erneutes Tiefziehen unter Vergrößerung mindestens einer der in Schritt a) gebildeten Aufnahmekammer und/oder unter Bildung mindestens einer weiteren Aufnahmekammer;
• d) Befüllen mindestens einer der in Schritt c) vergrößerten oder gebildeten Aufnahmekammern.

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

• a) deep-drawing a first wrapping material into the deep-drawing trough of a die, forming at least one receiving chamber;
• b) filling at least one of the receiving chambers formed in step a);
• c) lowering a part of the die and deep drawing again while enlarging at least one of the receiving chamber formed in step a) and / or forming at least one further receiving chamber;
• d) filling at least one of the receiving chambers enlarged or formed in step c).

In another preferred according to the invention At least one of the filled or unfilled receiving chambers is used for the procedure before lowering part of the die with a second covering material sealed.

• a) Tiefziehen eines ersten Hüllmaterials in die Tiefziehmulde einer Matrize unter Ausbildung mindestens einer Aufnahmekammer;
• b) Befüllen mindestens einer der in Schritt a) gebildeten Aufnahmekammern;
• c) Versiegeln mindestens einer der in Schritt a) gebildeten Aufnahmekammern mit einem zweiten Hüllmaterial;
• d) Absenken eines Teils der Matrize und erneutes Tiefziehen unter Vergrößerung mindestens einer der in Schritt a) gebildeten Aufnahmekammer und/oder unter Bildung mindestens einer weiteren Aufnahmekammer;
• e) Befüllen mindestens einer der in Schritt d) vergrößerten oder gebildeten Aufnahmekammern.

Another preferred subject of the present application is therefore a method for producing a container with at least two receiving chambers, comprising the steps:

• a) deep-drawing a first wrapping material into the deep-drawing trough of a die, forming at least one receiving chamber;
• b) filling at least one of the receiving chambers formed in step a);
• c) sealing at least one of the receiving chambers formed in step a) with a second wrapping material;
• d) lowering a part of the die and deep drawing again while enlarging at least one of the receiving chambers formed in step a) and / or forming at least one further receiving chamber;
• e) Filling at least one of the receiving chambers enlarged or formed in step d).

As a "deep drawing" or "deep drawing process" are in the frame the present application process for processing Designated packaging materials, in which these after optional Pretreatment with heat and / or solvent are brought into shape by means of an appropriately shaped die. The packaging material can, for example, as a plate or Foil between the two parts of the tool, the positive and the Negative, inserted and deformed by compressing these parts the deformation can, however, also be carried out by using a negative tool a vacuum and / or compressed air and / or the dead weight of the Included active ingredients or combinations of active ingredients.

From the series of deep-drawing processes described those methods are preferred in which the first wrapping material in the form of a slide a recessed die provided and by Exposure to compressed air from the top of the film or through Effect of a vacuum from the bottom of the foils, particularly preferred with the simultaneous action of compressed air and vacuum in the Wells of the die introduced and according to the shape of the Depression is formed. Draw particularly advantageous methods is characterized in that the Foil before deformation by exposure to heat and / or solvents is pretreated. In a further preferred process variant is a film after optional pretreatment (solvent, heat) The action of a stamp and / or by the action of weight of the product shaping pressed into the recess of a die.

The action of heat and / or solvents on the wrapping material serves to facilitate plastic deformation. The warming of the shell material can be, for example, by heat radiation, hot air or, particularly preferred, by direct contact with a hot plate respectively. Alternatively, you can for warming of the wrapping material but also heated rolls or rollers can be used. The duration the heat treatment and the temperature of the heat radiation, hot air or Heating plate surface is naturally by the Type of wrapping material used dependent. For water soluble or water-dispersible materials such as PVA-containing polymers or copolymers is a temperature between 90 and 130 ° C, especially between 105 and 115 ° C prefers. The duration of the heat treatment, in particular the contact time when using a heating plate is preferred between 0.1 and 7 seconds, particularly preferably between 0.2 and 6 seconds and especially between 0.3 and 4 seconds. Contact hours less than a second, especially in the range of 400 to 900 Milliseconds, preferably between 500 and 800 milliseconds for Materials made of polyvinyl alcohol have proven to be particularly advantageous.

In order to achieve a contact between the wrapping material to be deformed and the heating plates, be there are different options. For example, the wrapping material can be guided between two mutually opposite plates, at least one of which serves as a heating plate, and brought into direct contact with the surfaces thereof by lowering and / or lifting one of these plates. Alternatively, the wrapping material can also be guided under or over a heated surface and a contact can subsequently be made by blowing the material onto the surface by means of compressed air.

Are heating plates used to heat the shell materials used, so the heating preferably film-shaped shell material evenly over the entire surface of the film or unevenly through a so-called target heating. In a preferred embodiment of the method according to the invention The heating takes place in a targeted manner by means of the heating plate located in the Hot spots are.

The ones in the heating plates hot spots are can be planar, concave or convex. Are the heating yards convex or concave, so is the ratio of the maximum diameter of the heating yard to its maximum height, preferably greater than 2, especially preferably greater than 4 and especially larger than 8.

Through the target heating described above there is no grid or mesh on the film to be processed heated and little elastic film material, which has an undesirable deformation and stretching the film material, for example by its own weight the film or the tensile forces acting during film transport, in Area between the heated film pieces avoids. The spatial Orientation of the receiving troughs to each other and the spatial Orientation of the troughs within the film are based on this Stabilized in this way, the receiving troughs are thus when transported on to Fill, Sealing and separating in the intended positions and one incorrect filling, Sealing or separation is avoided.

