EP1100864A1

EP1100864A1 - Composition for use in a dishwashing machine

Info

Publication number: EP1100864A1
Application number: EP99944979A
Authority: EP
Inventors: Guido Waeschenbach; Ralf Wiedemann; Enric Carbonell; Ludwig Hertling; Natascha Wolf
Original assignee: Reckitt Benckiser NV
Current assignee: Reckitt Benckiser NV
Priority date: 1998-07-29
Filing date: 1999-07-29
Publication date: 2001-05-23
Also published as: CA2338710A1; WO2000006688A1; CA2338710C; US6800598B1; DE29919579U1; AU5768899A

Abstract

The invention relates to a composition for use in a dishwashing machine, characterized in that it consists of a base composition which becomes active substantially during the main wash cycle of the dishwashing machine; at least one particle having at least one core which contains at least one substance which becomes active substantially during the rinse cycle of the dishwashing machine; and a coating which substantially fully encloses the core(s) and contains at least one compound whose solubility increases as the concentration of a specific compound in the surrounding medium decreases. The invention provides for means to prevent a significant dissolution of the coating or a significant detachment of the coating from the core(s) until the start of the rinse cycle. The invention also relates to methods for running the dishwashing cycle in a dishwashing machine using the composition provided for by the invention.

Description

COMPOSITION FOR USE IN A DISHWASHER

The present invention relates to a composition for use in a dishwasher and a method for using it.

Although modern dishwashers in most cases have a large number of different wash programs, which differ in the duration and temperature of the individual wash cycles, all wash programs essentially consist of the following basic steps: pre-wash cycle; Main cleaning cycle; one or more intermediate rinse cycles; a rinse aid; and drying. While the actual machine dishwashing detergent, which is supposed to develop the cleaning effect, is added at the beginning of the main cleaning cycle, special agents are used in the rinse cycle, for example rinse aid. Rinse aids are intended to prevent water droplets from remaining on the dishes when rinsing with water, which, after drying, leave stains from dispersed substances / salts dissolved in the drops.

These two functionalities, namely on the one hand the cleaning action of the machine dishwashing detergent and on the other hand the described function of a rinse aid, have hitherto been achieved via two products metered in with separate metering devices and at different times in the dishwashing cycle.

In addition to the use of rinse aid, there is still a need for other substances that could develop their activity in the rinse cycle, e.g. antibacterial activity (e.g. cationic compounds or triclosan), silver preservatives (e.g. benzotriazole), fragrance (fragrances, perfume), bleaching / disinfection (e.g. chlorine bleach), odor masking agents (e.g. polyvinylpyrrolidone), anti-scale agents and enzymes for additional purposes (e.g. lipase to remove fat deposits in the dishwasher). However, today's dishwashers do not provide suitable dosing systems for this.

The aim of the present invention was to combine the detergent function and the function (s) of the substance (s) to be added in the rinse cycle, with the performance being as constant as possible compared to the results which can be achieved with a separate dosage 1 Hkim; ; : v. vci Lπm'u. V; v. du ncTFicrmu 'anderci substances as rinse aid in rinse aid'ant; to enable.

From the German laid-open documents 20 65 153 and 20 07 413 detergent tablets for use as detergents are known, in which, among other things, it is provided to combine two components with different functionality. In this case, a structure is provided from an enveloping shell, which is composed, for example, of two shell halves, which consist of a cleaning agent, and a cavity enclosed by the shells, which contains additives such as plasticizers, whitening agents, etc.

British Patent 1,390,503 discloses a liquid detergent which contains capsules which are insoluble in the composition but which release their contents when the composition is diluted with water. This goal is achieved in that the capsules are coated with a substance which has poor solubility in water solutions with high ionic strength, but becomes soluble when the ionic strength is reduced by dilution. It is noted that this technique can be used to include in the liquid detergent materials that are unstable in the liquid detergent itself or would create instability if added directly. It is also proposed to use this technique to delay the release of a specific substance. The use in machine dishwashing detergents is addressed and is proposed for the encapsulation of tribromosalicylanilide in order to stabilize it. The encapsulated material is removed within 2 minutes after diluting the detergent with water, i.e. already released in the main cleaning cycle.

US Pat. No. 4,082,678 describes a fabric conditioning product which comprises a closed container which contains a releasable agent which serves to insoluble or non-dispersible an inner container, which is normally water-soluble or water-dispersible, arranged in the container make, wherein the inner container contains a fabric conditioning agent. The inner container consists of a substance whose solubility in water is strongly dependent on the ionic strength or on the pH of the medium, and the agent which serves to make the inner container insoluble is a means of controlling the pH or the ionic strength. You ü. mi chi Pi.icnu.nnjeldurji. he, K OL A] ⁽ ι ⁽ -1417 (ι. <->] -2844κ M -2844 LM H-2859 ^' and 61 -28598 describe the production of pH-sensitive microcapsules for use in detergents. The pH-sensitive coating is a copolymer of the following monomers:

A) at least one basic monomer of the formula I:

RR ¹ i /

CH ₂ = C-COO (CH ₂ ) _x N

in which R is hydrogen or a methyl group, R ¹ and R ^{2 are} each an alkyl group with 1-3 carbon atoms and x is an integer from 1 -4;

B) at least one monomer that is insoluble or poorly soluble in water; and

C) at least one water-soluble monomer.

The polymers described are said to be insoluble at pH 9.5 or more and to become soluble at pH 8.5 or less. Different ingredients of detergent compositions are described, which can be coated successfully and effectively by the polymers described. The aim of the invention described there is to protect substances that are only supposed to develop their function in the rinse cycle until the beginning and then to release them as soon as possible. The use for dishwashers is not described.

A disadvantage of the solution described in these Japanese patent applications is that the coated particles are in direct contact with non-alkaline wash water at the start of the washing cycle, which can result in the protective coating becoming detached.

From Japanese patent KOKAI 50-77406 a washing aid is known which is surrounded by a water-soluble coating which is obtained by mixing polyvinyl acetal dialkylaminoacetate and at least one organic acid which is solid at room temperature. This protective cover is intended to be used during the washing aid Hiiupl aschεϊinges protect unc while releasing the rinse cycles. The described λ egg binding reacts to the change in pH between the main wash cycle and the rinse cycles. The appropriately coated particles are mixed with conventional powder detergent. Here, too, there is the disadvantage that the protective covering may become detached at the beginning of the washing cycle.

From European patent applications EP 0 284 191 A2 and 0 284 334 A2 a water-soluble polymer film for releasing washing additives in the washing cycle of washing machines is known, which remains intact during the normal washing cycle over a range of typical temperatures and dissolves quickly in the washing cycle. The applications point out that although the use of pH-sensitive coatings is well known, these films are normally also temperature-sensitive, so that they are not reliably stable during different wash cycle temperatures. As a solution, it is proposed to combine a pH-dependent material (which undesirably also shows a positive temperature-dependent dissolution behavior) with a material which shows a negative temperature-dependent solution behavior. This combination is intended to guarantee that the coatings will not come off at the high temperatures at the beginning of the wash cycle (especially the very high temperatures that occur in American machines). A use for machine dishwashing liquid is not addressed.

