EP1305396A2

EP1305396A2 - Hollow bodies with a compartment, containing a portion of a washing, cleaning or rinsing agent

Info

Publication number: EP1305396A2
Application number: EP01967120A
Authority: EP
Inventors: Henriette Weber; Sandra Hoffmann; Frank Meier; Rolf Bayersdörfer; Christian Block; Wilfried Rähse; Markus Semrau; Dieter Jung; Karl-Martin Faeser; Paul Birnbrich; Dieter Nickel
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2000-07-14
Filing date: 2001-07-04
Publication date: 2003-05-02
Anticipated expiration: 2021-07-04
Also published as: DE50111830D1; US7601679B2; DE50107923D1; US20080312123A1; ES2252286T3; EP1586631A3; EP1305396B1; US20040029764A1; EP1586631B1; JP2004504443A; WO2002006431A2; AU2001287580A1; WO2002006431A3; EP1586631A2; ES2279467T3; ATE350462T1; ATE308606T1; US7417019B2

Abstract

Portions (A) of laundry, dish-washing or other detergent in dimensionally-stable hollow molding(s) with at least one compartment comprise: (a) at least one detergent formulation (I); (b) that is (partly) surrounded by an uncompressed material (II) that gives the molding dimensional stability and can disintegrate; and (c) optionally partition(s) dividing the molding(s) into compartments. Independent claims are also included for: (a) portions (B) of laundry and other detergents in the form of hollow moldings sub-divided into not less than 2 (partly) filled compartments surrounded by (I); (b) portions (C) of laundry and other detergents (partly) comprising solidified material; (c) methods of producing portions of detergents in hollow moldings with compartment(s); and (d) a method of producing hollow moldings.

Description

Compartment hollow body

The present invention relates to washing, cleaning or rinsing agent portions which are contained in dimensionally stable hollow bodies with at least one compartment. The invention also relates to methods for producing compartment hollow bodies containing such detergent, cleaning agent or dishwashing agent portions. The invention further relates to washing, cleaning and rinsing processes in which the detergent, cleaning agent and rinsing agent preparations are metered in dimensionally stable hollow bodies with one or more separate compartments.

The state of the art describes extensively that detergents, cleaning agents or dishwashing detergents have hitherto usually been made available to the consumer in the form of spray-dried or granulated solid products or as liquid goods. Following the consumer's desire for convenient dosing options, in addition to the two classic variants mentioned, products in pre-portioned form have become established on the market and are also extensively described in the prior art. There are descriptions of washing, cleaning or rinsing agents in the form of pressed molded articles, that is tablets, blocks, briquettes, rings and the like, as well as portions of solid and / or liquid washing, cleaning or rinsing agents packed in bags.

In the case of single-dose quantities of detergents or cleaning agents that come onto the market packed in bags, bags made of water-soluble film have become established. These make it unnecessary for the consumer to tear open the packaging. In this way it is convenient to dose a single portion, which is dimensioned for a washing or 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, in a bowl or in a hand wash basin or sink. The pouch surrounding the detergent, detergent or detergent portion dissolves without residue when a certain temperature is reached. Detergents and cleaning agents packed in bags made of water-soluble film are also described in large numbers in the prior art. For example, the older patent application DE 198 31 703 discloses a portioned washing or cleaning agent preparation in a bag made of water-soluble film, in particular in a bag made of (optionally acetalized) polyvinyl alcohol (PVAL), in which at least 70% by weight of the particles of the washing or cleaning agent -Preparation have particle sizes> 800 μm. Such bags or "pouches" are very consumer-friendly and make dosing easier, but are not in all cases the suitable form for dosing Detergent, detergent and dishwashing preparations, in particular when solid and liquid washing, cleaning or rinsing active preparations are to be dosed side by side. Furthermore, such bags do not allow the incorporation of detergent, cleaning agent or dishwashing preparations present in unstable or volatile phases into the detergent, cleaning agent or dishwashing agent portion.

The publication DE-A 20 65 153 describes several-component surfactant moldings which consist of an outer shell made of sodium silicate and detergent components enclosed therein. The silicate shell is produced by pressure molding in two hemispheres, which are put together after filling in the amount of detergent components sufficient for a wash cycle and connected to form the shaped body. The process is extremely impractical and does not result in usable portions of detergent.

The publication DE-A 20 07 413 describes detergent molded articles consisting of a core made of one or more detergent components and a shell made of press-molded casing material, which consists predominantly of sodium metal silicate. The pressing of the wrapping material into half-shells and the filling and welding of the half-shells into the finished molding require complex technology, and many of the moldings break before they get into the washing process. .

The documents DE-A 198 34 181, DE-A 198 34 180 and DE-A 198 34 172 describe detergent, dishwashing detergent or cleaning / decalcifying agent preparations from a tablet produced by compression molding and consisting of two equal halves of one or more detergent, detergent or cleaning agent components and a core, optionally provided with an additional covering, of a further detergent, detergent or cleaning agent component. In addition to the fact that the production can only be carried out in a complicated, multi-stage process in this case, only a solid core can be incorporated into the tablet casing, unless premature dissolution of the tablet is to be initiated from the inside.

The invention had for its object to provide detergent, detergent or dishwashing preparations in which volatile and less volatile washing-active, cleaning-active or rinsing-active components can be assembled or mechanically unstable components can be incorporated without them - for example in the case of pressing into shaped bodies - are impaired in terms of their integrity. The invention was further based on the object of spatially separating detergent, cleaning agent or detergent components from one another and still making them up in the same detergent, cleaning agent or detergent portion, with the aim of exchange or a mutual impairment, which may be associated with loss of activity, as low as possible. This would also have the advantage that the storage stability of detergent, detergent or dishwashing preparations could be increased considerably and the contents of active substance could also be reduced in individual cases, since in the prior art when calculating them due to an expected loss of activity, some Components always had to be overdosed.

Surprisingly, it has now been found that detergent, cleaning agent or dishwashing agent portions can be filled into dimensionally stable hollow bodies with one or more separate compartments and thus dose amounts of the respective agents can be provided which, compared to compact shaped bodies or pouched preparations, provide considerable application technology Have advantages.

The invention relates to a detergent, cleaning agent or detergent portion contained in one or more dimensionally stable hollow bodies) with at least one compartment, which comprises:

(a) at least one wash-active, cleaning-active or rinse-active preparation;

(b) at least one at least one preparation according to (a) wholly or partly surrounding enclosure made of a non-pressed material which can be disintegrated under washing, cleaning or rinsing conditions and which gives the hollow body (s) dimensional stability; and.

(c) optionally one or more means (s) for compartmentalizing the dimensionally stable hollow body (s).

The invention further relates to a method for producing a portion of detergent, detergent or dishwashing detergent contained in one or more dimensionally stable hollow body (s) with at least one compartment according to the above and the following detailed description, which comprises the steps of: in a manner known per se produces one or more dimensionally stable hollow body (s), with the exception of processes for the manufacture of the hollow body (s) which are carried out under compression, these hollow body (s) optionally with one or more device (s) for compartmentalizing the / the provides dimensionally stable hollow body (s) and fills the compartment (s) with at least one washing-active, cleaning-active or rinsing-active preparation and, if appropriate, subsequently the dimensionally stable hollow body (s), forming a partial or complete enclosure around the washing-active ^), cleaning-active (n) or flush-active preparation (s) closes.

The invention also relates to a washing method, in particular a method for machine washing in a commercial washing machine, comprising the steps of one enters a detergent portion according to the above and the following detailed description in the washing machine, in particular in its dispenser or washing drum; the desired washing conditions are set; and when these conditions occur, the wash-active preparation (s) of the detergent portion are released into the wash liquor and brought into contact with the items to be washed.

The invention also relates to a cleaning process comprising the steps of adding a detergent portion to the cleaning liquor as described above and below in detail; the desired cleaning conditions are set; and when these conditions occur, the cleaning-active preparation (s) of the detergent portion are released into the cleaning liquor and brought into contact with the goods to be cleaned.

The invention also relates to a washing method, in particular a method for machine washing in a commercially available dishwasher, which comprises the steps of entering a portion of detergent according to the above and the detailed description below into the dishwasher, in particular into its washing-up chamber or into its washing compartment; the desired rinsing conditions are set; and when these conditions occur, the wash-active preparation (s) of the detergent portion are released into the wash liquor and these are brought into contact with the items to be washed.

In the context of the present invention, the term “detergent, cleaning agent or rinsing agent portion” is understood to mean a sufficient amount of a detergent, cleaning agent or rinsing agent for a washing, cleaning or rinsing process taking place in an aqueous phase. This can be, for example, a machine Washing, cleaning or rinsing process, as it is carried out with commercially available washing machines or dishwashers. According to the invention, however, this term also includes a handwashing cycle (for example carried out in a hand wash basin or in a bowl) or a handwashing dishwasher cycle or another process of the According to the invention, the detergent, cleaning agent or rinsing agent portions are preferably used in machine washing, cleaning or rinsing processes.

In the context of the present invention, the term “portion of detergent or cleaning agent or dishwashing detergent” includes a subset of a detergent or cleaning agent or detergent portion, which is present in a phase separated from other detergent or cleaning agent or dish detergent portions in spatial connection with other detergent or cleaning agent or dish detergent portions of the same detergent or cleaning agent or detergent portion, for example in one separate compartment in a dimensionally stable hollow body according to the invention, and which is prepared by suitable measures so that it is separated from other detergent or detergent or detergent portions of the same detergent or detergent or detergent portion in the fleet and optionally dissolved in it or can be suspended. A detergent or detergent or dishwashing portion can contain the same ingredients as another detergent or detergent or dishwashing portion of the same detergent or detergent or dishwashing portion; However, two portions of detergent or cleaning agent or dishwashing detergent preferably contain the same portion of detergent or cleaning agent or dishwashing detergent and contain different ingredients, in particular different detergent-active, detergent-active or dishwashing preparations.

According to the invention, the detergent or cleaning agent or detergent portions contain measured amounts of at least one washing-active, cleaning-active or rinsing-active preparation, usually measured amounts of several washing-active, cleaning-active or rinsing-active preparations. It is possible that the portions contain only wash-active, cleaning-active or rinse-active preparations of a certain composition. According to the invention, however, it is preferred that several, usually at least two, detergent-active, detergent-active or detergent-active preparations of different compositions are contained in the detergent or detergent or detergent portions. The composition can differ with regard to the concentration of the individual components of the wash-active, cleaning-active or rinse-active preparation (quantitative) and / or with regard to the type of the individual components of the wash-active, cleaning-active or rinse-active preparation (qualitative). It is particularly preferred that the components are adapted in terms of type and concentration to the tasks which the detergent or cleaning agent or detergent partial portions have to fulfill in the washing, cleaning or rinsing process.

In the context of the present invention, the term “washing-active or cleaning-active or rinsing-active preparation” means preparations of all conceivable substances relevant in connection with a washing or cleaning or rinsing process. These are primarily the actual detergents or cleaning agents or detergents with their individual components, which are explained in more detail below, including active substances such as surfactants (anionic, non-ionic, cationic and amphoteric surfactants), builders. dersubstanzen _, (inorganic and organic builder substances), bleaching agents (such as peroxo bleaching agents and chlorine bleaching agents), bleach activators, bleach stabilizers, bleaching 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 or rinsing-active preparations” is also understood to mean washing aids and cleaning aids or rinsing aids. Examples of these are optical brighteners, UV protective substances, so-called soil repellents, that is to say polymers which prevent the fibers from becoming soiled or hard Counteract surfaces (including crockery), as well as silver protection agents, colorants and decolorizing agents. According to the invention, laundry treatment agents such as fabric softener or dishwashing detergent additives such as rinse aid are also considered as wash-active or as cleaning-active or as rinse-active preparations.

According to the invention, the detergent, cleaning agent or detergent portions are contained in one or more dimensionally stable hollow body (s) with at least one compartment. 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 or rinsing process, in particular in conventional washing machines or dishwashers. Hollow bodies in the form of spheres, ellipsoids, cubes, cuboids, trapezoids, cones or pyramids or trochoids are conceivable; cuboid or trochoidal hollow bodies have proven themselves according to the invention and can therefore be used with advantage.

In preferred embodiments of the invention, the size of the hollow bodies is such that the hollow bodies can be inserted into the washing-in chamber of a commercially available washing machine or dishwasher, into nets or sacks or the like that run in the laundry. Particularly preferred embodiments of the detergent, detergent or dishwashing detergent portions according to the invention do not exceed a length (longest axis) of 10 cm, while the widths and heights are significantly lower, for example 1 to 5 cm.

According to the invention, the term “dimensionally stable hollow body” is understood to mean that the shaped bodies containing the detergent, cleaning agent or dishwashing agent portions have an inherent dimensional stability which enables them to be carried out under the usual conditions of manufacture, storage, transport and handling the consumer to have a structure which is stable against breakage and / or pressure and does not collapse and which also exists under the conditions mentioned have not changed over a long period of time. It is, according to the invention, irrelevant whether this structural stability is based solely on the properties of the dimensionally stable hollow body resulting from various parameters mentioned below or (also) on the presence of compartmentalization devices and / or (also) on filling with washing-active, cleaning-active or rinsing-active Preparations result. In preferred embodiments of the invention, the dimensionally stable hollow bodies themselves have sufficient inherent dimensional stability, since this has an advantageous effect on the ability to machine in the manufacture of the hollow bodies and the filling during the manufacture of the detergent, cleaning agent or detergent portions according to the invention ,

The pressure resistance of the dimensionally stable hollow bodies according to the invention is measured in the (per se usual) manner in such a way that empty hollow bodies, optionally provided with compartmentation devices, are closed with foils or lids and an internally applied, steadily increasing vacuum is applied to these hollow bodies at room temperature until the hollow body begins to collapse. The inherent dimensional stability of the hollow bodies should particularly preferably be such that, in the case of such vacuum collapse tests of hollow bodies which are not filled and optionally provided with compartmentalization devices, collapse does not begin before a vacuum of 900 mbar, preferably 750 mbar and in particular 500 mbar is reached , In this respect, the hollow bodies used according to the invention differ fundamentally from foils or so-called “pouches”, as are also used for the provision of detergents, cleaning agents or dishwashing detergents. These collapsing already occurs at a pressure which is only slightly below atmospheric pressure. In a similar manner, they differ the dimensionally stable hollow bodies according to the invention, however, also of coatings (subsequently applied to shaped bodies): the hollow bodies according to the invention represent an independent, self-supporting covering which, as a rule, already exists before being filled with one or more washing-active, rinsing-active or cleaning-active components ^) and subsequently In contrast, coatings are applied to existing moldings (for example compacts, granules, extrudates, etc.) and then dried or cured, and only then do they form an envelope surrounding the mold ,

It is particularly preferred according to the invention if the walls of the hollow bodies used according to the invention continue to form a good diffusion barrier, in the same way as the compartments to be explained in more detail below, in particular for substances which have an adverse effect on washing-active, cleaning-active or rinsing-active preparations, in particular gaseous substances and especially water vapor. Diffusion of water vapor should preferably be possible in a maximum amount of 350 g / (m ^2. 24 h), more preferably only in an amount in the range of at most 100 g / (m ^2. 24 h), even more preferably in an amount of at most 50 g / (m ² * 24 h).

According to the invention, particularly preferred embodiments of the detergent, detergent or detergent portions in the dimensionally stable hollow bodies also take into account that the portions contained in the hollow bodies are particularly advantageous, if not necessarily, by a - preferably controllable - water solubility of the hollow body material at a particular point in time of the washing, cleaning or rinsing process or when a certain pH value or a certain ionic strength of the washing liquor has been reached or also 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. Particularly preferred are materials for the hollow bodies 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 loosen when a certain parameter combination is set, while other parts do not loosen (but only later) or not at all. The latter can be achieved through different quality of the material as well as through different amounts of material (thickness of the wall) or also different geometries of the hollow bodies. 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 contents. 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.

It is also possible that the materials of the walls of the dimensionally stable hollow bodies consist of a washing-active, cleaning-active or rinsing-active agent, of which PVAL is an example, or contain such a builder. In the latter case, for example, washing-active, cleaning-active or rinsing-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 the washing, cleaning or rinsing cycle in which the active ingredient is needed, incorporated and during Loosening the material of the wall can be released into the fleet at the right time. An example of this may be fragrances which are desired in the last phase of the washing or cleaning or rinsing process, but also optical brighteners, UV protection substances, dyes and other washing-active, cleaning-active or rinsing-active preparations. The basic principle of incorporating such components (which are usually incorporated in small quantities) into the materials which form the encapsulation of the detergent, cleaning agent or dishwashing agent portions is the applicant's co-pending patent application 199 29 098.9, entitled “Active ingredient portion pack "whose disclosure is fully incorporated into the disclosure of the present application by reference.

In a special embodiment of the invention, it is also possible for the walls of the dimensionally stable hollow bodies, which contain the detergent, cleaning agent or detergent 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 allows water to penetrate into the hollow body and thereby accelerate the release of wash-active, rinse-active or cleaning-active components of the Portion contributes. Overall, the entire dimensionally stable hollow body is more quickly dissolved in such a packaging 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, in particularly preferred embodiments, can be chosen such that they optimally complement one another in terms of their properties (stability, heat resistance, water solubility, gas barrier properties, etc.).

In a particularly preferred embodiment of the invention, a detergent, cleaning agent or dishwashing detergent portion comprises a dimensionally stable hollow body comprising an enclosure wholly or partially surrounding at least one washing-active, cleaning-active or dishwashing preparation from a casing which can be disintegrated under washing, cleaning or rinsing conditions. ren, not pressed material with at least one compartment, the compartment (s) containing one or more washing-active, cleaning-active or rinsing-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 rooms can also be located within the walls of the dimensionally stable hollow body according to the invention. These can either be formed by the fact that individual rooms are separated from one another by walls, which are referred to in the context of the present invention as “compartmentalization devices” and spatially separate the same or different washing-active, rinsing-active or cleaning-active components or preparations, or that different ones wash-active, rinse-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 chamber or the compartment becomes wholly or partially , advantageously entirely, surrounded by the surrounding of a non-pressed material which can be disintegrated under washing, cleaning or rinsing conditions and which forms the wall of the dimensionally stable hollow body, in the compartment or in the comb r is / are one or more washing-active, cleaning-active or rinsing-active preparation (s) contained. In most embodiments of the invention, a compartment advantageously contains several wash-active, cleaning-active or rinse-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 dimensionally stable hollow body contains a plurality of compartments or chambers, each of which contains one or more washing-active, cleaning-active or rinsing-active preparation (s). Examples of this are cuboid or trochoidal dimensionally stable hollow bodies which have two, three or four or even more compartments, each containing one or more washing-active, cleaning-active or rinsing-active preparation (s). A great advantage of this embodiment of the invention is that the various washing-active, cleaning-active or rinsing-active preparations can be distributed over the compartments in the way that is best for the special requirements. Components that adversely affect each other's effectiveness (e.g. enzymes, alkali, bleach, etc.) or that would otherwise mix with one another (e.g. due to the state of matter) (e.g. solid and liquid components) can be spatially separated. On the other hand, it is it is possible to spatially separate components that should ideally be released into the respective fleet at different times of the washing, cleaning or rinsing process and to add them to the fleet at the optimum time.

The size and shape of the individual compartments within a dimensionally stable hollow body is not critical and can largely be adapted to the needs of the individual case. For certain wash-active, cleaning-active or rinse-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 to advantage, mixtures of certain preparations which are provided at the start of the washing, cleaning or rinsing cycle and are present in certain quantities can be spatially separated from other or required components and arranged in compartments of a different size become.

In a particularly preferred embodiment of a detergent, cleaning agent or dishwashing detergent portion contained in a dimensionally stable hollow body with at least one, preferably several, compartment (s), two or more compartments containing one or more washing-active, cleaning-active or rinsing-active preparation are used the hollow body, which are arranged enclosing each other. The compartments with the washing-active, cleaning-active or rinsing-active preparation (s) are therefore not arranged next to one another or one above the other, 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 by the next one, etc. In such a case, the washing-active, cleaning-active or rinsing-active substances can be distributed over the compartments in such a way that that the components required first in the washing, cleaning or rinsing 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 before the allocation is protected from water by the compartments located further out. 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 a detergent, detergent or dishwashing portion, which contains two or more dimensionally stable hollow bodies made from at least one washing-active, cleaning-active or rinsing-active preparation, completely or partially surrounding one or more washing, cleaning or Rinsing conditions of the integrable, non-pressed material (s) with at least one compartment each, the compartment (s) containing one or more washing-active, cleaning-active or rinsing-active preparation (s).

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

It corresponds to a preferred embodiment if the two or more dimensionally stable 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 rinsing 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 dimensionally stable hollow body (s) comprises one or more materials from the group consisting of polymers containing acrylic acid, polyacrylamides, oxazoiin polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and their mixtures comprises.

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), so-called "slip agents" (e.g. "Aerosil"), organic and inorganic pigments, Contain 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 lat, methyl acrylate, hydroxyethyl acrylate, ethylhexyl acrylate, butyl acrylate, and salts of acrylic acid such as sodium acrylate, methacrylic acid and its salts and their esters such as methyl methacrylate, ethyl methacrylate, trimethylammonium methyl methacrylate chloride (TMAEMC), methacrylate amidopropyl chloride (trimethylammonium). 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 its 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% by weight, the graft fraction should be 0 to 95% by weight, the latter may 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, especially 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;

Polyesters 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 of 200 to 35,000 g / mol);

Cellulose ether / ester, e.g. B. 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. According to the invention, the enclosure surrounding the at least one washing-active, rinsing-active or cleaning-active preparation consists of a non-pressed material which gives the hollow body dimensional stability. According to the invention, “non-pressed” material is understood to mean a material which, as in the prior art, is not produced by pressing (for example) wash-active, rinse-active or cleaning-active components or preparations to obtain a pressed body in which other wash-active, flush-active or cleaning-active components or preparations are embedded, but by any other molding techniques, as will be explained in detail below, for example deep drawing, casting, injection molding, sintering, etc. For inorganic materials which can also be used, casting can also be used be a preferred method of manufacture.

In a further preferred embodiment of the invention, the two or more dimensionally stable hollow bodies can consist of two or more different materials which, for example, can be selected from the materials listed above, but can also comprise other materials. In the case of the presence of several dimensionally stable hollow bodies, the 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 these can have similar materials of varying molecular weight (and therefore different solubility), PVAL materials having different degree of acetalization (and thus different solubility or different water dissolution temperature), materials with different fraction ^'of grafted comonomer o. Ä. Be.

It corresponds to a further preferred embodiment that in the case in which several dimensionally stable hollow bodies are present, these dimensionally stable 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 detergent portion contained in the compartment (s) of the hollow body.

Also preferred is an embodiment of the detergent, detergent or dishwashing agent portions according to the invention, in which the two or more dimensionally stable hollow bodies form a - particularly preferred, but not necessarily detachable - composite. A composite of two or more dimensionally stable hollow bodies can be used with particular advantage if either detergent, detergent or dishwashing agent portions of different compositions are to be metered (e.g. heavy-duty detergents and colored detergents; in the latter, for example, bleaching components are not or not in the same concentration is desired as in the former; the hollow body containing bleach could then be used by the user removed if colorful laundry is to be washed) or if - for example for small amounts of laundry or dishes - only a partial dose of the detergent or dishwashing detergent contained in dimensionally stable hollow bodies is to be used. Such a composite could particularly preferably be produced by gluing, fusing, welding or clamping the dimensionally stable hollow bodies; mechanical clamping also allowed the bond to be loosened easily. 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 rinsing process is completely dissolved and drawn off from the machine with the washing, cleaning or rinsing liquor.

For the materials from which the compartments are made, the above information on the materials of the dimensionally stable hollow bodies apply accordingly. With a view to a reliable and simple method of production, in a preferred embodiment of the invention the compartmenting devices within the dimensionally stable hollow bodies consist of the same materials as the hollow bodies themselves. This allows one-piece production in one process step and makes the production process particularly economical.

