Cleaning products for automatic dishwashers, methods for their manufacture and methods for cleaning and / or maintaining an automatic dishwasher

Abstract

Phosphate-free care product for an automatic dishwasher in a water-soluble coating in the form of a pre-portioned single dose, containing at least one powdered phase and at least one gel-like phase, wherein the gel-like phase is preferably a gel that is solid at room temperature (20 °C) and wherein the gel-like phase, based on the total weight of the phase, a) 10 to 20 wt.%, preferably 12 to 18 wt.%, in particular 12.7 to 15.5 wt.% polyvinyl alcohol and / or its derivatives, b) 27 to 35 wt.%, preferably 30.5 to 33 wt.%, in particular 31 to 32 wt.% 1,3-propanediol, c) 23 to 29.5 wt.%, preferably 25 to 28 wt.% glycerol, d) 12 to 18.5 wt% polyalkylene glycol, in particular 13.5 to 16.5 wt% polyalkylene glycol, and e) < 5 wt.%, preferably < 1 wt.% water contains and wherein the powdered phase comprises at least one organic acid in an amount of 20 to 90 wt.%, preferably 50 to 80 wt.%, particularly preferably 60 to 75 wt.%, based on the total weight of the powdered phase, and the powdered phase has a pH of 1 to 5 (1% at 20 °C) and wherein the at least one gel-like phase is in direct contact with the at least one powder-like phase.

Description

[0001] The present invention relates to a care product for automatic dishwashers, which is effective against limescale and grease deposits in an automatic dishwasher and can be used together with a machine dishwashing detergent in a normal dishwashing cycle without negatively affecting the cleaning performance of the dishwashing detergent, a manufacturing process for this care product, and a method for cleaning and / or maintaining a dishwasher using this product.

[0002] Limescale and grease deposits in automatic dishwashers, which accumulate through use, are typically removed nowadays with special cleaning agents. These agents contain acids to dissolve limescale and surfactants to remove grease. However, due to the acid content, these cleaning agents must be used in a separate program, otherwise the cleaning performance of neutral to alkaline detergents is significantly reduced, and the acidic agents can damage decorations and glassware. Using such cleaning agents therefore increases energy and water consumption. Furthermore, it is not particularly user-friendly due to the additional time required. Other cleaning agents are known that can be used together with a dishwasher detergent in a normal dishwasher cycle.These are often multi-phase products, for example a combination of powder and compressed tablet, to delay the release of some ingredients compared to others.

[0003] These multi-phase cleaning agents for automatic dishwashers, based on prior art technology, have several disadvantages in their production. For example, the manufacturing conditions for agents containing a powdered phase and a compressed tablet phase within a water-soluble coating must be closely monitored to ensure visually satisfactory products. This is the only way to guarantee that the tablet is simply embedded in the powder and that no powder gets between the tablet and the coating, which would result in a visual defect. This slows down the production process, as frequent corrections become necessary.

[0004] The prior art is known as DE 10 2021 203 174 A1, DE 10 2018 222 240 A1 and US 11 761 408 B2.

[0005] The specialist's task was therefore to provide a cleaning product for dishwashers that features an appealing, multi-stage design and is free of visual defects. At the same time, the product should offer the familiar high-quality, solid feel to the consumer. Furthermore, the product should deliver at least the same level of performance in cleaning the dishwasher, for example, by ensuring that the active ingredients are fully released during the pre-rinse cycle, if present, or at the beginning of the main wash cycle if no pre-rinse cycle is used.

[0006] The present problem was solved by a cleaning agent for automatic dishwashers, which contains a powder phase and a gel phase: A first object of the present invention thus relates to a phosphate-free care product for an automatic dishwasher in a water-soluble coating in the form of a pre-portioned single dose containing at least one powdered phase and at least one gel-like phase, wherein the gel-like phase is preferably a gel that is solid at room temperature (20 °C) and wherein the gel-like phase, based on the total weight of the phase, a) 10 to 20 wt.%, preferably 12 to 18 wt.%, in particular 12.7 to 15.5 wt.% polyvinyl alcohol and / or its derivatives, b) 27 to 35 wt.%, preferably 30.5 to 33 wt.%, in particular 31 to 32 wt.% 1,3-propanediol, c) 23 to 29.5 wt.%, preferably 25 to 28 wt.% glycerol, d) 12 to 18.5 wt% polyalkylene glycol, in particular 13.5 to 16.5 wt% polyalkylene glycol, and e) < 5 wt.%, preferably < 1 wt.% water contains and wherein the powdered phase comprises at least one organic acid in an amount of 20 to 90 wt.%, preferably 50 to 80 wt.%, particularly preferably 60 to 75 wt.%, based on the total weight of the powdered phase, and the powdered phase has a pH of 1 to 5 (1% at 20 °C) and wherein the at least one gel-like phase is in direct contact with the at least one powder-like phase.

[0007] According to the invention, a gel, or a gel-like phase, hereinafter also referred to as a gel phase, is understood to be a composition (or phase) that has an internally structuring network. This internally structuring (spatial) network is formed by the dispersion of a solid, but dispersed substance with long or highly branched particles and / or gelling agents, here polyvinyl alcohol and / or its derivatives, in at least one liquid (the at least one liquid is liquid at 20 °C). Such gel phases behave thermoreversibly.

[0008] The care product can contain one, two, three, four, or more gels or gel phases. These gels / gel phases can be identical or different. If there are multiple gels or gel phases, they are preferably distinguishable spatially, visually, and / or by their ingredients. If the gels / gel phases are different, they preferably contain different colorants and different amounts of active ingredients.

[0009] The gel is dimensionally stable. During its production, polyvinyl alcohol and / or its derivatives are brought into contact with glycerin. This yields a flowable mixture that can be shaped as desired. After a certain period, a gel / 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, and particularly preferably 5 minutes or less. To expedite production, it is even more preferred if the solidification time is significantly shorter than 5 minutes, particularly 2 minutes or less, even more preferably 1 minute or less, and most preferably 40 seconds or less. During this time, the gel yields to pressure but does not deform; instead, it returns to its original state when the pressure is removed.The gel is preferably elastic, in particular linear-elastic.

[0010] The gel is preferably a molded body. A molded body is a single body that stabilizes itself in its imprinted shape. This dimensionally stable body is formed from a molding compound (e.g., a composition) by deliberately bringing this compound into a predetermined shape, e.g., by pouring a liquid composition into a mold and subsequently hardening the liquid composition, e.g., within the framework of a sol-gel process.

[0011] Certain minimum requirements are placed on formulations of at least one gel phase. As already explained, the gel 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 gel transitions from a flowable state to a non-flowable, dimensionally stable state at room temperature. Room temperature is defined as a temperature of 20 °C.

[0012] The gel is a solid gel phase. It is preferably cut-resistant. For example, it can be cut with a knife after solidification without being further damaged, except at the point of the cut.