European patent application EP 0 481 547 A1 discloses multi-layer dishwasher detergent tablets with a core, a separating layer surrounding the core and an outer layer for the sequential release of the contents of the different layers. Basically, two tasks are to be solved with this tablet, namely 1) incompatible materials can be formulated together in a single tablet and released at different times in order to avoid mutual interference; and 2) Compositions that are designed to perform their functions at different times can be formulated in a single tablet.

A major disadvantage of this prior art is that the temperature and / or especially the contact time with the washing solution is used as a triggering factor for the initiation of the dissolution of the coating layer, ie for the material of the coating temperature-sensitive painting can be used. Since the temperature course in dishwashers can vary greatly depending on the program selected, it is difficult, if not impossible, to select a material for the cover that can be used for all possible programs in modern dishwashers. EP 0 481 547 AI itself admits (page 7, lines 37-43) that the selection of the material of the cladding layer must take into account device-specific and program-specific features. The practical usability of the products described is therefore clearly limited.

PCT application WO 95/29982 discloses a delayed-release machine dishwashing detergent in the form of a non-ionic surfactant, this non-ionic surfactant, together with an inorganic builder salt, forming a core particle which is provided with a wax-like coating to compensate for the delayed release Ensure release. This coating is a substance that does not melt at the working temperatures found in the cleaning cycle, but is gradually chemically disintegrated at alkaline pH so that an effective amount of the rinse aid remains at the end of the main cleaning cycle and is transferred to the rinse cycle.

The disadvantage of this is that the coating is made soluble by chemical saponification at alkaline pHs, so that the point in time at which the rinse aid substance is released from the core is a function of both the temperature and the length of the main cleaning cycle. The patent application does not contain any teaching on how to formulate a product with which the rinse aid is only released in the rinse cycle in all washing programs of every device type. In addition, the core active ingredient as rinse aid is a nonionic surfactant that is absorbed on an inorganic builder salt. This provides inferior rinse aid results, especially staining on glass. After all, the product is a mixture of granular detergent and granular rinse aid particles.

In view of the prior art described, the present invention is based on the object of creating a generic composition which can be used for most washing programs of various types of dishwasher and in each of these cases the substance (s) which have their action essentially only in the final rinse cycle should unfold, at the earliest at the beginning of the rinse cycle. The aim is to do this without restricting the selection for the cleaning medium. the substance used! eπ) for the rinse cycle and other ingredients of the composition.

According to the invention, this object is achieved with a generic composition which is characterized by a basic composition which essentially functions in the main cleaning cycle of the dishwasher; and at least one particle, having at least one core, which comprises at least one substance which functions essentially in the rinse cycle of the dishwasher, and an envelope which essentially completely surrounds the core (s) and which comprises at least one compound whose Solubility increases with decreasing concentration of a specific compound in the surrounding medium; means are provided to prevent a substantial dissolution of the covering or a substantial detachment of the covering from the core (s) by the start of the rinse cycle.

In an advantageous embodiment, the concentration of the specific compound in the local environment of the particle (s) is sufficiently high until the start of the rinse cycle in order to achieve a substantial dissolution of the covering or a substantial detachment of the covering from the core or to prevent from the cores.

Furthermore, it is preferably provided that the particle (s) is (are) coated with a substance which - largely independently of the concentration of the specific compound in the surrounding medium - dissolves or dissolves in the course of the main wash cycle of the dishwasher.

It is preferably provided that the base composition is in the form of a tablet.

One embodiment of the invention proposes that the at least one particle is arranged in or on the tablet in such a way that the concentration of the specific compound in the local environment of the particle (s) is sufficiently high until the tablet has completely dissolved to prevent a substantial dissolution of the casing or a substantial detachment of the casing from the core or cores. Special? it is preferred that the or. all particles are taken up in at least one cavity of the tablet completely surrounded by the base composition.

The at least one cavity may contain one or more particles which alone or taken together have (have) essentially the same volume as the cavity.

It is preferred that the at least one cavity has a larger volume than the or all of the particles that are or are accommodated in the respective cavity.

In an alternative of the invention, the particle (s) is (are) loosely arranged inside the cavity.

In another alternative, the particle (s) is (are) fixed in the interior of the cavity, preferably by an adhesive.

In a further embodiment it can be provided that the cavity is arranged essentially centrally in the interior of the tablet.

The invention also proposes that the tablet have a single, substantially spherical cavity.

It is provided according to the invention that a single, essentially spherical particle is accommodated in the cavity, the outside diameter of which is smaller than the inside diameter of the cavity.

In a further embodiment it is provided that the or all particles are or are received in at least one cavity of the tablet which is only partially surrounded by the base composition. It is still audited. that the cavity is a recess of one of the surfaces of the tablet. in which the particle (s) is (are) at least partially accommodated.

In a preferred embodiment it is provided that the particle is (are) received in the cavity or the recess such that it does not protrude above the surface (s) of the tablet.

In a particular embodiment, the invention proposes that the cavity or the depression contains only a single particle, the volume and shape of which in the region of the cavity or the depression corresponds substantially to the volume and the shape of the cavity or the depression and that this ( this) essentially completely.

It is preferably provided that the cavity or the depression has an essentially circular cross-sectional area parallel to one of the surface (s) to which it opens or in which it is arranged.

The invention also proposes that the cavity or recess only open to the surface (s) to the extent that the particle (s) contained therein does not pass through the opening (s) of the cavity or recess can (can).

It is preferred according to the invention that the particle (s) is (are) loosely arranged in the cavity or in the depression.

In a further alternative it is provided that the particle (s) is (are) fixed in the cavity or in the depression, preferably by means of an adhesive.

In one embodiment of the invention it is provided that the base composition comprises at least one composition which is selected from the group consisting of a dishwasher detergent composition, a water softener composition and a washing intensifier composition. In a preferred embodiment of the invention it is provided that the covering comprises at least one compound which is not or only slightly soluble at the concentration of the specific compound at the end of the main cleaning cycle of the dishwasher and which shows such a sufficient solubility at the concentration of the specific compound in the rinse cycle that it is so largely dissolved in the rinse cycle or detached from the core (from the cores) that an at least partial escape of the core material into the medium of the rinse cycle is made possible.

It is preferably provided that the solubility of the compound increases with a decreasing OH ion concentration and thus a decreasing pH in the surrounding medium.

It is particularly preferred that the compound shows no or only a low solubility at a pH value above 10 and shows such a sufficient solubility at a pH value below 9 that it is so largely dissolved in the rinse cycle or from the core (from the Cores) is replaced that an at least partial escape of the core material in the medium of the rinse aid is made possible.

It is further preferred that the compound comprises a polymer, preferably a pH sensitive polymer, which comprises at least one repeating unit which has at least one basic function which is not part of the backbone chain of the polymer.

In a preferred embodiment, the polymer comprises at least one repeating unit which is based on a compound which is selected from the group consisting of vinyl alcohol derivatives, acrylates or alkyl acrylates which comprise said basic function.

