WO2004031034A1

WO2004031034A1 - Shrunken moulded detergent bodies

Info

Publication number: WO2004031034A1
Application number: PCT/EP2003/010309
Authority: WO
Inventors: Sandra Hoffmann; Wilfried Rähse
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2002-09-26
Filing date: 2003-09-17
Publication date: 2004-04-15
Also published as: AU2003264299A1; DE10244803A1; DE10244803B4

Abstract

The invention relates to a method for the production of water-soluble filled portions, which pass through a shrunken layer of the enveloping material, comprising an agent, in particular a washing, conditioning and/or cleaning agent and the use thereof. The invention further relates to washing, cleaning and conditioning methods in which the washing, cleaning and conditioning agent preparations are dosed in water-soluble hollow bodies.

Description

"Shrinked Detergent Shapes"

The present invention relates to a method for producing water-soluble, filled hollow bodies which undergo a shrinking step of the casing material, containing an agent, in particular a washing, care and / or cleaning agent, and the use thereof. The invention further relates to washing, cleaning and care processes in which the detergent, cleaning agent and care agent preparations are metered into water-soluble hollow bodies.

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 envelop chemicals or consumer goods which are intended to be protected from the environment by the packaging, but at the same time also to protect consumers from direct contact with the packaging goods. In agrochemistry, the use of pesticides in water-soluble bags, which were produced by a thermoforming process, is known from the European patent application EP 0 608 910 A. The water-soluble packaging protects the user from contact with the toxic chemicals and also simplifies the dosage of the pesticides by simply adding a Pestizi.d sachet to a specified amount of water, in which the sachet and its contents can dissolve. The use of water-soluble packaging forms is also known in the pharmaceutical industry, for example capsules made of water-soluble hard gelatin containing pharmaceutical preparations are administered to consumers or patients.

Recently, the use of water-soluble packaging has also established itself on the market in the field of detergents and cleaning agents. In particular, the consumer is offered single-dose quantities of detergents and cleaning agents which are packaged in plastic bags. This enables the consumer to conveniently and easily dose the detergents and cleaning agents, since the products are already in pre-portioned form. The advantages of such individual portions lie in particular in the fact that the consumer is spared the tearing open of the packaging, as a result of which a convenient metering of a single portion measured for a washing and cleaning cycle by inserting the bag directly into the washing machine or dishwasher, especially in its washing-up chamber or by throwing the bag into a certain amount of water, for example in a bucket, a bowl or in the hand wash basin or sink. The foil pouch surrounding the detergent, cleaning agent or care agent portion dissolves get up when a certain temperature is reached. Detergents and cleaning agents packed in bags made of water-soluble film are described in large numbers in the prior art. For example, German patent application DE 19831703 discloses a portioned detergent or cleaning agent preparation in a bag made of water-soluble film, in particular in a bag made of (optionally acetalized) polyvinyl alcohol, in which at least 70% by weight of the particles of the detergent or cleaning agent preparation have particle sizes greater than 800 μm , Such foil bags are very user-friendly and facilitate dosing, but are not in all cases the suitable form for dosing detergent, cleaning agent and care product preparations. The consumer goods packed in bags have the particular disadvantage that the film bags are very sensitive to mechanical influences. During transport or handling, this can lead to undesired product leakage if the film is damaged due to carelessness. Simply touching it with pointed or cracked fingernails can already damage it and thus lead to undesirable consumer frustration, particularly in the area of household funds. Furthermore, it has proven to be extremely difficult to achieve a high degree of filling of the film bags. The higher the degree of filling of the water-soluble portions, the higher the risk of contamination of the sealed seams, which in turn can lead to leaky sealed seams and thus to product leakage, particularly in the case of liquid formulations. Due to the low degree of filling and possibly instability due to the film, the film bags do not have any elastic dimensional stability. When a deforming force is applied, the bags made of deformable films in their unfilled and filled state no longer assume their original shape, that is to say before the force is applied. The mechanical properties of such "flaccid" bags are often not reproducible and are therefore extremely difficult to stack or re-pack on an industrial scale. In addition, plump and flexible, elastic water-soluble portions are much more widely accepted by consumers, since a stronger impression also applies to laundry In addition to the advantageous aesthetic aspects, which play an important role in the consumer goods sector in particular, there is also the fact that the reproducibility creates a recognizable product design, while bulky detergent, cleaning and care product tablets also have better properties mechanical indexing and deformability values.

Processes for the production of film bags, in particular by the thermoforming process, have already been widely described in the prior art. The publications WO 00/55068, WO 00/55046, WO 00/55045, WO 00/55044, WO 00/55415 and WO 02/16207 describe thermoforming processes for the production of water-soluble portion bags which contain a thermoformed step through. For this purpose, a thermoformable, water-soluble film is first drawn into a cavity, the shape formed is then filled and, in a further step, covered and sealed with a second film.

Measures to increase the tear strength of the films have also already been described in the prior art. International application WO 00/55069 thus discloses the use of increased atmospheric humidity within a second outer packaging in which the water-soluble film bags are located. To maintain the increased humidity, the outer packaging must be equipped with a moisture barrier. The use of increased atmospheric humidity disclosed in the publication serves to make the film material more supple in order to reduce the susceptibility to cracks and additionally to increase the tightness of the sealing seams.

International patent application WO 02/16206 also discloses the use of a thermoforming process for the production of water-soluble portions. In order to obtain aesthetically pleasing, bulging film bags, the formulations contained in the bags have a gas development system that inflates the bags from the inside. Typical gas development systems are citrate / carbonate systems. The disadvantages of such enclosed gas development systems are that the formulations release gas before they are filled into the water-soluble containers, and thus the water-soluble containers are inflated in a non-reproducible or non-uniform manner become. Furthermore, in extreme cases, an uncontrolled gas release leads to the portions bursting or the sealing seams tearing open.

International patent application WO 02/16205 A1 also describes the attempt to provide bulging film moldings which have been produced by a thermoforming process. For this purpose, specially pre-dried polyvinyl alcohol films with a water content below 5% by weight are used in the thermoforming process. By pouring aqueous formulations into the bags made from dried film material, aesthetically pleasing moldings can be obtained. However, it is disadvantageous here that the manufacturing process is bound to aqueous, liquid formulations and that the film material has to be dried in a complex manner. In addition, it is not exactly reproducible to what extent the film has already been softened by the ambient air humidity before it is processed and thus already exceeds the required water content of below 5% by weight. The composition of the formulation encased by the dry film is also not reproducible and is sometimes very sensitive to water loss, for example by precipitating water-soluble constituents, so that not only the aesthetic appearance of transparent moldings can be significantly impaired, but also the performance requirements placed on the agent.

The object of the invention was therefore to provide a technically simple and reproducible process for producing water-soluble filled hollow bodies, in particular a portion containing detergent, cleaning agent or care agent, which overcomes the aforementioned disadvantages in the prior art. Another object of the invention was to provide a process for producing elastically deformable, water-soluble hollow bodies which, in addition to an excellent dissolution rate and textile protection, has good properties with regard to the packability 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, which contain agents, in particular washing, cleaning and / or care agents.

The invention therefore relates to a process for producing completely or partially water-soluble, filled hollow bodies, comprising an agent, comprising the steps:

a) forming a hollow body from a material containing at least one water-soluble polymeric thermoplastic

b) filling the hollow body with an agent, preferably a washing, care and / or cleaning agent,

c) liquid-tight sealing of the hollow body and

d) shrinking of the hollow body material enveloping the agent.

Another object of the invention is a washing method, in particular a method for machine washing in a commercially available washing machine, comprising the steps that

- At least one detergent portion of the detergent and / or cleaning agent-containing hollow body according to the invention in the washing machine, in particular in the dispenser and / or washing drum, enters; the desired washing conditions are set; and when these conditions occur, the hollow body and / or the compartments opens in the aqueous environment and the detergent-active preparation (s) of the detergent Dispense portion into the wash liquor so that it comes into contact with the items to be washed.

Another object of the invention is a cleaning process comprising the steps that

- At least one detergent portion of the detergent and / or cleaning agent-containing hollow body according to the invention in the cleaning liquor;

- you set the desired cleaning conditions; and

- When these conditions occur, the hollow body and / or the compartments opens in the aqueous environment and releases the cleaning-active preparation (s) of the detergent portion into the cleaning liquor so that it comes into contact with the items to be cleaned.

Another object of the invention is a washing method, in particular a method for machine washing in a commercially available dishwasher, comprising the steps of adding at least one detergent portion contained in the hollow body and / or compartments according to the invention to the dishwasher, in particular in its washing-up chamber and / or enters into their washroom; the desired rinsing conditions are set; and when these conditions occur, the hollow body and / or the compartments opens in the aqueous environment and releases the rinsing-active preparation (s) of the detergent portion into the rinsing liquor so that it comes into contact with the items to be cleaned.

An essential step for the method according to the invention is the shrinking of the hollow body material which envelops the agent and which has at least one water-soluble polymeric thermoplastic.

The shrinkage properties of polymeric fabrics are mainly due to deformation and molecular orientation, which are imprinted on the molecular structure of the material during the manufacture and processing of the polymeric fabric and are frozen on cooling. The molecular chains are then frozen in a non-equilibrium state of reduced entropy that is similar to that of a stretched gum. When the fabrics are heated above the glass transition temperature or, in the case of semi-crystalline substances, above the crystallite melting point, the blocking of this "rubber elasticity" is released and the molecules strive to return to the orientation-free state of equilibrium. This results in a shrinking in the direction of orientation when the surface formation can deform freely, or a shrinking force if the deformation is impeded, in practice, for example, when applying a film to the wrapped material. The shrinkage increases with increasing temperature until all blockages are released and the sample is in the isotropic state. The shrinking force, on the other hand, has a maximum as a function of the temperature, because with increasing temperature the force-deformation module becomes smaller and the material increasingly changes into a viscous state, the shrinking forces being reduced by stress relaxation. As the heated fabric cools down, the shrinking force in the heat usually increases. The shrinking force that occurs after cooling to room temperature is influenced by the size of the modulus of elasticity and the thermal expansion coefficient and - in the case of partially crystalline plastics - by crystallization processes during cooling. It is therefore different for the various fabrics depending on the heat shrinkage achieved. The different fabrics differ in the size of the shrinkage forces and in the temperature range in which shrinkage forces occur. Surprisingly, it was also found that for water-soluble polymer thermoplastics, the deformation and molecular orientation which is imprinted on a polymeric sheet, for example by stretching or stretching during the production and / or processing of the polymeric sheet, the molecular structure of the material, by conditioning in a solvent. , preferably polar solvent-containing atmosphere, particularly preferably by conditioning in an atmosphere with increased relative atmospheric humidity, at least partially, which can result in a shrinking process of the polymeric fabric.

Without being bound by theory, it is believed that the solvent supplied, advantageously the moisture supplied, causes the polymer material to dissolve, which gives the polymer strands the flexibility necessary for reorientation to a stress-free state. The result is a contraction of the polymeric sheet and thus a shrinkage. The present invention makes particular use of this surprisingly found shrinkage effect from the production of flexible, elastically deformable water-soluble portions.

In a preferred embodiment of the present invention, the shrinking of the hollow body material enveloping the agent is therefore triggered in an atmosphere with increased relative air humidity.

For this purpose, the filled and liquid-tightly closed hollow bodies can pass through an air-conditioned room or a climate chamber which have the ideal conditions for the shrinking process for the respective water-soluble thermoplastics. The shrinkage is ideally triggered by conditioning the filled and closed hollow body in an atmosphere with a relative atmospheric humidity above 50%, preferably above 65%, particularly preferably above 80%, further preferably above 85%, extremely preferably above 90%.

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

Depending on the nature and material of the water-soluble polymer thermoplastic and the desired shrinkage strength, the shrinking process by conditioning, for example in a climatic chamber, within a typical dwell time in which the filled and liquid-tightly sealed hollow bodies are exposed to the shrinking-triggering conditioning conditions, is preferably at most 24 hours at most 2 hours, particularly preferably at most 30 minutes, most preferably 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 proven to be effective and advantageous, in particular when shrinking (partially hydrolyzed) polyvinyl acetate as the hollow body material, that the conditions that trigger the shrinkage act on the filled, liquid-tightly sealed portions at time intervals. Different changing climates with different relative air humidities and different temperatures can be run through in possibly varying time intervals. In terms of process technology, such conditions can be realized in that the liquid-tightly sealed and filled portions on transport media, for example conveyor belts, pass through different climatic stations, each with different climates, for a certain time. Such climate stations with integrated conveyor belts and the possibility of the products running through various climates are known, for example, from the confectionery industry, in particular the chocolate industry. The Pater-noster versions of climate cabinets from Winkler & Dünnebier are only mentioned here as examples. In a preferred embodiment, the shrinkage is achieved by iterative conditioning of filled hollow bodies n times, with n> 2, preferably 2 to 500, particularly preferably 2 to 20, alternately for a certain time interval, preferably shorter than 1 hour, more preferably shorter than 10 minutes, particularly preferably between 0.1 seconds and 5 minutes, treated under shrinkage-triggering conditions, as described above, and then for an equidistant or different Time interval treated under non-shrink-triggering conditions or changed shrink-triggering conditions.

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

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

The prior art already contains numerous drying devices which are known to the person skilled in the art, such as, for example, hot or cold air blowers, drying ovens, infrared light stations or devices which emit microwave radiation and which 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 the methods known in the prior art and known to the person skilled in the art. It is crucial, however, that the hollow body material enveloping the agent is shrinkable. For the formation of the hollow body, it is possible to use flat structures, for example foils, which contain water-soluble thermoplastic and have undergone a deformation in the course of their manufacturing process, which has brought the polymer material into a non-equilibrium state. Examples of such shrinkable polymeric sheets are blown films. They can be used, for example, to produce tubular bags according to the methods known in the prior art liquid-tight sealing of a tube at one end, filling the one-sidedly sealed tube with an agent and liquid-tight sealing of the filled tube piece at the other end, the tube being extruded and preferably stretched or provided by a shrinkable film by vertical sealing, producing closed, filled hollow bodies , Other suitable manufacturing processes for the formation of hollow bodies which can hold an agent are, for example, deep-drawing processes in which shrinkable foils are drawn or pressed into a cavity, processes for producing bags with three external sealing seams or bags which have four sealing seams. as described for example in WO 99/16681 A1. In the context of the present invention, however, those methods are preferred in which the hollow body is formed by the application of heat.

Experience has shown that the range of temperature applications on thermoplastics is limited in the lower area by the embrittlement of the material and in the upper area by thermal decomposition.

In the context of the present invention, the hollow body is preferably formed in a temperature range between the onset of softening and thermal decomposition, preferably in the melt range, of the polymeric thermoplastic.

The range in which a polymer material is thermoformable and the temperature region in which shrinkage of the material occurs are between the temperature at which the material softens (softness temperature) and the melting temperature. During the production of shrinkable polymeric sheets, such as, for example, film films, a prestress (uniaxial or biaxial) is impressed on the sheet in its thermoelastic region. These tensions in the polymeric sheets are frozen in the system and can subsequently be relaxed again by raising the temperature or preferably, as described above, by conditioning in an atmosphere with increased atmospheric humidity. The shrinkage forces and the degree of shrinkage depend on the type of polymer, the thickness of the polymeric sheet, the size of the prestress and the conditions which trigger the shrinkage.

In a preferred embodiment, the, preferably blow-molded, hollow body with and without compartments can be "turned inside out", ie it can be pushed through in such a way that the original inside becomes the outside and vice versa. This flexibility leads in particular to that in comparison with rigid shaped bodies increased resistance to leakage under pressure, to avoid stress cracks or breakage. The hollow bodies produced according to the invention dissolve completely or substantially in water, the agents contained in the closed hollow body and / or in the compartments being released into the environment in this way. For example, the hollow bodies containing agents according to the method of the invention can be used in an aqueous machine washing, cleaning or care process. It is preferred to use the hollow bodies produced according to the invention in commercially available washing machines or dishwashers. It is also possible to use the hollow bodies according to the invention in hand basins or in a bowl. An aqueous environment surrounding it is important for the release of the agent contained in the hollow body / compartments.

For the purposes of this invention, flexible hollow bodies preferably also include elastic hollow bodies.

The term “elastic hollow body” is understood in particular to mean that the hollow bodies containing the agents, in particular detergents, cleaning agents and / or care products, have an inherent dimensional stability which enables them under the usual conditions of manufacture, storage, transport and handling by the consumer to have a structure which does not collapse and which is stable against breakage and / or pressure, the unfilled and / or filled with at least one agent, preferably glycerol, preferably blow-molded hollow body, when stretched along its longest axis, a yield stress of between ≥ 3 N / mm ² and <15 N / mm ² , and / or with a compression path 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 ^> 0.1 and ≤ 500 N along a path si is deformable and after the loss of force in the direction of the original returns to the original form, or assumes the original shape completely or almost completely after the loss of force, and / or has a return speed v of between> 0.01 mm / min and ≤ 650 mm / min after the loss of a deformation force, and / or the modulus of elasticity the hollow body wall of the flexible unfilled hollow body, preferably produced by means of blow molding, or filled with agents, preferably glycerol, to> 80% by volume, is <1 GNm ² , preferably ≤ 0.1 GNm ² , preferably ≤ 0.01 GNm ² , and / or in the case of a preferably blow-molded hollow body filled with an agent, preferably glycerol, of ≥ 80% by volume, a compression resistance F _ma of between ≥ 20 N and <2000 N occurs. According to the invention, it is of no influence whether this structural stability is based solely on the properties of the flexible, preferably elastic, hollow body resulting from various parameters mentioned below and / or on the presence of compartmentalization devices and / or on the filling with washing-active, cleaning-active substances and / or active care preparations results. In preferred embodiments of the invention, the flexible, preferably elastic, hollow bodies themselves have sufficient inherent dimensional stability, since this advantageously affects the ease of movement in machines during the manufacture of the hollow bodies and the filling during the manufacture of the detergents, cleaning agents or Serving agent portions affects.

