Cleaning product portion comprising powder and a shaped body of a certain height

Abstract

The present invention relates to a cleaning product portion preferably for mechanical dishwashing, which contains, in a water-soluble packaging including a receiving chamber and a sealing element, a powder and a shaped body of a height of 2.5 to 9 mm, preferably 2.75 to 6.0 mm, more preferably 3.0 to 5.5 mm.

Description

[0001] The present invention relates to a single-use cleaning agent portion as defined in claim 1, preferably for machine dishwashing, which in a water-soluble package comprising a receiving chamber and a closure element contains, in addition to a powder, a molded body having a height of 2.5 to 9 mm, preferably 2.75 to 6.0 mm, in particular 3.0 to 5.5 mm.

[0002] Cleaning agents are typically available in solid or liquid form (or as a flowing gel). Liquid cleaning agents, in particular, are becoming increasingly popular with consumers.

[0003] Solid cleaning agents have the advantage that, unlike liquid cleaning agents, they do not require preservatives. Liquid products are becoming increasingly prevalent in the market, particularly due to their rapid solubility and the resulting quick availability of their active ingredients. This allows consumers to use shorter wash cycles while still achieving good cleaning performance.

[0004] Furthermore, consumers have become accustomed to the convenient dosing of pre-portioned machine cleaning agents, such as dishwashing detergents, and use these products in tablet form (solid detergents) or in sachets, usually filled with a liquid detergent. Single-use portions in water-soluble sachets are enjoying increasing popularity among consumers, not only because they eliminate contact with the chemical composition, but also because of the attractive appearance of the sachets. The appearance of the dosage form is becoming increasingly important. Besides good cleaning performance and sufficient shelf life, good appearance is one of the deciding factors when choosing a product.

[0005] From the consumer's perspective, it is now desirable to combine the advantages of both product forms and to provide an improved dosage form, particularly for typically liquid cleaning agents, compared to the state of the art. This should allow for single-dose dispensing while simultaneously achieving a visually appealing appearance for the consumer. WO 2012 / 027404 A1 and EP 3434758 A1 disclose multiphase cleaning agents comprising a water-soluble coating and at least one gel phase and at least one powder phase.

[0006] It is also important for consumers that the single-use portion has visually structured areas that do not mix and are clearly separated. Besides an appealing appearance, it is crucial that the single-use portions are easy to manufacture, remain stable during storage, and do not leak. With single-use portions containing loose particles (such as powder), it has been observed that during manufacturing, individual powder particles unintentionally get between or onto the areas necessary for sealing the portions. This has several disadvantages. Firstly, consumers perceive the visual appearance of such cleaning portions as unclean, unstructured, and flawed. Secondly, such unclean sealing areas result in single-use portions that are not tightly sealed and are prone to leakage.Leaky packaging can cause the cleaning agent to leak from the single-use portion. This must be avoided to prevent contact between the consumer and other single-use portions stored in the same packaging. Furthermore, leaky packaging allows a relatively high level of moisture and / or air to reach the ingredients inside, which can reduce their effectiveness and / or cause them to clump together, thus reducing cleaning performance.

[0007] The object of the present invention is therefore to provide a dosage form for a cleaning agent that is easy to handle, stable (in particular stable in storage and transport), makes good use of space within the packaging and has good cleaning performance, is as sustainable as possible and requires less packaging material.

[0008] A first object of the present invention is therefore a single-use cleaning agent, comprising a) a water-soluble packaging comprising a1) at least one water-soluble receiving chamber a2) a water-soluble closing element closing at least this water-soluble receiving chamber b) a phosphate-free cleaning agent composition comprising b1) at least one gel phase b2) at least one powder, b3) at least one shaped body other than the powder, characterized in that the molded body has a height of 2.5 to 9 mm, preferably 2.75 to 6.0 mm, in particular 3.0 to 5.5 mm, wherein the at least one gel phase comprises water-soluble polymer from the group of optionally acetalized polyvinyl alcohols and their copolymers.

[0009] The single-dose cleaning agents according to the invention are used in particular for cleaning hard surfaces, especially dishes and other items to be washed. The cleaning agents according to the invention are in particular dishwashing detergents, especially machine dishwashing detergents for use in, or can be used in, a machine dishwasher.

[0010] The single-use cleaning agent unit comprises a water-soluble package. This package includes at least one water-soluble receiving chamber and a water-soluble sealing element that closes this water-soluble receiving chamber.

[0011] It can also contain several water-soluble receiving chambers, which are closed by the same or different water-soluble closure elements. According to the invention, at least one powder and at least one shaped body of the cleaning agent composition are contained together in a single receiving chamber. Further chambers can contain similar or different cleaning agent compositions.

[0012] Preferably, the packaging of the single-dose cleaning agent comprises exactly one water-soluble receiving chamber, exactly one water-soluble closure element, and the phosphate-free cleaning agent according to the invention.

[0013] The special features of the water-soluble packaging are described in more detail below. The preferred embodiments described in the manufacturing process also apply to the single-dose cleaning agent and vice versa.

[0014] The water-soluble packaging comprises at least one water-soluble receiving chamber, which can be formed using methods described below. It is formed from a water-soluble material, preferably a water-soluble shaped film or molded body, which forms or has a cavity into which the cleaning agent composition is poured. The cleaning agent composition is at least partially contained within the receiving chamber.

[0015] It is not necessary for the at least two packaging parts to be different. They can preferably be made of the same material and manufactured in the same way. In a preferred embodiment, these are two parts of a water-soluble film, in particular two parts of a water-soluble film of the same composition.

[0016] In another embodiment, the at least two packaging parts can be made of different materials, e.g., different films or materials with two different properties (e.g., a film soluble in hot and cold water). In this embodiment, it is preferred that a water-soluble film and another packaging part produced by injection molding are combined.

[0017] According to a particularly preferred embodiment of the present invention, the water-soluble packaging comprises at least one at least partially plastically deformed film. In particular, this plastic deformation of the film can be produced by methods known to those skilled in the art, such as deep drawing (with and without the application of a vacuum), blow molding, or stamping. In particular, the water-soluble coating comprises at least one at least partially plastically deformed film produced by deep drawing.

[0018] The sealing element is also made of water-soluble material, preferably in the form of a film. According to a particular embodiment, the sealing element is separate from or distinct from the receiving chamber before the receiving chamber is sealed.

[0019] The receiving chamber is sealed with the sealing element at the end of the filling process. Specifically, the bond between the receiving chamber and the sealing element, particularly the water-soluble film, is created by gluing, solvent sealing, water sealing, or heat sealing. The inside of the sealing element is the side facing the receiving chamber.

[0020] The present invention relates to a water-soluble package and a cleaning agent composition comprising at least one powder and at least one shaped body other than the powder. The cleaning agent composition is preferably contained entirely in (or within) the water-soluble package. The inside of the closure element is in contact with at least a portion of the cleaning agent composition within the single-use cleaning agent portion. The inside of the receiving chamber is also in contact with at least a portion of the cleaning agent composition.

[0021] According to the invention, the molded body is in contact (in direct contact) with the closure element, in particular with its inner surface. This means that the at least one molded body and also the at least one powder are arranged within the water-soluble packaging.

[0022] The use of phosphates (which, according to the invention, include both the phosphoric acid anion (orthophosphate) and the condensation products of orthophosphoric acid salts with the general formula M' n+2 P n O 3n+1) is almost completely avoided. The cleaning agent composition is therefore phosphate-free, i.e., it contains less than 0.1 wt% phosphate(s). Preferably, the entire single-use cleaning agent portion contains less than 0.1 wt% phosphate(s).

[0023] For the purposes of the present invention, "powder" is understood to mean a granular mixture composed of a multitude of loose, solid particles, which in turn may comprise so-called grains. A grain is a term used to describe the particulate components of powders (grains being the loose, solid particles), dusts (grains being the loose, solid particles), granules (loose, solid particles being agglomerates of several grains), and other granular mixtures. The term "powder" used here also includes mixtures of different powders and / or different granules and / or different compacts. Accordingly, "powder" also refers to mixtures of different powders with different granules and compacts. The powder preferably comprises various particles containing chemically distinct constituents.Furthermore, the powder's visual appearance may exhibit textural differences, such as coarse and fine particles, as well as particles or areas with different colors, either as a whole or as colored speckles. Even in such cases, however, the powder is preferably a single phase or is perceived as such.

[0024] The powder therefore comprises solid particles as a granular mixture, which preferably have a particle diameter X 50,3 (average by volume) of 10 to 1500 µm, more preferably of 200 µm to 1200 µm, and particularly preferably of 400 µm to 1000 µm. These particle sizes can be determined by sieving or by means of a Camsizer particle size analyzer from Retsch.

[0025] Preferably, at least 80% of the particles have a particle diameter of 100 to 2000 µm, more preferably of 150 µm to 1500 µm. According to a preferred embodiment, the powder has particles with a particle diameter X 50.3 (mean volume) up to 2000 µm, in particular up to 1000 µm.

[0026] According to a preferred embodiment, the powder within the meaning of the present invention comprises powders and / or granules as well as mixtures thereof.

[0027] A "molded body" within the meaning of the invention is a single body that stabilizes itself in its embossed shape. This dimensionally stable body is formed from a molding compound (e.g., a composition) by selectively shaping this compound into a predetermined form, for example, by pouring a flowable composition into a mold and subsequently hardening the liquid composition, by extruding a mixture of materials, or by compressing a particulate premix, for example, in a tableting process. The spatial shape of the molded body is, in principle, freely selectable; its surface can, for example, be convex, concave, or flat. However, certain spatial configurations have proven particularly advantageous with regard to the manufacturability, storage, and use of the molded bodies.

[0028] A single-use cleaning agent portion may contain more than one molded element, for example, two, three, or four. The molded elements may be identical in terms of their shape or composition, or they may differ in these properties. The molded elements may be arranged one above the other or side by side and will generally be in contact with each other. Several molded elements may also be in direct contact with the closure element. If the inside of the closure element is covered by molded elements to a certain extent, as described below, then the degree of coverage refers to the total coverage provided by all molded elements contained in the single-use cleaning agent portion.

[0029] According to the present invention, the molded body in contact with the closure element has a height of 2.5 to 9 mm, preferably 2.75 to 6.0 mm, and particularly 3.0 to 5.5 mm. Such molded bodies are particularly suitable for utilizing the available space in the receiving chamber in combination with the powder, while simultaneously achieving the advantages of covering the powder from the closure element. At the same time, the entire single-dose cleaning agent portion is stabilized by the presence of such molded bodies. Molded bodies with significantly lower heights than specified are generally more fragile, which means they cannot fulfill the purpose of the invention from the outset or not throughout the entire transport and / or storage period.Much thicker molded bodies have the disadvantage that they leave too little space in the single-dose cleaning agent portion for other important components that cannot be incorporated into the molded body without significant effort and / or loss of activity.

[0030] The shaped body in contact with the closure element preferably has substantially the same height. The shaped body also has substantially the same thickness. Substantially the same height is achieved when the height at individual points of the shaped body deviates by 10% or less, preferably by 5% or less.

[0031] Preferably, the molded body has at least one substantially flat side. "Substantially flat" in the context of the invention means that the flat side of the molded body has no significant protrusions or depressions. The deviation is 10% or less, preferably 5% or less. The underside, which is preferably in contact with the powder, and / or the top side, which is in contact with the inside of the closure element, can be substantially flat. Preferably, the molded body has at least one substantially flat top and / or bottom surface.

[0032] The molded bodies preferably have a flat underside, the largest diagonal of which is greater than the height (thickness) of the molded body, with the molded body being placed with its flat underside onto the surface of the powder. Such molded bodies can not only be manufactured easily, for example by casting or tableting, but can also be easily applied to the powder mechanically.