In principle, however, it is also possible to select the materials of the compartments independently of the materials of the dimensionally stable 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 rinse-active preparation). Examples of this are all the cases in which components of washing-active, cleaning-active or rinsing-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 meet these requirements, for example be substantially impermeable to water vapor to keep bleach free of moisture, or should be acid or alkali free to protect enzymes from premature breakdown. Such an inhibition of a reduction in activity not only directly contributes to 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 particularly preferred embodiments according to the invention, the comparing device (s) is (are) the device (s) which determine the quality and / or quantity of the release of components of a washing-active, cleaning-active or rinsing-active preparation. In cases in which the compartmenting devices have such a function, either components of the wash-active, cleaning-active or rinse-active preparations can advantageously be released into the fleet at different times of the washing, cleaning or rinsing process (qualitative control), or different quantities of certain (qualitatively identical) preparations can be released into the fleet (quantitative control).

In the former case, a dimensionally stable 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, rinsing) active components for the first, second and possibly further (washing, cleaning, rinsing) courses, which have different compositions, and set them at different times or at different times Temperatures of the washing, cleaning or rinsing process free.

In the second exemplary case mentioned, the dimensionally stable 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 rinsing-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 holes, larger amounts of substance can be exchanged between the interior of the compartment (s) and the outside environment (i.e. the liquor) and thus the desired higher concentrations of the washing-active, cleaning-active or rinsing-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 dimensionally stable hollow bodies. Examples of these, however, are not to be understood as a restriction should be the time, ie the expiry of a certain time, in which the walls of the dimensionally stable 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, ie the reaching of a certain temperature value in the course of the temperature profile of the washing, cleaning or rinsing process; the control via the temperature represents a reliable and therefore preferred embodiment, in particular in the case of dishwashing detergents, because of the temperature rising with each stage of the washing process; the pH value, ie the setting of a certain pH value in the course of a washing, cleaning or rinsing process by components of the washing-active, cleaning-active or rinsing-active preparation or the leaving of a certain pH value after the disintegration of a pH-influencing or determining one Component; the ionic strength; mechanical stability, which - depending on time, temperature or other parameters - can be a factor determining disintegration; the permeability for a certain component - primarily gaseous or liquid -; etc..

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 rinse-active preparation. This embodiment is particularly useful in those cases in which it is necessary for one or more active substances to be released into the washing, cleaning or rinsing liquor with a washing-active, cleaning-active or rinsing-active preparation with a predetermined kinetics. A special 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 dimensionally stable hollow body and / or the compartmentalization devices. In this way, a destructive influence of the liquor or only the Water is reduced to the active substance and the substance is actively released into the fleet 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 total amount of at least one component of at least one wash-active, cleaning-active or rinse-active preparation. This can be achieved with particular advantage in that one or several components (s) of at least one washing-active, cleaning-active or rinsing-active preparation are / are incorporated into the material of the compartmentalization device. Examples of such substances have already been mentioned above in connection with the material forming the stable hollow body (s) and include (but are not limited to) components which are present in relatively small amounts in the detergent, cleaning agent or dishwashing agent portions and are It is therefore relatively difficult to incorporate it into large batches of wash-active, cleaning-active or rinse-active preparations. A very simple incorporation into the materials of the compartmentalization devices is successful, and from these also a reliable, controllable release in the course of the washing, cleaning or rinsing 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 rinse-active preparation. This is preferred because the compartmentalization device is not only a component of the detergent, cleaning agent or detergent 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 detergent. , Cleaning or rinsing process is involved. Due to the large selection of materials available, there are numerous examples of this embodiment; Compartmentation devices which consist of or comprise polymers comprising (meth) acrylic acid and its derivatives (salts, esters) are particularly preferred.

According to a further preferred embodiment of the invention, the compartmenting device (s) consist of an interface between two adjoining components of a washing-active, cleaning-active or rinsing-active preparation or an interface between two adjacent washing-active, cleaning-active or rinsing-active preparations. In preferred embodiments of the invention, this can be the case, for example, if wash-active, cleaning-active or rinse-active preparations are formed into structures by means of suitable measures, for example by coextrusion, compression molding or rolling, of a plurality of components, the components of which have solidified interfaces to neighboring components. In these cases, activity-reducing or otherwise disadvantageous influences of the wash-active, cleaning-active or rinse-active preparations on one another can be minimized or even excluded. There is the possibility that either individual components of a washing-active, cleaning-active or rinsing-active preparation are combined to form adjoining interfaces, or that washing-active, cleaning-active or rinsing-active preparations, the of several components are combined to form interfaces. In the context of the dimensionally stable hollow bodies according to the invention, both can lead to detergent, cleaning agent or detergent portions with particularly advantageous properties, for example with good kinetics of dissolution of the components in the aqueous liquors.

A further preferred embodiment of the invention consists in a detergent, cleaning agent or detergent portion contained in one or more dimensionally stable hollow body (s) with at least one compartment, in which the dimensionally stable hollow body consists of a non-spherical hollow body having n delimiting surfaces, one surface of which takes on the function of a "lid" which, at the end of a process for producing the detergent, cleaning agent or dishwashing agent portions according to the invention, ie after filling the compartment (s) inside the hollow body with one or several wash-active, cleaning-active or rinse-active preparation (s) is applied while closing the hollow body. The “lid” is particularly preferably made of a material with controllable water solubility and can be glued, fused, welded to the rest of the hollow body by gluing, for example with a water-soluble adhesive or another known method for joining materials. This embodiment is particularly advantageous for the production of the detergent, cleaning agent or dishwashing agent portions according to the invention, since a gradual filling of the compartment (s) with one or more washing-active, cleaning-active or rinsing-active preparation is possible and handling leads to optimal results in later use, in particular for reliable control of the access of water or aqueous liquor to the inside of the dimensionally stable hollow body or the exit of washing-active, cleaning-active or rinsing-active preparation from the inside of the hollow body.

The detergent, cleaning agent or detergent 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 cleaning agents - Portions are at least partially in the form of shaped articles - binding and disintegration aids. These classes of substances are described below.

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. Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants are sulfonate-type Olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, into consideration, as can be obtained, for example, from C ₁₂ -i ₈ monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Alkansul- also suitable sulfonates, which are for example derived from C ₁₂ -ι ₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of 2-sulfofatty acids (ester sulfonates), for example the 2-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 half-esters of the C ₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂ o- 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, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C _{1 alkyl} sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred for washing technology reasons. 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. ₂ ι alcohols, such as 2-methyl-branched C ₉ . _ι Alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ -ι ₈ fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight. Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C for ₈ - ₁₈ - fatty alcohol radicals 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 whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Saturated 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 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 as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts. In a further embodiment of the invention, surfactants are used in the form of their magnesium salts.

In the context of the present invention, detergent, detergent or dishwashing agent portions are preferred which contain 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 15 to 25% by weight of one or more anionic surfactant (e), each based on the detergent, detergent or detergent portion.

When selecting the anionic surfactants that are used in the detergent, detergent and dishwashing agent portions according to the invention, there are no restrictions to be observed in the freedom of formulation. Preferred detergent, cleaning agent or detergent portions according to the invention, however, have a soap content which exceeds 0.2% by weight, based on the total weight of the detergent, cleaning agent or detergent portion. The preferred anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent, detergent or dishwashing detergent portions being 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight. % Fatty alcohol sulfate (s), each based on the weight of the detergent, detergent or detergent portion 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 radical 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 -i ₄ alcohols with 3 EO or 4 EO, C ₉ . _{ι r} alcohol with 7 EO, C ₁₃ . ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -ι ₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, and mixtures of C ₁₂ -i ₄ alcohol with 3 EO and C ₁₂ -ι ₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferably used nonionic surfactants, 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 esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkyl polyglycosides which can be used satisfy the general formula RO (G) _z , in which R represents a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G is the Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.

Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.

The detergent, detergent or dishwashing detergent portions according to the invention can preferably contain alkyl polyglycosides, the contents of the detergent and cleaning agent Portions of APG above 0.2% by weight, based on the entire preparation, are preferred. Particularly preferred portions of detergent, cleaning agent or detergent contain APG in amounts of 0.2 to 10% by weight, preferably in amounts of 0.2 to 5% by weight and in particular in amounts of 0.5 to 3% by weight .-%.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-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),

R ¹

R-CO-N- [Z] (I)

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R '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 which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated, derivatives thereof residue. [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

It may furthermore be preferred to use cationic surfactants in addition to anionic and nonionic surfactants. They are preferably used as washing performance boosters, whereby only small amounts of cationic surfactants are required. If cationic surfactants are used, they are preferably contained in the agents in amounts of 0.01 to 10% by weight, in particular 0.1 to 3.0% by weight.

In the cases in which the detergent, cleaning agent or rinsing agent portions according to the invention are detergents, these usually contain one or more surfactant (s) in total amounts of 5 to 50% by weight, preferably in amounts of 10 to 35 % By weight, with partial or large portions of the detergent portions according to the invention containing surfactants. In other words: the amount of surfactant does not have to be the same in all partial portions; rather, partial portions with a relatively larger and partial portions with a relatively smaller surfactant content can be provided.

In the cases in which the detergent, detergent or dishwashing detergent portions according to the invention are detergents, in particular dishwashing detergents, they usually contain one or more surfactant (s) in total amounts of 0.1 to 10% by weight, preferably in amounts of 0.5 to 5% by weight, with partial portions of the detergent or dishwashing agent portions according to the invention containing surfactants in larger or smaller amounts. In other words, the amount of surfactant does not have to be the same in all portions, even with detergents or dishwashing detergents; rather, partial portions with a relatively larger and partial portions with a relatively smaller surfactant content can be provided.

In addition to the wash-active substances, builders are the most important ingredients in detergents and cleaning agents. The detergent, detergent or dishwashing agent portions according to the invention can usually contain builders used in detergents, cleaning agents or dishwashing detergents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x 0 _{2x + 1} Η 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 are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. 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 disilicate Na ₂ Si ₂ 0 ₅ 'yH ₂ 0 are preferred, with β-sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171.

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 / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide 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. Compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

An optionally used finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. Zeolite P-type is particularly preferred as zeolite MAP (e.g. commercial product: Doucil A24 from Crosfield). However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ 0 ^• (1-n) K ₂ 0 ^• Al ₂ 0 ₃ ^• (2 - 2.5) Si0 ₂ '(3.5 - 5.5) H ₂ 0 can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is of course also possible to use the generally known phosphates as builders in detergents, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

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 their 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 action, the acids typically also have the property of an acidifying component and thus also serve to adjust a lower and milder pH value of detergent and cleaning agent portions according to the invention. In this context, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned in particular.

Polymeric polycarboxylates are also suitable as builders. 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 the present invention, the molar masses given for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were basically determined by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene acids are generally significantly higher than the molecular weights specified in the context of the present invention. Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights of 2,000 to 10,000 g / mol, particularly preferably 3,000 to 5,000 g / mol, can in turn be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid or 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 molar mass, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as the monomer. In particular, biodegradable polymers of more than two different monomer units are 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 as monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Further preferred copolymers are those which preferably contain 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 co-builder 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 their mixtures 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 processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights 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 action of a polysaccharide compared to dextrose, which is a DE of 100 owns. 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 2,000 to 30,000 g / mol can be used. A preferred dextrin is described in British patent application 94 19 091.

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. An oxidized oligosaccharide is also suitable. 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 co-builders. 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 for use in formulations containing zeolite and / or silicate are 3 to 15% by weight. ,

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

Another class of substances with co-builder properties are the phosphonates. These are in particular hydroxyalkane or aminoalkanephosphonates. Among the hydroalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt alkaline (pH = 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral-reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta and octasodium 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, in particular if the detergent or cleaning agent portions according to the invention also contain bleach, it may be preferred to use aminoalkane phosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as co-builders.

In addition to the surfactant and builder constituents mentioned, the detergents, cleaning agents or dishwashing agents according to the invention can contain further ingredients from the group of bleaching agents, bleach activators, alkalizing agents, acidifying agents, enzymes, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, which are customary in detergents, cleaning agents or rinsing agents. Contain silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors, decolorizing and staining agents, antibacterial substances and corrosion inhibitors.

Of the compounds which serve as bleaching agents and which supply H ₂ 0 ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents that can be used 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. If cleaning or bleaching preparations for machine dishwashing are produced, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate; (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxy-caproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamido operadipic acid and N-nonenate amidooper; and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassyl acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthalo (6) ) can be used. Chlorine or bromine-releasing substances can also be used as bleaching agents in compositions for machine dishwashing. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

In order to achieve an improved bleaching effect when washing, cleaning or rinsing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the detergent, detergent or detergent portions. 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 tetraacetylethylene diamine (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 isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin 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 detergent, detergent or detergent portions. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus 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 of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are particularly special Interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the compositions according to the invention can be, for example, approximately 0.1 to 5% by weight, preferably 0.1 to approximately 2% by weight.

According to the prior art, enzymes are primarily added to a cleaning agent preparation, in particular a dishwashing agent which is intended for the main wash cycle. The disadvantage here was that the optimum effect of the enzymes used restricted 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 detergent portion intended for the pre-rinse cycle and to then - more preferably - include such a preparation with a material of a dimensionally stable hollow body which is water-soluble even at low temperature, for example to Protect enzyme-containing preparation from loss of effectiveness due to environmental conditions. The enzymes are furthermore preferably optimized for use under the conditions of the pre-rinse cycle, 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 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 they 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 of a material soluble in cold water, 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.

According to a particularly preferred embodiment, the detergent, cleaning agent or dishwashing agent portions according to the invention also contain further additives, as are known from the prior art as additives for detergents or cleaning agents or dishwashing agents. Preparations are known. These can either be added to one or more portions of the detergent, detergent or dishwashing detergent portions according to the invention or, if necessary, all partial portions (washing-active, cleaning-active or rinsing-active preparations) or - as in the copending patent application No. 199 29 098.9 with the Title "Active ingredient portion pack" described - into the water-soluble, wash-active, cleaning-active or rinse-active preparations comprising materials of the dimensionally stable hollow body, so for example in the water-soluble wall material (s) are incorporated.

A preferred group of additives used according to the invention are optical brighteners. The optical brighteners customary in detergents can be used here. These are added as an aqueous solution or as a solution in an organic solvent to the polymer solution, which is converted into the wall of the dimensionally stable hollow body, or are added to a partial portion (washing-active preparation) of a detergent or cleaning agent in solid or liquid form. Examples of optical brighteners are derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Are suitable for. B. salts of 4, 4'-bis (2-anilino-4-morpholino1, 3,5-triazinyl-6-amino-) stilbene-2,2'-disulfonic acid or compounds of the same structure, which instead of the morpholino group a Diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the type of the substituted diphenylstyryl can be contained in the partial portions (detergent preparations) of the detergent or cleaning agent portions according to the invention, e.g. B. the alkali salts of 4,4'-bis (2-suifostyryl-) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl-) diphenyl or 4- (4-chlorostyryl-) 4 '- (2nd -sulfostyryl-) biphenyl. Mixtures of the aforementioned brighteners can also be used.

Another group of additives preferred according to the invention are UV protection substances. These are substances which are released in the washing liquor during the washing process or during the subsequent fabric softening process and which accumulate on the fiber in order to then achieve a UV protection effect. Products from Ciba Specialty Chemicals that are commercially available under the name Tinosorb ^R are 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 dimensionally stable hollow body or the compartmenting device, but also can control their wettability and the foam formation when dissolved, and foam inhibitors, but also bitter substances, which can prevent accidental swallowing of such hollow bodies or parts of such hollow bodies by children. Another group of additives preferred according to the invention are dyes, in particular water-soluble or water-dispersible dyes. Dyes are preferred here, as are usually used to improve the optical product appearance in detergents and cleaning agents and dishwashing detergents. The choice of such dyes does not pose any difficulties for the person skilled in the art, in particular since such customary dyes have a long shelf life and are insensitive to the other ingredients of the wash-active, cleaning-active or rinse-active preparations and to light, and have no pronounced substantivity to textile fibers, so as not to stain them. According to the invention, the dyes are present in the detergent or cleaning agent or detergent portions in amounts of less than 0.01% by weight.

Another class of additives that can be added to the detergent, detergent or detergent portions according to the invention are polymers. Among these polymers are, on the one hand, polymers which show cobuilder properties during washing or cleaning or rinsing, that is to say, for example, polyacrylic acids, also modified polyacrylic acids or corresponding copolymers. Another group of polymers are polyvinylpyrrolidone and other graying inhibitors, such as copolymers of polyvinylpyrrolidone, cellulose ether and the like. According to a further embodiment of the invention, so-called soil repellents, as are known to the person skilled in the detergent and cleaning agent and are described in detail below, are also suitable as polymers.

Another group of additives are bleaching catalysts, in particular bleaching catalysts for automatic dishwashing detergents or detergents. Complexes of manganese and cobalt are used here, especially with nitrogen-containing ligands.

Another preferred group of additives in the sense of the invention are silver protection agents. These are a large number of mostly cyclic organic compounds which are likewise familiar to the person skilled in the art and which help to prevent tarnishing of silver-containing objects during the cleaning process. Specific examples can be triazoles, benzotriazoles and their complexes with metals such as Mn, Co, Zn, Fe, Mo, W or Cu.

As further additives according to the invention, the detergent, detergent or dishwashing servings can also contain so-called soil repellents, i.e. polymers that build up on fibers or hard surfaces (for example on porcelain and glass), the oil and fat washability from textiles and the fat washability of porcelain and glass have a positive effect and thus counteract re-soiling. This effect is particularly evident when a textile or a hard object (porcelain, glass) is soiled that already previously washed several times with a washing or cleaning agent according to the invention, which contains this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups from 15 to 30% by weight and of hydroxypropoxy groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ethers, as well as the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

All of these additives are added to the detergent, detergent or dishwashing agent portions according to the invention in amounts of at most 30% by weight, preferably 2 to 20% by weight. As already mentioned, the addition can also be made to a material of a water-soluble enclosure of the dimensionally stable hollow body or to a material of the water-soluble comparing device (s) which is one of the washing-active, cleaning-active (s) or rinsing active preparation (s) comprises or holds in the corpus (s). In order to maintain the balance of the recipe, it is therefore possible for the person skilled in the art to either increase the weight of the polymer material for the wall of the hollow body or for the compartmentalization device (s), so as to exploit the depot effect which is achieved according to the invention , or to keep the additives mentioned additionally at least partially in the rest of the active detergent preparation. However, this is less preferred.

Fragrances are added to the detergent, detergent or detergent portions according to the invention in order to improve the overall aesthetic impression of the products and, in addition to the technical performance (fabric softening result), to provide the consumer with a sensoriscji 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, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexyl propylate propylate, styl pentylate. 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 together they produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures, such 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, lentil flower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrance content is usually in the range up to 2% by weight of the total detergent, cleaning agent or dishwashing agent portion.

The fragrances can be incorporated directly into the wash-active, cleaning-active or rinse-active preparations; 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 rinsing-active preparations) of the detergent, detergent or dishwashing agent portions according to the invention. However, it is particularly preferred that they are in a detergent portion in a partial detergent portion intended for the post-wash or fabric rinse cycle or in a detergent, particularly in a dishwashing detergent, in a portion of the detergent portion provided for the rinse or rinse cycle, special portion of detergent portion are included. According to the invention, you therefore have to use a material of the dimensionally stable hollow body or the compartmenting device which is water-soluble only under the conditions (in particular at the temperature) of the post-wash or rinse cycle and under the conditions (in particular at the temperature) of the preceding wash cycles or rinse cycles ( en) be included. According to the invention, this is feasible, for example, with a detergent, cleaning agent or dishwashing agent portion comprising a plurality of compartments in a dimensionally stable hollow body.

The detergent, cleaning agent or rinsing agent portions according to the invention contain, in a dimensionally stable hollow body with at least one compartment, one or more washing-active, cleaning-active or rinsing-active preparations in such quantities that they are sufficient for a washing, cleaning or rinsing process. Of course, a dosage is two he units (hollow bodies) are possible under special conditions (heavily soiled, eg heavily soiled laundry; heavily soiled dishes).

In a particularly preferred embodiment of the invention, a detergent, cleaning agent or dishwashing agent portion contained in one or more dimensionally stable hollow bodies) with at least one compartment comprises the at least one, preferably the plurality, washing-active, cleaning-active or rinsing-active ( n) Preparation (s) in one or more forms from the group of powders, granules, extrudates, pellets, beads, tablets, tabs, rings, blocks, briquettes, solutions, melts, gels, suspensions, dispersions, emulsions, foams and gases. There is no limit to the shape of the wash-active, cleaning-active or rinse-active preparation contained in one or more compartments of the dimensionally stable 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, detergent or dishwashing agent portions is possible and that a detergent, detergent or dishwashing agent portion suitable for the presentation of such fluid phases is provided , In the compartments of a hollow body, liquids, gels, gases or foams can be closed alone or together with solid components in one or more compartments and brought into contact with the objects to be washed, cleaned or rinsed when in use. This opens up a new freedom in the packaging of detergents, cleaning agents and detergents.

The detergent, cleaning agent or rinsing 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, no requirements are made of 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 non-pressed material which can be disintegrated under washing, cleaning or rinsing conditions and which gives the hollow body (s) dimensional stability, while the other parts of the enclosure are not necessarily dimensionally stable as defined above Must be senses. A preferred embodiment provides for the provision of open, dimensionally stable hollow molds (“shells”) which are filled and later closed, the sealing with a film being of particular importance. Another object of the invention is therefore a detergent, cleaning or rinsing agent portion in the form of an at least partially filled, divided into at least two compartments, comprising a hollow body

(a) a washing, cleaning or rinsing active preparation which consists of an enclosure (A) which is wholly or partly made of a non-pressed material which gives the hollow body (s) dimensional stability and can be disintegrated under washing, cleaning or rinsing conditions exists, is surrounded;

(b) a further washing, cleaning or rinsing active preparation which is not pressed by a casing (B) which is wholly or partly made of a shape (s) which can be disintegrated under washing, cleaning or rinsing conditions and which gives the hollow body (s) dimensional stability Material exists, is surrounded;

(c) optionally further washing, cleaning or rinsing active preparations, which optionally consist of enclosures which consist entirely or partially of a non-pressed material which gives the hollow body (s) dimensional stability and can be disintegrated under washing, cleaning or rinsing conditions, are surrounded;

(d) if appropriate, further washing, cleaning or rinsing active preparations in solid, dimensionally stable form.

In the context of the present invention, the term “enclosure” denotes the wall of a body which completely surrounds a washing, cleaning or rinsing active preparation. This body, in the interior of which the washing, cleaning or rinsing active preparation is present, can be complete or only partly consist of a non-pressed material which can be disintegrated under washing, cleaning or rinsing conditions and which gives the hollow body (s) dimensional stability.

In the context of the present invention, the term “hollow body” denotes the body that is formed from the contents and contents (corresponding to washing, cleaning or rinsing active preparation). The term “hollow body” includes both the individual parts (a) or (b) in the sense of the invention as well as the entire agent according to the invention, which is formed by joining parts (a) and (b) together. In other words, the washing, cleaning or rinsing active preparation enclosed by the enclosure (A) as a macroscopic object is just as much a (filled) “hollow body” in the sense of the present invention as the washing, cleaning or rinsing agent portion according to the invention is characterized in that it has at least two spatially separated areas which can contain different fillings. These spatially separated areas are "compartments" in the sense of the present invention. Of course, the hollow body, which is formed by the enclosure (A) and its contents, can also be divided into different compartments. These different compartments can then all contain one and the same washing, cleaning or rinsing active preparation. However, it is preferred to fill different washing, cleaning or rinsing active preparations into the individual compartments. Completely analogous considerations apply to the hollow body which is enclosed by the enclosure (B), so that the finished portions according to the invention have at least two compartments, but can also have three, four, five, six, seven, eight or more compartments. If the portion according to the invention has more than three compartments, these can be formed by subdividing only one of the part hollow bodies or by compartmentalizing both part hollow bodies. In the case of a four-compartment hollow body, it is possible to design the partial hollow bodies which are enclosed by the enclosures (A) and (B) in such a way that they are each divided into two compartments, but it is also possible only to divide the partial hollow body enclosed by the enclosure (A) or by the enclosure (B) into three compartments. The number of possibilities naturally increases with the number of the entire compartments - at the same time the complexity in the production increases, so that portions with two, three and four compartments according to the invention are particularly preferred.