The invention also provides that the polymer is a carbohydrate that is functionalized with said basic function.

The above-mentioned basic function is preferably an amine, particularly preferably a secondary or tertiary amine. In a preferred alternative, the repetition unit is based on a connection using the following formula III:

where G is a linking group which is selected from -COO-, -OCO-, -CONH-, - NHCO-, -NHCONH-, -NHCOO-, -OCONH- or -OCOO-, Ri independently of one another hydrogen or an alkyl group with Is 1-3 carbon atoms, R is independently hydrogen or an alkyl group of 1-5 carbon atoms and x is an integer from 1 to 6.

The repetition unit is preferably based on a compound with the following formula TV:

wherein R] is independently hydrogen or an alkyl group with 1-3 carbon atoms, R _{2 is} independently hydrogen or an alkyl group with 1-5 carbon atoms and x is an integer from 1 to 6.

Another embodiment provides that the basic function is an imine or a basic aromatic N-containing group, preferably a pyridine group or an imidazole group. In yet another embodiment it is provided that the pH-sensitive polymer is a polymer derived from chitosan.

Finally, the invention proposes that the compound comprise K-carrageenan.

In a particular embodiment of the invention it is provided that the core (s) comprise (s) at least one material selected from the group consisting of surfactants, antibacterial compositions, silver protection agents, fragrances, bleaches, disinfectants, There are agents for masking odors, anti-slip agents and enzymes.

It can be provided that the core or at least part of the cores is in the form of an encapsulated liquid, preferably in the form of a liquid contained in a gelatin capsule.

In a further embodiment it is provided that the core or at least part of the cores is in a solid form.

It is preferred that the core or at least some of the cores have a melting point of more than 35 ° C., preferably between 55 and 70 ° C.

The invention further relates to a method for carrying out a dishwashing cycle in a dishwasher, in which the composition according to the invention is added to the medium in the dishwasher at a suitable point in time during the pre-wash cycle or the main cleaning cycle.

In a special embodiment of the invention it is provided that, in the event that the base composition in the form of a tablet is not able to provide a concentration of the specific compound in the medium after its dissolution in the medium until the end of the main cleaning cycle, which is sufficiently high to be an essential one To prevent disintegration of the coating and substantial detachment of the coating from the core (s), this sufficient concentration of the specific compound is provided to the medium of the main cleaning cycle at an appropriate time by the addition of a further composition, such as, for example, a dishwasher detergent composition.

The composition according to the invention is distinguished by the fact that it delivers excellent results both in the main cleaning cycle and in the rinse cycle of a dishwasher. The basic composition, e.g. in the form of a tablet, is released during the main cleaning cycle and can develop its corresponding effect (cleaning, water softening, washing reinforcement, etc.). As the core material, the particle according to the invention contains the substance or substances which are intended to develop their main function in the rinse aid of the dishwasher, for example rinse aid.

This substance (s) is (are) protected by a coating which is stable at the concentration of a specific compound, for example a specific ion such as the OH ^' ion (and thus at a specific pH), and the temperature of the main cleaning cycle and does not dissolve or detach only insignificantly. Only when this concentration drops significantly due to dilution, ie at the beginning of the rinse cycle, is the solubility of the wrapping material reduced to such an extent that it quickly dissolves or dissolves and releases the actually effective core material into the surrounding medium. It is essential that the protection of the core material is effective from the addition of the composition according to the invention to the water until the start of the rinse cycle, ie even before the cleaning liquor reaches a sufficiently high concentration of the specific compound, as will be explained in more detail below.

As an alternative to the tablet form of the base composition which is preferably used, other dosage forms are also possible and are included in the scope of protection of the present invention. Thus, the particles with the coating which changes in solubility in response to a change in the concentration of the specific compound can be connected, for example coated, to the base composition by a granulation process or a similar process. In order to ensure any desired reduced contact between the casing and the base composition for this embodiment, the particles can be surrounded with a further protective jacket, which consists, for example, of a compound which is soluble in water regardless of the concentration of the specific compound. With this embodiment, the basic composition and the protective coating of the particles would also first be released during the main cleaning cycle and the particles protected with the coating according to the invention would again be left behind.

Unless the metering is provided by means of special metering aids which can hold back the particles according to the invention, the particles according to the invention should be selected so large that they are at least not discharged from the dishwasher to a significant extent during the pumping down after the main cleaning cycle and the intermediate rinsing cycle or rinsing cycles become.

The invention will now be described in more detail with reference to the following examples and drawings. In the drawings:

1 shows a typical pH profile of a dishwasher;

2 shows a first embodiment of the composition according to the invention in cross section;

3 shows a second embodiment of the composition according to the invention in cross section;

4 shows a third embodiment of the composition according to the invention in cross section;

5a and b show a fourth embodiment of the composition according to the invention in cross section and in plan view; and

Fig. 6 shows a fifth embodiment of the composition according to the invention in cross section.

Basically, the ion concentration or pH profiles of the cleaning or rinsing medium in a dishwasher depend on the contents of the cleaning or rinsing agents used. A typical pH profile when using a common basic Machine dishwashing detergent, for example CALGONlTd, results from Fig. 1 (dishwasher used: BOSCH model SMS 3047).

The vertical dashed division indicates the duration of the following steps: pre-rinsing, main cleaning, intermediate rinsing, rinsing. It is clear that the pH is in the range of 10.0 and 10.5 during most of the main cleaning cycle. After pumping out the wash liquor at the end of the main cleaning cycle and adding fresh water, the pH drops to a value of 9.0 during intermediate rinsing and to a value between 8.5 and 9.0 during rinsing.

2 to 6 show possible embodiments of the composition according to the invention. In all cases, the preferred tablet form is chosen for illustration.

Fig. 2 shows a tablet 1, which consists of two half-tablets 2 and 3, which may have different or the same composition. For example, one of the customary, commercially available 2-layer tablets can be used as a basis, in which the two layers usually have a different composition and are colored differently.

A roughly hemispherical recess 4 or 5 can be seen approximately in the center of both half-tablets, which when the tablet 1 is joined together form an approximately spherical cavity.

In the illustrated embodiment, a single particle 6, consisting of the core 8 and the sheath 9, is accommodated in this cavity, the outside diameter of which is slightly smaller than the inside diameter of the cavity in the tablet. In another embodiment of the invention, however, particle 6 can also completely fill the entire cavity of the tablet and rest on the walls thereof. If the inside diameter of the cavity is slightly larger than the outside diameter of the particle 6, this can either be loosely received in the cavity or fixed by an adhesive placed in the gap. In the embodiment in which the contact between the particle and the base composition surrounding it is reduced or completely prevented, there is the additional advantage that the manufacturing process, for example the pressing of the individual components in successive steps, causes deformation and possibly consequent damage of the core (the cores) and / or the coating of the core is reliably avoided, which could result in a reduction in the protective effect of the coating of the core (the cores). By preventing pressure on the particle at any stage in the manufacturing process, it can also be reliably prevented from "bleeding" into the material of the cladding and base composition at a particular composition of the core (s) Finally, with certain compositions of the casing 9 or the base composition 2, 3, it may be advantageous to avoid intimate full-surface contact, since otherwise undesirable reactions could occur in the boundary layers.