[0013] A phase, as defined in the present invention, is a spatial region in which physical parameters and chemical composition are homogeneous. 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 consumer can clearly distinguish the at least one powdered phase from the at least one gel phase. In the context of this application, the terms powdery, powder-shaped, and in the form of a powder are to be understood synonymously. Furthermore, the transition to granular or granular compositions is fluid. Therefore, within the scope of this application, granular or granular compositions are also understood to be powdery.If the care product according to the invention has more than one powder-like phase, these can also be distinguished from one another with the naked eye because, for example, they differ in color. The same applies if two or more gel phases are present. In this case, too, an optical distinction between the phases is possible, for example, due to a difference in color or transparency. Phases within the meaning of the present invention are thus self-contained regions that can be visually distinguished from one another by the consumer with the naked eye. The individual phases can have 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.

[0014] The gel is preferably translucent or transparent, resulting in a good optical appearance. Preferably, the transmission of the gel phase (without dye) is in the range of 100% to 20%, 100% to 30%, and particularly between 100% and 40%. To measure the light transmittance, the percentage of transmittance 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 12-hour storage period at room temperature, measured in a Lange LICO 300 color measurement system.

[0015] The care products according to the invention contain polyvinyl alcohol and / or its derivatives in an amount of 10 to 20 wt.%, in particular 12 to 18 wt.%, especially preferably in an amount of 12.7 to 14.6 wt.%, in each case based on the total weight of the gel.

[0016] Polyvinyl alcohols are thermoplastic polymers that are usually produced as a white to yellowish powder by hydrolysis of polyvinyl acetate. Partially hydrolyzed polyvinyl alcohol, which still contains up to 30 mol% unhydrolyzed acetyl groups, is to be understood as polyvinyl alcohol within the meaning of the invention. Polyvinyl alcohol (PVOH) is resistant to almost all anhydrous organic solvents. Polyvinyl alcohols with a molar mass of 30,000 to 60,000 g / mol are preferred.

[0017] According to a preferred embodiment, the gel comprises PVOH (polyvinyl alcohol). These gels or 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, during storage. In particular, they are also relatively unreactive with regard to direct negative interactions with components of a granular mixture, especially an additional powder phase. PVOH can, in particular, produce low-moisture or anhydrous gel phases. When PVOH is used as the polymer for the gel, 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 also visually advantageous. The rapid solidification of at least one PVOH gel phase allows for particularly quick further processing of the gel phases. Moreover, the good solubility of the generated gel phases is especially beneficial for the overall solubility of the single dose. In addition, gel phases with such short solidification times are advantageous because they prevent the at least one powdered phase dispensed onto them from sinking into the still-soft or not yet fully solidified gel. This would result in visually unappealing portions of the care product.

[0018] Particularly 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 85 to 90 mol%, in particular 87 to 89 mol%, for example 88 mol%, which accordingly still contain a residual content of acetyl groups.

[0019] 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. Exceval® AQ4104 from Kuraray is also suitable, for example. Particularly suitable are Mowiol C30, the Poval® grades, especially grades 3-83, 3-88, 6-88, 4-85, and particularly preferably 4-88, and most preferably Poval 4-88 S2, as well as Mowiol® 4-88 from Kuraray.

[0020] For the purposes of the invention, derivatives of PVOH 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.

[0021] Particularly preferred are derivatives 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. Within the scope of the present invention, it is preferred that the gel comprises a polyvinyl alcohol and / or its derivatives, preferably a polyvinyl alcohol, whose degree of hydrolysis is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 mol%, and most preferably 82 to 88 mol%.

[0022] The water solubility of polyvinyl alcohol can be modified by post-treatment with aldehydes (acetalization) or ketones (ketalization). These are also derivatives of polyvinyl alcohol. 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 excellent 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.

[0023] The care products contain 27.0 to 35.0 wt% 1,3-propanediol in the gel / gel phase, preferably 30.5 to 33.0 wt% 1,3-propanediol, particularly preferably 31.0 to 32.0 wt% 1,3-propanediol, most preferably 1,3-propanediol, based on the total weight of the gel.

[0024] According to the invention, the gel phase contains at least one polyalkylene glycol. Copolymers of ethylene oxide and propylene oxide are not considered polyalkylene glycols according to the invention. Preferably, the gel contains at least one polyethylene glycol and / or at least one polypropylene glycol, as well as mixtures thereof.

[0025] The gel contains 12 to 18.5 wt%, preferably 13.5 to 16.5 wt%, of at least one polyalkylene glycol, based on the total weight of the gel. Polyethylene glycol and / or polypropylene glycol, as well as mixtures thereof, are particularly preferred as the polyalkylene glycol. Polyethylene glycols with an average molar mass between approximately 100 and 8000 are especially suitable.

[0026] Preferably, the polyalkylene glycols used are liquid at 20 °C, 1 bar. According to the invention, polyethylene glycol(s) with an average molar mass of 200 to 600 g / mol are therefore preferably used in the at least one gel phase(s). In combination with polyvinyl alcohol, polyethylene glycols with an average molar mass between approximately 200 and approximately 600 g / mol, preferably between 300 and 500 g / mol, and particularly preferably between 350 and 450 g / mol (for example, around 400 g / mol INCI: PEG400), are used. Care products according to the invention are thus characterized in that they contain polyethylene glycol(s) with an average molar mass of 300 to 500 g / mol, particularly between 350 and 450 g / mol.

[0027] In a particularly preferred embodiment, component d) polyethylene glycols, preferably polyethylene glycol(s) with an average molar mass of 200 to 600, in particular of 350 to 450 g / mol, for example around 400 g / mol, are used in an amount of 13.5 to 16.5 wt.%.

[0028] According to a further embodiment, in addition to the aforementioned polyethylene glycols with an average molar mass of 200 to 600 g / mol, further polyalkylene glycols, in particular further polyethylene glycols, with an average molar mass between approximately 800 and 8000 g / mol, can be contained in at least one gel phase. These polyethylene glycols are particularly preferably used in amounts of 1 to 10 wt.%, preferably 2 to 5 wt.%, preferably based on the total weight of the gel.

[0029] The gel further comprises, as component c), 23 to 29.5 wt% glycerin based on the total weight of the gel. Particularly preferably, glycerin is present in the gel in an amount of 25 to 28 wt% based on the total weight of the gel.

[0030] The gel is essentially anhydrous. This means that the gel is preferably essentially free of water. "Essentially free" here means that the gel phase may contain small amounts of water. This water can be introduced into the phase, for example, through a solvent, as water of crystallization, or as a result of reactions between components of the phase. However, preferably only small amounts, and in particular no water, are used as a solvent for producing the gel phase. In this embodiment, the proportion of water in the gel phase is < 5 wt% water, preferably 4.9 wt% or less, 4 wt% or less, preferably 2 wt% or less, in particular 1 wt% or less, preferably < 1 wt%, particularly 0.5 wt% or less, in particular 0.1 wt% or 0.05 wt% or less. The values ​​in wt% refer to the total weight of the gel.

[0031] According to a particularly preferred embodiment, the invention relates to care products as described above, comprising a gel that is solid at room temperature (20 °C) and which, based on the total weight of the gel, a) 12 to 18 wt.%, in particular 12.7 to 15.5 wt.% PVOH, b) 30.5 to 33 wt.%, in particular 31 to 32 wt.% 1,3 propanediol, c) 23 to 29.5 wt.%, preferably 25 to 28 wt.% glycerol, d) 13.5 to 16.5 wt% polyethylene glycol(s) with an average molar mass of 200 to 600 g / mol, in particular of 350 to 450 g / mol, for example around 400 g / mol, and e) Contains < 5 wt.%, preferably < 1 wt.% water.

