DE10244803B4 - Shrunken detergent tablets - Google Patents

Abstract

A process for the production of completely or partially water-soluble, filled hollow bodies, containing an agent, comprising the steps: a) Forming a hollow body from a material containing at least one water-soluble polymeric thermoplastic, the hollow body being formed under stretching conditions and this process by means of an exogenous The temperature jump induced in the polymer thermoplastic is broken off in a defined manner, b) filling the hollow body with a detergent or cleaning agent, c) liquid-tight sealing of the hollow body and d) shrinking of the hollow body material enveloping the agent, wherein the induced temperature jump is caused by the filling of the hollow body with an agent a temperature below 15 ° C, is reached and wherein the shrinkage is triggered by conditioning the filled and closed hollow body in an atmosphere with a relative humidity above 50%.

Description

The present invention relates to a process for the preparation of water-soluble, filled hollow bodies, which undergo a shrinking step of the wrapping material, containing a washing or cleaning agent.

The use of water-soluble packaging in a wide variety of industrial applications is already part of the state of the art. As a rule, the water-soluble packaging materials encase chemicals or consumer goods that are to be protected from the environment by the packaging, but at the same time also protect the consumer or consumer from direct contact with the packaged goods. In agrochemicals, the use of pesticides in water-soluble bags, which were produced by a thermoforming process, from the European patent application EP 0 608 910 A known. The water-soluble packaging protects the user from exposure to the toxic chemicals and also simplifies the dosing of the pesticides by simply adding a pesticide bag to a given amount of water in which the bag and its contents dissolve. The use of water-soluble packaging forms is also known in the pharmaceutical industry, for example, capsules containing water-soluble hard gelatin containing pharmaceutical preparations are administered to the consumers or patients.

Recently, the use of water-soluble packaging has also established itself in the field of detergents and cleaners in the market. The consumer is here in particular single-dose amounts of detergents and cleaners, which are packaged in plastic bags, offered. The consumer is thereby enabled a convenient and simple dosage of detergents and cleaners, since the products are already present in pre-portioned form. The advantages of such individual portions are in particular due to the fact that the consumer is spared tearing open the packaging, thereby conveniently dosing a single, sized for a washing and cleaning portion by inserting the bag directly into the washing machine or dishwasher, especially in their Einspülkammer or by throwing the bag into a certain amount of water, for example in a bucket, a bowl or in the hand-washing or -spülbecken possible. The foil pouch surrounding the washing or cleaning agent portion dissolves on reaching a certain temperature. Detergents and cleaning agents packaged in bags made of water-soluble film are described in large numbers in the prior art, as disclosed in the German patent application DE 198 31 703 A1 a portioned detergent or cleaning agent preparation in a bag of water-soluble film, in particular in a bag of (optionally acetalized) polyvinyl alcohol, wherein at least 70 wt .-% of the particles of the detergent or cleaning agent preparation have particle sizes greater than 800 microns. Although such film bags are very consumer-friendly and facilitate dosing, but are not in all cases the appropriate form for dosing detergent and cleaning preparations. The bagged consumer goods in particular has the disadvantage that the foil bags are very sensitive to mechanical influences. During transport or handling, this can lead to unwanted product leakage if the film is damaged by carelessness. Just touching with pointed or cracked fingernails can already lead to damage and thus to an undesirable consumer budget frustration. Furthermore, it has proven to be extremely difficult to achieve a high degree of filling of the foil bag. The higher the degree of filling of the water-soluble portions, the higher the risk of contamination of the sealing seams, which in turn can lead to leaky sealing seams and thus to product leakage, in particular in the case of liquid formulations. Due to the low degree of filling and possibly due to film-induced instability, the foil bags have no elastic farm stability. When exposed to a deformation force, the bags of deformable films in the unfilled and filled state no longer assume their original shape, that is to say before the action of force, on their own. The mechanical properties of such "floppy" bags are often not reproducible and therefore extremely difficult to stack or re-pack on a commercial scale. In addition, plump and flexible elastic water-soluble portions experience a much higher consumer acceptance, since a stronger impression of a soft wash and cleaning agent also forms to the laundry. In addition to the advantageous aesthetic aspects, which plays an important role for the consumer, especially in the consumer goods sector, the reproducibility creates a recognizable product design. Impact-filled detergent tablets also have better mechanical loading and deformability values.

Methods for the production of foil bags, in particular by the thermoforming method, are already extensively described in the prior art. The pamphlets WO 00/55068 A1 . WO 00/55 046 A1 . WO 00/55 045 A1 . WO 00/55 044 A1 . WO 00/55 415 A1 and. WO 02/16207 A1 describe thermoforming processes for preparing water-soluble sachets which undergo a deep-drawing step. This will be a thermoformable water-soluble film first drawn into a cavity, the formed form then filled and covered in a further step with a second film and sealed.

Measures to increase the tensile strength of the films are also already described in the prior art. Thus, the international application discloses WO 00/55 069 A1 the use of increased humidity within a second outer packaging, in which the water-soluble film bags are located. In order to maintain the increased humidity, the outer packaging must be provided with a moisture barrier. The use of increased humidity disclosed in the document serves to soften the film material, thereby reducing its susceptibility to cracking and, in addition, increasing the tightness of the sealed seams.

The international patent application WO 02/16 206 A1 also discloses the use of a thermoforming process for making water-soluble portions. In order to obtain aesthetically pleasing, bulging foil pouches, the formulations contained in the pouches have a gas evolution system which inflates the pouches from within. Citrate / carbonate systems are typical gas evolution systems. The disadvantages of such entrapped gas evolution systems are that the formulations already deliver gas before being filled into the water-soluble containers and thus inflate the water-soluble containers in a non-reproducible or non-uniform manner become. Furthermore, an uncontrolled release of gas in extreme cases leads to bursting of the portions or to a tearing open of the sealing seams.

The international patent application WO 02/16205 A1 also describes the attempt to provide bulge-shaped film moldings which were produced by a thermoforming process. For this purpose, specially predried polyvinyl alcohol films with a water content below 5% by weight are used in the thermoforming process. By filling aqueous formulations into pouches made from dried sheet material, aesthetically pleasing moldings can be obtained. The disadvantage here, however, that the manufacturing process is bound to aqueous, liquid formulations and a complicated drying of the film material must be done. In addition, it is not exactly reproducible to what extent the film has already been softened before being processed by the atmospheric humidity of the environment and thus already exceeds the required water content of below 5% by weight. Also not reproducible is the composition of the wrapped of the dry film formulation, which can sometimes be very sensitive to loss of water, for example by precipitation of water-soluble ingredients, so that not only the aesthetic appearance of transparent moldings can be significantly affected, but also to the Medium asked performance requirements.

The object of the invention was therefore to provide a technically simple and reproducible method for producing water-soluble filled hollow body, in particular a detergent or detergent-containing portion, which overcomes the aforementioned disadvantages in the prior art. Another object of the invention was to provide a process for the production of elastically deformable, water-soluble hollow body, which in addition to an excellent dissolution rate and textile protection has good packaging properties in outer packaging.

Surprisingly, it has now been found that water-soluble flexible, preferably elastic hollow bodies can be produced by means of a shrinking step and contain detergents and / or cleaning agents.

The invention therefore provides a process for the preparation of completely or partially water-soluble, filled hollow bodies containing a washing or cleaning agent, according to claim 1.

A step which is essential for the process according to the invention is the shrinkage of the hollow body material enveloping the means, which comprises at least one water-soluble polymeric thermoplastic.

The shrinkage properties of polymeric fabrics are mainly due to deformation and molecular orientation, which are imparted to the molecular structure of the material during the production and processing of the polymeric sheet and frozen on cooling. The molecular chains are then frozen in a nonequilibrium state of reduced entropy similar to that of a stretched rubber. When the sheets are heated above the glass transition temperature or, in the case of semicrystalline materials, above the crystallite melting point, the blocking of this "rubber elasticity" is abolished, and the molecules return to the orientation-free state of equilibrium. This results in a shrinkage in the direction of orientation when the sheet can deform freely, or a shrink force when the deformation is hindered, in practice, for example when creating a film on the wrapped good. Shrinkage increases with increasing temperature until all blockages are dissolved and the sample is in the isotropic state. The shrinking force, however, has a maximum depending on the temperature, because with increasing temperature of the force-deformation module is smaller and the material increasingly merges into a viscous state, the shrinkage forces are reduced by stress relaxation. As the heated sheet cools, the heat shrinkage force usually increases. The after cooling to room temperature adjusting shrinkage force is influenced by the size of the modulus of elasticity change and the coefficient of thermal expansion and - in semi-crystalline plastics - by crystallization processes during cooling. It is therefore different in the different fabrics depending on the achieved shrinkage force in the heat. The different fabrics differ in the size of the shrink forces and in the temperature range in which shrink forces occur. Surprisingly, it has also been found that, for water-soluble polymeric thermoplastics, the deformation and molecular orientation imparted to a polymeric sheet by stretching or drawing in the production and / or processing of the polymeric sheet, the molecular structure of the material, by conditioning in an atmosphere with increased relative Humidity - at least partially - can be reversed, which has a shrinking process of the polymeric sheet result.

Without being bound by theory, it is believed that the added moisture causes polymer material to be dissolved, allowing the polymer strands the flexibility necessary to reorient into a stress-free state. The result is a contraction of the polymeric sheet and thus a shrinkage. In particular, the present invention uses this surprisingly found shrinkage effect for the production of flexible, elastically deformable water-soluble portions.

In the present invention, therefore, the shrinkage of the agent-enveloping hollow body material in an atmosphere of increased relative humidity is triggered. The filled and liquid-tight closed hollow body can go through an air-conditioned space or a climate chamber, which have the ideal conditions for the shrinkage process for the respective water-soluble thermoplastic.

Shrinkage by conditioning the filled and sealed hollow body is triggered in an atmosphere having a relative humidity above 50%, preferably above 65%, more preferably above 80%, more preferably above 85%, most preferably above 90%.

The shrinking process is particularly effective by conditioning at a temperature above 25 ° C, preferably above 30 ° C, more preferably above 35 ° C, most preferably between 40 and 60 ° C.

Depending on the nature and material of the water-soluble polymeric thermoplastic and the desired shrinkage strength of the shrinkage process by conditioning, for example, in a climatic chamber, within a typical residence time in which the filled and liquid-tight closed hollow body exposed to the shrinking conditioner conditioning conditions of at most 24 hours, preferably at most 2 hours, more preferably at most 30 minutes, most preferably carried out between 10 seconds and 15 minutes.

In a preferred embodiment of the method according to the invention, the shrinking process is triggered by iterative conditioning under possibly changing conditions.

It has proved to be effective and advantageous, in particular in the shrinkage of (partially hydrolyzed) polyvinyl acetate as a hollow body material, to allow the conditions triggering the shrinkage to act on the filled, liquid-tight sealed portions at time intervals. Different alternating climates with different relative humidities and different temperatures may be run through in possibly varying time intervals. Technically, such conditions can be realized in that the liquid-tight sealed and filled portions of transport media, such as conveyor belts, different climatic stations, each having different climates, go through for a certain time.

Such climatic stations with integrated conveyor belts and the possibility of passing the products through various climates are also known by way of example from the confectionery sector, in particular the chocolate industry. For example, the Father-noster versions of climate cabinets from Winkler & Dünnebier are mentioned here as examples.

In a preferred embodiment, the shrinkage is reduced by iteratively conditioning filled hollow bodies, n times, with n ≥ 2, preferably 2 to 500, more preferably 2 to 20, alternately for a given time interval, preferably shorter than 1 hour, more preferably shorter than 10 minutes, more preferably between 0.1 second and 5 minutes, under shrink-inducing conditions, as described above, and then treated for an equidistant or deviating time interval under non-shrinkage triggering conditions or altered shrinkage triggering conditions, triggered.

In a further preferred embodiment, the conditioning step (s) initiating the shrinkage of the water-soluble polymeric hollow body material is followed by at least one drying step, preferably by an optionally heated air stream and / or by a drying oven and / or in an atmosphere with elevated relative humidity Application of microwave irradiation on.

A drying step which takes place after the conditioning step (s) has an advantageous effect on the handling of the portions, since they lose their moisture on the surface of the enveloping body material and thus likewise lose the "slippery" haptic impression generally perceived as unpleasant for the consumer. Furthermore, the static friction increases on the surface of the portions, so that the further processing, for example, the packing of the portions by packaging machines or people in outer packaging is greatly facilitated. The downstream drying step not only contributes to improved handling and processability of the portions, but also has a positive effect on the desired shrinkage effect.

In the prior art are already numerous, familiar to the expert drying devices, such as hot or cold air blower, drying ovens, infrared light stations or microwave radiation emitting devices that can be used for drying.

The formation of a hollow body from a material containing at least one water-soluble thermoplastic can be carried out according to methods known to the person skilled in the art and known in the art. It is crucial, however, that the means enveloping hollow body material is shrinkable. Thus, for the formation of the hollow body water-containing thermoplastic-containing sheets, such as films may be used, which have undergone a deformation in the course of their manufacturing process, which has placed the polymer material in a non-equilibrium state. Examples of such shrinkable polymeric sheets are blown films. From them, according to the known in the prior art method for producing tubular bags, for example by liquid-tight sealing of a hose at one end, filling the one-sided sealed tube with a means and liquid-tight sealing of the filled tube piece at the other end, wherein the tube extruded and was preferably stretched or provided by a shrinkable film by vertical sealing, produce closed, filled hollow body. Further suitable manufacturing methods for the formation of hollow bodies which can receive a means are, for example, deep-drawing methods in which shrinkable films are pulled or pressed into a cavity, methods for producing bags with three outer sealing seams or also bags having four sealing seams, such as, for example in the WO 99/16681 A1 described.

In the context of the present invention, however, those methods are preferred in which the formation of the hollow body takes place by application of heat. However, experience has shown that the range of temperature applications on thermoplastics is limited in the lower range by the embrittlement of the material and in the upper range by the thermal decomposition.

In the context of the present invention, the formation of the hollow body preferably takes place in the melt region of the polymeric thermoplastic.

The region in which a polymeric material is thermoformable and the temperature region where shrinkage of the material occurs are between the temperature at which the material softens (softness temperature) and the melting temperature. During the manufacture of shrinkable polymeric sheets, such as film films, the sheet is biased (uniaxially or biaxially) in its thermoelastic region. These stresses in the polymeric sheets are frozen in the system and can subsequently be relaxed again by conditioning in an atmosphere of increased humidity. The shrinkage forces and the degree of shrinkage depend on the type of polymer, the thickness of the polymeric sheet, the magnitude of the preload and the shrinking conditions.

In a preferred embodiment, the, preferably blow-molded, hollow body with and without compartments "umkrempeln", ie it is puffed in such a way that the original inside becomes the outside and vice versa. This flexibility leads to the resistance to leaks under compressive stress, to avoid stress cracking or breakage, which is particularly high compared to rigid shaped bodies.

The hollow bodies produced according to the invention dissolve completely or substantially in water, in which way the agents contained in the closed hollow body and / or in the compartments are released into the environment. For example, the hollow bodies containing agents according to the method of the invention can be used in an aqueous mechanical washing or cleaning process. Preference is given to the use of the hollow body according to the invention in commercial washing machines or dishwashers. A use of the hollow body according to the invention in hand basins or in a bowl is also possible. Important for the release of the agent contained in the hollow body / compartments is a surrounding from the outside aqueous environment.

Flexible hollow bodies in the sense of this invention preferably also include elastic hollow bodies.

The term "elastic hollow body" is understood in particular to mean that the hollow bodies containing the detergent or cleaning agent have an intrinsic dimensional stability which enables them to break under normal conditions of manufacture, storage, transport and handling by the consumer and / or pressure to have a stable, non-coincident structure, wherein the filled with detergent or cleaning agent, preferably blow-molded hollow body having an elongation along its longest axis has a yield stress of between ≥ 3 N / mm ² and ≤ 15 N / mm ² , and / or at an upsetting distance of 22 mm vertically, centrally, in the direction of its shortest axis, a deformation work of between ≥ 0.05 Nm and ≤ 5 Nm occurs, and / or at a force F ₁ > 0.1 and ≤ 500 N along a path s _{1 is} deformable and returns after elimination of the force in the direction of the original shape, or after elimination of the Krafteinwirkun g completely or almost completely assumes the original shape, and / or, after elimination of a deformation force effect, has a return velocity v of between> 0.01 mm / min and ≤ 650 mm / min, and / or the modulus of elasticity of the hollow body wall of the flexible, preferably blow-molded with detergent or cleaning agent to ≥ 80 vol .-%, filled hollow body ≤ 1 GNm ² , preferably ≤ 0.1 GNm ² , preferably ≤ 0.01 GNm ² , and / or at one with detergent or cleaning agent to ≥ 80 Vol .-% filled preferably blow-molded hollow body an upsetting resistance F _max of between ≥ 20 N and ≤ 2000 N occurs.

It is according to the invention without influence, whether this structural stability from the resulting due to various parameters mentioned below properties of the flexible, preferably elastic, hollow body alone and / or from the presence of compartmentalization facilities and / or from the filling with washing active, cleaning active and / or care-active preparations results. In preferred embodiments of the invention, even the flexible, preferably elastic, hollow body itself have a sufficient intrinsic dimensional stability, since this has an advantageous effect on the mobility in machines in the manufacture of the hollow body and the filling during the preparation of the detergent or detergent portions ,

As mentioned above, the sheaths should preferably be at least partially reusible deformable (in case of irreversible deformation, no reset speed would be measurable). In preferred embodiments of the present invention, the deformation is completely reversible.

The force F ₁ is dependent on the indentation depth, since the hollow body, with and without compartments, offers increasing resistance to the penetrating body. First, it is only important for the present invention that at a force of 500 N or less, the hollow bodies can be deformed with and without compartments at all. In preferred embodiments of the present invention, the data refer to forces at penetration depths of a round rod with 8 mm diameter, in particular at a penetration depth equal to 1 mm, further at 10 mm penetration depth, preferably at 15 mm penetration depth, preferably at 20 mm penetration depth and more preferably at 22 mm penetration depth.

If the distance s _{1 is} defined, not only the force, but also the deformation work can be determined exactly. At a force by a round rod with 8 mm diameter and a penetration depth of S ₁ = 22 mm, the work of deformation is preferably produced by blow molding flexible, unfilled hollow body well below the values of comparable rigid unfilled bodies, where a deformation work of at least> 5 Nm must be made.

Another size for characterizing the portioned agents is the compression resistance. This can be determined in the form of a force-displacement diagram with commercially available tablet testers. For the purposes of the present invention, a Zwick type 1425 universal testing machine was used.

The determination of compression resistance is carried out according to DIN 55526 Part 1, characterized in that hollow body with and without compartments (= container) is placed upright between the plates of a pressure tester and compressed, the pressure force and the Plattenweg are recorded until the required compression resistance and Plattenweg be reached or failure occurs by critical deformation or leaking of the container.