Further compartments can not only be designed by dividing the partial hollow bodies which are enclosed by the enclosures (A) and (B). It is also possible according to the invention to provide additional partial hollow bodies which are enclosed by enclosures (C), (D), (E), (F) etc. with the partial hollow bodies enclosed by the enclosures (A) and (B) to unite to the total portion.

As already mentioned, a preferred embodiment provides for the provision of open, dimensionally stable hollow molds (“trays”) which are filled and subsequently closed, the sealing with a film being of particular importance here. Detergent, cleaning agent or detergent portions according to the invention Preferred, in which the enclosures (A) and (B) and optionally further enclosures to 20 to 90%, preferably 30 to 80% and in particular 40 to 70% of their surface from dimensionally stable, optionally one or more device (s) for Compartmental comprehensive shells exist, while the rest is formed by a water-soluble film.

In the simplest case, the partial hollow body is accordingly produced by producing an open shell of any shape, filling this shell and then closing it with a film. The kinetics of dissolution and thus the release of the filling can be controlled by carefully selecting the materials from which the shell and film are made. Under the term In the context of the present invention, “closing” is to be understood to mean that the film which closes the opening of the shell (s) is adhesively bonded to the edges of the shell.

The film that closes the opening of the shell is applied to the opening and firmly bonded to the edges thereof, which can be done, for example, by gluing, partial melting or by chemical reaction.

The sealing film can of course also be a laminate of several differently composed films, the opening of the shell can be released at certain times in the washing and cleaning cycle via different compositions of individual film layers.

Preferred film materials are the polymers known from the prior art. Particularly preferred are films made of a polymer with a molecular weight between 5000 and 500,000 daltons, preferably between 7500 and 250,000 daltons and in particular between 10,000 and 100,000 daltons. With regard to the media into which washing and cleaning agents are usually introduced, portions according to the invention in which the film consists of a water-soluble polymer are particularly preferred.

Such preferred polymers can be synthetic or natural in origin. If native or partially native polymers are used as film material, preferred film materials are selected from one or more substances from the group consisting of carrageenan, guar, pectin, xanthan, cellulose and their derivatives, starch and their derivatives and gelatin.

Carrageenan is an extract from North Atlantic red algae, which is one of the florid plants, and is named after the Irish coastal town of Carragheen. The carrageenan precipitated from the hot water extract of the algae is a colorless to sand-colored powder with molar masses of 100000-800000 and a sulfate content of approx. 25%, which is very easily soluble in warm water. There are three main components in carrageenan: The yellow-forming / fraction consists of D-galactose-4-sulfate and 3,6-anhydro-α-D-galactose, which are alternately glycosidically linked in the 1,3 and 1,4 positions (In contrast, agar contains 3,6-anhydro- -L-galactose). The non-gelling I fraction is composed of 1,3-glycosidically linked D-galactose-2-sulfate and 1,4-linked D-galactose-2,6-disulfate residues and is readily soluble in cold water. The i-carrageenan composed of D-galactose-4-suifate in 1,3-bond and 3,6-anhydro-aD-galactose-2-sulfate in 1,4-bond is both water-soluble and gel-forming. Other types of carrageenan are also designated with Greek letters: α, ß, γ, μ, v, ξ, π, ω, χ. Also the type of cations available (K, NH ₄ , Na, Mg, Ca) influences the solubility of the carrageenans. Semi-synthetic products that contain only one type of ion and can also be used as film materials in the context of the present invention are also called carrag (h) eenate.

The guar, also called guar flour, which can be used as film material in the context of the present invention is an off-white powder which is obtained by grinding the endosperm of the guar bean (Cyamopsis tetragonobolus). The main component of the guar is up to approx. 85% by weight of the dry substance guaran (guar gum, cyamopsis gum); Minor components are proteins, lipids and cellulose. Guaran itself is a polygalactomannan, i.e. a polysaccharide, the linear chain of unsubstituted (see formula I) and substituted in the C6 position with a galactose residue (see formula (II) mannose units in ß-D- (1-3> 4) linkage is constructed.

galactose

Manno

The ratio of l: ll is approximately 2: 1; contrary to the original assumption, the Il units are not strictly alternating, but are arranged in pairs or triplets in the polygalactomannan molecule. Information on the molecular weight of the guaran vary with values of about ⁵ 2,2 10 - 2,2 10 ⁶ g / mol depending on the degree of purity of the polysaccharide - the high value was determined on a highly purified product - significant and correspond to about 1350 -13500 sugar units / macromolecule. Guaran is insoluble in most organic solvents.

The pectins that can also be used as film material are high-molecular glycosidic plant substances that are very common in fruits, roots and leaves. The pectins consist essentially of chains of 1,4-α-glycoside. connected galacturonic acid units, the acid groups of which are 20-80% esterified with methanol, a distinction being made between highly esterified (> 50%) and low-esterified pectins (<50%). The pectins have a folding leaf structure and thus stand in the middle of starch and cellulose molecules. Your macromolecules still contain some glucose, galactose, xylose and arabinose and have weakly acidic properties.

Fruit pectin contains 95%, beet pectin up to 85% galacturonic acid. The molar masses of the various pectins vary between 10,000 and 500,000. The structural properties are also strongly dependent on the degree of polymerization; so form e.g. the fruit pectins in the dried state asbestos-like fibers, the flax pectins, on the other hand, fine, granular powder.

The pectins are produced by extraction with dilute acids, mainly from the inner parts of citrus fruit peel, leftovers or sugar beet pulp.

Xanthan can also be used as a film material according to the invention. Xanthan is a microbial anionic heteropolysaccharide that is produced by Xanthomonas campestris and some other species under aerobic conditions and has a molecular weight of 2 to 15 million Daltons. Xanthan is formed from a chain with ß-1, 4-bound glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan. Xanthan can be described by the following formula:

Basic unit of xanthan

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

In addition to cellulose and cellulose derivatives, (modified) dextrins, starch and starch derivatives can also be used as film materials. Suitable nonionic organic film materials 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 processes, for example acid-catalyzed or enzyme-catalyzed. 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 action 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.

Starch can also be used as film material for the portions according to the invention. Starch is a homoglycan, with the glucose units linked α-glycosidically. Starch is made up of two components of different molecular weights: approx. 20-30% o straight-chain amylose (MW. Approx. 50,000-150,000) and 70-80% branched-chain amylopectin (MW. Approx. 300,000-2,000,000), besides are contain small amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, intertwined chains with about 300-1200 glucose molecules due to the binding in the 1,4 position, the chain in the amylopectin branches after an average of 25 glucose units through 1,6 binding to form a knot-like structure with about 1500-12000 molecules of glucose. In addition to pure starch, starch derivatives which can be obtained from starch by polymer-analogous reactions are also suitable as film materials in the context of the present invention. Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.

Among the proteins and modified proteins, gelatin is of outstanding importance as a film material. Gelatin is a polypeptide (molecular weight: approx. 15,000-> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and depending on its provenance. The use of gelatin as a water-soluble coating material is extremely widespread, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules.

Other polymers which can be used as film materials are synthetic polymers which are preferably water-swellable and / or water-soluble. Such synthetic-based polymers can be “tailor-made” for the desired film permeability during storage and dissolution of the film when used. Particularly preferred film materials are selected from a polymer or polymer mixture, the polymer or at least 50% by weight of the polymer mixture being selected out

a) water-soluble nonionic polymers from the group of

a1) polyvinylpyrrolidones, a2) vinylpyrrolidone / vinyl ester copolymers, a3) cellulose ethers

b) water-soluble amphoteric polymers from the group of

b1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkylacrylamide / acrylic acid / alkyaminoalkyl (meth) acrylic acid copolymers b5) alkylacrylamide / methacrylic acid / alkylaminoalkyl (b) acrylamide -acrylic acid / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid

Copolymers b7) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate alkyl methacrylate

Copolymers b8) copolymers from b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids bδiii) optionally further ionic or nonionic monomers

c) water-soluble zwitterionic polymers from the group of

d) Acrylamidoalkyltrialkylammoniumchlorid / acrylic acid copolymers and their alkali and ammonium salts c2) Acrylamidoalkyltrialkylammoniumchlorid / methacrylic acid copolymers and their

Alkali and ammonium salts c3) methacroylethyl betaine / methacrylate copolymers

d) water-soluble anionic polymers from the group of

d1) vinyl acetate / crotonic acid copolymers d2) vinyl pyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers d4) graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid with polyalkylene oxides and / or polyalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the non-ionic type, d5ii) at least one monomer of the ionic type, dδiii) of polyethylene glycol and d5iv) a crosslinked agent d6) by copolymerization of a monomer each of the following three

Copolymers obtained in groups: dδi) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, d6iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or

Esters from the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-0 ₈ alcohol d7) terpolymers from crotonic acid, vinyl acetate and an allyl or methallyl ester dδ) tetra- and pentapolymer from dδi) crotonic acid or allyloxyacetic acid dδii) vinyl acetate or vinyl propionate dδiii) branched allyl or methallyl esters dδiv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters d9) crotonic acid copolymers with one or more monomers from the group

Ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts d10) Terpolymers from vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position e) water-soluble cationic polymers from the group of

e1) quaternized cellulose derivatives e2) polysiloxanes with quaternary groups e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and

Amides of acrylic acid and methacrylic acid e5) copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate e6) vinylpyrrolidone-methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol e8) under the I CI designations polyquaternium n. 18, polyquaternium n, polyquaternium n Polyquaternium 27 indicated polymers.

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

The films can be made from individual of the above-mentioned polymers, but mixtures or multilayered layer structures made of the polymers can also be used. The polymers are described in more detail below.

Water-soluble polymers preferred according to the invention are nonionic. Suitable non-ionogenic polymers are, for example:

Polyvinylpyrrolidones, as, for example, sold under the name Luviskol ^® (BASF). Polyvinylpyrrolidones are preferred nonionic polymers in the context of the invention.

Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones) j, abbreviation PVP, are polymers of the general formula (III)

which are prepared by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-radical formers (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer only provides products with low molecular weights. Commercial polyvinylpyrrolidones have molar masses in the range from approx. 2500-750000 g / mol, which are characterized by the K values and, depending on the K value, have glass transition temperatures of 130-175 °. They are presented as white, hygroscopic powders or as aqueous ones. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).

Vinylpyrrolidone / Vinylester copolymers, as are marketed, for example under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, both vinyl pyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.

The vinyl ester polymers are polymers accessible from vinyl esters with the grouping of the formula (IV)

- CH ₂ - CH - O

I

O ^ ^ R (iv)

as a characteristic basic building block of macromolecules. Of these, the vinyl acetate polymers (R = CH ₃ ) with polyvinyl acetates are by far the most important representatives as the most important representatives.

The vinyl esters are polymerized by free radicals using various processes (solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization). Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (III) and (IV)

Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and hydroxypropylcellulose methylhydroxy- as they are for example sold under the trademark Culminal® ^® and Benecel ^® (AQUALON).

Cellulose ethers can be described by the general formula (V)

in R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products at least one R in formula (III) is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose have reacted with the etherification reagent or how many moles of etherification reagent have been attached to an anhydroglucose unit on average , Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercial hydroxyethyl and hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1, 35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish white, odorless and tasteless powders in widely differing degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Polyvinyl alcohols, abbreviated as PVAL, are polymers of the general structure

[-CH ₂ -CH (OH) -] _n

which in small proportions also structural units of the type

[-CH ₂ -CH (OH) -CH (OH) -CH ₂ ]

contain. Since the corresponding monomer, the vinyl alcohol, is not stable in free form, polyvinyl alcohols are produced in solution via polymer-analogous reactions by hydrolysis, but technically in particular by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol). These technical processes also make PVAL accessible which contain a predeterminable residual proportion of acetate groups.

Thus, in the context of the present invention, the term “polyvinyl alcohol” includes homopolymers of vinyl alcohol, copolymers of vinyl alcohol with copolymerizable monomers or hydrolysis products of vinyl ester homopolymers or vinyl ester copolymers with copolymerizable monomers.

Commercial polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or δ7-89 mol% , therefore still contain a residual content of acetyl groups. The manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax. The polyvinyl alcohol coatings are largely impervious to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

Portions preferred in the context of the present invention are characterized in that the film consists of a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to δ9 mol% and in particular 82 to 8δ mol -%.

Polyvinyl alcohols of a certain molecular weight range are preferably used in the film, portions according to the invention are preferred in which the film consists of a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^"1 , preferably from 11,000 to 90,000 gmol ^{" 1} , particularly preferably from 12,000 to δθ,000 gmol ^"1 and in particular from 13,000 to 70,000 gmol ^{" 1} .

The degree of polymerization of such preferred polyvinyl alcohols is between approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1890, particularly preferably between approximately 240 to approximately 1680 and in particular between approximately 260 to approximately 1500.

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). Within the scope of the present invention, Other suitable polyvinyl alcohols are, for example, Mowiol 3-83, Mowiol 4-88, Mowiol 5-88 and Mowiol ^® δ-88.

Other polymers suitable according to the invention are water-soluble amphopolymers. Ampho-polymers are amphoteric polymers, ie polymers that contain both free amino groups and free -COOH or S0 ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - Contain COO ^" - or -S0 ₃ ^" groups, and summarized those polymers which contain -COOH or S0 ₃ H groups and quaternary ammonium groups. An example of the present invention amphopolymer suitable is that available under the name Amphomer ^® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (1, 1, 3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Methacrylic acid and its simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (e.g. acrylamidopropyl-trimethyl-ammonium chloride) and optionally further ionic or non-ionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art can be found. Terpolymers of acrylic acid, methyl acrylate and methacrylamido propyltrimoniumchlorid as they are available under the name Merquat ^® 2001 N commercially, are inventively particularly preferred amphopolymers. Other suitable amphoteric polymers are for example those available under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL) octylacrylamide / Methylmet acrylate / tert-butylaminoethyl methacrylate / 2-Hydroxypropyimethacrylat copolymers.

Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali and ammonium salts are preferred zwitterionic polymers. Further suitable zwitterionic polymers methacroylethylbetaine / methacrylate copoly ere are obtainable under the name Amersette® ^® (AMERCHOL).

Anionic polymers suitable according to the invention include a .:

Vinyl acetate / crotonic acid copolymers, such as are commercially available for example under the names Resyn ^® (National Starch), Luviset ^® (BASF) and Gafset ^® (GAF).

In addition to monomer units of the above formula (IV), these polymers also have monomer units of the general formula (VI):

[-CH (CH ₃ ) -CH (COOH) -] _n (VI) Vinylpyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF). A preferred polymer is that available under the name Luviflex VBM-35 ^® (BASF) vinylpyrrolidone / acrylate terpolymers.

Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, which are sold, for example, under the name Ultrahold ^® strong (BASF).

Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols

Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture with other copolymerizable compounds on polyalkylene glycols, are obtained by polymerization in the heat in a homogeneous phase by converting the polyalkylene glycols into the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid, in In the presence of radical formers.

Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as esters of acrylic acid or methacrylic acid, those which are used with low molecular weight aliphatic alcohols, in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2- Methyl-1-propanol, 2-methyl-2-propanol, 1-pentaneόl, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are available.

Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol which have the general formula VII

H- (0-CH ₂ -CH ₂ ) _n -OH (VII)

are sufficient, where n can take values between 1 (ethylene glycol) and several thousand. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the formula V mentioned above. According to this nomenclature (so-called INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance asso- ciation, Washington, 1997), for example, PEG-4, PEG-6, PEG-8, PEG-9, PEG-10, PEG-12, PEG -14 and PEG-16 can be used. Commercially available polyethylene glycols are, for example, under the trade name Carbowax ^® PEG 200 (Union Carbide), Emkapol ^® 200 (ICI Ame- ricas) Lipoxol ^® 200 MED (Huls America), polyglycol ^® E-200 (Dow Chemical), Alkapol ^® PEG 300 (Rhone-Poulenc), Lutrol ^® E300 (BASF) and the corresponding trade names with higher numbers.

Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula VIII

H- (0-CH-CH ₂ ) _n -OH (VIII)

CH ₃

are sufficient, where n can have values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetrapropylene glycol, i.e. the representatives with n = 2, 3 and 4 in formula VI.

In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used.

grafted and crosslinked copolymers from the copolymerization of i) at least one monomer of the nonionic type, ii) at least one monomer of the ionic type, iii) of polyethylene glycol and iv) a crosslinker

The polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000.

The nonionic monomers can be of very different types and the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene. The non-ionic monomers can likewise be of very different types, of which crotonic acid, allyloxyacetic acid, vinyl acetic acid, maleic acid, acrylic acid and methacrylic acid are particularly preferably contained in the graft polymers.

Preferred crosslinkers are ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucrose with 2 to 5 allyl groups per molecule of saccharin.

The grafted and crosslinked copolymers described above are preferably formed from: i) 5 to 85% by weight of at least one monomer of the nonionic type, ii) 3 to 80% by weight of at least one monomer of the ionic type, iii) 2 to 50% by weight, preferably 5 to 30% by weight of polyethylene glycol and iv) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii) is.

copolymers obtained by copolymerization of at least one monomer of each of the following three groups: i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or

Esters of short-chain saturated alcohols and unsaturated carboxylic acids, ii) unsaturated carboxylic acids, iii) esters of long chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group ii) with saturated or unsaturated, linear or branched C ₈ ₈ alcohol .ι

Short-chain carboxylic acids or alcohols are to be understood as meaning those having 1 to δ carbon atoms, the carbon chains of these compounds optionally being interrupted by double-bonded hetero groups such as -O-, -NH-, -S_.

Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester

These terpolymers contain monomer units of the general formulas (II) and (IV) (see above) and monomer units of one or more allyl or methallyesters of the formula IX: R ¹ R ³

I 'I

R ² -CC (0) -0-CH ₂ - C = CH ₂ (IX)

I CH ₃

wherein R ³ for -H or -CH ₃ , R ² for -CH ₃ or -CH (CH ₃ ) ₂ and R ¹ for -CH ₃ or a saturated straight-chain or branched C ₁ . ₆ alkyl radical and the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2.

The above-mentioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to δ6% by weight, preferably 71 to δ3% by weight of vinyl acetate and δ to 20% by weight, preferably 10 to 17% by weight .-% Allyl- or Methallyletsre of formula IX.

Tetra- and pentapolymers of i) crotonic acid or allyloxyacetic acid ii) vinyl acetate or vinyl propionate iii) branched allyl or methallyl esters iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters

Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts

Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position.

In the case of anionic polymers, film materials in particular are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals and dextrins, which are described below.

Usable organic film materials are, for example, the polycarboxylic acids which can be used in the form of their sodium salts but also in free form. Polymeric polycarboxylates 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.

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

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.

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.

To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers. Biodegradable polymers of more than two different monomer units are also particularly preferred as film materials, 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 are salts of acrylic acid and 2-alkylallylsulfonic acid and Derivatives included.

Further preferred copolymeric film materials 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 film materials are polymeric aminodicarboxylic acids, their salts or their precursors. Polyaspartic acids or their salts and derivatives are particularly preferred.

Other suitable film materials 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 made from dialdehydes such as glyoxal, Glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other polymers that can preferably be used as film materials are cationic polymers. The permanent cationic polymers are preferred among the cationic polymers. According to the invention, polymers which have a cationic group irrespective of the pH of the composition (ie both the film and the remaining portion) are referred to as “permanently cationic”. These are generally polymers which have a quaternary nitrogen atom, for example in the form an ammonium group.

Preferred cationic polymers are, for example

quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^® . The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives.

Polysiloxanes with quaternary groups, such as the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicon), Dow Corning ^® 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone) , SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-δO),

Cationic guar derivatives, such as, in particular, the products marketed under the trade names Cosmedia ^® Guar and Jaguar ^® ,

'Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (Dirhethyl- diallyl ammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers.

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as, for example, vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755.

Vinylpyrrolidone-methoimidazolinium chloride copolymers, as are offered under the name Luviquat ^® . quaternized polyvinyl alcohol

as well as those under the designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27

known polymers with quaternary nitrogen atoms in the main polymer chain. The polymers mentioned are named according to the so-called INCI nomenclature, with detailed information in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 * Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, to which express reference is made here becomes.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers. Cationic cellulose derivatives, in particular the commercial product Polymer ^® JR 400, are very particularly preferred cationic polymers.

Regardless of the chemical composition of the film, detergent, cleaning or rinsing agent portions according to the invention are preferred, which are characterized in that the film which forms part of the enclosure (A) or (B) has a thickness of 1 to 150 μm, preferably from 2 to 100 μm, particularly preferably from 5 to 75 μm and in particular from 10 to 50 μm.

In this way, a portion of washing, cleaning or rinsing agent according to the invention comprises two areas in which different ingredients are contained or different release mechanisms and release kinetics can be realized. The active substance contained in a compartment can assume any physical state or any form of presentation. Preferred detergent, cleaning agent or detergent portions contain the further active substance in at least one compartment in liquid, gel-like, pasty or solid form, see below.

When incorporating liquid, gel-like or pasty active substances or active substance mixtures, the composition of the casing and thus also the film must be matched to the filling in order to avoid premature destruction of the film or loss of active substance through the casing. This is only necessary to a lesser extent (chemical incompatibility) when solid substances are incorporated into the compartments, so that preferred detergent, cleaning or rinsing agent portions in at least one compartment contain further active substance in particle form, preferably in powdered, granular, extruded, pelletized form , prilled, flaked or tableted form. The enclosure closed by the film can be completely filled with washing, cleaning or rinsing active preparation. However, it is also possible to fill the respective hollow mold only partially before closing, in order in this way to enable the filled particles or liquids to move within the hollow mold. Particularly when filling with regularly shaped larger particles, attractive optical effects can be achieved. In this case, detergent, cleaning agent or detergent portions are preferred in which the volume ratio of the space enclosed by the film and the further enclosure to the washing, cleaning or rinsing active preparation contained in this space is 1: 1 to 100: 1, is preferably 1.1: 1 to 50: 1, particularly preferably 1.2: 1 to 25: 1 and in particular 1.3: 1 to 10: 1. In this terminology, a volume ratio of 1: 1 means that the mold is completely filled.

The time at which the washing-cleaning or rinsing-active preparation is released can be predetermined by suitable packaging of the non-pressed material which disintegrates under washing, cleaning or rinsing conditions and which gives the hollow body (s) shape stability, and the film material. For example, the film can be instantly soluble, so that the washing, cleaning or rinsing active preparation is dosed into the washing or cleaning liquor right at the beginning of the washing or cleaning cycle (or as soon as the film comes into contact with the washing, cleaning) - or rinsing liquor, ie in cases in which the portion according to the invention has no film on its outer surface, after the portion has fallen apart into the partial hollow bodies (A) or (B)).

The shape of the "shell" can be chosen freely, certain geometrical shapes such as hemispheres having proven to be preferred for aesthetic reasons. However, box shapes or shell-shaped shells are also possible according to the invention. The "shell" can have an edge that only has the material thickness, but it can also have a web edge which serves as a larger adhesive and sealing surface for the film. In a preferred embodiment of the present invention, the “shell” is produced from water-soluble thermoplastics by the injection molding process. In this process, any partition walls for the later formation of several compartments can also be injection molded. The “shell” is also produced from suitable materials by a melt casting process ( see below) is preferred.

The filled trays are sealed with film by means of a firmly bonded connection to their edges, which can be done, for example, by gluing, partial melting or by chemical reaction. In the case of divided trays, the covering film can be sealed not only at the edges of the outer periphery of the tray, but also with the upper one Edge of the inner partitions, so that a tight seal of the compartments is also guaranteed against each other. The capping film can also be designed in such a way that differently assembled film areas come to lie over the different compartments in order to influence the disintegration kinetics in aqueous solution and thus the release of the individual preparations from the compartments.