The creation of a Vacuum on the inside of the recesses of the die when deforming the film has the advantage that in the depression below of the deforming wrapping material Any air is removed and the deformed envelope material can be kept in the deformed state. Preferred continuous Thermoforming process, that is Procedure on a continuous die, in which the through Deformation generated receiving chambers until filling or sealing or even remain in the recesses of the die until they are cut out, are characterized in that the in the wells formed by a vacuum, which while of the shaping process and until the filling process is completed, preferably until the end of the Sealing, particularly preferably until the container is cut out the film grid stops, are kept in their deformed state. With discontinuous Process, that is Processes in which the film transport is interrupted periodically and the deformed shell material before filling removed from the wells of the matrices and into a filling station promoted it is preferred that the preformed containers in the filling station in or identical to the matrix recesses spatially similar Loading form are spent in which before and / or during and / or after filling, a vacuum is applied around the preformed receiving chambers in to keep their shape and, for example, shrinkage and / or To prevent wrinkles. The vacuum should be like this in everyone chosen be that the the shape of the receiving chambers formed from the flat foils kept the appropriate wrapping material not damaged by the action of the vacuum and spillage of the after filling in active substances (s) in the receiving chambers by shrinking back the receiving chamber is avoided. The exact value for the vacuum is among other things dependent on the type of wrapping material used or its wall thickness. Typically, however, a vacuum will range from 0.01 to 1 bar, preferably between 0.1 and 0.8 bar, particularly preferred between 0.2 and 0.6 bar.

The receiving chambers formed by deep drawing can have any technically feasible shape. Spherical-dome-shaped, cylindrical or cubic chambers are particularly preferred. Preferred receiving 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 preferred in alternative embodiments of the inventive method 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 one another. The base area of the receiving chambers can be convex, concave or planar, with planar base areas being preferred. The base area 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 in Preferred within the scope of the present application. In preferred embodiments of this application, the transition from the base area to the side wall (s) or the transition of the side walls into one another is designed in a rounded form. The receiving chambers therefore have no pointed or sharp outward, but rather rounded edges.

A preferred method according to the invention is therefore characterized in that the base areas of the Receiving chambers are planar.

The dimensions and volume of the receiving chambers formed by the shaping processing and interspaces will primarily be based on the later application of the resulting containers. In a preferred variant of the method according to the invention, the receiving chambers to a total volume between 0.1 and 1000 mL, preferably between 0.2 and 100 mL, particularly preferably between 0.4 and 50 mL, whole particularly preferably between 0.6 and 30 ml and in particular deep-drawn between 0.8 and 10 mL. It is within the scope of the method according to the invention in a preferred embodiment he wishes, that the at least two receiving chambers have the same spatial shape and an identical volume exhibit. In another preferred embodiment, the at least two in the container existing receiving chambers have different volumes, whereby The relationship 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 method according to the invention the container two receiving chambers of different volumes, the volume 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 reception chamber is. The volume of the individual chambers is preferably between 0.05 and 900 mL, particularly preferably between 0.1 and 90 mL, whole particularly preferably between 0.5 and 40 ml and in particular between 1.0 and 25 mL.

In a preferred embodiment of the method according to the invention point the container Receiving chambers with different depths. There is not necessarily a direct relationship with the depth of the chamber and the chamber volume. So in a container with two receiving chambers the receiving chamber with the smaller chamber depth definitely 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 method is preferred within the scope of the present application, in which the receiving chamber with the smaller chamber depth also a smaller one in comparison with the other receiving chamber (s) Has volume, with respect to the absolute volumes and the volume ratios reference is made to the above information.

According to a preferred method according to the invention manufactured containers have receiving chambers with vertically sloping side walls. However, containers in which at least one is particularly preferred Receiving chamber has an inclined side wall. In such reception rooms is the angle that is between the side wall and an imaginary one closing the receiving chamber Sealing therefore less than 90 °. Of course you can this angle for the different side walls of a single receiving chamber vary. Assigns the admission chamber only a single side wall on (cylinder-like receiving chambers) can with the appropriate shaping that used in deep drawing Thermoformed troughs even a single sidewall different Have angles. Preference is given to receiving chambers in which the said Angle 30 and 90 °, preferably between 35 and 89 °, particularly preferably between 40 and 88 ° and in particular between 45 and is 87 °.

The through the shaping processing generated receiving chambers can still have gradations. The corresponding, in a preferred Receiving chambers produced in a process variant accordingly have no flat side walls on, but rather have side walls, which by steps or curvatures Marked are. The number of curvatures can vary preferred methods are those in which the number of stages 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 side 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.

The generated by the deep drawing process Admission chamber (s) can with solids or liquids filled become. In step a) of the method according to the invention, more than one Chamber formed, so the filling of these two, three, four, five or more chambers take place at the same time or at different times. It is furthermore preferred at least one, preferably two, three, or four of the receiving chambers created in step a) before sealing not to be filled. The resulting packaging then excels when used in liquid, preferably aqueous Media by an increased Buoyancy off.

After filling, the filled receiving chambers can with another wrapping material be sealed. The sealing is preferably done by Exposure to pressure and / or heat and / or Solvent. The additional wrapping material used for sealing can be used with the in step a) of the method according to the invention used shell material may be identical, but may also differ in its composition or its thickness from this.

In a preferred embodiment of the method according to the invention becomes the surface of the wrapping material before sealing first by solvent dissolved (in the case of water soluble Foil is particularly suitable here water) and then by exposure sealed from pressure and / or heat. Suitable sealing temperatures for water-soluble wrapping materials are for example 120 to 200 ° C, preferably temperatures in the range of 130 to 170 ° C, in particular in the range of 140 to 150 ° C. The sealing pressure has been found to be in the range from 250 to 800 kPa, preferably 272 to 554 kPa, particularly preferably from 341 to 481 kPa proved to be advantageous. The sealing times are preferably at least 0.3 seconds, preferably between 0.4 and 4 seconds. Sealing temperatures, pressure and sealing times are used in addition to the shell material also determined by the sealing machine used. The seal seams show in a preferred method according to the invention a width between 0.5 and 7 mm, preferably between 1.0 and 6 mm and in particular between 1.5 and 5 mm. As sufficient Sealing seams with a width above are particularly durable 2 mm, preferably above 2.5 mm, particularly preferably above 3 mm and proven above 3.5 mm. Because the width of the Sealing seam depending on production can fluctuate even with a single packaging the aforementioned information about the width of the sealed seam to that measured for a single package minimal seam width. Sealing takes place especially then instead of when the contents liquid or is flowable. examples for such fillings are liquids, Gels or particulate Solids like powder.