The printing press was set to a compression speed of 10 mm / min. Afterwards the test procedure was started. The force applied to the portion at a penetration of 22 mm [N] was printed on the connected printer. The crush strength is given in N. Here, portioned means containing hollow body with and without compartments are preferred, wherein the compression resistance F _{max of} the portioned agent containing hollow body (= the filled hollow body with and without compartments) 20 to 2000 N, preferably 50 to 1000 N, particularly preferably 75 to 600 N, more preferably 100 to 500 N and in particular 150 to 400 N. For testing purposes, the hollow body, preferably produced by blow molding, with and without compartment, is filled to ≥80% by volume with detergent or cleaning agent.

It is preferred if the flexible, water-soluble, hollow body is formed in one piece or in several pieces.

The internal volume of the hollow body and / or the compartments preferably produced by blow-molding can be, for example, between 0.5 ml and 2000 ml, preferably between 2 ml and 500 ml, preferably between 5 and 250 ml, more preferably between 10 and 100 ml, more preferably between 20 and 75 ml, and most preferably between 40 and 50 ml.

The hollow body preferably produced by blow molding according to the invention and / or its compartment (e) is particularly preferably transparent and / or translucent.

Preferably, the hollow, unfilled or filled with detergent or cleaning agent filled hollow, unfilled or by shrinkage to a volume of at least 80% by volume has a volume reduction of at least 0.5%, preferably at least 1%, more preferably at least 1.5%, more preferably at least 2%, in particular at least 3%, particularly preferably at least 5%, more preferably at least 6% and advantageously at least 10% experience.

In a further preferred embodiment, the flexible hollow body filled with detergent or cleaning agent and having at least 80% by volume by the shrinking step has a length reduction along the longest axis of at least 0.2%, for example at least 0.5%, preferably at least 1%, more preferably at least 1.5%, more preferably at least 2%, especially at least 3%, especially preferably at least 5%, most preferably at least 6% and advantageously at least 10%.

Further preferred embodiments lead to detergent or detergent portions in which the portions contained in the hollow bodies or compartments by a - preferably controllable - water solubility of the hollow body material at a certain time of the washing or cleaning process or when reaching a certain pH or a certain ionic strength of the wash liquor or due to other controllable events or conditions in the aqueous liquor can be fed. The quality of the material as well as its quantity / strength directly influence these solubility properties. Particular preference is given to materials for the hollow bodies, which-based on a certain wall thickness, which determines the stability-dissolve at certain temperatures, pH values, ionic strengths, or after a certain residence time in the aqueous liquor. In this case, such a release process can capture the hollow body as a whole or only a part thereof, so that parts of the hollow body solve when setting a certain parameter combination, while other parts are not yet (but later) or not at all. The latter can be achieved by different quality of the material as well as by different amounts of material (thickness of the wall) or different geometries of the hollow body. For example, it is possible by the hollow body geometry the To complicate access to water and thus delay the dissolution process. In another preferred embodiment, it is possible to make walls of the hollow body of different thicknesses (nevertheless of the same material) and thus to allow earlier dissolution at the thinner locations. In likewise preferred embodiments, the walls of the hollow body can be made of materials of different water solubility, for example of polyvinyl alcohols (PVAL) with different residual acetate content. This leads to the formation of perforated walls, which allow water to penetrate into the hollow body and / or escape of the dissolved or undissolved ingredients from the hollow body.

Furthermore, it is possible that the materials of the walls of the flexible, preferably elastic, hollow bodies consist of a washing-active, cleaning-active or care-active active substance, for which PVAL is an example as a builder, or contain such. In the latter case, for example, washing active, cleaning active or care active ingredients that are present only in small amounts in the preparations and their uniform incorporation is therefore not unproblematic, in the material of the wall of the hollow body or in a part of the material of the wall of the hollow body, for example one which dissolves in the stage of the washing or cleaning cycle, in which the active ingredient is needed, incorporated and released when solving the material of the wall at the right time in the fleet. An example of this may be perfumes that are desired in the final phase of the washing or cleaning process, but also optical brighteners, UV protectants, dyes and other detergent-active, cleansing or care-active preparations. The basic principle of incorporation of such (usually incorporated in small amounts) components in the materials that form the enclosure of the detergent or detergent portions, the applicant's co-pending patent application 199 29 098.9 entitled "active ingredient portion package" can be seen the disclosure of which is incorporated by reference in its entirety into the disclosure of the present application.

In a particular embodiment of the invention, it is also possible that the walls of the flexible, preferably elastic, hollow body containing the detergent or cleaning agent portions, consist of different materials, so have a heterogeneous structure. For example, in a polymeric material forming the wall of the hollow body, islands could be dispersed from a foreign material insoluble in the polymer, for example from another polymer (having different water solubility) or even from a completely different substance (for example, an inorganic or organic substance), examples thereof are water-soluble salts such as sodium sulfate, sodium chloride, sodium carbonate, calcium carbonate, etc .; organic acids such as citric acid, tartaric acid, adipic acid, phthalic acid, etc .; Sugars such as maltoses, dextrose, sorbitol, etc .; zeolites; silicates; crosslinked, for example weakly crosslinked polymers such as polyacrylates, cellulose esters, cellulose ethers such as carboxymethylcellulose. Such a structure may be associated in particularly preferred embodiments of the invention with the advantage that the other substance dissolves faster in water than the polymer, which allows penetration of water into the hollow body and thereby accelerated release of washing active, nurturing or cleaning active components of the Portion contributes. Overall, the entire dimensionally stable hollow body is dissolved faster in such a packaging than a molded body made of a pure polymer material. Similarly, it is possible to form the walls of the hollow bodies of layers of two or more polymers, which can be selected in particularly preferred embodiments so that they complement each other optimally in terms of their properties (stability, heat resistance, water solubility, gas barrier properties, etc.).

In the context of the present invention, blow molding processes for producing filled, liquid-tightly sealed hollow bodies have proven to be particularly suitable. Blow molding methods suitable for the present invention include extrusion blow molding, coextrusion blow molding, injection stretch blow molding and dipping blowing. In addition to a simple, fast and safe manufacturability, the blow-molded hollow body additionally have the advantage that they are already produced by large-scale production of a stretched, that is shrinkable hollow body material, which allows excellent shrinkability of the filled and liquid-tight closed hollow body.

• (a) in einem ersten Schritt mittels Extrudieren ein Vorformling hergestellt wird und
• (b) in einem zweiten Schritt in einem Zyklus der Hohlkörper, vorzugsweise mittels eines unter Druck stehenden Gases, vorzugsweise Pressluft, und/oder durch Anlegen eines äußeren Vakuums aus Öffnungen der Kavität heraus geblasen, vorzugsweise zur endgültigen Hohlkörpergeometrie, und mit dem Mittel gefüllt, flüssigkeitsdicht verschlossen, sowie anschließend entformt wird.

The blow-molding process is preferably carried out by forming the hollow body by primary molding a preform, particularly preferably a tubular preform, from a blow molding composition based on a water-soluble polymeric thermoplastic, and then blow molding the preform into a hollow body. Preferred are methods in which

• (A) in a first step by extrusion, a preform is prepared and
• (B) in a second step in a cycle of the hollow body, preferably by means of a pressurized gas, preferably compressed air, and / or by applying an external vacuum blown out of openings of the cavity, preferably to the final hollow body geometry, and filled with the agent, sealed liquid-tight, and then removed from the mold.

• (a) in einem ersten Schritt mittels Extrudieren ein Vorformling hergestellt und in ein Formwerkzeug geführt wird und
• (b) in einem zweiten Schritt in einem Zyklus der Hohlkörper, vorzugsweise mittels eines unter Druck stehenden Gases, vorzugsweise Pressluft, und/oder durch Anlegen eines äußeren Vakuums aus Öffnungen der Kavität heraus geblasen wird, so daß sich das thermoplastische Material an das Formwerkzeug anlegt, wobei das Formwerkzeug gekühlt wird und/oder optional die Temperatur einer ggf. vorhandene Kopfbacke zum flüssigkeitsdichten Verschließen des Hohlkörpers über einen separaten Temperierkreislauf geregelt wird.

In a further preferred embodiment of the invention, the formation of the hollow body takes place in the

• (A) is produced in a first step by means of extrusion a preform and fed into a mold, and
• (B) is blown in a second step in a cycle of the hollow body, preferably by means of a pressurized gas, preferably compressed air, and / or by applying an external vacuum from openings of the cavity, so that the thermoplastic material is applied to the mold , Wherein the mold is cooled and / or optionally the temperature of any existing head jaw for liquid-tight sealing of the hollow body is controlled by a separate temperature control circuit.

A separate Temperierkreislauf for an optionally present head jaw has proved to be advantageous because the heat sealing of the hollow body by means of a head jaw usually requires higher temperatures than in the remaining part of the mold. If the seal is carried out by means of a head jaw, which is geometrically connected to the molding tool, excessive cooling of the head jaw can lead to leaky or defective seals. A separate temperature control circuit, which provides the temperature required for the heat-sealing is therefore preferred in the context of the present invention.

The wall thicknesses of the hollow body can be produced in different ways by blow molding, by varying the wall thicknesses of the preform, preferably along its vertical axis, according to different thickness, preferably by regulating the amount of thermoplastic material, preferably by means of an adjusting spindle during application of the preform from the extruder die, formed.

The hollow body may be blow molded with regions of different outer circumference and uniform wall thickness by varying the wall thicknesses of the preform, preferably along its vertical axis, preferably by regulating the amount of thermoplastic material by means of an adjusting spindle during application of the preform from the extruder die. formed.

In this way, different geometrical configurations of the hollow body can be blown with and without compartments. In a single cycle, bottles, balls, Santa Claus, Easter bunnies or other figures can be blown, which can be filled with medium, then sealed and then demoulded.

It is particularly advantageous that the hollow body can emboss and / or decorate during blow molding in the blow mold. By appropriate design of the blow mold, a motive can be mirror-inverted transferred to the hollow body. In this way, the surface of the hollow body can be designed practically arbitrary. For example, information such as calibration marks, application instructions, danger symbols, brands, weight, filling quantity, expiration date, images, etc. can be applied to the hollow body.

In a preferred embodiment, the preform, the hollow body and / or the liquid-tight closed hollow body of one or more component (s), wherein the component comprises one or more materials based on one or different water-soluble polymeric thermoplastics.

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

The shape factor in the sense of the present invention can be precisely determined by modern particle-measuring techniques with digital image processing. A common method is, for example, the Camsizer ^® system from Retsch Technology or KeSizer ^® of the company Kemira. These methods are based on that the hollow body or body are irradiated with a light source and the hollow body detected as projection surfaces, digitized and processed by computer technology. The determination of Surface curvature is carried out by an optical measuring method, in which the "shadow cast" of the hollow body to be examined is determined and converted into a corresponding form factor. The underlying principle for determining the shape factor has been described, for example, by Gordon Rittenhouse in "A visual method of estimating two-dimensional sphericity" in the Journal of Sedimentary Petrology, Vol. 13, No. 2, pages 79-81. The measuring limits of this optical analysis method are 15 μm to 90 mm. Methods for determining the shape factor for larger particles are known to those skilled in the art. These are usually based on the principles of the aforementioned methods. The release from the hollow bodies with and without compartments can be achieved either at different times that the blow-molded walls have different dissolution or disintegration rates. This is possible, for example, by the choice of material thickness.

The walls of the hollow body produced by blow molding and / or the compartments has a wall thickness of between 0.05-5 mm, preferably between 0.06-2 mm, preferably between 0.07-1.5 mm, more preferably between 0.08-1.2 mm, more preferably from 0.09-1 mm, and most preferably from 0.1-0.6 mm.

The filling opening of the hollow body after filling can be sealed in a liquid-tight manner, preferably by closing the material, preferably by means of thermal treatment, more preferably by setting up a molten metal.

The filling opening or openings of the hollow body can advantageously be sealed in a liquid-tight manner by thermal treatment, preferably by fusing the walls adjoining the opening, in particular by means of clamping jaws.

It is advantageous if the melt flow index of the water-soluble polymeric thermoplastic during extrusion, measured in the first step at 10 kg stamping load, between 1 and 30, preferably between 5 and 15, more preferably between 8 and 12 and / or the melt flow index of the water-soluble polymeric thermoplastic, measured at 2.16 kg stamping load, between 4 and 40, preferably between 5 and 20, particularly preferably between 8 and 15. In the context of the present invention, particularly suitable for blow molding polyvinyl alcohol types are medium to high viscosity and have, for example, values of 6-8 (at 230 ° C, 2.16 kg load, PVA blend manufacturer Texas Polymers "Vinex 2034" or " 2144 ") or 9-11 (at 190 ° C, 10 kg load, PVA blend" TP Vinex 5030 ").

The blow-molded hollow body and / or the respective compartments of the water-soluble hollow body can be filled from any direction, for example from above, from the side and / or from below.

The hollow body produced by blow molding according to the invention and / or its compartment (e) preferably has no seam, in particular no sealed seam, no squeeze seam and / or no groove, in particular flanged groove.

In one embodiment of the inventive method, a plurality of hollow bodies can also be formed in a hollow body by blow molding a preform having a plurality of layers, during which a gap is formed between the layers during blow molding so that these layers each form separate hollow bodies or compartments. These separate hollow bodies or compartments can be connected to one another.

In a preferred embodiment, it is possible by coextrusion to produce a preform having a plurality of layers, preferably 2 to 5, which is then blow-molded into a hollow body in which at least one wall of the hollow body and / or in which at least one wall of at least one compartment is formed in multiple layers ,

Serial, parallel and / or concentric arrangements of hollow bodies and / or compartments, preferably with walls of the same or different materials as described above, may preferably be produced by blow molding, preferably, but not exclusively, by including at least one double and / or one or more Multiple and / or coextrusion mandrel used. It is preferred if in this case the preforms are based on the same or different thermoplastics.

In a preferred embodiment, the hollow body, in particular produced by a blow-molding process, has no sealed seam, no pinch seam and / or no circumferential seam.

According to the invention, however, the multipart design of the blow-molded hollow bodies is particularly advantageous. Especially with regard to the dosing of consumers and / or in terms of product aesthetics and / or in view of the solubility and / or release of a coated agent in an aqueous solution and / or an application environment such as a washing or cleaning liquor show up improvements.

Individually packaged in containers made of water-soluble material preparations can be dosed consumer-friendly and represent a marked by particular aesthetics alternative to other single dosage forms, especially tablets. In many areas, this single dose is perceived as comfortable. The consumer takes the appropriate product, doses it and need not worry about the dimension of appropriate quantities. In many cases, this form of supply but also meets the criticism that a situation-dependent modification of the dosage is no longer possible and thus, for example, with one dosing unit too little, but with two units is overdosed. In the offer form of the tablet, the proposal is regularly brought to the manufacturers to design them as chocolate bars, so that the consumer can "break off" his individual dosing units as needed. Compared to powders or liquids on the one hand (complete dosing with almost unlimited variety of dosing) and tablets or so-called pouches on the other side (a Dosiermöglichkeit), there is still the desire for a product segment, for example, with two to twenty separately dosable units allows a situation-based dosage, without having to use an external measuring vessel every time.

In a particularly preferred embodiment of the method according to the invention, the water-soluble, blow-molded hollow bodies are formed in several pieces and have wall thicknesses of 0.05-5 mm in the region of the filled hollow volume.

The inventive method allows the production of filled and sealed containers and is preferably carried out in-line by the "blow-fill-seal" method (BFS technology). In this blow-molding / filling-closure technique, the respective desired shape is first blown, then filled with the contents and then sealed in one operation. In this case, a tube of plasticized water-soluble plastic material is extruded into an open blow mold, the blow mold is closed and, by creating a pressure gradient effective on the tube, it is expanded and applied to the forming wall of the blow mold to form the container.

Preferably, the blow-molded hollow body are designed in several pieces, d. H. that in the blow mold a plurality of separate hollow volumes are generated, which are connected to each other via webs. The webs are formed by pressing the two hose walls in the blow mold, where it has no cavities for forming the hollow volumes. The material thickness of the webs can be determined by the wall thickness of the extruded tube and the farm of the pressing tool, the wall thickness of the hollow volumes depends on the amount of polymer material that is available for a given volume of the hollow body to be produced. Depending on the shape of the contiguous hollow volumes to be produced, the wall thickness varies more or less strongly in the area of the hollow volumes. Usually, blow-molded hollow bodies have higher wall thicknesses in the vicinity of the bottom and top regions than in the middle of the container. Thicker wall thicknesses in the floor and head area can not only be the result of the blowing process, but in particular also be targeted by utilizing their thermal heat capacity in order to achieve a better sealability of the hose end pieces with minimized risk of leakage. In particular, when filling with colder content / agent compared to the preform, undesirable premature cooling and solidification of the thermoplastic melt may otherwise occur, resulting in insufficient and non-liquid sealed seal portions. In the case of the preferred multi-part hollow bodies, the wall thickness of the hollow bodies can also be slightly higher in the vicinity of the bridge than in the areas remote from the bridge ("bulged out").

The term "blow-molded hollow body" thus comprises a basic unit of at least two interconnected units ("hollow volumes") within a multi-block blister unit. The individual units or hollow volumes are preferably individually separable. For this purpose, the multiblock blister units can be provided with suitable squeeze lines and / or perforations which make it possible to separate a serviceable unit from the overall block.

A multiblock blister pack which can preferably be produced according to the invention has the following embodiment: it is formed from a tube which is congruent in its circumference and forms an elongated oval in its cross section, ie normal to the extruded longitudinal axis; these two Löngsseiten in Cross-sectional oval are welded mirror images of each other and form both adjacent surfaces and non-adjacent, namely the cavities having areas.

Inventive methods in which the water-soluble, blow-molded hollow body in the region of the filled hollow volume wall thicknesses of 0.06-2 mm, preferably between 0.07-1.5 mm, more preferably between 0.08-1.2 mm, even more preferably between 0.09-1 mm and most preferably between 0.1-0.6 mm are preferred.

The wall thickness of the webs connecting the filled hollow volumes is, in the case of a preferred process according to the invention, at most twice the wall thicknesses located in the region of the filled hollow volume. In particularly preferred methods, the webs connecting the filled hollow volumes are further thinned in their wall thickness by a preferably centrally extending pinch seam, preferably with an additional perforation line, to predetermined breaking points which are in the range from 5 to 200 .mu.m, preferably 10 to 150 .mu.m, particularly preferably 15 to 100 microns and in particular 20 to 70 microns are. The separability of the individual hollow volumes of the multi-block blister unit ("blow-molded hollow body") can thus be achieved by a sufficiently thin design of the webs or by a perforation of the webs.