The enclosures (A) and (B) and, if appropriate, further enclosures and / or further constituents of the portions according to the invention, in their entirety, form the detergent, cleaning agent or detergent portion according to the invention. It is preferred that the enclosures (A) and (B) and, if appropriate, further enclosures are joined together in such a way that the surface of the detergent, cleaning agent or detergent portion which is not formed by any part (d) which may be present is preferably at least 80% consists of at least 90% and in particular exclusively of the non-pressed material which gives the hollow body (s) dimensional stability.

In other words, the separately produced partial hollow bodies are joined to one another in such a way that only a small part (in particularly preferred cases no part at all) of the surface of the detergent, cleaning agent or detergent portion according to the invention is formed by film. Rather, the “outer skin” of the washing, cleaning or rinsing agent portion according to the invention consists predominantly (in particularly preferred cases: completely) of the non-pressed material which gives the hollow body dimensional stability.

The corresponding materials, their chemical and physical parameters and information on their processing are described above.

The washing, cleaning or rinsing agent portions according to the invention contain washing, cleaning or rinsing active preparations. These can be contained in any form of packaging in the partial hollow bodies or compartments. Particularly preferred washing, cleaning or rinsing agent portions are characterized in that at least one washing, cleaning or rinsing active preparation is present in liquid form in the enclosures (A) or (B).

This liquid must be chosen so that it does not attack the materials of the casing. Non-aqueous solutions, suspensions, dispersions or emulsions have proven themselves here. Especially when filling the partial hollow bodies with liquid washing, cleaning or rinsing active preparation, it is preferred if the enclosure is transparent or at least translucent in order to make the aesthetic appeal of the liquid filling visible from the outside. Here are washing, cleaning or rinsing agent portions according to the invention particularly preferred, in which at least one enclosure is transparent or translucent, the wall thickness of the material being 100 to 5000 μm, which is completely or partially made of a non-pressed material that disintegrates under washing, cleaning or rinsing conditions, which gives the hollow body (s) dimensional stability, is preferably 200 to 3000 μm, particularly preferably 300 to 2000 μm and in particular 500 to 1500 μm.

The washing, cleaning or rinsing agent portions according to the invention have at least two areas in which washing, cleaning or rinsing active preparation is located. As stated above, one of these preparations is preferably liquid. The second preparation can also be a liquid (possibly of a different composition), but it is also possible to use solids of any form here. It is particularly preferred here to fill the second cavity with a powdery to granular preparation.

The washing, cleaning or rinsing 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 the partial hollow body.

The partial hollow bodies, which contain washing, cleaning or rinsing active preparation in the enclosures (A) or (B), are combined with one another to form the detergent, cleaning agent or dishwashing agent portion according to the invention. According to the invention, one is not bound to connect only two partial hollow bodies. Rather, it is also possible to add further partial hollow bodies which contain washing, cleaning or rinsing-active preparation in further enclosures (C) or (D) etc. For reasons of process economy, partial hollow bodies are preferred which have flat connecting surfaces. Of course, one is not bound to connect only filled partial hollow bodies to one another for the detergent, cleaning agent or dishwashing agent portion according to the invention. Rather, it is also possible and preferred to add partial hollow bodies which contain washing, cleaning or rinsing active preparations in the enclosures (A) or (B) with further washing, cleaning or rinsing active preparations in solid, dimensionally stable form connect. Here, in particular, the connection of partial hollow bodies with tablets has proven to be particularly advantageous. Corresponding embodiments are described below.

As already mentioned above, the portions according to the invention are particularly suitable for releasing various washing, cleaning or rinsing active preparations from the enclosures (A) or (B) at different times. This controlled release of certain preparations serves to achieve improved results in the washing, cleaning or rinsing process. The release from the enclosures (A) or (B) can either be achieved at different times in that the parts of the respective enclosure which consist of the material which gives the shape of the hollow body have different dissolution or integration rates. This is for example by Choice of material thickness possible. For large-scale production, however, it is advantageous to choose the above-mentioned part of the enclosures (A) and (B) identically, since in this way only one process step has to be carried out where two independent process steps would otherwise be required. It is more elegant here to choose the other part of the enclosure (in preferred embodiments: the film closing the shell) differently for the enclosures (A) or (B) and in this way to release the preparation from the enclosures (A) or To achieve (B). Detergent, detergent or dishwashing detergent portions according to the invention are preferred here, in which the enclosures (A) and (B) are formed from an injection-molded half-shell sealed with film, the wall thickness of the shark shells of the enclosures (A) and (B) 100 is up to 1000 μm, preferably 150 to 700 μm and in particular 250 to 500 μm and the thickness of the film of the enclosure (A) is 10 to 200 μm, preferably 20 to 100 μm and in particular 40 to δO μm and the thickness of the film of the enclosure (B) 20 to 250 μm, preferably 40 to 200 μm and in particular 60 to 150 μm.

As detailed in Figure 4 below, the injection molding process can be facilitated by adding external plasticizers (e.g., glycerin) to the polymers or by using "internally" plasticized polymers.

Through the choice of different film thicknesses and / or film materials, the compositions of the partial hollow bodies (A) or (B), which are formed from the portions according to the invention by “falling apart” (see below) after being introduced into the application liquor It is preferred here to release the ingredients from the enclosure (A) into the application medium earlier than those from the enclosure (B), either by choosing a thicker film of the enclosure (B) and / or by chemically modifying the film Detergent, detergent or dishwashing detergent portions according to the invention are preferred here, in which the film of the enclosures (A) and (B) consists of thermoplastic polymers, the film of the enclosure (B) in the The application liquor is soluble more slowly or with a delay than the film of the enclosure (A).

Corresponding films made of water-soluble thermoplastics are commercially available. For example, a polyvinyl alcohol film is suitable for the enclosure (A), which dissolves quickly enough at 20 ° C, while in such a case a film with slower kinetics at 20 ° C, for example one, is selected for the enclosure (B) those with better solubility above 40 ° C or 50 or 60 ° C. When the closed enclosures (A) or (B) are combined to form the portion according to the invention, embodiments are preferred in which the outer area of the portion consists entirely of the dimensionally stable material (handling safety). In the above-mentioned example of the shells closed with foils, the foil sides are thus placed against one another and do not come into contact with the external environment after the connection of the closed enclosures (A) and (B), ie they are on the inside. It is crucial for the above-described type of controlled release by means of different film solubility that the closed enclosures (A) and (B) separate from one another in the application liquor, ie that the portions according to the invention "fall apart" in the application medium.

This can be achieved, for example, by connecting the closed enclosures (A) and (B) with an adhesion promoter which has an extremely high solubility. Upon contact with the application liquor, the adhesion promoter is quickly dissolved and releases the two partial hollow bodies from the portion, as a result of which the film sides come into contact with the liquor. Further information on adhesion promoters can be found below. In particular, the materials mentioned above for shells made of meltable materials are suitable as adhesion promoters. Urea as well as sodium or potassium hydrogen sulfate may only be mentioned here by way of example.

Particularly preferred detergent, cleaning or rinsing agent portions are characterized in that the closed enclosures (A) and (B) are connected with a water-soluble hot melt adhesive, so that the portion in the application liquor within 60 s, preferably within 30 s, so disintegrated that the film of the closed enclosures (A) or (B) comes into contact with the application fleet.

The filling of the partial hollow bodies (A) or (B) can be chosen as desired, numerous examples having already been described above. In the context of the present invention, particular preference is given to washing, cleaning or rinsing agent portions in which the closed container (A) contains a non-surfactant-rich basic detergent composition, preferably a liquid detergent, while the closed container (B) preferably contains a composition with further utility , in particular a bleaching composition and / or an enzyme composition and / or a fragrance preparation and / or a discoloration, graying or hardness inhibitor composition and / or a plasticizer composition.

The ingredients for the above-mentioned preparations are described in detail above. Of course, the above-mentioned principle can also be adapted for cleaning agents, for example for machine dishwashing agents in which the closed ne enclosure ^ A) contains a building material-rich detergent composition, while the closed enclosure (B) preferably contains a composition with further use, in particular a rinse aid composition and / or an enzyme composition and / or a fragrance preparation and / or a complexing agent composition and / or a polymer composition.

Another object of the present invention is a method for producing a detergent, cleaning agent or detergent portion contained in an at least partially filled hollow body divided into at least two compartments, comprising the steps

(i) production of dimensionally stable hollow bodies, optionally comprising one or more devices for compartmenting; (ii) filling the hollow bodies or compartments with wash-active, cleaning-active or rinse-active preparations; (iii) closing the dimensionally stable hollow bodies with the formation of closed enclosures (A), (B) and, if appropriate, further closed enclosures, in order to form the wash-active, cleaning-active or rinsing-active preparation (s); (iv) connecting the closed enclosures (A) and (B) and optionally further enclosures and / or further washing, cleaning or rinsing active preparations in solid, dimensionally stable form for washing, cleaning or rinsing agent portions.

Particularly preferred processes according to the invention are characterized in that step (i) comprises an injection molding process which is preferably carried out at a pressure between 100 and 5000 bar, preferably between 500 and 2500 bar, particularly preferably between 750 and 1500 bar and in particular between 1000 and 1250 bar preferably at temperatures between 100 and 250 ° C, preferably between 120 and 200 ° C and in particular between 140 and 1δ0 ° C, is carried out.

As was already explained in the description of the detergent, cleaning agent or detergent portions according to the invention, the individual hollow bodies are preferably not completely filled. Also preferred in the method according to the invention are those in which the hollow bodies or compartments in step (ii) contain 20 to 100%, preferably 30 to 95%, particularly preferably 40 to 90% and in particular 50 to δ5% of their volume washing, cleaning or rinsing active preparations are filled.

Foil materials and physical parameters of the foils have already been discussed in detail above. Analogously, those are preferred in the process according to the invention, with 6δ

which the hollow bodies are sealed by sealing with a water-soluble film, the film having a thickness of 1 to 150 μm, preferably 2 to 100 μm, particularly preferably 5 to 75 μm and in particular 10 to 50 μm.

After the production of the filled and with the enclosures (A) or (B) surrounding partial hollow bodies, these are joined together. Processes according to the invention are preferred here in which the connection of the enclosures (A) and (B) and, if appropriate, further enclosures and / or further washing, cleaning or rinsing active preparations in solid, dimensionally stable form for washing, cleaning or rinsing agent portion in step (iv) by cold sealing, gluing with water-soluble hot melt adhesives, gluing with adhesive solutions or mechanical connection.

In the context of the present invention, the partial hollow bodies are adhesively bonded to one another with adhesion promoters. Substances can be used as adhesion promoters which give the surfaces to which they are applied sufficient adhesion ("stickiness") so that the partial hollow bodies adhere to one another permanently. In principle, the relevant adhesive literature and in particular the monographs on this offer Substances mentioned, in the context of the present invention the application of melts, which act as an adhesion promoter at elevated temperature, but are no longer sticky after cooling but are solid, are of particular importance.

Processes according to the invention in which melting of one or more substances with a melting range from 40 ° C. to 75 ° C. are used as adhesion promoters in step iv) are therefore preferred.

Various requirements are placed on the adhesion promoters, which relate on the one hand to the melt or solidification behavior, but on the other hand also to the material properties in the solidified area at ambient temperature. Since the partial hollow bodies which are glued to one another are intended to hold together permanently during transport or storage, the adhesive bond must have a high level of stability with respect to shock loads occurring, for example, during packaging or transport. The adhesion promoters should therefore either have at least partially elastic or at least plastic properties in order to react to an impact load that occurs due to elastic or plastic deformation and not to break. The adhesion promoters should have a melting range (solidification range) in such a temperature range in which the partial hollow bodies or the preparations contained in them are not exposed to excessive thermal stress. On the other hand, however, the melting range must be sufficiently high to still offer effective adhesion at at least a slightly elevated temperature. According to the invention, the coating substances preferably have a melting point above 30 ° C. The The width of the bonding area of the adhesion promoters also has direct effects on the implementation of the process: the partial hollow body provided with the adhesion promoter must be brought into contact with the other partial hollow body (s) in the subsequent process step - in the meantime, the adhesiveness must not be lost. After sticking together, the adhesive strength should be reduced as quickly as possible in order to avoid unnecessary loss of time or to prevent caking and congestion in subsequent process steps or handling and packaging. In the case of the use of melts, the reduction in adhesion can be supported by cooling (for example blowing with cold air).

It has proven to be advantageous if the adhesion promoters do not have a sharply defined melting point, as is usually the case with pure, crystalline substances, but instead have a melting range that may include several degrees Celsius.

The adhesion promoters preferably have a melting range which is between approximately 45 ° C. and approximately 75 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range. The width of the melting range is preferably at least 1 ° C., preferably about 2 to about 3 ° C.

The properties mentioned above are usually fulfilled by so-called waxes. "Waxing" is understood to mean a number of natural or artificially obtained substances which generally melt above 40 ° C. without decomposition and which are relatively low-viscosity and not stringy even a little above the melting point. They have a strongly temperature-dependent consistency and solubility.

The waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes.

Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

The chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes. Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of substance that meet the requirements regarding the softening point can also be used as adhesion promoters. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ^® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ^® ETLP (Condea). Conversely, synthetic or partially synthetic esters from lower alcohols with fatty acids from native sources can also be used. Tegin ^® 90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances. Shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used as an adhesion promoter according to the invention.

The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. In step iv) an adhesion promoter can optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understand, for example, under the trade designation Argowax ^® (Pamentier & Co). In the context of the present invention, fatty acid glycerol esters or fatty acid alkanolamides can also be used, at least in part, as a constituent of the adhesion promoter, but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.

If a temperature-controlled release of the partial hollow bodies adhered to one another is desired, the adhesion promoters should have as little water solubility as possible, even in water at an elevated temperature, in order to largely avoid temperature-independent release of the coated active substances.

The adhesion promoters to be applied in process step iv) can be pure substances or substance mixtures. In the latter case, the melt can contain varying amounts of adhesion promoter and auxiliary substances.

The principle described above serves to delay the detachment of the partial hollow bodies which are glued to one another in step iv) at a specific point in time, for example in the cleaning cycle of a dishwasher, and can be used particularly advantageously. if the main wash cycle is carried out at a lower temperature (for example 55 ° C.), so that the active substance is only released from the adhesive layer in the final rinse cycle at higher temperatures (approx. 70 ° C.).

However, the principle mentioned can also be reversed to the effect that the partial hollow bodies are not released from one another in a delayed manner, but accelerated. This can be achieved in a simple manner in the process according to the invention by using release accelerators instead of release retarders as the adhesion promoter in step iv), so that the partial hollow bodies do not separate more slowly, but faster. In contrast to the poorly water-soluble adhesion promoters described above, preferred adhesion promoters are readily water-soluble for rapid detachment. The water solubility of the adhesion promoters can be increased significantly by certain additives, for example by incorporating easily soluble salts or shower systems. Solvent-accelerated adhesion promoters (with or without the addition of other solubility improvers) lead to rapid detachment and thus, depending on the type and thickness of the film, to release the washing-, rinsing- or cleaning-active preparations at the beginning of the washing, rinsing or cleaning cycle.

The release acceleration can also be achieved or supported by certain geometric factors. Detailed explanations can be found below.

The above-mentioned synthetic waxes from the group of polyethylene glycols and polypropylene glycols are particularly suitable as adhesion promoters for the accelerated release. In addition to the PEG and PPG, which can preferably be used as adhesion promoters, other substances can of course also be used, provided they have a sufficiently high water solubility and a melting point above 30 ° C.

In addition to melting, other substances can also be applied as adhesion promoters in step iv) of the process according to the invention. For this purpose, concentrated salt solutions are suitable, for example, which after application of the active substances are converted into an adhesion-promoting salt crust by crystallization or evaporation / evaporation. It is of course also possible to use supersaturated solutions or solutions of salts in solvent mixtures.

Solutions or suspensions of water-soluble or water-dispersible polymers, preferably polycarboxylates, can also be used as adhesion promoters in step iv). The substances mentioned have already been described due to their cobuilder properties. Other particularly suitable adhesion promoters are solutions of water-soluble substances from the group (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, gelatin and mixtures thereof. These substances have already been described above as film materials.

Adhesion promoter can preferably be applied to the edge region of the closed partial hollow body in different ways. For example, it is possible to wet the closed partial hollow body with adhesive on one side and then to place it in the cavity. This technology is technologically simple to implement, but it harbors the risk that the adhesive wets the entire film and thus complicates any controlled release controlled by the film. In this variant, the amount of adhesive can be controlled by varying the rheological properties of the adhesion promoters.

A further possibility, which is preferred in the context of the present invention, of applying adhesion promoters is to move the surfaces to be wetted (as a rule the edges of the partial hollow bodies) past adhesive metering systems. This is achieved by means of nozzles that meter the adhesion promoter, brushes or fleeces impregnated with adhesion promoters, or by rollers. The latter process design is particularly easy to implement.

The abovementioned possibilities of joining partial hollow bodies to one another can also be used to make the entire portion according to the invention or parts thereof more quickly soluble. If, for example, two partial hollow bodies are glued to one another on their flat surfaces (usually the opening of the “shell” which is closed with a film), under conditions of use, water access to the adhesive is only possible at the edges if the portion according to the invention has not yet been dissolved Using highly water-soluble adhesion promoters, the connection can practically only be released when part of the total portion has dissolved.

The disadvantages mentioned can be overcome by targeted application of the adhesion promoter. For example, it is possible and preferred not to apply the adhesion promoter with its flat surfaces when connecting two partial hollow bodies, but rather only to apply "adhesion promoter points" at the contact edge or at the corners. These are immediately exposed to the water in use, If two partial hollow bodies with a square contact surface are connected to one another in this way, the adhesion promoter does not have to be applied to all four edges, but can help to separate the connection even faster, only to the four corners to apply adhesion promoter points individual adhesive agent points are dispensed with, so that, for example, only two diagonally opposite corners of contact are provided with adhesive agent.

In summary, if a faster dissolution of the entire portion or individual parts is desired, a quick increase in surface area by separating the adhesive bond is optimal. This can be achieved or supported by choosing an inexpensive form of adhesive bond. In such cases, line bonding is preferable to surface bonding, with point bonding being particularly preferred.

The process for producing the detergent, cleaning agent or detergent portion according to the invention contained in one or more dimensionally stable hollow body (s) with at least one compartment is carried out in a manner known per se in that in a first step one or more dimensionally stable hollow body (s) manufactures. This can be done, for example, by deep drawing, casting (for example by methods known or modified from the confectionery industry), injection molding, sintering or casting (for example) inorganic mixtures. In the manufacture of the dimensionally stable hollow bodies according to the invention, processes for producing the hollow body (s) which are carried out under compression are excluded.

Methods for thermoforming polymers by deep drawing are known as such from the prior art. A plate or film of a polymer is formed into a desired blank from a dimensionally stable polymer by means of a deep-drawing press consisting of a stamp and die. The disadvantage of this procedure for the present case of the production of a hollow body is the fact that when the blank is removed from the mold, a vacuum is created inside the hollow body, which must be released by blowing in a gas. This makes the otherwise technically simple deep-drawing press complex. Furthermore, with the deep-drawing procedure, only very irregular wall thicknesses s of the dimensionally stable hollow body can be realized. In addition, with the deep-drawing procedure, dimensionally stable hollow bodies with compartmentalization devices cannot be produced in one step.

According to a further procedure, blanks for dimensionally stable hollow bodies can also be produced by pouring the polymer into appropriately prepared molds. The process variant of the casting not only allows the use of meltable polymers as wall materials, but also other meltable substances.

The production of the outer hollow molds can be carried out economically using so-called casting techniques, this technology in particular allowing the greatest possible flexibility with regard to processing into the hollow mold and with regard to the material systems used. all Pouring techniques in common is the forming of a flowable mixture that is solidified under suitable conditions.

Another object of the invention is a method for producing portioned detergents or cleaning agents, comprising the steps:

i) producing an open hollow mold by solidification; ii) filling the hollow mold with detergent or cleaning agent; iii) optionally closing the mold.

The production of the open hollow mold comprises the formation of a deformable, preferably flowable mixture or such a substance and the solidification into a dimensionally stable hollow mold. In the context of the present invention, "solidification" denotes any hardening mechanism which, from a deformable, preferably flowable mixture or such a substance or mass, provides a body which is solid at room temperature without the need for compressive or compacting forces The purpose of the present invention is therefore, for example, the curing of melts of substances which are solid at room temperature by cooling. "Solidification processes" in the sense of the present application are also the hardening of deformable masses through time-delayed water binding, through evaporation of solvents, through chemical reaction, crystallization etc. as well as the reactive hardening of flowable powder mixtures to form stable hollow bodies. As already stated above, tabletting belongs -, pelleting, briquetting processes etc., i.e. pressing processes, not in this category.

In summary, methods according to the invention are preferred in which the open hollow form is caused by time-delayed water binding, by cooling below the melting point, by evaporation of solvents, by crystallization, by chemical reaction (s), in particular polymerization, by changing the rheological properties, e.g. is produced by changing shear, by sintering or by means of radiation curing, in particular by UV, alpha-beta or gamma rays.

The solidification mechanisms mentioned are described in detail below.

It is not necessary for the implementation of the method according to the invention that the open hollow mold is produced and, for example, stored temporarily until it is filled. Rather, steps i) and ii) of the method according to the invention can also be carried out simultaneously by filling a hollow mold “in situ”, ie directly during its production. This is particularly the case when hollow molds are produced from self-solidifying materials (for example by cooling) under the Schjηelzpunkt or by time-delayed water binding) easily realized by, the inside and outside are metered filling the material for the mold in a form by a two-fluid nozzle which, like a Daniell ^'shear valve is constructed. This "one-shot" process, which is described in detail below, enables the economical production of large quantities of moldings.

Accordingly, methods according to the invention are preferred in which steps i) and ii) are carried out simultaneously.

Of course, however, it is also possible to carry out the method according to the invention “step by step” so that, for example, hollow bodies are produced and subsequently filled. This technology includes the possibility of changing the formulation of the detergent or cleaning agent filled in step ii) without the method This procedure is recommended especially for detergents or cleaning agents which cannot be metered or cannot be metered well via two-component nozzles, and methods in which steps i) and ii) are carried out in succession are accordingly preferred embodiments of the present invention.

Regardless of whether the "shell" (the open hollow mold) is produced before filling or simultaneously with it, the shell production comprises informing a deformable mixture which solidifies ("solidifies") during or after the informing the hollow mold. The formable mixture, which can also consist of a single substance, can be in the form of a powder, a liquid, a gel, a melt, etc., one or more of the solidification mechanisms mentioned above being used, depending on the composition.

From the point of view of process economy, melts are particularly preferred because they simply solidify below the melting point and are generally easy to process. Processes according to the invention are therefore particularly preferred in which the open hollow mold is produced in step i) by solidification of a melt, the melt consisting of a material whose melting point is in the range from 40 to 1000 ° C., preferably from 42.5 to 500 ° C, particularly preferably from 45 to 200 ° C and in particular from 50 to 160 ° C.

Substances that are particularly suitable for carrying out this variant of the method according to the invention are, for example, polyethylene glycols

H- (0-CH ₂ -CH ₂ ) _n -OH in which the degree of polymerization n can assume values between approximately 30 and several thousand. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number that corresponds to the number n in the above-mentioned formula. Commercially available polyethylene glycols are, for example, under the trade name Carbowax ^® PEG (Union Carbide), Emkapol ^® (ICI Americas), Lipoxol ^® (Huls America), polyglycol col ^® E (Dow Chemical), Alkapol ^® PEG (Rhone-Poulenc), Lutrol ^® E (BASF). The molar masses of preferred polyethylene glycols are in the range between 1500 and 35000 Daltons, preferably between 2000 and 30,000 Da, particularly preferably between 3000 and 25000 Da and in particular between 4000 and 20,000 Da.

Polypropylene glycols (abbreviation PPG) can also be used

H- (0-CH-CH ₂ ) _n -OH

I

CH ₃ _ι

in which the degree of polymerization n can also assume values between approximately 30 and several thousand. With regard to the molecular weights of PPG to be used with preference, what has been said for PEG applies analogously.

The polyethylene or polypropylene glycols can be used in a mixture with other substances as a shell material with particular advantage. Particularly suitable additives to the polyalkylene glycols are polymers or polymer mixtures, the polymer or at least 50% by weight of the polymer mixture being selected from graft copolymers which can be obtained by grafting (a) polyalkylene oxides with (b) vinyl acetate. These polymers are described in more detail below.