By sealing the receiving chambers let yourself not just a contact of the filled Active substances or active substance mixtures with each other or with the surrounding the atmosphere (E.g. atmospheric oxygen, air humidity) or skin contact with the Avoid consumers, the sealing rather allows by choice suitable sealing materials also control the Release of those inside the sealed cavity Actives. An example for such control is the use of water-soluble or water-dispersible Sealing and / or wrapping materials with different solubilities with the aim of defining the content of individual reception chambers in a timed manner Order in the surrounding watery Release medium. Can be realized within the scope of the present Registration procedure in which it concerns the sealing of the enveloping materials used by the same or different materials. In a preferred one embodiment are the same wrapping materials for the Sealing of the receiving chambers used. This embodiment allows the simultaneous release of those located under the sealing surfaces Contents. In a further preferred embodiment differ from those used to seal the receiving chambers Materials.

Characteristic of the method according to the invention is that a Part of the die is lowered. Within the scope of the present application it is preferred to have one located in the deep-drawing recess of the die Web or stamp and / or at least the deep-drawing trough in step a) lower part of the die that partially surrounds it.

As a stamp are part of the present application such movable tools within the Thermoformed recess of the die denotes that no contact with the sidewalls the deep-drawing trough. The minimum distance of the stamp from the side walls the deep-drawing trough is sufficient to deep-draw the in Step a) used foils between the stamp and the side wall guarantee. This distance is preferably at least 3 mm, preferably at least 5 mm, particularly preferably between 8 and 120 mm, very particularly preferably between 10 and 90 mm and in particular between 12 and 70 mm.

As a web in the context of the present Registration of such moving tools within the deep-drawing trough the die designates having at least one contact area one of the side walls the deep-drawing trough, in which a deep-drawing of a film between the web and the side wall is not possible. The distance between Bridge and side wall in this contact area preferably less than 1000 μm, preferably less than 500 μm, particularly preferably less than 400 μm and in particular less than 300 μm.

In the context of the present inventions, in particular those methods are preferred in which the web or stamp is lowered to less than 95%, preferably less than 80%, particularly preferably to less than 65% and in particular less than 50% of its original height. The original height of the web or stamp is the height of the section of the web or stamp that protrudes from the bottom surface of the deep-drawing trough of the die and over which the first covering material was drawn in step a) of the method according to the invention. At the beginning of the process in step a), the tip of the web or stamp, or the upper parts of the web or stamp, can both protrude beyond the plane formed by the surface of the die, and also be in register with this plane, depending on each other but are also below this level. All three process variants are preferred in the context of the present application.

In a preferred embodiment of the method according to the invention the bridge or stamp in step d) to a height between 5 and 95%, preferably between 10 and 855, particularly preferably between 15 and 75% and especially between 20 and 65% of its original Lowered height.

The web or stamp preferably have a maximum width between 0.5 and 50 mm, preferably between 0.6 and 40 mm, particularly preferably between 0.7 and 30 mm and in particular between 0.8 and 20 mm.

Next to a bridge or a stamp can in the method according to the invention also one or more parts) of the die surrounding the deep-drawing trough are lowered, these preferably completely, for example, the deep-drawing trough surrounded in the form of a ring. Methods according to the invention are further preferred, in which the entire deep-drawing recess in the die, including one of these Deep-drawing trough surrounding part of the die is lowered.

By lowering part of the Matrix in the process according to the invention the volume of the deep-drawing trough is reduced by the volume of the Tool enlarged. This Volume increase is preferred in the invention Process between 0.5 and 40 ml, preferably between 0.7 and 25 ml, preferably between 0.8 and 20 ml, particularly preferably between 0.9 and 16 ml and in particular between 1.0 and 13 ml.

The ratio of the volume of the deep-drawing trough before lowering the tool to the volume of the deep-drawing trough lowering the tool preferably between 1:40 and 40: 1, preferably between 1:38 and 38: 1 and especially between 1:32 and 32: 1.

In a preferred embodiment of the method according to the invention becomes the container or at least one receiving chamber of the container after lowering the Tool with a third wrapping material sealed. This third wrapping material can be identical to the first and / or the second shell material or differ from these.

In a further preferred embodiment of the method according to the invention will the container or at least one receiving chamber of the container after lowering the Tool and filling at least one of the receiving chambers formed or enlarged by the lowering with a third wrapping material sealed. This third wrapping material can be identical to the first and / or the second shell material or differ from these.

Before, simultaneously with or after this the last sealing step is that in the method according to the invention manufactured container preferably by the action of knives or punches with training one around the top of the container isolated brim. The width of this brim is included among other parameters also from the choice of to manufacture the appropriate container the thermoforming process used. With these procedures can be distinguish two variants, all of which are used to carry out the inventive method are particularly preferred. These are procedures in which the shell material horizontally into a forming station and from there in a horizontal manner for filling and / or sealing and / or separating is performed, again in this case distinguish between continuous and discontinuous processes and methods in which the wrapping material has a continuously rotating Form roller guided becomes. During execution continuous process in which the deformed shell material after deep drawing to fill and / or sealing and / or separating remains in the deep-drawing trough tend to have smaller brim widths in the range of 1 to 4 mm realizable while in discontinuous processes the brim widths tend to be in the range from 2.5 to 5 mm.

In the method according to the invention are generally all envelope materials that can be processed by deep-drawing processes can be used, but the use of water-soluble or water-dispersible Packaging materials is preferred. Preferred methods according to the invention are therefore characterized in that at least one of the used shell materials water soluble or is water-dispersible, with one being particularly preferred embodiment of the method according to the invention at least two of the shell materials used, preferably the first and the second or the first and the third, in terms of their dissolution properties differ.