Since each hollow volume is filled individually by means of a Fülldorns, it is possible to fill the individual hollow volumes with different compositions. In this way, for example, detergents or cleaning agents can be prepared in multiblock blister form, in which the consumer the present in a void volume agent for an added benefit (for example, additional bleach and / or additional brightener for white laundry, additional color transfer inhibitors for coloreds, additional enzymes for certain contaminants such Blood etc.) or can not use by separating the corresponding hollow volume. This function can be carried out to the extent that each individual hollow volume of a multiblockblister unit is filled differently - however, for reasons of process economy and consumer convenience, it is preferred that the number of different compositions present in a multiblockblister unit be manageable, usually one, two or three compositions. to keep.

It is also possible to fill two differently composed agents in one and the same hollow volume and to separate them within a hollow volume of each other. This embodiment has the advantage that the consumer can not separate the compositions from each other, since he would have to destroy the hollow volume, but still incompatible substances (in the washing or cleaning agents such as bleach and enzymes) can be assembled side by side. The separation into several compartments within a hollow volume succeeds either by correspondingly shaped hollow volumes with a plurality of cavities which can not be separated from one another or by the production of hollow volumes which have partitions.

The latter embodiment is preferred and can be realized simply by extruding a tube of plasticized plastic material and at least one partition formed from the plastics material and extending continuously inside the tube into an open blow mold, closing the blow mold and creating one on the tube effective pressure gradient of this expanded and applied to the formation of the container to the forming wall of the blow mold. Hereby, by closing the opened blow mold, the front end of the tube and the front end of each partition are welded together to close the container bottom connected to each partition wall, the expansion of the tube by supplying blown air from the container bottom opposite to the container neck End of the closed blow mold ago so that the blowing air on both sides of each partition wall expands to form separate chambers in the container.

Due to the fact that according to the invention, the ends of the tube and the dividing wall, ie the parts of the plastics material reaching the lower end of the blow mold during the extrusion process, are welded to form the container bottom, the upper end of the mold cavity is associated with the container neck. Accordingly, further processing of the expanded container within the closed tuyere can be carried out by, after expanding the container by blowing air introduced through the container neck on both sides adjacent to each partition, the filling process for each inner container chamber is performed through the container neck, without To open blow mold or to remove the container.

However, a production variant of compartmented hollow volumes may also be preferred, in which the at least one co-extruded dividing wall itself represents a coextruded, preferably elongated, in cross-section to an oval, preferably concentric tube. This can be blown and filled only on both sides analogous to the blowing and filling process described above, so that again mutatis mutandis by collapse of the central, enclosed volume one, so quasi two-layer, dividing wall results. However, it may also be desired to fill the middle compartment by providing a further blowing and filling mandrel. It is further conceivable to extend this principle to the coextrusion of several bubble-extruded and filled compartments, wherein it may be particularly preferred to different hoses / preforms by a different choice of materials different properties such as a barrier function, a function as a mechanical stability transmitter, a function as a temperature switch shall be included. Furthermore, however, it may also be desirable to bring together the tubes / preforms co-extruded from different materials or partition walls into multilayer hoses / preforms, ie to allow them to collapse. In this way, one-chambered hollow volumes can be produced, which are covered by multilayer sheaths; Examples which may be mentioned are combinations of polyethylene glycol, preferably on the inside, as sticky, with PVA or recycled polymer, preferably on the inside, with fresh thermoplastic.

The filling process can be carried out both in single-chamber hollow volumes as well as in the multi-chamber hollow volumes by means of a combined blowing and Fülldornes or by a separate Fülldorn which is introduced after retraction of the mandrel from the container neck in this. A particular advantage of the BFS method is that after filling of the container neck of the container by means of a still-closed blow mold additional welding process finished molded and can be hermetically sealed at the same time with a closure formed by the welding process. This can be done by moving upper welding jaws or head jaws, which are arranged at the top of the blow mold. In this case, any desired form and / or closure operations can be carried out, for example, a tear-off at a predetermined breaking point or separation point closure can be formed, preferably in the form of a rotary toggle closure. It is understood that an external thread on the container neck could be formed to form a screw with a separate closure element. In the case of moldings, because of their water-soluble nature of the polymer shell (s), a particularly preferred upper closure form is represented merely by sealing and severing overhanging plug material, more or less analogous to welding the front tube or partition wall end (s) to the hollow body bottom. The welding operation performed on the neck of the container may provide for separate closures for each chamber of the container or a closure closing all the chambers of the container together.

The formation of a self-subdivided extrusion hose can be achieved, for example, by providing the end of the extruder device facing the blow mold with a nozzle ring in which a nozzle core is arranged coaxially to the nozzle longitudinal axis, whose core tip defines an annular outlet with the end region of the nozzle ring the extruded plastic material emerges in the form of a hose. The molten plastic material passes to the outlet via an annular gap formed between the nozzle ring and the nozzle core. This annular gap narrows at the transition between the core tip and the upstream adjoining part of the nozzle core, so that there is a storage area for the supplied plastic material.

The core tip is bolted to the adjoining, upstream portion of the nozzle core via an externally threaded pin such that the facing surfaces of the core tip and subsequent portion of the nozzle core are spaced apart. The corresponding surface of the core tip forms a funnel surface, while the facing surface of the remainder of the nozzle core defines a conical surface. These surfaces, which preferably include inclination angles of 65 ° or 60 ° to the longitudinal axis of the nozzle, form between them a guide device for plastic material branched off from the annular gap, which enters the storage area between the surfaces. By drilling in the external thread having pin of the core tip of this branched plastic material passes into a formed in the front of the core tip outlet slot. From there, the branched plastic material exits as transverse within the extruded tube web, which forms the partition wall after the expansion of the tube in the thereby formed container. On both sides next to the exit slot, d. H. On both sides of the exiting from the exit slot plastic sheet, in the end face of the core tip preferably each have an outlet opening for supporting air, which are connected via branch lines, which are formed in the male thread having pins, with a central air duct.

The air supplied from the air duct via the outlet openings is provided as supporting air, which only prevents the collapse of the extruded tube and its sticking to the partition wall forming the web. The expansion of the container in the blow mold is carried out in an additional step by means of a blowing and filling mandrel, which has in an analogous arrangement to the outlet openings of the core tip blowing openings for the supply aufweiender blast air. These blowing openings can then also serve as filling openings for the supply of the filling material to the container chambers.

As mentioned above, the shape of the container neck of the container produced by the process according to the invention is carried out by means of upper movable welding jaws on the relevant blow mold. By the upper welding jaws any closure training may be in the way during the shaping of the container neck, as is well known in the art for example according to the Einkammerbehältern bottelpack ^® system of the company Rommelag. For example, a rotary toggle closure can be formed on the neck of the container. Here, the welding operation is carried out so that both chambers are closed by a twisting knob, which is separable at a separating point designed as a predetermined breaking point by being rotated by means of its molded-on handle.

After retraction of the mandrel and insertion of a Fülldornes, each having a filling opening for each separated by the partition container chamber, both chambers can now be filled while the container is still within the blow mold.

After filling, the Fülldorn is withdrawn, and the upper welding jaws are moved together to perform on the container neck another welding process in which the container neck is finally formed and simultaneously closed.

After filling the container and retracting the filling mandrel, inserts may be inserted into the container neck, if desired, prior to hermetically sealing the container. It may be further active substance in solid form (for example an enzyme tablet) or non-functional "gimmicks" or other foreign part, which can be inserted by means of vacuum gripper before the welding jaws are moved together to weld the insert and at the same time a hermetic seal to build.

The inventive method is not limited in terms of the size of the multiblock blister pack and the individual hollow volume. Preferred processes according to the invention are characterized in that the filling volume of a filled hollow body is 1 to 1000 ml, preferably 2 to 500 ml, particularly preferably 5 to 250 ml, more preferably 10 to 100 ml and in particular 15 to 50 ml.

Also with regard to the number of hollow volumes to be combined into a multiblock blister pack, the method according to the invention is not limited. Preference is given here to processes in which a filled container is formed from a series of 2 to 100, preferably from 2 to 50, particularly preferably from 3 to 20 and in particular from 4 to 12, filled hollow volumes connected to one another via webs.

The release of the hollow bodies produced in the process according to the invention is carried out by disintegration or dissolution of the container wall under conditions of use. It must not be necessary that the entire container dissolves before release occurs. According to the invention, a faster release can be achieved by providing the container wall with special "predetermined breaking points" which quickly disintegrate or dissolve under conditions of use and thus lead to an early release of the ingredients. Here erfinungsgemäße procedures are preferred, in which the water-soluble, blow-molded hollow body in the region of the filled hollow volume have a region of lesser wall thickness, which is preferably mechanically protected by recess. The areas of lesser wall thickness in this case are 0.1 to 0.9 times, preferably 0.2 to 0.85 times, particularly preferably 0.3 to 0.8 times and in particular 0.5 - Up to 0.75 times the wall thickness of the hollow volumes.

The shape of the containers, d. H. both the Multiblockblisters and the individual hollow volume can be chosen arbitrarily. Preferred methods are characterized in that the filled hollow volumes are rotationally symmetrical to their longest axis and preferably to the normal formed on the Quetschfläche. This preferred form preferably has a length: diameter ratio of 1.5: 1 to 50: 1 for the single void volume, with ratios of 4: 1 to 10: 1 being preferred. The connecting webs are preferably arranged along the long hollow-volume sides in such forms.

It may also be preferred that the filled hollow volumes to the normal to the squish surface are not formed Rotatiossymmetrisch. This can be achieved, for example, by the choice of a blow mold whose depth is more than 0.5 times the pitch width. When the extruded tube is now blown between two such molds, a hollow volume is created which has a width (expansion in the direction of the squish surface, perpendicular to the extrusion direction of the original tube) corresponding to the pitch width of the blow mold but a depth (extension in the direction of the normal on the squish surface and perpendicular to the extrusion direction of the original tube), which is a multiple of the pitch width. Such ovalized hollow bodies may be preferred, wherein in particular width: depth ratios of 1: 1.1 to 1: 3, preferably from 1: 1.2 to 1: 2.5 and in particular from 1: 1.3 to 1: 2 , are preferred.

Preferred processes are also characterized in that the filled hollow volumes have a length (along the extrusion direction of the original tube) of from 30 to 120 mm, preferably from 40 to 100 mm and in particular from 45 to 70 mm.

Between the individual connecting webs, the filled hollow volumes in preferred processes have a width (in the direction of the squish surface, perpendicular to the extrusion direction of the original tube) of 10 to 70 mm, preferably 15 to 60 mm and in particular 20 to 40 mm.

Another suitable method for forming a hollow body is the thermoforming process. In a preferred embodiment, the formation of the hollow body is carried out by thermoforming a sheet material based on a water-soluble polymeric thermoplastic.

The formation of the hollow body takes place by equipping a packaging machine with a roll of film material which is pulled through a heating zone (contact, heat or heating by irradiation) and a molding station equipped with cavities is passed to be deep-drawn there , The water-soluble film material is clamped in the forming station where it is pressed into the cavities, wherein the layer thickness decreases in proportion to the increase of the Obefläche. A characteristic unit for the molding process is the so-called deep drawing ratio H: D, which defines the relationship between the height of the molded article H and its diameter D. The thermoforming ratio is material-dependent and also limited by the desired minimum thickness of the packaging. Immediately after the thermoforming process, the deep-drawn containers are filled with a detergent or cleaning agent and sealed with a film liquid-tight.

In principle, this method can be carried out by a variety of different techniques. The industrially most important method is to form a heated preform by using vacuum or compressed air, as well as mechanical stretching.

The shaping is preferably carried out in the rubber-elastic temperature range, particularly preferably in a temperature range between incipient softening and the melting range. By deep drawing, the introduction of a frozen orientation should be achieved as far as possible. Depending on material and temperature, geometric thermoforming ratios of several hundred percent can be achieved by thermoforming. The preferred materials for such a process include the below-mentioned water-soluble thermoplastic polymers, and particularly preferred are films in the form of laminates having preferably 2 to 5 layers. Laminates have the additional advantage of combining the economically preferred properties of several polymers in a film. However, two or more superimposed films can be simultaneously formed by the thermoforming process into a hollow body.

Thermoforming is a stretching operation that is usually practiced in a continuous process. The object to be manufactured is fastened at its corners and the enlargement of the geometry surface is accompanied by the reduction of the wall thickness. Two types of industrial thermoforming machines are available on the market: 1. Single-station machines and 2. Multi-station machines.

With single-station machines, the heating step and the forming step take place in the same station. Usually, the heating system is transported to the article. Occasionally, however, the attached preform is also transported to the heating zone. With multi-station machines, the heating and forming process takes place at different stations.

Heating is the first step in all thermoforming techniques and is also extremely important for the final quality of forming. The method involves heating the film material of from its initial temperature to its molding temperature. Since the film thicknesses can vary over a wide range, several preheating methods, such as convection heating, contact heating and / or heating by infrared radiation have become established.

In all techniques, the heating can be either one-sided or two-sided. The heating with infrared radiation is advantageous because the energy input can be made directly on the material, so that a high thermal energy density can be registered in the polymer material, wherein the time of heating is reduced, without causing thermal damage to the polymer surface.

In all thermoforming processes, the heated preform is rapidly biaxially drawn. This process usually takes place within a short time interval, for example below 0.5 seconds, and may be considered as isothermal as long as the polymer material is being annealed without contact with the mold wall). Upon contact with the walls of the cavity into which the polymeric material is drawn, the polymeric material immediately cools. Mechanical stretching mechanisms, compressed air and vacuum are used to carry out the stretching process.

In a preferred embodiment, the formation of the hollow body takes place by deep drawing of a foil material into a cavity, preferably by additionally applying a vacuum out of openings of the cavity.

In a preferred embodiment, one of the sides of the polymer material is cooled by contact of the polymeric material with the cavity surface, whereby the other surface can be cooled by convection. Convective cooling is achieved by air and its free convection or by the use of fans. To enhance the cooling effect, cooled air or moisture can also be used depending on the process.

The major advantages of the thermoforming process compared to alternative fabrication techniques are the low cost, the short process times and, if multi-cavity molds are used, the high throughput rates.

By stretching or drawing the water-soluble thermoplastic, the polymer chains are more oriented. In order to achieve the desired shrinkage effect according to the invention, it is advantageous, as already described in the blow molding process, to freeze the orientation, for example by an exogenously induced temperature jump.

It has been found that stretched, preferably blown, films are shrinkable. Preferred in the context of the present invention is therefore the liquid-tight sealing of the hollow body formed by the thermoforming process and subsequently filled with a stretched, preferably blown, film. By using a stretched film for closing the thermoformed hollow body is achieved that the closure film (cover sheet), namely the stretched film, also contributes to the final shrinkage of the hollow body. The sealing preferably takes place as a heat seal, by means of a heat-sealing plate, the cover sheet with the deep-drawn bottom sheet along the cavity bounding flange by the action of heat, preferably additionally by the action of pressure, is welded. Of particular advantage in this type of seal are the continuous peripheral sealing seams which, in comparison to tubular bags with additional vertical sealing seams, have no overlapping sealing area, that is to say no area where sealing seams intersect. Preferably, the cavities have no acute angles or sharp edges, particularly preferred are round, in particular hemispherical cavities or those having rounded corner regions. Advantageously, the rounded corner regions and / or flange areas are provided with heat and pressure-resistant deformable rubber materials, for example made of silicone polymers, in order to avoid any damage to the film or the sealing seam which may occur due to rough surfaces or edges and points. The cavities are in preferred embodiments not individually, but as a mold nests, that is as a mold with a plurality of cavities, for example as a plate, in which several cavities arranged in rows and rows. In a particularly preferred embodiment, the cavities are offset or in the form of hexagons, particularly preferably with rounded corners, in order to keep the film residues occurring when the individual filled and sealed hollow bodies are cut out as small as possible.

In one embodiment of the invention, the hollow bodies formed by the thermoforming process are in two or more pieces. Thus, for example, entire mold nests having a plurality of hollow bodies, which are linked to one another via film webs, can be provided. In a preferred embodiment the contiguous hollow body are at least partially filled with different agents, so that the consumer depending on the needs and purpose of a filled hollow body break out of the dressing or can dissolve out. The different means containing hollow body, for example, by a different color or by different states of matter of the means, such as powdery and liquid, the consumer be identified.

In a particularly preferred embodiment of the present invention, the hollow bodies have two or more compartments. In this case, for example, two prefilled and sealed hollow bodies produced by the thermoforming method can be sealed to one another via their respective cover sheets, as can be seen, for example, in US Pat WO 01/03 676 A1 is described. As a result, capsules can be obtained which have two thermoformed halves (compartments). The advantage of such two- or multi-compartment systems is not only the ability to separate each other interfering active substances from each other, but also the fact that now the capsule consists of two shrinkable, since deep-drawn hollow bodies. In a further preferred embodiment, the production of two- or multi-compartment systems takes place in that an already formed, preferably thermoformed, filled and liquid-tight sealed hollow body for liquid-tight sealing of another thermoformed and filled with a means hollow body is used. Preferably, the cover sheet of an already filled and sealed hollow body for liquid-tight sealing of the next filled thermoformed hollow body is used. The advantage of this technique for producing Mehrkompartimert systems is the low cost of materials and the presence of large quantities of stretched or deep-drawn films, which are of great importance for the shrinking step.

A further preferred method for producing completely or partially water-soluble filled hollow body is the rotary-Die method, as described for example in the WO 97/35 537 A1 for the preparation of water-soluble capsules is described.

In a preferred embodiment of the invention, the formation of the hollow body takes place in the course of a rotary die process.

The preparation of the filled hollow body takes place in that a liquid detergent or cleaning agent is injected via a metering device by means of a filling wedge locally between two bands of water-soluble polymeric thermoplastic, which are located on two mutually parallel rotatably mounted forming rollers, the hollow surfaces on their lateral surfaces have, whose shape corresponds to half a hollow body to be produced. The sealing takes place by pressure contact of the two foil strips. In a preferred embodiment, to improve the seal, at least one of the water-soluble film strips is dissolved with a solvent prior to the molding process. Further preferred is the heat sealing of the two hollow body halves. For this purpose, the two forming rollers can advantageously serve as electrodes for the dielectric fusing of the films together. To facilitate the shaping process by injecting the liquid agent, a vacuum can advantageously be applied to the cavities. As a result, the injection pressure of the liquid can be reduced and thus the risk of contamination of the polymer material with liquid contents at the sealing positions is reduced. Advantageously, the molding rolls in the region of the forming roll webs on roughening. The roughening of the forming roll webs increases the static friction for the film strips from which the portions are produced.

About the shape of the molds in the mold rolls hollow body can be produced with almost any geometry. A preferred default is that they have a mirror plane. Geometries such as sphere, eggs, cubes, figures are preferred in the context of this invention.

About the metering a precisely metered amount of the agent is injected into the forming hollow body. It is particularly advantageous if the injection shock is followed by a return stroke of the metering device. It is thus a dripping or stringing of the agent, which in turn can lead to contamination of the water-soluble film in the sealing position, avoided. It is of particular advantage if the film strips are heated before their stretching operation by injecting the liquid or by applying the vacuum, as already mentioned in the thermoforming method and blow molding method, in order to generate stresses within the thermoplastic which try to relax in the final shrinking step and therefore give the hollow body the particular flexibility and elasticity.