The unfilled hollow bodies, with and without compartments of the portioned agents according to the invention, can preferably be at least partially reversibly deformed by the action of force and have a certain restoring speed after the force has ceased to exist. High restoring speeds (for example> 2000 mm / min) are achieved by rigid bodies which "spring back" into the initial shape, provided they do not remain in the pressed-in state. This behavior of the "spring back" is undesirable since stress cracks in the hollow body in this way with and without compartments that allow product leakage. It is therefore necessary, on the one hand, to ensure a low return speed of the hollow body with and without compartments, on the other hand, the hollow body with and without compartments should be able to be deformed without breaking or cracking.

As mentioned above, the envelopes according to the invention should preferably be at least partially reversibly deformable (in the case of irreversible deformation, no restoring speed would be measurable). In preferred embodiments of the present invention, the deformation is completely reversible, i.e. Portioned washing, rinsing or cleaning agents according to the invention are preferred, in which the unfilled casing returns to its original shape after the application of the force.

The force F ^ depends on the indentation depth, since the hollow body, with and without compartments, opposes increasing resistance to the penetrating body. First of all, it is important for the present invention that the hollow bodies with and without compartments can be deformed at all with a force of 500 N or less. In preferred embodiments of the present invention, the details relate to forces at penetration depths of a round rod with an 8 mm diameter, in particular at a penetration depth greater than or 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-i is defined, not only the force but also the deformation work can be exactly determined. When force is exerted by a round rod with a diameter of 8 mm and a penetration depth of Si = 22 mm, the deformation work in the flexible, unfilled hollow bodies, which are preferably produced by means of blow molding, is significantly below the values of comparable rigid unfilled bodies, in which a deformation work of at least> 5 Nm must be done.

As mentioned above, the hollow bodies according to the invention should be able to be deformed at least partially reversibly with and without compartments (in the case of irreversible deformation, no return speed would be measurable). In preferred embodiments of the present invention, the deformation is completely reversible, i.e. Portioned agents according to the invention are preferred in which the unfilled hollow body, with and without compartments, returns to its original shape after the application of the force.

In an embodiment suitable according to the invention, the flexible, unfilled or ≥ 80% by volume filled with glycerol is preferably made by blow molding by a force F ^ ≤ 500 N along a path s- _\ = 22 mm, in particular by a force F ^ ≤ 100 N along a path Si = 22 mm, preferably by a force Fi ≤ 60 N along a path Si = 22 mm, preferably by a force Fi ≤ 40 N along a path Si = 22 mm and more preferably by a force F- _\ ≤ 20 N along a path si = 22 mm, vertical, central, in the direction of the shortest axis of the hollow body, deformable.

Unless otherwise stated, the hollow bodies filled with agent with and without compartments were tested at temperatures of 20.degree. C., the hollow body with and without compartments, for example, preferably being filled with ≥ 80% by volume with glycerol as the test medium.

It is advantageous if the flexible, unfilled or ≥ 80% by volume hollow body, which is preferably produced by blow molding, has a restoring speed v <1000 mm / min, in particular v <500 mm / min, preferably v <100 mm, after the force has ceased to apply / min, preferably v <50 mm / min, more preferably v <10 mm / min and particularly preferably v ≤ 1 mm / min. The deformation work required to deform the flexible, unfilled hollow body, which is preferably produced by means of blow molding, should be w <1.0 Nm along a path s = 22 mm, preferably w läng 0.75 Nm along a path Si = 22 mm and preferably w <0 , 50 Nm along a path s-ι = 22 mm. To determine the deformation work, the deformation force w acts vertically, centrally, in the direction of the shortest axis of the hollow body.

The deformation work required to deform the flexible hollow body, which is preferably produced by blow molding and is ≥ 80% by volume filled with glycerol, should be w ≤ 5.0 Nm along a path Si = 22 mm, preferably w ≤ 2.5 Nm along a path si = 22 mm, preferably w ≤ 1 Nm along a path Si = 22 mm, more preferably w ≤ 0.75 Nm along a path si = 22 mm and in particular w ≤ 0.5 Nm along a path Si = 22 mm. To determine the deformation work, the deformation force w acts vertically, centrally, in the direction of the shortest axis of the hollow body.

Another parameter for characterizing particularly preferred portioned agents according to the invention is the crush resistance. This can be determined in the form of a force-displacement diagram using commercially available tablet testing devices. A Zwick type 1425 universal testing machine was used for the purposes of the present invention.

The compression resistance is determined in accordance with DIN 55526 Part 1 by placing and compressing hollow bodies with and without compartments (= container) standing upright between the plates of a pressure test device, whereby the pressure force and the plate travel are recorded until the required compression resistance and plate travel reached or failure occurs due to critical deformation or leakage of the container.

The printing press was set to an upsetting speed of 10 mm / min. The test process was then started. The force [N] exerted on the portion at a penetration depth of 22 mm was printed out on the connected printer. The crush resistance is given in N. Hollow bodies containing portioned agents according to the invention are preferred here with and without compartments, the compression resistance F _ma χ of the hollow body containing portioned agents (= the filled hollow bodies 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 test purposes, the hollow body, preferably produced by blow molding, with and without a compartment is filled to an extent of 80 80% by volume with agent, preferably glycerin. The crush resistance of the flexible, unfilled or> 80 vol.% Hollow body, preferably produced by blow molding, should be between 75 to 400 N, preferably between 100 to 300 N and in particular between 150 to 250 N.

The modulus of elasticity of the hollow body wall of the flexible unfilled hollow body produced by blow molding or filled with> 80 vol.% Glycerol should be <1 GNm ² , preferably ≤ 0.1 GNm ² , preferably <0.01 GNm ² .

It is preferred according to the invention 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 and / or its compartment (s) produced according to the invention, preferably by means of blow molding, is particularly preferably transparent and / or translucent.

The flexible, unfilled or ≥ 80% by volume hollow body filled with at least one agent or glycerol as test agent preferably has a shrinking volume reduction of at least 0.5%, preferably at least 1%, particularly preferably at least 1.5%, more preferably at least 2%, in particular at least 3%, particularly preferably at least 5%, extremely preferably at least 6% and advantageously at least 10%.

In a further preferred embodiment, the flexible, unfilled or ≥ 80% by volume hollow body filled with at least one agent or glycerol as test agent has a length reduction along the longest axis of at least 0.2%, for example at least 0, by the shrinking step. 5%, preferably at least 1%, particularly preferably at least 1.5%, further preferably at least 2%, in particular at least 3%, particularly preferably at least 5%, extremely preferably at least 6% and advantageously at least 10%. Further preferred embodiments contain detergent, cleaning agent and / or care agent portions, the portions contained in the hollow bodies or compartments being water-soluble, preferably controllable, of the hollow body material at a specific point in time of the washing, cleaning or care process or when it is reached a certain pH value or a certain ionic strength of the wash liquor or due to other controllable events or conditions can be fed into the aqueous liquor. The quality of the material as well as its quantity / strength have a direct influence on these solubility properties. Materials for the hollow bodies are particularly preferred which - based on a certain wall thickness, which also determines the stability - dissolve in the aqueous liquor at certain temperatures, pH values, ionic strengths or after a certain residence time. Such a loosening process can capture the hollow body as a whole or only a part of it, so that parts of the hollow body come loose when a certain parameter combination is set, while other parts do not come loose (but only 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 to make the access to water more difficult due to the hollow body geometry and thus to delay the dissolving process. In another preferred embodiment, it is possible to design walls of the hollow body of different thicknesses (nevertheless from the same material) and thus to enable them to be released earlier at the thinner points. In likewise preferred embodiments, the walls of the hollow body can be produced from materials of different water solubility, for example from 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 to release the dissolved or undissolved constituents 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 maintenance-active agent, of which PVAL is an example as a builder, or contain one. In the latter case, for example, washing-active, cleaning-active or maintenance-active substances, which are only present in small amounts in the preparations and whose uniform incorporation is therefore not unproblematic, can, for example, in the material of the wall of the hollow body or in part of the material of the wall of the hollow body one that dissolves in the stage of washing, cleaning and / or care, in which the active ingredient is needed, incorporated and when the material of the wall is detached at the right time to be released into the fleet. An example of this may be fragrances that are desired in the last phase of the washing, cleaning and / or care process, but also optical brighteners, UV protection substances, dyes and other washing-active, cleaning-active or care-active preparations. The basic principle of incorporating such components (which are usually incorporated in small quantities) into the materials which form the portions of the detergent, cleaning agent and / or care agent portions is the applicant's co-pending patent application 199 29 098.9, entitled “Active ingredient - portion pack ", the disclosure of which is fully incorporated by reference into the disclosure of the present application.

In a special embodiment of the invention it is also possible for the walls of the flexible, preferably elastic, hollow bodies, which contain the detergent, cleaning agent or care agent portions, to consist of different materials, that is to say they have a heterogeneous structure. For example, in a polymer material forming the wall of the hollow bodies, islands of a foreign material that is not soluble in the polymer could be dispersed, for example of another polymer (with different water solubility) or even of a completely different substance (for example an inorganic or organic substance). Examples include 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 carboxymethyl cellulose. In particularly preferred embodiments of the invention, such a structure can be associated with the advantage that the other substance dissolves faster in water than the polymer, which enables water to penetrate into the hollow body and thereby accelerate the release of wash-active, care-active or cleaning-active components of the Portion contributes. Overall, the entire dimensionally stable hollow body is also more quickly dissolved in such an assembly than a shaped body made of a pure polymer material. Similarly, it is possible to form the walls of the hollow bodies from layers of two or more polymers, which can be selected in particularly preferred embodiments in such a way that their properties (stability, heat resistance, water solubility, gas barrier properties, etc.) complement one another optimally.

In the context of the present invention, blow molding processes for the production of filled, liquid-tightly closed hollow bodies have proven to be particularly suitable. Blow molding methods suitable according to the invention include extrusion blow molding, coextrusion blow molding. sen, spray-stretch bias and immersion bladders. In addition to simple, quick and safe producibility, the blow-molded hollow bodies also have the advantage that, due to the production process, they are already built up over a large area from an expanded, that is to say shrinkable, hollow body material, which allows the filled and liquid-tightly closed hollow bodies to shrink well.

The blow molding process is preferably carried out in that the hollow body is formed by primary shaping of a preform, particularly preferably a tubular preform, from a blow molding composition based on a water-soluble polymer thermoplastic, and then blowing the preform into a hollow body. Methods in which are preferred

(a) in a first step, a preform is produced by extrusion and

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

In a further preferred embodiment of the invention, the hollow body in which

(a) in a first step, a preform is produced by extrusion and is guided into a molding tool, 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 out of openings in the cavity, so that the thermoplastic material is applied to the mold , wherein the molding tool is cooled and / or optionally the temperature of a possibly existing head jaw for liquid-tight sealing of the hollow body is regulated via a separate temperature control circuit.

A separate temperature control circuit for an optionally available head cheek has proven to be advantageous since the heat sealing of the hollow body by means of a head cheek generally requires higher temperatures than in the remaining part of the molding tool. If the sealing 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 faulty seals. A separate temperature control circuit that Sealing required temperature is therefore preferred in the context of the present invention.

The wall thicknesses of the hollow body can be produced differently in some areas by means of blow molds, by correspondingly varying the wall thicknesses of the preform, preferably along its vertical axis, preferably by regulating the amount of thermoplastic material, preferably by means of an adjusting spindle when the preform is removed from the extruder nozzle, formed.

The hollow body can be biased with areas of different outer circumference and constant wall thickness by changing the wall thickness of the preform, preferably along its vertical axis, correspondingly to different thicknesses, preferably by regulating the amount of thermoplastic material by means of an adjusting spindle when the preform is removed from the extruder nozzle, formed.

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

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

In a preferred embodiment, the preform, the hollow body and / or the liquid-tightly closed hollow body consists of one or more component (s), the component comprising one or more materials based on one or different water-soluble polymer thermoplastics.

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

The release from the hollow body with and without compartments can either be achieved at different times by the fact that the blow-molded walls have different dissolution or disintegration speeds. This is possible, for example, by choosing the material thickness.

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

The filling opening of the hollow body after filling can be closed in a liquid-tight manner, preferably by material closure, preferably by means of thermal treatment, particularly preferably by putting on a hot melt.

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

It is advantageous if the melt flow index of the water-soluble polymer thermoplastic during extrusion, measured in the first step at 10 kg punch load, between 1 and 30, preferably between 5 and 15, particularly preferably between 8 and 12 and / or the melt flow index (MFI) of the water-soluble polymer thermoplastic, measured at 2.16 kg stamp load, between 4 and 40, preferably between 5 and 20, particularly preferably is between 8 and 15. Polyvinyl alcohol types which are particularly suitable for blow molding in the context of the present invention are medium to highly viscous and have, for example, MFI values of 6-8 (at 230 ° C., 2.16 kg load, PVA blend from 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 according to the invention by means of blow molding and / or its compartments) preferably has no seam, in particular no sealing seam, no pinch seam and / or no groove, in particular flange groove.

In one embodiment of the method according to the invention, a plurality of hollow bodies can also be formed in a hollow body by blow molding a preform with a plurality of layers, an intermediate space being formed between the layers during the 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, a preform with several layers, preferably 2 to 5, can be produced by means of coextrusion, 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 multi-layered ,

Serial, parallel and / or concentric arrangements of hollow bodies and / or compartments, preferably with walls made of the same or different materials, as described above, can preferably be produced by means of blow molding, preferably, but not exclusively, by using at least one double and / or multiple and / or coextrusion blow mandrel used. It is preferred if 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 sealing seam, no pinch seam and / or no circumferential seam.

According to the invention, however, the multi-piece design of the blow-molded hollow body is particularly advantageous. Particularly with regard to the dosing sovereignty of consumers and / or with regard to product aesthetics and / or with regard to the solubility and / or release of a coated agent in an aqueous solution and / or an application environment such as, for example, a washing or cleaning liquor improvements.

Preparations individually packaged in containers made of water-soluble material can be dosed in a consumer-friendly manner and represent an alternative to other single dosage forms, in particular tablets, characterized by special aesthetics. In many areas, this individual dosage is perceived as convenient. The consumer takes the corresponding product, doses it and does not have to worry about the dimensions of suitable quantities. In many cases, this form of offer also meets the criticism that a situation-dependent change in the dosage is no longer possible and thus, for example, one dosage unit is too little, but two units dose too much. In the form of the tablet, the manufacturer regularly suggests that it be designed like chocolate bars so that the consumer can "cancel" his individual dosing units as required. Compared to powders or liquids on the one hand (complete dosing sovereignty with almost unlimited variety of dosing options) ) and tablets or so-called pouches on the other hand (a dosing option), there is still the desire for a product segment that allows, for example, with two to twenty separately dosed units, a situation-dependent dosing without having to use an external measuring vessel each time.

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

The process according to the invention enables the production of filled and closed containers and is preferably carried out in-line according to the "blow-fill-seaP" process (BFS technology). In this blow molding / filling and sealing technique, the desired shape is first blown, then with the content filled and then closed in one operation a tube of plasticized water-soluble plastic material is extruded into an open blow mold, the blow mold is closed and expanded by generating an effective pressure gradient on the tube and applied to the shaping wall of the blow mold to form the container.

According to the invention, the blow-molded hollow bodies are preferably designed in several pieces, i.e. that several, separate hollow volumes are generated in the blow mold, which are connected to one another via webs. The webs are created by pressing the two hose walls together in the blow mold, where this has no cavities to form the hollow volumes. The material thickness of the webs can be determined by the wall thickness of the extruded tube and the shape of the pressing tool, the wall thickness of the hollow volumes depends on the amount of polymer material that is available for a specific volume of the hollow body to be produced. Depending on the shape of the interconnected hollow volumes to be produced, the wall thickness varies more or less strongly in the area of the hollow volumes. Blow-molded hollow bodies usually have greater wall thicknesses in the vicinity of the bottom and head regions than in the center of the container. Thicker wall thicknesses in the bottom and head area can not only be the result of the blowing process, but in particular can also be specifically set using their thermal heat capacity in order to achieve better sealability of the hose end pieces with a minimized risk of leakage. Particularly when filling with content / agent that is colder than the preform, this could otherwise lead to undesired premature cooling and solidification of the thermoplastic melt, which would result in inadequate and not liquid-tightly sealed closure parts. In the case of the multi-piece hollow bodies preferred according to the invention, the wall thickness of the hollow bodies can also be slightly higher near the web than in the areas (“bulged”) away from the web.

The term “blow-molded hollow body” thus encompasses a basic unit or unit of at least two interconnected units (“hollow volumes”) within a multiblock blister unit. The individual units or hollow volumes can preferably be separated individually. For this purpose, the Mulfi block blister units can be provided with suitable pinch seams and / or perforations which enable a usable unit to be separated from the entire 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 which has an elongated oval in cross section, that is to say normal to the extruded longitudinal axis forms; these two long sides in the cross-sectional oval are welded to one another in mirror image and form both surfaces which are in contact with one another and areas which are not in contact with one another, namely the cavities.