• 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 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 ☐-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 receiving chambers and for sealing them are listed below. The polymers mentioned can be used as a sealing material or shell 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) 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) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers / Methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b7) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers b8) copolymers from b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids b8iii) optionally further ionic or 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 vinylbenzene, acrylate, vinylbenzene, acrylate Salts d10) terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the ☐ 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 the dialkylaminoacrylate and methacrylate e6) vinylpyrrolidone-methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol e8) under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

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.

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

In a preferred process variant comprises the container 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 procedure 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 that consists in the method according to the invention first wrapping material used 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 ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88 and Mowiol ^® 8-88.

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), 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 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, with the glucose units linked α-glycosidically. Starch is made up of two components of different molecular weights: 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). It also contains small amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, intertwined chains with about 300 to 1,200 glucose molecules as a result of the binding in the 1,4-position, the chain in the amylopectin branches to an knot-like structure after an average of 25 glucose units through 1,6-binding with about 1,500 to 12,000 molecules of glucose. In addition to pure starch, starch derivatives which are obtainable by polymer-analogous reactions from starch are also suitable for producing water-soluble coatings for the detergent, dishwashing detergent and cleaning agent portions. Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches 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 at least one of the wrapping materials used is transparent or translucent.

For example, for deep drawing and / or sealing material used is preferably transparent. For the purposes of this invention, transparency is understood to mean 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.

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 ingredients before decomposition or deactivation by exposure to light protect. Antioxidants and UV absorbers have proven particularly suitable here and fluorescent dyes.

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 longer-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. In addition, substituted benzotriazoles, such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpro pyl-) monosodium salt (Ciba ^® Fast H), 3-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 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 a mixture of substances located in a receiving chamber, be included.

Another preferred one The class of stabilizers are the fluorescent dyes. Count among them the 4,4'-diamino-2,2'-stilbene disulfonic acids (flavonic acids), 4,4'-distyrylbiphenylene, Methyl umbelliferones, coumarins, 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 to the total weight of one in a receiving chamber Substance mixture, 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 wt .-% may be included.

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.

In a preferred method according to the invention consists of at least one of the shell material used (ien) from a water-soluble or water-dispersible polymer, preferably a polymer film.

Preferred process variants are characterized in that the step a) of the inventive method 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 foils used can be single or multi-layer foils (laminate foils). 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 resulting container has at least two receiving chambers, each with different Means filled become. The funds can themselves in their composition, as well as in composition and Differentiate physical state. 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 a firm, 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.

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.

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% of the average particle size of this Powder differ.

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 solid (s) 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 triglyceride (s) 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.

As fatty acids are used in the present Sign aliphatic saturated or unsaturated, carboxylic acids labeled with branched or unbranched carbon chain. For the Production of fatty acids there are a variety of manufacturing methods. While the lower fatty acids mostly based on oxidative processes based on alcohols and / or aldehydes as well as aliphatic or acyclic hydrocarbons, are the higher Homologues are mostly still easiest today by saponification naturally Fat accessible. Due to advances in the field of transgenic plants are now almost unlimited possibilities to vary the fatty acid spectrum given in the storage fats of oil plants. Preferred fatty acids have a melting point in the context of the present invention, the processing of these fats as a material or component a casting allowed. There are fatty acids proven to be particularly advantageous which have a melting point above Have 25 ° C. Preferred matrix materials and / or components are therefore capric acid and / or undecanoic and / or lauric acid and / or tridecanoic 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 arachidic acid and / or erucic acid and / or Elaeosterarinsäure. But also fatty acids with a melting point below 25 ° C can be part of the matrix for casting or other of the above solids are used.

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 advantageous if the containers produced in the invention tern enclosed solids, in particular the preferably enclosed casting, contain waxes as matrix material. Preferred waxes have a melting range that is between approximately 45 ° C. and approximately 75 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range. Waxes with such a melting range are on the one hand dimensionally stable at room temperature, but melt at temperatures of 30 ° C. to 90 ° C. which are typical for machine dishwashing and are therefore more readily water-dispersible 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 contains / contain one or more of those enclosed in the containers produced according to the invention Solids, but preferably one produced by melt solidification Cast body, predominantly Share of paraffin wax (parrafins) 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. Particularly suitable are paraffin wax contents (based on the total weight of the matrix materials) from about 60% by weight, about 70% by weight or about 80% by weight, with still higher Fractions of, for example, more than 90% by weight are particularly preferred are. In a special embodiment the invention consists of the entire material material of one or more of those produced in the invention container filled Paraffin wax solids.

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 the wax esters can be 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 7 ° C, particularly preferably from more than 60 ° C.

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.

Preferably, the paraffin wax content of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature (generally about 10 to about 30 ° C.) is 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 Acusol ^® -820 (methacrylic acid (stearyl alcohol-20-EO) 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 β-D-glucose, D-manose, D-glucuronic acid, Schönes GmbH) , Deuteron ^® -XN (nonionic 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 acid ester copolymer dispersion, 25% in water, Stockhausen ), SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo ^® -S (high molecular weight s polysaccharide, stabilized with formaldehyde, Shell) and Shellflo ^® -XA (xanthan biopolymer, stabilized with formaldehyde, Shell).

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 or spaces are suitable for the liquids and solids mentioned above. In the case of solids, a distinction is made between powders, granules, extrudates, compactates, Casting bodies 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 even for a long 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 spatial-geometric due to the production Form 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.

Behälter mit drei Aufnahmekammern

The following tables list the containers that can be produced using two or three filled receptacles according to the preferred methods of the invention. The receiving troughs filled with liquid, powder or granules preferably have a seal. In the case of the receiving troughs filled with compactates, extrudates, castings or dimensionally stable gels, the sealing is optional, but is preferred. Container with two receiving chambers

Container with three receiving chambers

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. At least one method according to the invention is particularly preferred Receiving chamber with a casting body (melt), at least one additional receiving chamber is filled with a solid.

Suitable as mentioned at the beginning the method according to the invention for portioning, packaging and dosing of active ingredients or Active substance mixtures. In preferred embodiments of the method according to the invention, it is the active substances in the filled substances or active ingredient mixtures from the fields of pharmaceuticals, cosmetics, Feed, crop protection or fertilizer, Adhesives, food and / or personal care products, preferably however from the field of washing and cleaning-active substances.