[0032] According to a particularly preferred embodiment, the invention relates to care products as described above, comprising a gel that is solid at room temperature (20 °C) and which, based on the total weight of the gel, a) 12.7 to 15.5 wt% PVOH, b) 31 to 32 wt% 1,3 propanediol, c) 25 to 28 wt% glycerin, d) 13.5 to 16.5 wt% polyethylene glycol(s) with an average molar mass of 350 to 450 g / mol, for example around 400 g / mol, and e) Contains < 1 wt% water.

[0033] These formulations exhibit particularly good flow properties during dispensing and a conveniently short solidification time after dispensing and cooling, while also showing minimal syneresis. This means that no significant amounts of liquid ingredients leak from the gel. Visible leakage of liquid from the gel ("sweating") makes the gel more difficult to handle. Consumers perceive this as both aesthetically unappealing and a quality defect. Depending on the gel's form, this seepage can also make safe handling difficult. Leakage from the gel should be avoided as much as possible, since it can lead to interactions between the liquid and any ingredients present in a subsequent phase and / or a water-soluble coating within the product.This can lead to aesthetically undesirable discoloration or the inactivation of sensitive ingredients, as well as the dissolution or softening of coatings, such as water-soluble coatings. Preferably, less than 5% by weight, preferably less than 3% by weight, and particularly less than 1.5% by weight of liquid escapes, based on the total weight of the gel, measured after one week of storage of the freshly poured gel at a temperature of 20°C.

[0034] These and other aspects, features, and advantages of the invention will become apparent to the person skilled in the art upon studying the present detailed description and claims. Any feature from one aspect of the invention can be used in 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.

[0035] “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.

[0036] 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.

[0037] All percentages given in connection with the compositions described herein refer, unless explicitly stated otherwise, to wt%, in each case to the mixture or phase in question.

[0038] Furthermore, the gel must be stable under normal storage conditions. The gel phase is a component of a care product according to the invention. Such products are typically stored in a household for a certain period of time. Storage usually takes place near the washing machine or dishwasher. The gel should be stable for such storage. Thus, the gel 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.

[0039] It is preferred that the gel penetrates the spaces of the immediately adjacent powder phase by a maximum of 1 mm during the storage period of 4 weeks at 25 °C.

[0040] A change in volume or shrinkage during storage would be detrimental, 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, resulting in unstable components and thus potentially impacting the product's effectiveness.

[0041] The powdered phase contains at least one organic acid in an amount of 20 to 90 wt.%, preferably 50 to 80 wt.%, and particularly preferably 60 to 75 wt.%, based on the total weight of the powdered phase. This refers to the amount of anhydrous acid. Generally, polycarboxylic acids are suitable as acids, whereby polycarboxylic acids are understood to be those carboxylic acids that possess more than one acid function. Aminocarboxylic acids are also suitable, such as aspartic acid, methylglycine diacetic acid (MGDA), glutamic diacetic acid (GLDA), or ethylenediamine diacetic acid. Iminodisuccinic acid (IDS) and iminodiacetic acid (IDA) are also suitable. However, it is preferred that the acids used are not aminocarboxylic acids.

[0042] According to the invention, it is preferred that the organic acid used is a polycarboxylic acid, preferably selected from the group consisting of oxalic acid, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, or mixtures thereof.

[0043] A preferred object is therefore the care product according to the invention, wherein the organic acid is a polycarboxylic acid, preferably selected from the group consisting of oxalic acid, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid or mixtures thereof.

[0044] The powdered phase has a pH value of 1 to 5 (1% at 20 °C). According to the invention, it is preferred that the pH value of the powdered phase is from 2 to 4.5, particularly preferably from 2.5 to 4 (1% at 20 °C).

[0045] The composition according to the invention is designed such that the at least one gel-like phase is in direct contact with the at least one powder-like phase. This means that no other phase is arranged between these two phases. In particular, this also means that no film of water-soluble material, such as that used, for example, for the water-soluble coating, is arranged between the at least one gel-like phase and the at least one powder-like phase, separating the gel-like and powder-like phases from each other. The at least one gel-like phase and the at least one powder-like phase are therefore located in the same chamber of the water-soluble coating.

[0046] Furthermore, according to the invention, it is preferred that the care product is contained in a water-soluble single-chamber bag.

[0047] In addition to the organic acid, the powdered phase contains at least 10% by weight of other ingredients, based on the total weight of the powdered phase.

[0048] According to the invention, it is preferred that the powdered phase contains the conjugate base of the organic acid, preferably in an amount of 1 to 30 wt.%, particularly preferably in an amount of 10 to 25 wt.%, based on the total weight of the powdered phase. For example, citrate can be used when citric acid is used as the organic acid. It is therefore a preferred feature that the powdered phase contains the conjugate base of the organic acid, preferably in an amount of 1 to 30 wt.%, particularly preferably in an amount of 10 to 25 wt.%, based on the total weight of the powdered phase.

[0049] Another preferred feature is that the powdered phase has a base other than the conjugate base of the organic acid, preferably in an amount of 1 to 30 wt.%, particularly preferably 10 to 25 wt.%, based on the total weight of the powdered phase.

[0050] Additional bases that can be used include carbonates and silicates, which are described in more detail under the additional structural materials; the use of acetates is also possible. Furthermore, other ingredients such as sulfates, for example sodium sulfate, other fillers, colorants, and fragrances can be added to the powdered phase.

[0051] It is preferred that the amount of organic acid in the cleaning agent, and in particular the amount of organic acid in the powdered phase, is suitable for reducing or eliminating limescale deposits in the dishwasher. It is especially preferred that the cleaning agent has a pH value of 1 to 5 (1% at 20 °C). It is more preferred that the pH value of the cleaning agent is 2 to 4.5, and particularly preferably 2.5 to 4 (1% at 20 °C).

[0052] In addition to other ingredients, surfactants can also be used for cleaning and maintaining automatic dishwashers; preferably, these are non-ionic surfactants. It is therefore preferable for the maintenance product according to the invention to contain one or more non-ionic surfactants. The non-ionic surfactant can be present in the at least one powdered phase and / or in the at least one gel-like phase. Any non-ionic surfactant known to those skilled in the art can be used in the maintenance products described herein. However, in preferred embodiments, non-ionic surfactants from the group of alkoxylated alcohols are used.One class of preferably applicable non-ionic surfactants, which can be used either as a sole non-ionic surfactant or in combination with other non-ionic surfactants, are therefore alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty alcohols.

[0053] In various preferred embodiments, a fatty alcohol alkoxylate, in particular a fatty alcohol ethoxylate, is used. In particular, non-end-capped fatty alcohol alkoxylates are preferred. In preferred embodiments, the fatty alcohol ethoxylate has the formula R 1 -O-(EO) m -H , where R 1 a linear or branched, substituted or unsubstituted alkyl group with 12 to 24, in particular 14 to 20, in particular 16 to 18 C atoms; EO is an ethylene oxide unit; and m is 10 to 50, in particular 20 to 30, preferably 22 to 27, in particular 25.