Processes according to the invention in which the water-soluble, blow-molded hollow bodies in the region of the filled hollow volume have wall thicknesses of 0.06-2 mm, preferably between 0.07-1.5 mm, more preferably between 0.08-1.2 mm, more preferably between 0.09-1 mm and most preferably between 0.1-0.6 mm are preferred.

In the method preferred according to the invention, the wall thickness of the webs connecting the filled hollow volumes is a maximum of twice the wall thicknesses located in the area 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 running squeeze seam, preferably with an additional perforation line, to predetermined breaking points which are in the range from 5 to 200 μm, preferably 10 to 150 μm, particularly preferably 15 to 100 μm and in particular 20 to 70 μm. The separability of the individual hollow volumes from the multi-block blister unit ("blow-molded hollow body") can thus be achieved by making the webs sufficiently thin or by perforating the webs.

Since each hollow volume is filled individually using a filling mandrel, it is possible to fill the individual hollow volumes with different compositions. In this way, detergents or cleaning agents can be produced in multi-block blister form, for example, in which the consumer finds the agent in a hollow volume for an additional benefit (for example additional bleaching agent and / or additional brightener for white laundry, additional color transfer inhibitors for colored laundry, additional enzymes for certain soiling such as Blood, etc.) or cannot be used by separating the corresponding hollow volume. This function can be carried out to such an extent that each individual hollow volume of a multiblock blister unit is filled differently - for reasons of process economy and user friendliness, however, it is preferred to have a manageable number of the different compositions present in a multiblock blister unit, usually one, two or three compositions. to keep.

It is also possible to fill two differently composed agents into one and the same hollow volume and to separate them from one another within a hollow volume. This embodiment has the advantage that the consumer does not mix the compositions which can separate, since it would have to destroy the hollow volume for this, but nonetheless incompatible substances (in the area of detergents or cleaning agents, for example, bleaching agents and enzymes) can be assembled side by side. The separation into several compartments within a hollow volume is achieved either by appropriately shaped hollow volumes with a plurality of cavities which cannot be separated from one another or by producing hollow volumes which have dividing walls.

The last-mentioned embodiment is preferred and can be realized simply by extruding a tube of plasticized plastic material and at least one partition formed from the plastic material and extending continuously inside the tube into an open blow mold, closing the blow mold and by generating one on the tube effective pressure gradient this is expanded and applied to form the container on the shaping wall of the blow mold. In this case, by closing the opened blow mold, the front end of the hose and the front end of each partition wall are welded together in order to close the container bottom connected to each partition wall, the expansion of the hose by supplying blown air from the container bottom opposite to the container neck The end of the closed blow mold is carried out in such a way that the blow air expands on both sides of each partition in order to form separate chambers in the container.

Characterized in that according to the invention the front ends of the hose and the relevant partition during extrusion, that is to say the parts of the plastic 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 of the blow mold is assigned to the container neck. Accordingly, the further processing of the expanded container can be carried out within the closed blow mold by, after the expansion of the container by means of blown air which is introduced through the container neck on both sides next to each partition, the filling process for each inner container chamber is carried out through the container neck without the Open the blow mold or remove the container.

However, a manufacturing variant of compartmentalized hollow volumes can also be preferred, in which the at least one co-extruded partition itself represents a coextruded tube, preferably concentric in cross-section elongated to an oval. Analogous to the blowing and filling process described above, this can only be blown and filled on both sides, so that a collapse of the central, enclosed volume again results in a quasi two-layer partition. But it can also be desired to also fill the middle compartment by providing a further blowing and filling mandrel. It is also conceivable to extend this principle to the coextrusion of several blown extruded and filled compartments, it being particularly preferred to give the individual hoses / preforms different properties such as a barrier layer function, a function as a mechanical stability transmitter, a function by a different choice of material to be added as a temperature switch. Furthermore, it may also be desirable to bring the hoses / preforms coextruded from different materials or partitions into multilayer hoses / preforms, ie to collapse them. In this way, single-chamber hollow volumes can be produced, which are encompassed by multi-layer shells; Examples include combinations of polyethylene glycol, preferably on the inside, as sticky, with PVA or recycled polymer, preferably on the inside, with fresh thermoplastics.

The filling process can be carried out both in the case of single-chamber hollow volumes and also in the case of the multi-chamber hollow volumes by means of a combined blowing and filling mandrel or by means of a separate filling mandrel which is inserted into the container neck after the blowing mandrel has been withdrawn. A particular advantage of the BFS process is that, after the container has been filled, the container neck can be finished by means of an additional welding process which is carried out while the blow mold is still closed, and at the same time can be hermetically sealed with a closure formed by the welding process. This can be done by movable upper welding jaws or head jaws, which are arranged on the top of the blow mold. Any desired desired shape and / or closure processes can be carried out, for example a closure that can be torn off at a predetermined breaking point or separation point can be formed, preferably in the form of a rotary toggle closure. It goes without saying that an external thread could also be formed on the container neck in order to form a screw closure with a separate closure element. In the case of the moldings according to the invention, due to their water-soluble nature of the polymer casing (s), a particularly preferred upper closure form is represented by merely sealing and separating protruding slug material, quasi analogously to the welding of the front hose or partition wall end (s) to the hollow body floor. In the welding process carried out on the neck of the container, separate closures can be formed for each chamber of the container or a closure that closes all the chambers of the container together.

The formation of an intrinsically divided extrusion tube can be achieved, for example, in that the end of the extruder device facing the blow mold is provided with a Nozzle ring is equipped, in which a nozzle core is arranged coaxially to the longitudinal axis of the nozzle, the core tip of which defines an annular outlet with the end region of the nozzle ring, from which extruded plastic material emerges in the form of a tube. The melted plastic material reaches 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 part of the nozzle core, so that there is a storage area for the supplied plastic material.

The core tip is screwed to the adjoining, upstream part of the nozzle core via a pin with an external thread in such a way that the surfaces of the core tip and the subsequent part of the nozzle core facing one another are arranged at a distance from one another. The corresponding surface of the core tip forms a funnel surface, while the facing surface of the remaining nozzle core defines a conical surface. These surfaces, which preferably include angles of inclination of 65 ° or 60 ° with respect to the longitudinal axis of the nozzle, form between them a guide device for plastic material branched off from the annular gap, which occurs between the surfaces at the storage area. Through holes in the pin of the core tip, which has an external thread, this branched-off plastic material reaches an exit slot formed in the front of the core tip. From there, the branched-off plastic material emerges as a web running transversely within the extruded tube, which, after the tube has been expanded, forms the partition in the container formed in the process. On both sides next to the outlet slot, i.e. On both sides of the plastic sheet emerging from the exit slot, there is preferably an exit opening for supporting air in the end face of the core tip, which are connected to a central air duct via branch lines which are formed in the pin having the external thread.

The air supplied from the air duct via the outlet openings is provided as supporting air, which merely prevents the extruded hose from collapsing and sticking together with the web forming the partition. The expansion of the container in the blow mold takes place in an additional work step by means of a blowing and filling mandrel which, in an arrangement analogous to the outlet openings of the core tip, has blowing openings for the supply of expanding blowing 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 containers produced by the method according to the invention takes place by means of upper movable welding jaws on the relevant blow mold. The upper welding jaws can be used to form any type of closure when shaping the container neck in the manner known in the relevant technology for single-chamber containers, for example according to the botteipack ^® system from Rommelag. For example, a rotary toggle closure can be formed on the container neck. Here, the welding process is carried out in such a way that both chambers are closed by a twist-off toggle, which can be separated at a separation point designed as a predetermined breaking point, by rotating it with the aid of its molded-on handle.

After pulling back the blow mandrel and inserting a filling mandrel, which has a filling opening for each container chamber separated by the partition, both chambers can now be filled while the container is still inside the blow mold.

After filling, the mandrel is withdrawn and the upper welding jaws are moved together in order to carry out a further welding process on the neck of the container, in which the neck of the container is finally formed and at the same time closed.

After the container has been filled and the filling mandrel withdrawn, if desired, inserts can be introduced into the container neck before the container is hermetically sealed. This can be further active substance in solid form (for example an enzyme tablet) or non-functional "gimmicks" or another foreign part that can be inserted using a vacuum gripper before the welding jaws are moved together in order to weld around the insert and at the same time a hermetic seal to build.

The method according to the invention is not restricted with regard to the size of the multiblock blister pack and the individual hollow volume. Preferred methods 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, further preferably 10 to 100 ml and in particular 15 to 50 ml.

The method according to the invention is also not restricted with regard to the number of hollow volumes to be combined to form a multiblock blister pack. Methods are preferred 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 hollow bodies produced in the process according to the invention are released by disintegration or dissolution of the container wall under conditions of use. It is not necessary for the entire container to dissolve before a release occurs. A faster release can take place according to the invention in that the container wall is provided with special “predetermined breaking points” which disintegrate or dissolve quickly under conditions of use and thus lead to an early release of the ingredients. Processes according to the invention are preferred here in which the water-soluble, blow-molded Hollow bodies in the area of the filled hollow volume have an area of lesser wall thickness, which is preferably mechanically protected by countersinking, the areas of lesser wall thickness being 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 to 0.75 times the wall thickness of the hollow volumes.

The shape of the containers, i.e. Both that of the multiblock blister and that of the individual hollow volume can be chosen as desired. Preferred methods are characterized in that the filled hollow volumes are rotationally symmetrical to their longest axis and preferably to the normal on the squeeze surface. This preferred shape preferably has a length: diameter ratio of 1.5: 1 to 50: 1 for the individual hollow volume, ratios of 4: 1 to 10: 1 being preferred. In such forms, the connecting webs are preferably arranged along the long sides of the hollow volume.

It can also be preferred according to the invention that the filled hollow volumes are not rotationally symmetrical to the normal to the squeezing surface. This can be achieved, for example, by choosing a blow mold whose depth is more than 0.5 times the division width. If the extruded tube is now blown between two such molds, a hollow volume is created that has a width (extension in the direction of the squeeze surface, perpendicular to the extrusion direction of the original tube) that corresponds to the pitch of the blow mold, but a depth (extension in the direction of the normal) on the squeezing surface and perpendicular to the direction of extrusion of the original hose), which has a multiple of the pitch. Such ovalized hollow bodies can be preferred, with in particular width: depth ratios of 1: 1, 1 to 1: 3, preferably of 1: 1.2 to 1: 2.5 and in particular of 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 30 to 120 mm, preferably 40 to 100 mm and in particular 45 to 70 mm.

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

Another suitable method for forming a hollow body is the thermoforming method. In a preferred embodiment, the hollow body is formed by thermoforming a film material based on a water-soluble polymeric thermoplastic.

The hollow body is formed by equipping a packaging machine with a roll of film material which is drawn through a heating zone (contact, heat or heating by irradiation) and passing a molding station equipped with cavities in order to be deep-drawn there , The water-soluble film material is clamped in the forming station and is pressed into the cavities, the layer thickness decreasing in proportion to the enlargement of the surface. 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 depends on the material and is also limited by the desired minimum thickness of the packaging. Immediately after the thermoforming process, the deep-drawn containers are filled with an agent, preferably a washing, care and / or cleaning agent, and sealed with a film in a liquid-tight manner.

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

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

Thermoforming is a stretching process that is usually carried out in a continuous process. The object to be manufactured is attached to its corners and the enlargement of the geometry area goes hand in hand with the reduction in 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 item. Occasionally, the attached preform is also transported to the heating zone. With multi-station machines, the heating and molding 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 the mold formation. The process involves heating the film material 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, heating can take place on one or both sides. Heating with infrared radiation is advantageous since the energy input can take place directly on the material, so that a high thermal energy density can be introduced into the polymer material, the heating time being reduced without causing thermal damage to the polymer surface.

In all thermoforming processes, the heated preform is quickly drawn biaxially. This process usually takes place within a short time interval, for example less than 0.5 seconds, and can be regarded as isothermal as long as the polymer material is released (without contact with the mold wall). Upon contact with the walls of the cavity into which the polymer material is drawn, the polymer material cools down immediately. Mechanical drawing mechanisms, compressed air and vacuum are used to carry out the stretching process. In a preferred embodiment, the hollow body is formed by deep-drawing a film material into a cavity, preferably by additionally applying a vacuum out of openings in the cavity.

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

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

The polymer chains become more oriented by stretching or pulling the water-soluble thermoplastic. In order to achieve the shrinkage effect desired according to the invention, it is advantageous, as already described in the blow molding process, to freeze the orientation, for example by means of an exogenously induced temperature jump. It has been found that stretched, preferably blown, films can be shrunk. Preferred within the scope of the present invention is therefore the liquid-tight sealing of the hollow body formed by the thermoforming process and subsequently filled with an stretched, preferably blown, film. The use of an stretched film for closing the thermoformed hollow body ensures that the sealing film (cover film), namely the stretched film, also makes a contribution to the final shrinking of the hollow body. The sealing is preferably carried out as a heat seal in that the cover film is welded to the deep-drawn base film along the flange delimiting the cavity by the action of heat, preferably additionally by the action of pressure, by means of a heat seal plate. Of particular advantage with this type of sealing are the continuously surrounding sealing seams, which, in comparison to tubular bags with additional vertical sealing seams, do not have an overlapping sealing area, that is to say no area where sealing seams cross. The cavities preferably have no acute angles or sharp edges; particularly preferred are round, in particular hemispherical cavities or those which have rounded corner regions. The rounded corner areas and / or flange areas are advantageously equipped with heat- and pressure-resistant deformable rubber materials, for example made of silicone polymers, in order to avoid damage to the film or the sealing seam that may occur due to rough surfaces or edges and tips. The cavities are in preferred embodiments not individually, but rather as mold cavities, that is to say as a mold with a multiplicity of cavities, for example as a plate, in which there are 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 obtained when the individual filled and sealed hollow bodies are cut out as small as possible.

In one embodiment of the invention, the hollow bodies according to the invention formed by the thermoforming process are in two or more pieces. For example, entire mold cavities with a plurality of hollow bodies which are linked to one another via film webs can be provided. In a preferred embodiment, the coherent hollow bodies are at least partially filled with different agents, so that the consumer can break out or detach a filled hollow body from the dressing, depending on the need and intended use. The hollow bodies containing different agents can be made known to the consumer, for example, by a different coloring or by different aggregate states of the agents, for example powdery and liquid.

In a particularly preferred embodiment of the present invention, the hollow bodies according to the invention have two or more compartments. In this case, for example, two filled and sealed hollow bodies produced by the thermoforming process can be sealed with one another via their respective cover films, as is described, for example, in WO 01/03676 A1. As a result, capsules can be obtained which have two thermoformed halves (compartments). The advantage of such two- or multi-component systems lies not only in the possibility of separating active substances which interfere with one another, but also in the fact that the capsule now consists of two shrinkable, since deep-drawn hollow bodies. In a further preferred embodiment, the manufacture of two- or multi-compartment systems takes place in that an already formed, preferably thermoformed, filled and liquid-tightly sealed hollow body is used for the liquid-tight sealing of a further thermoformed hollow body filled with an agent. The cover film of an already filled and closed hollow body is preferably used for the liquid-tight sealing of the next filled thermoformed hollow body. The advantage of this technology for the production of multi-compartment systems lies in the low material expenditure and the presence of large quantities of stretched or deep-drawn foils, which are of great importance for the shrinking step. A further preferred method for producing completely or partially water-soluble filled hollow bodies is the rotary die method, as is described, for example, in WO 97/35537 for the production of water-soluble capsules.

In a preferred embodiment of the invention, the hollow body is formed in the course of a rotary die process.

The filled hollow bodies are produced in that a liquid agent, preferably a washing, care and / or cleaning agent, is injected locally via a metering device by means of a filler wedge between two belts made of water-soluble polymeric thermoplastic, which are mounted on two rotatably parallel bearings Forming rollers are located, which have hollow shapes on their circumferential surfaces, the shape of which corresponds to half a hollow body to be produced. The sealing is done by pressure contact of the two foil tapes. In a preferred embodiment, in order to improve the sealing, at least one of the water-soluble film tapes is dissolved with a solvent before the molding process. Heat sealing of the two hollow body halves is further preferred. For this purpose, the two shaping rollers can advantageously serve as electrodes for the dielectric fusion of the foils with one another. A vacuum can advantageously be applied to the cavities to facilitate the molding process by injecting the liquid agent. This leads to the fact that the injection pressure of the liquid can be reduced and thus the risk of contamination of the polymer material with liquid filling material at the sealing positions is reduced. The shaping rollers advantageously have roughening in the region of the shaping roller webs. The roughening of the form roller webs increases the static friction for the film strips from which the portions are made.

The shape of the hollow molds in the forming rollers enables hollow bodies with almost any geometry to be produced. A preferred requirement is that they have a mirror plane. Geometries such as balls, eggs, cubes, figures are preferred in the context of this invention.

A precisely measured amount of the agent is injected into the developing hollow body via the metering device. It is particularly advantageous if the injection pulse is followed by a return stroke of the metering device. This prevents dripping or stringing of the agent, which in turn can lead to contamination of the water-soluble film in the area of the sealing position. It is particularly advantageous if the film strips are heated before their stretching process by injecting the liquid or by applying the vacuum, as already mentioned in the thermoforming process and blow molding process, in order to generate tensions within the thermoplastic. who try to relax in the final shrinking step and therefore give the hollow body its special flexibility and elasticity.