In a particularly preferred embodiment, two-compartment hollow bodies filled by means of the rotary-die process are produced, as described explicitly in US Pat WO 00/28 976 A1 is described.

The filled hollow body can be punched or cut out of the film strips or be presented in several pieces. In the case of multi-part dosage forms, the connecting webs, as well as in the produced by the thermoforming process or blow molding multi-piece dosage forms, advantageously provided with perforations, so that the consumer is a separation of individual hollow body is facilitated.

It has been found in the aforementioned method, in particular in the blow molding process, that the conditions for the shrinkage of the means enveloping the hollow body material are particularly favorable if the formation of the hollow body or the blow molding of the preform to a hollow body under the enveloping hollow body material mechanically stretching conditions, preferably in more than one preferred direction occurs. This process is stopped in a defined way and indeed by means of an exogenously induced in the polymeric thermoplastic temperature jump, whereby it is cooled in the range of his, preferably below its softening temperature.

Due to the rapid cooling of the water-soluble polymeric thermoplastic is achieved that the polymeric sheet formed by the mechanically stretching conditions stresses in the thermoplastic "frozen", that is, remain fixed. The higher the extent of the frozen tension remaining in the thermoplastic sheet, the higher the shrinkability of the thermoplastic in the shrinking step essential to the invention.

The temperature difference (delta T) that the thermoplastic undergoes as a result of the temperature jump decides to what extent the voltages impressed on the polymer are retained.

In one embodiment of the present invention, the exogenously induced temperature jump is achieved by filling the hollow body with a detergent or cleaning agent. The agent is filled at a temperature below 15 ° C.

To achieve bulging, aesthetically appealing-looking portions, it has proved to be particularly advantageous in the context of the present invention, when a cooled gas is added to the hollow body in the course of the inventive method before the liquid-tight sealing of the hollow body. Gases in the context of the present invention are all substances which have a boiling point below 25 ° C. at an air pressure of 1 bar. When added to the hollow body, the cooled gas advantageously has a temperature below 20 ° C., preferably below 10 ° C., more preferably below 0 ° C., in particular below -10 ° C., particularly preferably below -20 ° C. , advantageously below -60 ° C, for example -70 ° C, -78 ° C, -100 ° C or about -190 ° C.

The advantage of cooled gases lies in their occurring during heating and constant pressure strong increase in volume, resulting in a "pumping" of the filled hollow body. This volume expansion is particularly drastic when the gaseous substances at 25 ° C. are added to the hollow bodies as solids or liquids, which is particularly preferred in the context of the invention. Due to the ease of handling and the economically easy access liquefied gases such as liquid nitrogen, butane, propane, argon have proven. However, the use of solid carbon dioxide, which is also known as dry ice, has proven to be particularly advantageous. It can be easily dosed in the form of pellets with the other ingredients in the molded hollow body or can also be introduced into the hollow body after filling, followed by the liquid-tight closing of the hollow body as a subsequent step. By warming the gases to room temperature, these expand and form plump, elastic, liquid-tight sealed hollow body.

The enveloping material of water-soluble thermoplastics surrounding the filled hollow body advantageously forms a barrier layer for the gases to be used. In the context of this invention, the listed polyvinyl alcohols have proven particularly suitable, which has an excellent barrier layer for a large number of gases, in particular for carbon dioxide.

Particularly advantageous is the use of gases that can be easily detected so-called test gases. The escape of these gases from the filled hollow body is, due to the build-up of internal pressure during heating, is particularly quickly detected quickly if there is a defect in the envelope body material. The detection can take place, for example, in a vacuum chamber in addition Gas-specific sensors are mounted. For leak detection, the closed and filled hollow bodies may be passed, for example, through a tunnel with a slight vacuum, where highly sensitive detectors indicate traces of the indicator gas. Depending on the detector, in principle, all gases or gas mixtures are available as test gases, but preferably the gases selected from the group noble gases such as helium, neon, xenon or argon, and nitrogen, carbon dioxide, carbon monoxide, gaseous hydrocarbons such as butane, propane, ethane , Methane, fluorocarbons, as well as any mixtures of the aforementioned gases. Particularly preferred are mixtures of carbon dioxide with carbon monoxide and / or hydrogen and / or noble gases. Preference is furthermore given to gas mixtures of nitrogen with hydrogen, preferably with a molar mixing ratio of nitrogen: hydrogen of greater than 1: 1, preferably greater than 5: 1, more preferably greater than 8: 1 and in particular 95: 5. Hydrogen-containing test gas mixtures are preferred because of their excellent detectability. Hydrogen-containing test gas detectors are sold, for example, by the company Sensitor Technologies, Mühlheim, Germany under the name H 2000.

Following the liquid-tight closure of the preferably blow-molded hollow body, the method according to the invention can be followed by an additional detection step for leaks. In particular, in the industrial application of the method according to the invention with a high product throughput, it is advantageous to check the filled blow-molded hollow body directly after its production for leaks to the contamination of other filled hollow bodies, optionally in the same outer packaging as the damaged filled hollow body to avoid and ensure quality assurance. Although a purely visual assessment of the hollow body produced is possible in principle, but offers little economic benefits, especially in industrial production with high product throughput, as very labor-intensive. Electronic detection systems for leaks have proven to be particularly advantageous. A particularly suitable detection system for the determination of leaks in, in particular with liquids, filled, preferably blow-molded hollow bodies is the high-voltage leak detector (HVLD detector, high-voltage leak detector) marketed by the company Rommelag. The detection method is based on the electrical conductivity of the filling material, which is enveloped by a non-conductive or only slightly conductive polymer. If there is a leak, the discharge current flows through the leakage opening into the hollow body and the detection of this current leads to the ejection of the damaged, filled hollow body. Suitable detectors are, for example, the HVLD 923 and HVLD 924 ex Rommelag.

In a preferred embodiment, in particular by means of blow molding, at least one hollow body region and / or compartment region with at least one outer surface of between 0.01 mm ² and 10 cm ² can be produced, the wall thickness of this surface increasing faster in an aqueous solution to ensure it is less than the wall thickness of the adjacent area. Without being limited to specific wall thicknesses, the wall thicknesses of these outer surface areas are preferably below 80 μm, more preferably below 60 μm, even more preferably below 50 μm, particularly preferably in the range from 10 to 30 μm.

Advantageously, the regions of lesser wall thickness are produced by impressing information such as calibration marks, application instructions, danger symbols, marks, weight, filling quantity, expiration date, images, particularly preferably by imprinting a logo.

The wall thickness of the hollow body and / or the compartments, which is preferably formed by blow molding, should be designed so that the agent contained in the hollow body and / or in the compartments, in particular detergents and / or cleaning agents, within the aqueous application liquor within ≦ 5 min, preferably within ≦ 3 min, preferably within ≦ 1 min, partially or completely liberated.

To determine the release time, the hollow bodies with and without compartment in 10 liters of agitated water, stirrer speed ≥ 60 U / min, with the water at 90 ° C, preferably at 60 ° C, more preferably at 40 ° C, even more preferred is heated to 30 ° C and particularly preferably to 20 ° C. More preferably, the release time is determined directly in the aqueous application liquor of at least one commercially available washing and / or dishwashing machine.

The water-soluble thermoplastic used in formation, preferably by blow molding, of the hollow body and / or the compartments is preferably selected from the group comprising polyvinyl alcohol (PVA), acetalized polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, starch and derivatives of the abovementioned substances, in particular derivatives the polyvinyl alcohol (PVA), acetalated polyvinyl alcohol, cellulose and / or mixtures of the aforementioned polymers, wherein polyvinyl alcohol and partially hydrolyzed polyvinyl acetate is particularly preferred.

The polyvinyl alcohols described above are commercially available, for example under the trade name Mowiol ^® ex Clariant (risen in the Kuraray Specialties Europe KSE). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88, Mowiol ^® 8-88 and L648, L734, Mowitlex LPTC 221 ex Clariant / KSE as well as the compounds of the firm Texas Polymers such as Vinex 2034.

Further polyvinyl alcohols which are particularly suitable as material for the hollow bodies are shown in the following table: description Degree of hydrolysis [%] Molecular weight [kDa] Melting point [° C] Airvol ^® 205 88 15-27 230 Vinex ^® 2019 88 15-27 170 Vinex ^® 2144 88 44-65 205 Vinex ^® 1025 99 15-27 170 Vinex ^® 2025 88 25-45 192 Gohsefimer ^® 5407 30-28 23,600 100 Gohsefimer ^® LL02 41-51 17,700 100

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

The water-soluble thermoplastic used in the formation, preferably by blow-molding, of the hollow body and / or the compartments can additionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and / or mixtures the above polymers.

It is preferred if the water-soluble thermoplastic used to form the hollow body and / or the compartments comprises a polyvinyl acetate whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

More preferably, the water-soluble thermoplastic used to form, preferably by blow-molding, the hollow body and / or the compartments comprises a polyvinyl alcohol whose average molecular weight is in the range of 10,000 to 100,000 gmol ^-1 , preferably 11,000 to 90,000 gmol ^-1 preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 .

Preferred in the context of the present invention are polyvinyl alcohols which have a narrow molecular weight distribution, particularly preferably with a distribution ratio of d10: d50> 0.66.

In a further embodiment, the material used to form the hollow body comprises the water-soluble polymeric thermoplastics in amounts of at least 50% by weight, preferably at least 70% by weight, more preferably at least 80% by weight and in particular at least 90 Wt .-%, each based on the weight of the entire hollow body material.

To facilitate their preparation, in particular with regard to their production by blow molding, the hollow body plasticizing aids, ie plasticizers may contain. This may be advantageous in particular when polyvinyl alcohol or partially hydrolyzed polyvinyl acetate has been selected as the material for the hollow bodies. Glycerol, triethanolamine, ethylene glycol, propylene glycol, diethylene or dipropylene glycol, diethanolamine and methyldiethylamine have proved particularly suitable as plasticizing auxiliaries. However, depending on the amount and type of plasticizers, the surfaces of the processed water-soluble polymeric thermoplastics can provide the consumer with a haptic impression of "stickiness". Because of their excellent plasticizing. Effect and the reduced stickiness of the surfaces of the hollow bodies produced according to the invention contain the water-soluble, polymeric thermoplastics in a particularly preferred embodiment as plasticizers mono-, di- or triglycerides, preferably mono-, di- or triglycerides which are at least C ₆ - C ₃₀ fatty acid residue are linked, particularly preferably those which at least linked to a C ₁₂ -C ₂₄ fatty acid radical, in particular glycerol monostearate or glycerol monooleate.

It is advantageous if the water-soluble polymeric thermoplastic plasticizer in amounts of at least> 0 wt .-%, preferably of at least> 1 wt .-%, more preferably of 10 wt .-%, particularly preferably of ≥ 20 wt .-% and in particular of ≥ 30 wt .-%, each based on the weight of the entire hollow body material contains.

The flexible, preferably elastic, water-soluble hollow body may have flange parts and optionally connected by positive engagement and / or material closure, preferably by welding with at least one other mold and / or closed.

It is preferred if, in particular in the case of the hollow bodies produced by the blow molding process, at least one wall of the hollow body and / or at least one wall of at least one compartment is formed in a multi-layered manner.

It is also preferred if at least two layers of the wall of the hollow body and / or at least two layers of at least one compartment are configured, in particular in the case of the hollow bodies produced by the blow molding process, so that a gap is formed between the layers.

In a particularly preferred embodiment, the invention leads to a detergent or cleaning agent portion comprising a flexible, preferably elastic, hollow body of at least one washing active, cleaning active or care active preparation wholly or partially surrounding enclosure of a disintegratable under washing or cleaning conditions, preferably blow-molded material comprising at least one compartment, wherein the compartment (s) contains one or more detergent-active, cleaning-active or care-active preparations).

In the mentioned embodiment, the one hollow body comprises at least one compartment, ie a chamber, in its interior. Such a chamber or such a compartment is usually limited by walls (in only one compartment, these are the walls of the hollow body) limited space. Within the walls of the flexible, preferably elastic, hollow body produced according to the invention, however, several rooms may be located. These can be formed either by separating individual spaces from one another by walls which in the context of the present invention are referred to as "compartmentalizing devices" and spatially separating the same or different washing-active, care-active and / or cleaning-active components or preparations, or that various washing-active, care-active or cleaning-active components or compositions are directly adjacent to one another but do not mix with one another. In such a case, the interfaces (phase interfaces) of the contiguous components or compositions are virtually the compartmentation devices. The chamber or compartment is wholly or partially, advantageously completely, surrounded by the enclosure of a disintegratable under washing or cleaning conditions, preferably blow-molded, material which forms the wall of the flexible, preferably elastic, hollow body. In the compartment or in the chamber, one or more detergent-active, cleaning-active or care-active preparation (s) is / are contained. In most embodiments of the invention, a compartment advantageously contains a plurality of detergent-active, detergent-active or protein-active preparations; However, the case of the presence of only one such preparation in a compartment or in a chamber is also conceivable.

In a particularly preferred embodiment of the invention, the hollow body contains in its interior a plurality of compartments or chambers each containing one or more detergent-active, cleaning-active or care-active preparation (s). Examples of these are cuboidal or trochoidal, in particular spherical, flexible, preferably elastic, hollow bodies which have two, three or four or even more compartments, each containing one or more detergent-active, cleaning-active or care-active preparation (s). A great advantage of this embodiment of the invention is that the various detergent-active, cleaning-active or care-active preparations can be distributed to the compartments as best for the specific requirements. Thus, components that adversely affect each other in their effectiveness (for example, enzymes, alkali, bleach, etc.) or otherwise - for example, due to the state of aggregation - would mix together, such as solid and liquid components, are spatially separated. On the other hand, it is possible to use components that optimally at different times of the washing or cleaning process in the each fleet should be released, spatially separated from each other and give each at the optimum time in the fleet.

The size and shape of the individual compartments within a flexible, preferably elastic, hollow body is not critical and can be largely tailored to the needs of the individual case. Thus, for certain detergent-active, cleaning-active or tell-tale preparations or mixtures thereof, which are present in larger quantities, larger compartments can be provided than for preparations which are present only in small quantities. In other embodiments of the invention which can be used with advantage, mixtures of certain preparations, which are provided at the beginning of the washing or cleaning cycle and are present in specific amounts, can be spatially separated from other components or components required in other quantities and arranged in compartments of a different size.

In a particularly preferred embodiment of a flexible, preferably elastic, hollow body with at least one, preferably a plurality of compartment (s) containing the detergent or cleaning agent portion, two or more, one or more washing active, cleaning active or care-active preparation (s) containing Includes compartments of the hollow body, which are arranged enclosing each other. The compartments with the detergent-active, cleaning-active and / or care-active preparation (s) are thus not arranged side by side or above / below each other in the hollow body, but enclosing each other, for example more or less concentric ("onion model") or more or less coaxial ("Multi-layered rod model") or such that the innermost compartment is completely surrounded by the next outer one, possibly completely again from the following, etc. In such a case, the detergent-active, cleaning-active or care-active substances can be distributed among the compartments be that the first required in the washing or cleaning process components are contained in the outermost compartment, which is first exposed to the entry of water or liquor, while a later required component (s) in (one) on inside compartment (s) is / are arranged and before the Z Ingress of water is protected by the further outward compartments. In the context of this embodiment, it is not necessary that the inner compartments are completely enclosed by the outer; a partial enclosure is also within the scope of the present invention.

According to a further preferred embodiment, the invention leads to a detergent or cleaner portion containing flexible, preferably elastic, hollow body, wherein the wall of the hollow body and / or the compartments comprises at least one detergent active, cleaning active and / or caring active preparation under washing - or cleaning conditions is disintegratable. It is preferred if the material used to produce the hollow body and / or the compartments and / or the preform comprising at least one water-soluble thermoplastic already comprises a washing-active, cleaning-active and / or care-active preparation which is disintegratable under washing or cleaning conditions.

The size, shape and arrangements of the compartment (s) and the at least one detergent-active, cleaning-active or care-active preparation may be designed in the same way as in the embodiments described above, ie. H. it can be arranged in a flexible, preferably elastic, hollow body one or more compartments of any shape and size, each with one or more washing active, cleaning active or care-active preparation (s). In the present case, however, several such flexible, preferably elastic, hollow body are present together.

It corresponds to a preferred embodiment, when the two or more flexible, preferably elastic, hollow body made of several different materials or (possibly similar) materials with different properties that are - disintegrated under washing or cleaning conditions - with particular advantage. Such materials of the high body (s) include, but are not limited to, one or more water-soluble polymer (s), preferably one or more of polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, (optionally acetalized), Gelatin, cellulose, and their derivatives and mixtures thereof, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).

In a further, likewise preferred embodiment, it is advantageous in accordance with the invention if the flexible element (s), preferably elastic (s), hollow body comprises one or more materials from the group of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes , Polyesters and polyethers and mixtures thereof.