[0054] In particularly preferred embodiments, the fatty alcohol ethoxylate has the formula R 1 -O-(EO) m -H , where R 1 a linear or branched, substituted or unsubstituted alkyl group with 16 to 18 carbon atoms; EO is an ethylene oxide unit; and m is 20 to 30, preferably 22 to 27, particularly 25.

[0055] In one embodiment, the alkyl group R 1 a linear, preferably unsubstituted, alkyl group with 16 to 18 carbon atoms.

[0056] The non-ionic surfactant is preferably a fatty alcohol ethoxylate that is solid under standard conditions (temperature 25°C, pressure 1013 mbar) and can preferably be used in the form of a powder or granules.

[0057] In a preferred embodiment, the conditioning agent contains less than 1% by weight of non-ionic surfactant, based on the total weight of the agent. In the same or another preferred embodiment, the powdered solid phase and / or the gel phase contains less than 1.0% by weight of non-ionic surfactant, based on the total weight of the respective phase. Preferably, the non-ionic surfactant is a fatty alcohol ethoxylate as described above.

[0058] In another preferred embodiment, the at least one powdered solid phase comprises 1.0 to 10 wt.% of nonionic surfactant, based on the total weight of the respective phase. In these embodiments, the amount of nonionic surfactant in the entire compound can be higher than 1 wt.%, based on the total weight of the compound. Preferably, the proportion of nonionic surfactant in the entire compound in these cases is 1 to 5 wt.%. Preferably, the nonionic surfactant is a fatty alcohol ethoxylate as described above.

[0059] In a further preferred embodiment, the at least one gel-like phase comprises 1.0 to 10 wt.% of nonionic surfactant, based on the total weight of the respective phase. In these embodiments, the amount of nonionic surfactant in the entire compound can be higher than 1 wt.%, based on the total weight of the compound. Preferably, the proportion of nonionic surfactant in the entire compound in these cases is 1 to 5 wt.%. Preferably, the nonionic surfactant is a fatty alcohol ethoxylate as described above.

[0060] The gel / gel-like phase more preferably comprises a further anionic polymer, in particular polycarboxylates. These can act either as structural components and / or as thickening polymers. According to the invention, the gel can further comprise anionic polymers or copolymers with structural component properties. Preferably, this is a polycarboxylate. Preferably, an acrylate homopolymer and / or a copolymer polyacrylate, preferably a sulfopolymer, preferably a copolymer polysulfonate, or preferably a hydrophobically modified copolymer polysulfonate is used as the polycarboxylate. The copolymers can have two, three, four, or more different monomer units. Preferred copolymer polysulfonates contain, in addition to sulfonic acid group-containing monomer(s), at least one monomer from the group of unsaturated carboxylic acids.According to a particularly preferred embodiment, the gel-like phase contains a polymer comprising at least one sulfonic acid group-containing monomer, preferably in addition to sulfonic acid group-containing monomer(s) at least one monomer from the group of unsaturated carboxylic acids.

[0061] Unsaturated carboxylic acids of the formula R1(R2)C=C(R3)COOH are particularly preferred as unsaturated carboxylic acid(s), in which R1 to R3 independently represent -H, -CH3, 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 -COOR4, where R4 is a saturated or unsaturated, straight-chain or branched hydrocarbon group with 1 to 12 carbon atoms. 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 also be used, of course. For sulfonic acid group-containing monomers, those of the formula R5(R6)C=C(R7)-X-SO3H are preferred, in which R5 to R7 independently represent -H, -CH3, 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 -NH2, -OH or -COOH, or -COOH or -COOR4, where R4 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 -(CH2)n- with n = 0 to 4, -COO-(CH2)k- with k = 1 to 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- and -C(O)-NH-CH(CH3)-CH2-.Among these monomers, preferred are those of the formulas H2C=CH-X-SO3H, H2C=C(CH3)-X-SO3H or HO3S-X-(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- with n = 0 to 4, -COO-(CH2)k- with k = 1 to 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- and -C(O)-NH-CH(CH3)-CH2-.

[0062] According to a particularly preferred embodiment, the gel / gel phase contains a polymer comprising acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid as a sulfonic acid group-containing monomer. 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 wholly or partially neutralized, meaning that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and especially sodium ions. The use of partially or fully neutralized sulfonic acid group-containing copolymers is preferred according to the invention. The monomer distribution of the copolymers preferably used according to the invention is, in copolymers containing only carboxylic acid group-containing monomers and sulfonic acid group-containing monomers, preferably 5 to 95 wt.% each, more 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 care products 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.

[0063] 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 been particularly successful in improving the rinsing performance of dishwashing detergents according to the invention. The gel particularly preferably 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, in particular hydrophobic monomers is used.

[0064] Preferably, nonionic monomers of the general formula R1 (R 2)C=C(R 3)-X-R4 are used, in which R1 to R 3 independently represent -H, -CH3 or -C2H5, X represents an optional spacer group selected from -CH2-, -C(O)O- and -C(O)-NH-, and R4 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.

[0065] 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 C22-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, methacrylic acid 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.

[0066] Surprisingly, it has been shown that PVOH and / or its derivatives, together with anionic polymers or copolymers, particularly with copolymers containing sulfonic acid groups, lead 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. No material loss occurs even within packaging. Therefore, the gel preferably comprises PVOH, polyethylene glycol(s) with an average molar mass of 200 to 600 g / mol, glycerol, and an anionic copolymer / polymer. The proportion of the anionic polymer is preferably 0.5 wt.% to 20 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.Sulfopolymers, in particular the preferred copolymeric polysulfonates, which, in addition to sulfonic acid group-containing monomer(s) and at least one monomer from the group of unsaturated carboxylic acids, especially acrylic acid, also ensure an excellent surface gloss. Furthermore, fingerprints do not remain visible. Therefore, the proportion of sulfopolymers, in particular the preferred copolymeric polysulfonates, which, in addition to sulfonic acid group-containing monomer(s) and at least one monomer from the group of unsaturated carboxylic acids, especially acrylic acid, in the aforementioned 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 18 wt.%, particularly 4 wt.% to 15 wt.%, and preferably 5 wt.% to 12 wt.% based on the weight of the gel phase.In a particularly preferred embodiment, the gel therefore comprises PVOH as well as a sulfopolymer, in particular the preferred copolymeric polysulfonates, which, in addition to sulfonic acid group-containing monomer(s), contain at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, and at least one polyhydric alcohol.