In a particularly preferred embodiment, two-compartment hollow bodies filled using the rotary die process are produced, as is explicitly described in WO 00/28976.

The filled hollow bodies can be punched out or cut out of the foil strips or are presented in several pieces. In the case of multi-part dosage forms, the connecting webs, as also in the multi-part dosage forms produced by the thermoforming or blow molding method, are advantageously provided with perforations, so that it is easier for the consumer to separate individual hollow bodies.

In a further embodiment, the hollow body or parts of the hollow body can be formed by an injection molding process. The injection molded parts can subsequently be given shrinking properties by uni- or biaxial stretching, or the injection molded hollow bodies are closed with shrinkable materials, for example shrink films.

It has been found in the abovementioned processes, in particular in the blow molding process, that the conditions for shrinking the hollow body material enveloping the agent are particularly favorable if the formation of the hollow body or the blow molding of the preform into a hollow body under the mechanically stretching conditions under the enveloping hollow body material, preferably in more than one preferred direction. It is further preferred if this process is terminated in a defined manner, preferably by means of a temperature jump induced exogenously in the polymer thermoplastic, as a result of which this is cooled into the region of its, preferably below, its softening temperature.

As a result of the rapid cooling of the water-soluble polymer thermoplastic, it is achieved that the stresses imposed on the polymeric sheet by the mechanically stretching conditions are "frozen" in the thermoplastic, that is to say remain fixed. The higher the extent of the frozen tension remaining in the thermoplastic sheet, the higher The exogenously induced temperature jump of the thermoplastic can be achieved, for example, by cooled molds or cavities into which the warmer thermoplastic is drawn and / or blown. The molds or cavities are preferably by separate cooling circuits thermostatically controlled can be adapted to the required cooling conditions. the temperature gradient can also or additionally be achieved by cooling gases which support the formation of the hollow body, for example by cooled supporting or compressed air during the blow molding or thermoforming process. In addition to preheated air, the use of inert gases, such as carbon dioxide or nitrogen, is particularly suitable here, since these gases additionally protect components of the agent to be coated, which are sensitive to oxidation, from oxidation by atmospheric oxygen.

The temperature difference (Delta T) that the thermoplastic experiences as a result of the jump in temperature also determines the extent to which the stresses applied to the polymer are retained.

In a preferred embodiment, the cooling temperature jump induced exogenously in the polymer thermoplastic has a delta T of at least 5 ° C., preferably at least 10 ° C., more preferably at least 15 ° C., even more preferably at least 30 ° C. and particularly preferably at least 50 ° C. on.

In a further embodiment of the present invention, the exogenously induced temperature jump is achieved by filling the hollow body with an agent, preferably a washing, care and / or cleaning agent. The agent is preferably at a temperature below the melt temperature, preferably below the softening temperature of the water-soluble thermoplastic and / or at a temperature below 50 ° C., preferably below 35 ° C., more preferably below 25 ° C., even more preferably below 20 ° C. and particularly preferably bottled below 15 ° C.

In order to achieve bulky, aesthetically pleasing portions, it has proven particularly advantageous in the context of the present invention if, in the course of the method according to the invention, a cooled gas is added to the hollow body before the hollow body is sealed. Gases in the sense of the present invention are all substances which have a boiling point below 25 ° C. at an air pressure of 1 bar. When it is added to the hollow body, the cooled gas advantageously has a temperature below 20 ° C., preferably below 10 ° C., particularly 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 the large increase in volume that occurs with heating and constant pressure, which leads to a "pumping up" of the filled hollow bodies. 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 Liquefied gases such as liquid nitrogen, butane, propane and argon have proven to be economically easy to access. However, the use of solid carbon dioxide, which is also known as dry ice, has proven to be particularly advantageous. It can easily be metered into the shaped hollow body in the form of pellets with the other ingredients or can also be introduced into the hollow body after filling, which is followed by the liquid-tight closing of the hollow body as a subsequent step. When the gases are warmed to room temperature, they expand and form plump, elastic, liquid-tight, hollow bodies.

The enveloping material made of water-soluble thermoplastics surrounding the filled hollow bodies advantageously forms a barrier layer for the gases to be used. Within the scope of this invention, the polyvinyl alcohols listed have proven to be particularly suitable, as they have an excellent barrier layer for a large number of gases, in particular for carbon dioxide.

The use of gases that are easy to detect, so-called test gases, is particularly advantageous. The escape of these gases from the filled hollow body is, due to the internal pressure that builds up when heated, can be detected particularly reliably quickly if there is a defect in the envelope material. The detection can take place, for example, in a vacuum chamber in which gas-specific sensors are additionally attached. For leak detection, the closed and filled hollow bodies can be guided through a tunnel with a slight vacuum, for example, where highly sensitive detectors show traces of the indicator gas. Depending on the detector, in principle all gases or gas mixtures are suitable as test gases, but the gases are preferably selected from the group of 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. Mixtures of carbon dioxide with carbon monoxide and / or hydrogen and / or noble gases are particularly preferred. Also preferred are 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, particularly preferably greater than 8: 1 and in particular 95: 5. Hydrogen-containing test gas mixtures are preferred according to the invention because of their excellent detectability. Test gas detectors containing hydrogen are sold, for example, by Sensitor Technologies, Mühlheim, Germany under the name H 2000.

In a further preferred embodiment of the method according to the invention, an additional detection step for leaks follows the liquid-tight sealing of the preferably blow-molded hollow body. Especially in industrial applications Fertilizing the method according to the invention with a high product throughput, it is advantageous to check the filled blow-molded hollow bodies for leaks immediately after their production, in order to avoid the contamination of further filled hollow bodies, which may be in the same outer packaging as the damaged filled hollow body and ensure quality assurance. A purely visual assessment of the hollow bodies produced is possible in principle, but offers little advantages from an economic point of view, particularly in industrial production with high product throughput, since it is very labor-intensive. Electronic detection systems for leaks have proven to be particularly advantageous. A particularly suitable detection system for determining leaks in preferably blow-molded hollow bodies, in particular filled with liquids, is the high-voltage leak detector (HVLD detector) sold by Rommelag. The detection method is based on the electrical conductivity of the filling material, which is encased by a non-conductive or only weakly 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 discharge 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 being faster dissolution in an aqueous solution to ensure that the wall thickness of the adjacent surface is less. 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.

The areas with a lower wall thickness are advantageously produced by embossing information, such as calibration marks, application instructions, hazard symbols, brands, weight, filling quantity, expiry date, images, particularly preferably by embossing a logo.

The wall thickness of the hollow body and / or the compartments, which is preferably formed by blow molding, should be designed such that the agent contained in the hollow body and / or in the compartments, in particular washing and / or cleaning agent, into the aqueous application liquor within 5 5 minutes, preferably partially or completely released within ≤ 3 min, preferably within ≤ 1 min. To determine the release time, the hollow bodies, with and without a compartment, were placed in 10 liters of agitated water, stirrer speed> 60 rpm, 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. The release time is more preferably determined directly in the aqueous application liquor of at least one washing machine and / or dishwasher which is commercially available.

The water-soluble thermoplastic used in the 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, polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose, starch and derivatives of the aforementioned substances, in particular derivatives of polyvinyl alcohol (PVA), acetalized polyvinyl alcohol, cellulose and / or mixtures of the abovementioned polymers, polyvinyl alcohol and partially hydrolyzed polyvinyl acetate being particularly preferred.

The polyvinyl alcohols described above are commercially available (absorbed into the Kuraray Specialties Europe KSE), for example under the trade name Mowiol ^® ex Clariant. Particularly suitable in the context of the present invention, polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88, Mowiol ^® 8-88 and L648, L734, Mowiflex LPTC 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 can be found in the table below:

Other polyvinyl alcohols suitable as material for the hollow mold 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 of 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 Makes up 88 mol%.

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

In the context of the present invention, preference is given to 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 polymer thermoplastics in amounts of at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight and in particular at least 90 % By weight, in each case based on the weight of the entire hollow body material.

To facilitate their manufacture, in particular with regard to their manufacture by blow molding, the hollow bodies can contain plasticizing aids, ie plasticizers. This can be particularly advantageous if polyvinyl alcohol or partially hydrolyzed polyvinyl acetate have been selected as the material for the hollow bodies. Glycerin, triethanolamine, ethylene glycol, propylene glycol, diethylene or dipropylene glycol, diethanolamine and methyldiethylamine have proven particularly useful as plasticizers. Depending on the amount and type of plasticizer, the surfaces of the processed water-soluble polymer thermoplastics can give the consumer a haptic impression of "stickiness". Because of their excellent softening effect and the reduced stickiness of the surfaces of the hollow bodies produced according to the invention, the water-soluble polymer thermoplastics contain in one particularly preferred embodiment as plasticizer mono-, di- , or triglycerides, preferably mono-, di- or triglycerides, which are linked to at least one C ₆ -C ₃₀ fatty acid residue, particularly preferably those which are linked to at least one C ₁₂ -C ₂₄ fatty acid residue, in particular glycerol monostearate or glycerol monooleate ,

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

The flexible, preferably elastic, water-soluble hollow body can have flange parts and, if appropriate, be connected and / or closed by at least one further hollow shape by positive locking and / or material locking, preferably by welding.

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 multiple layers.

It is also preferred if, in particular in the case of the hollow bodies produced by the blow molding process, at least two layers of the wall of the hollow body and / or at least two layers of at least one compartment are designed in such a way that an intermediate space is formed between the layers.

In a particularly preferred embodiment of the invention, a detergent, cleaning agent and / or care agent portion comprises a flexible, preferably elastic, hollow body made of at least one detergent-active, cleaning-active or care-active preparation completely or partially surrounding a washing, cleaning or care condition disintegratable, preferably blow-molded, material with at least one compartment, the compartment (s) containing one or more wash-active, cleaning-active or care-active preparation (s).

In the embodiment mentioned, the one hollow body comprises at least one compartment, ie a chamber, in its interior. Such a chamber or such a compartment is generally a space delimited by walls (in the case of only one compartment these are the walls of the hollow body). However, several spaces can also be located within the walls of the flexible, preferably elastic, hollow body according to the invention. This can either be formed in that individual rooms are separated from one another by walls, which are referred to as "compartmentalization devices" in the context of the present invention and spatially separate the same or different washing-active, care-active and / or cleaning-active components or preparations from one another , or that different washing-active, care-active or cleaning-active components or compositions directly adjoin one another, but do not mix with one another, in such a case the interfaces (phase interfaces) of the adjoining components or compositions are the compartmentalization devices the compartment is wholly or partially, advantageously entirely, surrounded by the enclosure from a material which can be disintegrated under washing, cleaning and / or care conditions, preferably blow-molded, and which covers the wall of the flexible, preferably elastic, hollow body One or more wash-active, cleaning-active or care-active preparation (s) are / are contained in the compartment or in the chamber. In most embodiments of the invention, a compartment advantageously contains several wash-active, cleaning-active or care-active preparations; However, it is also conceivable for only one such preparation to be present in a compartment or in a chamber.

In a particularly preferred embodiment of the invention, the hollow body contains a plurality of compartments or chambers in its interior, each of which contains one or more washing-active, cleaning-active or care-active preparation (s). Examples of this are cuboid or trochoidal, in particular spherical, flexible, preferably elastic, hollow bodies which have two, three or four or even more compartments, each of which contains one or more washing-active, cleaning-active or care-active preparation (s). A great advantage of this embodiment of the invention is that the various washing-active, cleaning-active or maintenance-active preparations can be distributed over the compartments in the way that is best for the special requirements. Components that adversely affect each other in their effectiveness (for example enzymes, alkali, bleach, etc.) or that would otherwise mix, for example due to the state of matter, such as solid and liquid components, can be spatially separated from one another. On the other hand, it is possible to spatially separate components that should ideally be released into the respective fleet at different times of the washing, cleaning or care process and to add them to the fleet at the optimum time. The size and shape of the individual compartments within a flexible, preferably elastic, hollow body is not critical and can largely be adapted to the needs of the individual case. For certain washing-active, cleaning-active or care-active preparations or mixtures thereof, which are present in large quantities, larger compartments can be provided than for preparations which are only present 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, cleaning or care course and are present in certain quantities can be spatially separated from other components or those required in other quantities and arranged in compartments of a different size become.

In a particularly preferred embodiment of a flexible, preferably elastic, hollow body with at least one, preferably several compartment (s) containing detergent, cleaning agent or care agent portion, two or more, one or more washing-active, cleaning-active or care-active preparation ( en) containing compartments of the hollow body, which are arranged enclosing each other. The compartments with the wash-active, cleaning-active and / or care-active preparation (s) are therefore not arranged next to one another or one above the other or one below the other in the hollow body, but rather enclosing one another, for example more or less concentrically (“onion model”) or more or less coaxially ("Multi-layer rod model") or in such a way that the innermost compartment is completely surrounded by the next outer one, if necessary completely again by the next, etc. In such a case, the washing-active, cleaning-active or care-active substances can be distributed to the compartments in this way be that the components required first in the washing, cleaning or care process are contained in the outermost compartment, which is the first to be exposed to the ingress of water or liquor, while (a) later required component (s) in ( a) compartment (s) located further inside is / are and in front the access of water is protected by the compartments located further outside. In the context of this embodiment, it is not necessary for the compartments lying inside to be completely enclosed by the outer compartments; partial enclosure is also within the scope of the present invention.

According to a further preferred embodiment, the invention relates to at least one flexible, preferably elastic, hollow body containing a detergent, cleaning agent and / or care agent portion, the wall of the hollow body and / or the compartments comprising at least one washing-active, cleaning-active and / or care-active preparation includes, which can be disintegrated under washing, cleaning or care conditions. It is preferred if the material used for the production of the hollow body and / or the compartments and / or the preform, comprising at least one water-soluble thermoplastic, already comprises washing-active, cleaning-active and / or maintenance-active preparation, which is carried out under washing, cleaning and / or care conditions is disintegrable.

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

It corresponds to a preferred embodiment if the two or more flexible, preferably elastic, hollow bodies consist of several different materials or (possibly similar) materials with different properties which - with particular advantage - can be disintegrated under washing, cleaning or care conditions. Such materials of the hollow body (s) include, but are not limited to, one or more water-soluble polymer (s), preferably one or more materials from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinyl pyrrolidone, polyethylene oxide, Gelatin, cellulose, and their derivatives and their mixtures, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).

In a further, likewise preferred embodiment, it is advantageous according to the invention if the flexible (s), preferably elastic (s), hollow body comprises one or more materials from the group consisting of polymers containing acrylic acid, polyacrylamides, oxazoline polymers, polystyrene sulfonates , Polyurethanes, polyesters and polyethers and mixtures thereof.

One or more materials can be mentioned with particular advantage from the following exemplary, but not restrictive list:

- Mixtures of 50 to 100% polyvinyl alcohol or poly (vinyl alcohol - co - vinyl acetate) with molecular weights in the range from 10,000 to 200,000 g / mol and acetate contents from 0 to 30 mol%; these can include processing additives such as plasticizers (glycerin, sorbitol,

Water, PEG etc.), lubricants (stearic acid and other mono-, di- and tricarboxylic acids), contain so-called "slip agents" (eg "Aerosil"), organic and inorganic pigments, salts, blowing agents (citric acid-sodium bicarbonate mixtures); Acrylic acid-containing polymers, such as. B. copolymers, terpolymers or tetrapolymers which contain at least 20% acrylic acid and have a molecular weight of 5,000 to 500,000 g / mol; particularly preferred as comonomers are acrylic acid 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 methyl methacrylate chloride, TMA -trimethylammonium chloride (MAPTAC). Other monomers such as acrylamide, styrene, vinyl acetate, maleic anhydride, vinyl pyrrolidone can also be used with advantage;

Polyalkylene oxides, preferably polyethylene oxides with molecular weights of 600 to 100,000 g / mol and their derivatives modified by graft copolymerization with monomers such as vinyl acetate, acrylic acid and their salts and their esters, methacrylic acid and their salts and their esters, acrylamide, styrene, styrene sulfonate and vinyl pyrrolidone (example: Poly (ethylene glycol - graft - vinyl acetate) The polyglycol content should be 5 to 100 wt .-%, the grafting content should be 0 to 95 wt .-%, the latter can consist of one or more monomers Graft fraction of 5 to 70% by weight; the water solubility decreases with the graft fraction;

Polyvinyl pyrrolidone (PVP) with a molecular weight of 2,500 to 750,000 g / mol; Polyacrylamide with a molecular weight of 5,000 to 5,000,000 g / mol; Polyethyloxazoline and polymethyloxazoline with a molecular weight of 5,000 to 100,000 g / mol;

Polystyrene sulfonates 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, vinyl pyrrolidone; 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, especially the reaction products of diisocyanates (e.g. TMXDI) with polyalkylene glycols, in particular polyethylene glycols with a molecular weight of 200 to 35,000, or with other difunctional alcohols to products with molecular weights of 2,000 to 100,000 g / mol;

Polyester with molecular weights of 4,000 to 100,000 g / mol, based on dicarboxylic acids (e.g. terephthalic acid, isophthalic acid, phthalic acid, sulfoisophthalic acid, oxalic acid, succinic acid, sulfosuccinic acid, glutaric acid, adipic acid, sebacic acid, etc.) and diols (e.g. polyethylene glycols, for example with molecular weights from 200 to 35,000 g / mol);

Cellulose ether / ester, e.g. Cellulose acetates, cellulose butyrates, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, methyl hydroxypropyl cellulose, etc .;

- Polyvinyl methyl ether with molecular weights of 5,000 to 500,000 g / mol;

- Graft polymers which are obtainable by radical polymerization of vinyl esters of aliphatic C1-C24 carboxylic acids in the presence of polyethers with an average molecular weight of at least 300 (number average), for example by the radical polymerization of vinyl acetate in the presence of polyethylene glycols with a molecular weight of 500 to 100,000 , preferably a molecular weight of 1,000 to 50,000, and hydrolysis of 20 to 100 mol% of the vinyl acetate units of the graft polymers, as disclosed in WO 02/31096 A1.