• – Mischungen aus 50 bis 100% Polyvinylalkohol oder Poly(vinylalkohol – co – vinylacetat) mit Molekulargewichten im Bereich von 10.000 bis 200.000 g/mol und Acetatgehalten von 0 bis 30 Mol-%; diese können Verarbeitungszusätze wie Weichmacher (Glycerin, Sorbit, Wasser, PEG usw.), Gleitmittel (Stearinsäure und andere Mono-, Di- und Tricarbonsäuren), sogenannte ”Slipmittel” (z. B. ”Aerosil”), organische und anorganische Pigmente, Salze, Blasformmittel (Citronensäure-Natriumbicarbonat-Mischungen) enthalten;
• – Acrylsäure-haltige Polymere, wie z. B. Copolymere, Terpolymere oder Tetrapolymere, die mindestens 20% Acrylsäure enthalten und ein Molekulargewicht von 5.000 bis 500.000 g/mol besitzen; als Comonomere sind besonders bevorzugt Acrylsäureester wie Ethylacrylat, Methylacrylat, Hydroxy-ethylacrylat, Ethylhexylacrylat, Butylacrylat, und Salze der Acrylsäure wie Natriumacrylat, Methacrylsäure und deren Salze und deren Ester wie Methylmethacrylat, Ethylmethacrylat, Trimethylammoniummethylmethacrylatchlorid (TMAEMC), Methacrylat-amidopropyl-trimethylammoniumchlorid (MAPTAC). Weitere Monomere wie Acrylamid, Styrol, Vinylacetat, Maleinsäureanhydrid, Vinylpyrrolidon sind ebenfalls mit Vorteil verwendbar;
• – Polyalkylenoxide, bevorzugt Polyethylenoxide mit Molekulargewichten von 600 bis 100.000 g/mol und deren durch Pfropfcopolymerisation mit Manomeren wie Vinylacetat, Acrylsäure und deren Salzen und deren Estern, Methacrylsäure und deren Salzen und deren Estern, Acrylamid, Styrol, Styrolsulfonat und Vinylpyrrolidon modifizierte Derivate (Beispiel: Poly-(ethylenglykol – graft – vinylacetat). Der Polyglykol-Anteil sollte 5 bis 100 Gew.-% betragen, der Pfropfanteil sollte 0 bis 95 Gew.-% betragen; letzterer kann aus einem oder aus mehreren Monomeren bestehen. Besonders bevorzugt ist ein Pfropfanteil von 5 bis 70 Gew.-%; dabei sinkt die Wasserlöslichkeit mit dem Pfropfanteil;
• – Polyvinylpyrrolidon (PVP) mit einem Molekulargewicht von 2.500 bis 750.000 g/mol;
• – Polyacrylamid mit einem Molekulargewicht von 5.000 bis 5.000.000 g/mol;
• – Polyethyloxazolin und Polymethyloxazolin mit einem Molekulargewicht von 5.000 bis 100.000 g/mol;
• – Polystyrolsulfonate und deren Copolymere mit Comonomeren wie Ethyl-(meth-)acrylat, Methyl(meth-)acrylat, Hydroxyethyl(meth-)acrylat, Ethylhexyl(meth-)acrylat, Butyl(meth-)acrylat und den Salzen der (Meth-)Acrylsäure wie Natrium-(meth-)acrylat, Acrylamid, Styrol, Vinylacetat, Maleinsäureanhydrid, Vinylpyrrolidon; der Comonomer-Gehalt sollte 0 bis 80 Mol-% betragen, und das Molekulargewicht sollte im Bereich von 5.000 bis 500.000 g/mol liegen;
• – Polyurethane, insbesondere die Umsetzungsprodukte von Diisocyanaten (z. B. TMXDI) mit Polyalkylenglykolen, insbesondere Polyethylenglykolen des Molekulargewichts 200 bis 35.000, oder mit anderen difunktionellen Alkoholen zu Produkten mit Molekulargewichten von 2.000 bis 100.000 g/mol;
• – Polyester mit Molekulargewichten von 4.000 bis 100.000 g/mol, basierend auf Dicarbonsäuren (z. B. Terephthalsäure, Isophthalsäure, Phthalsäure, Sulfoisophthalsäure, Oxalsäure, Bernsteinsäure, Sulfobernsteinsäure, Glutarsäure, Adipinsäure, Sebacinsäure usw.) und Diolen (z. B. Polyethylenglykole, beispielsweise mit Molekulargewichten von 200 bis 35.000 g/mol);
• – Celluloseether/ester, z. B. Celluloseacetate, Cellulosebutyrate, Methylcellulose, Hydroxypropylcellulose, Hydroxyethylcellulose, Methylhydroxypropylcellulose usw.;
• – Polyvinylmethylether mit Molekulargewichten von 5.000 bis 500.000 g/mol;
• – Pfropfpolymere, die erhältlich sind durch radikalische Polymerisation von Vinylestern von aliphatischen C1-C24-Carbonsäuren in Gegenwart von Polyethern eines mittleren Molekulargewichts von mindestens 300 (Zahlenmittel), beispielsweise durch die radikalische Polymerisation von Vinylacetat in Gegenwart von Polyethylenglycolen mit einem Molekulargewicht von 500 bis 100000, vorzugsweise einem Molekulargewicht von 1000 bis 50000, und Hydrolyse von 20 bis 100 Mol-% der Vinylacetateinheiten der Pfropfpolymere, wie in der WO 02/31096 A1 offenbart.

With particular advantage, one or more materials may be cited from the following illustrative but non-limiting list:

• Mixtures of 50 to 100% polyvinyl alcohol or poly (vinyl alcohol-co-vinyl acetate) having molecular weights in the range of 10,000 to 200,000 g / mol and acetate contents of 0 to 30 mol%; these may include processing additives such as plasticizers (glycerine, sorbitol, water, PEG, etc.), lubricants (stearic acid and other mono-, di- and tricarboxylic acids), so-called "slip agents" (eg "Aerosil"), organic and inorganic pigments, Salts, blowing agents (citric acid-sodium bicarbonate mixtures);
• - Acrylic acid-containing polymers, such as. Copolymers, terpolymers or tetrapolymers containing at least 20% of acrylic acid and having a molecular weight of from 5,000 to 500,000 g / mol; Particularly preferred comonomers are acrylic esters such as ethyl acrylate, methyl acrylate, hydroxyethyl acrylate, ethylhexyl acrylate, butyl acrylate, and salts of acrylic acid such as sodium acrylate, methacrylic acid and their salts and their esters such as methyl methacrylate, ethyl methacrylate, trimethylammonium methylmethacrylate chloride (TMAEMC), methacrylate-amidopropyltrimethylammonium chloride (MAPTAC ). Other monomers such as acrylamide, styrene, vinyl acetate, maleic anhydride, vinyl pyrrolidone are also useful with advantage;
• Polyalkylene oxides, preferably polyethylene oxides having molecular weights of 600 to 100,000 g / mol and their derivatives by graft copolymerization with manomeres such as vinyl acetate, acrylic acid and their salts and their esters, methacrylic acid and its salts and their esters, acrylamide, styrene, styrene sulfonate and vinylpyrrolidone modified derivatives (Example The amount of polyglycol should be from 5 to 100% by weight, the amount of grafting should be from 0 to 95% by weight, the latter being composed of one or more monomers a graft content of 5 to 70 wt .-%, while the water solubility decreases with the grafting;
• Polyvinylpyrrolidone (PVP) having a molecular weight of 2,500 to 750,000 g / mol;
• Polyacrylamide having a molecular weight of 5,000 to 5,000,000 g / mol;
• Polyethyloxazoline and polymethyloxazoline having a molecular weight of 5,000 to 100,000 g / mol;
• Polystyrenesulfonates and their copolymers with comonomers such as ethyl (meth) acrylate, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, butyl (meth) acrylate and the salts of (meth) ) Acrylic acid such as sodium (meth) acrylate, acrylamide, styrene, vinyl acetate, maleic anhydride, vinylpyrrolidone; the comonomer content should be 0 to 80 mol%, and the molecular weight should be in the range of 5,000 to 500,000 g / mol;
• Polyurethanes, in particular the reaction products of diisocyanates (eg TMXDI) with polyalkylene glycols, in particular polyethylene glycols of molecular weight 200 to 35,000, or with other difunctional alcohols to give products having molecular weights of 2,000 to 100,000 g / mol;
• Polyesters having molecular weights of 4,000 to 100,000 g / mol, based on dicarboxylic acids (eg terephthalic acid, isophthalic acid, phthalic acid, sulfoisophthalic acid, oxalic acid, succinic acid, sulfosuccinic acid, glutaric acid, adipic acid, sebacic acid etc.) and diols (eg polyethylene glycols , for example, with molecular weights of 200 to 35,000 g / mol);
• - Cellulose ethers / esters, z. Cellulose acetates, cellulose butyrates, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, methyl hydroxypropyl cellulose, etc .;
• Polyvinyl methyl ether having molecular weights of 5,000 to 500,000 g / mol;
• Graft polymers obtainable by free-radical polymerization of vinyl esters of aliphatic C 1 -C 24 -carboxylic acids in the presence of polyethers of average molecular weight of at least 300 (number average), for example by the radical polymerization of vinyl acetate in the presence of polyethylene glycols having a molecular weight of 500 to 100,000 , preferably a molecular weight of 1000 to 50,000, and hydrolysis of 20 to 100 mole% of the vinyl acetate units of the graft polymers as described in U.S. Pat WO 02/31096 A1 disclosed.

In a further preferred embodiment of the invention, the two or more flexible, preferably elastic, hollow body may consist of two or more different materials, which may be selected for example from the materials listed above, but may also comprise other materials. With particular advantage, in the case of the presence of a plurality of flexible, preferably elastic, hollow bodies, the walls (= walls) of these hollow bodies may consist of two or more similar materials, for example materials of the same monomer building blocks, but materials with different properties. Examples include similar materials of different molecular weight (and thus different solubility), PVAL materials with different degree of acetalization (and thus different solubility or different solution temperature in water), materials with different amounts of grafted co-monomers o. Ä. Be.

It corresponds to a further preferred embodiment that, in the case in which a plurality of flexible, preferably elastic, hollow bodies are present, these flexible, preferably elastic, hollow bodies have a different geometric shape. This can be advantageous to different Dissolution behavior or different kinetics of the release of the contained in the / the compartment (s) of the hollow body detergent or cleaning agent portion lead.

Further preferred is an embodiment of the detergent or cleaner portions prepared according to the invention, in which the two or more flexible, preferably elastic, hollow bodies form a composite - particularly preferred, but not necessarily detachable. A composite of two or more flexible, preferably elastic, hollow bodies can be used with particular advantage if either detergent or detergent portions of different composition are to be metered (for example heavy-duty detergent and colored laundry detergent, in the latter example, bleaching components are not or not the bleach-containing hollow body could then be removed by the user if colored laundry is to be washed) or if, for example for small amounts of laundry or crockery, only a partial dose of the laundry detergent contained in flexible, preferably elastic, hollow bodies is present. Portion should be used. Particularly preferably, such a composite could be produced by gluing, fusing, welding or clamping the flexible, preferably elastic, hollow bodies; Mechanical clamping also allows easy release of the composite. In particularly preferred embodiments, such composite hollow bodies are again detachable from one another in an aqueous environment, for example by using a water-soluble adhesive; This could ensure that a composite used in the automatic washing or cleaning process is completely dissolved and removed from the machine with the washing, cleaning or rinsing liquor.

For the materials that make up the devices for compartmentalizing, the above information on the materials of the flexible, preferably elastic, hollow body apply accordingly. With regard to a reliable and simple method of production, in a preferred embodiment of the invention, the compartmentalizing devices within the flexible, preferably elastic, hollow bodies of the same materials as the hollow body itself. This allows the one-piece production in one process step and makes the manufacturing process particularly economical.

In principle, however, it is also possible to select the materials of the devices for compartmentalizing independently of the materials of the flexible, preferably elastic, hollow bodies. This has the advantage that special requirements in terms of properties, for example in the water solubility, the compartmenting facilities can be taken into account.

In a preferred embodiment of the invention, the compartmentation device (s) is one (or more) an activity reduction of at least one component of a detergent-active, cleaning-active or care-active preparation inhibiting device (s). Examples of these are all the cases in which components of washing-active, cleaning-active or care-active preparations are spatially separated taking into account a mutual impairment of their activity. The compartmentalizing devices should then have properties that meet these requirements, for example, be substantially impervious to water vapor to keep bleach free of moisture, or should be acid or alkali free to protect enzymes from premature decomposition. Such inhibition of activity reduction not only directly contributes to a better activity of the particular protected component, but also allows to reduce the amounts of such components, since an excess is no longer required in anticipation of the otherwise usual loss of activity.

In other particularly preferred embodiments, the compartmentation device (s) is / are a device (s) that determines the quality and / or quantity of release of components of a detergent-active, cleaning-active or caring-active preparation. In the cases where the compartmenting devices have such a function, either components of the detergent-active, cleaning-active or care-active preparations may advantageously be dispensed into the liquor at different times of the washing or cleaning process (qualitative control), or they may different quantities of certain (qualitatively identical) preparations are released into the fleet (quantitative control).

In the former case, a flexible, preferably elastic, hollow body, for example, several compartments whose walls have a different solubility (or temperature of dissolution) in water or in the liquor. The compartments contain (washing, cleaning) active components for the first, second and optionally further (washing, cleaning) courses, which have different compositions, and set them at different times or at different temperatures of the washing or cleaning process free.

In the second exemplary case, the flexible, preferably elastic, hollow bodies may have walls and compartmentalizing devices, for example only, in which materials are incorporated which dissolve at different temperatures or under different other boundary conditions. For example, in the compartment walls first small holes form, which allow only a weak mass transfer between individual compartments and the outside environment and thus deliver only small amounts of a washing active, cleaning active or care-active preparation in the fleet; under other, later adjustable conditions, the holes or pores are enlarged because in other conditions soluble wall components dissolve; Larger holes allow larger amounts of material to be exchanged between the interior of the compartment (s) and the outside environment (ie, the liquor) and thus adjust the desired higher concentrations of the detergent-active, cleaning-active or caring-active preparation in the liquor.

• – die Zeit, d. h. der Ablauf einer bestimmten Zeit, in der die Wände der flexiblen, vorzugsweise elastischen, Hohlkörper und/oder die Kompartimentierungs-Einrichtungen mit einem bestimmten Medium, beispielsweise mit einer wäßrigen Flotte, in Kontakt stehen, wobei eine zuverlässige Zeitsteuerung eine lineare Lösungskinetik voraussetzt;
• – die Temperatur, d. h. das Erreichen eines bestimmten Temperaturwertes im Verlauf des Temperaturprofils des Wasch- oder Reinigungsvorgangs; die Steuerung über die Temperatur stellt insbesondere bei Geschirrpflegemitteln wegen der mit jeder Stufe des Pflegevorgangs steigenden Temperatur eine zuverlässige und damit bevorzugte Ausführungsform dar;
• – der pH-Wert, d. h. die Einstellung eines bestimmten pH-Wertes im Verlauf eines Wasch-, Reinigungsvorgangs durch Komponenten der waschaktiven, reinigungsaktiven oder pflegeaktiven Zubereitung oder das Verlassen eines bestimmten pH-Wertes nach Zerfall einer den pH-Wert beeinflussenden oder bestimmenden Komponente;
• – die Ionenstärke;
• – die mechanische Stabilität, welche – in Abhängigkeit von der Zeit, von der Temperatur oder von anderen Parametern – ein die Desintegration bestimmender Faktor sein kann;
• – die Permeabilität für eine bestimmte – vornehmlich gasförmige oder flüssige – Komponente; und dergleichen.

Possible "switches" of the release of the components by the compatibilizers are, in particularly preferred embodiments, physicochemical parameters which effect the disintegration of the compartmentalizing devices and / or the walls of the flexible, preferably elastic, hollow bodies. Examples thereof, which should not be construed as limiting, are

• - The time, ie the passage of a certain time in which the walls of the flexible, preferably elastic, hollow body and / or the compartmentalization devices with a certain medium, for example, with an aqueous liquor in contact, with a reliable timing a linear Requires solution kinetics;
• - The temperature, ie the achievement of a certain temperature value in the course of the temperature profile of the washing or cleaning process; the control over the temperature is a reliable and therefore preferred embodiment, especially for tableware because of the rising with each stage of the care process temperature;
• The pH, ie the setting of a specific pH in the course of a washing, cleaning operation by components of the detergent-active, cleaning-active or care-active preparation or leaving a certain pH after decomposition of a component influencing or determining the pH;
• - the ionic strength;
• Mechanical stability, which may be a factor determining disintegration, depending on time, temperature or other parameters;
• The permeability for a particular component, mainly gaseous or liquid; and the same.

The aforementioned parameters are only examples that are not intended to limit the invention.

In a further preferred embodiment of the invention, the compartmentation device (s) is / are the activity of at least one component of a detergent-active, cleaning-active or care-active preparation-controlling device (s). This embodiment is particularly useful in cases where it is necessary that the release of one or more active ingredients a washing active, cleaning active or care-active preparation with a given kinetics in the washing, cleaning or rinsing liquor takes place. A particular example is a so-called "controlled release" release, which can be controlled according to the parameters given above on the properties of the wall of the flexible, preferably elastic, hollow body and / or the Kompartimentierungsseinrichtungen. In this way, a destructive effect of the liquor or alone of the water on the active substance can be reduced and the substance can be actively released into the liquor for a longer time.

It is a further preferred embodiment of the invention that one or more compartmentalizing device (s) contain a part or the total amount of at least one component of at least one detergent-active, cleaning-active or care-active preparation. This can be achieved with particular advantage by incorporating one or more component (s) of at least one detergent-active, cleaning-active or care-active preparation into the material of the compartmenting device. Examples of such substances have already been mentioned above in connection with the flexible, preferably elastic, hollow body-forming material and include (but are not limited to) components which are contained in relatively small amounts in the detergent or cleaning agent portions and Therefore, it is relatively difficult to incorporate it into large mass mixtures of washing-active, cleaning-active or care-active preparations. A very simple incorporation succeeds in the materials of Kompartimentierungs facilities, and from these also manages a reliable, controllable release during the washing or cleaning process. By suitable choice of materials, the release can also be carried out with "controlled release" kinetics.

A further, likewise preferred embodiment of the invention consists in that one or more compartmentalizing device (s) consists partly or wholly of at least one component of at least one washing-active, cleaning-active or care-active preparation. This is preferred because it means that the compartmentalizing device is not only a kinetics of the release influencing or even controlling component of the detergent or cleaning agent portion according to the invention, but at the same time as a component in the success of the washing and cleaning process involved is. Due to the wide variety of available materials, there are numerous examples for this embodiment; particularly preferred are compartmentalizing devices consisting of or comprising (meth) acrylic acid and its derivatives (salts, esters) comprising polymers.

According to a further preferred embodiment of the invention, the compartmentalizing device (s) consist of an interface between two adjacent components of a washing-active, cleaning-active or care-active preparation or an interface between two adjoining washing-active, cleaning-active or care-active preparations. In preferred embodiments of the invention, this may be the case, for example, when washing-active, cleaning-active or care-active preparations are blown by means of suitable measures, for example by coextrusion in the blow molding compound, from which the hollow body with and without compartments is then blow-molded via a preform. In these cases, activity-reducing or otherwise disadvantageous influences of the washing-active, cleaning-active or care-active preparations can be minimized or even eliminated. There is the possibility that either individual components of a detergent-active, cleaning-active or care-active preparation are combined to form adjacent boundary surfaces or that washing-active, cleaning-active or care-active preparations which are mixtures of several components are combined to form interfaces. Both can in the context of flexible, preferably elastic, hollow body to detergent or detergent portions with particularly advantageous properties, for example, with good dissolution kinetics of the components in the aqueous liquors.

A further preferred embodiment of the invention consists in a detergent or cleaning agent portion contained in one or more flexible, preferably elastic, hollow body (s) with at least one compartment, in which the flexible, preferably elastic, hollow body comprises an area delimiting n, non-spherical hollow body, one surface of which performs the function of a "lid" used to complete a process for preparing the detergent or cleaning agent portions according to the invention, d. H. after filling the compartment (s) in the interior of the hollow body with one or more detergent-active, cleaning-active or care-active preparation (s), is applied while closing the hollow body. The "lid" particularly preferably consists of a material with controllable water solubility and can be bonded to the remaining hollow body by bonding, for example with a water-soluble adhesive, fusing, welding or another known method of joining materials. This embodiment is particularly advantageous for the preparation of detergent or cleaner portions, since a gradual filling of the compartment (s) with one or more detergent-active, cleaning-active or care-active preparation is possible and the handling during later use leads to optimum results, in particular a reliable control of the access of water or aqueous liquor to the interior of the flexible, preferably elastic, hollow body or the outlet of washing-active, cleaning-active or care-active preparation from the interior of the preferably blow-molded hollow body.