In a preferred embodiment of the invention it is provided that the surface of the particle is at most partially in direct contact with the surface of the basic composition of the tablet surrounding it. This can be done in the ways specifically described and illustrated in this application, but also in any other way with which the intended purpose is achieved. Examples are the loose arrangement of a smaller particle in a larger cavity, the fixing of a smaller particle in the larger cavity in such a way that there is no or only partial contact between the particle and the base composition, the application of a protective coating over the covering of the core according to the invention , Etc..

The term “local environment” as used in connection with a particular embodiment of the particle according to the invention is intended to denote the immediate environment around this particle. The concentration of the specific compound in this local environment of the particle is the determining factor for its stability. In the preferred embodiments in tablet form, this concentration in the local environment of the particle is determined, at least until the tablet is essentially completely dissolved, by molecules dissolving from it. The origin of the “specific compound” is therefore preferably - at least in the initial phase of the Main cleaning cycle - a compound of the basic composition forming the tablet or is generated by this in the surrounding medium. In the most typical case, the usual basic dishwashing detergents are OH ^" ions, the concentration of which can be expressed as pH.

If a (e.g. basic) machine dishwashing detergent composition is not used as the basic composition, but e.g. a water softener composition or a washing booster composition, the protection of the coating of the particle can only be ensured by a sufficiently high concentration of the specific compound in the local environment of the particle until the basic composition, e.g. the tablet is completely dissolved, namely in cases where the base composition is not able to provide a sufficiently high corresponding concentration in the wash liquor. In these cases, the sufficiently high concentration in the wash liquor (and thus also in the local environment of the particle (s)) is achieved by dissolving the actual dishwasher detergent (or another special additive).

Of course, not only a conventional adhesive can be used to fix the particle in the cavity, but also other compositions and agents that serve the same purpose, for example mechanical fixation, such as e.g. sufficient friction between the tablet and particles in at least some places or a plug connection between the tablet and particles. In addition, other compounds, preferably melting or dissolving during the main cleaning cycle, are also possible as fixing agents between the particle and the tablet.

Of course, various other geometric shapes are possible for the design of the cavity in the tablet or the particle accommodated therein, such as, for example, ellipsoid, cylinder, etc. The shape and size of the cavity in the tablet and that of the particle accommodated therein do not have to be correspond with each other. For example, a cylindrical particle can be accommodated in a spherical cavity. All possible further possible combinations are conceivable within the scope of the present invention. It is also possible to fill the cavity not only with one particle, but with several smaller particles. FIG. 3 shows a second embodiment of the composition according to the invention on the basis of a conventional 2-layer tablet 1. Here, the upper half tablet 3 consists of two parts, which both provide a sufficient cavity 5 for receiving the particle 6 and an opening to the side 11 of the tablet. In this case, the particle 6 is therefore not completely surrounded by the basic composition of the tablet 1, so that it is visible from the outside in the interior of the tablet 1. In this case, too, the particle in the cavity 5 can either be loosely received (provided that by appropriate selection of the size of the particle 6 on the one hand and the size of the opening of the cavity 5 to the side 11 of the tablet it is ensured that the particle or particles in the cavity do not pass through the opening can or can pass through) or be fixed in the interior of the cavity 5 by appropriate means, such as or adhesive.

A third possible embodiment results from Fig. 4. This time, the basis is provided by a tablet 1 ', which has a uniform structure, i.e. consists only of a layer 2 'with a uniform composition and color. A recess 4 'is formed in this layer 2' by means of a suitable device. In this recess 4 'the particle 6' is introduced, which in this case, since the recess on the side 11 'of the tablet 1 is open to the extent that without fixation, the particle could fall out of the recess, for example with an adhesive 10 'or a fixing intermediate layer or mechanically (eg by friction) in the recess. Of course, this principle can also be applied to multilayer tablets.

In this case too, a wide variety of geometric embodiments are possible. For example, the depression can have an essentially circular cross section parallel to the side 11 '. However, any number of other cross sections is also conceivable, for example any polygon. As in the embodiment according to FIG. 3, the particle 6 'accommodated in the depression 4' can take on any shape (such as ellipsoid, cylinder, cuboid, etc.) (and is independent of the shape of the depression 4 ').

It can also be considered to fix the particle 6 'in a cavity open on both sides in the tablet, for example in a cylindrical hole 4' passing through the tablet body 1 ', in which a corresponding cylindrical particle 6' is fixed (Fig. 5a and b). A further possible embodiment results from FIG. 6. This is essentially structured like the embodiment according to FIG. 4, ie a tablet 1 ', which is constructed uniformly, ie only from a layer 2 "with a uniform composition and color In the present case, however, the particle 6 "does not only contain a core (as in FIG. 4), but also a multiplicity of cores 8", which are all embedded in an envelope 9 ". In this embodiment, it is also possible, for example, to incorporate cores of different composition and different shape (encapsulated material or solid cores) into a 6 "particle.

Both in the illustrated embodiments and in other conceivable alternatives, it is essential that for the particles containing the substance (s) to be released in the rinse cycle, at least in the first phase of the main cleaning cycle, a local environment with a sufficient concentration of the specific compound, which as "Trigger" for the dissolution of the envelope is present, ie in a phase in which this concentration is still relatively low, i.e. is briefly in an area in which there would be an increased solubility of the coating. In this way it is ensured that the covering has sufficient stability up to the final rinse cycle.

example 1

Manufacture of the core

a. Core for a particle for the controlled release of a rinse aid in the rinse aid cycle

The core of the particle or particles, which is only supposed to develop its actual activity in the rinse aid cycle, must include at least one substance which acts as a rinse aid with this target. A low-foaming, nonionic surfactant is advantageously used in the present invention. Such surfactants are, for example, fatty alcohol ethoxylates, fatty alcohol ethoxylate / propoxylates, ethoxylate / propoxylate polymers, such as, for example, the products from the Synperonic® and Brij® series from ICI, the products from the Plurafac®, Pluronic® and Lutensol® series from BASF, the products from the Genapol® series from Clariant, and the products from the Poly-tergent® series from Olin.

Other possible examples of non-ionic surfactants are alkyl polyglycosides, glucamides and alkyl pyrrolidones. In addition, of course, all other surfactants can be considered that can develop the desired effectiveness as rinse aid.

Most of the substances known for use as rinse aid are liquids or waxy solids. For the use in the present invention, however, the state of matter of the substance which acts as a rinse aid does not play a decisive role. If liquids are to be used, they can be capsule-containing, e.g. Gelatin capsules are presented or are transferred in a wrappable state by other suitable measures. Solids can usually be provided directly with the coating, the coating method possibly having to be based on the corresponding substance.