The graft copolymers suitable as an additive to polyalkylene glycols in the context of the present invention can be obtained by grafting a polyalkylene oxide with vinyl acetate, it being possible for the acetate groups of the vinyl acetate to be partially saponified. Particularly suitable polyalkylene oxides are polymers with ethylene oxide, propylene oxide and butylene oxide units, polyethylene oxide being preferred. The graft copolymers can be prepared, for example, by dissolving the polyalkylene oxides in vinyl acetate and continuously. or batch polymerization after addition of a polymerization initiator, or by semi-batch polymerization in which part of the polymerization mixture of polyalkylene oxide, vinyl acetate and polymerization initiator is heated to polymerization temperature, after which the rest of the mixture to be polymerized is added. The graft copolymers can also be obtained by introducing polyalkylene oxide, heating to the polymerization temperature and adding vinyl acetate and polymerization initiator either all at once, batchwise or, preferably, continuously.

Processes preferred within the scope of the present invention use in step i) melts from polyalkylene glycols which contain at least one polymer which can be obtained by grafting (a) polyalkylene oxides having a molecular weight of 1500 to 70,000 gmol ^"1 with (b) vinyl acetate in a weight ratio of (a) :( b) from 100: 1 to 1: 5, the acetate groups optionally being saponified up to 15%. In preferred embodiments of the present invention, the molecular weight of the polyalkylene oxides contained in the graft copolymers is from 2000 to 50,000 gmol ^"1 , preferably 2500 to 40,000 gmol ^"1 , particularly preferably 3000 to 20,000 gmol ^{" 1} and in particular 4000 to 10,000 gmol ^"1 .

Depending on the desired properties of the open hollow form, the proportion of the individual monomers of the graft copolymers added to the melt can vary. Polymers are preferred in which the vinyl acetate content is 1 to 60% by weight, preferably 2 to 50% by weight, particularly preferably 3 to 40% by weight and in particular 5 to 25% by weight, based in each case on the graft copolymer , is.

A graft copolymer which is particularly preferred in the context of the present invention is based on a polyethylene oxide with an average molecular weight of 6000 gmol ^"1 (corresponding to 136 ethylene oxide units), which contains about 3 parts by weight of vinyl acetate per part by weight of polyethylene oxide. This polymer, which has an average molecular weight of about 24000 gmol ^"1 is sold commercially by BASF under the name Sokalan ^® HP22.

Another class of substances which is outstandingly suitable as a material for the open hollow form are aliphatic and aromatic dicarboxylic acids which can be melted individually, in a mixture with one another or in a mixture with other substances and processed according to the invention. Particularly preferred dicarboxylic acids are summarized in the table below: 7δ

Instead of the dicarboxylic acids mentioned or in a mixture with them, the corresponding anhydrides can also be used, which is particularly advantageous in the case of glutaric acid, maleic acid and phthalic acid.

In addition to the dicarboxylic acids, carboxylic acids and their salts are also suitable as materials for the production of the open hollow form. From this class of substances, citric acid and trisodium citrate as well as salicylic acid and glycoic acid have proven to be particularly suitable. It is also particularly advantageous to use fatty acids, preferably those with more than 10 carbon atoms, and their salts as the material for the open hollow form. Carboxylic acids which can be used in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (oenanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid etc. The use of Fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), triacotonic acid (melotonic acid), cerotonic acid (melotonic acid) as well as the unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-linadol acid) , 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatreic acid (linolenic acid) For reasons of cost, it is preferred not to use the pure species, but rather technical mixtures of the individual acids, such as those from the Fat cleavage are accessible. Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C _10, 4δ wt .-% C _12: 1 wt .- δ% C ₁₄ 10 wt .-% C _16, 2 % By weight C ₈ , 8% by weight> C ₁₈ -, 1% by weight C ₁₈ -), palm kernel oil fatty acid (approx. 4% by weight C ₈ , 5% by weight C ₁₀ , 50% by weight) -% C ₁₂ , 15% by weight C ₁₄ , 7% by weight C ₁₆ , 2% by weight C ₁₈ , 15% by weight C ₁₈ -, 1% by weight C ₁₈ -), tallow fatty acid ( approx. 3 wt% C ₁ , 26 wt% C ₁₆ , 2 wt% C ₁₆ -, 2 wt% C ₁₇ , 17 wt% C ₁₈ , 44 wt% C ₁₈ -, 3% by weight C ₁₈ -, 1% by weight C ₁₈ -), hardened tallow fatty acid (approx. 2% by weight C ₁₄ , 28% by weight C ₁₆ , 2% by weight C ₁₇ , 63 wt .-% C, _8, 1 wt .-% C _18), technical grade oleic acid (about 1 wt .-% C _12, 3 wt .-% C _14, 5 wt .-% C _16, 6 wt .-% C ₁₆ -, 1 wt .-% C ₁₇ , 2 wt .-% C ₁₈ , 70 wt .-% Cι ₈ -, 10 wt .-% C ₁₈ -, 0.5 wt .-% C ₁₈ -), technical palmitin / stearic acid (approx. 1% by weight C ₂ , 2% by weight C ₁₄ , 45% by weight C ₁₆ , 2% by weight C ₁₇ , 47% by weight C ₁₈ , 1 wt% C ₁₈ -) and soybean oil fatty acid (approx. 2 wt% C _14l 15 wt .-% C _16, 5 wt .-% C ₁₈₎ 25 wt .-% C ₁₈ - 45 wt .-%

The above-mentioned carboxylic acids are largely obtained industrially from native fats and oils by hydrolysis. While the alkaline saponification which was carried out in the past century led directly to the alkali salts (soaps), only water is used on an industrial scale to split the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage. The alkali metal salts of the abovementioned carboxylic acids or carboxylic acid mixtures can also be used for the preparation of the open hollow mold, if appropriate in a mixture with other materials.

Other suitable materials that can be processed into open hollow molds via the state of the melt are hydrogen carbonates, in particular the alkali metal hydrogen carbonates, especially sodium and potassium hydrogen carbonate, and the hydrogen sulfates, in particular alkali metal hydrogen sulfates, especially potassium hydrogen sulfate and / or sodium hydrogen sulfate. The eutectic mixture of potassium hydrogen sulfate and sodium hydrogen sulfate has also proven to be particularly suitable, which consists of 60% by weight of NaHS0 ₄ and 40% by weight of KHS0 ₄ .

Other suitable materials for the open hollow mold, which can be processed in step i) of the process according to the invention via the state of the melt, are sugar. In the context of the present invention, the term “sugar” denotes single and multiple sugars, that is to say monosaccharides and oligosaccharides in which 2 to 6 monosaccharides are linked to one another in an acetal-like manner. In the context of the present invention, “sugars” are therefore monosaccharides, disaccharides, trisaccharides, tetrahydrosaccharides. , Penta and hexasaccharides. 30

Monosaccharides are linear polyhydroxy aldehydes (aldoses) or polyhydroxy ketones (ketoses). They usually have a chain length of five (pentoses) or six (hexoses) carbon atoms. Monosaccharides with more (heptoses, octoses, etc.) or fewer (tetroses) carbon atoms are relatively rare. Monosaccharides sometimes have a large number of asymmetric carbon atoms. For a hexose with four asymmetric carbon atoms, this results in a number of 24 stereoisomers. The orientation of the OH group at the highest numbered asymmetric C atom in the Fischer projection divides the monosaccharides into D- and L- configured rows. In the naturally occurring monosaccharides, the D configuration is much more common. If possible, monosaccharides form intramolecular hemiacetals, so that ring-like structures of the pyran (pyranoses) and furan type (furans) result. Smaller rings are unstable, larger rings are only stable in aqueous solutions. The cyclization creates another asymmetric carbon atom (the so-called anomeric carbon atom), which doubles the number of possible stereoisomers. This is indicated by the prefixes α- u. ß- expressed. The formation of the hemiacetals is a dynamic process that depends on various factors such as temperature, solvent, pH, etc. Mixtures of both anomeric forms are usually present, sometimes also as mixtures of the furanose and pyranose forms.

Monosaccharides which can be used as sugar in the context of the present invention are, for example, the tetroses D (-) - erythrose and D (-) - threose and D (-) - erythrulose, the pentoses D (-) - ribose, D (-) - ribulose, D (-) - arabinose, D (+) - xylose, D (-) - xylulose as well as D (-) - lyxose and the hexoses D (+) - allose, D (+) - old rose, D (+) - glucose , D (+) - Mannose, D (-) - Gulose, D (-) - ldose, D (+) - Galactose, D (+) - Talose, D (+) - Psicose, D (-) - Fructose, D (+) - sorbose and D (-) - tagatose. The most important and most widespread monosaccharides are: D-glucose, D-galactose, D-mannose, D-fructose, L-arabinose, D-xylose, D-ribose and the like. 2-deoxy-D-ribose.

Disaccharides are made up of two simple monosaccharide molecules linked by glycosidic bonds (D-glucose, D-fructose, etc.). If the glycosidic bond lies between the acetal carbon atoms (1 for aldoses and 2 for ketoses) of both monosaccharides, the ring shape is fixed in both; the sugars show no mutarotation, do not react with ketone reagents and no longer have a reducing effect (Fehling negative: trehalose or sucrose type). If, on the other hand, the glycosidic bond connects the acetal carbon atom of one monosaccharide with any of the second, this can still assume the open-chain form, and the sugar has a reducing effect (Fehling positive: maltose type). The main disaccharides are sucrose (cane sugar, sucrose), trehalose, lactose (milk sugar), lactulose, maltose (malt sugar), cellobiose (cellulose breakdown product), gentobiose, melibiose, turanose and others.

Trisaccharides are carbohydrates that are made up of 3 glycosidically linked monosaccharides and for which the incorrect name triosen is sometimes encountered. Trisaccharides occur relatively rarely in nature, examples are gentianose, kestose, maltotriose, melecitose, raffinose, as well as streptomycin and validamycin as examples of trisaccharides containing amino sugar.

Tetrasaccharides are oligosaccharides with 4 monosaccharide units. Examples of this class of compounds are stachyose, lychnose (galactose-glucose-fructose-galactose) and secalose (from 4-fructose units).

In the context of the present invention, saccharides from the group consisting of glucose, fructose, sucrose, cellubiosis, maltose, lactose, lactulose, ribose and mixtures thereof are preferably used as sugars.

Another particularly preferred material for the open hollow form is urea, the diamide of carbonic acid, which is sometimes also referred to as carbamide and can be described by the formula H ₂ N-CO-NH ₂ . Urea forms colorless, odorless crystals of density 1, 335, which melt at 133 ° C. Urea is soluble in water, methanol, ethanol and glycerin with a neutral reaction. Especially when mixed with other substances, urea is an excellent material for the hollow mold. For example, polyethylene and propylene glycols, fragrances, dyes, etc. can be melted together with the urea in large quantities and processed into the open hollow form without impairing the mechanical and haptic properties of the hollow form.

Other suitable materials which can be added to the above-mentioned meltable substances in large quantities are silicates, phosphates and / or starches.

When processing the melts into an open hollow form, it can be advantageous to add additives to the melts. In addition to the dyes and fragrances used for aesthetic reasons, disintegration aids, reinforcing fibers or liquid binders have proven to be particularly suitable. Disintegration aids are described in detail above; natural or synthetic polymer fibers can be considered as reinforcing fibers. Microcrystalline cellulose is also suitable as an additive. In summary, processes according to the invention are preferred in which the melt in step i) contains one or more substances from the groups of carboxylic acids, carboxylic acid anhydrides, dicarboxylic acids, dicarboxylic acid anhydrides, hydrogen carbonates, hydrogen sulfates, polyethylene glycols, polypropylene glycols, sodium acetate trihydrate and / or urea in amounts of contains at least 40% by weight, preferably at least 60% by weight and in particular at least 80% by weight, in each case based on the melt.

The formable mixtures can solidify by various mechanisms, the time-delayed water binding, the evaporation of solvents, the crystallization, the chemical reaction (s), in particular polymerization, the change in the rheological properties e.g. by changing the shear of the mass (s) and the radiation hardening by UV, alpha beta or gamma rays as the most important hardening mechanisms in addition to the already mentioned cooling below the melting point.

In processes which are likewise preferred in the context of the present invention, the solidification takes place by means of time-delayed water binding.

The time-delayed water binding can be implemented in different ways. There are, for example, raw materials or raw material mixtures that contain hydratable, water-free raw materials or raw materials in low hydration levels that can change into stable, higher hydrates, as well as water. The formation of the hydrates, which does not occur spontaneously, then leads to the binding of free water, which in turn leads to a hardening of the mixtures with formation of the hollow form. Shaping processing with low pressures is then no longer possible, and there are hollow bodies that are stable in handling. '

The time-delayed water binding can also take place, for example, by incorporating hydrate-containing salts, which dissolve in their own crystal water when the temperature rises, into the masses. If the temperature drops later, the water of crystallization is bound again, which leads to a loss of formability with simple means and to a solidification of the masses.

The swelling of natural or synthetic polymers as a time-delayed water binding mechanism can also be used in the process according to the invention. Mixtures of unswollen polymer and suitable swelling agent, for example water, diols, glycerol, etc., can be incorporated into the compositions here, with swelling and curing taking place after shaping. δ3

The most important mechanism of hardening through time-delayed water binding is the use of a combination of water and water-free or low-water raw materials that slowly hydrate. For this purpose, there are in particular substances which contribute to the cleaning performance in the washing or cleaning process. In the process according to the invention, preferred ingredients of the hollow molds are, for example, phosphates, carbonates, silicates and zeolites.

It is particularly preferred if the hydrate forms formed have low melting points, since in this way a combination of the curing mechanisms is achieved by internal drying and cooling. Preferred processes are characterized in that the starting materials for the hollow mold contain 10 to 95% by weight, preferably 15 to 90% by weight, particularly preferably 20 to δ5% by weight and in particular 25 to δO% by weight of anhydrous substances which, by hydration, change into a hydrate form with a melting point below 120 ° C., preferably below 100 ° C. and in particular below δ0 ° C.

The deformable properties can be influenced by adding plasticizing aids such as polyethylene glycols, polypropylene glycols, waxes, paraffins, nonionic surfactants etc. Further information on the substance classes mentioned can be found above.

Raw materials to be preferably used in the production of the open hollow molds come from the group of the phosphates, alkali metal phosphates being particularly preferred. These substances are used in the production in anhydrous or low-water form and the desired plastic or deformable properties of the masses are set with water and optional plasticizing aids. After the shaping processing, the shaped hollow molds are then cured by hydration of the phosphates.

In preferred processes, the mixtures used to produce the hollow molds contain phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 20 to δO% by weight, preferably of 25 to 75 wt .-% and in particular from 30 to 70 wt .-%, each based on their weight.

If phosphates are used as the only hydratable substances, the amount of water added should not exceed their water binding capacity in order to keep the content of free water in the hollow bodies low. In total, methods have been found to be preferred for complying with the aforementioned limit values in which the weight ratio 64

nis of phosphate at (en) to water in the mixtures for producing the hollow molds is less than 1: 0.3, preferably less than 1: 0.25 and in particular less than 1: 0.2.

Other ingredients that can be contained in place of or in addition to phosphates are carbonates and / or hydrogen carbonates, the alkali metal salts and, in particular, the potassium and / or sodium salts being preferred. The statements made above also apply here with regard to the water content. In particular, processes have been found to be preferred in which the weight ratio of carbonate (s) and / or hydrogen carbonate (s) to water in the mixtures for producing the hollow molds is less than 1: 0.2, preferably less than 1: 0, 15 and in particular less than 1: 0.1.

Further ingredients which may be present instead of or in addition to the phosphates and / or carbonates / bicarbonates mentioned are silicates, the alkali metal silicates and, in particular, the amorphous and / or crystalline potassium and / or sodium disilicates being preferred. The statements made above also apply here with regard to the water content of the masses. i

The weight ratio of water to certain ingredients in mixtures to be processed according to the invention preferably into hollow bodies was specified above. After processing, this water is preferably bound in the form of water of hydration, so that the hollow molds produced in step i) preferably have a significantly lower free water content. Preferred cavity molds are essentially water-free, i.e. in a state in which the content of liquid, i.e. water not present in the form of water of hydration and / or constitutional water is less than 2% by weight, preferably less than 1% by weight and in particular even less than 0.5% by weight, based in each case on the moldings. Accordingly, water can essentially only be present in chemically and / or physically bound form or as a constituent of the raw materials or compounds present as a solid, but not as a liquid, solution or dispersion in the end products of step i). At the end of the manufacturing process, the hollow bodies advantageously have a water content of not more than 15% by weight, this water therefore not being in liquid free form, but being chemically and / or physically bound, and it is particularly preferred that the content of water not bound to zeolite and / or silicates in the solid premix is not more than 10% by weight and in particular not more than 7% by weight.

Hollow molds which are particularly preferred in the context of the present invention not only have an extremely low proportion of free water, but are preferably still themselves in the 65

Able to bind more free water. In preferred processes, the water content of the hollow molds is 50 to 100% of the calculated water binding capacity.

The water binding capacity is the ability of a substance (here: the hollow form) to absorb water in a chemically stable form and ultimately indicates how much water can be bound by a substance or a shaped body in the form of stable hydrates. The dimensionless value of the water binding capacity (WBV) is calculated from:

«• 18th

WBV = -

M

where n is the number of water molecules in the corresponding hydrate of the substance and M is the molar mass of the non-hydrated substance. This results, for example, in the water-binding capacity of anhydrous sodium carbonate (formation of sodium carbonate monohydrate)

WBV = - = 0.17,

2 - 23 + 12 + 3 - 16

The value WBV can be calculated for all hydrate-forming substances which are used in the mixtures to be processed into hollow molds according to the invention. The total water-binding capacity of the formulation then results from the percentage of these substances. In preferred hollow forms, the water content is then between 50 and 100% of this calculated value.

In addition to the water content of the hollow molds and the ratio of water to certain raw materials, information can also be given about the absolute water content of the mixtures to be processed according to the invention. In particularly preferred processes, the mixtures used to produce the hollow molds have / have a water content of 2.5 to 30% by weight, preferably 5 to 25% by weight and in particular 7.5 to 20% by weight during processing. %, in each case based on the mass.

In summary, preferred process variants according to the invention are those in which the production of the open hollow mold in step i) takes place by means of time-delayed water binding, the solidifying mass, based on its weight, being particularly preferably 10 to 95% by weight, preferably 15 to 90% by weight Contains 20 to 85 wt .-% and in particular 25 to 80 wt .-% of anhydrous substances that harden through hydration. Another mechanism by which the solidification to the hollow form can take place in step i) of the method according to the invention is the evaporation of solvents. For this purpose, solutions or dispersions of the desired ingredients can be prepared in one or more suitable, volatile solvent (s) which release these solvents after the shaping processing step and thereby harden. Examples of suitable solvents are lower alkanols, aldehydes, ethers, esters, etc., the selection of which is made depending on the further composition of the mixtures to be processed. Particularly suitable solvents for such processes are ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2 , 2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol and the acetic acid esters of the abovementioned alcohols, in particular ethyl acetate.

The evaporation of the solvents mentioned can be accelerated by heating following the shaping or by air movement. Combinations of the measures mentioned are also suitable for this, for example blowing on the hollow body with warm or hot air.

Processes according to the invention are preferred here in which the open hollow mold is produced in step i) by evaporation of solvents, the solidifying mass based on its weight being 1 to 50% by weight, preferably 2 to 40% by weight and in particular 5 contains up to 30 wt .-% evaporable solvent.

Another mechanism which can be the basis for solidification to the hollow form in step i) of the process according to the invention is crystallization.

Crystallization as the mechanism underlying the solidification can be used, for example, by melting crystalline substances as the basis for one or more formable mixtures. After processing, such systems go into a higher order state, which in turn leads to hardening of the entire hollow body formed. However, crystallization can also be carried out by crystallization from supersaturated solution. In the context of the present invention, supersaturation is the term for a metastable state in which more of a substance is present in a closed system than is required for saturation. A supersaturated solution obtained, for example, by hypothermia therefore contains more solute than it should contain in thermal equilibrium. The excess of dissolved substance can be caused by seeding with germs or dust particles or by shaking the system for crystallization. In the context of the present invention, the term “oversaturated” always refers to a temperature of 20 ° C.

The term "solubility" in the present invention means the maximum amount of a substance that the solvent can absorb at a certain temperature, i.e. the proportion of the solute in a solution saturated at the temperature in question. If a solution contains more solute than it should contain in the thermodynamic equilibrium at a given temperature (e.g. in the case of solvent evaporation), it is called supersaturated. Vaccinating with germs can cause the excess to precipitate out as the bottom of the now only saturated solution. However, a solution saturated with one substance can also dissolve other substances (e.g. you can still dissolve sugar in a saturated saline solution).

As described above, the state of supersaturation can be achieved by cooling a solution as long as the solute is more soluble in the solvent at higher temperatures. Other ways of achieving supersaturated solutions are, for example, combining two solutions, the ingredients of which react to form another substance that does not immediately fail (prevented or delayed precipitation reactions). The latter mechanism is particularly suitable as the basis for the formation of mixtures to be processed according to the invention.

In principle, the state of supersaturation can be achieved with any type of solution, although, as already mentioned, the principle described in the present application is used in the production of detergents and cleaning agents. Accordingly, some systems that tend to form supersaturated solutions in principle are less suitable according to the invention, since the underlying substance systems cannot be used ecologically, toxicologically or for economic reasons. In addition to nonionic surfactants or common non-aqueous solvents, methods according to the invention with the last-mentioned curing mechanism are therefore particularly preferred, in which an over-saturated aqueous solution is used as the basis for at least one mixture to be processed.

As already mentioned above, the state of supersaturation in the context of the present invention relates to the saturated solution at 20 ° C. By using solutions with a temperature above 20 ° C, the state of supersaturation can easily be reached. Processes according to the invention in which the mixture solidifying by crystallization has a temperature between 35 and 120 ° C., preferably between 40 and 110 ° C., particularly preferably between 45 and 90 ° C. and in particular between 50 and 80 ° C. during processing preferred in the context of the present invention. 8δ

Since the hollow bodies produced are generally neither stored at elevated temperatures nor used later at these elevated temperatures, the cooling of the mixture leads to the precipitation of the proportion of solute from the supersaturated solution that exceeds the saturation limit at 20 ° C. in the solution was included. The supersaturated solution can thus be divided into a saturated solution and a soil body when it cools down. However, it is also possible that recrystallization and hydration phenomena cause the supersaturated solution to solidify upon cooling to a solid. This is the case, for example, when certain hydrated salts dissolve in their crystal water when heated. When cooling, oversaturated solutions are often formed here, which solidify through mechanical action or the addition of germs to a solid - the salt containing water of crystallization as the state that is thermodynamically stable at room temperature. This phenomenon is known, for example, from sodium thiosulfate pentahydrate and sodium acetate trihydrate, the latter salt in the form of the supersaturated solution, in particular, which can be used advantageously in the process according to the invention. Special detergent and cleaning agent ingredients, such as phosphonates, also show this phenomenon and are ideally suited as granulation aids in the form of solutions. For this purpose, the corresponding phosphonic acids (see below) are neutralized with concentrated alkali water, whereby the solution heats up due to the heat of neutralization. On cooling, solids of the corresponding alkali metal phosphonates are formed from these solutions. By incorporating further detergent and cleaning agent ingredients into the still warm solutions, masses of different composition that can be processed according to the invention can be produced. Particularly preferred processes according to the invention are characterized in that the supersaturated solution serving as the basis for the solidifying mixture solidifies to a solid at room temperature. It is preferred here that the previously supersaturated solution, after solidification to a solid by heating to the temperature at which the supersaturated solution was formed, cannot be converted back into a supersaturated solution. This is for example the case with the mentioned. Phos- phonates the case.