[0067] According to a particularly preferred embodiment, the invention relates to a care product described herein comprising a gel that is solid at room temperature (20 °C) and which, based on the total weight of the gel, a) 12 to 18 wt.%, in particular 12.7 to 15.5 wt.% PVOH, b) 30.5 to 33 wt.%, in particular 31 to 32 wt.% 1,3 propanediol, c) 23 to 29.5 wt.%, preferably 25 to 28 wt.% glycerol, d) 13.5 to 16.5 wt% polyethylene glycol(s) with an average molar mass of 200 to 600 g / mol, in particular of 350 to 450 g / mol, for example around 400 g / mol, e) < 5 wt.%, preferably < 1 wt.% water and f) 5 to 12 wt.%, in particular 7 to 10.5 wt.% of a sulfonic acid group-containing polymer, preferably a polymer comprising at least one sulfonic acid group-containing monomer and at least one monomer from the group of unsaturated carboxylic acids, in particular a polyacrylate copolymer with AMPS as the sulfonic acid group-containing monomer, based on the total weight of the gel.

[0068] According to a particularly preferred embodiment, the invention relates to a care product described herein, comprising a gel that is solid at room temperature (20 °C), which, based on the total weight of the gel, a) 12.7 to 15.5 wt% PVOH, b) 31 to 32 wt% 1,3 propanediol, c) 25 to 28 wt% glycerin, d) 13.5 to 16.5 wt% polyethylene glycol(s) with an average molar mass of 350 to 450 g / mol, for example around 400 g / mol, e) < 1 wt.% water f) 5 to 12 wt.%, in particular 7 to 10.5 wt.% of a sulfonic acid group-containing polymer, preferably a polymer comprising at least one sulfonic acid group-containing monomer and at least one monomer from the group of unsaturated carboxylic acids, in particular a polyacrylate copolymer with AMPS as the sulfonic acid group-containing monomer, based on the total weight of the gel.

[0069] The care product according to the invention comprises at least one powdered phase and at least one gel or gel phase. The care product can have one, two, three, or more distinct powdered phases; likewise, it can have one, two, three, four, or more distinct gel phases. Preferably, the care product according to the invention comprises one solid phase and one gel phase. Particularly preferably, the care product comprises two solid phases and one gel phase. More preferably, it comprises two solid phases and two gel phases. A further preferred embodiment is one in which the care product comprises three solid phases and one or two gel phases. In a preferred embodiment, the care product comprises three powdered phases and one, two, or three gel phases. In another preferred embodiment, the care product comprises one powdered phase and one, two, or three gel phases.

[0070] The weight ratio of the total amount of the at least one powdered or granular phase to the total amount of the at least one gel phase (gel-like phase) is preferably 40:1 to 2:1, particularly preferably 20:1 to 4:1, and in particular 14:1 to 6:1, for example 12:1 to 8:1. The total weight of all phases in a single serving of the care product is preferably between 8 and 30 g, in particular 10 to 25 g, and particularly preferably 12 to 21 g, for example 13 to 17 g per serving. This weight ratio results in a good concentration of the respective ingredients of the powdered or granular phase and the gel phase in a single cleaning or care application. A care product is preferred in which the total weight of a single dose is 8 to 30 g, in particular 10 to 25 g, preferably 12 to 21 g, and particularly preferably 13 to 17 g.

[0071] According to the invention, the at least one solid phase and the gel are adjacent to each other over a full or partial surface. It is preferred that the two phases are directly adjacent to each other. If the at least one solid phase and the gel are directly adjacent to each other over a full or partial surface, 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 solid phase, but rather that even after prolonged storage, the at least one solid phase and the gel 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.

[0072] The care products, and also the gel-like phase of the care products, are not films. Rather, they are formed bodies with a non-film-like thickness. They therefore have a layer thickness of at least 0.3 mm, preferably at least 0.7 mm, particularly at least 1.0 mm, and most preferably at least 1.2 mm. The layer thickness is measured in the plane of least extent.

[0073] Part of the invention also includes a method for producing the care product according to the invention. In this method, one or more water-soluble films are used, which form the water-soluble coating of the single-dose unit.

[0074] Another object of the invention is therefore a method for producing a care product according to the invention. a) Providing a mold with at least one mold cavity; optionally including a ridge for dividing the bottom of the mold cavity; b) Applying a water-soluble film to the mold cavity; c) Forming an open chamber in the mold cavity by deforming the water-soluble film; d) Filling the open chamber with at least one gel-like phase; e) optionally filling the open chamber or parts thereof with at least one further gel-like phase, wherein this second gel phase may optionally be different from the gel phase according to d); f) optionally allow at least one gel phase to solidify; g) subsequently filling the open chamber with at least one powdered phase; h) Provision of a second water-soluble film as a lid; i) Placing the open chamber and the lid on top of each other to seal the pre-portioned single dose at a sealing area; j) Sealing the lid to the open chamber to form a pre-portioned single dose comprising a water-soluble coating.

[0075] The water-soluble film can comprise one or more structurally different water-soluble polymer(s). Particularly suitable water-soluble polymer(s) for the first water-soluble film are polymers from the group of (optionally acetalized) polyvinyl alcohols (PVALs) and their copolymers.

[0076] Water-soluble films for producing the portion unit are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which is preferably in the range of 10,000 to 1,000,000 gmol⁻¹, more preferably from 20,000 to 500,000 gmol⁻¹, particularly preferably from 30,000 to 100,000 gmol⁻¹, and especially from 40,000 to 80,000 gmol⁻¹. Preferred water-soluble films comprise at least 30 wt.%, preferably at least 50 wt.%, and particularly at least 70 wt.% polyvinyl alcohol or polyvinyl alcohol copolymers. The production of the polyvinyl alcohol and polyvinyl alcohol copolymers generally involves the hydrolysis of intermediate polyvinyl acetate. 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 particularly 82 to 88 mol%.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 monomers include ethylene-unsaturated dicarboxylic acids, for example, itaconic acid, maleic acid, fumaric acid, and mixtures thereof.

[0077] Suitable water-soluble films for use in the portion units 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 films from Kuraray, as well as the Hi-Selon series from Mitsubishi Chemical Corporation.

[0078] The first water-soluble film supplied in step b) preferably has a thickness of 60 to 2000 µm, preferably of 60 to 800 µm and particularly of 60 to 200 µm.

[0079] The second water-soluble film supplied in step h) preferably has a thickness of 80 µm or less, in particular 65 µm or less, most preferably 55 µm or less.

[0080] With regard to the mechanical stability of the single-dose care product 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 particularly from 2:1 to 1.2:1. Preferably, the second water-soluble film added in step h) is thinner than the first water-soluble film added in step b).

[0081] The number of gel-like compositions introduced into the receiving chamber can vary. For example, in step d) of the process, only a single gel-like phase may be introduced into the receiving chamber. Alternatively, and to increase formulation flexibility and improve product appearance, two, three, or four gel-like phases may be introduced into the receiving chamber in step d). The two, three, four, or more gel-like phases preferably differ in their composition and may, for example, include different active ingredients, have different active ingredient concentrations, or be of different colors. Optionally, the other gel-like phases mentioned may also be introduced in an optional step e).If, in steps d) and e), more than one gel-like composition is introduced into the receiving chamber (e.g., two, three, or four), these two, three, or four gel-like compositions are preferably 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-like compositions and improves the product appearance.

[0082] In step g), the powder is preferably filled into the receiving chamber such that the surface of the gel-like phase(s) facing the opening of the receiving chamber is completely covered with powder. The fill level of the receiving chamber, which is at least partially filled in step g), is preferably above 20 vol.%, more preferably above 50 vol.%, and particularly above 80 vol.%.