For the purposes of the present invention, melt mixtures have proven to be particularly advantageous which provide solid surfactant particles with a melting point of more than 35 ° C., preferably between about 55 to 70 ° C.

The combinations of various polyethylene glycols resulting from the following Table 1 with the surfactant Synperonic RA 30, a block ethylene oxide / propylene oxide bound to a C ₁₃ -C ₁₅ alcohol, (C ₁₃ / Ci ₅ θ (EO) ₆ (PO ) ₃ ), were produced as melt mixtures in the form of cylinders weighing approximately 0.25 g. The melting point determinations gave the values given in Table 1. Table 1

Although all combinations can be regarded as fundamentally suitable, the 50:50 mixture A33 in particular showed outstanding stability and was easy to handle, especially with regard to the subsequent coating process. All samples showed rapid dissolution in water, so that optimal activity as rinse aid is guaranteed in every case.

Of course, the invention is in no way limited to the combinations shown as examples. Basically - as already stated - any type of surfactant that can be used as rinse aid can be used in the present invention. b. Core for a particle for the controlled release of a fragrance in the rinse aid

Bleach-containing, i.e. Oxidizing dishwashing detergent compositions severely limit the uses of fragrances that can be used in such compositions. The controlled release of a fragrance in the rinse aid would allow far greater flexibility in the use of fragrances.

For the controlled release of a fragrance or a fragrance composition in the rinse cycle, a core for a corresponding particle according to the invention can be produced by mixing a mixture of 50% by weight of melted polyethylene glycol, e.g. PEG 8000, 25% by weight of fragrance or fragrance composition and 25% by weight of diethyl phthalate are cooled in a mold to form a, for example, spherical particle with a weight of, for example, 0.75 g.

c. Core for a particle for the controlled release of an antibacterial composition in the rinse aid

Using a particle or cores according to the invention, which comprises an antibacterial composition, in a tablet for use in a dishwasher would open up the possibility of simultaneously releasing two different compositions in the rinse cycle, namely the antibacterial composition from the core (s) of the particle according to the invention and the rinse aid from the usual dosing device of the dishwasher.

A corresponding core is produced for such a particle by cooling a mixture of 100% molten benzalkonium chloride (Barquat® MS-100) in a mold in order to produce a spherical particle with a weight of, for example, 0.64 g. d. Core for a particle for the controlled release of enzymes in the rinse cycle

Since proteases, which are usually used in dishwashing detergent compositions, have been shown to degrade lipases and thus reduce their activity, it would be desirable to incorporate such lipases into the core (s) of a particle according to the invention, so that the lipases would only be released in the rinse aid in a controlled manner , which could allow optimal performance of these enzymes.

For this purpose e.g. 0.4 g of a granular lipolytic enzyme (e.g. Lipolase® 100T (Novo)) in a hard gelatin capsule with e.g. rounded cylindrical shape, e.g. the way it is used for pharmaceuticals.

Example 2

Screening process for wrapping materials

As stated above, it is essential for the present invention that the material for the coating of the particle core (s), which comprise the substance which functions essentially in the rinse aid of the dishwasher Shows solubility, which depends on the concentration of a specific compound selected. In this way the coating in the main cleaning cycle is essentially insoluble and is made soluble and detaches from the particle if this concentration drops during the intermediate rinsing cycle (rinsing cycles) or the rinse cycle.

It has been observed that the dilution due to the pumping out of the wash liquor and the inflow of fresh water which occurs in the course of the various rinse cycles causes the corresponding concentration to be 20 to 200 times between the end of the main wash cycle and the last rinse cycle sinks. Based on this observation, a method of screening the suitability of different polymers for use as wrapping materials has been developed which consists in determining the solubility of such polymers at two different concentrations, at least 20 times, more preferably 200 times apart.

The concentration values of the specific compound that should be used in the screening of the polymers depend on the formulation of the base composition of the tablet into which the coated particle is to be incorporated.

In fact, the highest concentration value used for the screening process should correspond to the concentration of the selected compound found in the wash liquor after the dishwasher detergent has completely dissolved. Once this concentration is determined, the lower concentration should be set 20 to 200 times below this higher value.

With these tasks, it is within the average skill and knowledge of one of ordinary skill in the art to determine the values for the concentrations of test solutions that should be used in the test procedures described below.

Procedure for preparing the test solution and for performing and evaluating the tests

The materials to be examined are dissolved in solvents in which they are easily soluble. The solutions are distributed on glass plates and then dried at room temperature until they have a constant weight.

The glass plates are placed in a beaker with test solution at a controlled temperature. The solution is then stirred with a magnetic stirrer at a controlled stirring speed. After approx. 10 minutes, the glass plates are removed from the beaker taken and dried at room temperature to constant weight. The results are expressed as weight loss [%].

Of course, the screening methods must be adapted to the composition of the dishwasher detergent, since this has the essential influence on the concentration of the specific compound or the pH profile in the dishwashing cycle. In any case, the aim is to check the degree of solubility of the corresponding materials in two different states, namely high or low concentration of the specific compound or pH.

With these specifications, it is only within the skill of a person skilled in the art to set up special test parameters for the screening. Two screening methods are shown below by way of example, with which some of the possible materials for the coating of the particles according to the invention were tested.

Screening procedure 1:

Screening method 1 was carried out using buffer solutions as the medium for the simulation of the wash liquor. For this purpose, two buffer solutions were prepared as follows:

Stock solution: 7.507 g glycine buffer (Merck 104169)

5.850 g NaCl made up to 1000 ml with water.

pH 8 buffer solution: 500 ml stock solution 500 ml dist. H ₂ O 1, 23 gl N NaOH pH 10 buffer solution: 500 ml stock solution

500 ml dist. H ₂ O

32.6 g IN NaOH.

Screening procedure 2:

Screening Procedure 2 was performed on the following detergent formulation to simulate the conditions in different stages of a dishwasher cycle. Concentrations of 4 to 5 g / 1 are common for detergent loading in the washing cycle. Concentrations of around 20-40 mg / 1 are common for the rinse aid.

Detergent formulation:

Ingredient weight%

Sodium perborate monohydrate 9.00

Sodium tripolyphosphate 48.00

Sodium carbonate 28.00

Polyethylene glycol 4.00

Polymer 1.50

TAED 3.00

Enzymes 1.50

Surfactant 3.50

Additives 1.50

Total 100.00 Screening procedure 3:

Screening method 3 is used to screen for compounds whose solubility changes depending on the concentration of potassium ions. The compounds determined using such screening methods can be used if, as described above, there is a correspondingly high concentration of potassium ions in the main cleaning cycle, which is correspondingly reduced by dilution in the rinse cycle.

The screening method 3 was carried out with the following formulation in order to simulate corresponding conditions.

Formulation:

Example 3

Selection of materials for the coating of the particles

Using the screening methods described in Example 2, various materials were examined for their suitability as a coating for the particles according to the present invention. One of these materials, hereinafter referred to as "Polymer 1", is a polymer as described in Japanese Patent Application KOKAI 61-28440, ie a polymer of the general formula II with l / (l + m + n) = 0.35; m / (l + m + n) = 0.45; 1 + m + n = 1500-1800.