[0033] It is particularly preferred if the molded body has a flat underside, the largest diagonal of which is more than 1.5 times, preferably more than 2 times, the height of the molded body, wherein the molded body is placed with its flat underside onto the surface of the powder. This results in excellent powder coverage, especially at high coverage levels.

[0034] It is particularly preferred if such (preferably essentially flat) shaped bodies of the aforementioned thickness / height, in particular a height / thickness of 2.75 to 6.0 mm, produce a high coverage of the inside of the closure element of more than 80%, particularly preferably more than 85% of its surface, thereby making particularly favorable use of the space provided by the receiving chamber for the various components / phases of the cleaning agent composition, without powder coming into contact with the closure element to a large extent and further reducing the already mentioned negative consequences, such as abrasion, puncture of the closure element, in particular of a closure film.

[0035] According to a particularly preferred embodiment, the molded body has a substantially flat top and bottom surface, the top surface having substantially full-surface contact with the closure element.

[0036] A preferred arrangement according to the invention is that the inner surface of the closure element is in contact with the powder to less than 10% of its area. This is advantageous for efficient, and in particular trouble-free, manufacturing, the strength of the closure between the receiving chamber and the closure element, and the optical properties of the single-use portion, since in this case there is less opportunity for the powder to reach the closure surfaces, e.g., in the case of deep-drawn receiving chambers, the surfaces directly adjacent to the formed chamber.

[0037] Surprisingly, it has been shown that single-use cleaning agent portions, in which a molded body is arranged in a water-soluble package consisting of a receiving chamber and a closure element in such a way that less than 10% of the inner surface of the closure element is in contact with the powder, exhibit fewer leaks. These single-use portions are also easier to produce, have a stable storage life, offer good cleaning performance, and are perceived as particularly appealing by consumers.

[0038] Especially when the sealing element is a water-soluble film, it is important that the interface between the receiving chamber and the sealing element is free of powder particles. Otherwise, the seal between the receiving chamber and the sealing element will be incomplete and, in the worst case, permeable to the cleaning agent composition. The stability of the single-use portion, particularly during storage and / or transport, can also be improved by minimizing the powder's contact with the inside of the sealing element. This prevents damage, bulging, or even puncturing the sealing element in places, as well as wear and tear from prolonged friction and / or chafing. Reducing or avoiding contact between the powder and the inside of the sealing element allows for a reduction in the sealing element's thickness, for example.The thickness of the sealing film can be chosen to be smaller, which is advantageous in terms of sustainability by using less packaging material.

[0039] In a particularly preferred embodiment, the single-use cleaning agent portions contain exactly one molded element, which, according to the invention, is arranged such that it is in direct contact with the closure element. This simplifies the production of such single-use portions because only a single molded element needs to be applied, inserted, or otherwise positioned.

[0040] In preferred embodiments of the present invention, the inner surface of the closure element is in contact with the powder to less than 8%, in particular less than 6%, and most particularly less than 3%. The less contact the inner surface of the closure element has with the powder, the more stable the cleaning agent portion is, both during production and storage.

[0041] According to a preferred embodiment, the molded body according to the invention is a preformed molded body. Such a preformed molded body has already acquired its shape before being placed in the receiving chamber. This decouples the production of the molded body from the production of the single-use portion (particularly in terms of time). The production steps for the entire single-use cleaning agent portion can therefore be carried out in rapid succession and are not extended by the solidification times of the molded body, which are necessary when this molded body is produced in situ, for example, when it is introduced into the receiving chamber as a flowable premix.

[0042] Ingredients can also be incorporated into the pre-formed molded bodies which cannot be incorporated into gel phases, especially those introduced into the receiving chamber as a flowable composition, due to the processability of the ingredients themselves, the manufacturing process of the gel phases, and / or their material properties.

[0043] According to the invention, at least one shaped body must be arranged in such a way that it is in direct contact with the closure element and that less than 10% of the inside of the closure element is in contact with the powder.

[0044] According to a particularly preferred embodiment, the inside of the closure element is not in contact with the powder. The advantages already described are greatest in this embodiment.

[0045] According to a preferred embodiment, the molded part is arranged in the chamber such that it is in direct contact with the powder. This allows the molded part to effectively cover the powder, preventing it from coming into contact with the inside of the closure element and potentially compromising the seal of the single-serve portion.

[0046] According to a preferred embodiment, the molded body is arranged such that the inner surface of the closure element is covered by the at least one molded body to more than 70%, preferably more than 75%, particularly more than 80%, and especially more than 85%. This can be achieved, in particular, by placing the molded body onto or into the receiving chamber from above after the powder has been poured into it. The molded body then largely covers the phase formed by the powder and at least largely prevents contact between the powder and the inner surface of the closure element after the single-use cleaning portion has been sealed. The previously described negative consequences of large-area contact between the surface and the powder are thus avoided. The closure element rests directly on the molded body during direct contact.

[0047] According to a preferred embodiment, the side of the molded body that is in contact with the closure element (contact side) has at least 70%, preferably at least 75%, particularly at least 80%, and most preferably more than 85% of its surface in contact with the inside of the closure element. This design has the advantage that this arrangement prevents powder particles from getting between the closure element and the molded body after production, for example, during transport. The problems of abrasion, puncture, etc., described above are thereby further reduced.

[0048] Particularly preferably, this side of the molded body has substantially full-surface contact with the closure element. Substantially full-surface contact means that at least 90% of the surface of the contact side is in direct contact with the inside of the closure element. The closure element then rests on the molded body during this direct contact.

[0049] The molded bodies according to the invention preferably have a flat underside, the largest diagonal of which is greater than the height of the molded body. Preferably, its largest diagonal is more than 1.5 times, and preferably more than 2 times, the height of the molded body, with the molded body resting on the surface of the powder with its flat underside. Such an arrangement results in a particularly large coverage of the inside of the closure element without significantly reducing the space available within the receiving chamber.

[0050] In a further preferred embodiment, the molded body has a top surface that is substantially parallel to the underside. "Substantially parallel" means that deviations from complete parallelism of approximately 10%, preferably 5%, are still possible. Such surfaces arise from production variations or certain production processes and may, for example, exhibit slightly roughened, bumpy surfaces. However, such surfaces are included in the invention. This design advantageously allows a flat closure element (in particular, a flat, water-soluble film) to be easily applied to a plane-parallel top surface.

[0051] The underside of the molded body is in contact with the powder, while the top side is in contact with the closure element.

[0052] According to a preferred embodiment, the closure element comprises a water-soluble film. The closure element is preferably a water-soluble film. Suitable water-soluble films are described in more detail in connection with the methods according to the invention.

[0053] Due to the arrangement according to the invention, in which as little powder as possible comes into contact with the water-soluble film sealing the receiving chamber, the thickness of the film can be reduced because the aforementioned negative effects caused by the powder do not occur, and thus the contact with the powder is minimal. This has the advantage that, and therefore for the environmentally friendly and sustainable use of packaging material, a film with a thinner film than that used in conventional water-soluble single-use portions can be selected.

[0054] According to a particularly preferred embodiment, the water-soluble film has a thickness of 80 µm or less, preferably 70 µm or less, particularly 65 µm or less, and most preferably 60 µm. Most preferably, the film thickness can be 55 µm or less, resulting in a significant saving of packaging material. In a further preferred embodiment, the water-soluble film forming the closure element has a smaller thickness than the average thickness of the water-soluble receiving chamber. The average thickness of the water-soluble receiving chamber is determined by measuring the thickness and calculating the arithmetic mean. This also results in a saving of material for packaging the single-use portion.

[0055] According to a further preferred embodiment, the total weight of the single-dose cleaning agent portion is from 10 g to 25 g, preferably from 12 g to 22 g, and particularly preferably from 13 g to 20 g. Such cleaning agent portions are suitable for making good use of the dosing chamber of dishwashers, but do not require an excessive amount of packaging material.

[0056] The total weight of the powder in the single-use cleaning agent portions according to the invention is from 12 to 22 g, preferably from 7 g to 20 g, preferably from 8 to 15 g, and particularly preferably from 10 g to 12 g.

[0057] Preferably, the total weight of a molded body in the single-use cleaning agent portions according to the invention is from 4 g to 8 g, preferably from 5 to 7 g.

[0058] According to a further preferred embodiment, the weight ratio of powder to molded body is from 4:1 to 1:1, preferably from 3.75:1 to 1.25:1, particularly from 3.5:1 to 1.5:1, and most preferably from 3.25:1 to 1.75:1. Such ratios have proven to be particularly advantageous with regard to space utilization in the single-use cleaning agent portions according to the invention. In particular, this allows the various active ingredients in the powder and molded body to be well distributed and simultaneously separated.

[0059] A phase, as defined in the present invention, is a spatial region in which physical parameters and / or the chemical composition are homogeneous overall. A phase differs from another phase by various characteristics, such as ingredients, physical properties, external appearance, etc. Preferably, different phases can be visually distinguished. For example, the gel phase is clearly distinguishable for the consumer from the optically coherent particulate phase formed by the powder, as well as from the solid body. If the cleaning agent according to the invention has more than one gel phase, these can also be distinguished from one another with the naked eye, for example, because they differ in color. The same applies if two or more gel phases are present.In this case, too, the phases can be visually distinguished, for example, based on a difference in color or transparency. Phases within the meaning of the present invention are therefore self-contained regions that can be visually distinguished from one another by the consumer with the naked eye. The individual phases can exhibit different properties during use, such as the rate at which the phase dissolves in water and thus the rate and sequence of release of the ingredients contained in the respective phase.

[0060] Such an arrangement with separate phases advantageously reduces negative interactions between incompatible ingredients by incorporating each incompatible ingredient into only one of the phases: the at least one molded body, the at least one powder, or the gel phase(s). The activity of these ingredients is then maintained over a longer period and does not decrease over time due to the reduced contact between the phases resulting from the phase separation. By introducing at least one molded body that differs from the powder, these active ingredients with negative interactions can be effectively separated without requiring unnecessary separating material. This also improves the product's activity and storage stability.

[0061] According to the invention, the cleaning composition comprises at least one gel phase, at least one powder and at least one shaped body.

[0062] The at least one gel phase contained in the water-soluble receiving chamber according to the invention and the shaped body according to the invention are distinct from one another. They are at least optically separable from one another and form different phases.

[0063] Preferably, the at least one gel phase is not in contact with the closure element; in particular, all gel phases are not in contact with the closure element.

[0064] It is further preferred if the at least one gel phase (and most preferably all gel phases) are not in contact with the molded body.

[0065] In a further preferred embodiment, the powder is located between the at least one gel phase and the molded body, so that the at least one gel phase(s) is in contact with the powder but not with the molded body. Advantageously, this allows incompatible ingredients to be effectively separated, thus improving storage stability and / or cleaning performance.

[0066] Preferably, the molded body is arranged in the chamber such that it is not in direct contact with the at least one gel phase, preferably with all gel phases. This reduces migration, e.g. of solvents or other low-molecular-weight compounds, between the molded body and the gel phase.

[0067] By introducing at least one gel phase and at least one shaped body that is different from / distinguishable from the gel phase and powder, and which do not come into direct contact with each other, these active ingredients with negative interactions can be separated effectively and efficiently without requiring additional and / or unnecessary separating material. This also improves the product's activity and / or storage stability.

[0068] Such an arrangement with separate phases advantageously reduces negative interactions between incompatible ingredients by incorporating each incompatible ingredient into only one of the phases: the at least one molded body, the at least one powder, or the gel phase(s). The activity of these ingredients is then maintained over a longer period and does not decrease over time due to the reduced contact between the phases resulting from the phase separation.