In a further preferred embodiment of the invention, the two or more flexible, preferably elastic, hollow bodies can consist of two or more different materials, which can be selected, for example, from the materials listed above, but can also comprise other materials. In the event of the presence of a plurality of flexible, preferably elastic, hollow bodies, the walls (= walls) of these hollow bodies can be made of two or more similar materials, for example materials made of the same monomer units, but materials with different properties. Examples of this can be similar materials with different molecular weights (and thus different solubilities), PVAL materials with different degrees of acetalization (and thus different solubilities or different solution temperatures in water), materials with different proportions of grafted co-monomers or the like.

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 different geometric shapes. This can advantageously lead to different dissolving behavior or different kinetics of the release of the detergent, cleaning agent or care agent portion contained in the compartment (s) of the hollow body.

Also preferred is an embodiment of the detergent, cleaning agent or care agent portions according to the invention, in which the two or more flexible, preferably elastic, hollow bodies form a - particularly preferred, but not necessarily detachable - portion. form a covenant. A composite of two or more flexible, preferably elastic, hollow bodies can be used with particular advantage if either detergent, cleaning agent or care agent portions of different compositions are to be dosed (e.g. heavy-duty detergent and colored detergent; in the latter there are, for example, bleaching components not desired or not in the same concentration as in the former; the hollow body containing bleach could then be removed by the user if colored laundry is to be washed) or if - for example for small amounts of laundry or dishes - only a partial dose of those in flexible, preferably elastic, hollow bodies contained detergent or care agent portion should be used. Such a composite could particularly preferably be produced by gluing, fusing, welding or clamping the flexible, preferably elastic, hollow bodies; mechanical clamping also allows the bond to be easily loosened. In particularly preferred embodiments, such composite hollow bodies can be detached from one another again in an aqueous environment, for example by using a water-soluble adhesive; this could ensure that a composite used in the automatic washing, cleaning or care process is completely dissolved and pulled out of the machine with the washing, cleaning or rinsing liquor.

The above information on the materials of the flexible, preferably elastic, hollow bodies applies correspondingly to the materials from which the compartments are made. With a view to a reliable and simple method of manufacture, in a preferred embodiment of the invention the compartmenting devices within the flexible, preferably elastic, hollow bodies consist of the same materials as the hollow bodies themselves. This allows one-piece manufacture in one process step and makes the manufacturing process particularly economical.

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

In a preferred embodiment of the invention, the compartmentalization device (s) is / are one (or more) devices which inhibit the activity of at least one component of a wash-active, cleaning-active or care-active preparation). Examples of this are all the cases in which components of wash-active, clean preparation or care-active preparations are spatially separated from one another, taking into account a mutual impairment of their activity. The compartmentalization devices should then have properties which take these requirements into account, for example be essentially impermeable to water vapor in order to keep bleaching agents free of moisture, or should be acid or alkali-free in order to protect enzymes from premature decomposition. Such an inhibition of a reduction in activity not only contributes directly to a better activity of the respective protected component, but also allows the amounts of such components to be reduced, since an excess is no longer necessary in anticipation of the otherwise usual loss of activity. In other embodiments which are particularly preferred according to the invention, the compartmentalization device (s) is (are) the device (s) determining the quality and / or quantity of the release of components of a wash-active, cleaning-active or care-active preparation. In the cases in which the compartmenting devices have such a function, either components of the washing-active, cleaning-active or care-active preparations can advantageously be released into the fleet at different times of the washing, cleaning and / or care process ( qualitative control), or different quantities of certain (qualitatively identical) preparations can be released into the fleet (quantitative control).

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

In the second exemplary case mentioned, the flexible, preferably elastic, hollow bodies — for example only — can have walls and compartmentalization devices into which materials are incorporated that dissolve at different temperatures or under different other boundary conditions. For example, small holes first form in the compartment walls, which allow only a weak exchange of substances between individual compartments and the outside environment and thus only release small amounts of a washing-active, cleaning-active or maintenance-active preparation into the fleet; under other conditions that can be set later, the holes or pores are enlarged because soluble wall components dissolve under other conditions; through the larger ones Holes can be used to exchange larger amounts of substance between the interior of the compartment (s) and the outside environment (ie the liquor) and thus the desired higher concentrations of the wash-active, cleaning-active or care-active preparation in the liquor can be set.

In particularly preferred embodiments, possible “switches” for the release of the components by the complementing devices are physicochemical parameters which bring about or control the disintegration of the compartmenting devices and / or the walls of the flexible, preferably elastic, hollow bodies. Examples of these, however, are should not be construed as a limitation

- the time, i.e. the expiry of a certain time in which the walls of the flexible, preferably elastic, hollow bodies and / or the compartmentalization devices are in contact with a certain medium, for example with an aqueous liquor, reliable timing presupposing a linear solution kinetics;

- the temperature, d. H. reaching a certain temperature value in the course of the temperature profile of the washing, cleaning or care process; the control via the temperature represents a reliable and therefore preferred embodiment, in particular in the case of tableware care products, because of the temperature rising with each stage of the care process;

- the pH, d. H. the setting of a certain pH value in the course of a washing, cleaning or care process by components of the wash-active, cleaning-active or care-active preparation or leaving a certain pH value after the disintegration of a component which influences or determines the pH value;

- the ionic strength;

- mechanical stability, which - depending on time, temperature or other parameters - can be a factor determining disintegration;

- The permeability for a certain - primarily gaseous or liquid - component; 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 compartmentalization device (s) is (are) the device (s) controlling the activity of at least one component of a wash-active, cleaning-active or care-active preparation. This embodiment is particularly useful in cases where it is necessary that the release of one or more active ingredients takes place in a washing-active, cleaning-active or maintenance-active preparation with a predetermined kinetics in the washing, cleaning or rinsing liquor. A particular example is a so-called “controlled release” release, which can be controlled according to the parameters specified above via the properties of the wall of the flexible, preferably elastic, hollow body and / or the compartmentalization devices a destructive influence of the liquor or only the water on the active substance is reduced and the substance is actively released into the liquor over a longer period of time.

It corresponds to a further preferred embodiment of the invention that one or more compartmentalization device (s) contains / contain part or the entire amount of at least one component of at least one wash-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 wash-active, cleaning-active or maintenance-active preparation into the material of the compartmentalization device. Examples of such substances have already been mentioned above in connection with the material (s) forming the flexible, preferably elastic, hollow body and include (but are not limited to) components which are present in relatively small amounts in the detergent, cleaning agent or care agent portions are contained and are therefore relatively difficult to incorporate into large mass batches of wash-active, cleaning-active or care-active preparations. A very simple incorporation into the materials of the compartmentation devices is successful, and from these also a reliable, controllable release during the course of the washing, cleaning or care process. With a suitable choice of materials, the release can also take place with “controlled release” kinetics.

A further, likewise preferred embodiment of the invention consists in that one or more compartmentalization device (s) consist in part or in total of at least one component of at least one wash-active, cleaning-active or care-active preparation. This is preferred because the compartmentalization device is not only a component of the detergent, cleaning agent or care agent portion according to the invention which influences or even controls the kinetics of the release, but at the same time is also a component of the success of the Washing, cleaning or care process is involved. Due to the large selection of materials available, there are numerous examples of this embodiment; are particularly preferred Compartmenting devices which consist of or comprise polymers comprising (meth) acrylic acid and its derivatives (salts, esters).

According to a further preferred embodiment of the invention, the compartmenting device (s) consist of an interface between two adjacent components of a wash-active, cleaning-active or care-active preparation or an interface between two adjacent wash-active, cleaning-active or care-active preparations. In preferred embodiments of the invention, this can be the case, for example, if washing-active, cleaning-active or maintenance-active preparations are processed by means of suitable measures, for example by coextruding in the bias 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 wash-active, cleaning-active or care-active preparations on one another can be minimized or even excluded. There is the possibility that either individual components of a wash-active, cleaning-active or care-active preparation are combined to form adjoining interfaces, or that wash-active, cleaning-active or care-active preparations which are mixtures of several components are combined to form interfaces. In the context of the flexible, preferably elastic, hollow bodies according to the invention, both can lead to detergent, cleaning agent and / or care agent 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, cleaning agent and / or care 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 consists of a n non-spherical hollow bodies having delimiting surfaces, one surface of which takes on the function of a "lid" which serves to conclude a method for producing the detergent, cleaning agent or care agent portions according to the invention, ie after filling the compartment (s) ^) is applied inside the hollow body with one or more washing-active, cleaning-active or maintenance-active preparation (s) while closing the hollow body. The “lid” is particularly preferably made of a material with controllable water solubility and can be glued to the rest of the hollow body, for example with a wa water-soluble adhesive, fusing, welding or any other known method for connecting materials. This embodiment is for the Manufacture of the detergent, cleaning agent or care agent portions according to the invention is particularly advantageous, since it is possible to gradually fill the compartment (s) with one or more washing-active, cleaning-active or maintenance-active preparation and handling during later use leads to optimal results, in particular to one reliable control of the access of water or aqueous liquor to the inside of the flexible, preferably elastic, hollow body or the exit of washing-active, cleaning-active or care-active preparation from inside the preferably blow-molded hollow body.

According to the invention, the hollow body (s) and / or the compartments contain measured quantities, i.e. Portions, preferably at least one wash-active, cleaning-active or care-active preparation, usually measured amounts of several wash-active, cleaning-active or care preparations. It is possible that the portions contain only washing-active, cleaning-active or nourishing preparations of a certain composition. According to the invention, however, it is preferred that several, usually at least two, wash-active, cleaning-active or care-active preparations of different compositions are contained in the detergent, cleaning agent and / or care agent portions. The composition can differ with regard to the concentration of the individual components of the wash-active, cleaning-active or care-active preparation (quantitative) and / or with regard to the type of the individual components of the wash-active, cleaning-active or care-active preparation (qualitative). It is particularly preferred that the components are adapted in terms of type and concentration to the tasks that the detergents, cleaning agents and / or partial care agent portions have to perform in the washing, cleaning and / or care process.

In the context of the present invention, the term “wash-active or cleaning-active or care-active preparation” is understood to mean preparations of all conceivable substances relevant in connection with a washing, cleaning and / or care process. In the case of washing and cleaning agents, these are primarily the actual detergents and / or cleaning agents with their individual components, which are explained in the further course of the description, including active substances such as surfactants (anionic, non-ionic, cationic and amphoteric surfactants), builder substances (inorganic and organic builder substances), bleaching agents (such as, for example, peroxo Bleach and chlorine bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes, special polymers (for example those with cobuilder properties), graying inhibitors, dyes and fragrances (perfumes), without the term being restricted to these substance groups. However, the term “washing-active or cleaning-active preparations” also includes washing aids and cleaning aids, including rinsing aids. Examples of these are optical brighteners, UV protection substances, so-called soil repellents, that is to say polymers which prevent the re-soiling of fibers or hard surfaces (including Tableware) as well as silver protection agents, colorants and decolorizing agents. Care products, such as laundry treatment agents, in particular fabric softener or dishwashing agent additives such as rinse aid, are considered according to the invention as detergent-active or as cleaning-active or as active-care preparations.

According to the invention, the detergent, cleaning agent or care agent portions are contained in one or more flexible, preferably elastic, hollow body (s) and / or one or more compartments. In this context, the exact shape of the hollow body is no more critical than its size; the only requirement in this regard is that the shape and size correspond to the later use, that is to say use in a washing, cleaning and / or care process, in particular in conventional washing machines or dishwashers. Hollow bodies in the form of spheres, ellipsoids, cubes, cuboids, trapezoids, cones, pyramids or trochoids are conceivable; cuboidal or trochoidal hollow bodies have proven themselves very well according to the invention and can therefore be used with advantage. Spherical hollow bodies, in particular spheres, are most preferred.

In preferred embodiments of the invention, the size of the hollow bodies is such that the hollow bodies can be inserted into the washing-up chamber of a commercially available washing machine or dishwasher, in which washing nets or sacks or the like can be entered. Particularly preferred embodiments of the detergent, cleaning agent or care agent portions according to the invention do not exceed a length (longest axis) of 10 cm, while the sizes of the width and height are significantly lower, for example 1 to 5 cm.

Usually, however, the hollow bodies according to the invention filled with detergents, cleaning agents or care products are put directly with the laundry into the washing drum of an automatic 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 washing-active substances. It is even more preferred if this is in the hollow body and / or the comparator. detergents and / or cleaning agents containing timents is free of cationic surfactants and / or amphoteric surfactants.

The hollow body and / or compartments of the hollow body, which contain detergent, cleaning and / or care-active preparation, can be combined to form the detergent, cleaning agent and / or care agent portion according to the invention. According to the invention, 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 which have flat connecting surfaces are preferred. Of course, one is not bound to connect only filled hollow bodies with and / without compartments to one another for the detergent, cleaning agent or care agent portion according to the invention. Rather, it is also possible and preferred to use hollow bodies which contain washing, cleaning or care-active preparation in compartments (A) or (B) with further washing, cleaning and / or care-active preparations containing, preferably blow-molded, compartments and / or to connect hollow bodies. In particular, the connection 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 filled with a different content and / or a different composition of active substances which are active in washing, cleaning and / or care.

The water-soluble hollow bodies, which preferably contain blowing agents, in particular detergents, care and / or cleaning agents, have 2 to 40 compartments, preferably 2 to 4, more preferably 2 to 3 compartments.

It is preferred if the content of anionic surfactant is between 3% by weight and 40% by weight and the content of nonionic surfactant is between 15% and 65% by weight, based on the total proportion by weight of that contained in the hollow body Washing and / or

Detergent, the total content of anionic surfactant and nonionic surfactant ≤

Is 100% by weight.

The substances in the blow-molded hollow body and / or the respective compartments - as wash-active, cleaning-active, maintenance-active substances can be cationic surfactants, amphoteric surfactants, builder substances, bleaching agents, bleaching activators, bleaching stabilizers, bleaching catalysts, enzymes, polymers, cobuilders, alkalizing agents, acidifying agents, anti-oxidizing agents agents, silver protection agents, colorants, optical brighteners, UV protection substances, fabric softener and / or rinse aid.

However, it is also provided according to the invention that the, preferably blow-molded, water-soluble hollow body and / or at least one compartment contains agents selected from the group comprising pharmaceuticals, crop protection agents, foods, detergents, cleaning agents, care agents, cosmetics, hair dyes, agrochemicals, fertilizers, building materials and / or glue.

The hollow bodies according to the invention with and without compartments can be used in particular for agrochemicals, such as fertilizers and crop protection agents, foods and food additives, animal feed, pharmaceuticals, colorants and fragrances and / or the like.

The, preferably blow-molded, water-soluble hollow body and / or its compartments can contain practically any conceivable agent. In a preferred embodiment, the agent for filling the hollow body is an aqueous washing and / or cleaning and / or textile care agent with a water content above 3% by weight, preferably above 6% by weight, particularly preferably above 10 % By weight, extremely preferably above 16% by weight, in each case based on the total agent.

Another requirement is, but does not have to be, that the hollow body is used for release in an aqueous environment. This can, but need not, limit the selection of the agents that can be used according to the invention.

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

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

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

The agent, in particular washing, care and / or cleaning agent, can be produced in the solid, liquid and / or gel form, preferably in the form of particles, suspensions, emulsions, a homogeneous product, preferably by means of blow molding, with and without compartments Solutions, pastes and / or in the form of transparent solutions, with the aqueous portion of the formulation optionally up to 95% by weight, preferably from 3 to 80% by weight, particularly preferably in the range from 6 to 50% by weight, is based on the total average.

The hollow body according to the invention, preferably produced by means of blow molding, and / or the compartment (s) can contain a multi-phase agent, in particular washing and / or cleaning agent, preferably a temporary two-phase or three-phase mixture which forms separate phases when left to stand and temporarily shakes when shaken , reversible, can be converted into a phase, for example into an emulsion, suspension or dispersion.

The multiphase agent can in particular be a washing, care and / or cleaning agent, which preferably comprises at least one aqueous and / or non-aqueous phase, preferably at least one non-aqueous phase being liquid or solid and particularly preferably at least one aqueous phase in gel form.

The hollow body produced according to the invention, preferably by means of blow molding, and / or the compartments can contain 20 to 100%, preferably 30 to 99%, particularly preferably 40 to 98% and in particular 50 to 95% of their volume with detergents, in particular washing and care products - and / or cleaning agents are filled.

The hollow body, and / or its compartments, preferably produced by blow molding, can contain at least one, preferably several, wash-active (s), cleaning-active (s), rinse-active (s), care-active (s), pharmaceutically active preparation (s), foods , Crop protection agents, fertilizers, building materials, hair treatment agents, personal care products, cosmetics, wallpaper paste or adhesive, for example in the form of powder, granules, extrudates, pellets, beads, tablets, tabs, rings, blocks, briquettes, solutions, Melt, gels, suspensions, dispersions, emulsions, foams and / or gases, partially or completely filled.