The polymer was prepared in the customary manner by bulk polymerization. The results of the screening tests were as follows:

Screening procedure 1:

Polymer 1 films were made from a 10% solution in isopropanol.

Screening procedure 2:

Polymer 1 films were made from a 10% solution in a mixture of water and 1N HCl (17: 1).

The invention is of course not limited to this exemplary polymer, although there is of course already a large variation possibility with regard to the polymers mentioned in Japanese patent applications KOKAI 60-141705, 61-28440, 61-28441, 61-28596, 61-28597 and 61-28597 is or can be extended to compounds of the formula TV:

wherein Rj is independently hydrogen or an alkyl group with 1-3 carbon atoms, R _{2 is} independently hydrogen or an alkyl group with 1 to 5 carbon atoms and x is an integer from 1 to 6.

In addition, within the larger class of compounds with formula III:

where G is a linking group which is selected from -COO-, -OCO-, -CONH-, - NHCO-, -NHCONH-, -NHCOO-, -OCONH- or -OCOO-, Ri independently of one another hydrogen or an alkyl group with 1 -3 carbon atoms, R _{2 is} independently hydrogen or an alkyl group with 1-5 carbon atoms and x is an integer from 1 to 6, for example polymers with a repeating unit can be used, which are based on a compound of the formula V.

For example, a pH-sensitive polymer (“Polymer 2”) with the repeating unit VI, which is commercially available from the company SANKYO under the brand name AEA®.

The screening method 2 described above was also carried out with “Polymer 2”:

15 g "Polymer 2" and 5 g Mowiol® 3-98 (Clariant) were dissolved in 200 ml of a mixture of water / ethanol / IN HCl 12: 8: 1. Films were formed and tested as described above. The following results were obtained receive:

Other polymers which show the desired properties or can be modified in a simple manner so that they are suitable for the purposes of the present invention are polymers of isomers or derivatives of pyridine, preferably copolymers with styrene or acrylonitrile, of the following formulas VII and VIII, in which G represents a substituent at any point on the pyridine ring.

A polymer according to Formula VIII above, namely poly (4-vinylpyridine-styrene) copolymer (Scientific Polymer Products, Inc.), "Polymer 3", was tested according to screening method 2 described above:

10 g "Polymer 3" was dissolved in 230 ml water / IN HCl 6.25: 1. The formation of the films and the tests were carried out as described above. The following results were obtained:

Other polymers are (e.g. statistical) polymers derived from chitosan based on the following monomer units IX and X

In addition, it is also possible to use substances or substance mixtures in the coating of the core material which react with respect to their solubility behavior to a change in the ion concentration, ie polymers which are sensitive to ion concentration. The partially hydrolyzed polyvinyl acetates described in the publications EP 0 284 191 A2 and EP 0 284 334 A2 (commercially available under the Brand names Mowiol® (Clariant)) into consideration, which show a corresponding ion concentration dependence in the presence of borates due to the complexation of the borates with polyols. The first successful tests were carried out with the Mowiol® 56-88 product.

Another polymer which is sensitive to ion concentration is the polysaccharide K-carrageenan, which has been found in screening method 3 (see Example 2) to be a polymer which depends on the potassium ion concentration in the surrounding medium in terms of its solubility. K-Carrageenan is represented by the following formula XI:

This polymer, designated "Polymer 4", was tested according to screening method 3 described above:

4 g of K-carrageenan were dissolved in 96 g of water. 10 g Mowiol® 18-88 was dissolved in 90 g water and both solutions were mixed. The resulting solution was used to form the films and run the tests as described above. The following results were obtained.

The above list of compounds which are suitable for the wrapping according to the invention is of course not exhaustive. Further polymers which change their solubility in the desired range by changing the concentration of a specific compound, for example the pH, are conceivable or can be developed and are therefore within the scope of the present invention. Among other things, compounds which react with regard to their solubility behavior to the change in the concentration of non-ionic compounds in the surrounding medium are also suitable for the coating according to the invention. In addition, the substances suitable for the coating according to the invention are not limited to polymeric compounds, although such compounds are described here as preferred embodiments

With the aid of the screening methods or screening methods specified above, which are adapted to the measurement of a specific concentration sensitivity, various materials which are commercially available or obtainable by simple modifications can be examined for their suitability in the present invention. The selection of such polymers is a task which the average person skilled in the art can solve without difficulty, given the correspondingly clear target and the specified screening method.

Example 4

Production of a particle according to the invention

The different cores described in Example 1 were used as the basis for the production of particles according to the invention. These cores were provided in a device for applying a film coating, as is known from the pharmaceutical industry (for example from the companies Lödige, Hüttlin, GS, Manesty and Driam), individually or in pairs (FIG. 6) with a covering.

In the event that the core (s) has an ingredient which shows a certain incompatibility with the material of the casing, the core (s) can be provided with a protective coating before applying this casing be provided. Various materials known from the prior art can be considered for this, such as, for example, cellulose loose, cellulose derivatives, polyvinyl alcohol, polyvinyl alcohol derivatives and mixtures thereof. Although not absolutely necessary, such a protective coating was used in all cases when using the cores from Example 1, a 10% strength by weight aqueous solution of a polyvinyl alcohol, for example the Mowiol® 5-88 (Clariant) polyvinyl alcohol, preferably being used Use came. The amount of the protective coating applied can easily be varied by the person skilled in the art depending on the composition of the core (s) and adapted accordingly. Initial tests have given good results with 3% by weight in the case of la, 2% by weight in the case of Ib, 3% by weight in the case of LC and 4% by weight in the case of the polymer (dry matter), in each case based on the mass of the entire particle.

The concentration-sensitive coating can in principle be applied to the core (s) or protective coating in any quantity and thickness, as long as it is ensured that the coating detaches or dissolves quickly enough in the rinse cycle so that the ( substance contained in the kernels) can develop its effect. In a preferred embodiment, 1-10% by weight, preferably 4-8% by weight, of the concentration-sensitive coating material (dry mass), based on the mass of the entire particle, is applied to the cores.

The particles according to the invention should preferably have a size such that they are not, or at least not to a considerable extent, removed from the dishwasher by the pumping-down processes after the main cleaning cycle or the intermediate rinsing cycle. A size of approximately 1 cm in diameter is usually sufficient for this. Smaller or larger dimensions can of course be chosen as long as the functionality is guaranteed overall.

"Polymer 1" from Example 3 was used as the coating for the further tests and applied as a 10% strength solution of the polymer in 0.055 N aqueous HCl. Example 5

Production of a 2-layer dishwasher tablet with rinse aid particles

A typical 2-layer dishwasher tablet, which is suitable for holding a rinse aid particle in a cavity formed therein according to the present invention, can be obtained by pressing the powdery ingredients in machines known from the prior art and using basically from the prior art operating parameters known in the art are produced. A possible form of such a tablet is a cuboid tablet consisting of two layers of essentially the same thickness, a hemispherical recess being formed in the largest area of each of these layers, so that when the two half-tablets are joined together, an essentially spherical cavity is formed on the inside (see Fig. 2).