[0069] According to a preferred embodiment, the at least one gel phase and / or the molded body are in contact with the powder. In particular, both the at least one gel phase, and preferably all gel phases, are in contact with the powder. It is especially preferred if all gel phases and the at least one molded body are in contact with the powder. Preferably, the gel phases and the molded body(ies) do not have direct contact with each other. Advantageously, incompatible ingredients can thus be introduced into a single chamber and effectively separated from each other by their distribution in the gel phases or the molded body, thereby improving storage stability and / or cleaning performance.

[0070] In a preferred embodiment, the powder is located between the at least one gel phase and the molded body, so that the at least one, in particular the gel phase(s), is / are in contact with the powder but not with the molded body. Advantageously, this allows incompatible ingredients to be effectively separated, thus improving storage stability and / or cleaning performance.

[0071] Preferably, the molded body and the gel phase(s) are not located in the same region / level of the single-use cleaning agent portion. Preferably, the gel phase(s) are located at the very bottom (lowest level) in the direction of filling of the single-use cleaning agent portion, the powder in the middle (middle level), and the molded body at the top (uppermost level), so that it can come into direct contact with the sealing agent.

[0072] According to the invention, the single-use cleaning agent portion comprises at least one gel phase distinct from the molded body. This at least one gel phase is contained in the receiving chamber.

[0073] The at least one gel phase and the at least one shaped body differ from each other in at least one respect with regard to their material properties and / or manufacturing methods. For example, they differ with regard to their chemical composition and / or their physical properties (especially preferably their translucency, strength, elasticity).

[0074] According to a preferred embodiment, the molded body and the at least one gel phase have different chemical compositions. In particular, the at least one molded body differs from the at least one gel phase in its chemical composition, especially in the type and / or quantity of the ingredients it contains. In particular, the at least one gel phase exhibits a non-negligible deviation from the composition of the at least one molded body.

[0075] The at least one gel phase therefore preferably has a composition in which less than 85 wt.%, preferably less than 80 wt.%, in particular less than 75 wt.% of the ingredients, based on the total weight of the gel phase, are identical to the composition of the molded body.

[0076] According to a preferred embodiment, the gel phase comprises at least two, preferably at least three, in particular preferably at least four ingredients that are not contained in the at least one molded body and / or the at least one molded body comprises at least two, preferably at least three, in particular preferably at least four ingredients that are not contained in the at least one gel phase.

[0077] This has the advantage that incompatible ingredients can be distributed across the different phases (gel phase(s), molded body, powder) in such a way that direct contact between these ingredients is minimized and side reactions / losses of activity are reduced, without the need for additional, process-related separation measures, such as additional partitions within the single-use cleaning agent portion.

[0078] According to the invention, the gel phase is dimensionally stable at room temperature (20 °C, 1 bar). This is achieved using a flowable mixture which can be shaped as desired.

[0079] After a certain period, a gel phase is obtained that retains its predetermined shape, i.e., it is dimensionally stable. This period, the solidification time, is preferably 15 minutes or less, preferably 10 minutes or less, particularly preferably 5 minutes or less, and most preferably 2 minutes or less. The at least one gel phase is preferably elastic, in particular linearly elastic. The at least one gel phase yields to pressure but does not deform; instead, it returns to its original state when the pressure is removed. The at least one gel phase is cut-resistant. For example, it can be cut with a knife after solidification without being damaged beyond the cut itself. Furthermore, the at least one gel phase is particularly flexible. Due to its flexibility and elasticity, it can assume any desired shape.This also means high breaking strength, which allows for good handling during manufacturing and with regard to transport and storage.

[0080] Preferably, the at least one gel phase is elastic, while the molded body according to the invention has only a low elasticity.

[0081] A force / displacement diagram was created to measure the elasticity of at least one gel phase. The mass was poured into a gel body measuring 47 x 19 x 8 mm and stored at room temperature for 12 hours prior to measurement. The sample was placed in modified plastic inserts with external dimensions of 25 x 20 x 20 mm and a 10 x 10 x 20 mm recess for the mass to be measured. A Lloyd LRX+ (Lloyd Instruments) with a 5 kN measuring head was used as the measuring instrument. A feed rate of 50 mm / min and a measurement point of 1 N preload (zero point) were set. The result is the force in N required to compress the molded body by 8 mm. Due to the elasticity of the gel phase, the original dimensions of the gel phase were restored within 15 minutes after the measurement was completed. Preferably, the values ​​measured in this way (for a compression of 8 mm) lie between 10 N and 40 N, preferably between 15 N and 30 N.

[0082] According to a further preferred embodiment, the at least one gel phase and the at least one molded body have different elasticities. It is particularly preferred that the at least one gel phase is deformable and / or elastic, while the at least one molded body is not easily deformable and / or less elastic.

[0083] Reduced elasticity of a molded part, especially when in direct contact with the closure element, leads to a stiffening and stabilization of the basic shape of the single-use cleaning agent portion. This ensures the powder is held securely in place without compromising the strength and structure of the single-use cleaning agent portion.

[0084] To measure the low elasticity and / or tensile strength of the molded part, a force / displacement diagram was created. A molded part with dimensions of 45 x 35 x 3.4 mm was produced and stored at room temperature for 12 hours before measurement. The part to be tested was placed on the jaws of a vise in such a way that it rested stably and that between 70 and 90% of the test piece's surface area was freely positioned between the two contact surfaces (jaws).

[0085] A Texture Analyser TA.XT plus (Stable Micro Systems Ltd) was used as the measuring instrument, along with the Exponent software (Stable Micro Systems Ltd.) and a 19 mm diameter ball. The following settings were used: a pre-test feed rate of 1 mm / sec, a test feed rate of 0.5 mm / sec, a post-test feed rate of 2 mm / sec, and a pre-test force of 5 grams at a distance of 3 mm. The result is the penetration depth of the ball, in mm, required for the molded part to break. The preferred molded parts broke at the above settings at a penetration depth of 0.1 mm to 1.0 mm, preferably from 0.15 mm to 0.8 mm, and particularly from 0.2 mm to 0.6 mm.

[0086] According to a particularly preferred embodiment, the gel phase does not contain dibenzylidene sorbitol. According to a very particularly preferred embodiment, the gel phase does not contain a benzylidene alditol compound. According to a particularly preferred embodiment, the cleaning agents are powders and the at least one gel phase contains no dibenzylidene sorbitol, and in particular no benzylidene alditol.

[0087] These and other aspects, features, and advantages of the invention will become apparent to the person skilled in the art upon studying the following detailed description and claims. Each feature from one aspect of the invention can be incorporated into any other aspect of the invention. Furthermore, it is understood that the examples contained herein are intended to describe and illustrate the invention, but do not limit it, and in particular, the invention is not limited to these examples. All percentages are weight percentages unless otherwise stated. Numerical ranges specified in the format "from x to y" include the stated values. If several preferred numerical ranges are specified in this format, it is understood that all ranges resulting from the combination of the different endpoints are also included.

[0088] "At least one," as used herein, means one or more, i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, or more. When referring to an ingredient, the statement refers to the type of ingredient and not the absolute number of molecules. Thus, "at least one bleach catalyst," for example, means at least one type of bleach catalyst, i.e., it could refer to one type of bleach catalyst or a mixture of several different bleach catalysts. When used with weight specifications, the statement refers to all compounds of the specified type contained in the composition / mixture, i.e., the composition contains no further compounds of that type beyond the specified quantity of the relevant compounds.

[0089] When reference is made to molar masses herein, these values ​​always refer to the number-mean molar mass Mn, unless explicitly stated otherwise. The number-mean molar mass can be determined, for example, by gel permeation chromatography (GPC) according to DIN 55672-1:2007-08 using THF as the eluent. The mass-mean molar mass Mw can also be determined by GPC, as described for Mn.

[0090] All percentages given in connection with the compositions described herein refer, unless explicitly stated otherwise, to wt%, in each case to the respective phase (i.e. the powder, the gel phase(s), the molded body).

[0091] Certain minimum requirements are placed on the formulation of the at least one gel phase. As already explained, the gel phase must solidify within the shortest possible time. Long solidification times would lead to long production times and thus high costs. According to the invention, solidification time means the period during which the at least one gel phase transitions from a flowable state at 20 °C to a non-flowable, dimensionally stable state at room temperature. Room temperature is defined as a temperature of 20 °C.

[0092] Furthermore, the gel phase must be stable under normal storage conditions. The gel phase according to the invention is a component of a cleaning agent. Cleaning agents are typically stored in a household for a certain period of time. Storage usually takes place near the washing machine or dishwasher. For such storage, the gel phase should be stable. Thus, the gel phase should remain stable even after a storage period of, for example, 4 to 12 weeks, particularly 10 to 12 weeks or longer, at temperatures up to 40°C, particularly at 30°C, particularly at 25°C, or at 20°C, and should not deform or otherwise change in consistency during this time.

[0093] According to a preferred embodiment, the at least one gel phase is introduced in situ into the receiving chamber and solidifies into a solid gel phase(s) at 1 bar and 20 °C, while the molded body is pre-fabricated, and is introduced as a solid body into the cleaning agent portion.

[0094] Visually, the gel phase surface should be clearly distinguishable from the powder and / or the molded body, for example, by a pronounced gloss. The powder surface is usually not glossy, but rather matte, dull, or lackluster, so a gloss finish allows for good differentiation, making the cleaning agent more appealing to consumers. The molded body, on the other hand, is preferably not transparent.

[0095] A change in volume or shrinkage during storage would be disadvantageous, as this would reduce consumer acceptance of the product. Leakage of liquid or seepage of components from the gel phase is also undesirable. Here, too, the visual appearance is relevant. Leakage of liquid, such as solvents, can affect the stability of the gel phase, meaning the components are no longer securely contained and the washing or cleaning effect can be compromised.

[0096] Preferably, the single-use cleaning agent portion contains two or more, preferably three or more, gel phases in the chamber that are distinct from the molded body. The gel phases can be visually identical or differ in shape or color. Furthermore, the cleaning agent portion can contain several gel phases that differ in their chemical composition due to the presence or absence of one or more active ingredients. Preferably, however, the chemical composition remains essentially the same. Most importantly, the gel phases remain distinct from the at least one molded body.

[0097] The chemical composition of the gel phases is considered substantially identical if at least 85% by weight of the ingredients are identical. Preferably, ingredients may be varied by 0.001 to 14% by weight, more preferably by 0.01 to 10% by weight, and most preferably by 0.1 to 7% by weight of the ingredients, based on the total weight of the respective gel phase. This has the advantage that the properties of the gel phases, particularly their processing properties, do not change to such an extent that the manufacturing and processing conditions are significantly altered. Larger changes in the composition of the gel phases than described above have a negative impact on these properties, especially processing properties such as setting time.

[0098] One or more gel phases can preferably be translucent or transparent, resulting in a good optical appearance. The transmission of the gel phase (without dye) is preferably in the range of 100% to 20%, between 100% and 30%, and particularly between 100% and 40%. To measure the light transmittance, the transmittance in % at 600 nm against water as a reference at 20 °C was determined. For this purpose, the mixture was poured into the provided 11 mm round cuvettes and, after a storage period of 12 hours at room temperature, measured in a LICO 300 color measurement system according to Lange. For example, all or none of the gel phases can be translucent or transparent. The presence of opaque and translucent gel phases in the single-dose cleaning agent is preferred according to the invention.

[0099] According to a preferred embodiment, several gel phases are arranged side by side in the receiving chamber. The gel phases are preferably not in direct contact with each other.

[0100] According to a particularly preferred embodiment, three or four gel phases are arranged in the receiving chamber, which are different from the molded body.

[0101] Furthermore, it is preferred that the at least one powder and the at least one gel phase are in direct contact with each other. In this case, there should be no negative interaction between the ingredients of the powder and the gel phase(s). "No negative interaction" here means, for example, that no ingredients or solvents migrate from one phase to the other, or that the stability, in particular storage stability (preferably at 4 weeks and a storage temperature of 30 °C), and / or the aesthetics of the product are not impaired in any way, for example, by color changes, the formation of moist-looking edges, a blurring of the boundary between the two phases, or similar issues.