The supersaturated solution serving as the basis for the solidifying mixture can - as mentioned above - be obtained in several ways and then processed according to the invention after optional addition of further ingredients. A simple way is, for example, that the supersaturated solution serving as the basis of the solidifying mixture is prepared by dissolving the solute in heated solvent. If in this way higher amounts of the solute are dissolved in the heated solvent than would dissolve at 20 ° C, then there is a supersaturated solution within the meaning of the present invention, which is either hot (see above) or cooled and in the metastable state in the form can be brought. δ9

It is also possible to dehydrate salts containing hydrate water by "dry" heating and to dissolve them in your own water of crystallization (see above). This is also a method of producing supersaturated solutions that can be used in the context of the present invention.

Another way is to add a gas or another liquid or solution to a non-supersaturated solution so that the solute reacts in the solution to a poorly soluble substance or dissolves poorly in the mixture of solvents. Combining two solutions, each containing two substances that react with each other to form a poorly soluble substance, is also a method for producing supersaturated solutions, as long as the poorly soluble substance does not immediately fail. Processes which are likewise preferred in the context of the present invention are characterized in that the supersaturated solution which serves as the basis for the solidifying mixture is prepared by combining two or more solutions. Examples of such ways to make supersaturated solutions are discussed below.

Preferred methods according to the invention are characterized in that the supersaturated aqueous solution by combining an aqueous solution of one or more acidic ingredients of detergents and cleaning agents, preferably from the group of surfactant acids, builder acids and complexing agents, and an aqueous alkali solution, preferably an aqueous alkali hydroxide solution , in particular an aqueous sodium hydroxide solution.

Among the representatives of the compound classes mentioned above, the phosphonates in particular have an outstanding position in the context of the present invention. In preferred processes according to the invention, therefore, the supersaturated aqueous solution is combined by combining an aqueous phosphonic acid solution with concentrations above 45% by weight, preferably above 50% by weight and in particular above 55% by weight, based in each case on the phosphonic acid solution and an aqueous sodium hydroxide solution Concentrations above 35 wt .-%, preferably above 40 wt .-% and in particular above 45 wt .-%, each based on the sodium hydroxide solution.

According to the invention, the solidifying mixture (s) can also be cured by chemical reaction (s), in particular polymerization. In principle, all chemical reactions are suitable which, starting from one or more liquid to pasty substances, lead to solids by reaction with (another) substance (s). Chemical recations that do not suddenly lead to the state change mentioned are particularly suitable. From the variety of chemical reactions that lead to the solidification phenomenon, reactions are particularly suitable in which the structure of larger molecules from smaller molecules he follows. This in turn preferably includes reactions in which many small molecules react to (one) larger molecule (s). These are so-called polyreactions (polymerization, polyaddition, polycondensation) and polymer-analogous reactions. The corresponding polymers, polyadducts (polyaddition products) or polycondensates (polycondensation products) then give the finished hollow body its strength.

With regard to the intended use of the products produced according to the invention, it is preferred to use the formation of such solid substances from liquid or pasty starting materials as the curing mechanism, which in the washing and cleaning agent are anyway present as ingredients, for example cobuilders, soil repellents or soil release Polymers are to be used. Such cobuilders can originate, for example, from the groups of polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, etc. These classes of substances have been described above.

Another mechanism by which the hardening of the solidifying mixture (s) can take place in the process according to the invention is the hardening which takes place by changing the rheological properties.

This takes advantage of the property that certain substances, under the influence of shear forces, sometimes change their rheological properties drastically. Examples of such systems which are known to the person skilled in the art are, for example, layered silicates which. have a strong thickening effect under shear in suitable matrices and can lead to cut-resistant masses.

Of course, two or more curing mechanisms can also be combined or used simultaneously in a solidifying mixture. Here, for example, crystallization with simultaneous solvent evaporation, cooling with simultaneous crystallization, water binding ("internal drying") with simultaneous external drying etc. are appropriate.

Another preferred mechanism by which deformable, preferably flowable, mixture can solidify is sintering. The sintering represents the provision of a particle heap preformed in the shape of the later hollow body, which is converted into a compact hollow body part under the influence of external conditions (temperature, radiation, reactive gases, liquids, etc.). Examples of sintering processes are the production of shaped bodies by microwaves known from the prior art, or radiation curing. Another preferred sintering process for the production of hollow bodies is reactive sintering. The starting components are brought into shape and subsequently solidified by reacting component A and component B with one another, components A and B being mixed with the starting components, applied thereto or added after the information has been brought about.

When this method is carried out, components A and B react with one another to solidify the individual ingredients. The reaction product formed from components A and B connects the individual starting components in such a way that a solid, relatively break-resistant hollow body is obtained.

With this method, hollow bodies with good decay are obtained. Since the binding of the individual ingredients takes place through reactive sintering and is not due to the "stickiness" of the granules of the premix, it is not necessary to adapt the formulation to the binding properties of the individual ingredients. These can be adapted as required depending on their effectiveness ,

In order to cause components A and B to react with one another, it has proven to be advantageous if the starting components are mixed with component A or coated with them before they are brought into shape. Examples of compounds of component A are the alkali metal hydroxides, in particular NaOH and KOH, alkaline earth metal hydroxides, in particular Ca (OH) ₂ , alkali metal silicates, organic or inorganic acids, such as citric acid, or acidic salts, such as hydrogen sulfate, anhydrous hydratable salts or salts containing hydrate water, such as soda , Acetates, sulfates, alkali metalates, where the abovementioned compounds can, if possible, also be used in the form of their aqueous solutions.

Component B is selected such that it reacts with component A without the application of higher pressures or a substantial increase in temperature, with the formation of a solid, with solidification of the other starting components present. Examples of compounds of component B are CO ₂ , NH ₃ , water vapor or spray, salts of hydrate water which optionally react with the anhydrous salts present as component A by hydrate migration, hydrated salts which form hydrates and the salts of the component containing hydrate water A react with hydrate migration, S0 ₂ , S0 ₃ , HCl, HBr, silicon halides such as SiCI ₄ or Kiselsäureester S (OR) _x R ^' ₄ .

The above-mentioned components A and B are interchangeable, provided two components are used which react with one another during sintering. In a preferred embodiment of this production route, the starting components are mixed or coated with compounds of component A and then mixed with the compounds of component B. It has proven particularly suitable if the compounds of component B are gaseous. The molded components (hereinafter referred to as preforms) can then either be gassed in a simple form or introduced into a gas atmosphere. A particularly preferred combination of components A and B are concentrated solutions of the alkali metal hydroxides, in particular NaOH and KOH, and alkaline earth metal hydroxides, such as Ca (OH) ₂ , or alkali metal silicates as component A and CO ₂ as component B.

To carry out process step i) according to the invention, the starting components are first brought into shape, ie they are usually filled into a die which has the outer shape of the hollow body to be produced. The starting components are preferably in powdery to granular form. First, they are mixed or coated with component A. After filling into the die or mold, it has proven to be preferred to press the starting components lightly, for example by hand or with a stamp at a pressure which is below the above-mentioned values, is in particular below 100 N / cm ² . It is also possible to compress the premix by vibration (knock compression).

If component A is not already in a mixture with the starting components, they are then coated with it and component B is added. After the reaction, a break-resistant hollow body is obtained without exposure to pressure or temperature.

If one of the components A or B is a gas, a preform can e.g. be mixed with it so that the gas flows through it. This procedure allows the molded article to harden evenly within a short time.

In a further process variant, a preform is introduced into an atmosphere of the reactive gas. This variant is easy to carry out. It is possible to produce hollow bodies that have a hardness gradient, i.e. Hollow bodies that only have a hardened surface up to hollow bodies that are fully hardened.

A preform or the premix can also be reacted with the reactive gas under excess pressure. This variant of the method has the advantage that the surface hardens quickly to form a hard shell, the hardening process already being stopped here or, as described above, with increasing hardening stages, completely hardened moldings can also be produced.

The above process variants can also be combined by first flowing reactive gas through the preform to displace air. The preform is then exposed to a gas atmosphere at normal pressure. The reaction between the gas and the second component automatically draws gas into the mold.

In one possible embodiment of the present invention, it is not the starting mixture but rather a preform that has already been shaped that is coated with component A and then reacted with component B. It hardens the layer on the surface of the preform, while the loose or slightly compressed structure remains in the core. Hollow bodies of this type are distinguished by particularly good disintegration behavior.

In summary, process variants are also preferred in which the open hollow mold is produced in step i) by sintering, the flowable mixture being solidified by the action of temperature or chemical reaction.

Regardless of the solidification mechanism in the production of the hollow mold, methods according to the invention are preferred in which the hollow mold produced in step i) has wall thicknesses of 100 to 6000 μm, preferably 120 to 4000 μm, particularly preferably 150 to 3000 μm and in particular 200 to 2500 μm, with wall thicknesses below 2000 μm being preferred.

The hollow mold in step i) can be produced using different techniques, some of which depend on the type of solidification mechanism. In the simplest case, a flowable mixture is poured into an appropriate mold, left to harden there and then removed from the mold. A disadvantage here is the design of the shape, since the desired wall thicknesses of the hollow bodies formed do not allow complicated geometries to be filled quickly.

Alternatively, the solidifying mixture can be filled into a mold that is only designed as a cavity. If you let the mixture solidify there, you would get a compact body, not a hollow shape. Appropriate process control can ensure that the mixture first solidifies on the wall of the mold. If the mold is turned over after a certain time t, the excess mixture flows off and leaves a lining of the mold, which itself is a hollow mold, which is removed from the mold after complete solidification. that can. As already mentioned, the filling can also take place before demolding; filling during the solidification process is also possible.

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

As an alternative to completely filling the mold and pouring excess mixture, the mold can only be partially filled. In these cases, the mixture is pressed against the wall of the die mold with a suitable stamp, where it solidifies to form the hollow body. This process variant represents an intermediate form between the "pouring technique" and the casting technique in negative forms of the hollow body. Corresponding processes in which in step i) an open die form is filled with the flowable shell material and the material is pressed onto the walls of the mold by a stamp and a hollow mold of this type is therefore also preferred. Particularly advantageous in this process, which is also referred to as the “cold stamp method”, is the possibility of also producing large numbers of pieces with a precisely defined wall thickness of the hollow body. In addition, the process is largely insensitive to fluctuating flow properties and can also be used with higher-viscosity mixtures. ;

The methods described above are particularly suitable for producing hollow bodies which have a shape without undercuts, i.e. have the shape of a "shell", i.e. an opening area which corresponds to the largest horizontal cross-sectional area. These "shells" can be filled and optionally closed.

With regard to the shape of the shells, the person skilled in the art has no limits in the selection. From the hemisphere to square ("cardboard-like" shells to complicated structures with a pronounced surface structure (e.g. in the form of nutshells or animal shapes), all hollow bodies can be produced.

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

The hollow molds are filled with detergent or cleaning agent during or after production. All ready-made detergents or cleaning agents can be introduced into the hollow mold in liquid, pasty, gel-like, powdered, extruded, granulated, pelletized, flaky or tableted form. However, it is not necessary to fill in a finished detergent or cleaning agent; rather, individual detergent or cleaning agent ingredients or precursors thereof can also be introduced into the hollow body.

Powder: bicarbonates, silicates, potash, soda, zeolites, polymers (PEG, maleic acid-polyacrylic acid copolymer salts, citric acid, citrates, sugar, soap, disintegrants and disintegrants, sulfates, phosphates, perborates, carboxymethyl cellulose (CMC), LAS powder ( linear alkylbenzenesulfonates), FAS powder (fatty alcohol sulfates).

Pastes: surfactant pastes (LAS paste, aqueous FAS paste), water glass

Compounds: tower powder (spray agglomerates), LAS compounds, FAS compounds, TAED, percarbonate, enzyme extrudates, crude extrudate, nonionic surfactant compounds

Liquids: polymer solutions (maleic acid-polyacrylic acid copolymer salts in aqueous solutions), phosphonate solutions (aqueous), perfume oils, enzyme solutions, chlorine bleaching solutions, hydrogen peroxide solutions, cationic surfactant solutions, nonionic surfactants

The liquids can also be in the form of a gel (due to higher active substance concentrations or by adding thickeners, eg Tixogel ^® (Süd-Chemie)). The solids can also be processed as solutions or suspensions, the liquids as compounds in bound form.

The examples given above show that all of the substances or mixtures of substances mentioned can be introduced into the hollow bodies or into the compartments of the hollow bodies. The liquid and pasty media (which occur in the upstream manufacturing stages in the above-mentioned states) usually have to be dried or absorbed on carriers. When filling in compartments, these assembly stages are no longer required, which represents a further advantage of the method according to the invention. After filling, the open hollow mold can be closed. This is necessary for liquid or pasty fillings to prevent the filling from escaping before use. In the case of fillings that remain firmly in the hollow mold, the mold may not be closed if desired. Closure can also be indicated in such cases for aesthetic reasons.

The optional closing of the hollow form can be done in different ways. In the case of moldings with a bunghole, this can be closed, for example, by inserting a suitable part. Open hollow molds in the form of hollow bodies without undercuts can be closed with foils or covered with additional material for the hollow mold after filling. The optional sealing with foils is described below.

The film, which closes the opening (s) of the hollow mold (s), is applied to the surface of the hollow mold and bonded to it, which can be done, for example, by gluing, partial melting or by chemical reaction. It is possible to apply the film to all surfaces of the hollow mold (ie not only via the opening) and to bond it firmly, so that the film constitutes a coating, a "coating" of the entire molded body. Preferred detergent and cleaning agent portions produced according to the invention are, however, characterized in that the film does not enclose the entire molded body.

For reasons of process economy and aesthetic impression, it is preferred that the film is applied only in such a way that it fulfills a function, i.e.. serves to close the mold.

The sealing film can of course also be a laminate of several differently composed films, the opening of the hollow mold can be released at certain times in the washing and cleaning cycle by means of different compositions of individual film layers.

Preferred film materials have already been described in detail above.

Regardless of the chemical composition of the film, methods according to the invention are preferred in which the film used in step iii) to close the hollow mold has a thickness of 1 to 150 μm, preferably 2 to 100 μm, particularly preferably 5 to 75 μm and in particular from 10 to 50 μm. Due to the division into hollow form and filling, a molded body produced according to the invention comprises two areas in which different ingredients are contained or different release mechanisms and release kinetics can be realized. The active substance contained in the hollow form can assume any physical state or any form of presentation. Preferred detergent or cleaning agent portions contain the further active substance in liquid, gel-like, pasty or solid form.

When liquid, gel-like or pasty active substances or active substance mixtures are incorporated, the composition of the hollow body and the film must be matched to the filling in order to avoid premature destruction of the film or loss of active substance through the hollow body. This is only necessary to a lesser extent (chemical incompatibility) when solid substances are incorporated into the hollow mold, so that in preferred manufacturing processes the detergent or cleaning agent composition filled into the hollow mold is in particulate form, preferably in powdered, granular, extruded, pelletized, prilled , flaky or tableted form.

The hollow mold closed by the film can be completely filled with further active substance. However, it is also possible to fill the hollow mold only partially before closing, in order in this way to enable the filled particles or liquids to move within the hollow mold. Particularly when filling with regularly shaped larger particles, attractive optical effects can be achieved. Detergent or cleaning agent portions produced according to the invention are preferred in which the volume ratio of the space enclosed by the film and the hollow body to the active substance contained in this space is 1: 1 to 100: 1, preferably 1.1, 1: 50: 1, is particularly preferably 1.2: 1 to 25: 1 and in particular 1.3: 1 to 10: 1. In this terminology, a volume ratio of 1: 1 means that the mold is completely filled.

Depending on the size of the hollow mold, the density of the hollow body, the density of the active substance in the hollow mold and the degree of filling of the hollow mold, the proportion of the further active substance in the hollow mold can make up different proportions of the overall molded body. Detergent or cleaning agent portions produced according to the invention are preferred in which the weight ratio of hollow body to the active substance contained in the space enclosed by the film and the hollow body is 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3 : 1 to 50: 1 and in particular 4: 1 to 30: 1. The weight ratio defined above is the ratio of the mass of the unfilled hollow body to the mass of the filling. The mass of the film is not taken into account in this calculation. The time at which the substances contained in the hollow body are released can be predetermined by suitable packaging of the hollow body and film material. For example, the film can be instantly soluble, so that the active substance contained in the hollow form is dosed into the washing or cleaning liquor right at the beginning of the washing or cleaning cycle. As an alternative to this, the film can be so poorly soluble that only the shaped body is dissolved and the active substance contained in the hollow mold is thereby released.

Depending on this release mechanism, it is possible, for example, to produce moldings in which the active substance contained in the hollow mold is present in the cleaning liquor before the components of the hollow body are dissolved or after this has happened. On the one hand, detergent tablets are preferred, which are characterized in that the active substance contained in the space enclosed by the film and the hollow body dissolves faster than the hollow body. However, detergent tablets in which the active substance contained in the space enclosed by the film and the hollow body dissolves more slowly than the hollow body are also preferred embodiments of the present invention.

As an alternative to sealing with a film, the filled hollow bodies can also be closed by applying a melt, solution, emulsion or dispersion of the film materials mentioned above. The sealing layer forms from the melt, solution, emulsion or dispersion by cooling or evaporation of the solvent, i.e. the sealing "film" is created on the hollow mold. This alternative can be used in particular with completely filled hollow molds, while only partially filled hollow molds are expediently sealed in a different way, provided that a "mobility" of the content is important, for example as special incentive to buy.

Of course, the hollow bodies can also be produced in step i) in such a way that they can be connected to a further filled hollow body and closed in this way. Such bodies are composed of two half-shells without undercuts and have an equatorial plane. The latter does not necessarily have to be arranged in the center, but can, for example, also be in the upper or lower third, fourth, fifth, etc. This procedure is facilitated if the hollow bodies produced in step i) have flange parts. Alternatively, the molded parts can only adhere to one another via the boundary edges of the opening surfaces. Methods are also preferred in which the hollow form has flange parts and is sealed in step iii) by welding with a further hollow form. A complete one. The production process is explained below using the example of a melt as the starting material for the hollow mold - of course, all the other solidification mechanisms mentioned above can be used completely analogously. In a first preliminary stage, the molded shell material is melted in a storage container and tempered to the required casting temperature, which can optionally be pre-crystallized. The melt is then fed to the dosing stations via heated and / or insulated line systems; in parallel, the individual molds are preheated or cooled to the desired temperature.

The liquid melt is metered into the mold troughs in a casting machine, these being filled up to the upper die edge. As a rule, several identical molds run past the casting machine and are filled. After leaving the casting machine (or driving past the dosing head), the filled molds are either fed to a cooling section or moved or "parked" until the melt begins to solidify from the outside. This is essential for the later wall thickness of the molded shell to be formed among other things, the substance-dependent cooling time.

After the specified time has elapsed, the mold is turned upside down or turned upside down, so that the not yet solidified and excess melt mass runs out of the mold into a waiting reservoir for recycling into the process. Depending on the material system and in particular in the case of slowly solidifying melts, no completely solidified shell is yet formed at the time of emptying, so that mainly the adhesion to the casting mold ensures that the melt mass remains in the mold. The adhesive shell formation can be supported by an eccentric movement of the mold, the centrifugal forces evenly transporting the still flowing melt to the mold surface and ensuring the formation of a shell with an even wall thickness. Degassing the melt by vibrating the mold may also be necessary.

After this, the formation of the shell can be completed by cooling. If necessary, the remainder of the shell protruding over the edge of the casting mold can be cut off, whereby knives or thermal rollers can be used.

The formed shell is then filled and the filling is later cooled if necessary. Depending on the desired type of closing, the mold is completely or only partially filled. To seal the mold, a sealing barrier layer can be applied (especially in the case of liquid fillings), which consists of a substance that has a lower melting point than the shell material and can be sprayed well. The mold can then be firmly closed by filling the molded shell with filling with the Schmejze for the shell material. The mold can again be vibrated during the solidification time for uniform lid formation and for the necessary degassing. The solidification to the finished molded body can also be promoted here by passing through a cooling section.

Finally, the moldings are removed from the mold in a mold emptying station. For this purpose, the mold is turned from top to bottom so that the molded body formed can fall down onto a conveyor belt or be put down. This removal from the mold can be supported by twisting / twisting the mold or by hitting the back of the mold.

As already mentioned, the moldings produced according to the invention can be produced in any shape and size and combine a high aesthetic appeal with great technical flexibility and the possibility of realizing various product advantages such as control-led release concepts.

Another object of the present invention are portioned detergents or cleaning agents with a detergent or cleaning agent composition which at least partially comprises solidified material and is characterized in that the enclosure has a wall thickness of 100 to 6000 microns and consists of a material which consists of time delayed water binding, by cooling below the melting point, by evaporation of solvents, by crystallization, by chemical reaction (s), in particular polymerization, by changing the rheological properties, for example was produced by changing shear, by sintering or by means of radiation curing, in particular by UV, alpha-beta or gamma rays.

The mechanisms by which the formation of the hollow form can take place have been described in detail above. These statements also apply to the encapsulation of the washing or cleaning agents according to the invention. The term "at least partially comprised of solidified material" denotes that at least a part of the surface of the detergent or cleaning composition is covered by solidified material as defined above. The portion not covered by solidified material can either be included in other ways (eg covered with foil, see above) or have direct contact with the atmosphere Since the detergent or cleaning agent composition is filled into a hollow mold according to the manufacturing process described above, portioned detergent or cleaning agents according to the invention are preferred here, in which the enclosure comprises at least 50 %, preferably at least 60%, particularly preferably at least 70% and in particular at least 80%) of the surface of the portioned agent. Similar statements can be made about the masses that embrace and embrace. Portioned detergents or cleaning agents are preferred in which the ratio of the masses of contents and contents is in the range from 10: 1 to 1: 1000, preferably from 2: 1 to 1: 100, particularly preferably from 1: 1 to 1:50 and in particular from 1: 5 to 1:25.

As mentioned above, melts are particularly suitable. Accordingly, preference is also given to the portioned washing or cleaning agents according to the invention in which the enclosure consists of a material whose melting point is in the range from 40 to 250.degree.

Certain substances, which have been described in detail above, are also particularly suitable as enclosures for portioned washing or cleaning agents. Portioned washing or cleaning agents preferred in the context of the present invention are characterized in that the containment comprises one or more substances from the groups of dicarboxylic acids, dicarboxylic acid anhydrides, hydrogen carbonates, hydrogen sulfates and / or urea in amounts of at least 40% by weight, preferably at least 60 Wt .-% and in particular at least 80 wt .-%, each based on the mass of the containment.

The detergent or cleaning agent composition at least partially included in the enclosure can be in any form, as described in detail above. Portioned detergents or cleaning agents, in which the detergent or cleaning agent composition in question is in liquid, pasty, gel-like or particulate form or in the form of a suspension or emulsion and is completely enclosed by the encapsulation, are therefore a further preferred embodiment of the present invention.

According to the invention, it is particularly preferred to produce the dimensionally stable hollow body (optionally comprising one or more means (s) for compartmentalizing) by injection molding. In particular, thermoplastic polymers can be processed excellently into dimensionally stable hollow bodies, in particular, if appropriate, into dimensionally stable hollow bodies, which contain compartments in their interior. The injection molding of suitable materials takes place according to methods known per se at high pressures and temperatures, for example at temperatures between 100 and 220 ° C, in particular above the softening point of the thermoplastic, for example at 140 ° C and higher, in particular at approximately 180 ° C, and a pressure between 500 and 2,000 bar, preferably of> 1,000 bar, in particular at approx. 1,400 bar, with the steps of closing the mold connected to the extruder for injection molding, injecting the polymer at high temperature and pressure, cooling the injection-molded molding, opening the mold and removing the molded blank. Further optional steps such as the application of release agents, demolding etc. are known to the person skilled in the art and can be carried out using technology known per se:

The advantages of the procedure for producing the dimensionally stable hollow bodies by injection molding lie in the sophisticated technology of this procedure, the high flexibility with regard to the materials that can be used, the possibility of obtaining exactly the desired wall thicknesses s of the molding or dimensionally stable hollow body and the possibility of all of this Step with high reproducibility to produce a dimensionally stable hollow body with one or more integral compartmentalization device (s).