The composition of the dishwasher tablets is based on commercially available products. An example of the composition is shown in Table 2 below. Of course, other compositions can also be considered, in particular those which are optimized to support the compound surrounding the core, for example in the provision of alkalinity.

Table 2

For the tests carried out in Examples 6 and 7, half tablets with a weight of approximately 11.5 g were produced. The cavity created when the half tablets were put together had an inner diameter of approximately 1.2 cm.

The rinse aid particle produced according to Examples 1a and 4 is placed in the hemispherical recess of the white or colored half-tablet. Then a fixing substance is e.g. apply an adhesive (e.g. polyethylene glycol, polyvinyl ether, polyvinyl alcohol, silicate, preferably melted PEG 4000) to the corresponding surface of the half-tablet and possibly also to the rinse aid particle and the second half tablet (colored or white) to the first half tablet with rinse aid -Pressed particles.

Example 6

In this example, a test is described with which the transfer of the rinse aid surfactant into the rinse aid cycle can be demonstrated when the tablet produced according to Example 5 is used.

The rinse aid particles each have an average surfactant or polyethylene glycol content of about 0.37 g. The average amount of water in the rinse aid is about 5.0 l. The maximum amount of surfactant plus PEG to be expected in the rinse aid should therefore be 0.148 g / 1 when using one tablet per dishwashing cycle.

Three different tests were carried out with three different tablets in a BOSCH SMS 3047 dishwasher. The water hardness was about 17 ^° dH. 1. Dishwasher detergent tablet without rinse aid particles; Temperature 65 ^° C.

2. Dishwasher detergent tablet with rinse aid particles (example 6); Temperature 65 C.

3. Dishwasher detergent tablet with rinse aid particles (example 6); Temperature 55 ^° C.

In each experiment, a minimum of 1 liter of wash liquor was removed from the rinse aid just before the water was drained. The samples were labeled 1.1 to 3.3. The lye was then analyzed to determine the total amount of surfactant plus polyethylene glycol in the rinse aid. The measurements were carried out by extracting surfactant and PEG, evaporating the solvent and carrying out a gravimetric determination of the non-volatile residue.

It should be pointed out that this analysis method detects both the nonionic surfactant and the polyethylene glycol.

Table 3

Example 7

The test described in this example is used to test the composition according to the invention with regard to its effectiveness in the rinse aid.

As a comparison with the dishwasher detergent tablet with rinse aid particles produced according to the invention, as produced in Example 6, the rinse aid performance was added separately. nem dishwashing detergent ^] and rinse aid, the dishwashing detergent corresponding to the tablet composition of the tablet according to the invention and a commercial rinse aid being used. The dishwasher used was a BOSCH SMS 3047. The water hardness was about 17 to 19 ^° dH. The set temperature was 65 ^° C. The dishwasher was loaded with 20 glasses, 20 black porcelain plates and 20 pieces of cutlery.

The contamination of the dishwasher load was carried out as follows:

50 g minced meat (SchweimRind, 1: 1) was fried with 2 g fat. After a light brown color was reached, a sauce containing 100 ml of water, 1 g of sauce binder and 2.5 g of instant sauce was added to the meat.

This material was put in the dishwasher and the sieve was closed with a stopper to keep the dirt in the machine until the end of the washing program. The dishwashing detergent was added at the beginning of the rinse cycle. Dishwasher loading was assessed 10 minutes after the end of the dishwashing cycle.

The visual assessment was based on the following ranking table:

4 points = without any stains

3 points = 1 to 4 spots

2 points = more than 4 spots to VΛ of the surface covered with spots

1 point =! covered with spots to ¹ Λ of the surface

0 points = almost completely covered with stains.

The stain prevention performance is expressed in percent. 100% performance means the maximum possible score of 228 points. The results are summarized in Table 4 below: Table 4

The results show an excellent rinse aid of the composition according to the invention. This was particularly pronounced with porcelain and glass, whereby the performance with cutlery was comparable to that of conventional compositions. Surprisingly, this has even shown that the rinse aid of the composition according to the invention is sometimes superior to the conventional procedure of metering in the detergent and rinse aid separately.

The features of the invention disclosed in the above description, the claims and the drawings can be essential both individually and in any combination for realizing the invention in its various embodiments.

Claims

Speeches

1. Composition for use in a dishwasher, characterized by

- a basic composition (2, 3; 2 ') which functions essentially in the main cleaning cycle of the dishwasher; and

- At least one particle (6; 6 '; 6 "), with

- At least one core (8; 8 '; 8 "), which comprises at least one substance that functions essentially in the rinse cycle of the dishwasher, and

a sheath (9; 9 '; 9 ") which substantially completely surrounds the core (s) and which comprises at least one compound whose solubility increases with decreasing concentration of a specific compound in the surrounding medium;

means are provided to substantially dissolve the casing (9; 9 '; 9 ") or substantially detach the casing (9; 9'; 9") from the core (8; 8 ') or to prevent from the cores (8 ").

2. Composition according to claim 1, characterized in that the concentration of the specific compound in the local environment of the (the) particle (s) (6; 6 '; 6 ") until the start of the rinse cycle is sufficiently high to reach this To prevent a substantial dissolution of the casing (9; 9 '; 9 ") or a substantial detachment of the casing (9; 9'; 9") from the core (8; 8 ') or from the cores (8 ").

3. Composition according to claim 2, characterized in that the (the) particle (6; 6 '; 6 ") is (are) coated with a substance which - largely independent of the concentration of the specific compound in the surrounding medium - dissolves or dissolves in the course of the main wash cycle of the dishwasher.

4. Composition according to one of claims 1 to 3, characterized in that the basic composition is in the form of a tablet (1; 1 ').

5. Composition according to claim 4, characterized in that the at least one particle (6; 6 '; 6 ") is arranged in or on the tablet (1; 1') such that the concentration of the specific compound in the local environment of (the) particle (particles) until the tablet (1; 1 ') is substantially completely dissolved in order to prevent a substantial dissolution of the casing or a substantial detachment of the casing from the core (s).

6. The composition according to claim 5, characterized in that the or all particles (6) in at least one of the base composition (2,3) completely enclosed cavity (4,5) of the tablet (1) is or are.

7. The composition according to claim 6, characterized in that the at least one cavity (4,5) contains one or more particles (6) which alone or taken together have (have) substantially the same volume as the cavity (4, 5).

8. The composition according to claim 6, characterized in that the at least one cavity has a larger volume than the or all particles (6) which is or are received in the respective cavity (4, 5).

9. The composition according to claim 8, characterized in that the (the) particle (6) inside the cavity (4, 5) is loosely arranged (are).

10. The composition according to claim 8, characterized in that the (the) particles (6) in the interior of the cavity (4, 5) is (are) fixed.

1 1. Composition according to claim 10, characterized in that the (the) particles (6) inside the cavity (4, 5) is (are) fixed by an adhesive.