[0102] In a particularly preferred embodiment, the powder is located in the receiving chamber such that, if one or more gel phases are present in the receiving chamber, the powder completely covers the surface of the gel phase(s) facing the opening of the receiving chamber.

[0103] Surprisingly, it has been found that particularly good storage stability is achieved when the gel phase has a low water content. Low water content, as used in the present invention, means that small amounts of water can be used to produce the at least one gel phase. The water content in the gel phase is particularly 20% by weight or less, preferably 15% by weight or less, particularly 12% by weight or less, and especially between 5% and 10% by weight. The values ​​in wt% refer to the total weight of the gel phase.

[0104] According to a further embodiment, the gel phase, the powder, and / or the molded body are essentially anhydrous. This means that the gel phase is preferably essentially free of water. "Essentially free" here means that the various phases may contain small amounts of water. This water can be introduced into the phase, for example, by a solvent, as water of crystallization, or as a result of reactions between components of the phase. In this embodiment, the proportion of water in the respective phase is 4.9 wt.% or less, 4 wt.% or less, preferably 2 wt.% or less, in particular 1 wt.% or less, especially 0.5 wt.% or less, and in particular 0.1 wt.% or 0.05 wt.% or less. The values ​​in wt.% refer to the total weight of the respective phase (gel phase, powder, molded body).

[0105] According to a particularly preferred embodiment, the weight of all gel phases is between 0.1 g and 4 g, preferably between 0.4 and 3 g, and particularly preferably between 0.7 and 2.5 g.

[0106] Particularly in single-use cleaning agent portions, which have a total weight of 12 to 22 g, particularly preferably 13 g to 20 g, and comprise at least one molded body with a total weight of 4 to 8 g, particularly 5 to 7 g, as well as powder with a total weight of 8 to 15 g, particularly preferably 10 g to 12 g, the weight of all gel phases is 0.4 to 3 g, particularly preferably 0.7 to 2.5 g.

[0107] According to a further preferred embodiment, the weight ratio of the molded body to the gel phase(s) (sum of all gel phases) is from 8:1 to 1:2, preferably from 6:1 to 1:1, particularly from 4.5:1 to 1.5:1, and most preferably from 4:1 to 1.75:1. In the case of several gel phases, the total weight of all gel phases serves to calculate the specified weight ratios (corresponding to the sum of all gel phases). Such ratios lead to particularly good utilization of the different phases within the single-use cleaning agent portion.

[0108] In a further embodiment of the present invention, it is preferred that the weight ratio of the powder to the gel phase (or to the sum / total weight of all gel phases) is from 20:1 to 1:1, preferably from 12:1 to 1.5:1, in particular from 10:1 to 2:1, most preferably from 8:1 to 2.5:1.

[0109] The gel phase comprises at least one gelling agent. According to the invention, the at least one gel phase comprises a water-soluble polymer from the group of optionally acetalized polyvinyl alcohols (PVOH) and their copolymers.

[0110] For the purposes of the invention, copolymers of polyvinyl alcohol are preferably copolymers of polyvinyl alcohol with other monomers, in particular copolymers with anionic monomers. Preferably suitable anionic monomers are vinylacetic acid, alkyl acrylates, maleic acid and their derivatives, in particular monoalkyl maleates (especially monomethyl maleate), dialkyl maleates (especially dimethyl maleate), maleic anhydride, fumaric acid and their derivatives, in particular monoalkyl fumarate (especially monomethyl fumarate), dialkyl fumarate (especially dimethyl fumarate), fumaric anhydride, itaconic acid and its derivatives, in particular monomethyl itaconate, dialkyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid (methyl maleic acid) and its derivatives, monoalkyl citraconic acid (especially methyl citraconic acid), dialkyl citraconic acid (dimethyl citraconic acid), citraconic anhydride, mesaconic acid (methyl fumaric acid) and its derivatives, monoalkyl mesaconate, dialkyl mesaconate, mesaconic anhydride.Glutaconic acid and its derivatives, monoalkyl glutaconate, dialkyl glutaconate, glutaconic anhydride, vinylsulfonic acid, alkylsulfonic acid, ethylenesulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate and their combinations, as well as the alkali metal salts or esters of the aforementioned monomers.

[0111] Particularly preferred are the copolymers of PVOH selected from copolymers of polyvinyl alcohol with a monomer, in particular selected from the group consisting of monoalkyl maleates (especially monomethyl maleate), dialkyl maleates (especially dimethyl maleate), maleic anhydride, and combinations thereof, as well as the alkali salts or esters of the aforementioned monomers. The values ​​specified for polyvinyl alcohols themselves apply to the suitable molar masses.

[0112] According to the invention, the at least one gel phase comprises polyvinyl alcohol and / or optionally acetalized polyvinyl alcohols, hereinafter referred to as PVOH. These gel phases produced in this way have a particularly high melting point, are dimensionally stable (even at 40 °C), and do not change their shape, or only minimally, even during storage. In particular, they are also relatively unreactive with regard to direct negative interactions with components of the powder. PVOH can also readily produce low-moisture or anhydrous gel phases. When PVOH is used as the polymer for the at least one gel phase, low-viscosity melts are obtained at 110-120 °C, which makes them particularly easy to process. In particular, the gel phase can be filled quickly and precisely into the water-soluble coating without clumping or inaccurate metering.Furthermore, these gel phases adhere particularly well to the water-soluble coating, especially if the coating is also made of PVOH. This is visually advantageous. The rapid solidification of at least one PVOH gel phase allows for particularly fast further processing of the gel phases. Moreover, the good solubility of the resulting gel phases is especially beneficial for the overall solubility of the cleaning agent.

[0113] According to the invention, the gel phase comprises PVOH in a proportion of approximately 5 wt.% to 40 wt.%, in particular 7 wt.% to 35 wt.%, preferably 8.5 wt.% to 25 wt.%. Significantly lower proportions of PVOH do not lead to the formation of a stable gel phase. The values ​​are based on the total weight of the gel phase(s).

[0114] Polyvinyl alcohols are thermoplastic polymers that are typically produced as a white to yellowish powder by the hydrolysis of polyvinyl acetate. Polyvinyl alcohols (PVOH) are resistant to almost all anhydrous organic solvents. Polyvinyl alcohols with a molar mass of 30,000 to 60,000 g / mol are preferred.

[0115] Within the scope of the present invention, it is preferred that the at least one gel phase comprises polyvinyl alcohol, the degree of hydrolysis of which is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 mol% and especially 82 to 88 mol%.

[0116] Preferred are polyvinyl alcohols in the form of white-yellowish powders or granules with degrees of polymerization in the range of approximately 100 to 2500 (molar masses of approximately 4000 to 100,000 g / mol) and degrees of hydrolysis of 80 to 99 mol%, preferably 80 to 90 mol%, in particular 87 to 89 mol%, for example 88 mol%, which accordingly still contain a residual content of acetyl groups (acetalized polyvinyl alcohol).

[0117] PVOH powders with the aforementioned properties, suitable for use in at least one gel phase, are marketed, for example, under the names Mowiol® or Poval® by Kuraray. The Poval® grades, especially grades 3-83, 3-88, and preferably 4-88, as well as Mowiol® 4-88 from Kuraray, are particularly suitable.

[0118] The water solubility of polyvinyl alcohol can be modified by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols that are acetalized or ketalized with the aldehyde or ketone groups of saccharides or polysaccharides, or mixtures thereof, have proven particularly advantageous due to their exceptionally good cold water solubility. The reaction products of polyvinyl alcohol and starch are also extremely beneficial. Furthermore, the water solubility can be modified by complexation with nickel or copper salts or by treatment with dichromates, boric acid, or borax, thus allowing it to be precisely adjusted to desired values.

[0119] According to the invention, the at least one gel phase can further comprise anionic polymers or copolymers with structural properties. The polymers listed below can, optionally, also be contained in at least one of the other phases of the cleaning agent. Preferably, this is a polycarboxylate. Preferably, a copolymeric polyacrylate, preferably a sulfopolymer, preferably a copolymeric polysulfonate, or preferably a hydrophobically modified copolymeric polysulfonate is used as the polycarboxylate. The copolymers can have two, three, four, or more different monomer units. Preferred copolymeric polysulfonates contain, in addition to sulfonic acid group-containing monomer(s), at least one monomer from the group of unsaturated carboxylic acids.

[0120] Unsaturated carboxylic acids of the formula R 1< (R 2< )C=C(R 3< )COOH are particularly preferred, in which R 1< to R 3< independently represent -H, -CH 3 , a straight-chain or branched saturated alkyl group with 2 to 12 carbon atoms, a straight-chain or branched, mono- or poly-unsaturated alkenyl group with 2 to 12 carbon atoms, alkyl or alkenyl groups substituted with -NH2, -OH or -COOH as defined above, or -COOH or -COOR 4< , where R 4< is a saturated or unsaturated, straight-chain or branched hydrocarbon group with 1 to 12 carbon atoms.

[0121] Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid, or mixtures thereof. Unsaturated dicarboxylic acids can, of course, also be used.

[0122] For the sulfonic acid group-containing monomers, those of the formula R 5< (R 6< )C=C(R 1< )-X-SO 3 H are preferred, in which R 5< to R 7< independently represent -H, -CH 3 , a straight-chain or branched saturated alkyl group with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl group with 2 to 12 carbon atoms, alkyl or alkenyl groups substituted with -NH 2 , -OH or -COOH, or -COOH or -COOR 4<, where R 4< is a saturated or unsaturated, straight-chain or branched hydrocarbon group with 1 to 12 carbon atoms, and X represents an optional spacer group selected from -(CH 2 ) n - with n = 0 to 4. -COO-(CH 2 ) k - with k = 1 to 6, -C(O)-NH-C(CH 3 ) 2 -, - C(O)-NH-C(CH 3 ) 2 -CH 2 - and -C(O)-NH-CH(CH 3 )-CH 2 -.

[0123] Among these monomers, preferred are those of the formulas H₂C=CH-X-SO₃H, H₂C=C(CH₃)-X-SO₃H, or HO₃SX-(R₆<)C=C(R₇<)-X-SO₃H, in which R₆< and R₇< are independently selected from -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, and -CH(CH₃)₂, and X represents an optional spacer group selected from -(CH₂)ₙ (n = 0 to 4), -COO-(CH₂)ₖ (k = 1 to 6), -C(O)-NH-C(CH₃)₂, -C(O)-NH-C(CH₃)₂, and -C(O)-NH-CH(CH₃)₂. )-CH 2 -.

[0124] Particularly preferred sulfonic acid group-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, metallylsulfonic acid, allyloxybenzenesulfonic acid, metallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, and mixtures of the aforementioned acids or their water-soluble salts. In the polymers, the sulfonic acid groups can be present wholly or partially in neutralized form, meaning that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and especially for sodium ions.The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

[0125] The monomer distribution of the copolymers preferably used according to the invention is, in the case of copolymers containing only carboxylic acid group-containing monomers and sulfonic acid group-containing monomers, preferably 5 to 95 wt.% each, and particularly preferably the proportion of the sulfonic acid group-containing monomer is 50 to 90 wt.% and the proportion of the carboxylic acid group-containing monomer is 10 to 50 wt.%, the monomers being preferably selected from those mentioned above. The molar mass of the sulfo copolymers preferably used according to the invention can be varied to adapt the properties of the polymers to the desired application. Preferred cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 g·mol⁻¹, preferably of 4000 to 25,000 g·mol⁻¹, and particularly of 5000 to 15,000 g·mol⁻¹.