The water-soluble, flexible, preferably elastic, closed hollow body, preferably in the middle of blow molding, produced according to the invention can contain at least one agent, in particular a washing, care and / or cleaning agent.

The agent, in particular detergents, care and / or cleaning agents containing, preferably by means of blow molding, water-soluble, flexible, preferably elastic, closed hollow bodies produced according to the invention can be used for treatment, healing, washing, care, gluing, fertilizing, for vermin control, for treatment of plants and / or for cleaning, in particular for washing, rinsing and / or cleaning soft and / or hard surfaces.

It has surprisingly been found that certain water-soluble thermoplastics or polymeric fabrics made therefrom, in particular polyvinyl alcohol and partially hydrolyzed polyvinyl acetate, are permeable to water vapor. It has now been found that the enveloped agents are able to absorb water by means of the water vapor permeability of the enveloping hollow body material and thus increase their volume. The increase in volume of the agent leads to a "pumping up" of the filled, liquid-tightly closed hollow body and thus additionally contributes to the production of elastically deformable, water-soluble hollow bodies which have a "plump" appearance. According to the invention, preference is therefore given to means for filling the hollow body which have a water content which is below the equilibrium value which the means has in the portion when stored at 30 ° C. and a relative atmospheric 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, water absorption can make a significant contribution to increasing the volume.

The detergent, cleaning agent and / or care agent portions according to the invention contain one or more substances from the group of surfactants, surfactant compounds, builders, bleaching agents, bleach activators, enzymes, foam inhibitors, colorants and fragrances and - in the event that the detergents or Detergent portions are at least partially in the form of molded articles - 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 washing-active substances.

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

The portioned washing, care or cleaning agents according to the invention can be packaged as washing agents, as cleaning agents or as maintenance agents, depending on which ingredients are enclosed by the hollow body with and without compartments. In addition to textile detergents, cleaning agents for machine or manual dishwashing, universal household cleaners, toilet cleaners, glass cleaners, etc. can be produced. Depending on the application, the selection of the ingredients in the detergent, care or cleaning agent compositions which are present within the hollow body with and without compartments can be different. Important ingredients of these compositions are described below.

The detergent, care and / or cleaning agent compositions preferably contain surfactant (s), anionic, nonionic, cationic and / or amphoteric surfactants being used. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants in textile detergents, the proportion of anionic surfactants being greater than the proportion of nonionic surfactants. The total surfactant content of the detergent, care or cleaning agent 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 an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ . ₁ -alcohols with 3 EO, 4 EO or 7 EO, C ₉ .n-alcohol with 7 EO, C ₁₃ . ₁₅ - alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ . ₁₈ alcohols with 3 EO, 5 EO or 7 EO and Mixtures of these, such as mixtures of Cι ₂ .ι ₄ alcohol with 3 EO and C ₁₂ . ₁₈ alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. 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, mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks, but statistically. Such products can be obtained from the simultaneous action of ethylene and propylene oxide on fatty alcohols.

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

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

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

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

I

R-CO-N- [Z] I in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula II

R ¹ -0-R ²

I

R-CO-N- [Z] II in the R for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ¹ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ² for represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 8 alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted by at least two hydroxyl groups, or alkoxylated , preferably ethoxylated or propoxylated derivatives of this radical.

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

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

Low-foaming nonionic surfactants are preferably used in automatic dishwashing detergents. Machine dishwashing detergents according to the invention particularly preferably contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred compositions are characterized in that they contain nonionic surfactant (s) (e) having a melting point above 20 ^C C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, contain.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If highly viscous 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 that have a waxy consistency at room temperature are also preferred.

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

In a preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16th ₂₀ alcohol), preferably a C ₁₈ alcohol and at least 12 mole, preferably at least 15 mol and recovered in particular at least 20 moles of ethylene oxide , Among these, the so-called "narrow ranks ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred agents according to the invention contain ethoxylated niotene sid (s) which consist of C ₆ . ₂ o-monohydroxy alkanols or C _{_6-20} alkylphenols or to 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 (are) obtained.

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Such PO units preferably make up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant out. 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 makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass 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% by weight, preferably up to 20% by weight and in particular up to 15% by weight, of the total molecular weight of the nonionic Make up surfactants.

Other nonionic surfactants with melting points above room temperature which are particularly preferably used contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which comprises 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol 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, care or cleaning agent according to the invention contains nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (CH ₃ ) 0] _x [CH ₂ CH ₂ 0] _y [CH ₂ CH (OH) R ² ],

in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y stands for a value of at least 15.

Other preferred nonionic surfactants are the end group-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stand for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, - CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

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

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula can be used

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 represents} H and x assumes values from 6 to 15.

If the last-mentioned statements are summarized, portioned washing, care or cleaning agents according to the invention are preferred, the end group-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] jOR ²

contain, in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl stands for x between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5, with surfactants of the type

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ²

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

The agents according to the invention can contain, for example, cationic compounds of the formulas III, IV or V as cationic active substances:

(III)

R ¹

R ¹ -N < ⁺ > - - (CH_) _π -CH-CH ₂ (IV)

I

IIIIIR ¹ TT

R ² R ²

R ¹

I

R ³ -N ⁽⁺⁾ - - (CH_) _n , -TR ² (V)

I

IR ⁴

wherein each group R ^{1 is} independently selected from C ^ alkyl, aikenyl 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. Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C ₉ . ₁₃ -Alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C ₁₂ . ₁₈ -monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration. Alkanesulfonates which are derived from C ₁₂ are also suitable. ₁₈ alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfonated 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.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₂ -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₂ -C ₁₅ alkyl sulfates and C ₁ - Ci ₅ alkyl sulfates are preferred from a washing-technical point of view. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 mol of ethylene oxide. ₂₁ alcohols, such as 2-methyl-branched C ₉ alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ . ₁₈ fatty alcohols with 1 to 4 EO are suitable. You will be in Because of their high foaming behavior, cleaning agents are used only in relatively small amounts, for example in amounts of 1 to 5% by weight.

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

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

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

The anionic surfactant content of preferred textile detergents according to the invention is 5 to 25% by weight, preferably 7 to 22% by weight and in particular 10 to 20% by weight, in each case based on the total composition.

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

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

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

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric acid H ₃ P0 _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ P0 ₄ , exists as a dihydrate (density 1, 91 like ^"3 , melting point 60 °) and as a monohydrate (density 2.04 like ^{" 3} ). Both salts are white powders, which are very easily soluble in water, lose the water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ 0 ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ 0 ₉ ) and Maddrell's salt (see below). NaH ₂ P0 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 PÖ ₄ , is a white salt with a density of 2.33 ^"3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 ₃ ) χ] and is light soluble in water ^•

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

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

Tetrasodium diphosphate (sodium pyrophosphate), Na P ₂ 0, exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1.836 like ^{" 3} , melting point 94 ° with loss of water) , Substances are colorless crystals that are soluble in water with an alkaline reaction. Na P ₂ 0 ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ^ O ^ exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 ^"3 , which is soluble in water, the pH of the 1% solution at 25 ° is 10.4.

Condensation of the NaH ₂ P0 ₄ or the KH ₂ P0 ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates. The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (Ö) (ONa) -0] _n that crystallizes with 6 H ₂ 0 -Na with n = 3. About 17 g of the salt of water free of water of crystallization dissolve in 100 g of water at room temperature, about 20 g at 60 ° and around 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (> 23% P ₂ 0 ₅ , 25% K ₂ 0). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates, which can also be used in the context of the present invention. These occur, for example, when hydrolysing sodium tri-metaphosphate with KOH:

(NaP0 ₃ ) ₃ + 2 KOH - »Na3K ₂ P ₃ O ₁₀ + H ₂ 0

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

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

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

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and is represented by the formula nNa ₂ 0 ^• (1-n) K_O 'Al ₂ 0 ₃ ^• (2 - 2.5) Si0 ₂ ^• (3, 5 - 5.5) H ₂ 0

can be described. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Other important builders are in particular the carbonates, citrates and silicates. Trisodium citrate and / or pentasodium thpolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicates and / or metasilicates are preferably used. Alkali carriers can be present as further constituents. Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the abovementioned substances are considered to be alkali carriers, alkali metal carbonates, in particular sodium carbonate, in particular sodium bicarbonate or sodium sesquicarbonate being used for the purposes of this invention.

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

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

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

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

Another possible group of ingredients are the chelating agents. Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination point on a central atom, ie being at least “bidentate”. In this case, stretching is normally carried out Compounds formed into rings by complex formation via an ion The number of ligands bound depends on the coordination number of the central ion. Common chelate complexing agents preferred in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Complex-forming polymers, that is to say polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and which generally react with suitable metal atoms to form chelate complexes, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or can belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.

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

In the context of the present invention, particular preference is given to detergents, care products or cleaning agents which comprise one or more chelate complexing agents from the groups of (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, (ii) nitrogen-containing mono- or polycarboxylic acids, (iii) geminal diphosphonic acids, (iv) aminophosphonic acids, (v) phosphonopolycarboxylic acids, (vi) cyclodextrins

in amounts above 0.1% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight, in each case based on the weight of the Dishwashing detergent included. All complexing agents of the prior art can be used in the context of the present invention. These can belong to different chemical groups. The following are preferably used individually or in a mixture with one another: 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, hydroxyethyl- iminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserine diacetic acid, N, N-di- (ß-hydroxyethyl) -glycine, N- (1, 2-dicarboxy-2-hydroxyethyl) -glycine, N- (1, 2-dicarboxy -2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA), c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues with up to 8 carbon atoms and containing hydroxyl or amino groups Derivatives thereof and 1-aminoethane-1, 1-diphosphonic acid, their higher homologues with up to 8 carbon atoms as well as derivatives thereof containing hydroxyl or amino groups, d) aminophosphonic acids such as E. thylenediaminetetra (methylenephosphonic acid), diethylene-triaminepenta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid), e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1, 2,4-tricarboxylic acid and f) cyclodextrins.

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

Deposit-inhibiting polymers can also be contained in the agents according to the invention. These substances, which can have different chemical structures, originate, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, polymers with molecular weights below 15,000 daltons being preferred.

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

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

The acids themselves can also be used. In addition to their builder effect, 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 cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

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

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

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 500 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1000 to 4000 g / mol, can in turn be preferred from this group. Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention. The copolymers containing sulfonic acid groups are described in detail below.

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

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

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

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

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon 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. Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

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

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

Further usable organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and at most two acid groups.

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

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

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

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

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

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

The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.12 to about 2% by weight. According to the state of the art, enzymes are primarily added to a cleaning agent preparation, in particular to a dish care product which is intended for the main wash cycle. The disadvantage here was that the optimum effect of the enzymes used limited the choice of temperature and problems also occurred with the stability of the enzymes in a strongly alkaline environment. With the detergent or cleaning agent portions according to the invention, it is possible to introduce enzymes into a separate compartment and then also to use them in the pre-rinse cycle and thus to use the pre-rinse cycle in addition to the main rinse cycle for enzyme action on soiling of the wash ware.

It is therefore particularly preferred according to the invention to add enzymes to the wash-active preparation or partial portion of a detergent or care agent portion intended for the pre-rinse cycle, and then to include such a preparation — more preferably — with a material of a flexible, preferably elastic, hollow body that is already water-soluble at low temperature , for example, to protect the enzyme-containing preparation from a loss of activity due to environmental conditions. The enzymes are furthermore preferably optimized for use under the conditions of the pre-care program, for example in cold water.

The detergent portions according to the invention can be advantageous if the enzyme preparations are in liquid form, as some of them are commercially available, because then a quick effect can be expected that already occurs in the (relatively short and cold water) pre-rinse cycle. Even if - as usual - the enzymes are used in solid form and these are provided with a hollow body covering made of a water-soluble material that is already soluble in cold water, the enzymes can develop their effect before the main wash or main wash cycle. The advantage of using a casing made of water-soluble material, in particular made of cold water-soluble material, is that the enzyme (s) quickly comes into effect in cold water after the casing has been dissolved. This can extend their effectiveness, which benefits the washing or rinsing result.

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

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

Non-aqueous solvents which can be used in the agents according to the invention come, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n -butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy -2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents. Non-aqueous solvents can be used in the liquid detergents according to the invention in amounts 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 agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known sauces can be used here or lyes, provided that their use is not prohibited for technical or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 5% by weight of the total formulation.

In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to textile fibers, in order not to dye them.

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

Optical brighteners (so-called "whiteners") can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances attach to the fibers and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, wherein the absorbed from sunlight ultraviolet light is radiated as pale bluish fluorescence and pure for the yellow shade of the grayed or yellowed laundry White results. Suitable compounds originate for example from the substance classes of ^{4,4'-diamino-2,2'-stilbenedisulfonic} ( Flavonic acids), 4,4'-distyryl-biphenylene, methylumbelliferones, coumarins, dihydroquinolinones, 1, 3-diarylpyrazolines, naphthalic imides, benzoxazole, benzisoxazole and benzimidazole systems as well as the pyrene derivatives substituted by heterocycles Brighteners are usually mixed in quantities en 0.05 and 0.3 wt .-%, based on the finished agent, used. Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof in amounts of 0.1 to 5% by weight, based on the composition, are preferably used

If the agents according to the invention are packaged as agents for automatic dishwashing, further ingredients can be used. Today, machine-washed dishes are often subject to higher requirements than hand-washed dishes. For example, dishes that have been completely cleaned of food residues are not considered to be perfect if, after machine dishwashing, they still have whitish stains due to water hardness or other mineral salts, which, due to the lack of wetting agents, come from dried water drops. To obtain crystal-clear and spotless dishes, rinse aid is therefore used successfully today. The addition of rinse aid at the end of the wash program ensures that the water runs off the items to be washed as completely as possible, so that the different surfaces are residue-free and flawlessly shiny at the end of the wash program. The automatic cleaning of dishes in household dishwashers usually comprises a pre-wash, a main wash and a rinse cycle, which are interrupted by intermediate wash cycles. In most machines, the pre-wash cycle for heavily soiled dishes can be switched on, but is only selected by the consumer in exceptional cases, so that in most machines a main wash cycle, an intermediate rinse cycle with pure water and a rinse cycle are carried out. 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 non-ionic surfactants as the main component. Such rinse aids are in liquid form and are widely described in the prior art. Your main task is to prevent limescale and deposits on the dishes. The agents according to the invention can be formulated as "normal" cleaners, which are used together with commercially available supplements (rinse aid, regeneration salt). However, with the products according to the invention, the additional dosage of rinse aid can be dispensed with. These so-called "2in1" products - Products simplify handling and relieve the consumer of the additional dosage of two different products (detergent and rinse aid).

Even when using "2-in-1" products, two dosing processes are required to operate a household dishwasher at intervals, since after a certain number of rinsing processes the regeneration salt has to be refilled in the water softening system of the machine. These water softening systems consist of ion exchange polymers which are added to the machine Soften hard water and regenerate it afterwards with a rinse with salt water.

However, it is also possible to provide products according to the invention which, as so-called “3-in-1” products, combine the conventional cleaners, rinse aids and a salt replacement function. For this purpose, automatic dishwashing detergents according to the invention are preferred which additionally contain 0.1 to 70% by weight of copolymers from i) unsaturated carboxylic acids ii) monomers containing sulfonic acid groups iii) optionally containing further ionic or nonionic monomers.

These copolymers have the effect that the items of tableware treated with such agents become significantly cleaner in subsequent cleaning operations than items of tableware that have been washed with conventional agents.

As an additional positive effect, there is a shortening of the drying time of the dishes treated with the cleaning agent, i.e. the consumer can take the dishes out of the machine and reuse them earlier after the cleaning program has ended.

The invention is characterized by an improved “cleanability” of the treated substrates in later cleaning processes and by a considerable reduction in the drying time compared to comparable agents without the use of polymers containing sulfonic acid groups. In the context of the teaching according to the invention, drying time is generally understood as meaninging the meaning, i.e. the time which elapses until a dish surface treated in a dishwasher is dried, but in particular the time which elapses, up to 90% of one with a cleaning or Rinse aid is dried in a concentrated or diluted form treated surface.

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 which R ¹ to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids that can be described by 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) preferred.

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula VII

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (VII),

in which R ⁵ to R ⁷ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group , which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) -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-S0 ₃ H (Vlla),

H ₂ C = C (CH ₃ ) -X-S0 ₃ H (Vllb),

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (Vllc), in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and - C (0) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (0) NH-CH (CH ₂ CH ₃ ) in the formula VIIa), 2-acrylamido-2-propanesulfonic acid (X = -C (0) NH-C (CH ₃ ) ₂ in the formula VIIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (0) NH-CH (CH ₃ ) CH ₂ - in the formula Vlla), 2-methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (0) NH-CH (CH ₃ ) CH ₂ - in formula VIIIb), 3-methacrylamido-2-hydroxy-propanesulfonic acid (X = - C (0) NH-CH ₂ CH (OH) CH ₂ - in formula VIIIb), allylsulfonic acid (X = CH ₂ in formula VIIIa), methallylsulfonic acid (X = CH ₂ in formula VIIIb), allyloxybenzenesulfonic acid (X = -CH ₂ - 0-C ₆ H ₄ - in formula XVIIa), methallyloxybenzenesulfonic acid (X = -CH ₂ -0-C ₆ H - in formula VIIIb), 2-hydroxy- 3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2- propen1-sulfonic acid (X = CH ₂ in formula VIIb), styrene sulfonic acid (X = C ₆ H ₄ in formula VIIa), vinyl sulfonic acid (X not present in formula VIIa), 3-sulfopropyl acrylate (X = -C (0) NH-CH ₂ CH ₂ CH ₂ - in Formula VIII), 3-sulfopropyl methacrylate (X = -C (0) NH-CH ₂ CH ₂ CH ₂ - in formula VIIIb), sulfomethacrylamide (X = -C (0) NH- in formula VIIIb), sulfomethyl methacrylamide (X = -C (0) NH-CH ₂ - in formula VIIIb) and water-soluble salts of the acids mentioned.