The simultaneous portioning of several different fillings requires hollow bodies which contain compartmentalization devices. The production of such hollow bodies from several adjoining compartments encounters difficulties with conventional methods. The present application discloses a method for producing such hollow bodies and the detergent, detergent or dishwashing agent portions that can be produced therefrom.

Another object of the invention is a method for producing a detergent, cleaning agent or detergent portion contained in one or more dimensionally stable hollow body (s) with at least one compartment

(a) at least one wash-active, cleaning-active or rinse-active preparation;

(b) at least one surrounding the at least one preparation according to (a) completely or partially from a non-pressed material which disintegrates under washing, cleaning or rinsing conditions and gives the hollow body (s) dimensional stability; and

(c) optionally one or more means (s) for compartmentalizing the dimensionally stable hollow body (s), comprising the steps (i) production of the dimensionally stable hollow body (if appropriate one or more devices) for compartmentalization) by injection molding;

(ii) filling the compartment (s) with at least one wash-active, cleaning-active or rinse-active preparation;

(iii) if necessary, then closing the dimensionally stable hollow body (s) to form a partial or complete enclosure around the washing-active preparation, cleaning-active or rinsing-active preparation (s).

For this purpose, a hollow body is injection molded in step (i), which has one or more spaces for accommodating preparations which are active in washing, rinsing or cleaning. The injection molding of suitable materials is carried out according to methods known per se at high pressures and temperatures with the steps of closing the mold connected to the extruder for injection molding, injecting the polymer at high temperature and high pressure, cooling the injection-molded molding, opening the mold and removing the mold shaped blank. Further optional steps such as the application of release agents, demolding etc. are known to the person skilled in the art and can be carried out using technology known per se.

The advantages of the method of producing the dimensionally stable hollow bodies by injection molding lie in the sophisticated technology of this method, the high flexibility with regard to the materials that can be used, the possibility of obtaining exactly the desired wall thickness s of the molded part or dimensionally stable hollow body and the possibility of being all in one Step with high reproducibility to produce a dimensionally stable hollow body with one or more integral compartmentalization device (s).

In preferred processes according to the invention, step (i) is carried out at a pressure between 100 and 5000 bar, preferably between 500 and 2500 bar, particularly preferably between 750 and 1500 bar and in particular between 1000 and 1250 bar.

The temperature of the material to be injection molded is preferably above the melting or softening point of the material and thus also depends on the type of material for the hollow body. In preferred processes according to the invention, step (i) is carried out at temperatures between 100 and 250 ° C., preferably between 120 and 200 ° C. and in particular between 140 and 180 ° C.

The tools that hold the materials are preferably preheated and have temperatures above room temperature, temperatures between 25 and 60 ° C. and in particular from 35 to 50 ° C. being preferred. Regardless of the material used for the hollow body (see below), but depending on the desired dissolution properties, the thickness of the wall can be varied. On the one hand, the wall should be chosen so thin that rapid dissolution or disintegration is achieved and the ingredients are quickly released into the application liquor, but a certain minimum thickness is also required in order to give the hollow shape the desired stability, in particular dimensional stability.

According to the invention, the term “dimensionally stable hollow body” is understood to mean that the shaped bodies containing the detergent, cleaning agent or dishwashing agent portions have an inherent dimensional stability which enables them to be carried out under the usual conditions of manufacture, storage, transport and handling the consumer has a non-collapsing structure that is stable against breakage and / or pressure and that does not change over a long period of time even under the conditions mentioned, according to the invention it has no influence whether this structural stability results from the properties resulting from various parameters mentioned below of the dimensionally stable hollow body alone or (also) from the presence of compartmentalization devices and / or (also) from the filling with washing-active, cleaning-active or rinse-active preparations. In preferred embodiments of the invention, the dimensionally stable hollow body already has he himself has sufficient inherent dimensional stability, since this has an advantageous effect on the smooth running in machines during the production of the hollow bodies and the filling during the production of the detergent, cleaning agent or detergent portions according to the invention.

The pressure resistance of the dimensionally stable hollow bodies according to the invention is measured in the (per se usual) manner in such a way that empty hollow bodies, optionally provided with compartmentation devices, are closed with foils or lids and an internally applied, steadily increasing vacuum is applied to these hollow bodies at room temperature until the hollow body begins to collapse. The inherent dimensional stability of the hollow bodies should particularly preferably be such that, in the case of such vacuum collapse tests of hollow bodies which are not filled and optionally provided with compartmentalization devices, collapse does not begin before a vacuum of 900 mbar, preferably 750 mbar and in particular 500 mbar is reached , In this respect, the hollow bodies used according to the invention differ fundamentally from foils or so-called “pouches”, as are also used for the provision of detergents, cleaning agents or dishwashing detergents. These collapsing already occurs at a pressure which is only slightly below atmospheric pressure. In a similar manner, they differ the dimensionally stable hollow bodies according to the invention, however, also of coatings (subsequently applied to shaped bodies): The hollow bodies according to the invention represent an independent, self-supporting covering which, as a rule, is filled with one or more washing-active, rinsing-active or cleaning-active components before filling. te (n) exists and is then filled. In contrast, coatings are applied to existing moldings (e.g. compacts, granules, extrudates, etc.) and then dried or cured; only then do they form an envelope surrounding the molded body.

In preferred processes according to the invention, hollow bodies are produced in step (i), in which collapse does not begin before a vacuum of 250 mbar, preferably 100 mbar and in particular 20 mbar is reached.

Preferred methods according to the invention are therefore characterized in that the wall thickness of the enclosure (b) produced in step (i) is 100 to 5000 μm, preferably 200 to 3000 μm, particularly preferably 300 to 2000 μm and in particular 500 to 1500 μm.

The use of polymers which have a flow index (MFI) below 120, preferably below 10 and in particular below 8 is preferred.

The dimensionally stable hollow body produced by injection molding regularly does not have closed walls on all sides and is open on at least one of its sides - in the case of a spherical or elliptical body in the region of part of its shell - due to the production process. Through the remaining opening, one or more washing-active, cleaning-active or rinsing-active preparation (s) are / are filled into the compartment (s) formed in the interior of the dimensionally stable hollow body. This also takes place in a manner known per se, for example in the context of production processes known from the confectionery industry; Procedures that run in several steps are also conceivable. A one-step procedure is particularly preferred if, in addition to solid preparations, preparations (liquids or emulsions, suspensions) comprising liquid components or even preparations (foams) comprising gaseous components are incorporated into the detergent, detergent or detergent portions in the hollow bodies should.

Polymers are particularly suitable as materials for the hollow body to be produced in step (i), with methods according to the invention being preferred in which the enclosure (b) produced in step (i) is 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.

The use of water-soluble polymers as material for the hollow bodies is particularly preferred. Processes have proven themselves here which are characterized in that the enclosure (b) produced in step (i) comprises one or more water-soluble polymer (s), preferably one Material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).

In the context of the present invention, polyvinyl alcohols are particularly preferred as coating materials. "Polyvinyl alcohols" (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure

which in small proportions (approx. 2%) also structural units of the type

contain.

Commercial polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , therefore still contain a residual content of acetyl groups. The manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax. The polyvinyl alcohol coatings are largely impervious to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through. Processes preferred in the context of the present invention are characterized in that the hollow bodies consist of a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably δO to 90 mol%, particularly preferably δ1 to 89 mol% and in particular 82 to 8δ mol -%.

Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the hollow bodies, with methods according to the invention being preferred in which the hollow bodies which are produced in step (i) consist of a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^'1 , preferably from 11,000 to 90,000 gmol ^"1 , particularly preferably from 12,000 to δθ,000 gmol ^{" 1} and in particular from 13,000 to 70,000 gmol ^"1 .

The degree of polymerization of such preferred polyvinyl alcohols is between approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1690, particularly preferably between approximately 240 to approximately 16δ0 and in particular between approximately 260 to approximately 1500.

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-δ3, Mowiol ^® 4-88, Mowiol ^{® 5-8δ} and Mowiol ^{® δ-88th}

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-δ2, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX ^® 72.5, 78, B72, Fδ0 / 40, F8δ / 4, Fδδ / 26, Fδδ / 40, Fδδ / 47 (trademark of Harlow Chemical Co.), Goh- senol ^® 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).

To facilitate the injection molding process (that is, their manufacture), the hollow bodies can contain plasticizing aids. This can be particularly advantageous if polyvinyl alcohol or partially hydrolyzed polyvinyl acetate have been selected as the material for the hollow bodies. The proportion of plasticizers (based on the polymer) is usually up to 15% by weight, values between 5 and 10% by weight being preferred. Glycerin, triethanolamine, ethylene glycol, propylene glycol, diethylene or dipropylene glycol, diethanolamine and methyldiethylamine have proven particularly useful as plasticizers.

In addition to plasticizing aids, demolding additives are important auxiliary substances that can be used in the injection molding compounds. From the groups of fatty substances and the feinteili- gen substances in particular stearic acid and / or stearates and pyrogenic silica (Aerosil ^®), talcum, and have proven this in the present invention. The proportion of the demolding additives (based on the polymer) is usually up to 5% by weight, values between 0.5 and 2.5% by weight being preferred.

Other substances that can be used as mold release agents come in particular from the group of fatty substances. In the context of this application, fatty substances are understood to mean liquid to solid substances from the group of fatty alcohols, fatty acids and fatty acid derivatives, in particular the fatty acid esters, at normal temperature (20 ° C.). In the context of the present application, reaction products of fatty alcohols with alkylene oxides are among the surfactants (see above) and are not fatty substances in the sense of the invention. According to the invention, fatty alcohols and fatty alcohol mixtures, fatty acids and fatty acid mixtures, fatty acid esters with alkanols or diols or polyols, fatty acid amides, fatty amines etc. can preferably be used as fatty substances.

As fatty alcohol, for example, the alcohols 1-hexanol (capro alcohol), 1-heptanol (enant alcohol), 1-octanol (caprylic alcohol), 1-nonanol (pelargon alcohol), 1-decanol (capric alcohol), 1-undecanol, which are accessible from native fats and oils , 10-undecen-1-ol, 1-dodecanol (lauryl alcohol), 1-tridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (cetylaic alcohol), 1-heptadecanol, 1-octadecanol ( Stearyl alcohol), 9-cis-octadecen-1-ol (oleyl alcohol), 9-trans-octadecen-1-ol (erucyl alcohol), 9-cis-octadecen-1, 12-diol (ricinolaikohol), all-cis- 9,12-octadecadien-1-ol (linoleyl alcohol), all-cis-9,12,15-octadecatrien-1-ol (linolenyl alcohol), 1-nonadecanol, 1-eicosanol (arachidyl alcohol), 9-cis-eicosen -1-ol (gadoleyl alcohol), 5,8,11, 14-eicosatetraen-1-ol, 1-heneicosanol, 1-docosanol (behenyl alcohol), 1-3-cis-docosen-1-ol (erucyl alcohol), 1-3-trans-docosen-1-ol (brassidyl alcohol) and mi mixtures of these alcohols. According to the invention are also Guerbet alcohols and oxo alcohols, for example C ₃ . ₁₅ oxo alcohols or mixtures of C ₁₂ . ₁₈ -Alcohols with Cι ₂ _ι ₄ - alcohols can be used as fatty substances without any problems. Of course, it may also be alcohol mixtures are used, for example, such as the C produced by polymerization of ethylene by Ziegler ₁₆ -ι ₈ alcohols. Specific examples of alcohols which can be used as component b) are the above-mentioned alcohols and lauryl alcohol, palmityl and stearyl alcohol and mixtures thereof.

Preferred mold release additives are C ₁₀ . ₃ o-fatty alcohol, preferably C ₁₂ . ₂₄ - fatty alcohols with particular preference for 1-hexadecanol, 1-octadecanol, 9-cis-octadecen-1-ol, all-cis-9, 12-octadecadien-1 -ol, all-cis-9, 12, 15-octadecatriene -1 -ol, 1 -docosanol and their mixtures.

Fatty acids can also be used as mold release agents. Technically, most of these are obtained from native fats and oils by hydrolysis. While the alkaline saponification which was carried out in the past century led directly to the alkali salts (soaps), only water is used on an industrial scale to split the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage. Carboxylic acids which can be used as fatty substances in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. Preferred within the scope of the present invention Compound the use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacotanoic acid, Triacotanoic acid (melissic acid) and the unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaadadic acid), 9-octadecenoic acid (9-octadecenoic acid), 9-octadecenoic acid (elaecadic acid), 9-octadecenoic acid (elecadic acid), 9-octadecenoic acid (elecadic acid), 9-octadecenoic acid ), 9t, 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatreic acid (Lin olensäure). Of course, tridecanoic acid, pentadecanoic acid, margaric acid, nonadecanoic acid, erucic acid, elaeostearic acid and arachidonic acid can also be used. For reasons of cost, it is preferred not to use the pure species, but rather technical mixtures of the individual acids, as are accessible from fat cleavage. Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C12, 18 wt .-% _C14, 10 wt .-% C _1β, 2 wt. -% C _18, 8 wt .-% C ₁₈ - 1 wt .-% C ₁₈ -), palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt .-% C ₁₂ , 15% by weight C ₁₄ , 7% by weight C ₁₆ , 2% by weight C ₁₈ , 15% by weight C ₁₈ -, 1% by weight C ₁₈ ••), tallow fatty acid (approx 3% by weight C ₁₄ , 26% by weight C ₁₆ , 2% by weight C ₁₆ -, 2% by weight C ₁₇ , 17% by weight C ₁₈ , 44% by weight C ₁₈ - , 3 wt% C ₁₈ -, 1 Wt.% C ₁₈ • ^• •), hardened tallow fatty acid (approx. 2 wt.% C ₁₄ , 2δ wt.% C ₁₆ , 2 wt.% C ₁₇ , 63 wt.% C ₁₈ , 1 wt % C ₁₈ -), technical oleic acid (approx. 1% by weight C ₁₂ , 3% by weight C ₁₄ , 5% by weight C ₁₆ , 6% by weight C ₁₆ -, 1% by weight % C _17l 2% by weight C ₁₈ , 70% by weight C ₈ -, 10% by weight C ₁₈ -, 0.5% by weight C ₁₈ -), technical palmitin / stearic acid (approx. 1% by weight) .-% C _12, 2 wt .-% C ₁₄ 45 wt .-% C _16, 2 wt .-% C ₁₇ 47 wt .-% C _18: 1 wt .-% C ₁₈ -), and soybean oil fatty acid ( approx. 2 wt% C ₄ , 15 wt% C ₁₆ , 5 wt% C ₁₈ , 25 wt% C ₁₈ , 45 wt% C ₁₈ , 7 wt% C ₁₈ -).

The esters of fatty acids with alkanols, diols or polyols can be used as fatty acid esters, fatty acid polyol esters being preferred. Suitable fatty acid polyol esters are monoesters and diesters of fatty acids with certain polyols. The fatty acids which are esterified with the polyols are preferably saturated or unsaturated fatty acids having 12 to 13 carbon atoms, for example lauric acid, myristic acid, palmitic acid or stearic acid, preference being given to using the technically obtained mixtures of the fatty acids, for example those of coconut, Acid mixtures derived from palm kernel or taig fat. In particular, acids or mixtures of acids with 16 to 18 carbon atoms, such as, for example, tallow fatty acid, are suitable for esterification with the polyhydric alcohols. In the context of the present invention, sorbitol, trimethylolpropane, neopentyl glycol, ethylene glycol, polyethylene glycols, glycerol and polyglycerols are suitable as polyols which are esterified with the abovementioned fatty acids.

Preferred embodiments of the present invention provide that glycerol is used as the polyol which is esterified with fatty acid (s). Accordingly, fatty substances from the group of fatty alcohols and fatty acid glycerides are preferred as mold release additives. Particularly preferred mold release agents are fatty substances from the group of fatty alcohols and fatty acid monoglycerides. Examples of such preferred fatty substances are glycerol monostearic acid esters or glycerol monopalmitic acid esters. I,

In order to prevent undesirable changes in the injection molding compounds caused by the action of oxygen and other oxidative processes, these 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.

In preferred methods according to the invention, the material for the hollow mold, the wall thickness and the size of the hollow mold are chosen so that the hollow body dissolves in still water of 20 ° C. in less than 300 seconds, preferably in less than 60 seconds, or the ingredients of the The filling releases. It is not necessary for the entire molded body to dissolve spontaneously. Rather, it is sufficient if all components within the Dissolve the application period under the application conditions. For conventional washing or rinsing processes, this means temperatures of 20 ° C. and above, mechanical action and times of less than 200 minutes, preferably less than 60 minutes, in particular less than 20 minutes. The release of the ingredients of at least one compartment should, however, preferably take place in less than 300 seconds, in particular in less than 60 seconds. This can be done by using disintegration aids, by sealing a compartment with a thin, water-soluble film, by dissolving a “stopper” that closes an opening, or in another conventional manner.

Further information on ingredients (a) and their division into individual compartments as well as information on process steps (ii) and (iii) can be found in the above statements.

The production of injection molded hollow bodies, the injection molding composition comprising water-soluble polymers, has not hitherto been described in the prior art. The present invention therefore furthermore relates to an injection molding process for hollow bodies which comprise such polymers, that is to say a process for the production of hollow bodies by injection molding, which is characterized in that the injection molding composition comprises one or more water-soluble polymers, preferably one or more Material (s) from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof, particularly preferably (optionally acetalized) polyvinyl alcohol (PVAL).

As already described above, methods according to the invention are preferred in which the injection molding composition comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 8δ mol -%.

The statements made above also apply to the molecular weight distribution; Processes according to the invention are preferred here in which the injection molding compound 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 δθ,000 gmol ^"1 and in particular from 13,000 up to 70,000 gmol ^"1 .

The processes according to the invention can be carried out with particular advantage if the proportion of water-soluble polymers in the injection molding compound is high. The entire injection molding composition preferably consists only of the water-soluble polymers and optionally auxiliaries (see above). Methods according to the invention are preferred here, in which the Injection molding compound the polymers mentioned in amounts of at least 50% by weight, preferably at least 70% by weight, particularly preferably at least δO% by weight and in particular at least 90% by weight, in each case based on the weight of the injection molding compound, contains.

With regard to the other process parameters (pressure, temperature) and the moldings which are preferably to be produced, what has been said above applies analogously.

The dimensionally stable hollow body produced by injection molding regularly does not have closed walls on all sides and is open on at least one of its sides - in the case of a spherical or elliptical body in the region of part of its shell - due to the production process. Through the remaining opening, one or more washing-active, cleaning-active or rinsing-active preparation (s) are / are filled into the compartment (s) formed in the interior of the dimensionally stable hollow body. This also takes place in a manner known per se, for example in the context of production processes known from the confectionery industry; Procedures that run in several steps are also conceivable. A one-step procedure is particularly preferred if, in addition to solid preparations, preparations (liquids or emulsions, suspensions) or even preparations (foams) comprising liquid components are incorporated into the detergent, detergent or dishwashing detergent portions in the hollow bodies should be.

In a particularly preferred embodiment of the method according to the invention, one or more washing-active, cleaning-active or rinsing-active preparation (s) are / are filled into compartments which are surrounding one another, preferably concentrically or coaxially with one another, or into the form concentrically or coaxially with one another or partially or completely surrounding one another Compartments brought. These, if appropriate together with one or more washing-active, cleaning-active or rinsing-active preparation (s), are introduced into a separately produced dimensionally stable molded body. It is possible that the compartments partially or completely surrounding one another, preferably the compartments arranged concentrically or coaxially to one another, in addition to one or more other compartments filled with one or more washing-active, cleaning-active or rinsing-active preparation (s) in the dimensionally stable Hollow bodies are present or are contained therein alone.

In a final step, the dimensionally stable hollow body, which contains one or more wash-active, cleaning-active or rinse-active preparation (s) in one compartment or is distributed in several compartments, is sealed and the preparation (s) is sealed inside. As already described above, this can be done by applying a "cover" to the still open (nth) surface of the dimensionally stable hollow body or - in the case of spherical or elliptical hollow bodies - by applying a corresponding partial spherical shell or partial elliptical shell to the opening. The application can preferably be carried out by gluing, preferably with a water-soluble adhesive, by fusing, by welding or by other types of connection known to the person skilled in the art.

Finally, the invention also relates to a washing method, in particular a method for machine washing in a commercially available washing machine, which comprises the steps of introducing a detergent portion into the washing machine, in particular into its washing-up chamber or washing drum, as described above; sets the desired washing conditions; and when these conditions occur, the wash-active preparation (s) of the detergent portion are added to the wash liquor and bring them into contact with the items to be washed.

A detergent which can preferably be used in such a washing process comprises several “phases” which are contained in compartments in a dimensionally stable hollow body comprising a detergent portion according to the invention. The means for compartmenting, preferably at least one wall of each compartment, dissolves due to the inherent properties of the material that forms the respective wall when certain parameters are set in water or in the aqueous liquor. The following “phases” can be mentioned by way of example for a detergent according to the invention:

Phase 1: anionic surfactant, non-ionic surfactant, polycarboxylate, citrate, citric acid, phosphonates, enzymes (without protease);

Phase 2: soda, alkali carrier, protease;

Phase 3: alkaline builders, zeolite, silicates, perborate, percarbonate, carboxymethyl cellulose;

Phase 4: Perfume, optical brighteners, soil repellants, plasticizers (including esterquats).

The water solubility of the walls / compartments surrounding the phases can be adjusted in such a way that 5 to 10 minutes after opening one compartment each time until the contents of the next compartment are released.

Simplified forms of the detergent portion can be prepared by omitting phase 2 and its content on phases 1 (protease) and 3 (soda, alkali). liträger) is distributed, and that in a further simplification, in addition to phase 2, phase 4 is omitted, perfume, optical brighteners and soil repellants are added to phase 3 and the fabric softener is dosed in a separate product.

The invention also relates to a cleaning process comprising the steps of adding a detergent portion to the cleaning liquor as detailed above; sets the desired cleaning conditions; and when these conditions occur, the cleaning-active preparation (s) of the detergent portion are added to the cleaning liquor and bring them into contact with the items to be cleaned.

The invention also relates to a washing method, in particular a method for machine washing in a commercially available dishwasher, which comprises the steps of entering a detergent portion according to the detailed description above into the dishwasher, in particular into its washing-up chamber or in its washing compartment; sets the desired rinsing conditions; and when these conditions occur, the rinse-active preparation (s) of the detergent portion are added to the rinse liquor and bring them into contact with the items to be rinsed.

With the detergent, detergent or detergent portions according to the invention, the objects are achieved in an advantageous manner. In this way, incompatible washing-active, cleaning-active or rinsing-active preparations or their components can be spatially separated and, owing to the lack of a common contact surface, no reactions can occur with one another, in particular no reaction which impairs the activity of the respective preparation. This leads to an increased storage stability of the detergent, cleaning agent or detergent portions, in particular in the case of increased active substance concentrations, to an improved washing performance due to the lack of loss of activity and to a saving of active substance, since the excess of active substance to be used earlier due to the expected loss of activity can be omitted in the detergent, detergent or detergent portions according to the invention. Furthermore, the skilled person opens up new recipe possibilities for the combination of substances previously regarded as incompatible in detergent, cleaning agent or detergent preparations. Due to the spatial separation of the individual components, the technological functions of the individual components can be optimized independently of one another, without the effects of the components on one another being feared. There are also clear advantages for the user. The detergent, cleaning agent or detergent portions contained in the hollow bodies with one or more compartments promise a constant and pre-assembled dosage with all the components required or desired for the entire washing, cleaning or rinsing process. There is no dust formation during dosing, and there is no fear of product spillage, contact with active ingredients or accidents due to the absorption of active ingredients. The metering takes place in one step, and the solubility of the enclosure or of the hollow body material for releasing the ingredients takes place reliably according to predetermined or predetermined kinetics, so that the washing, cleaning or rinsing results improve significantly compared to powdered agents or pressed Shaped bodies of the same composition without compartmentalized separation of the components.

Examples:

a) Injection molding compartments:

Polyvinyl alcohol granules (Vinex ^® 2019 from Texas Polymers) were melted on a hydraulic screw injection molding machine from Arburg and injected into simple tools with a hot runner nozzle. In example 1 a trochoidal shell with three corrugated partitions and a peripheral edge was produced, in example 2 a hemisphere with a peripheral stacking attachment and an edge.