Preferred active substances or mixtures of active substances from the field of cosmetics are in particular hair setting agents, Hair styling and hair coloring agents. 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 method according to the invention is characterized in that it the filled in Agent (s) are detergents or cleaning agents. Particularly preferred are washing and cleaning active substances from the group 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, Color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Corrosion inhibitors, antistatic agents, phobing and impregnating agents, Swelling and anti-slip agents, non-aqueous solvents, fabric softeners, protein hydrolyzate as well as UV absorbers.

Bleaching agents and bleach activators can be included in the agents produced 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 peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxyaloacidoperoxycaproic acid (Pε) )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipinic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxydiperoxybiperyldoxybiperyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutanoic acid, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Are the manufactured according to the invention Detergents used as automatic dishwashing detergents, they can Bleach activators contain to when cleaning at temperatures of 60 ° C and including achieving 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. Suitable substances are the O- and / or N-acyl groups of the above Number of carbon atoms and / or optionally substituted benzoyl groups wear. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated Glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24 Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24 Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂CN, -CH₃, -CH₂CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂OH, -CH₂CH₂-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 represents} -H, -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, -CH₂CH₂CH₃, -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-CH₂CH₂)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 additionally can also 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, the cationic nitrile from the group of these substances 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 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 ones produced according to the invention Means, 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% by weight, 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, exhibit.

In addition to the ingredients mentioned Bleaching agents and bleach activators are builders other important ingredients of detergents. Preferred manufactured according to the invention Means 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. 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 Na ₂ O: SiO ₂ modulus of 1: 2 to 1: 3.3 can also be used, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which 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 the sharp X-ray reflections that are typical of crystalline substances, but at most one or more maxima of the scattered X-rays which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite 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 is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula n Na ₂ O · (1 - n) K ₂ O · Al ₂ O ₃ · (2–2.5) SiO ₂ · (3.5–5.5) H ₂ O can be described. 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, NaH ₂ PO 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 des 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 is 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, wherein for the purposes of this invention preferably the alkali carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate can be used.

If the agents produced according to the invention are used in automatic dishwashing, water-soluble builders are preferred, since they generally have less tendency to form insoluble residues on dishes and hard surfaces. Common builders are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and silicates. Trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of the disilicate and / or metasilicate are preferably used for the production of tablets for machine dishwashing. Beson a builder system containing a mixture of tripolyphosphate and sodium carbonate is preferred. A builder system which contains a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.

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 these are citric acid, adipic acid, Succinic acid, Glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), unless such use for ecological reasons is 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 detergents produced according to the invention which, as so-called “3 in 1” products, combine the conventional detergents, rinse aids and a salt replacement function. -% 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.

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 stands for 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 = H), 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 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 ) -.

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-hydroxypropanesulfonic 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 shape l 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(R³)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 ³ ) 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 stands for an optionally available 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) if appropriate, further ionic or nonionic monomers are 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 (IIc), 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 (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 )
• 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 produced 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 copolymerization of acrylic acid with a sulfonic acid group-containing acrylic acid derivative. 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 ) - 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 contain 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 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 ) - 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 ) - stands, 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), 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 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 groups 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 machine Dishwashing detergents are characterized in that the copolymers have molar masses of 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).

Preferred manufactured according to the invention Agents which are used as automatic dishwashing agents, can to improve the rinse aid result as dispersed substances also amphoteric or cationic polymers contain. These particularly preferred polymers are characterized in that that she have at least one positive charge. Such polymers are preferably water soluble or water dispersible, that is, they exhibit in water 25 ° C one solubility above 10 mg / ml.

Cationic or amphoteric polymers particularly preferably contain at least one ethylenically unsaturated monomer unit of the general formula R ¹ (R ² ) C = C (R ³ ) R ⁴ in which R ¹ to R ⁴ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above, a heteroatomic group with at least one positively ended group, a quaternized nitrogen atom or at least one amine group with a positive charge in the pH range between 2 and 11 or for -COOH or -COOR ⁵ , where R ^{5 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Examples of the aforementioned (non-polymerized) monomer units are diallylamine, methyldiallylamine, dimethyldimethylammonium salts, aceylamidopropyl (trimethyl) ammonium salts (R ¹ , R ² , and R ³ , = H, R ⁴ = C (O) NH (CH ₂ ) ₂ N ⁺ ( CH ₃ ) ₃ X ^☐ ), methacrylamidopropyl (trimethyl) ammonium ^salts (R ¹ and R ² = H, R ³ = CH ₃ H, R ⁴ = C (O) NH (CH ₂ ) ₂ N ⁺ (CH ₃ ) ₃ X ^☐ ).

Unsaturated carboxylic acids of the general formula are particularly preferred as a constituent of the amphoteric polymers R ¹ (R ² ) C = C (R ³ ) COOH used, 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.

Particularly preferred amphoteric polymers contain, as monomer units, derivatives of diallylamine, in particular Dimethyldiallylammonium salt and / or methacrylamidopropyl (trimethyl) ammonium salt, preferably in the form of chloride, bromide, iodide, hydroxide, phosphate, sulfate, Hydrosulfate, ethyl sulffasts, methyl sulfate, mesylate, tosylate, Formates or acetates in combination with monomer units from the group the ethylenically unsaturated Carboxylic acids.