[0126] In a further preferred embodiment, the copolymers comprise, in addition to a carboxyl group-containing monomer and a sulfonic acid group-containing monomer, at least one nonionic, preferably hydrophobic, monomer. The use of these hydrophobically modified polymers has particularly improved the rinsing performance of dishwashing detergents according to the invention.

[0127] Particularly preferably, the at least one gel phase further comprises an anionic copolymer, wherein the anionic copolymer is a copolymer comprising i) Monomers containing carboxylic acid groups ii) Monomers containing sulfonic acid groups iii) Non-ionic monomers, especially hydrophobic monomers is used.

[0128] Preferably, nonionic monomers of the general formula R 1< (R 2< )C=C(R 3< )-XR 4< are used, in which R 1< to R 3< independently represent -H, -CH 3 or - C 2 H 5, X represents an optional spacer group selected from -CH 2 -, - C(O)O- and -C(O)-NH-, and R 4< represents a straight-chain or branched saturated alkyl group with 2 to 22 carbon atoms or an unsaturated, preferably aromatic group with 6 to 22 carbon atoms.

[0129] Particularly favored nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4,4-trimethylpentene-1, 2,4,4-trimethylpentene-2,2,3-dimethylhexene-1, 2,4-diemethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4,4-dimethylhexane-1, ethylcyclohexyne, 1-octene, α-olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-Octadecene and C 22-α-olefin, 2-styrene, α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N-(methyl)acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, N-(2-ethylhexyl)acrylamide, octyl acrylateMethacrylic acid octyl ester, N-(octyl)acrylamide, acrylic acid lauryl ester, methacrylic acid lauryl ester, N-(lauryl)acrylamide, acrylic acid stearyl ester, methacrylic acid stearyl ester, N-(stearyl)acrylamide, acrylic acid behenyl ester, methacrylic acid behenyl ester and N-(behenyl)acrylamide or mixtures thereof, in particular acrylic acid, ethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and mixtures thereof.

[0130] According to the invention, the at least one gel phase can also contain further polymers. The presence of polyalkylene glycols, in particular polyethylene glycols, in the gel phase is preferred.

[0131] Polyethylene glycols with an average molar mass between approximately 100 and 8000 are particularly suitable. The aforementioned polyethylene glycols are especially preferred in amounts of 1 to 40 wt.%, preferably 5 to 35 wt.%, and particularly 10 to 30 wt.%, for example 15 to 25 wt.%, preferably based on the total weight of the gel phase.

[0132] Surprisingly, it has been shown that PVOH, in combination with anionic polymers or copolymers, particularly sulfopolymers, also leads to the formation of gel phases with insensitive surfaces. These surfaces can be touched by the end user without any material adhering to their hands. Even within packaging, no material abrasion occurs. Therefore, the gel phase preferably comprises PVOH and an anionic copolymer / polymer. The proportion of the anionic polymer is preferably 1 wt.% to 35 wt.%, particularly 3 wt.% to 30 wt.%, especially 4 wt.% to 25 wt.%, preferably 5 wt.% to 20 wt.%, for example 10 wt.%, based on the total weight of the gel phase. Sulfopolymers also ensure an excellent surface gloss. Furthermore, fingerprints are not retained.Therefore, the proportion of sulfopolymers, in particular sulfopolymers with AMPS as the sulfonic acid group-containing monomer, for example Acusol 590, Acusol 588 or Sokalan CP50, is preferably 1 wt.% to 25 wt.%, in particular 3 wt.% to 15 wt.%, particularly 4 wt.% to 12 wt.%, preferably 5 wt.% to 10 wt.% based on the weight of the gel phase. In a particularly preferred embodiment, the at least one gel phase therefore comprises PVOH as well as a sulfopolymer and at least one polyhydric alcohol.

[0133] A particularly preferred embodiment relates to at least one gel phase or gel phases containing polyvinyl alcohol as a polymer, as described above, in combination with polyethylene glycols. Polyethylene glycols with an average molar mass between approximately 100 and approximately 2000 g / mol, preferably between 200 and 1000 g / mol, and particularly preferably between 300 and 800 g / mol (for example, around 400 g / mol INCI: PEG400), are particularly preferred in combination with polyvinyl alcohol.

[0134] In particular, it is advantageous that the at least one gel phase comprising polyvinyl alcohol additionally contains polyethylene glycols with an average molar mass of approximately 300 to 800 g / mol in amounts of 10 to 30 wt% based on the total weight of the at least one gel phase. Surprisingly, it has been shown that the addition of polyethylene glycols, especially those with average molar masses up to 800 g / mol, to the at least one gel phase leads to an acceleration of the solidification time of the gel phases. This is particularly advantageous for production processes, as further processing of the solidified gel phases can be carried out much faster and thus generally more cost-effectively.

[0135] Particularly preferably, the at least one gel phase comprises at least one alkanetriol and / or at least one alkanediol, preferably at least one C3 to C6 alkanetriol and / or at least one C3 to C5 alkanediol as a polyhydric alcohol. More preferably, it comprises one alkanetriol and one alkanediol as at least one polyhydric alcohol. Particularly preferred is a gel phase comprising at least one (optionally acetalized) PVOH, as well as one C3 to C5 alkanediol and one C3 to C6 alkanetriol.

[0136] Surprisingly, it has been shown that combining a suitable triol (alcantriol) with a suitable diol (alkanediol) results in particularly short solidification times. The resulting gel phases are also transparent and have a glossy surface, which contributes to the appealing visual appearance of the cleaning agent according to the invention. The terms diol and alkanediol are used synonymously here. The same applies to triol and alkanetriol.

[0137] The amount of alkanediols and / or alcanetriols used in the gel phases according to the invention is preferably at least 45% by weight, and in particular 55% by weight or more. Preferred amounts are from 5% by weight to 75% by weight, and in particular from 10% by weight to 70% by weight, based on the total weight of the gel phase.

[0138] Particularly preferred are the C3 to C6 alkanetriol glycerol and / or 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (also called 1,1,1-trimethylolpropane). The C3 to C5 alkanediol is preferably 1,3-propanediol and / or 1,2-propanediol. Surprisingly, it has been found that the chain length of the diol, and in particular the position of the OH groups, influences the transparency of the gel phase. Preferably, therefore, the OH groups of the diol are not arranged on immediately adjacent carbon atoms. In particular, there are three or four carbon atoms, and especially three carbon atoms, between the two OH groups of the diol. The diol 1,3-propanediol is particularly preferred. Surprisingly, it has been shown that particularly good results are achieved with mixtures containing glycerin and 1,3-propanediol and / or 1,2-propanediol.

[0139] If glycerol is present in the gel phase as an alkanetriol, the proportion of glycerol based on the total weight of the gel phase is preferably 5 wt.% to 70 wt.%, in particular 10 wt.% to 65 wt.%, especially 20 wt.% to 40 wt.%.

[0140] If several alkanediols are contained in the gel phase, the proportion of alkanediols, based on the total weight of the gel phase, is preferably 5 wt.% to 70 wt.%, in particular 7 wt.% to 65 wt.%, especially 10 wt.% to 40 wt.%.

[0141] If the gel phase comprises at least one alkanediol, in particular 1,3-propanediol or 1,2-propanediol, the proportion of alkanediol, in particular 1,3-propanediol or 1,2-propanediol, based on the total weight of the gel phase, is preferably 5% to 70% by weight, in particular 10% to 65% by weight, and particularly 20% to 45% by weight. If 1,3-propanediol is included in the gel phase, the proportion of 1,3-propanediol, based on the total weight of the gel phase, is in particular 10% to 65% by weight, and particularly 20% to 45% by weight. A gel phase containing 20% ​​to 45% by weight of 1,3-propanediol and / or 1,2-propanediol and 10% to 65% by weight of glycerol, each based on the total weight of the gel phase, is particularly preferred.

[0142] It has been shown that rapid solidification of a gel phase at 20 °C is possible in these areas, and that the resulting phases are storage-stable and transparent. The glycerin content, in particular, affects the curing time.

[0143] If the at least one gel phase according to the invention comprises a C3 to C6 alkanetriol and a C3 to C5 alkanediol, their weight ratio is preferably 3:1 to 2:1. In particular, their weight ratio is 2:1 if glycerol and 1,3-propanediol are included as polyhydric alcohols. Surprisingly, it has been found that, at these weight ratios, storage-stable, glossy, transparent gel phases can be obtained within short solidification times at 20°C of 10 minutes or less.

[0144] Particularly preferred embodiments of the present invention comprise at least one gel phase comprising 8 to 20 wt.% PVOH, 15 to 30 wt.% 1,3-propanediol, 30 to 40 wt.% glycerol, 5 to 15 wt.% sulfonic acid group-containing polyacrylate copolymer, and 2-15 wt.% polyethylene glycol (preferably with an average molar mass of 200-600 g / mol), wt.% each based on the total weight of the gel phase.

[0145] The cleaning agent according to the invention preferably comprises at least one surfactant. This surfactant is selected from the group consisting of anionic, nonionic, and cationic surfactants. The cleaning agent according to the invention may also contain mixtures of several surfactants selected from the same group.

[0146] According to the invention, the powder, the molded body, and / or optionally the gel phase(s) each comprise at least one surfactant. However, it is also possible that only the powder phase, the gel phase, or the molded body comprises at least one surfactant. If at least two phases (powder, molded body, and / or gel phase(s)) comprise a surfactant, these are preferably different surfactants. However, it is also possible that the powder phase, the molded body, and / or the gel phase contain the same surfactant or surfactants. According to the invention, the at least one powder and / or at least one gel phase preferably contain at least one nonionic surfactant. All nonionic surfactants known to those skilled in the art can be used. Preferably, low-foaming nonionic surfactants are used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. These are specified in more detail below.

[0147] Another class of preferably used non-ionic surfactants, which are used either as the sole non-ionic surfactant or in combination with other non-ionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

[0148] Non-ionic surfactants of the amine oxide type, for example N-cocosalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides, may also be suitable. The amount of these non-ionic surfactants is preferably no more than that of the ethoxylated fatty alcohols, and in particular not more than half of it.

[0149] The cleaning agents according to the invention, particularly those for machine dishwashing, preferably contain non-ionic surfactants from the group of alkoxylated alcohols. Preferably, alkoxylated, and advantageously ethoxylated, alcohols, especially primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, are used as non-ionic surfactants. The alcohol residue may be linear or, preferably, methyl-branched at the 2-position, or the mixture may contain both linear and methyl-branched residues, as is typically the case in oxo alcohol residues. However, alcohol ethoxylates with linear residues derived from 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 moles of EO per mole of alcohol, are particularly preferred.Preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 8-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.

[0150] Preferred alcohol ethoxylates exhibit a narrow range of homologs (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohols with 14 EO, 25 EO, 30 EO, or 40 EO.

[0151] Ethoxylated niotenes obtained from C6-20 monohydroxyalkanols, C6-20 alkylphenols, or C16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles, and particularly more than 20 moles of ethylene oxide per mole of alcohol are particularly preferred. A particularly preferred niotene is obtained from a straight-chain fatty alcohol with 16 to 20 carbon atoms (C16-20 alcohol), preferably a C18 alcohol, and at least 12 moles, preferably at least 15 moles, and particularly at least 20 moles of ethylene oxide. Among these, the so-called "narrow-range ethoxylates" are particularly preferred.

[0152] Preferred surfactants come from the groups of alkoxylated niotonic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) niotonic surfactants are also characterized by good foam control.

[0153] Particularly preferred niotenes for low-foaming niotenes within the scope of the present invention have proven to be those comprising alternating ethylene oxide and alkylene oxide units. Among these, surfactants with EO-AO-EO-AO blocks are preferred, wherein one to ten EO or AO groups are bonded together before a block of the other groups follows. Here, nonionic surfactants of the general formula are used. preferably, in which R 1< represents a straight-chain or branched, saturated or, in particular, polyunsaturated C 6-24 -alkyl or -alkenyl group; each group R 2< or R 3< is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH(CH 3 ) 2 and the indices w, x, y, z independently represent integers from 1 to 6.