The mold temperature was 40 ° C, the demoulding was carried out using an air-assisted wiper system. Further operating parameters are summarized in Table 1:

Table 1: Injection molding [process step (i)]

The molded dishes produced in the manner described above were placed in water and the time taken for them to decay or to dissolve completely:

Polyvinyl alcohol granulate (Vinex ^® 2019 from Texas Polymers) was melted on a hydraulic screw injection molding machine from Arburg and injected into simple tools with a hot runner nozzle, the shell being in the shape of a hemisphere with a circumferential stacking attachment and a rim. The mold temperature was 40 ° C, the demoulding was carried out using an air-assisted wiper system. Further operating parameters are summarized in Table 1:

Table 1: Injection molding [process step (i)]

A half-shell was filled with a low-water, commercially available liquid detergent (Persil Gel, commercial product from the applicant) and sealed with a polyvinyl alcohol film from Greensol. A second half-shell was filled with an extruded heavy-duty detergent containing bleach (Persil ^® Megaperls ^® , commercial product of the anmeider) and then also closed with a PVAI film. The two partial hollow bodies in the closed enclosures (A) and (B) were then glued together using a glue.

b) Enamel compartments:

1. Production of hollow balls with bunghole:

3 g of the substances listed below were metered into a molten form in a closable double mold made of thematic plastic (Makrolon ^® ), in which the upper and lower shells each had the shape of a hemisphere (radius = 1 cm) and the mold in the closed state swiveled in all directions for a minute and rotated in space. After demolding, spherical hollow bodies with wall thicknesses between 700 and 1000 μm were obtained, which could be filled with detergent or cleaning agents through a bunghole.

113

2. Manufacture _, of hemispheres:

Coated aluminum molds with ejector stamps were filled up to the upper edge with the melts listed in the table below and, after a certain dwell time, the non-solidified liquid was freed by rotating the mold by 10 °. The hemispherical hollow bodies were then removed from the mold and stored temporarily for further processing. At the same time, the solubility of the shaped bodies was investigated by placing the hemispheres in a 2-liter beaker, which was filled with 1 liter of distilled water at 25 ° C. and was moved at 60 rpm using a magnetic stirrer. The results of these tests are shown in the table below:

The hemispheres were filled with a detergent composition as an example and sealed. The detergent composition had the following composition:

The filled hollow bodies were closed with a polyvinyl alcohol film (type M6630, Greensol).

The portions according to the invention were distinguished by a firm bond between the film and the hollow body, so that no loss of active substance could occur.

Claims

claims

1. Detergent, cleaning agent or detergent portion contained in one or more dimensionally stable hollow body (s) with at least one compartment, comprising

(a) at least one wash-active, cleaning-active or rinse-active preparation;

(b) at least one enclosure which completely or partially surrounds the at least one preparation according to (a) from a non-pressed material which disintegrates under washing, cleaning or rinsing conditions and gives the hollow body (s) dimensional stability; and

2. Detergent, detergent or detergent portion according to claim 1, comprising a dimensionally stable hollow body comprising at least one washing-active, cleaning-active or rinsing-active preparation completely or partially surrounding a non-pressed material which can be disintegrated under washing, cleaning or rinsing conditions at least one compartment, the compartment (s) containing one or more wash-active, cleaning-active or rinse-active preparation (s).

3. Detergent, detergent or dishwashing portion according to claim 2, comprising two or more compartments containing one or more washing-active, cleaning-active or rinsing-active preparations) which are arranged in a surrounding manner.

4. Detergent, detergent or dishwashing detergent portion according to claim 1, comprising two or more dimensionally stable hollow bodies consisting of at least one washing-active, cleaning-active or rinsing-active preparation completely or partially surrounding enclosure from one or more disintegrable under washing, cleaning or rinsing conditions, non-pressed material (s) with at least one compartment each, the compartment (s) containing one or more washing-active, cleaning-active or rinsing-active preparation (s).

5. Detergent, detergent or dishwashing portion according to claim 4, wherein the two or more dimensionally stable hollow bodies consist of a plurality of non-pressed materials which can be disintegrated under washing, cleaning or rinsing conditions.

6. Detergent, cleaning agent or detergent portion in the form of an at least partially filled, divided into at least two compartments, comprising

(a) a washing, cleaning or rinsing active preparation, which comprises an enclosure (A) which is wholly or partly composed of one under washing, cleaning or rinsing conditions disintegratable, which gives the hollow body (s) dimensional stability, is not pressed, is surrounded;

7. washing, cleaning or detergent portion according to claim 6, characterized in that the enclosures (A) and (B) and optionally further enclosures to 20 to 90%, preferably to 30 to 60% and in particular to 40 to 70 % of their surface consist of dimensionally stable shells, optionally comprising one or more devices for compartmenting, while the rest is formed by a water-soluble film.

δ. Detergent, detergent or dishwashing detergent portion according to one of claims 6 or 7, characterized in that the enclosures (A) and (B) and, if appropriate, further enclosures are joined together in such a way that the part (d) which may not be present is formed Surface of the detergent, cleaning agent or detergent portion consists of at least δO%, preferably at least 90% and in particular exclusively of the non-pressed material which gives the hollow body (s) shape stability,

9. washing, cleaning or rinsing agent portion according to one of claims 6 to 8, characterized in that at least one washing, cleaning or rinsing active preparation is present in the enclosures (A) or (B) in liquid form.

10. washing, cleaning or rinsing agent portion according to one of claims 6 to 9, characterized in that at least one enclosure is transparent or translucent, the wall thickness of the whole or in part from a disintegrable under washing, cleaning or rinsing conditions, the non-pressed material imparting the hollow body (s) shape stability is 100 to 5000 μm, preferably 200 to 3000 μm, particularly preferably 300 to 2000 μm and in particular 500 to 1500 μm.

11. washing, cleaning or detergent portion according to one of claims 6 to 10, characterized in that the enclosures (A) and (B) are formed from an injection-molded half-shell sealed with film, the wall thickness of the half-shells of the enclosures ( A) and (B) is 100 to 1000 μm, preferably 150 to 700 μm and in particular 250 to 500 μm and the thickness of the film of the enclosure (A) is 10 to 200 μm, preferably 20 to 100 μm and in particular 40 to 60 μm and the thickness of the film of the enclosure (B) is 20 to 250 μm, preferably 40 to 200 μm and in particular 60 to 150 μm.

12. washing, cleaning or detergent portion according to claim 11, characterized in that the film of the enclosures (A) and (B) consists of thermoplastic polymers, the film of the enclosure (B) being soluble in the application liquor more slowly or with a delay is as the foil of the enclosure (A).

13. washing, cleaning or rinsing agent portion according to one of claims 11 or 12, characterized in that the connection of the enclosures (A) and (B) is carried out with a water-soluble hot melt adhesive, so that the portion in the application liquor within 60 s, preferably within 30 s, so disintegrated that the foil of the enclosures (A) or (B) comes into contact with the application liquor.

14. Detergent, cleaning or rinsing agent portion according to one of claims 11 to 13, characterized in that the enclosure (A) contains a non-surfactant-rich basic detergent composition, preferably a liquid detergent, while the enclosure (B) preferably contains a composition with further utility , in particular a bleaching composition and / or an enzyme composition and / or a fragrance preparation and / or a discoloration, graying or hardness inhibitor composition and / or a plasticizer composition.

15. Detergent, cleaning agent or detergent portion according to one or more of claims 1 to 14, wherein the dimensionally stable hollow body (s) is one or more water-soluble polymer (s), preferably a material 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).

16. detergent, detergent or detergent portion according to one or more of claims 1 to 14, wherein the dimensionally stable hollow body (s) comprises one or more materials from the group consisting of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene rolsulfonate, polyurethanes, polyesters and polyethers and mixtures thereof comprises.

17. Portioned detergent or cleaning agent with a detergent or cleaning agent composition, which is at least partially comprised of solidified material, characterized in that the enclosure has a wall thickness of 100 to 6000 microns and consists of a material which is delayed by water binding, by cooling below the melting point, by evaporation of solvents, by crystallization, by chemical Rekation (s), in particular _{polymerization.} by changing the rheological properties, for example by changing shear, by sintering or by means of radiation curing, in particular by UV, alpha-beta or gamma rays.

18. Portioned detergent or cleaning agent according to claim 17, characterized in that the enclosure consists of a material whose melting point is in the range from 40 to 250 ° C.

19. Portioned detergent or cleaning agent according to one of claims 17 or 18, characterized in that the enclosure covers at least 50%, preferably at least 60%, particularly preferably at least 70% and in particular at least 60% of the surface of the portioned agent.

20. Portioned detergent or cleaning agent according to one of claims 1δ or 19, characterized in that the enclosure comprises one or more substances from the groups of dicarboxylic acids, dicarboxylic acid anhydrides, hydrogen carbonates, hydrogen sulfates and / or urea in amounts of at least 40% by weight, preferably contains at least 60 wt .-% and in particular at least δO wt .-%, each based on the mass of the enclosure.

21. Portioned detergent or cleaning agent according to one of claims 17 to 20, characterized in that the detergent or cleaning agent composition included is in liquid, pasty, gel-like or particulate form or in the form of a suspension or emulsion and is completely enclosed by the enclosure.

22. Portioned detergent or cleaning agent according to one of claims 17 to 21, characterized in that the ratio of the masses of containment and content in the range from 10: 1 to 1: 1000, preferably from 2: 1 to 1: 100, particularly preferably from 1: 1 to 1:50 and in particular from 1: 5 to 1:25.

23. Detergent, cleaning agent or detergent portion according to claim 6 or 17, wherein the dimensionally stable hollow body (s) consist of several materials, preferably of similar materials with different properties.

24. Detergent, detergent or detergent portion according to one or more of claims 4 to δ, wherein two or more dimensionally stable hollow bodies have different shapes.

25. Detergent, cleaning agent or detergent portion according to one or more of claims 4 to 9, wherein the two or more dimensionally stable hollow bodies form a releasable bond, preferably releasably connected to one another by gluing, welding, fusing or clamping.

26. Detergent, detergent or dishwashing portion according to one or more of claims 1 to 10, wherein the compartmentalization device (s) (a) an activity reduction of at least one component of a washing-active, cleaning-active or rinsing-active component (s) ) is / are.

27. Detergent, cleaning agent or detergent portion according to one or more of claims 1 to 10, wherein the compartmentalization device (s) (one) the quality and / or quantity of the release of components of a washing-active, cleaning-active or rinsing-active The device (s) determining the preparation is / are.

2δ. Serving detergent, detergent or detergent portion according to claim 12, wherein the compartment (s) (s) the release of at least one component of a detergent-active, detergent-active or detergent-active preparation in a detergent. The cleaning or rinsing liquor by means of physicochemical parameter-controlling device (s) is / are, preferably (a) the release by means of disintegration after a certain time, at a certain temperature, at a certain pH, at a certain ionic strength, on the basis of a certain mechanical Stability and / or facility (s) controlling a certain permeability is / are.

29. Detergent, detergent or dishwashing portion according to one or more of claims 1 to 10, wherein the compartmentalization device (s) (a) control the activity of at least one component of a detergent-active, detergent-active or detergent-active device (s) ) is / are.

30. The detergent, detergent or dishwashing portion according to claim 14, wherein the compartmentalization device (s) are (a) a controlled release effect providing devices) or (a) disintegrable device (s), preferably Perforation-generating or generating device (s).

31. Detergent, detergent or dishwashing portion according to one or more of claims 1 to 15, wherein one or more compartmentalization device (s) contains / contain part or the total amount of at least one component of at least one detergent-active, detergent-active or detergent-active preparation ,

32. Detergent, cleaning agent or rinsing agent portion according to one or more of claims 1 to 15, wherein one or more compartmentalization device (s) consist in part or in total of at least one component of at least one washing-active, cleaning-active or rinsing-active preparation.

33. Detergent, cleaning agent or detergent portion according to one or more of claims 1 to 17, wherein the compartmentalization device (s) consists of an interface between two adjoining components of a washing-active, cleaning-active or rinsing-active preparation or an interface between two adjoining wash-active, cleaning-active or rinse-active preparations.

34. Detergent, detergent or detergent portion according to one or more of claims 1 to 16, comprising at least one, preferably more, wash-active, cleaning-active or rinse-active preparation (s) from the group consisting of anionic, non-ionic, cationic and amphoteric surfactants , Builder substances, bleaching agents, bleach activators, bleach stabilizers, bleaching catalysts, enzymes, polymers, cobuilders, alkalizing agents, acidifying agents, anti-deposition agents, silver protective agents, colorants, optical brighteners, UV protective substances, fabric softeners, rinse aids, in one for a washing, cleaning and Sufficient rinse cycle.

35. Detergent, detergent or dishwashing portion according to one or more of claims 1 to 19, comprising the at least one, preferably the plurality, washing-active, cleaning-active or rinsing-active preparation (s) in one or more forms from the group of powders, granules, extrudates, pellets, beads, tablets, tabs, rings, blocks, briquettes, solutions, melts, gels, suspensions, dispersions, emulsions, foams and gases.

36. A method for producing a portion of detergent, cleaning agent or dishwashing detergent contained in one or more dimensionally stable hollow body (s) with at least one compartment, comprising the steps that one or in a manner known per se manufactures several dimensionally stable hollow body (s), with the exception that processes for the manufacture of the hollow body (s) which are carried out under compression are excluded, this hollow body (s) optionally provided with one or more device (s) for compartmentalizing the dimensionally stable hollow body (s) and the compartment (s) are filled with at least one wash-active, cleaning-active or rinse-active preparation and, if appropriate, then subsequently the dimensionally stable hollow body, forming a partial or complete enclosure around the wash-active, cleaning-active or rinse-active preparation (s) ) closes.

37. A method for producing a detergent, cleaning agent or detergent portion contained in a hollow body which is at least partially filled and divided into at least two compartments, comprising the steps

(i) production of dimensionally stable hollow bodies, optionally comprising one or more devices for compartmenting;

(ii) filling the hollow bodies or compartments with washing-active, cleaning-active or rinsing-active preparations;

(iii) closing the dimensionally stable hollow bodies with the formation of closed enclosures (A), (B) and, if appropriate, further closed enclosures, in order to form the wash-active, cleaning-active or rinsing-active preparation (s);

(iv) connecting the closed enclosures (A) and (B) and optionally further enclosures and / or further washing, cleaning or rinsing active preparations in solid, dimensionally stable form for washing, cleaning or rinsing agent portions.

3δ. Process according to Claim 31, characterized in that step (i) comprises an injection molding process which is preferably carried out at a pressure between 100 and 5000 bar, preferably between 500 and 2500 bar, particularly preferably between 750 and 1500 bar and in particular between 1000 and 1250 bar preferably at temperatures between 100 and 250 ° C, preferably between 120 and 200 ° C and in particular between 140 and 160 ° C.

39. The method according to any one of claims 37 or 33, characterized in that the hollow bodies or compartments in step (ii) to 20 to 100%, preferably 30 to 95%, particularly preferably 40 to 90% and in particular 50 to 35% of their volume can be filled with washing, cleaning or rinsing active preparations.

40. The method according to any one of claims 37 to 39, characterized in that the closing of the hollow body is carried out by sealing with a water-soluble film, the film having a thickness of 1 to 150 microns, preferably from 2 to 100 microns, particularly preferably from 5 to 75 μm and in particular from 10 to 50 μm.

41. The method according to any one of claims 37 to 40, characterized in that the connection of the closed enclosures (A) and (B) and optionally further enclosures and / or further washing, cleaning or rinsing active preparations in solid, dimensionally stable form for washing -, Detergent or detergent portion in step (iv) by cold sealing, gluing with water-soluble hot melt adhesives, gluing with adhesive solutions or mechanical connection.

42. The method according to claim 36, wherein the manufacture of the dimensionally stable hollow body (s) is carried out by deep drawing, casting or injection molding.

43. A method for producing portioned detergents or cleaning agents, comprising the steps:

44. The method according to claim 43, characterized in that the open hollow form by delayed water binding, by cooling below the melting point, by evaporation of solvents, by crystallization, by chemical reaction (s), in particular polymerization, by changing the rheological properties, e.g. is produced by changing shear, by sintering or by means of radiation curing, in particular by UV, alpha-beta or gamma rays.

45. The method according to any one of claims 43 or 44, characterized in that steps i) and ii) are carried out simultaneously.

46. The method according to any one of claims 43 or 44, characterized in that steps i) and ii) are carried out in succession.

47. The method according to any one of claims 43 to 46, characterized in that the production of the open hollow mold in step i) is carried out by solidification of a melt, the 123

The melt consists of a material whose melting point is in the range from 40 to 1000 ° C., preferably from 42.5 to 500 ° C., particularly preferably from 45 to 200 ° C. and in particular from 50 to 160 ° C.

48. The method according to any one of claims 43 to 46, characterized in that the production of the open hollow mold in step i) is carried out by time-delayed water binding, the solidifying mass based on its weight 10 to 95 wt .-%, preferably 15 to 90 % By weight, particularly preferably 20 to 85% by weight and in particular 25 to 80% by weight of anhydrous substances which cure by hydration.

49. The method according to any one of claims 43 to 46, characterized in that the production of the open hollow mold in step i) is carried out by evaporation of solvents, the solidifying mass based on its weight 1 to 50 wt .-%, preferably 2 to 40 % By weight and in particular 5 to 30% by weight of vaporizable solvent.

50. The method according to any one of claims 43 to 46, characterized in that the production of the open hollow mold in step i) is carried out by sintering, the flowable mixture being solidified by the action of temperature or chemical reaction.

51. The method according to any one of claims 43 to 50, characterized in that the hollow mold produced in step i) wall thicknesses of 100 to 6000 microns, preferably from 120 to 4000 microns, particularly preferably from 150 to 3000 microns and in particular from 200 to 2500 microns has, wall thicknesses below 2000 microns are preferred.

52. The method according to any one of claims 43 to 51, characterized in that in step i) an open die shape is filled with the flowable shell material and the excess mass is emptied after a time t between 0 and 5 minutes.

53. The method according to any one of claims 43 to 51, characterized in that in step i) an open die form is filled with the flowable shell material and the material is pressed by a stamp on the walls of the mold and a hollow mold is thus produced.

54. The method according to any one of claims 43 to 51, characterized in that in step i) a closable double mold is filled with the later solidifying mass and is moved for a time t between 0 and 5 minutes.

55. The method according to any one of claims 47 or 51 to 54, characterized in that the melt in step i) one or more substances from the groups of carboxylic acids, carboxylic anhydrides, dicarboxylic acids, dicarboxylic anhydrides, bicarbonates, hydrogen sulfates, polyethylene glycols, polypropylene glycols, sodium acetate trihydrate and / or urea in amounts of at least 40% by weight, preferably at least 60% by weight and in particular at least 80% by weight, in each case based on the melt.

56. The method according to any one of claims 43 to 55, characterized in that the hollow form has flange parts and is sealed in step iii) by welding with a further hollow form.

57. The method of claim 36 or 42, wherein the manufacture of the dimensionally stable, optionally one or more means (s) for compartmentalizing hollow body) is effected by injection molding.

53. The method according to one or more of claims 36 or 42 to 43, wherein the dimensionally stable, optionally one or more device (s) for compartmentalizing comprising is / are made incompletely closed, the one or more in the incompletely closed hollow body The compartment (s) formed is / are filled with at least one washing-active, cleaning-active or rinsing-active preparation and, if appropriate, the hollow body (s) is closed to form a partial or complete enclosure of the at least one washing-active, cleaning-active or rinsing-active preparation.

59. The method according to claim 58, wherein dimensionally stable, non-spherical hollow bodies having n delimiting surfaces are produced as blanks with (n-1) surfaces and optionally one or more means (s) for compartmentalizing by injection molding, the / those formed in the blanks (n) compartment (s) is / are filled with at least one wash-active, cleaning-active or rinse-active preparation and the filled blank is completely closed while applying the nth delimiting surface of the hollow body (s).

60. The method according to claim 36 and 42, wherein one or more washing-active, cleaning-active or rinsing-active preparation (s) are filled into compartments which are completely surrounding one another, preferably concentrically or coaxially arranged with one another, or are brought into the form of compartments arranged concentrically or coaxially with one another and these, if necessary together with one or more washing-active, cleaning active or rinse-active preparation (s), introduced into a separately produced dimensionally stable molded body and this is optionally completely sealed.

61. A process for producing a detergent, cleaning agent or detergent portion contained in one or more dimensionally stable hollow body (s) with at least one compartment

(a) at least one wash-active, cleaning-active or rinse-active preparation;

(c) optionally one or more means (s) for compartmentalizing the dimensionally stable hollow body (s), comprising the steps

(v) production of the dimensionally stable hollow body (s), optionally comprising one or more devices) for compartmentalization, by injection molding;

(vi) filling the compartment (s) with at least one wash-active, cleaning-active or rinse-active preparation;

(vii) if necessary, subsequently closing the dimensionally stable hollow body (s) to form a partial or complete enclosure around the washing-active, cleaning-active or rinsing-active preparation (s).

62. The method according to claim 61, characterized in that step (i) is carried out at a pressure between 100 and 5000 bar, preferably between 500 and 2500 bar, particularly preferably between 750 and 1500 bar and in particular between 1000 and 1250 bar.

63. The method according to any one of claims 61 or 62, characterized in that step (i) is carried out at temperatures between 100 and 250 ° C, preferably between 120 and 200 ° C and in particular between 140 and 180 ° C.

64. The method according to any one of claims 61 to 63, characterized in that the wall thickness of the enclosure (b) produced in step (i) is 100 to 5000 μm, preferably 200 to 3000 μm, particularly preferably 300 to 2000 μm and in particular 500 to 1500 μm.

65. The method according to any one of claims 61 to 64, characterized in that the enclosure (b) produced in step (i) comprises one or more materials from the group consisting of acrylic acid containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof.

66. The method according to any one of claims 61 to 65, characterized in that the enclosure (b) produced in step (i) comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol ( PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).

67. Process for the production of hollow bodies by injection molding, characterized in that the injection molding composition comprises one or more water-soluble polymer (s), preferably one or more materials from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, Polyethylene oxide, gelatin, cellulose, and their derivatives and their mixtures, particularly preferably (optionally acetalized) polyvinyl alcohol (PVAL).

68. The method according to claim 67, characterized in that the injection molding compound comprises a polyvinyl alcohol, the degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 8δ mol% is.

69. The method according to any one of claims 67 or 68, characterized in that the injection molding compound comprises a polyvinyl alcohol, the molecular weight in the range of 10,000 to 100,000 gmol ^"1 , preferably from 11,000 to 90,000 gmol ^{" 1} , particularly preferably from 12,000 to δθ,000 gmol ^"1 and in particular from 13,000 to 70,000 gmol ^{" 1} .

70. The method according to any one of claims 67 to 69, characterized in that the injection molding compound said polymers in amounts of at least 50 wt .-%, preferably at least 70 wt .-%, particularly preferably at least 60 wt .-% and in particular of at least 90 wt .-%, each based on the weight of the injection molding compound.

71. Washing method, in particular method for machine washing in a commercially available washing machine, comprising the steps of introducing a detergent portion according to one of claims 1 to 20 into the washing machine, in particular into the washing-up chamber or washing drum; sets the desired washing conditions; and when these conditions occur, the wash-active preparation (s) of the detergent portion are placed in the wash liquor and bring them into contact with the items to be washed.

72. A cleaning method comprising the steps of adding a detergent portion according to any one of claims 1 to 20 to the cleaning liquor; sets the desired cleaning conditions; and when these conditions occur, the cleaning-active preparation (s) of the detergent portion are added to the cleaning liquor and bring them into contact with the items to be cleaned.

73. Washing method, in particular method for machine washing in a commercially available dishwasher, comprising the steps of entering a detergent portion according to claims 1 to 20 into the dishwasher, in particular into its washing-up chamber or into its washing compartment; sets the desired rinsing conditions; and when these conditions occur, the rinse-active preparation (s) of the detergent portion are added to the rinse liquor and bring them into contact with the items to be rinsed.