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 an autoclave 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, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% _C14, 10 wt .-% C _16, 2 wt .-% _C18, 8 wt .-% _{C18 ',} 1 wt .-% C _18''), palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt _12% C, 15 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 15 wt .-% _{C18 ',} 1 wt .-% C _18''), tallow ( approx. 3 wt% C ₁₄ , 26 wt% C ₁₆ , 2 wt% C _{16 '} , 2 wt% C ₁₇ , 17 wt% C ₁₈ , 44 wt% C _{18 '} , 3 wt% C _18'' , 1 wt% C _18''' ), hardened tallow fatty acid (approx. 2 wt% C ₁₄ , 28 wt% C ₁₆ , 2 wt% C ₁₇ , 63% by weight C ₁₈ , 1% by weight C _{18 '} ), technical oleic acid (approx. 1% by weight C ₁₂ , 3% by weight C ₁₄ , 5% by weight C ₁₆ , 6 wt% C _{16 '} , 1 wt% C ₁₇ , 2 wt% C ₁₈ , 70 wt% C _18' , 10 wt% C _{18 '} , 0.5 wt% % C _{18 '''),} technical palmitic / stearic acid (about 1 wt .-% C _12, 2 wt .-% C ₁₄ 45 wt .-% C _16, 2 wt .-% C _17, 47 wt. % C ₁₈ , 1% by weight C _{18 '} ) and soybean oil fatty acid (approx. 2% by weight C ₁₄ , 15% by weight C ₁₆ , 5% by weight C ₁₈ , 25% by weight C _{18 '} , 45% by weight C _18'' , 7% by weight C _18''' ).

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 can also be used as anionic surfactants in acid form in the context of the present invention. Alkanesulfonic acids can contain the sulfonic acid group in a terminal bond (primary alkanesulfonic acids) or along the carbon chain (secondary alkanesulfonic acids), only the secondary alkanesulfonic acids being of commercial importance. These are made by sulfochlorination or sulfoxidation of linear hydrocarbons. In Reed sulfochlorination, n-paraffins are reacted with sulfur dioxide and chlorine under irradiation with UV light to give the corresponding sulfochlorides, which, when hydrolysed with alkalis, provide the alkanesulfonates directly, and when reacted with water, the alkanesulfonic acids. Since di- and polysulfochlorides as well as chlorinated hydrocarbons as Ne byproducts of the radical reaction can occur, the reaction is usually carried out only up to degrees of conversion of 30% and then stopped.

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 alkenesulfonic acids, which 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 from linear Olefins accessible are. This will be on an industrial scale Petroleum fractions with molecular sieves into the n-paraffins of the desired Purity separated and dehydrated to the n-olefins, with both α- and i-olefins result. The resulting olefins then become more acidic in the presence Catalysts reacted with benzene to the alkylbenzenes, the Choice of the Friedel-Crafts catalyst has an impact on the Isomer distribution of the resulting linear alkylbenzenes has: The use of aluminum trichloride is the content of the 2-phenyl isomers in a mixture with the 3, 4, 5 and other isomers at approx. 30% by weight, however, if hydrogen fluoride is used as a catalyst, reduce the 2-phenyl isomer content to approx. 20% by weight. The sulfonation The linear alkylbenzenes finally succeed on an industrial scale with oleum, sulfuric acid or gaseous Sulfur trioxide, the latter being by far the most important. For sulfonation special film or tube bundle reactors are used, which deliver as a product a 97 wt .-% alkylbenzenesulfonic acid (ABSS), which in Can be used in the context of the present invention as anionic surfactant acid is.

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 and which have a tetralin content of less than 5% by weight, based on the alkylbenzene sen. 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 Use advantage as active substance. The cationic surfactant can be in be delivered directly to the mixer in its delivery form, or in Form of a liquid to pasty Cationic surfactant preparation form are sprayed onto the solid carrier. Let such cationic surfactant preparation forms by mixing commercially available cationic surfactants with auxiliaries such as nonionic surfactants, polyethylene glycols or polyols. Lower alcohols such as ethanol and isopropanol can also be used the amount of such lower alcohols in the liquid cationic surfactant formulation for the reasons mentioned above should be below 10% by weight.

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 surfactant (s) 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 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of 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 mole of 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 XIII as nonionic 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 XIII 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. Regardless of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, compositions prepared 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 is up 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.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula (XIV) R ¹ O [CH ₂ CH (R ³ ) O] _x R ² (XIV) in which R ^{1 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{2 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which is preferably between 1 and 5 have hydroxyl groups and are preferably further functionalized with an ether group, R ^{3 is} 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 40.

In the case of particularly preferred nonionic surfactants of the above formula (XIV), R ^{3 is} H. In the resulting end-capped poly (oxyalkylated) nonionic surfactants of the formula (XV) R ¹ O [CH ₂ CH ₂ O] _x R ² (XV) those nonionic surfactants are particularly preferred in which R ^{1 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, R ^{2 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and x stands for values between 1 and 40.

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

The 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 1 Q 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 XVII,

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 1 Q 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 XVIII,

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-Anloxy-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. Should he Contain containers such agents according to the invention, 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 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of 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 mole of 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, the 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. Become used at room temperature highly viscous nonionic surfactants, it is preferred that these a viscosity above 20 Pas, preferably above 35 Pas and in particular above Have 40 Pas. Also nonionic surfactants, which are waxy at room temperature Have consistency are preferred.

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 Mol 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, of 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 formula have values of k = 1 and j = 1, so that the above formula can be used 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 produced 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 produced 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 (Karlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and no longer assigned to the subtilisins in the narrower sense the proteases TW3 and TW7 Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark, and subtilisins 147 and 309 are sold under the trade names Esperase ^® and Savinase ^® from Novozymes The protease from Bacillus lentus DSM 5483 is derived from the variants known as BLAP ^® .

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

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermophilus 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. stearothermophilus 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 produced 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 ^®, Bacillis 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. Other important commercial products, the preparations originally sold by Gist-Brocades M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OP ^® and lipase PL ^® to mention, also the product Lumafast ^® from Genencor.

Agents produced according to the invention can, in particular if you for the treatment of textiles are intended, contain cellulases, Depending on the 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 Melanocarpus, 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 produced 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 effect, washing or cleaning agents according to the invention can use oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain. Suitable commercial products are Denilite ^® 1 and 2 from Novozymes. Advantageously, organic, particularly preferably aromatic, are additionally preferably used interacting compounds are added to the enzymes in order to increase the activity of the oxidoreductases concerned (enhancers) or to ensure the flow of electrons in the case of very different redox potentials between the oxidizing enzymes and the soiling (mediators).

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 agents 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.