According to the invention, the hollow body (s) and / or the compartments contain metered quantities, i. H. Portions, preferably at least one detergent-active, cleaning-active or care-active preparation, usually measured amounts of several washing-active, cleaning-active or care-producing preparations. It is possible that the portions contain only detergent active cleaning or care preparations of a particular composition. According to the invention, however, it is preferred that several, usually at least two, wash-active, cleaning-active or pilea-reactive preparations of different composition are contained in the detergent or cleaner portions. The composition may be (qualitatively) different with regard to the concentration of the individual components of the washing-active, cleaning-active or care-active preparation (quantitatively) and / or with regard to the nature of the individual components of the washing-active, cleaning-active or care-active preparation. It is particularly preferred that the components are adapted in terms of nature and concentration to the tasks that have to fulfill the detergent or detergent partial portions in the washing or cleaning process.

In the context of the present invention, the term "washing-active or cleaning-active or care-active preparation" is understood to mean all conceivable substances of relevance in connection with a washing or cleaning process. In the case of detergents and cleaners, these are primarily the actual detergents and / or cleaners with their individual components explained in more detail later in the description. These include active ingredients such as surfactants (anionic, nonionic, cationic and amphoteric surfactants), builders (inorganic and organic builders), bleaches (such as peroxy bleach and chlorine bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes, specialty polymers ( for example, those with cobuilder properties), grayness inhibitors, dyes and fragrances (perfumes), without the term being limited to these substance groups.

However, the term "washing-active or cleaning-active preparations" is also understood to mean washing auxiliaries and cleaning auxiliaries, including rinse aids. Examples of these are optical brighteners, UV protectants, so-called Soil Repellents, ie polymers which counteract re-soiling of fibers or hard surfaces (including dishes), as well as silver protectants, colorants and decolorizing agents. Care products, such as laundry treatment agents, in particular fabric softeners or dishwashing detergent additives, such as rinse aids, are also regarded as detergent-active or as cleaning-active or care-active preparations.

According to the invention, the detergent or cleaner portions are contained in one or more flexible, preferably elastic, hollow body (s) and / or one or more compartments. The exact shape of the hollow body is just as critical in this context as its size; The only requirement in this regard is that shape and size are in accordance with the later use, ie use in a washing or cleaning process, in particular in conventional washing machines or dishwashers. Conceivable hollow bodies in spherical, ellipsoidal, cubic, cuboid, trapezoidal, conical or pyramid or Trochoidform; cuboidal or trochoidal hollow bodies have proven themselves and can therefore be used with advantage. Most preferred are spherical hollow bodies, in particular spheres.

The size of the hollow body is in preferred embodiments of the invention such that the hollow body can be entered into the dispensing compartment of a commercial washing machine or dishwasher, in the laundry entraining nets or bags o. Ä. Particularly preferred embodiments of the detergent or cleaning agent portions do not exceed a length (longest axis) of 10 cm, while the sizes of the width and the height are significantly lower, for example 1 to 5 cm. Usually, however, filled with detergents or cleaners hollow body are added directly to the laundry in the washing drum of a washing machine.

It is particularly preferred if the washing and / or cleaning agent contained in the hollow body and / or the compartments comprises anionic surfactants and / or nonionic surfactants as the washing-active substances. It is even more preferable if the washing and / or cleaning agent contained in the hollow body and / or the compartments is free of cation surfactant and / or amphoteric surfactants.

The hollow bodies and / or compartments of the hollow body, which contain washing, cleaning and / or care-active preparation, can be combined with one another for the detergent or cleaning agent portion. Here one is not bound to connect only two compartments. Rather, it is also possible to add further compartments and / or hollow bodies which contain washing, cleaning and / or care-active preparation in further compartments. For reasons of process economy, compartments and / or hollow bodies are preferred which have flat connecting surfaces. Of course, it is not bound to only filled hollow body with and / or compartments to each other to the detergent or detergent portion to connect. On the contrary, it is also possible and preferred to use hollow bodies which contain washing, cleaning or care-active preparation in the compartments (A) or (B) with further compartments containing washing, cleaning and / or care-active preparations, preferably blow-molded compartments and / or to connect hollow bodies. Here, in particular the joining of, preferably blow-molded, hollow bodies with tablets has proven to be particularly advantageous. The respective compartments of the water-soluble hollow body can be washed with a different content and / or a different composition of washing; cleaning and / or care active active substances are filled.

The water-soluble Hahlkörper containing preferably prepared by blow molding detergents or cleaning agents have 2 to 40 compartments, preferably 2 to 4, preferably 2 to 3 compartments, on.

Preferably, when the content of anionic surfactant is between 3% by weight to 40% by weight, and the nonionic surfactant content is between 15% by weight and 65% by weight,
based on the total weight fraction of the washing and / or cleaning agent contained in the hollow body, wherein the content of Anionentensid and nonionic surfactant is ≤ 100 wt .-% total.

Cationic surfactants, amphoteric surfactants, builders, bleaches, bleach activators, bleach stabilizers, bleach catalysts, enzymes, polymers, cobuilders, alkalizing agents, acidifiers, anti-redeposition agents, silver protectants may be used in the blow-molded hollow body and / or the respective compartments as washing-active, cleaning-active, care-active substances , Colorants, optical brighteners, UV protectants, washers and / or rinse aids.

The, preferably blow-molded, water-soluble hollow body and / or its compartments may contain an aqueous washing and / or cleaning agent having a water content of above 3% by weight, preferably above 6% by weight, particularly preferably above 10% by weight. %, most preferably above 16 wt .-%, each based on the total agent.

Another requirement is, but not necessarily, that the hollow body be used for release in an aqueous environment. This may or may not be limiting for the choice of means that are usable.

It is preferred if at least one enzyme-containing compartment free of bleach and / or at least one bleach-containing compartment is free of enzyme.

It is advantageous if the wall thickness of the hollow body and / or the compartments are preferably formed by means of blow molding so that the enzymes contained in at least one hollow body and / or in at least one compartment at least partially or completely before the contained in the or at least one other compartment Bleaching agent are released into the aqueous application liquor.

The wall thickness of the hollow body and / or the compartments can be formed, preferably by blow molding, in such a way that the enzymes contained in the hollow body and / or in at least one compartment are at least partially or completely ≥ 60 s, preferably ≥ 120 s, more preferably ≥ 240 s and most preferably ≥ 360 s are released into the aqueous application liquor before the bleach containing in the or at least one other compartment.

The hollow body with and without compartments produced by blow molding, preferably, may contain the detergent or cleaning agent in solid form, liquid form and / or gel form, preferably in the form of particles, suspensions, emulsions, homogeneous solutions, pastes and / or in the form of more transparent Solutions, wherein the aqueous portion of the formulation is optionally up to 95 wt .-%, preferably from 3 to 80 wt .-%, particularly preferably in the range of 6 to 50 wt .-%, each based on the total agent.

The hollow body and / or the compartment (s) produced, preferably by blow molding, can contain a multiphase agent, in particular washing and / or cleaning agents, preferably a temporary two- or three-phase mixture which forms separate phases on standing and is temporarily shaken off by shaking, reversible, can be converted into a phase, for example in an emulsion, suspension or dispersion.

The multiphase agent may, in particular, be a washing or cleaning agent which preferably comprises at least one aqueous and / or non-aqueous phase, wherein preferably at least one non-aqueous phase is liquid or solid, and more preferably at least one aqueous phase is gel-like.

The hollow bodies and / or the compartments produced preferably by blow molding may contain from 20 to 100%, preferably from 30 to 99%, more preferably from 40 to 98%, and in particular from 50 to 95%, by volume, in particular detergent or cleaning agent to be filled.

The hollow body, preferably blow-molded, and / or its compartments may contain at least one, preferably several, wash-active, cleaning-active, rinse-active (s), care-active preparation (s), for example in the form of powders, granules, extrudates, pellets, pearls, tablets, tabs, rings, blocks, briquettes, solutions, melts, gels, suspensions, dispersions, emulsions, foams and / or gases , partially or completely filled.

Surprisingly, it has been found that certain water-soluble thermoplastics or polymeric fabrics produced therefrom, in particular polyvinyl alcohol and partially hydrolyzed polyvinyl acetate, are permeable to water vapor. It has now been found that the coated means are able to absorb water by means of the water vapor permeability of the enveloping hollow body material and thus increase their volume. The volume enlargement of the agent leads to a "pumping" of the filled liquid-tight closed hollow body and thus contributes in addition to the production of elastically deformable, water-soluble hollow body, which show a "bulging" appearance at. Preference is therefore given to means for filling the hollow body, which have a water content which is below the equilibrium value, the agent has in the portion when stored at 30 ° C and a relative humidity of 80%, particularly preferably when stored at 23 ° C and a relative humidity of 50%.

Depending on the structure and composition of the agent, the water absorption can make a significant contribution to the increase in volume.

The detergent or cleaner portions contain one or more substances from the group of surfactants, surfactant compounds, builders, bleaching agents, bleach activators, enzymes, foam inhibitors, dyes and fragrances and - in the event that the detergent or cleaner portions at least for Part as a shaped body present - binding and disintegration aids. These classes of substances are described below.

In a preferred embodiment of the invention, the agent is a washing and / or cleaning agent which comprises anionic surfactants and / or nonionic surfactants as detergent substances.

To develop the washing performance, the washing and cleaning agent portions may contain surface-active substances from the group of anionic, nonionic, zwitterionic or cationic surfactants, with anionic surfactants being clearly preferred for economic reasons and because of their power spectrum.

The portioned detergents or cleaners can be formulated as detergents or as cleaners, depending on which ingredients are enclosed by the hollow body with and without compartments. In addition to laundry detergents, for example, detergents for machine or manual dishwashing, universal household cleaner, toilet cleaner, glass cleaner, etc. can be produced. Depending on the application, the choice of ingredients may be different in the detergent or cleaning compositions that are present within the hollow bodies with and without compartments. Important ingredients of these compositions are described below.

The detergent or cleaning compositions preferably contain surfactant (s) using anionic, nonionic, cationic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants in the case of textile detergents, where the proportion of anionic surfactants should be greater than the proportion of nonionic surfactants. The total surfactant content of the detergent composition is preferably below 30% by weight based on the total agent.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for. From coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO, 4 EQ or 7 EO, C _9-11 alcohols 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 of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. 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 These are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, it is also possible to use mixed alkoxylated nonionic surfactants in which EO and PO units are not randomly distributed but statistically distributed. Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

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

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

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

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with 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 residue.

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

The content of preferred portioned washing or cleaning compositions of nonionic surfactants suitable for textile washing is from 5 to 20% by weight, preferably from 7 to 15% by weight and in particular from 9 to 14% by weight, in each case based on the total composition.

In dishwasher detergents, low-foaming nonionic surfactants are preferably used. With particular preference, automatic dishwashing detergents contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred agents are characterized by containing nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C, and most preferably between 26.6 and 43, 3 ° C, included.

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

Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.

A particularly preferred room temperature solid nonionic surfactant 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 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred agents ethoxylated (s) Niotensid (s), the / of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred rinse aids are characterized in that they contain ethoxylated and propoxylated nonionic surfactants, in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Surfactants are included.

More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% 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 trimethylolpropane.

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

A further preferred portioned washing or cleaning agent contains nonionic surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ], in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical 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 for values between 0.5 and 1.5 and y is a value of at least 15.

Other 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 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula may 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, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

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

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is to 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 is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

If one summarizes the latter statements, portioned washing or cleaning agents are preferred, 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 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² in which x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

Anionic, cationic and / or amphoteric surfactants may also be used in conjunction with the surfactants mentioned, these having only minor importance because of their foaming behavior in dishwasher detergents and usually only in amounts below 10% by weight, in most cases even below 5% by weight .-%, for example, from 0.01 to 2.5 wt .-%, each based on the agent used. The agents may thus contain as surfactant component also anionic, cationic and / or amphoteric surfactants.

R¹

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. As cationic active substances, the agents may contain, for example, cationic compounds of the formulas III, IV or V:
As cationic active substances, the agents according to the invention may contain, for example, cationic compounds of the formulas III, IV or V:

R ¹

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.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of □ sulfo fatty acids (ester sulfonates), z. As the ☐-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids suitable.

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

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which, for example, according to the U.S. Patents 3,234,258 or 5,075,041 are manufactured and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

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

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and in particular from natural fatty acids, for. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.

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

The content of preferred textile detergents in anionic surfactants is 5 to 25 wt .-%, preferably 7 to 22 wt .-% and in particular 10 to 20 wt .-%, each based on the total agent.

In the context of the present invention, preferred agents additionally comprise one or more substances from the group of builders, bleaches, bleach activators, enzymes, electrolytes, nonaqueous solvents, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-wrinkling agents, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents and UV absorbers.

Builders which may be present in the compositions include in particular phosphates, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

The use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with particular preference of pentasodium or Pentakalkumtriphosphat (sodium or potassium tripolyphosphate) in the detergent industry have the greatest importance.

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt of density 2.33 gcm ^-3 a melting point 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is readily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water.

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

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.

Condensation of the NSH ₂ PO ₄ or of the KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n - Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° about 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two applicable; It is also possible to use mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate.

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

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification 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 do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of 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 dissolution delay compared with the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), produced by the company CONDEA Augusts S. p. A. sold under the brand name VEGOBOND AX ^® and by the formula nNa ₂ O · (1 - n) K ₂ O · Al ₂ O ₃ · (2 - 2.5) SiO ₂ · (3.5-5.5) H ₂ O can be described. The zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 microns (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.

Other important builders are in particular the carbonates, citrates and silicates. Preference is given to using trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicatic builders from the class of disilicates and / or metasilicates.

As further constituents alkali carriers may be present. Suitable alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances, preference being given for the purposes of this invention to using the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate.

Particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate.

Also particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.

In addition, further ingredients may be present, washing or cleaning agents are preferred, which additionally contain one or more substances from the group of Acidifizierungsmittel, chelating agents or the deposit-inhibiting polymers.

Acidifying agents are both inorganic acids and organic acids, provided that they are compatible with the other ingredients. For reasons of consumer protection and handling safety in particular the solid mono-, oligo- and polycarboxylic acids are used. Again preferred from this group are citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and also polyacrylic acid. Also, the anhydrides of these acids can be used as Acidifizierungsmittel, in particular maleic anhydride and succinic anhydride are commercially available. Organic sulfonic acids such as sulfamic acid are also usable. A commercially available as an acidifier in the context of the present invention is also preferably usable Sokalan ^® DOS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) and adipic acid ( at most 33% by weight).

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

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

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

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

in Mengen oberhalb von 0,1 Gew.-%, vorzugsweise oberhalb von 0,5 Gew.-%, besonders bevorzugt oberhalb von 1 Gew.-% und insbesondere oberhalb von 2,5 Gew.-%, jeweils bezogen auf das Gewicht des Geschirrspülmittels, enthalten.Particular preference is given to washing or cleaning agents which contain one or more chelate complexing agents from the groups of

• (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
• (ii) nitrogen-containing mono- or polycarboxylic acids,
• (iii) geminal diphosphonic acids,
• (iv) aminophosphonic acids,
• (v) phosphonopolycarboxylic acids,
• (vi) cyclodextrins

in amounts above 0.1 wt .-%, preferably above 0.5 wt .-%, more preferably above 1 wt .-% and in particular above 2.5 wt .-%, each based on the weight of Dishwashing detergent, included.

• a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure,
• b) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N-Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-asparaginsäure oder Nitrilotriessigsäure (NTA),
• c) geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon,
• d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylen-triaminpenta(methylenphosphonsäure) oder Nitrilotri(methylenphosphonsäure),
• e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure sowie
• f) Cyclodextrine.

In the context of the present invention, all complexing agents of the prior art can be used. These can belong to different chemical groups. Preferably, used individually or in admixture with each other:

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

For the purposes of this patent application, polycarboxylic acids a) are understood as meaning carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl groups and the hydroxyl groups contained in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. At the required alkaline pH values of the treatment solutions, these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

Scale-inhibiting polymers may also be included in the compositions. These substances, which could be constructed chemically different, for example, from the groups of low molecular weight polyacrylates having molecular weights between 1000 and 20,000 daltons, with polymers having molecular weights below 15,000 daltons are preferred.

Scale-inhibiting polymers may also have co-builder properties. As organic cobuilders it is possible in particular to use in the dishwasher detergents polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and also phosphonates. These classes of substances are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

As a builder or coating inhibitor further polymeric polycarboxylates are suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70000 g / mol.

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

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 500 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 1000 to 10 000 g / mol, and particularly preferably from 1000 to 4000 g / mol, may again be preferred from this group.

Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or polyunsaturated compounds are particularly preferred in the compositions used nonionic monomers. The sulfonic acid group-containing copolymers are described in detail below.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

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

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

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.

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

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

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

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. As a builder it is from the class of Phosphonates preferably used HEDP. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition to the substances from the mentioned substance classes, the compositions may contain other customary ingredients of detergent detergents, where in particular bleaching agents, bleach activators, enzymes, silver protectants, dyes and fragrances are of importance. These substances will be described below.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the detergent tablets. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.

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

Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation. The proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.12 to about 2 wt .-%.

Enzymes are added to the prior art primarily a detergent composition, in particular added to a dish care product intended for the main rinse. Disadvantage was that the optimal effect of enzymes used limited the choice of temperature and also encountered problems in the stability of the enzymes in a strongly alkaline environment. With the washing or cleaning agent portions, it is possible to introduce enzymes in a separate compartment and then to use them in the pre-wash and thus to use the pre-rinse cycle in addition to the main rinse for an enzyme action on contamination of the dishes.

It is therefore particularly preferred to add the washing-active preparation or partial portion of a detergent portion intended for the prewash cycle to enzymes and then to further comprise such a preparation with a water-soluble material of a flexible, preferably elastic, hollow body which is already water-soluble at low temperature protect enzyme-containing preparation from loss of effect due to environmental conditions.

Advantageously, the detergent portions can then be when the enzyme preparations are liquid, as they are sometimes available commercially, because then a rapid effect can be expected, which already occurs in (relatively short and carried out in cold water) pre-wash. Even if - as usual - the enzymes are used in solid form and they are provided with a hollow body enclosure made of a water-soluble material that is already soluble in cold water, the enzymes can unfold their effect before the main wash or main cleaning. Advantage of the use of an enclosure of water-soluble material, in particular from cold water-soluble material is that the enzyme / enzymes in cold water after dissolution of the enclosure comes to effect quickly / come. Thus, their duration of action can be extended, which benefits the washing or rinsing results.

The automatic dishwashing detergents may contain corrosion inhibitors for the protection of the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

As electrolytes from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl ₂ in the compositions is preferred. The proportion of electrolytes in the agents is usually 0.5 to 5 wt .-%.