Other suitable ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. The content of monomers of group iii) in the polymers used according to the invention is preferably less than 20% by weight, based on the polymer. Polymers to be used with particular preference consist only of monomers of groups i) and ii).

In summary, copolymers of i) unsaturated carboxylic acids of the formula VI.

R ¹ (R ² ) C = C (R ³ ) COOH (VI), «

in which R ¹ to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or for -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,

ii) Monomers of the formula VII containing sulfonic acid groups

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (VII),

in which R ⁵ to R ⁷ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) -NH-CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers

particularly preferred.

Particularly preferred copolymers consist of i) one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and / or maleic acid ii) one or more monomers containing sulfonic acid groups of the formulas VIIa, VIIb and / or VIIc:

H ₂ C = CH-X-S0 ₃ H (Vlla),

H ₂ C = C (CH ₃ ) -X-S0 ₃ H (Vllb),

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (Vllc), 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 represents an optionally available spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and - C (0) -NH-CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers.

The copolymers contained in the compositions according to the invention can 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 compounds can be combined from group iii). Particularly preferred polymers have certain structural units, which are described below.

For example, agents according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula VIII

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VIII),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is preferred.

These polymers are produced by copolymerization of acrylic acid with a sulfonic acid group-containing acrylic acid derivative. If the sulfonic acid group-containing acrylic acid derivative is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have structural units of the formula IX

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (IX),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Completely analogously, acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Agents according to the invention which contain one or more copolymers are structural units of the formula X

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (X),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, represents -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are preferred, likewise a preferred embodiment of the present invention, just as agents are preferred which are characterized in that they are 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 (0) -Y-S0 ₃ H] _p - (XI),

Instead of or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly preferred monomer from group i). In this way, preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers, the structural units of the formula XI

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (XI),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is preferred, and for 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 (0) 0-Y-S0 ₃ H] _p - (XII),

In summary, automatic dishwashing agents according to the invention are preferred which contain, as ingredient b), one or more copolymers which have structural units of the formulas VII and / or VIII and / or IX and / or X and / or XI and / or XII - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VII),

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VIII),

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) N-S0 ₃ H] _p - (IX),

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (X),

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (XI),

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) ON-S0 ₃ H] _p - (XII),

All or part of the sulfonic acid groups in the polymers can be in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions. Corresponding agents which are characterized in that the sulfonic acid groups in the copolymer are partially or fully neutralized are preferred according to the invention.

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

In the case of terpolymers, those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred ,

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

The content of one or more copolymers in the agents according to the invention can vary depending on the intended use and the desired product performance, preferred inventions Machine dishwashing detergents according to the invention are characterized in that they contain the copolymer (s) in amounts of from 0.25 to 50% by weight, preferably from 0.5 to 35% by weight, particularly preferably from 0.75 to 20 % By weight and in particular from 1 to 15% by weight.

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

The agents according to the invention can also be packaged as fabric softeners or washing additives. Depending on the intended use, additional ingredients can be used. Fabric softener compositions for rinse bath finishing are widely described in the prior art. Typically, these compositions contain as the active substance a cationic quaternary ammonium compound which is dispersed in water. Depending on the content of active substance in the finished plasticizer composition, one speaks of 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 associated lower packaging and transport costs, the textile softener concentrates have advantages from an ecological point of view and have become more and more established on the market. Due to the incorporation of cationic compounds, which have only a low solubility in water, conventional fabric softener compositions are in the form of dispersions, have a milky, cloudy appearance and are not translucent. For reasons of product aesthetics, however, it may also be desirable to provide the consumer with translucent, clear fabric softeners that stand out visually from the known products.

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

The esterquats produced in this way are outstandingly suitable for producing portions according to the invention which can be used as fabric softeners. Since, depending on the choice of the trialkanolamine, the fatty acids and the dicarboxylic acids and the quaternizing agent, a large number of suitable products can be prepared and used in the agents according to the invention, a description of the ester quats to be used according to the invention via their route of preparation is more precise than the specification of a general formula.

The components mentioned, which react with one another to give the esterquats to be used with preference, can be used in varying proportions 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, which optionally alkoxylates and then in was quaternized in a known manner, is present in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30% by weight. The use of triethanolamine is particularly preferred, so that further preferred portioned fabric softeners of the present invention are 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, that optionally alkoxylated and then quaternized in a manner known per se, in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30% by weight.

All acids obtained from vegetable or animal oils and fats can be used as fatty acids in the reaction mixture to produce the esterquats. A fatty acid that is not solid at room temperature, i.e. pasty to liquid, fatty acid can be used.

The fatty acids can be saturated or mono- to polyunsaturated regardless of their physical state. Of course, not only "pure" fatty acids can be used, but also the technical fat obtained from the splitting of fats and oils. Acid mixtures, these mixtures 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 producing the ester quats for the clear aqueous fabric softener according to the invention: caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-ol acid, arachic acid , Behenic acid, ligonoceric acid, cerotinic acid, melissic acid, 10-undecenoic acid, petroselinic acid, petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, linolaidic acid, α- and ß-eläosterainic acid, gadolinic acid, erucic acid, brassidic acid. Of course, the fatty acids with an odd number of carbon atoms can also be used, 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 softener is a reaction product of trialkanolamines with a mixture of fatty acids of the formula XIII,

R ¹ -CO-OH (XIII)

in which R1-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 was optionally alkoxylated and then quaternized in a manner known per se, contained in the compositions in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30% by weight.

Suitable dicarboxylic acids which are suitable for producing the esterquats to be used in the agents according to the invention are, in particular, saturated or mono- or polyunsaturated αω-dicarboxylic acids. Examples include the saturated species oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic and dodecanoic acid, brassylic acid, tetra- and pentadecanoic acid, thapic acid as well as hepta-, octa- and nonadecanoic acid Eicosanoic and heneicosanoic acid and phellogenic acid called. Dicarboxylic acids which follow the general formula XXIII are preferably used in the reaction mixture, so that portioned agents according to the invention are preferred which are 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 represents an optionally hydroxyl-substituted alkylene group with 1 to 10 carbon atoms, in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, which has optionally been alkoxylated and then quaternized in a manner known per se, in quantities from 2 to 60, preferably 3 to 35 and in particular 5 to 30% by weight in the compositions.

Of the large number of esterquats that can be prepared and used according to the invention, those in which the alkanolamine is treithanolamine and the dicarboxylic acid is adipic acid have proven particularly useful. Thus, in the context of the present invention, agents are particularly preferred which are 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 then carried out in a manner known per se was quaternized in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30 wt .-% in the compositions

Irrespective of whether they are formulated as textile detergents, washing aids or fabric softeners, the agents according to the invention can also be provided with further additional benefits. For example, color transfer inhibiting compositions, agents with an “anti-gray formula”, agents with ironing relief, agents with special fragrance release, agents with improved dirt detachment or prevention of re-soiling, antibacterial agents, UV protective agents, color-refreshing agents, etc. can be formulated. Some examples are explained below:

Since textile fabrics, in particular made from rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers prevent bending and kinking. If pressing and squeezing across the grain are sensitive, the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

To combat microorganisms, the agents according to the invention can contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides etc. Important substances from these groups are, for example, benzalkonium chlorides, alkyl arlylsulfonates, halophenols and phenol mercuric acetate, it being possible to dispense entirely with these compounds in the agents according to the invention.

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

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

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

Finally, the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone with sub- stituents in 2- and / or 4-position. Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid are also suitable.

Other conceivable additives which are preferred in special embodiments are surfactants, which in particular can influence the solubility of the water-soluble wall of the flexible, preferably elastic, hollow body or the compartmenting device, but can also control their wettability and the foam formation when dissolved, and also foam inhibitors, but also Bitter substances that can prevent children from accidentally swallowing such hollow bodies or parts of such hollow bodies.

Fragrances are added to the detergent, cleaning agent and / or care agent portions according to the invention in order to improve the overall aesthetic impression of the products and, in addition to the technical performance (fabric softener result), to provide the consumer with a sensorially typical and distinctive product. Individual fragrance compounds can be used as perfume oils or fragrances, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-t-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylateylatepionate pylyl propionate. The ethers include, for example, benzyl ethyl ether. The aldehydes include e.g. B. linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lileal and bourgeonal.

The ketones include the ionones, α-isomethyl ionone and methyl cedryl ketone. Alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include terpenes such as limonene and pinene. Mixtures of different fragrances are preferably used which are coordinated with one another in such a way that they together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures as are obtainable 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, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdana oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil. The fragrance content is usually in the range of up to 2% by weight of the total detergent, cleaning agent or care agent portion.

The fragrances can be incorporated directly into the wash-active, cleaning-active or care-active preparation (s); However, it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of textiles due to a slower fragrance release. Cyclodextrins, for example, have proven themselves as such carrier materials. The cyclodextrin perfume complexes can also be coated with other auxiliaries.

The perfumes and fragrances can in principle be contained in each of the portions (washing-active or cleaning-active or maintenance-active preparations) of the detergent, cleaning agent or care agent portions according to the invention. However, it is particularly preferred that they are used in a detergent portion in a partial detergent portion provided for the post-wash cycle or fabric rinse cycle or in a detergent, especially in a dish care product, in a partial detergent provided for the rinse cycle or rinse cycle. Portion, especially portion of care product, are included. Therefore, according to the invention, you have to use a flexible, preferably elastic, hollow body or material that is water-soluble only under the conditions (in particular at the temperature) of the post-wash or after-care program, and under the conditions (in particular at the temperature) of the preceding washes or rinses the compartmentalization device (s) may be included. According to the invention, this is feasible, for example, with a plurality of compartments in a flexible, preferably elastic, detergent, cleaning agent or care agent portion comprising hollow bodies.

The detergent, cleaning agent or care agent portions according to the invention contain, in a flexible, preferably elastic, hollow body with and without compartments, one or more washing-active, cleaning-active and / or care-active preparations in such quantities that they are suitable for a washing, cleaning and / or care process is sufficient. It goes without saying that two units (hollow body) can be dosed under special conditions (heavily soiled, e.g. heavily soiled laundry; heavily soiled dishes).

In a particularly preferred embodiment of the invention, one in one or more flexible, preferably elastic, hollow body (s) with at least one compartment comprises portion of detergent, cleaning agent or care agent contained the at least one, preferably the several, wash-active (s), cleaning-active or care-active (n) preparations) in one or more forms from the group of powders, granules, extrudates, pellets , Pearls, tablets, tabs, rings, blocks, briquettes, solutions, melts, gels, suspensions, dispersions, emulsions, foams and gases. Gels are preferred and liquid detergents, cleaning agents and / or care agents are most preferred. There is no limit to the shape of the washing-active, cleaning-active and / or care-active preparation contained in one or more compartments of the flexible, preferably elastic, hollow body, as long as the hollow body can be used in the intended manner. It is to be seen as an essential advantage of the invention that for the first time the use of fluid phases in detergent, cleaning agent and / or care agent portions is possible and a detergent, cleaning agent and / or care agent suitable for the administration of such fluid phases Portion is provided. In the compartments of a hollow body, liquids, gels, gases or foams can be sealed alone or together with solid components in one or more compartments and brought into contact with the objects to be washed, cleaned or cared for when in use. This opens up a new freedom in the packaging of detergents, cleaning agents and care products.

The detergent, cleaning agent or care agent portions disclosed here consist of an outer hollow shape which contains one or more fillings. The hollow form can be divided into several compartments by partitions, whereby several fillings can be present separately from one another within the same hollow body. Except for the compatibility with the material of the hollow mold, there are no requirements for the fillings, so that both solid and liquid phases (systems) can be portioned.

The invention also relates to filled hollow bodies, which only partially consist of a preferably blow-molded material which disintegrates under washing, cleaning or care conditions and which gives the hollow body (s) dimensional stability, while the other parts of the casing are not necessarily flexible, preferably elastic, in defined above must be.

The detergent, cleaning and / or care agent portions according to the invention can preferably be used for the separation of incompatible active substances by dividing them into several separate areas. The table below gives a non-restrictive overview of possible active substances and their division into different compartments. It was also specified in which packaging the corresponding preparation is contained in compartment (A) or (B).

extrusion blow molding

It was converted into a tubular preform in an extruder based on a water-soluble polymer thermoplastic polymer mass (bias molding compound). An open end of the hose was closed under thermal treatment. The preform was then inflated, the compressed air being fed through a blow pin was led, which also formed the opening of the blow molding according to the invention. The blow molded body was filled and demolded.

Compartments can be produced, for example, by, at predetermined points on the wall (s) of the still moldable blow molded body, by appropriate devices in the blow mold, with the formation of subdivisions, i.e. closed cavities, merging and liquid-tight, preferably by thermal treatment, connects. However, preforms can also be used, with separate cavities, which are then blow-molded into a blow-molded body with several compartments. However, several hollow bodies with and without a compartment can also be combined.

Coextrusionsblasen

In this special form of extrusion blow molding, the hollow bodies are manufactured with and without compartments from several layers of material. The preform is produced by several extruders acting on a common tube tool, so that a preform with several layers is created, which is then blow-molded into a hollow body.

Injection stretch blow molding

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

The subject matter of the invention is explained in more detail with reference to the following examples, which are not to be understood as restricting the inventive state.

Examples EXAMPLE 1

On a discontinuously tapped blow-fill-seal machine from Rommelag / Kocher-Plastik type "bottelpack-System 2012" (with quadruple blow head, sequential flow), PVA blend "KSE Mowiflex LPTC 221" was produced in different runs with a steady as well as increasing Temperature profile (180 ° C extruder zones, 180 to 196 ° C die) melted thermoplastic in the extruder and blown out to four tube preforms at the same time. In this case, faster extruder speeds in the range above 50 rpm compared to slow speeds in the range of 5 rpm proved to be advantageous in order to ensure complete melting without specks.

The residence time of the bias molding compound was 3 minutes in order to prevent the post-crosslinking of the PVA. After this measure, thermal damage to the material could no longer be demonstrated, which was expressed in a constant molecular weight (determined by GPC at approx. 70,000 g / mol) of the raw material in comparison with the individual four hose sections in the area of the measurement spread. In this case, liquid detergent portions were produced in the form of balls branded on both sides with the "Henkel" oval or "Liquits" lettering as a predetermined breaking point (by 4 mm deep engraving) with an outer diameter of 47.7 mm. 50 ml of liquid detergent formulation from Table 1 were filled per ball. The total casing weight was 1.5 g in one test.

^a] C ₁₂ . ₁₄ -fatty alcohol + 5-EO + 4-PO ex Sasol

^[b] Dodecylbenzenesulfonic acid monoethanolamine salt ex Sasol

^[cl coconut oil fatty acid cut (C _8-0 ₈ fatty acid) ex Cognis

^[d] Diethylenetriaminepentamethylenephosphonic acid hepta sodium salt ex Solutia ^[e] Acrylic copolymer, containing carboxyl groups ex 3V Sigma ^f] Protease ex Biozym ^t9] Amylase ex Novo ^[h] Cellulase ex Novo ^w Distyrylbiphenyl-Devat, anionic ex Ciba

It was possible to obtain very regularly shaped products in all four cavities, as can be seen from the following Table 2 for the 1.5 g spherical shell.

Using a so-called SWDR spindle on the blow head for regulating the hose wall thickness, wall thickness distribution widths (including the base and head cheek area) that were further optimized could be generated across the entire hollow body surface.

But even without this, the release times and the total release times at 30, 40, 60 and 90 ^C C in the range of commercially available liquid detergent sachets were in the application test in water (beaker and convection basin), with the release time in particular - apparently also due to the predetermined breaking points - being at least halved , which meant an even faster effectiveness of the detergent content.

As a further test method relevant for the application, a mechanical load test was used. For example, a compression test with round rod 0 = 8 mm was carried out on a test machine from Zwick for compression tests with a height-controlled test path of 22 mm in multiple determination (repeat measurement on one body each by repeatedly running the same test program). As an example, Table 3 shows that the molded articles tested were so flexible that the indentation process could be repeated several times (here: eight times), even in such a way that the standard The deviation of the measurement for this method was low (here: below 4% of the mean).

The mechanical test again showed a high level of flexibility and resilience of the tested

Body, as exemplified by a repeat test for a filled ball with 1.5 g

Envelope weight shown in Table 3 below.

Table 3 Push-in test with round rod 0 = 8 mm, 22 mm test weight on Zwick testing machine

EXAMPLE 2:

Filled blown bodies according to the invention from Example 1 were subjected to indentation tests with round rod 0 8 mm on the Zwick testing machine for compression tests, varying the height of the test path of 10 mm, 13 mm, 16 mm, 19 mm and 22 mm (double determination) ,

The measured values can be found in the graphic representation of the attached diagram.