One in an agent according to the invention contained protein and / or enzyme can be particularly during the Storage against damage such as inactivation, denaturation or decay, for example through physical influences, Oxidation or proteolytic cleavage are protected. With microbial Obtaining the proteins and / or enzymes is an inhibition of Proteolysis is particularly preferred, especially if the agents Proteases included. Agents produced in accordance with the invention can contain stabilizers for this purpose; the provision of such Agent is a preferred embodiment of the present invention represents.

A group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, Borax, boric acids, boronic acids or their salts or esters are used, especially 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 sulfite or reducing sugars increase the stability of the enzymes across from oxidative decay.

Combinations of stabilizers are preferably used, for example made of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compound with reducing salts. The action of peptide-aldehyde stabilizers can be increased by the combination with boric acid and / or boric acid derivatives and polyols and can be further enhanced by the additional use of divalent cations, such as calcium ions.

Is particularly preferred in the frame of the present invention the use of liquid enzyme formulations. Here are manufactured according to the invention Preferred means that additionally Enzymes and / or enzyme preparations, preferably solid and / or liquid Protease preparations and / or amylase preparations, in quantities from 1 to 5% by weight, preferably from 1.5 to 4.5 and in particular from 2 to 4% by weight, based in each case on the total composition.

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 ₅ 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 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.

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.

As perfume oils or fragrances can in Individual fragrance compounds within the scope of the present invention, e.g. synthetic products of the ester, ether, aldehyde type, Ketones, alcohols and hydrocarbons can be used. fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Count among the ethers e.g. benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, among the Ketones e.g. the Jonone, ∝-isomethylionon and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly the terpenes like limes and pinene. However, mixtures are preferred different fragrances, which together make an appealing Generate fragrance. Such perfume oils can also natural Contain fragrance mixtures as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Likewise 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 smell 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.

The smell of the water-soluble containers according to the invention or the solids contained in them (product fragrance) and, after the cleaning and care process has ended, the laundry fragrance, for example, can also be influenced by a suitable selection of the fragrances or perfume oils mentioned. Due to their design, in particular due to the openings in the outer wall, water-soluble containers according to the invention are particularly suitable in comparison to completely closed containers to ensure an unmistakable product fragrance even when using smaller amounts of fragrance, whereby in particular also more volatile fragrances can be used, while To achieve a sufficient scent of laundry, the use of stronger odoriferous substances is advantageous. Adhesive odoriferous substances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, bergamot oil, champagne flower oil, noble fir oil, noble pine cone oil, elemi oil, eucalyptus oil, fennel oil, spruce oil. Galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil, iris oil, kajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine oil, krautem oil oil, cumin oil, coriander oil, coriander oil, coriander oil lime oil, mandarin oil, melissa oil, ambrette seed oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, orange oil, oregano, palmarosa oil, patchouli, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, pimento oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery oil, spike oil, Star anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, lemon oil, lemon oil and cypress oil. However, the higher-boiling or solid odorants of natural or synthetic origin can also be used in the context of the present invention as adherent odorants or odorant mixtures, that is to say fragrances. These compounds include the compounds mentioned below and mixtures of these: ambrettolide, α-amyl cinnamaldehyde, anethole, anisaldehyde, anise alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzyl benzate, boryl formate benzyl benzyl benzate, benzyl formate benzyl benzyl benzate, benzyl formate benzyl benzyl benzate, benzyl benzate benzyl benzyl benzate benzyl benzyl benzate benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzoate , Bornyl acetate, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchylacetate, geranyl acetate, geranyl formate, heliotropine, heptinocarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroquinone dimethyl ether, hydroquinone dimethyl ether, hydroquinone dimethyl ether, hydroquinone dimethyl ether , Isoeugenolmethylether, Isosafrol, Jasmon, Kampfer, Karvakrol, Karvon, p-Cresolmethylether, Coumarin, p-Methoxyacetophenon, Methyl-n-amylketone, Methylanthranilsäuremethylester, p-Methylacetophenone, Methylchavikol, p-Methylchinaphtholin, nyl-β-methyl -nonylacetaldehyde, methyl-n-nonyl ketone, muscon, β-N aphtholethyl ether, β-naphthol methyl ether, nerol, nitrobenzene, n-nonylaldehyde, nony alcohol, n-octylaldehyde, p-oxy-acetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde dimethyl acetal, phenyl acetic acid, salicylic acid, salicylic acid, salicylic acid, salicylic acid, salicylic acid, salicylic acid, salicylic acid, salicylic acid, salicylic acid, salicylic acid, salicylic acid, salicylic acid, Santalol, Skatol, Terpineol, Thymen, Thymol, γ-Undelacton, Vanilin, Veratrumaldehyde, Cinnamaldehyde, Cimate Alcohol, Cinnamic Acid, Ethyl Cinnamate, Benzyl Cinnamate. The more volatile fragrances include, in particular, the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more volatile fragrances are alkyisothiocyanates (alkyl mustards), butanedione, limonene, linalool, linaylacetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinylacetate, citral, citronellal.

To the aesthetic impression of the agent according to the invention can improve they are dyed with suitable dyes. Preferred dyes, the selection of which is of no difficulty for the person skilled in the art high storage stability and insensitivity to the rest Ingredients of the agents and against light. Enclose the inventive container washing and detergents for textile cleaning should be used Dyes continue to have no pronounced substantivity towards textile fibers so as 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 “whiteners”) can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles Fiber and create a brightening and feigned bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and gives the white of the grayed or yellowed laundry pure white. Suitable compounds originate, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distryl-biphenyls, methylumbellifenones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides, benzoxazole , Benzisoxazole and benzimidazole systems as well as 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 carboxylic 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 fight microorganisms can the agents according to the invention contain antimicrobial agents. A distinction is made here depending on the antimicrobial spectrum and mechanism of action between Bacteriostatics and bactericides, fungistats and fungicides etc. Important substances from these groups are, for example, benzalkonium chlorides, Alkylarlyl sulfonates, halophenols and phenol mercuric acetate, wherein in the inventive means also entirely these connections can be dispensed with.