Non-aqueous solvents that can be used in the agents, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible in the specified concentration range with water. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane- or butanediol, glycerol, diglycol, propyl- or butyldiglycol, 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, ethyl or propyl ether, dipropylene glycol monomethyl, or ethyl ether, di-isopropylene glycol monomethyl, or ethyl ether, methoxy, ethoxy or Butoxytriglykol, 1-butoxyethoxy-2-propanol, 3-methyl 3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents. Non-aqueous solvents may be used in the liquid detergents in amounts of between 0.5 and 10% by weight, but preferably below 5% by weight and in particular below 3% by weight.

In order to bring the pH of the agent in the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, if their use not prohibited for application or environmental reasons or for reasons of consumer protection. Usually, the amount of these adjusting agents does not exceed 5% by weight of the total formulation.

In order to improve the aesthetic impression of the agents, they can be dyed with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to textile fibers so as not to stain them.

Suitable foam inhibitors which can be used in the compositions are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials. Suitable anti-redeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.

Optical brighteners (so-called "whiteners") may be added to the compositions to eliminate graying and yellowing of the treated fabrics. These substances are absorbed by the fiber and cause whitening and bleaching by transforming invisible ultraviolet radiation into visible long wavelength light, emitting the ultraviolet light absorbed from the sunlight as a faint bluish fluorescence, and pure yellow with the yellowed or yellowed wash White results. Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbene disulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives. The optical brighteners are usually used in amounts between 0.05 and 0.3 wt .-%, based on the finished composition.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and other than the above-mentioned starch products can be used, for. Degraded starch, aldehyde levels, etc. Also, polyvinylpyrrolidone is useful. However, preference is given to using cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the compositions

If the agents are formulated as a means for automatic dishwashing, then further ingredients can be used. Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So even a completely cleaned of leftovers dishes is then rated as not flawless if it has after dishwasher washing whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets. In order to obtain crystal-clear and spotless dishes, one uses therefore successfully today rinse aid. The addition of rinse aid at the end of the washing program ensures that the water runs as completely as possible from the items to be washed, so that the different surfaces at the end of the washing program are residue-free and flawless gloss. The automatic cleaning of dishes in household dishwashers usually includes a pre-wash, a main wash, and a rinse cycle interrupted by intermediate rinses. In most machines, the pre-rinse for heavily soiled dishes is switchable, but is selected only in exceptional cases by the consumer, so that in most machines a main rinse, an intermediate rinse with pure water and a rinse cycle are performed. The temperature of the main wash cycle varies between 40 and 65 ° C, depending on the machine type and program level selection. In the rinse cycle, rinse aids are added from a dosing tank in the machine, which usually contain nonionic surfactants as the main constituent. Such rinse aids are in liquid form and are widely described in the art. Your task is primarily to prevent limescale and deposits on the dishes.

The agents can be formulated as "normal" cleaners which are used in conjunction with commercial supplements (rinse aid, regenerating salt). With particular advantage but can be dispensed with the products on the additional dosage of rinse aid. These so-called "2in1" products lead to a simplification of handling and relieve the consumer of the burden of additional dosage of two different products (cleaner and rinse aid).

Even with the use of "2in1" products, two dosing operations are required at regular intervals to operate a domestic dishwasher, because after a certain number of rinses, the regeneration salt must be replenished in the water softening system of the machine. These water softening systems consist of ion exchange polymers which soften the hard water entering the machine and are regenerated by a rinsing with salt water following the washing program.

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

enthalten.However, it is also possible to provide products which, as so-called "3in1" products, combine conventional cleaners, rinse aids and a salt replacement function. For this machine dishwashing detergents are preferred which additionally contain from 0.1 to 70% by weight of copolymers

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

contain.

These copolymers cause the dishware treated with such agents to become significantly cleaner in subsequent cleanings than do the dishware which has been rinsed by conventional means.

As an additional positive effect occurs a shortening of the drying time of the treated with the detergent dishes, d. H. the consumer can take the dishes from the machine earlier and reuse them after the cleaning program has ended.

The invention is characterized by an improved "cleanability" of the treated substrates in subsequent cleaning operations and by a significant reduction in the drying time compared to comparable agents without the use of sulfonic acid-containing polymers.

Drying time is generally understood to mean the meaning of the word, that is, the time that elapses until a dish surface treated in a dishwasher has dried, but in particular the time that elapses, to 90% with concentrated or diluted detergent or rinse aid Form treated surface is dried.

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

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

In the sulfonic acid-containing monomers, those of the formula VII are preferred, R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (VII), in the R ⁵ to R ⁷ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals is as defined above or is -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _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 VIIa, VIIb and / or VIIc, H ₂ C = CH-X-SO ₃ H (VIIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (VIIb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (VIIc), in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _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 VIIa), 2-acrylamido-2-propanesulfonic acid (X = -C ( O) NH-C (CH ₃ ) ₂ in formula VIIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula VIIe), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula VIIb), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C (O) NH-CH ₂ CH (OH) CH ₂ - in formula VIIb), allylsulfonic acid (X = CH ₂ in formula VIIa), methallylsulfonic acid (X = CH ₂ in formula VIIb), allyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ in formula XVIIa), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula VIIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid (X = CH ₂ in formula VIIb), styrenesulfonic acid (X = C ₆ H ₄ in formula VIIa), vinylsulfonic acid (X not present in formula VIIa), 3-sulfopropyl acrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in Forme l VIIa), 3-sulfopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula VIIb), sulfomethacrylamide (X = -C (O) NH- in formula VIIb), sulfomethylmethacrylamide (X = - C (O) NH-CH ₂ - in formula VIIb) and water-soluble salts of said acids.

Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. The content of the polymers used in monomers of group iii) is preferably less than 20% by weight, based on the polymer.

Particularly preferred polymers to be used consist only of monomers of groups i) and ii).

• i) ungesättigten Carbonsäuren der Formel VI. R¹(R²)C=C(R³)COOH (VI), 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 VII. R⁵(R⁶)C=C(R⁷)-X-SO₃H (VII), 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 esättigter 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)- 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 the formula VI. R ¹ (R ² ) C = C (R ³ ) COOH (VI), in the R ¹ to R ³ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -O-OH or -COOH-substituted alkyl or alkenyl radicals as defined above or -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
• ii) sulfonic acid group-containing monomers of the formula VII. R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (VII), in the R ⁵ to R ⁷ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group , which is selected from - (CH ₂ ) - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -
• iii) optionally further ionic or nonionic monomers

particularly preferred.

• i) einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln VIIa, VIIb und/oder VIIc: H₂C=CH-X-SO₃H (VIIa), H₂C=C(CH₃)-X-SO₃H (VIIb), HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H (VIIc), 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 of acrylic acid, methacrylic acid and / or maleic acid
• ii) one or more sulfonic acid group-containing monomers of the formulas VIIa, VIIb and / or VIIc: H ₂ C = CH-X-SO ₃ H (VIIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (VIIb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (VIIc), in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n , - where 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 used in the compositions may contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) with all representatives from group ii) and all representatives from group iii) can be combined. Particularly preferred polymers have certain structural units, which are described below.

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

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

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

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). In this way, preferred agents are obtained, which are characterized in that they contain one or more copolymers, the structural units of the formula XI - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XI), in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred and to agents which are characterized in that they contain one or more copolymers, the structural units of the formula XII - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (XII), in which m and p are each an integer between 1 and 2,000, and a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y is -O - (CH ₂ ) _n - where n = 0 to 4, -O- (C ₆ H ₄ ) -, -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , are preferred.

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

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, d. H. in that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. Corresponding agents, which are characterized in that the sulfonic acid groups in the copolymer partially or fully neutralized, are preferred.

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

In the case of terpolymers, particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,

The molecular weight of the polymers used in the agents can be varied to match the properties of the polymers to the desired end use. Preferred automatic dishwashing agents 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 compositions may vary depending on the application and the desired product performance, preferred automatic dishwashing compositions being characterized by containing the copolymer (s) in amounts of from 0.25 to 50% by weight, preferably from 0.5 to 35 wt .-%, particularly preferably from 0.75 to 20 wt .-% and in particular from 1 to 15 wt .-%.

As already mentioned above, particularly preferably both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers are used in the compositions. The polyacrylates were described in detail above. Particularly preferred are combinations of the above-described sulfonic acid-containing copolymers with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons. Such polyacrylates are commercially available under the trade name Sokalan ^® PA15 and Sokalan ^® PA25 (BASF).

The agents can also be formulated as fabric softeners or washing additives. Depending on the intended use further ingredients can be used. Softener compositions for rinse-aid are broadly described in the art. Usually, these compositions contain as active substance a cationic quaternary ammonium compound which is dispersed in water. Depending on the content of active substance in the finished plasticizer composition, this is referred to as dilute, ready-to-use products (active substance contents below 7% by weight) or so-called concentrates (active substance content above 7% by weight). Because of the lower volume and the concomitantly reduced packaging and transport costs, the textile softener concentrates have advantages from an ecological point of view and have become more and more prevalent in the market. Due to the incorporation of cationic compounds which have only a low water solubility, conventional fabric softener compositions are in the form of dispersions, have a milky-cloudy appearance and are not translucent. For reasons of product aesthetics, it may also be desirable to provide the consumer with translucent, clear fabric softeners which visually stand out from the known products.

As textile-softening active substance, portioned fabric softeners preferably contain cationic surfactants, which have already been described in detail above (formulas XII, XIII and XIV). Particularly preferred "soft care portions" contain so-called ester quats. While there are a large number of possible compounds from this class of substances, esterquats are particularly preferably used which can be prepared in a manner known per se by reacting trialkanolamines with a mixture of fatty acids and dicarboxylic acids, optionally subsequent alkoxylation of the reaction product and quaternization, as described in US Pat of the DE 195 39 846 A1 is described.

The esterquats prepared in this way are outstandingly suitable for producing portions which can be used as fabric softeners. Since, depending on the choice of trialkanolamine, the fatty acids and the dicarboxylic acids and the quaternizing a variety of suitable products can be prepared and used in the agents, a description of the preferably used esterquats is more precise over their preparation route than the specification of a general formula.

The abovementioned components which react with one another to give the esterquats which are preferably to be used can be used in varying proportions relative to one another. In the context of the present invention, portioned fabric softeners are preferred in which a reaction product of trialkanolamines with a mixture of fatty acids and dicarboxylic acids in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, optionally alkoxylated and then in is quaternized in known manner, in amounts of 2 to 60, preferably 3 to 35 and especially 5 to 30 wt .-% is included. Particularly preferred is the use of triethanolamine, so that further preferred portioned fabric softener of the present invention, a reaction product of triethanolamine with a mixture of fatty acids and dicarboxylic acids in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, the optionally alkoxylated and then quaternized in a conventional manner, in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30 wt .-%.

As fatty acids, all acids obtained from vegetable or animal oils and fats can be used in the reaction mixture for the preparation of the esterquats. It is also possible to use a non-solid, ie pasty to liquid, fatty acid at room temperature in the reaction mixture as the fatty acid.

The fatty acids can be saturated or mono- to polyunsaturated regardless of their state of aggregation. Of course, not only "pure" fatty acids can be used but also the technical fatty acid mixtures obtained from the fats and oils cleavage, these mixtures again being clearly preferred from an economic point of view.

For example, individual species or mixtures of the following acids can be used in the reaction mixtures for preparing the esterquats for the clear aqueous softeners: caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-ol acid, arachidic acid, behenic acid, Lignoceric acid, cerotic acid, melissinic acid, 10-undecenoic acid, petroselinic acid, petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, linolaidic acid, α- and β-estarainic acid, gadoleic acid, erucic acid, brassidic acid. Of course, the fatty acids having an odd number of carbon atoms are also usable, for example undecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, heneicosanoic acid, tricosanoic acid, pentacosanoic acid, heptacosanoic acid.

In the context of the present invention, the use of fatty acids of the formula XIII in the reaction mixture for the preparation of the esterquats is preferred, so that preferred portioned fabric softeners are a reaction product of trialkanolamines with a mixture of fatty acids of the formula XIII, R ¹ -CO-OH (XIII) in which R 1-CO- is an aliphatic, linear or branched acyl radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds and dicarboxylic acids in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5 : 1, which is optionally alkoxylated and then quaternized in a conventional manner, in amounts of 2 to 60, preferably 3 to 35 and especially 5 to 30 wt .-% in the compositions.

Suitable dicarboxylic acids which are suitable for the preparation of the esterquats to be used in the compositions are, in particular, saturated or mono- or polyunsaturated α, ω-dicarboxylic acids. Examples include the saturated species of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, undecane and dodecanoic acid, brassylic acid, tetra- and pentadecanoic acid, thapic acid and hepta-, octa- and nonadecanoic, eicosane and heneicosanoic acid as well as phellogenic acid. Dicarboxylic acids which follow the general formula XXIII are preferably used in the reaction mixture, so that portioned agents are preferred which comprise a reaction product of trialkanolamines with a mixture of fatty acids and dicarboxylic acids of the formula XIV, HO-OC- [X] -CO-OH (XIV) in which X is an optionally hydroxy-substituted alkylene group having 1 to 10 carbon atoms, in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, which is optionally alkoxylated and then quaternized in a conventional manner, in quantities from 2 to 60, preferably 3 to 35 and in particular 5 to 30 wt .-% in the compositions.

Among the multitude of esterquats which can be prepared and used, those in particular in which the alkanolamine is trethanolamine and the dicarboxylic acid adipic acid have once again proved particularly suitable. Thus, in the context of the present invention, agents are particularly preferred which comprise a reaction product of triethanolamine with a mixture of fatty acids and adipic acid in a molar ratio of 1: 5 to 5: 1, preferably 1: 3 to 3: 1, which is subsequently in a manner known per se in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30 wt .-% in the compositions

The agents can - regardless of whether they are formulated as a laundry detergent, laundry detergent or softener - also be equipped with other additional benefits. Here, for example, color transfer inhibiting compositions, anti-gray formula agents, ironing facilitators, fragrance release agents, soil repellency improvers, antibacterial agents, UV protectants, color refreshing agents, etc. can be formulated. Some examples are explained below:
Since textile fabrics, in particular of rayon, rayon, cotton and their mixtures, can crumple because the individual fibers against bending, kinking. Pressing and squeezing across the fiber direction are sensitive, the means may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

For controlling microorganisms, the agents may contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistats and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, and the compounds according to the invention can be completely dispensed with.

In order to prevent undesirable changes in the agents and / or the treated textiles caused by oxygen and other oxidative processes, the agents may contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

Increased comfort may result from the additional use of antistatic agents added to the compositions. Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges. External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) -dimethylbenzylammonium chlorides are suitable as antistatic agents for textiles or as an additive to laundry detergents, wherein a softening effect is additionally achieved.

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

Finally, the agents may also contain UV absorbers which are applied to the treated fabrics and improve the lightfastness of the fibers. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are 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 urocanic acid.

Further conceivable additives, which are preferred in specific embodiments, are surfactants which, in particular, can influence the solubility of the water-soluble wall of the flexible, preferably elastic, hollow body or the compartmentation device, but can also control their wettability and foaming on dissolution, as well as foam inhibitors, but also Bitter substances that can prevent accidental ingestion of such hollow body or parts of such hollow body by children.

Fragrances are added to the detergent or cleaning agent portions to improve the aesthetic overall impression of the products and to provide the consumer in addition to the technical performance (fabric softening result) a sensory typical and distinctive product. As perfume oils or perfumes, individual perfume compounds can be used, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, pt-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. Count to the Ethern for example, benzyl ethyl ether. The aldehydes include, for. B. linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, purple and bourgeonal.

The ketones include the ionones, α-isomethylionone, and methyl cedryl ketone. The alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include terpenes such as limonene and pinene. Preference is given to using mixtures of different fragrances which are coordinated with one another in such a way that together they produce an attractive fragrance note. Such perfume oils may also contain natural fragrance mixtures as are available from plant sources. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are nutmeg oil, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroliol, orange peel oil and sandalwood oil.

Usually, the content of perfumes in the range up to 2 wt .-% of the total detergent or detergent portion.

The fragrances can be incorporated directly into the detergent-active, cleaning-active or care-active preparation (s); but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the laundry and provide a slower fragrance release for long-lasting fragrance of textiles. As such carrier materials, for example, cyclodextrins have been proven. The cyclodextrin-perfume complexes can additionally be coated with other auxiliaries.

The perfumes and fragrances can in principle be contained in each of the partial portions (washing-active or cleaning-active or care-active preparations) of the detergent or cleaner portions. However, it is particularly preferred that they are in a detergent in a provided for the post-wash cycle or fabric conditioner portion detergent portion or in a detergent, especially in a dish care product, provided in a rinse or rinse cycle Teil-Reinigungsmittel- Portion, especially part-care-portion, are included. You must therefore of a water-soluble only at the conditions (especially at the temperature) of Nachwaschgangs or after-care, at the conditions (especially at the temperature) of the previous washes or rinses water-insoluble material of the flexible, preferably elastic, hollow body or the compartmenting device (s) comprises. This is feasible, for example, with a detergent or cleaner portion comprising a plurality of compartments in a flexible, preferably elastic, hollow body.

The detergent or cleaner portions contain in a flexible, preferably elastic, hollow body with and without compartments one or more detergent-active, cleaning-active and / or care-active preparations in such amounts that they are sufficient for a washing or cleaning process. Of course, a dosage of two units (hollow body) under special conditions (heavily soiled, eg heavily greased laundry, heavily soiled dishes) possible.

In a particularly preferred embodiment of the invention, a detergent or cleaner portion contained in one or more flexible, preferably elastic, hollow body (s) with at least one compartment leads to the at least one, preferably the several, wash-active, cleaning-active (n ) or caring active preparation (s) in one or more forms from the group of powders, granules, extrudates, pellets, beads, tablets, tabs, rings, blocks, briquettes, solutions, melts, gels, suspensions, dispersions, emulsions, Foams and gases. Gels are preferred and most preferred are liquid detergents or cleaners. The form of the washing-active, cleaning-active and / or care-active preparation contained in one or more compartments of the flexible, preferably elastic, hollow body is therefore not limited, as long as the hollow body can be used in the intended manner. It is to be regarded as a significant advantage of the invention that for the first time the use of fluid phases in detergent or detergent portions is possible and a suitable for the administration of such fluid phases detergent or detergent portion is provided. Thus, in the compartments of a hollow body, liquids, gels, gases or foams may be closed alone or together with solid constituents in one or more compartments and, in use, brought into contact with the objects to be washed or cleaned. This achieves a new freedom in the preparation of detergents or cleaning agents.

The detergent or cleaner portions disclosed herein consist of an outer mold containing one or more fillings. In this case, the mold through partitions in several Subdivided compartments, whereby several fillings can be present separately within the same hollow body. In addition to the compatibility with the material of the mold, no requirements are placed on the fillings, so that both solid and liquid phases (systems) can be portioned.