[0154] Preferred niotenes of the above formula can be prepared from the corresponding alcohols R1-OH and ethylene or alkylene oxide by known methods. The R1 group in the above formula can vary depending on the origin of the alcohol. If native sources are used, the R1 group has an even number of carbon atoms and is generally unbranched, with linear groups from native alcohols with 12 to 18 carbon atoms, for example, from coconut, palm, tallow, or oleyl alcohol, being preferred. Alcohols accessible from synthetic sources include, for example, the Guerbet alcohols or methyl-branched groups at the 2-position, or linear and methyl-branched groups in the mixture, as are commonly found in oxo alcohol groups.Regardless of the type of alcohol used to produce the niotenes contained in the agents, niotenes are preferred in which R 1< in the above formula represents an alkyl group with 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and especially 9 to 11 carbon atoms.

[0155] In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit, which alternates with the ethylene oxide unit in the preferred niotenes. However, other alkylene oxides are also suitable, where R2 and R3 are independently selected from -CH2CH2-CH3 or -CH(CH3)2, respectively. Niotenes of the above formula are preferably used, where R2 and R3 represent a residue of -CH3, w and x independently represent values ​​of 3 or 4, and y and z independently represent values ​​of 1 or 2.

[0156] Other preferably used non-ionic surfactants are non-ionic surfactants of the general formula R 1< O(AlkO) x M(OAlk) y OR 2< , where R 1< and R 2< independently represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl group with 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl group with 2 to 4 carbon atoms; x and y independently represent values ​​between 1 and 70; and M represents an alkyl group from the group CH 2 , CHR 3< , CR 3< R 4< , CH 2 CHR 3< and CHR 3< CHR 4< , where R 3< and R 4< independently represent a branched or unbranched, saturated or unsaturated alkyl group with 1 to 18 carbon atoms.

[0157] Preferably nonionic surfactants of the general formula R 1< -CH(OH)CH 2 -O(CH 2 CH 2 O) x CH 2 CHR(OCH 2 CH 2 ) y -CH 2 CH(OH)-R 2< , where R, R 1< and R 2< independently represent an alkyl or alkenyl group with 6 to 22 carbon atoms; x and y independently represent values ​​between 1 and 40.

[0158] Particularly preferred are compounds of the general formula R1 -CH(OH)CH2 -O(CH2CH2O)xCH2CHR(OCH2CH2)yO-CH2CH(OH)-R2, in which R represents a linear, saturated alkyl group with 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently have values ​​of 20 to 30. Such compounds can be obtained, for example, by reacting alkyldiols HO-CHR-CH2-OH with ethylene oxide, followed by a reaction with an alkyl epoxide to seal the free OH groups and form a dihydroxy ether.

[0159] Preferred nonionic surfactants are those of the general formula R 1< -CH(OH)CH 2 O-(AO) w -(AO) x -(A"O) y -(A‴O) z -R 2< , in which R 1< represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl residue; R 2< represents hydrogen or a linear or branched hydrocarbon residue with 2 to 26 carbon atoms; A, A', A" and A‴ independently represent a residue from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH(CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH(CH 3 )-CH 2 -, -CH 2 -CH(CH 2 -CH 3 ), w, x, y and z represent values ​​between 0.5 and 120, where x, y and / or z can also be 0. By adding the aforementioned non-ionic surfactants of the general formula R 1 -CH(OH)CH 2 O-(AO) w -(A'O) x -(A"0) y -(A‴O) z -R 2 , hereinafter also referred to as "hydroxy mixed ether", surprisingly significantly improves the cleaning performance of preparations according to the invention, both in comparison to surfactant-free systems and in comparison to systems containing alternative non-ionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

[0160] Particularly preferred are end-group-capped poly(oxyalkylated) niosurfactants which, according to the following formula In addition to a residue R1<, which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, the compound further comprises a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residue R2< with 1 to 30 carbon atoms, where n represents values ​​between 1 and 90, preferably values ​​between 10 and 80, and particularly values ​​between 20 and 60. Surfactants of the above formula in which R1< represents C7 to C13, n represents a natural number from 16 to 28, and R2< represents C8 to C12 are particularly preferred.

[0161] Particularly preferred are surfactants of the formula R1< O[CH2CH(CH3)O] x [CH2CH2O] y CH2CH(OH)R2< , where R1< represents a linear or branched aliphatic hydrocarbon residue with 4 to 18 carbon atoms or mixtures thereof, R2< represents a linear or branched hydrocarbon residue with 2 to 26 carbon atoms or mixtures thereof, and x represents values ​​between 0.5 and 1.5 and y represents a value of at least 15. Examples of these nonionic surfactants include the C2-26 fatty alcohol (PO)1-(EO)15-40-2-hydroxyalkyl ethers, and in particular the C8-10 fatty alcohol (PO)1-(EO)22-2-hydroxydecyl ethers.

[0162] Particularly preferred are end-group-capped poly(oxyalkylated) niotenes of the formula R 1< O[CH 2 CH 2 O] x [CH 2 CH(R 3< )O] y CH 2 CH(OH)R 2< , in which R 1< and R 2< independently represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon residue with 2 to 26 carbon atoms, R 3< is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3, -CH(CH 3 ) 2 , preferably, however, represents -CH 3, and x and y independently represent values ​​between 1 and 32, wherein niotenes with R 3< = -CH 3 and values ​​for x from 15 to 32 and y from 0.5 and 1.5 are particularly preferred.

[0163] Other preferably usable niotenes are the end-capped poly(oxyalkylated) niotenes of the formula R 1< O[CH 2 CH(R 3< )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2< , in which R 1< and R 2< represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues with 1 to 30 carbon atoms, R 3< represents H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl residue, x represents values ​​between 1 and 30, k and j represent values ​​between 1 and 12, preferably between 1 and 5. If the value x > 2, each R 3< in the formula above R 1< O[CH 2 CH(R 3< )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2< can be different. R 1< and R 2< are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues with 6 to 22 carbon atoms, with residues having 8 to 18 carbon atoms being particularly preferred.For the remainder R 3<, H, -CH 3 or -CH 2 CH 3 are particularly preferred. Particularly preferred values ​​for x are in the range of 1 to 20, especially from 6 to 15.

[0164] As described above, each R3< in the formula above can be different if x > 2. This allows the alkylene oxide unit within the square brackets to be varied. For example, if x represents 3, the R3< group can be chosen to form ethylene oxide (R3<= H) or propylene oxide (R3<= CH3) units, which can be joined together in any order, such as (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO), and (PO)(PO)(PO). The value 3 for x is chosen here as an example and can certainly be larger, with the range of variation increasing with increasing x values ​​and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa.

[0165] Particularly preferred end-capped poly(oxyalkylated) alcohols of the formula above have values ​​of k = 1 and j = 1, so that the above formula simplifies to R1< O[CH2CH(R3< )O] x CH2CH(OH)CH2OR2<. In the latter formula, R1<, R2<, and R3< are defined as above, and x represents numbers from 1 to 30, preferably from 1 to 20, and particularly from 6 to 18. Surfactants in which the R1< and R2< substituents have 9 to 14 carbon atoms, R3< represents hydrogen, and x takes on values ​​from 6 to 15 are particularly preferred. Finally, the nonionic surfactants of the general formula R1< -CH(OH)CH2O-(AO) w -R2< have proven to be particularly effective, in which R 1< represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or -alkenyl residue; R 2< represents a linear or branched hydrocarbon residue with 2 to 26 carbon atoms; A represents a residue from the group CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH(CH 3 ), preferably for CH 2 CH 2 , and w represents values ​​between 1 and 120, preferably 10 to 80, in particular 20 to 40.

[0166] Examples of these non-ionic surfactants include the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.

[0167] Preferably, the at least one first and / or the at least one gel phase contains at least one non-ionic surfactant, preferably a non-ionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the non-ionic surfactant in the total weight of the gel phase is preferably 0.5 wt.% to 30 wt.%, preferably 5 wt.% to 25 wt.% and in particular 10 wt.% to 20 wt.%.

[0168] In a further preferred embodiment, the non-ionic surfactant of the first and / or gel phase is selected from non-ionic surfactants of the general formula R 1< -O(CH 2 CH 2 O) x CR 3< R 4< (OCH 2 CH 2 ) y OR 2< , in which R 1< and R 2< independently represent an alkyl or alkenyl group with 4 to 22 carbon atoms; R 3< and R 4< independently represent H or an alkyl or alkenyl group with 1 to 18 carbon atoms; and x and y independently represent values ​​between 1 and 40.

[0169] Compounds of the general formula R1< -O(CH2CH2O)x CR3< R4< (OCH2CH2)y OR2< are particularly preferred, where R3< and R4< represent H and the indices x and y independently take values ​​from 1 to 40, preferably from 1 to 15. Compounds of the general formula R1< -O(CH2CH2O)x CR3< R4< (OCH2CH2)y OR2< are especially preferred, where the R1< and R2< are independently saturated alkyl groups with 4 to 14 carbon atoms and the indices x and y independently take values ​​from 1 to 15, and particularly from 1 to 12. Compounds of the general formula R 1< -O(CH 2 CH 2 O) x CR 3< R 4< (OCH 2 CH 2 ) y OR 2< are also preferred, in which one of the residues R 1< and R 2< is branched.Compounds of the general formula R 1< -O(CH 2 CH 2 O) x CR 3< R 4< (OCH 2 CH 2 ) y OR 2< are particularly preferred, in which the indices x and y independently take values ​​from 8 to 12.

[0170] The specified carbon chain lengths and degrees of ethoxylation or alkoxylation of the niotenes represent statistical averages, which may be whole numbers or fractions for a specific product. Due to the manufacturing processes, commercial products of the aforementioned formulas usually do not consist of a single individual compound, but rather of mixtures. This can result in average values ​​for both the carbon chain lengths and the degrees of ethoxylation or alkoxylation, and consequently, fractions.

[0171] Of course, the aforementioned non-ionic surfactants (niotenes) can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.

[0172] Particularly preferred are nonionic surfactants with a melting point above room temperature. Nonionic surfactant(s) with a melting point above 20°C, preferably above 25°C, particularly preferably between 25 and 60°C, and especially between 26.6 and 43.3°C, is / are particularly preferred.

[0173] Suitable nonionic surfactants with melting or softening points within the specified temperature range include, for example, low-foaming nonionic surfactants that can be solid or highly viscous at room temperature. If nonionic surfactants that are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pa·s, preferably above 35 Pa·s, and particularly above 40 Pa·s. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.

[0174] The niotenoid, which is solid at room temperature, preferably contains propylene oxide (PO) units in the molecule. Preferably, such PO units constitute up to 25 wt.%, particularly preferably up to 20 wt.%, and especially up to 15 wt.% of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols that additionally contain polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol portion of such niotenoid molecules preferably constitutes more than 30 wt.%, particularly preferably more than 50 wt.%, and especially more than 70 wt.% of the total molar mass of such niotenoids. Preferred compositions are characterized in that they contain ethoxylated and propoxylated niotenoids in which the propylene oxide units constitute up to 25 wt.%, preferably up to 20 wt.%, and especially up to 15 wt.% of the total molar mass of the nonionic surfactant.

[0175] Other particularly preferred niotenes with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend comprising 75 wt% of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol ethylene oxide and 44 mol propylene oxide, and 25 wt% of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 mol ethylene oxide and 99 mol propylene oxide per mol trimethylolpropane.

[0176] In a preferred embodiment, the weight fraction of the non-ionic surfactant in the total weight of the single-use cleaning agent portion is 0.1 to 20 wt.%, particularly preferably 0.5 to 15 wt.%, and especially 1.5 to 10 wt.%.