[0083] With regard to the subsequent optical and haptic properties of the care product portion unit, it is particularly preferred if the receiving chamber, which is at least partially filled in step g), has a fill level of 60 to 120 vol.%, preferably 80 to 110 vol.% and particularly 90 to 100 vol.%.

[0084] The receiving chamber, at least partially filled, is sealed in step j) of the process. Sealing is preferably carried out under the influence of solvent or heat.

[0085] It is preferred according to the invention that the aforementioned manufacturing process comprises the following further steps: k) Transport of the pre-portioned single dose comprising a water-soluble coating through a shrink tunnel by means of a transport device and shrinking of the water-soluble coating of the single dose in the shrink tunnel to form a pre-shrunk single dose; l) Cooling the pre-shrunk single dose on a cooling section outside the first shrink tunnel; m) Transport of the pre-shrunk single dose by means of a transport device through a shrink tunnel and shrinking of the water-soluble film of the pre-shrunk single dose in the shrink tunnel to form a shrunken single dose.

[0086] When steps k) to m) are carried out, the water-soluble film is shrunk in a device specifically designed for this purpose, which is called a shrink tunnel. A shrink tunnel allows for the targeted heating of the water-soluble film enclosing the single-dose care product. The shrink tunnel has a conveying system that transports the single-dose product through the tunnel. This conveying system can, for example, be a circulating conveyor belt. Heat transfer in the shrink tunnel can be achieved, for example, by thermal radiation or hot air. In such processes, the water-soluble film is preferably shrunk in step k) by the application of hot air.

[0087] For reasons of process economy, it is preferred if the single dose in step k) rests on the transport device with the first water-soluble film.

[0088] In the first shrink tunnel, the hot air preferably has a temperature of 120 to 290°C, more preferably 140 to 260°C, and particularly 175 to 230°C. In step k), the residence time of the single dose in the shrink tunnel is preferably 1 to 10 seconds, more preferably 2 to 6 seconds.

[0089] After exiting the shrink tunnel, the pre-shrunk single-dose unit is cooled in step I). Cooling is preferably achieved using cold air, preferably at a temperature of 5 to 35°C, particularly preferably 10 to 30°C, and especially 15 to 25°C. Cooling stabilizes the shrinkage result, allows for the rapid further processing of the single-dose unit, and thus prepares the subsequent process steps. In step I), the residence time of the pre-shrunk single-dose unit on the cooling section is 1 to 60 seconds, preferably 5 to 30 seconds.

[0090] To achieve a more uniform shrinkage result and a particularly advantageous feel and appearance, it has proven helpful to turn the pre-shrunk single-use dose in step m) before it enters the shrink tunnel. The single-use dose can be turned manually or mechanically. Mechanical turning of the single-use dose is preferred.

[0091] Preferably, in step m), the single dose rests on the transport device together with the second water-soluble film. It is particularly preferred if, as described above, the single dose rests on the transport device together with the first water-soluble film in step k) and together with the second water-soluble film in step m).

[0092] The heat transfer in step m) can, as in step k), be carried out, for example, by thermal radiation or hot air. Preferably, the water-soluble film is shrunk in step m) by the action of hot air.

[0093] In the second shrink tunnel, the hot air preferably has a temperature of 120 to 290°C, more preferably 140 to 260°C, and particularly 175 to 230°C. The dwell time of the single dose in the shrink tunnel in step m) is preferably 1 to 10 seconds, more preferably 2 to 6 seconds.

[0094] The shrink tunnels used in step k) and step m) can be identical or different. In other words, the single dose can be transported through the same shrink tunnel in both step k) and step m), but the shrink tunnels in step k) and step m) can also be different from each other. Preferred method variants are characterized by the fact that - the residence time of the single dose in the first shrink tunnel in step k) differs from the residence time in the second shrink tunnel in step m) and / or - the hot air temperature in the first shrink tunnel in step k) differs from the hot air temperature in the second shrink tunnel in step m).

[0095] As already mentioned following step k), the shrunken single-use doses are preferably cooled using cold air following step m).

[0096] According to the invention, it is preferred that the feel of the care product not only meets consumer needs, but also that this haptic impression is quantifiable and that the production process can be monitored through regular testing. Such quantification is possible by determining the strength using force-displacement measurements. In force-displacement measurements suitable for quantifying the feel of the product according to the invention, the test product is placed on a holder with a seal facing upwards and subjected to pressure from above using a spherical body (diameter d = 19 mm). In suitable measurements, the penetration depth is, for example, 8 mm. The penetration depth can also be less, e.g., 6 mm, or greater, e.g., 10 mm. However, for the comparability of the results obtained, it is crucial to compare only results with the same penetration depth.Furthermore, it is important that the measurement only begins once the pouch surface is reached, meaning that any upward-protruding seal seam is not part of the measurement. This means that both the penetration depth (e.g., 8 mm) and the force measurement to be documented only begin once the pouch surface is reached. In this context, the pouch surface is understood to be the outer surface of the structure that encloses the care product composition and on whose inner surface at least one phase of the care product is located. The seal seam of a single-dose unit is not considered the pouch surface. To ensure such a start to the measurement, a trigger force can be defined, for example, which must be exceeded before the measurement begins (e.g., 10 g). The penetration depth of the spherical body is reached within a short timeframe during such measurements. A test speed of 25 mm / sec is common, for example.

[0097] Results are obtained regarding the required weight force in grams per tested penetration depth. The required weight force for the achieved penetration depth can be described by the parameter PF for pouch strength (PF = required weight force for penetration depth). According to the invention, it is preferred that the pre-portioned single dose has a pouch strength of at least 1000 g for 8 mm, preferably at least 1200 g for 8 mm, and particularly preferably 1400 g for 8 mm.

[0098] Also part of the present invention is a method for cleaning and / or maintaining an automatic dishwasher, in which, during a normal cleaning cycle for cleaning items to be washed, in particular dirty dishes, a care product formulated separately from the dishwasher detergent is added as described above.

[0099] It is preferred that the cleaning agent is dosed into the interior of the automatic dishwasher at the beginning of the cleaning cycle, preferably before the machine dishwashing detergent.

[0100] For both the conditioning effect and performance of the cleaning agent, as well as for the further course of the cleaning cycle or the entire dishwashing process, it is preferable if the cleaning agent is completely dissolved during the pre-rinse cycle. Therefore, methods are particularly preferred in which the cleaning agent is dosed into the interior of the automatic dishwasher at the beginning of the cleaning cycle, preferably before the dishwasher detergent, and is completely dissolved during the pre-rinse cycle.