12. Composition according to one of claims 6 to 11, characterized in that the cavity (4, 5) is arranged substantially centrally in the interior of the tablet (1).

13. Composition according to one of claims 6 to 12, characterized in that the tablet (1) has a single, substantially spherical cavity (4, 5).

14. Composition according to one of claims 8 to 13, characterized in that in the cavity (4, 5) a single, substantially spherical particle (6) is received, the outer diameter of which is smaller than the inner diameter of the cavity.

15. The composition according to claim 5, characterized in that the or all particles (6 '; 6 ") is or are received in at least one cavity (4') of the tablet (1 '), which is only partially from the basic composition ( 2 ') is surrounded.

16. The composition according to claim 15, characterized in that the cavity is a recess (4 ') in one of the surfaces (11') of the tablet (1 '), in which the (the) particle (6'; 6 ") at least is partially included.

17. The composition according to claim 15 or 16, characterized in that the particle (s) (6 '; 6 ") is (are) received in the cavity or the recess (4') such that it (they) do not have the Surface (s) (11 ') of the tablet (1') protrudes (protrude).

18. Composition according to one of claims 15 to 17, characterized in that the cavity or the recess (4 ') contains only a single particle (6'; 6 "), the volume and shape of which in the region of the cavity or the recess with the Volume and the shape of the cavity or the recess (4 ') essentially coincides and that this (these) essentially completely.

19. The composition according to any one of claims 15 to 18, characterized in that the cavity or the recess (4 ') parallel to one of the surface (s) (11') to which it opens or in which it is arranged, has an essentially circular cross-sectional area.

20. Composition according to one of claims 15 to 19, characterized in that the cavity or the recess (4 ') opens to the surface (s) (11') only to such an extent that the (the) received therein ( n) particles (6 '; 6 ") cannot (can) pass through the opening (s) of the cavity or of the depression (4').

21. The composition according to claim 20, characterized in that the (the) particle (6 '; 6 ") in the cavity or in the recess (4') is loosely arranged.

22. Composition according to one of claims 15 to 20, characterized in that the particle (s) (6 '; 6 ") is (are) fixed in the cavity or in the recess (4').

23. The composition according to claim 22, characterized in that the particle (s) (6 '; 6 ") is (are) fixed in the cavity or in the recess (4') with an adhesive (10 ').

24. Composition according to one of the preceding claims, characterized in that the basic composition (2, 3; 2 ') comprises at least one composition which is selected from the group consisting of a machine dishwashing detergent composition, a water softener composition and a washing intensifier composition.

25. Composition according to one of the preceding claims, characterized in that the covering (9; 9 '; 9 ") comprises at least one compound which is not or only slightly soluble at the concentration of the specific compound at the end of the main cleaning cycle of the dishwasher and at the concentration of the specific compound in the rinse cycle shows such a sufficient solubility that it is so largely dissolved in the rinse cycle or detached from the core (s) that a at least partial leakage of the core material into the rinse aid medium is made possible.

26. The composition according to claim 25, characterized in that the solubility of the compound increases with falling OH ^' ion concentration and thus decreasing pH in the surrounding medium.

27. The composition according to claim 26, characterized in that the compound shows no or only low solubility at a pH above 10 and shows such a sufficient solubility at a pH below 9 that it is so largely dissolved or in the rinse cycle detached from the core (from the cores) so that an at least partial escape of the core material into the medium of the rinse aid is made possible.

28. The composition according to any one of claims 25 to 27, characterized in that the compound comprises a polymer.

29. The composition according to claim 28, characterized in that the compound comprises a pH-sensitive polymer which comprises at least one repeating unit which has at least one basic function which is not part of the backbone chain of the polymer.

30. The composition according to claim 29, characterized in that the polymer comprises at least one repeating unit based on a compound selected from the group consisting of vinyl alcohol derivatives, acrylates or alkyl acrylates, which comprise said basic function.

31. The composition according to claim 29, characterized in that the polymer is a carbohydrate which is functionalized with said basic function.

32. Composition according to one of claims 29 to 31, characterized in that the basic function is an amine.

33. Composition according to claim 32, characterized in that the basic function is a secondary or tertiary amine.

34. Composition according to claim 33, characterized in that the repeating unit is based on a compound having the following formula III:

R ₂

where G is a linking group which is selected from -COO-, -OCO-, -CONH-, - NHCO -, - NHCONH -, - NHCOO -, -OCONH - or - OCOO -, Ri independently of one another hydrogen or an alkyl group with Is 1-3 carbon atoms, R _{2 is} independently hydrogen or an alkyl group of 1-5 carbon atoms and x is an integer from 1 to 6.

35. Composition according to claim 34, characterized in that the repeating unit is based on a compound having the following formula IV:

wherein Ri is independently hydrogen or an alkyl group with 1-3 carbon atoms, R is independently hydrogen or an alkyl group with 1-5 carbon atoms and x is an integer from 1 to 6.

36. Composition according to one of claims 29 to 31, characterized in that the basic function is an imine.

37. Composition according to one of claims 29 to 31, characterized in that the basic function is a basic aromatic N-containing group.

38. Composition according to claim 37, characterized in that the basic function is a pyridine group.

39. Composition according to claim 37, characterized in that basic function is an imidazole group.

40. Composition according to claim 31, characterized in that the pH-sensitive polymer is a polymer derived from chitosan.

41. Composition according to claim 25, characterized in that the compound comprises K-carrageenan.

42. Composition according to one of the preceding claims, characterized in that the core (s) comprises (s) at least one material selected from the group consisting of surfactants, antibacterial compositions, silver protection agents, fragrances, bleaches, disinfectants , Odor masking agents, anti-fouling agents and enzymes.

43. Composition according to 42, characterized in that the core (8; 8 ') or at least part of the cores (8 ") is in the form of an encapsulated liquid.

44. Composition according to claim 43, characterized in that the core (8; 8 ') or at least part of the cores (8 ") is in the form of a liquid contained in a gelatin capsule.

45. Composition according to claim 42, characterized in that the core (8; 8 ') or at least part of the cores (8 ") is in a solid form.

46. Composition according to claim 45, characterized in that the core (8; 8 ') or at least part of the cores (8 ") has a melting point of more than 35 ° C.

47. Composition according to claim 46, characterized in that the core (8; 8 ') or. at least some of the cores (8 ") have a melting point of between 55 and 70 ° C.

48. Method for carrying out a dishwashing cycle in a dishwasher, characterized in that a composition according to one of claims 1 to 47 is added to the medium in the dishwasher at a suitable time during the pre-wash cycle or the main cleaning cycle.

49. The method according to claim 48, characterized in that, in the event that the base composition in the form of the tablet is not able to provide a concentration of the specific compound in the medium after its dissolution in the medium until the end of the main cleaning cycle that is sufficiently high to prevent substantial disintegration of the wrapping and substantial detachment of the wrapping from the core (s), this sufficient concentration of the specific compound by adding another composition, such as a dishwasher detergent composition, to the medium of the main cleaning cycle is provided at a suitable time.