[0177] All anionic surfactants are suitable for use in dishwashing detergents. These are characterized by a water-soluble anionic group, such as a carboxylate, sulfate, sulfonate, or phosphate group, and a lipophilic alkyl group with approximately 8 to 30 carbon atoms. The molecule may also contain glycol or polyglycol ether groups, ester, ether, and amide groups, as well as hydroxyl groups. Suitable anionic surfactants are preferably in the form of sodium, potassium, and ammonium salts, as well as mono-, di-, and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group. However, zinc, manganese(II), magnesium, calcium, or mixtures thereof can also serve as counterions.

[0178] Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

[0179] Instead of or in combination with the surfactants mentioned above, cationic and / or amphoteric surfactants, such as betaines or quaternary ammonium compounds, can also be used. However, it is preferred that no cationic and / or amphoteric surfactants are used.

[0180] Preferred cleaning agents according to the invention are further characterized in that they contain less than 5.0 wt.% anionic surfactant in the at least one powder phase, the at least one molded body and / or the at least one gel phase, particularly in the powder phase, and most preferably in the entire cleaning agent, since the addition of anionic surfactants has proven to be disadvantageous with regard to the phase properties, in particular their hardness, friability (abrasion behavior) and post-hardening behavior.

[0181] Substances that also serve as ingredients in cosmetic products are referred to below, where applicable, according to the International Nomenclature of Cosmetic Ingredients (INCI). Chemical compounds bear an INCI name in English. The INCI names can be found in the "International Cosmetic Ingredient Dictionary and Handbook, 7th Edition (1997)," published by The Cosmetic, Toiletry and Fragrance Association (CTFA), Washington, D.C. (USA). The abbreviation CAS indicates that the following sequence of numbers is a designation from the Chemical Abstracts Service.

[0182] The cleaning agents according to the invention contain ingredients known to those skilled in the art, in particular those for machine dishwashing detergents, such as builders, bleaching agents, bleach activators, bleach catalysts, enzymes, especially proteases and / or amylases, and dispersing polymers. Furthermore, they may contain pH adjusters, glass corrosion inhibitors, other solvents, thickeners, sequestrants, electrolytes, corrosion inhibitors, especially silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances (especially in the powder), additives to improve drainage and drying properties, preservatives, and antimicrobial agents (disinfectants) in quantities typically not exceeding 5% by weight.

[0183] The cleaning agent according to the invention comprises at least one powder and at least one gel phase. The cleaning agent can have one, two, three, or more different powders present as separate phases; likewise, it can have one, two, three, or more separate gel phases, which may be identical or distinguishable with respect to color, shape, and / or chemical composition. The cleaning agent preferably comprises a molded body, a powder, and at least two gel phases. A further preferred embodiment is one in which the single-use cleaning agent portion comprises a powder, a molded body, and three or four gel phases.

[0184] According to the invention, the at least one powder and the at least one gel phase are fully or partially adjacent to each other. It is preferred that the two phases are directly adjacent. If the at least one powder and the at least one gel phase are directly adjacent to each other, stability is important in addition to the shortest possible solidification time of the at least one gel phase. Stability here means that components contained in the gel phase do not migrate into the at least one powder, but rather that even after prolonged storage, the powder and the at least one gel phase remain optically separate and do not interact with each other, such as through diffusion of liquid components from one phase to the other or reaction of components of one phase with those in the other phase.Surprisingly, it has been shown that this can be achieved by a gel phase containing glycerol, at least one C3 to C5 alkanediol, or glycerol, PVOH and at least one C3 to C5 alkanediol.

[0185] In a particularly preferred embodiment, the single-use cleaning agent portion according to the invention, comprising the cleaning agent composition according to the invention, comprising at least one powder, at least one shaped body other than the powder, and optionally at least one gel phase, does not contain any phases that are liquid at 20 °C, 1 bar. The phases present (powder, shaped body, and gel phase(s)) are solid at 20 °C, 1 bar, in order to prevent mixing and / or dissolution of individual active ingredients and / or phases and to allow the advantages realized by the present invention to materialize. Should liquid phases actually be desired, these must be contained in other chambers of the single-use cleaning agent portion.

[0186] Another subject matter of the present application is a method for cleaning hard surfaces, in particular dishes, in which the surface is treated in a manner known per se using a cleaning agent according to the invention. In particular, the surface is brought into contact with the cleaning agent according to the invention. The cleaning is carried out in particular with a cleaning machine, preferably a dishwasher.

[0187] Another object of the present invention is the use of a cleaning agent for cleaning hard surfaces, in particular dishes, especially in machine dishwashers.

[0188] In a preferred embodiment, the present application relates to machine dishwashing detergents. According to this application, machine dishwashing detergents are defined as compositions that can be used to clean soiled dishes in a machine dishwashing process. Thus, the machine dishwashing detergents according to the invention differ, for example, from machine rinse aids, which are always used in combination with machine dishwashing detergents and do not have any cleaning effect of their own.

[0189] Another subject matter of this application is a method for producing a previously described single-dose cleaning agent according to the invention, comprising the following steps i) Providing a water-soluble receiving chamber; ii) Introducing at least one gel phase into the receiving chamber; iii) Filling at least one powder into the receiving chamber; iv) Applying a molded body to the powder; v) Closing the filled receiving chamber with a water-soluble closure element, wherein the at least one gel phase comprises a water-soluble polymer from the group consisting of optionally acetalized polyvinyl alcohols and their copolymers.

[0190] Several different processes are suitable for manufacturing the water-soluble receiving chamber, including casting or compacting water-soluble substances or mixtures, optionally containing washing or cleaning agents. However, due to their high process efficiency, injection molding of water-soluble material and, in particular, deep drawing of water-soluble films are preferred for producing the water-soluble receiving chamber.

[0191] The water-soluble material or film forming the receiving chamber can comprise one or more structurally distinct water-soluble polymers. Particularly suitable water-soluble polymers include those from the group of (optionally acetalized) polyvinyl alcohols (PVOHs) and their copolymers.

[0192] Water-soluble films for the production of the water-soluble packaging are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol⁻¹, preferably from 20,000 to 500,000 gmol⁻¹, particularly preferably from 30,000 to 100,000 gmol⁻¹ and particularly from 40,000 to 80,000 gmol⁻¹.

[0193] The production of polyvinyl alcohols and polyvinyl alcohol copolymers generally involves the hydrolysis of intermediate polyvinyl acetates. Preferred polyvinyl alcohols and polyvinyl alcohol copolymers have a degree of hydrolysis of 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and especially 82 to 88 mol%.

[0194] Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylene-unsaturated carboxylic acid, its salt, or its ester. Particularly preferred are such polyvinyl alcohol copolymers containing, besides vinyl alcohol, sulfonic acids such as 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, or mixtures thereof; among the esters, C1-4 alkyl esters or hydroxyalkyl esters are preferred. Further suitable monomers include ethylene-unsaturated dicarboxylic acids, for example, itaconic acid, maleic acid, fumaric acid, and mixtures thereof.

[0195] Suitable water-soluble films for use in the water-soluble packaging according to the invention are films marketed by MonoSol LLC, for example, under the designations M8630, M8720, M8310, C8400, or M8900. Other suitable films include films designated Solublon® PT, Solublon® GA, Solublon® KC, or Solublon® KL from Aicello Chemical Europe GmbH, or the VF-HP film from Kuraray, as well as the Hi-Selon series from Mitsubishi Chemical Corporation.

[0196] The water-soluble films may contain additional active ingredients or fillers, as well as plasticizers and / or solvents, especially water.

[0197] Other active ingredients include, for example, materials that protect the detergent ingredients encapsulated by the film from degradation or deactivation by light exposure. Antioxidants, UV absorbers, and fluorescent dyes have proven particularly suitable for this purpose.

[0198] Examples of plasticizers that can be used include glycerin, ethylene glycol, diethylene glycol, propanediol, 2-methyl-1,3-propanediol, sorbitol or mixtures thereof.

[0199] To reduce its coefficient of friction, the surface of the water-soluble film of the detergent portion unit can optionally be dusted with fine powder. Sodium aluminosilicate, silicon dioxide, talc, and amylose are examples of suitable powders.

[0200] The single-use cleaning agent portions according to the invention comprise at least one powder and at least one shaped body different from the powder, wherein the powder and the shaped body are supplemented according to the invention by at least one gel phase. As described above, the gel phase is different from the powder and the shaped body.

[0201] The gel phase is preferably introduced into the receiving chamber before the powder. The number of gel phases introduced into the receiving chamber can vary. For example, in step ii) of the process, only a single gel phase can be introduced into the receiving chamber. Alternatively, and to increase formulation flexibility and improve product appearance, two, three, or four gel phases can be introduced into the receiving chamber in step ii). The two, three, four, or more gel phases preferably differ in their composition and include, for example, different active ingredients, have different active ingredient concentrations, or different colors.

[0202] If, in step ii), more than one gel phase, for example two, three, or four gel phases, are introduced into the receiving chamber, these two, three, or four gel phases should preferably be introduced into the receiving chamber in such a way that they are not in direct contact with each other. This procedure avoids undesirable reactions between individual active ingredients contained in the different gel phases and improves the product appearance.

[0203] In step iii) of the process, at least one powder is filled into the receiving chamber. If one or more gel phases were introduced into the receiving chamber in the previous step, the powder in step iii) is preferably filled into the receiving chamber in such a way that the surface of the gel phase(s) facing the opening of the receiving chamber is completely covered with powder.

[0204] For efficient filling of the receiving chambers with the powder, it has proven advantageous if the powder has a flowability of greater than 40%, preferably greater than 50%, and in particular greater than 60%, relative to the standard.

[0205] The free-flowing property of the powder refers to its ability to flow freely under its own weight. Free-flowing property is determined by measuring the discharge time of 1000 ml of cleaning agent powder from a standardized, initially sealed, flow test funnel with a 16.5 mm diameter outlet. This is done by measuring the time for the complete discharge of the granular mixture, particularly the powdered phase, preferably the powder and / or granules, e.g., the powder, after opening the outlet. This time is then compared to the discharge rate (in seconds) of a standard test sand, whose discharge rate is defined as 100%. The defined sand mixture used to calibrate the flow test apparatus is dry sea sand. Sea sand with a particle diameter of 0.4 to 0.8 mm is used, available, for example, from Carl Roth, Germany, CAS No. [14808-60-7].For drying, the sea sand is dried for 24 hours at 60 °C in a drying oven on a plate with a maximum layer height of 2 cm before measurement.

[0206] Preferred embodiments of the powders according to the invention have an angle of repose / slope of 26 to 35°, 27 to 34°, and 28 to 33°, wherein the angle of repose is determined according to the method described below after 24 hours following the production of the granular mixture of the solid composition, in particular the powdered solid phase, preferably the powder and / or granules, and storage at 20°C. Such angles of repose have the advantage that the filling of the cavities with the at least one solid phase can be carried out relatively quickly and precisely.

[0207] To determine the angle of repose (or angle of slope) of the powder, a 400 ml powder hopper with a 25 mm diameter outlet is suspended vertically in a stand. The hopper is raised at a speed of 80 mm / min using a manually operated knurled wheel, causing the granular mixture, particularly the powdered phase (preferably the powder and / or granules), to trickle out. This forms a so-called cone of repose. The height and diameter of the cone are determined for each particulate phase. The angle of repose is then calculated by multiplying the cone height by the cone diameter by 100.