[0101] In particular, the invention is described by the following points: Item 1: Phosphate-free care product for an automatic dishwasher in a water-soluble coating in the form of a pre-portioned single dose, containing at least one powdered phase and at least one gel-like phase, wherein the gel-like phase is preferably a gel that is solid at room temperature (20 °C) and wherein the gel-like phase, based on the total weight of the phase, a) 10 to 20 wt.%, preferably 12 to 18 wt.%, in particular 12.7 to 15.5 wt.% polyvinyl alcohol and / or its derivatives, b) 27 to 35 wt.%, preferably 30.5 to 33 wt.%, in particular 31 to 32 wt.% 1,3-propanediol, c) 23 to 29.5 wt.%, preferably 25 to 28 wt.% glycerol, d) 12 to 18.5 wt% polyalkylene glycol, in particular 13.5 to 16.5 wt% polyalkylene glycol, and e) < 5 wt.%, preferably < 1 wt.% water contains and wherein the powdered phase contains at least one organic acid in an amount of 20 to 90 wt.%, preferably 50 to 80 wt.%, particularly preferably 60 to 75 wt.%, based on the total weight of the powdered phase, and the powdered phase has a pH value of 1 to 5 (1% at 20 °C) and wherein the at least one gel-like phase is in direct contact with the at least one powder-like phase. Point 2: Care product according to point 1, wherein the organic acid is a polycarboxylic acid, preferably selected from the group consisting of oxalic acid, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid or mixtures thereof. Point 3: Care product according to one of the previous points, wherein the pre-portioned single dose has a pouch strength of at least 1000 g for 8 mm, preferably at least 1200 g for 8 mm, particularly preferably 1400 g for 8 mm. Point 4: Care product according to one of the previous points, wherein the care product is in a water-soluble single-chamber bag. Point 5: Care product according to one of the preceding points, wherein the powdered phase contains the corresponding base of the organic acid, preferably in an amount of 1 to 30 wt.%, particularly preferably 10 to 25 wt.%, based on the total weight of the powdered phase. Point 6: Care product according to one of the preceding points, wherein the weight ratio of the totality of the at least one powdered phase to the totality of the at least one gel-like phase is 40:1 to 2:1, in particular 20:1 to 4:1, preferably 14:1 to 6:1, particularly preferably 12:1 to 8:1. Point 7: Care product according to one of the previous points, wherein the care product has a pH value of 1 to 5 (1% at 20 °C). Point 8: Care products according to one of the previous points, wherein the powdered solid phase and / or the gel phase contains less than 1.0 wt% of non-ionic surfactant, based on the total weight of the respective phase. Point 9: Care products according to one of points 1 to 7, wherein at least one powdered solid phase contains 1.0 to 10 wt% of non-ionic surfactant, based on the total weight of the respective phase. Point 10: Care products according to one of points 1 to 7 and 9, wherein at least one gel-like phase has a non-ionic surfactant content of 1.0 to 10 wt%, based on the total weight of the respective phase Item 11: Care product according to one of the preceding points, wherein the total weight of the single dose is 8 to 30 g, in particular 10 to 25 g, preferably 12 to 21 g, particularly preferably 13 to 17 g. Point 12: Method for manufacturing a care product according to one of points 1 to 11, comprising a) Providing a mold with at least one mold cavity; optionally including a ridge for dividing the bottom of the mold cavity; b) Applying a water-soluble film to the mold cavity; c) Forming an open chamber in the mold cavity by deforming the water-soluble film; d) Filling the open chamber with at least one gel-like phase; e) optionally filling the open chamber or parts thereof with at least one further gel-like phase, wherein this second gel phase may optionally be different from the gel phase according to d); f) optionally allow at least one gel phase to solidify; g) subsequently filling the open chamber with the at least one powdered phase; h) Provision of a second water-soluble film as a lid; i) Placing the open chamber and the lid on top of each other to seal the pre-portioned single dose at a sealing area; j) Sealing the lid to the open chamber to form a pre-portioned single dose comprising a water-soluble coating. Point 13: The procedure according to point 12 includes the further steps: k) Transport of the pre-portioned single dose comprising a water-soluble coating through a shrink tunnel by means of a transport device and shrinking of the water-soluble coating of the single dose in the shrink tunnel to form a pre-shrunk single dose; l) Cooling the pre-shrunk single dose on a cooling section outside the first shrink tunnel; m) Transport of the pre-shrunk single dose by means of a transport device through a shrink tunnel and shrinking of the water-soluble film of the pre-shrunk single dose in the shrink tunnel to form a shrunken single dose. Item 14: Method for cleaning and / or maintaining an automatic dishwasher, wherein in a normal cleaning cycle for cleaning items, especially dirty dishes, a care product formulated separately from the dishwasher detergent according to one of points 1 to 11 is added using a machine dishwashing detergent. Point 15: Method according to point 14, wherein the care product is dosed into the interior of the automatic dishwasher at the beginning of the cleaning cycle, preferably before the machine dishwashing detergent. Item 16: Procedure according to point 14 or 15, whereby the care product is completely dissolved in the pre-rinse cycle. Examples of implementation: Compositions:

[0102] A care product according to the invention (E1+G) and a dishwashing product known on the market (V1+G) (Somat Excellence 4in1 Caps) were produced:

[0103] The powdered phases were composed as follows: Table 1: powdered phase in wt.% E1 V1 Anhydrous sodium citrate 18,9 15-20 Phosphonate (e.g. HEDP) 2,5-7,5 MGDA, sodium salt 0-25 Disilicate, sodium salt 5-35 soda 3,8 10-25 SILVER PROTECTION (e.g., cysteine) 0,0-1,0 Percarbonate, sodium salt 10-15 Bleaching catalyst (preferably Mn-based) 0,02-0,5 Bleach activator (e.g. TAED) 1-3 Non-ionic surfactant(s), e.g. fatty alcohol alkoxylate, preferably 20-40 EO, possibly endcapped 2,5-10 Polycarboxylate 4-10 Cationic copolymer 0-0,75 Disintegrant - (e.g. Crosslinked PVP) 0-1,5 Protease preparation (tq) 1,5-5 Amylase preparation (tq) 0,5-3 perfume 0,05-0,25 dye 0,0-1 0,0-1 Zinc salt (e.g. acetate) 0,1-0,3 Sodium sulfate 10 0,0 - 10 Water 0,0-1,5 pH adjusters (e.g. citric acid) 0-1,5 Process aids 0-5 Citric acid, anhydrous 67

[0104] The gel-like phases G (G1, G2) were composed as follows: Table 2: gel-like phases in wt.% G1 G2 Polymer comprising monomers containing acrylic acid and amidopropylsulfonic acid 10 10 1,3-Propanediol 32 29 Glycerin 26 24 Non-ionic surfactant* 0 7 PEG 400 15 14 PVOH (Mowiol 4-88) 15 14 Misc (including process aids, pH adjusters, perfume, dye, residual water) add 100 add 100 Fatty alcohol alkoxylate, preferably 20-40 EO, endcapped

[0105] The solubility of the gel phases G1 and G2 is approximately identical in both cold (approx. 15 °C) and warm water (approx. 45 °C) in terms of quantity and speed.

[0106] For the care product according to the invention (E1+G), 17g of the powdered phase (E1), 2.2g of the gel phase (G1) and a total of 0g of the gel phase (G2) were used. The care product according to the invention has a pH value of 3.42 (1%, 20 °C).