The filled detergent portions from Example 1 had previously been conditioned. The detergent portions according to the invention were conditioned immediately after their manufacture in a climatic chamber for 5 minutes at 40 ° C. and 90% relative atmospheric humidity. After 24 hours, the detergent portions were conditioned once more in the climatic chamber at 40 ° C. and 90% relative humidity and then dried in a drying oven at 70 ° C. for 20 minutes. The detergent portions produced according to the invention have the dashed-drawn course in the force-displacement diagram. Detergent portions not according to the invention which were not subjected to any conditioning were used as a reference. In diagram 1 they show the course with the solid line.

It can be clearly seen from the diagram that the filled hollow bodies produced according to the invention have a more plump shape than the hollow bodies which have not undergone any conditioning step, which can be recognized by the higher resistance forces.

Claims

claims

1. A method for producing completely or partially water-soluble, filled hollow bodies, comprising an agent, comprising the steps of: a) forming a hollow body from a material containing at least one water-soluble polymeric thermoplastic b) filling the hollow body with an agent, preferably a washing agent, Care and / or cleaning agent, c) liquid-tight sealing of the hollow body and d) shrinking of the hollow body material enveloping the agent

2. The method according to claim 1, characterized in that the shrinkage is triggered by conditioning the filled and closed hollow body in an atmosphere with increased relative humidity.

3. The method according to claim 2, characterized in that the shrinkage by conditioning the filled and closed hollow body in an atmosphere with a relative humidity above 50%, preferably above 65%, particularly preferably above 80%, further preferably above 85% , is most preferably triggered above 90%.

4. The method according to any one of claims 2 or 3, characterized in that the shrinking process by conditioning at a temperature above 25 ° C, preferably above 30 ° C, particularly preferably above 35 ^C C, most preferably between 40 and 60 ° C is triggered.

5. The method according to any one of claims 2 to 4, characterized in that the shrinking process is triggered by conditioning within a residence time of at most 24 hours, preferably at most 2 hours, particularly preferably at most 30 minutes, most preferably between 10 seconds and 15 minutes.

6. The method according to any one of claims 1 to 5, characterized in that the shrinking process is triggered by iterative conditioning under possibly changing conditions.

7. The method according to any one of claims 2 to 6, characterized in that the / - the conditioning step (s) in an atmosphere with increased relative humidity at least one drying step, preferably by an optionally heated air flow and / or by a drying oven and / or by using microwave radiation.

8. The method according to any one of the preceding claims, characterized in that the formation of the hollow body takes place in a temperature range between the beginning of softening and thermal decomposition, preferably in the melt range, of the polymeric thermoplastic.

9. The method according to any one of the preceding claims, characterized in that the formation of the hollow body under the enveloping hollow body material mechanically stretching conditions, preferably in more than one preferred direction, and further preferably this process is terminated in a defined manner, preferably by means of an exogenous in the polymer thermoplastic induced temperature jump, whereby this is cooled in the range of its, preferably below its, softening temperature.

10. The method according to claim 9, characterized in that the exogenously induced in the polymer thermoplastic, cooling temperature jump a delta T of at least 5 ° C, preferably at least 10 ° C, more preferably at least 15 ° C, even more preferably at least 30 ° C and particularly preferably comprises at least 50 ° C.

11. The method according to any one of the preceding claims, characterized in that the means for filling the hollow body with a temperature below the melt temperature, preferably below the softening temperature of the water-soluble thermoplastic and / or with a temperature below 50 ° C, preferably below 35 ° C. , more preferably below 25 ° C, even more preferably below 20 ° C and particularly preferably below 15 ° C.

12. The method for producing according to any one of the preceding claims, characterized in that the melt flow index of the water-soluble polymer thermoplastic at 10 Kg between 1 and 30, preferably between 5 and 15, particularly preferably between 8 and 12 and / or Melt flow index (MFI) of the water-soluble polymer thermoplastic at 2.16 kg is between 4 and 40, preferably between 5 and 20, particularly preferably between 8 and 15.

13. The method for producing according to any one of the preceding claims, characterized in that the formation of the hollow body by primary shaping of a preform, preferably a tubular preform, from a bias molding compound based on a water-soluble polymeric thermoplastic, and then blow molding the preform into a hollow body.

14. A method for producing according to claim 13, characterized in that

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

15. The method for producing according to one of claims 13 or 14, characterized in that the wall thicknesses of the hollow body can be formed differently in some areas by changing the wall thicknesses of the preform, preferably along its vertical axis, correspondingly different thicknesses, preferably by regulating the amount of thermoplastic Material, preferably by means of an adjusting spindle when the preform is brought out of the extruder nozzle.

16. The method for producing according to one of the preceding claims, characterized in that the preform, the hollow body and / or the liquid-tightly closed hollow body made of one or more component (s), the one or more materials, based on one or different water-soluble polymeric thermoplastics , include, exists.

17. The method for producing according to one of the preceding claims, characterized in that the preform, the hollow body and / or the liquid-tightly closed hollow body is tubular, spherical or bubble-shaped, the spherical hollow body having a shape factor (= shape factor) of> 0 , 8, preferably of> 0.82, preferably> 0.85, more preferably> 0.9 and particularly preferably of> 0.95.

18. A method of manufacturing according to any one of the preceding claims, characterized in that serial, parallel and / or concentrically arranged hollow bodies and / or compartments are produced, preferably, but not exclusively, by at least one double and / or multiple and / or coextrusion blow pin.

19. A method for producing according to one of claims 13 to 18, characterized in that a preform with several layers, preferably 2 to 5, is produced by coextrusion, 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 constructed in multiple layers.

20. A method for manufacturing according to any one of claims 13 to 19, characterized in that

(c) in a first step, a preform is produced by extrusion and guided into a molding tool, and (d) 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 out of openings in the cavity, so that the thermoplastic material is applied to the mold , wherein the molding tool is cooled and / or optionally the temperature of a possibly existing head jaw for liquid-tight sealing of the hollow body is regulated via a separate temperature control circuit.

21. A method for producing according to one of claims 1 to 12, characterized in that the hollow body is formed by thermoforming a film material based on a water-soluble polymeric thermoplastic.

22. The method for producing according to claim 21, characterized in that the hollow body is formed by deep-drawing a film material into a cavity, preferably by additionally applying a vacuum out of openings in the cavity.

23. A method for producing according to any one of claims 1 to 12, characterized in that the hollow body is formed in the course of a rotary die process.

24. The method for producing according to one of claims 1 to 12, characterized in that the formation of the hollow body or parts of the hollow body is carried out by injection molding.

25. The method for producing according to one of the preceding claims, characterized in that 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 is} produced, the wall thickness of this surface being faster To ensure dissolution in an aqueous solution is less than the wall thickness of the adjacent surface and is 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.

26. The method according to claim 25, characterized in that the smaller wall thicknesses are made by embossing a logo.

27. The method for producing according to one of the preceding claims, characterized in that the wall thickness of the hollow body and / or the compartments is designed such that the agent, in particular washing and / or cleaning agent, contained in the hollow body and / or in the compartments, is partially or completely released into the aqueous application liquor within ≤ 5 min, preferably within ≤ 3 min, preferably within ≤ 1 min, particularly preferably within ≤ 30 seconds.

28. The method for producing according to any one of the preceding claims, characterized in that the internal volume of the hollow body produced and / or the compartments between 0.5 ml and 2000 ml, preferably between 2 ml and 500 ml, preferably between 5 and 250 ml, further preferably between 10 and 100 ml, more preferably between 20 and 75 ml and most preferably between 40 and 50 ml.

29. A process for the preparation according to one of the preceding claims, characterized in that the agent, preferably a detergent, cleaning agent or textile care agent, is in liquid form and / or gel form, preferably in the form of suspensions, in the hollow body and / or the compartments produced , Emulsions, homogeneous solutions, pastes and / or in the form of transparent solutions, the aqueous portion of the formulation optionally being up to 95% by weight, preferably from 3 to 80% by weight, particularly preferably in the range from 6 to 50% by weight .-%, each based on the total average.

30. A method of manufacturing according to any one of the preceding claims, characterized in that a multi-phase agent, in particular washing and / or cleaning agent, is added to the hollow body and / or the compartments produced, preferably a temporary two- or three-phase mixture, which separate when left standing Forms phases and can be temporarily converted into a phase by shaking in the form of an emulsion, suspension or dispersion.

31. A process for the preparation according to claim 30, characterized in that the multi-phase agent, in particular washing and / or cleaning agent, comprises at least one aqueous and / or non-aqueous phase, preferably at least one non-aqueous phase being liquid or solid and particularly preferably at least one aqueous Phase is gel-shaped.

32. 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 one relative humidity of 80%, particularly preferred when stored at 23 ° C and a relative humidity of 50%.

33. A method for manufacturing according to one of the preceding claims, characterized in that the water-soluble thermoplastic used to form the hollow body and / or the compartments is selected from the group comprising polyvinyl alcohol (PVA), acetalized polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose, starch and derivatives of the aforementioned substances, in particular derivatives of polyvinyl alcohol (PVA), acetalized polyvinyl alcohol, cellulose and / or mixtures of the aforementioned Polymers, with polyvinyl alcohol and partially hydrolyzed polyvinyl acetate being particularly preferred.

34. 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 contain polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfo- nate, polyurethane, polyester, polyether and / or mixtures of the above polymers are added.

35. 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, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably constitutes 81 to 89 mol% and in particular 82 to 88 mol%.

36. 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 alcohol, the molecular weight of which is in the range from 10,000 to 100,000 gmol ^"1 , preferably from 11,000 to 90,000 gmol ^"1 , particularly preferably from 12,000 to 80,000 gmol ^{" 1} and in particular from 13,000 to 70,000 gmol ^"1 .

37. 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 alcohol which has a narrow molecular weight distribution, particularly preferably with a distribution ratio of d10: d50> 0, 66th

38. A method for producing according to one of the preceding claims, characterized in that the material used to form the hollow body contains the water-soluble polymer thermoplastics in amounts of at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 80 % By weight and in particular at least 90% by weight, in each case based on the weight of the entire hollow body material.

39. Process for the preparation according to one of the preceding claims, characterized in that the water-soluble polymer thermoplastic softener in amounts of at least> 1 wt .-%, preferably ≥ 10 wt .-%, particularly preferably ≥ 20 Wt .-% and in particular of> 30 wt .-%, each based on the weight of the entire hollow body material contains.

40. The method according to any one of the preceding claims, characterized in that the water-soluble polymer thermoplastic as a plasticizer mono-, di- or triglycerides, preferably mono-, di- or triglycerides, which is linked at least to a C ₆ -C ₃₀ fatty acid residue are, particularly preferably those which are linked to at least one C ₁₂ -C ₂₄ fatty acid residue, in particular glycerol monostearate or glycerol monooleate.

41. The method according to any one of the preceding claims, characterized in that the hollow body and / or the compartments with 20 to 100%, preferably 30 to 99%, particularly preferably 40 to 98% and in particular 50 to 95% of their volume Agents, in particular washing and / or cleaning agents, are filled.

42. The method according to any one of the preceding claims, characterized in that the hollow body and / or the compartments with at least one, preferably several, wash-active (s), cleaning-active (s), rinse-active (s), care-active (s), pharmaceutically active Preparation (s) and / or with at least one food, crop protection agent, fertilizer, hair treatment agent, body care agent, cosmetics, building material, wallpaper paste or adhesive in the form of powder, granules, extrudates, pellets, beads, tablets, tabs, rings, blocks, briquettes, Fills solutions, melts, gels, suspensions, dispersions, emulsions, foams and / or gases partially or completely.

43. The method according to any one of the preceding claims, characterized in that the hollow body and / or at least one compartment is transparent and / or translucent.

44. The method according to any 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 is formed in multiple layers.

45. 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 are designed in such a way that an intermediate space is formed between the layers.

46. The method for producing 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.

47. The method according to any one of the preceding claims, characterized in that the hollow body has no sealing seam, no pinch seam and / or no peripheral seam.

48. Process for the preparation according to one of the preceding claims, characterized in that the agent is a washing and / or cleaning agent and comprises anionic surfactants and / or nonionic surfactants as washing-active substances.

49. Process for the preparation according to one of the preceding claims, characterized in that the agent for filling the hollow body is an aqueous washing and / or cleaning and / or textile care agent with a water content above 3% by weight, preferably above 6 % By weight, particularly preferably above 10% by weight, extremely preferably above 16% by weight, in each case based on the total agent.

50. The method according to any one of the preceding claims, characterized in that the flexible hollow body produced to ≥ 80 vol .-% filled with at least one agent or glycerol as a test agent by a force Fi ≤ 500 N along a path

= 22 mm, in particular by a force F ^ ≤ 100 N along a path si = 22 mm, preferably by a force F ^ ≤ 60 N along a path si = 22 mm, more preferably by a force F ^ ≤ 40 N along one Path si = 22 mm and even more preferably by a force F ₁ ≤ 20 N along a path s-ι = 22 mm, vertically, centrally, in the direction of its shortest axis of the hollow body, is deformable.

51. A method for manufacturing according to one of the preceding claims, characterized in that the flexible, unfilled or ≥ 80 vol .-% filled with at least one agent or glycerol as a test agent hollow body after removal of the force, a return speed v ≤ 1000 mm / min , in particular v 500 500, preferably v 100 100 mm / min, preferably v <50 mm / min, more preferably v 10 10 mm / min and particularly preferably v <1 mm / min.

52. A method for producing according to one of the preceding claims, characterized in that the compression resistance of the flexible, unfilled or ≥ 80% by volume filled with at least one agent or glycerol as a test agent hollow body 75 to 400 N, preferably from between 100 to 300 N and in particular from between 150 to 250 N.

53. A method for producing according to one of the preceding claims, characterized in that the portion produced flexible, unfilled or filled to ≥ 80 vol .-% with at least one agent or glycerol as a test agent by a force Fi ≤ 100 N along a Travel Si = 22 mm is deformable and after the loss of force has a return speed v ≤ 100 mm / min.

54. A method for manufacturing according to one of the preceding claims, characterized in that the flexible, unfilled or> 80 vol .-% filled with at least one agent or glycerol as a test agent hollow body by shrinking a volume reduction of at least 0.5%, preferably at least 1%, particularly preferably at least 1.5%, further preferably at least 2%, in particular at least 3%, particularly preferably at least 5%, extremely preferably at least 6% and advantageously at least 10%.

55. A method for manufacturing according to one of the preceding claims, characterized in that the flexible, unfilled or to ≥ 80 vol .-% filled with at least one agent or glycerol as the test hollow body by the shrinking step a length reduction along the longest axis of at least 0 , 2%, for example at least 0.5%, preferably at least 1%, particularly preferably at least 1.5%, further preferably at least 2%, in particular at least 3%, iris particularly preferably at least 5%, extremely preferably at least 6% and advantageously at least 10 % having.

56. The method according to any one of the preceding claims, characterized in that an additional detection step for leaks is carried out following the liquid-tight sealing of the blow-molded hollow body.

57. The method according to claim 56, characterized in that the detection of leaks is carried out with a high-voltage leakage detector or in a vacuum chamber.

58. The method according to any one of claims 56 or 57, characterized in that the detection of leaks by means of a test gas, preferably in a vacuum tunnel.

59. The method according to any one of the preceding claims, characterized in that a cooled gas is added to the hollow body before the liquid-tight closure of the hollow body.

60. The method according to claim 59, characterized in that the cooled gas when it is added to the hollow body has a temperature below 20 ° C, preferably below 10 ° C, particularly preferably below 0 ° C, in particular below -10 ° C , particularly preferably below -20 ° C, advantageously below -60 ° C.

61. The method according to claim 59 or 60, characterized in that the gas is dry ice or a liquefied gas.

62. The method according to any one of claims 59 to 61, characterized in that the gas is a test gas, preferably for leak detection.

63. Portion, preferably containing detergents, care and / or cleaning agents, according to one of the preceding claims.

64. Use of the portion, in particular containing washing, care and / or cleaning agents, for treating, healing, washing, maintaining and / or for cleaning and / or for cosmetic purposes, in particular for washing, rinsing and / or cleaning soft and / or hard surfaces.

65. Washing method, in particular method for machine washing in a commercially available washing machine, comprising the steps that one

- At least one detergent portion of the detergent and / or cleaning agent-containing hollow body according to one of the preceding claims in the washing machine, in particular in the dispenser and / or washing drum, enters; the desired washing conditions are set; and when these conditions occur, the hollow body and / or the compartments opens in the aqueous environment and releases the wash-active preparation (s) of the detergent portion into the wash liquor so that it comes into contact with the items to be washed.

66. Cleaning procedure, comprising the steps that one

- At least one detergent portion of the detergent and / or cleaning agent-containing hollow body according to one of the preceding claims in the cleaning liquor; the desired cleaning conditions are set; and

67. Washing method, in particular method for machine washing in a commercially available dishwasher, comprising the steps of adding at least one detergent portion contained in the hollow body and / or compartments according to one of the preceding claims to the dishwasher, in particular in its washing-up chamber and / or in enters the wash cabinet; the desired rinsing conditions are set; and when these conditions occur, the hollow body and / or the compartments opens in the aqueous environment and releases the rinsing-active preparation (s) of the rinsing agent portion into the rinsing liquor so that it comes into contact with the items to be cleaned.