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 surface-active Antistatic agents can be broken down into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphoric (phosphoric acid esters) and divide sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable also as antistatic for Textiles or as an additive to detergents, with an additional Finishing effect is achieved.

Phobing and impregnation processes are used to finish textiles with substances that prevent dirt from accumulating or make it easier to wash out. Preferred waterproofing and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum and. Zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or polymerizable compounds coupled with perfluorinated acyl or sulfonyl radical. Antistatic agents can also be included. The dirt-repellent finish with phobing and impregnating agents is often classified as an easy-care finish. The penetration of the impregnating agent in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension. Another area of application of waterproofing and impregnating agents is the water-repellent finishing of textile goods, tents, tarpaulins, leather etc., which, in contrast to waterproofing, does not close the fabric pores, which means that the fabric remains breathable (hydrophobic). The hydrophobizing agents used for hydrophobizing coat textiles, leather, paper, wood etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups. Suitable water repellents are e.g. B. paraffins, waxes, metal soaps, etc. with additives to aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, silicones, organotin compounds and glutardialdehyde and perfluorinated compounds. The hydrophobized materials do not feel greasy; nevertheless - similar to greased substances - drops of water roll off them without wetting them. So z. B. silicone-impregnated textiles a soft handle 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.

For the care of textiles and Improvement of the textile properties such as a softer "handle" (finish) and reduced electrostatic charge (increased Comfort) the agents according to the invention softener contain. The active ingredients in fabric softener formulations are "esterquats", quaternary ammonium compounds with two hydrophobic residues, such as, for example, disteraryldimethylammonium chloride, which, however, because of its insufficient biodegradability increasingly through quaternary ammonium compounds is replaced, the ester groups in their hydrophobic residues as predetermined breaking points for the biodegradation included. Such "esterquats" with improved biodegradability are available, for example, that he Mixtures of methyldiethanolamine and / or triethanolamine esterified with fatty acids and then the reaction products in a manner known per se quaternized with alkylating agents. Also suitable as a finish is dimethylolethylene urea.

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-N- 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 can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Furthermore, sub substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, 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.

Detergents for automatic dishwashing can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents and glass corrosion inhibitors 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 consisting of 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-MeTACN) Mn ^IV (m-0) ₃ Mn ^IV (Me-MeTACN)] ²⁺ (PF ₆ ^- ) ₂ ,
[Me-TACN) Mn ^III (m-0) (m-0Ac) ₂ Mn ^III (Me-TACN)] ²⁺ (PF ₆ ^- ) ₂ and
[Me-MeTACN) Mn ^III (m-0) (m-0Ac) ₂ Mn ^III (Me-MeTACN)] ²⁺ (PF ₆ ^- ) ₂ , where Me-TACN is 1,4,7-trimethyl-1, 4,7-triazacyclononane and Me-MeTACN 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 manufactured according to the invention Means continue to reduce one or more substances Glass corrosion included. Within the scope of the present application especially additives 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 the group zinc oleate, zinc stearate, zinc gluconate, zinc acetate, Zinc lactate and zinc citrate.

Another subject of the present Registration are deep-drawing matrices with lowerable sections, preferably lowerable stamps and / or lowerable webs.

Another subject of the present Registration is the use of deep-drawing dies with lowerable Sub-areas, preferably lowerable stamps and / or removable Ridges for the production of packaging for active substances or active substance mixtures.

Suitable active substances are in particular all active substances or active substance mixtures the fields of pharmaceuticals, cosmetics, feed, crop protection or fertilizers, Adhesives, food and / or personal care products, preferably however from the area of washing and cleaning active substances.

Preferred active substances or mixtures of active substances from the field of cosmetics are in particular hair setting agents, Hair styling and hair coloring agents. 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.

Are particularly preferred substances active in washing and cleaning 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, Color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Corrosion inhibitors, antistatic agents, phobing and impregnating agents, Swelling and anti-slip agents, non-aqueous solvents, fabric softeners, protein hydrolyzate as well as UV absorbers.

For a detailed description of these substances or mixtures of substances is to avoid of repetitions referenced above in the text.

Claims (12)

A method of making a container comprising the steps: a) deep-drawing a first wrapping material into the deep-drawing trough a die forming at least one receiving chamber; b) Lowering a part of the die and deep drawing with enlargement at least one of the receiving chamber formed in step a) and / or under Formation of at least one other admission chamber. A method according to claim 1, characterized in that at least one of the receiving chambers before and / or after lowering a part the matrix is affected becomes. Method according to one of claims 1 or 2, characterized in that that at least one of the filled or unfilled Receiving chambers before lowering part of the die with a second wrapping material is sealed. Method according to one of claims 1 to 3, characterized in that the existence Web or stamp located in the deep-drawn recess of the die and / or an at least partially surrounding the deep-drawing trough in step a) Part of the die is lowered. A method according to claim 4, characterized in that the Web or stamp a maximum width between 0.5 and 50 mm, preferably between 0.6 and 40 mm, particularly preferably between 0.7 and 30 mm and in particular between 0.8 and 20 mm. Method according to one of claims 4 or 5, characterized in that that the Web or stamp in step d) to less than 95%, preferably less than 80%, particularly preferably less than 65% and in particular less than 50% of its original Lowered height becomes. Method according to one of claims 1 to 6, characterized in that that one of the envelope materials used water soluble or is water dispersible. Method according to one of claims 1 to 7, characterized in that that at least one of the wrapping materials used is transparent or translucent. Method according to one of claims 1 to 8, characterized in that one of the wrapping materials used from a water soluble or water-dispersible polymer, preferably a polymer film. Method according to one of claims 1 to 9, characterized in that that the used envelope materials from water soluble or water-dispersible material and different dissolution rates exhibit. Deep-drawing dies with lowerable sections, preferably lowerable stamps and / or lowerable webs. Use of deep-drawing dies with lowerable ones Sub-areas, preferably lowerable stamps and / or removable Ridges for the production of packaging for active substances or active substance mixtures.