[0107] For the commercially available dishwashing product (V1+G), 17g of the powder phase (V1), 1.4g of the gel phase (G1), and a total of 0.8g of the gel phase (G2) were used. The commercially available dishwashing product has a pH value of 10.50 (1% solution, 20°C). Manufacturing process:

[0108] The care product according to the invention (E1) and the commercially known dishwashing product (V1) were produced in the same way: A water-soluble film was fed into a mold with a mold cavity and formed into the cavity, creating a receiving chamber. The receiving chamber was filled with the gel phases, which flowed upon heating, resulting in a partially filled chamber. Upon cooling to room temperature, this solidified. Subsequently, the remaining gel phases were added in the same manner. The solidified phases were completely covered with the powdered phase. The partially filled receiving chamber was then sealed by applying a second PVOH-containing film and heat-sealing, creating a portioned unit in a water-soluble coating. The portioned unit was then treated several times with hot air. i) in a first shrink tunnel for a period of 6 seconds with hot air at a temperature of 210°C; ii) After passing through a cooling section outside the first shrink tunnel, the pre-shrunk single-use doses were again shrunk in a second shrink tunnel.

[0109] The product was treated with hot air at a temperature of 170°C for a period of 6 seconds. The portion units were oriented with the solidified gel-like composition facing upwards in the first shrink tunnel and downwards in the second shrink tunnel.

[0110] Alternatively, some products were not treated in a shrink tunnel, but manually treated from all sides with hot air (170 °C) for approximately 7 seconds.

[0111] Force-displacement measurements: The strength of a care product according to the invention (E1) and a commercially available dishwashing product (V1) was compared. Force-displacement measurements were performed using a Texture Analyser TA.XT plus (Stable Micro Systems). The test product was placed on a holder with the seal facing upwards and subjected to pressure from above using a spherical body (diameter d = 19 mm). The penetration depth was 8 mm. The measurement only began once the pouch surface was reached; that is, the upward-protruding seal was not part of the measurement (for the example given here, this corresponds to the following trigger force, which had to be exceeded at the start of the measurement: 10 g). The test speed was 25 mm / sec. Ten repeat measurements were performed for each product type. Table 3: E1 V1 Weight force applied in grams (g) (mean (n=10)) 1610 402

[0112] It became clear that the product according to the invention required higher pressure to achieve this penetration depth than the commercially available dishwashing product. The weight force required for the achieved penetration depth can be described by the parameter PF for pouch strength (PF = weight force required for penetration depth). For example E1, it is 1610 g for 8 mm, while for the comparative example V1 it is only 402 g for 8 mm. Accordingly, the strength of the product according to the invention is higher, which is why the tactile impression is of higher quality.

[0113] Solubility: The solubility of the cleaning agent (E1) according to the invention in cold water was tested. In a BEKO type b300 dishwasher, program: ECO 50°C, it was checked whether residues of the powdered and / or gel phases were present in the machine immediately after the end of the pre-rinse cycle when the cleaning agent according to the invention was placed on the bottom of the machine before the start of the wash cycle. No residues of the cleaning agent according to the invention were detected after the end of the pre-rinse cycle.

Claims

[1] Phosphate-free care product for an automatic dishwasher in a water-soluble coating in the form of a pre-portioned single dose containing at least one powder phase and at least one gel phase, wherein the gel phase is preferably a gel that is solid at room temperature (20 °C) and wherein the gel phase, based on the total weight of the phase, a) 10 to 20 wt.%, preferably 12 to 18 wt.%, in particular 12.7 to 15.5 wt.% polyvinyl alcohol and / or its derivatives, b) 27 to 35 wt.%, preferably 30.5 to 33 wt.%, in particular 31 to 32 wt.% 1,3-propanediol, c) 23 to 29.5 wt.%, preferably 25 to 28 wt.% glycerol, d) 12 to 18.5 wt% polyalkylene glycol, in particular 13.5 to 16.5 wt% polyalkylene glycol, and e) < 5 wt.%, preferably < 1 wt.% water contains and wherein the powdered phase comprises at least one organic acid in an amount of 20 to 90 wt.%, preferably 50 to 80 wt.%, particularly preferably 60 to 75 wt.%, based on the total weight of the powdered phase, and the powdered phase has a pH of 1 to 5 (1% at 20 °C) and wherein the at least one gel-like phase is in direct contact with the at least one powder-like phase. [2] Care product according to claim 1, wherein the organic acid is a polycarboxylic acid, preferably selected from the group consisting of oxalic acid, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid or mixtures thereof. [3] Care product according to one of the preceding claims, wherein the pre-portioned single dose has a pouch strength of at least 1000 g for 8 mm, preferably at least 1200 g for 8 mm, particularly preferably 1400 g for 8 mm. [4] Care product according to any of the preceding claims, wherein the powdered phase contains the corresponding base of the organic acid, preferably in an amount of 1 to 30 wt.%, particularly preferably 10 to 25 wt.%, based on the total weight of the powdered phase. [5] Care product according to any of the preceding claims, wherein the weight ratio of the totality of the at least one powdered phase to the totality of the at least one gel-like phase is 40:1 to 2:1, in particular 20:1 to 4:1, preferably 14:1 to 6:1, particularly preferably 12:1 to 8:

1. [6] Care product according to any of the preceding claims, wherein the care product has a pH value of 1 to 5 (1% at 20 °C). [7] Care product according to any of the preceding claims, wherein the powdered solid phase and / or the gel phase comprises less than 1.0 wt.% of non-ionic surfactant and / or wherein the at least one powdered solid phase comprises 1.0 to 10 wt.% of non-ionic surfactant and / or wherein the at least one gel phase comprises 1.0 to 10 wt.% of non-ionic surfactant, based on the total weight of the respective phase. [8] Method for producing a care product according to any one of claims 1 to 7 comprising a) Providing a mold with at least one mold cavity; optionally including a ridge for dividing the bottom of the mold cavity; b) Applying a water-soluble film to the mold cavity; c) Forming an open chamber in the mold cavity by deforming the water-soluble film; d) Filling the open chamber with at least one gel-like phase; e) optionally filling the open chamber or parts thereof with at least one further gel-like phase, wherein this second gel phase may optionally be different from the gel phase according to d); f) optionally allow at least one gel phase to solidify; g) subsequently filling the open chamber with the at least one powdered phase; h) Provision of a second water-soluble film as a lid; i) Placing the open chamber and the lid on top of each other to seal the pre-portioned single dose at a sealing area; j) Sealing the lid to the open chamber to form a pre-portioned single dose comprising a water-soluble coating. [9] The method of claim 8 comprising the further steps: k) Transporting the pre-portioned single dose comprising a water-soluble coating through a shrink tunnel by means of a transport device and shrinking the water-soluble coating of the single dose in the shrink tunnel to form a pre-shrunk single dose; i) Cooling the pre-shrunk single dose on a cooling section outside the first shrink tunnel; m) Transport of the pre-shrunk single dose by means of a transport device through a shrink tunnel and shrinking of the water-soluble film of the pre-shrunk single dose in the shrink tunnel to form a shrunken single dose. [10] Method for cleaning and / or maintaining an automatic dishwasher, wherein in a normal cleaning cycle for cleaning items to be washed, in particular dirty dishes, a care product formulated separately from the dishwasher according to one of claims 1 to 7 is added using a machine dishwashing detergent.