Preferably, the washing or cleaning portions can be used by their division into several separate areas for the separation of incompatible active ingredients. The table below gives a non-limiting overview of possible drugs and their division into different compartments. It was also specified in which packaging the corresponding preparation in the compartment (A) or (B) is included. Compartment (A) Compartment (B) Bleaching agent (powdered preparation) Bleach activator (liquid preparation) Bleaching agent (powdered preparation) Enzymes (liquid preparation) Bleaching agent (powdered preparation) Dyes and fragrances (liquid preparation) Bleaching agent (powdered preparation) optical brighteners (liquid preparation) Bleaching agent (powdered preparation) Silver protection agent (liquid preparation) Bleaching agent (granular preparation) Bleach activator (liquid preparation) Bleaching agent (granular preparation) Enzymes (liquid preparation) Bleaching agent (granular preparation) Dyes and fragrances (liquid preparation) Bleaching agent (granular preparation) optical brighteners (liquid preparation) Bleaching agent (granular preparation) Silver protection agent (liquid preparation) Bleaching agent (extruded preparation) Bleach activator (liquid preparation) Bleaching agent (extruded preparation) Enzymes (liquid preparation) Bleaching agent (extruded preparation) Dyes and fragrances (liquid preparation) Bleaching agent (extruded preparation) optical brighteners (liquid preparation) Bleaching agent (extruded preparation) Silver protection agent (liquid preparation) Bleaching agent (powdered preparation) Bleach activator (powdered preparation) Bleaching agent (powdered preparation) Enzymes (powdered preparation) Bleaching agent (powdered preparation) Dyes and fragrances (powdered preparation) Bleaching agent (powdered preparation) optical brightener (powdered preparation) Bleaching agent (powdered preparation) Silver protection agent (powdered preparation) Bleaching agent (granular preparation) Bleach activator (powdered preparation) Bleaching agent (granular preparation) Enzymes (powdered preparation) Bleaching agent (granular preparation) Dyes and fragrances (powdered preparation) Bleaching agent (granular preparation) optical brightener (powdered preparation) Bleaching agent (granular preparation) Silver protection agent (powdered preparation) Bleaching agent (extruded preparation) Bleach activator (powdered preparation) Bleaching agent (extruded preparation) Enzymes (powdered preparation) Bleaching agent (extruded preparation) Dyes and fragrances (powdered preparation) Bleaching agent (extruded preparation) optical brightener (powdered preparation) Bleaching agent (extruded preparation) Silver protection agent (powdered preparation) Bleaching agent (powdered preparation) Bleach activator (granular preparation) Bleaching agent (powdered preparation) Enzymes (granular preparation) Bleaching agent (powdered preparation) Dyes and fragrances (granular preparation) Bleaching agent (powdered preparation) optical brightener (granular preparation) Bleaching agent (powdered preparation) Silver protection agent (granular preparation) Bleaching agent (granular preparation) Bleach activator (granular preparation) Bleaching agent (granular preparation) Enzymes (granular preparation) Bleaching agent (granular preparation) Dyes and fragrances (granular preparation) Bleaching agent (granular preparation) optical brightener (granular preparation) Bleaching agent (granular preparation) Silver protection agent (granular preparation) Bleaching agent (extruded preparation) Bleach activator (granular preparation) Bleaching agent (extruded preparation) Enzymes (granular preparation) Bleaching agent (extruded preparation) Dyes and fragrances (granular preparation) Bleaching agent (extruded preparation) optical brightener (granular preparation) Bleaching agent (extruded preparation) Silver protection agent (granular preparation) Bleaching agent (powdered preparation) Bleach activator (extruded preparation) Bleaching agent (powdered preparation) Enzymes (extruded preparation) Bleaching agent (powdered preparation) Dyes and fragrances (extruded preparation) Bleaching agent (powdered preparation) optical brighteners (extruded preparation) Bleaching agent (powdered preparation) Silver protection agent (extruded preparation) Bleaching agent (granular preparation) Bleach activator (extruded preparation) Bleaching agent (granular preparation) Enzymes (extruded preparation) Bleaching agent (granular preparation) Dyes and fragrances (extruded preparation) Bleaching agent (granular preparation) optical brighteners (extruded preparation) Bleaching agent (granular preparation) Silver protection agent (extruded preparation) Bleaching agent (extruded preparation) Bleach activator (extruded preparation) Bleaching agent (extruded preparation) Enzymes (extruded preparation) Bleaching agent (extruded preparation) Dyes and fragrances (extruded preparation) Bleaching agent (extruded preparation) optical brighteners (extruded preparation) Bleaching agent (extruded preparation) Silver protection agent (extruded preparation) Surfactants (liquid preparation) Bleach activator (liquid preparation) Surfactants (liquid preparation) Enzymes (liquid preparation) Surfactants (liquid preparation) Dyes and fragrances (liquid preparation) Surfactants (liquid preparation) optical brighteners (liquid preparation) Surfactants (liquid preparation) Silver protection agent (liquid preparation) Surfactants (powdered preparation) Bleach activator (liquid preparation) Surfactants (powdered preparation) Enzymes (liquid preparation) Surfactants (powdered preparation) Dyes and fragrances (liquid preparation) Surfactants (powdered preparation) optical brighteners (liquid preparation) Surfactants (powdered preparation) Silver protection agent (liquid preparation) Surfactants (granular preparation) Bleach activator (liquid preparation) Surfactants (granular preparation) Enzymes (liquid preparation) Surfactants (granular preparation) Dyes and fragrances (liquid preparation) Surfactants (granular preparation) optical brighteners (liquid preparation) Surfactants (granular preparation) Silver protection agent (liquid preparation) Surfactants (extruded preparation) Bleach activator (liquid preparation) Surfactants (extruded preparation) Enzymes (liquid preparation) Surfactants (extruded preparation) Dyes and fragrances (liquid preparation) Surfactants (extruded preparation) optical brighteners (liquid preparation) Surfactants (extruded preparation) Silver protection agent (liquid preparation) Surfactants (liquid preparation) Bleach activator (granular preparation) Surfactants (liquid preparation) Enzymes (granular preparation) Surfactants (liquid preparation) Dyes and fragrances (granular preparation) Surfactants (liquid preparation) optical brightener (granular preparation) Surfactants (liquid preparation) Silver protection agent (granular preparation) Surfactants (powdered preparation) Bleach activator (powdered preparation) Surfactants (powdered preparation) Enzymes (powdered preparation) Surfactants (powdered preparation) Dyes and fragrances (powdered preparation) Surfactants (powdered preparation) optical brightener (powdered preparation) Surfactants (powdered preparation) Silver protection agent (powdered preparation) Surfactants (granular preparation) Bleach activator (powdered preparation) Surfactants (granular preparation) Enzymes (powdered preparation) Surfactants (granular preparation) Dyes and fragrances (powdered preparation) Surfactants (granular preparation) optical brightener (powdered preparation) Surfactants (granular preparation) Silver protection agent (powdered preparation) Surfactants (extruded preparation) Bleach activator (powdered preparation) Surfactants (extruded preparation) Enzymes (powdered preparation) Surfactants (extruded preparation) Dyes and fragrances (powdered preparation) Surfactants (extruded preparation) optical brightener (powdered preparation) Surfactants (extruded preparation) Silver protection agent (powdered preparation) Surfactants (liquid preparation) Bleach activator (granular preparation) Surfactants (liquid preparation) Enzymes (granular preparation) Surfactants (liquid preparation) Dyes and fragrances (granular preparation) Surfactants (liquid preparation) optical brightener (granular preparation) Surfactants (liquid preparation) Silver protection agent (granular preparation) Surfactants (powdered preparation) Bleach activator (granular preparation) Surfactants (powdered preparation) Enzymes (granular preparation) Surfactants (powdered preparation) Dyes and fragrances (granular preparation) Surfactants (powdered preparation) optical brightener (granular preparation) Surfactants (powdered preparation) Silver protection agent (granular preparation) Surfactants (granular preparation) Bleach activator (granular preparation) Surfactants (granular preparation) Enzymes (granular preparation) Surfactants (granular preparation) Dyes and fragrances (granular preparation) Surfactants (granular preparation) optical brightener (granular preparation) Surfactants (granular preparation) Silver protection agent (granular preparation) Surfactants (extruded preparation) Bleach activator (granular preparation) Surfactants (extruded preparation) Enzymes (granular preparation) Surfactants (extruded preparation) Dyes and fragrances (granular preparation) Surfactants (extruded preparation) optical brightener (granular preparation) Surfactants (extruded preparation) Silver protection agent (granular preparation) Surfactants (liquid preparation) Bleach activator (extruded preparation) Surfactants (liquid preparation) Enzymes (extruded preparation) Surfactants (liquid preparation) Dyes and fragrances (extruded preparation) Surfactants (liquid preparation) optical brighteners (extruded preparation) Surfactants (liquid preparation) Silver protection agent (extruded preparation) Surfactants (powdered preparation) Bleach activator (extruded preparation) Surfactants (powdered preparation) Enzymes (extruded preparation) Surfactants (powdered preparation) Dyes and fragrances (extruded preparation) Surfactants (powdered preparation) optical brighteners (extruded preparation) Surfactants (powdered preparation) Silver protection agent (extruded preparation) Surfactants (granular preparation) Bleach activator (extruded preparation) Surfactants (granular preparation) Enzymes (extruded preparation) Surfactants (granular preparation) Dyes and fragrances (extruded preparation) Surfactants (granular preparation) optical brighteners (extruded preparation) Surfactants (granular preparation) Silver protection agent (extruded preparation) Surfactants (extruded preparation) Bleach activator (extruded preparation) Surfactants (extruded preparation) Enzymes (extruded preparation) Surfactants (extruded preparation) Dyes and fragrances (extruded preparation) Surfactants (extruded preparation) optical brighteners (extruded preparation) Surfactants (extruded preparation) Silver protection agent (extruded preparation)

extrusion blow molding

It was converted in an extruder plasticizable polymer composition (blow molding compound) based on a water-soluble polymeric thermoplastic into a tubular preform. An open end of the tube was closed under thermal treatment. Thereafter, the preform was inflated, wherein the compressed air was supplied through a mandrel, which also formed the opening of the blow molded article at the same time. The blow molding was filled and demolded.

Compartments can be produced, for example, by placing them at predetermined locations of the wall (s) of the still malleable blow molded article, by means of corresponding devices in the blow mold, forming them with the formation of subdivisions, i. H. closed cavities, merges and liquid-tight, preferably by thermal treatment, connects. However, it is also possible to use preforms with separate cavities which are then blow-molded into a blow-molded article having a plurality of compartments. However, it is also possible to combine several hollow bodies with and without compartments.

Coextrusionsblasen

In this special form of extrusion blow molding, the hollow bodies with and without compartments are made of several material layers. The preform is created by having multiple extruders act on a common tube tool to form a multi-layer preform which is then blow-molded into the hollow body.

Injection stretch blow molding

In contrast to extrusion blow molding, the preform is produced by means of injection molding. After transfer to a conditioning station of not yet cooled preform is transferred to a blow mold and there axially pre-stretched by applying a mechanical force and inflated with high air pressure to the hollow body, so that a stretching takes place.

Claims (43)

Process for the preparation of completely or partially water-soluble, filled hollow bodies, comprising an agent, comprising the steps: a) forming a hollow body of a material containing at least one water-soluble polymeric thermoplastic, wherein the formation of the hollow body takes place under stretching conditions and this process is terminated by means of an exogenously induced in the polymeric thermoplastic temperature jump is discontinued, b) filling the hollow body with a washing or cleaning agent, c) liquid-tight closure of the hollow body and d) shrinking of the hollow body material enveloping the means, wherein the induced temperature jump is achieved by filling the hollow body with an agent having a temperature below 15 ° C, and wherein the shrinkage is initiated by conditioning the filled and sealed hollow body in an atmosphere having a relative humidity above 50%. A method according to claim 1, characterized in that the shrinking process is triggered by conditioning at a temperature above 25 ° C. A method according to claim 1 or claim 2, characterized in that the shrinking process is triggered by conditioning within a residence time of at most 24 hours. Process according to one of claims 2 to 3, characterized in that at least one drying step is followed by the conditioning step (s) in an atmosphere with elevated relative humidity. Method according to one of the preceding claims, characterized in that the formation of the hollow body takes place in the melt region of the polymeric thermoplastic. Method according to one of the preceding claims, characterized in that the formation of the hollow body takes place under stretching conditions in more than one preferred direction. Production process according to one of the preceding claims, characterized in that the melt flow index of the water-soluble polymeric thermoplastic at 10 kg is between 1 and 30. Method for the production according to one of the preceding claims, characterized in that the formation of the hollow body takes place by prototyping a preform from a blow molding compound based on a water-soluble polymeric thermoplastic, and then blow-molding the preform into a hollow body. Process for the preparation according to claim 8, characterized in that (A) in a first step by extrusion, a preform is prepared and (B) in a second step in a cycle of the hollow body is blown and filled with the agent, sealed liquid-tight, and then removed from the mold. Process for the preparation according to one of claims 8 or 9, characterized in that the wall thicknesses of the hollow body can be formed differently in regions differently by forming the wall thicknesses of the preform correspondingly different thicknesses. Manufacturing method according to one of the preceding claims, characterized in that the preform, the hollow body and / or the liquid-tight closed hollow body of one or more component (s) comprising one or more materials based on one or different water-soluble polymeric thermoplastics , consists. Method for producing according to one of the preceding claims, characterized in that the preform, the hollow body and / or the liquid-tight verschiossene hollow body is tubular, spherical or bubble-shaped, wherein the spherical hollow body has a form factor of> 0.8. Process for the preparation according to one of the preceding claims, characterized in that serial, parallel and / or concentrically arranged hollow bodies and / or compartments are produced by using at least one double and / or multiple and / or coextrusion blow mandrel. Process for the production according to one of Claims 8 to 13, characterized in that a preform having a plurality of layers is produced by coextrusion, which is then blow-molded into a hollow body, wherein at least one wall of the hollow body and / or at least one wall at least one Compartment is multi-layered. Production process according to one of Claims 8 to 14, characterized in that (C) in a first step by means of extrusion, a preform is produced and fed into a mold and (D) is blown in a second step in a cycle of the hollow body, so that the thermoplastic material is applied to the mold, wherein the mold is cooled and / or optionally the temperature of any existing head jaw for liquid-tight sealing of the hollow body via a separate Temperature control is regulated. Production process according to one of Claims 1 to 8, characterized in that the formation of the hollow body takes place by thermoforming a film material based on a water-soluble polymeric thermoplastic. Process for the preparation according to Claim 16, characterized in that the formation of the hollow body takes place by deep drawing of a film material into a cavity. Process for the preparation according to one of Claims 1 to 7, characterized in that the formation of the hollow body takes place in the course of a rotary die process. Manufacturing process according to one of the preceding claims, characterized in that at least one hollow body region and / or compartment region having at least one outer surface of between 0.01 mm ² and 10 cm ^{2 is} produced, the wall thickness of said surface being increased in order to achieve faster dissolution in ensuring an aqueous solution is less than the wall thickness of the adjacent area. A method according to claim 19, characterized in that the smaller wall thicknesses occur by imprinting a logo. Process for the preparation according to one of the preceding claims, characterized in that the wall thickness of the hollow body and / or the compartments is formed such that the agent contained in the hollow body and / or in the compartments in the aqueous application liquor within ≤ 5 min partially or completely released. Process for the preparation according to one of the preceding claims, characterized in that the internal volume of the hollow body produced and / or the compartments is between 0.5 ml and 2000 ml. Process for the preparation according to one of the preceding claims, characterized in that the agent is added in liquid form and / or gel form to the produced hollow body and / or the compartments. Process for the preparation according to one of the preceding claims, characterized in that the produced hollow body and / or the compartments a multiphase agent is added, which forms separate phases on standing and by shaking temporarily in the form of an emulsion, suspension or dispersion reversible in one phase can convict. Production process according to claim 24, characterized in that the multiphase agent comprises at least one aqueous and / or non-aqueous phase. Process for the preparation according to one of the preceding claims, characterized in that the means for filling the hollow body from step b) has a water content which is below the equilibrium value which the agent has in the portion when stored at 30 ° C and a relative humidity of 80%. Production process according to one of the preceding claims, characterized in that the water-soluble thermoplastic used to form the hollow body and / or compartments is selected from the group comprising polyvinyl alcohol (PVA), acetalated polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, starch and derivatives the aforementioned substances. Process for the preparation according to one of the preceding claims, characterized in that the water-soluble thermoplastics used to form the hollow body and / or the compartments additionally polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, Polyester, polyethers and / or mixtures of the above polymers are added. Process for the preparation according to one of the preceding claims, characterized in that the water-soluble thermoplastic used to form the hollow body and / or the compartments comprises a polyvinyl acetate whose degree of hydrolysis makes up 70 to 100 mol%. Production process according to one of the preceding claims, characterized in that the water-soluble thermoplastic used to form the hollow body and / or the compartments comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^-1 . Process for the preparation according to one of the preceding claims, characterized in that the material used to form the hollow body contains the water-soluble polymeric thermoplastics in amounts of at least 50 wt .-%, based on the weight of the entire hollow body material. Process for the preparation according to one of the preceding claims, characterized in that the water-soluble polymeric thermoplastic plasticizer in amounts of at least> 1 wt .-%, based on the weight of the entire hollow body material containing. Method according to one of the preceding claims, characterized in that the water-soluble polymeric thermoplastic plasticizer contains mono-, di- or triglycerides. Method according to one of the preceding claims, characterized in that the hollow body and / or the compartments are filled to 20 to 100% of its volume with means. Method according to one of the preceding claims, characterized in that the hollow body and / or the compartments with at least one wash-active, cleaning-active, rinse-active, care-active (s) preparation (s) in the form of powder, Granules, extrudates, pellets, beads, tablets, tabs, rings, blocks, briquettes, solutions, melts, gels, suspensions, dispersions, emulsions, foams and / or gases partially or completely fills. Method according to one of the preceding claims, characterized in that the hollow body and / or at least one compartment is transparent and / or translucent. Method according to one of the preceding claims, characterized in that at least one wall of the hollow body and / or at least one wall of at least one compartment forms a multilayered. Method according to one of the preceding claims, characterized in that at least two layers of the wall of the hollow body and / or at least two layers of at least one compartment designed so that a gap between the layers is formed. Process for the preparation according to one of the preceding claims, characterized in that the flexible, water-soluble hollow body is formed in one piece or in several pieces. Method according to one of the preceding claims, characterized in that the hollow body has no sealed seam, no squeeze seam and / or no circumferential seam. Method for producing according to one of the preceding claims, characterized in that the washing and / or cleaning agent comprises anionic surfactants and / or nonionic surfactants as detergent substances. Process for the preparation according to one of the preceding claims, characterized in that the hollow body filled to an extent of ≥80% by volume with an agent has a volume reduction of at least 0.5% by means of shrinkage. Process for the preparation according to one of the preceding claims, characterized in that the ≥ 80 vol .-% filled with a means hollow body by the shrinking step has a length reduction along the longest axis of at least 0.2%.

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