[0208] Particularly suitable are powders that exhibit a free-flowing capacity relative to the aforementioned standard test substance of greater than 40%, preferably greater than 50%, particularly greater than 55%, particularly preferably greater than 60%, and particularly preferably between 63% and 80%, for example between 65% and 75%. Particularly suitable are granular mixtures of a solid composition, especially powders and / or granules that exhibit a free-flowing capacity relative to the aforementioned standard test substance of greater than 40%, preferably greater than 45%, particularly greater than 50%, particularly preferably greater than 55%, and particularly preferably greater than 60%, wherein the free-flowing capacity is measured 24 hours after the powder has been produced and stored at 20°C.

[0209] Lower flowability values ​​are generally unsuitable, as precise powder dosing is essential from a process engineering perspective. Values ​​greater than 50%, particularly greater than 55%, and preferably greater than 60% (where flowability is measured 24 hours after powder production and storage at 20°C) have proven advantageous. This is because the good dosing properties of the granular mixtures, especially the powdered phases, preferably the powders and / or granules, result in only minor fluctuations in the dosed quantity or composition. More precise dosing leads to consistent product output, thus avoiding economic losses due to overdosing. Furthermore, the ease of dosing the granular mixtures, especially the powdered phase, preferably the powders and / or granules, e.g., the powder, is advantageous, as it allows for a faster dosing process.Furthermore, such good flowability better prevents the powder from getting onto the part of the water-soluble coating that is necessary for creating the seal.

[0210] Following step iii), the fill level of the receiving chamber is preferably above 60 vol.%, in particular above 70 vol.%.

[0211] In step iv), which follows step iii), the molded body is applied to the powder. This is preferably done such that the surface of the powder facing the opening of the receiving chamber is covered by the molded body to more than 75%, preferably more than 75%, more preferably more than 75%, in particular more than 80%, and most preferably more than 85%.

[0212] The application in step iv) can be achieved by placing pre-formed shapes or by in situ application by solidifying a flowable melt or gel.

[0213] The shaped body applied, preferably laid, onto the powder in step iv) is preferably pre-formed, i.e., it is not obtained in situ in step iv) by solidification of a flowable melt or a flowable gel.

[0214] The shape of the molded body is generally freely selectable; its side surfaces can, for example, be convex, concave, or flat. However, certain spatial configurations have proven particularly advantageous with regard to the manufacturability and processing of the molded bodies.

[0215] The molded parts used in step iv) preferably have a flat underside whose largest diagonal is greater than the height of the molded part, and the molded part is placed with its flat underside onto the surface of the powder. Such molded parts can not only be produced easily, for example by casting or tableting, but can also be easily applied to the powder mechanically. It is preferred that the molded part in step iv) has a flat underside whose largest diagonal is more than 1.5 times, preferably more than 2 times, the height of the molded part, and that the molded part is placed with its flat underside onto the surface of the powder.

[0216] For manufacturability, for example with regard to demolding the molded part from a mold, it has proven advantageous if the underside of the gel body has no corners. Preferred gel bodies are therefore characterized by oval undersides or, alternatively, by ellipsoidal or round, preferably round, undersides. Corresponding molded parts with a non-angular underside are also preferred by many consumers due to their appearance. Therefore, molded parts with a bottom and a top surface connected by a cylindrical outer surface are preferred, for example.

[0217] In preferred process variants in step iv) the molded body has an oval underside and the molded body is placed with the flat underside onto the surface of the powder, or in step iv) the molded body has an ellipsoidal or round, preferably a round, underside and the molded body is placed with the round underside onto the surface of the powder.

[0218] Advantages regarding space utilization during manufacturing and packaging can be achieved through the use of angular molded parts. For example, if the molded parts are cast in the form of sheets which are subsequently cut into smaller parts, angular undersides are advantageous because such parts can be cut without producing any waste. In an alternative embodiment of the process, the molded parts used in step iv) therefore have angular undersides, in particular triangular, square, or hexagonal undersides, and are placed on the surface of the powder with these undersides facing down. For further processing or packaging, it can be advantageous if the molded part has an angular underside with rounded corners.

[0219] With regard to the manufacture, packaging and use of the detergent portion units, it has also proven advantageous if the molded body placed on the powder with its underside in step iv) has a top surface that is parallel to the underside.

[0220] In a first preferred geometric embodiment, the molded body has a bottom and a top surface with the same geometric shape, and the bottom and top surfaces have the same area. As previously described, such molded bodies can be easily produced, for example, by casting sheets and subsequently cutting the sheets into individual gel bodies. Furthermore, these molded bodies can be more easily spatially aligned when placed onto the powder in step iv) than molded bodies with lower body symmetry. This is particularly true for molded bodies that also have a top surface that is plane-parallel to the bottom surface. Examples of such molded bodies are circular cylinders, elliptical cylinders, parallelepipeds, rhombohedrons, right or oblique prisms, cuboids, or cubes.The group of circular and elliptical cylinders includes, in turn, vertical circular and elliptical cylinders, as well as oblique circular and elliptical cylinders. Due to their ease of manufacture by singulation from a sheet, shaped bodies in the form of vertical circular cylinders, vertical elliptical cylinders, right prisms, right cuboids, or cubes are preferred.

[0221] In an alternative embodiment, the shaped body has a bottom and a top surface with the same geometric shape, but with different surface areas. Such shaped bodies may be preferred due to their attractive appearance or optimized fit, combined with relatively simple manufacturing. Examples of such shaped bodies are circular or elliptical cylinders with a convex or concave bottom surface and a flat top surface, or with a flat bottom surface and a convex or concave top surface. Further examples include truncated cones or truncated pyramids.

[0222] To achieve the reduced contact area between the powder and the inside of the closure element that is characteristic of the subject matter of the application, it is preferred in step iv) to place a shaped body onto the powder, the underside of which has an outline that is modeled on the opening surface of the receiving chamber, and to place the shaped body with its underside onto the surface of the powder.

[0223] A replica is a two-dimensional shape, in this case the outline of the underside of the mold body, which is similar to the two-dimensional shape of another surface, in this case the outline of the opening surface of the receiving chamber, for example with regard to the number of corners present or the ratio of the side lengths or the radii of curvature of the sides or corners.

[0224] In step iv), if a shaped body is placed on the powder, the underside of which has an outline that replicates the outline of the opening area of ​​the receiving chamber, this shaped body typically has an underside area that is smaller than the outline area of ​​the receiving chamber opening. In preferred process variants, the shaped body in step iv) therefore has an underside whose outline is obtained from the outline of the opening area of ​​the receiving chamber by a reduction factor of 0.75 to 0.98, and the shaped body is placed with its underside facing down onto the surface of the powder.

[0225] Following step iv), the fill level of the receiving chamber is preferably above 85 vol.%, in particular above 94 vol.%.

[0226] In step v), the filled water-soluble receiving chamber is preferably sealed with a water-soluble film.

[0227] If the water-soluble receiving chamber provided in step i) is obtained by deep drawing a first water-soluble film and sealed with a second water-soluble film in step v), it is preferred, in order to reduce the amount of film used, if the second water-soluble film has a smaller thickness than the first water-soluble film.

[0228] In such a case, the first water-soluble film preferably has a thickness of 60 to 2000 µm and the second water-soluble film a thickness of 40 to 120 µm. It is particularly preferred if the second water-soluble film has a thickness of 80 µm or less, preferably 70 µm or less, particularly 65 µm or less, and most preferably 55 µm or less. Such small film thicknesses are achievable in the inventive method, despite filling the water-soluble receiving chamber with powder, without any loss of mechanical stability of the single-dose cleaning agent portion, for example, caused by individual powder particles puncturing the sealing film, even when using shrink-fitting processes, since the sealing film is only in very limited contact with the powder due to the use of the applied molded body.

[0229] With regard to the mechanical stability of the single-dose cleaning agent while simultaneously minimizing the use of packaging materials, it is preferred if the ratio of the thickness of the first water-soluble film to the thickness of the second water-soluble film is from 3:1 to 1:1, preferably from 2.5:1 to 1.1:1, and in particular from 2:1 to 1.2:1.

[0230] To improve the product's feel and appearance, the sealed, filled receiving chamber is heated in a further step (vi) for a period of 0.5 to 20 seconds to temperatures above 120°C, preferably in the range of 140 to 220°C. This heat treatment shrinks the water-soluble packaging material used, particularly the water-soluble film. The single-dose cleaning agent gains stability, and penetration of the powder between the molded body and the inside of the closure element is prevented.

Claims

1. Single-use cleaning agent portion comprising a) a water-soluble package comprising a1) at least one water-soluble receptacle a2) a water-soluble closure element sealing at least said water-soluble receptacle b) a phosphate-free cleaning agent composition comprising b1) at least one gel phase b2) at least one powder, b3) at least one shaped body different from the powder, characterized in that the molded body has a height of 2.5 to 9 mm, preferably 2.75 to 6.0 mm, in particular 3.0 to 5.5 mm. wherein the at least one gel phase comprises a water-soluble polymer from the group consisting of (optionally acetalized) polyvinyl alcohols and their copolymers.

2. A single-use cleaning agent portion according to claim 1, wherein the molded body is arranged in the chamber such that it is in direct contact with the closure element.

3. A single-use cleaning agent portion according to one of the preceding claims, characterized in that the inner surface of the closure element is covered by the at least one molded body over more than 70%, preferably more than 75%, in particular more than 80%, and most particularly more than 85% of its surface area.

4. A single-use cleaning agent portion according to one of the preceding claims, characterized in that the molded body has at least one substantially flat side, preferably a substantially flat top and / or bottom side.

5. A single-use cleaning agent portion according to one of the preceding claims, characterized in that the total weight of the molded body is from 4 g to 8 g, preferably from 5 g to 7 g.

6. A single-use cleaning agent portion according to any of the preceding claims, characterized in that the weight ratio of powder to molded body is from 4:1 to 1:1, preferably from 3.75:1 to 1.25:1, in particular from 3.5:1 to 1.5:1, and most preferably is from 3.25:1 to 1.75:1.

7. A method for producing a cleaning agent portion unit in a water-soluble package according to any one of claims 1 to 6, comprising the successive steps i) providing a water-soluble receiving chamber; ii) introducing at least one gel phase into the receiving chamber; iii) filling the receiving chamber with at least one powder; iv) applying a molded body onto the powder; v) sealing the filled receptacle with a water-soluble closure element, wherein the molded body according to step iv) has a height of 2.5 to 9 mm, preferably 2.75 to 6.0 mm, in particular 3.0 to 5.5 mm, wherein the at least one gel phase comprises a water-soluble polymer from the group consisting of (optionally acetalized) polyvinyl alcohols and their copolymers.

8. A method according to any of the preceding claims, wherein the molded body in step iv) has a bottom surface whose contour replicates the opening area of the cavity, and the molded body is placed with the bottom surface on the surface of the powder.

9. A method according to any one of the preceding claims, wherein the water-soluble receiving chamber is obtained by deep-drawing a first water-soluble film and is sealed in step v) with a second water-soluble film, and the second water-soluble film has a thickness less than that of the first water-soluble film.

10. A method according to claim 9, wherein the second water-soluble film has a thickness of 80 µm or less, preferably 70 µm or less, more preferably 65 µm or less, and most preferably 55 µm or less.

11. A method according to any one of the preceding claims, wherein the powder is filled into the receiving chamber in step iii) such that the surface of the gel phase(s) facing the opening of the receiving chamber is completely covered with powder.

12. A method according to any of the preceding claims, wherein in step iv) the molded body is placed on the powder such that more than 75%, in particular more than 80%, and most preferably more than 85% of the surface of the powder facing the opening of the receiving chamber is covered by the molded body.

13. A method according to any of the preceding claims, wherein in step iv) the molded body has a bottom surface whose outline is obtained by reducing the outline of the opening area of the receiving chamber by a factor of 0.75 to 0.98, and the molded body is placed with the bottom surface on the surface of the powder.

14. A method according to any of the preceding claims, wherein the molded body in step iv) is preformed (and is not produced in situ by introducing a flowable component).

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