Care product for automatic dishwashers

Abstract

The present invention relates to a care product for an automatic dishwasher, comprising at least one powder phase and at least one gel phase, and to a production process for this care product and to a method using the care product.

Description

[0001] Care products for dishwashers

[0002] 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 production process for this care product, and a process for cleaning and / or maintaining a dishwasher using this product.

[0003] Limescale and grease deposits in automatic dishwashers that develop through use are usually removed with special dishwasher cleaners. These cleaners contain acids for limescale removal and surfactants for grease removal.

[0004] Due to the acid they contain, such cleaning products must be used in a separate program, as otherwise the cleaning performance of neutral to alkaline dishwashing detergents is significantly reduced, and the acidic agents can be harmful to decor and glassware. The use of such cleaning products therefore increases energy and water consumption. Furthermore, it is not particularly user-friendly due to the additional time required. Other cleaning products are known that can be used together with automatic dishwashing detergent in a normal dishwashing cycle. These are often multi-phase products, for example, a combination of powder and compressed tablets, designed to delay the release of some ingredients over others.

[0005] These state-of-the-art multi-phase care products for automatic dishwashers have several disadvantages in their production. For example, the conditions during the production of products containing a powder and a compressed phase in the form of a tablet in a water-soluble coating must be closely monitored to ensure visually satisfactory products. This is the only way to ensure that the tablet is only immersed in the powder and that no powder gets between the tablet and the film, which would represent an optical defect. This slows down the production process, as frequent adjustments are necessary.

[0006] The expert's task was therefore to provide a care product for automatic dishwashers that features a multi-phase design appealing to consumers and is free of visual defects. At the same time, consumers should experience the familiar high-quality, solid feel when handling the product. Furthermore, the product should provide at least the same level of performance in dishwasher care, for example, by fully releasing the active ingredients in the pre-wash cycle, if present, or at the beginning of the main wash cycle if no pre-wash cycle is run. This task was solved by a care product for automatic dishwashers that contains a powder phase and a gel phase:

[0007] A first aspect 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 contains, 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.% of polyvinyl alcohol and / or its derivatives, b) 27 to 35 wt.%, preferably 30.5 to 33 wt.%, in particular 31 to 32 wt.% of 1,3-propanediol, c) 23 to 29.5 wt.%, preferably 25 to 28 wt.% of glycerol, d) 12 to 18.5 wt.% of polyalkylene glycol, in particular 13.5 to 16.5 % by weight of polyalkylene glycol, and e) < 5% by weight, preferably < 1% by weight of water and wherein the powdery phase contains at least one organic acid in an amount of 20 to 90% by weight.-%, preferably from 50 to 80 wt.%, particularly preferably from 60 to 75 wt.%, based on the total weight of the powdery phase, and the powdery 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 powdery phase.

[0008] A gel, or gel-like phase, hereinafter also referred to as a gel phase, is understood according to the invention 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 distributed 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.

[0009] The care product can contain one, two, three, four, or more gels or gel phases. The gels / gel phases can be the same or different. In the case of multiple gels or

[0010] Gel phases are preferably distinguishable spatially, visually and / or based on their ingredients. If the gels / gel phases are different, they can preferably contain different dyes and different additions of active ingredients. The gel is dimensionally stable. During production, the polyvinyl alcohol and / or its derivatives are brought into contact with glycerin. This results in a flowable mixture that can be formed into a desired shape. After a certain period of time, a gel / gel phase is obtained that remains in the specified shape, i.e., is dimensionally stable. This period, the setting time, is preferably 15 minutes or less, more preferably 10 minutes or less, particularly preferably 5 minutes or less.To speed up production, it is even more preferred if the setting time is significantly shorter than 5 minutes, especially 2 minutes or less, even more preferably 1 minute or less, most preferably 40 seconds or less. The gel yields to pressure but does not deform as a result, but returns to its original state once the pressure is removed. The gel is preferably elastic, especially linearly elastic.

[0011] 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 shaping this compound into a predetermined shape, e.g., by pouring a liquid composition into a mold and subsequently curing the liquid composition, e.g., in a sol-gel process.

[0012] Formulations containing at least one gel phase must meet certain minimum requirements. As already explained, the gel must set within the shortest possible time. Long setting times would result in a long production time and thus high costs. According to the invention, setting time is the period of time during which the gel, during production, transforms from a flowable state to a non-flowable, dimensionally stable state at room temperature. Room temperature is understood to mean a temperature of 20°C.

[0013] The gel is a solid gel phase. It is preferably cut-resistant. For example, it can be cut with a knife after solidification without further damage except at the site of the cut.

[0014] A phase within the meaning of the present invention is a spatial region in which physical parameters and the chemical composition are homogeneous. One phase differs from another phase by various features, for example ingredients, physical properties, external appearance, etc. Preferably, different phases can be visually distinguished. This allows the consumer to clearly distinguish the at least one powdery phase from the at least one gel phase. In the context of this application, the terms powdery, powder-like, and in the form of a powder are to be understood as synonymous. Furthermore, the transition to granular or grainy compositions is fluid. Therefore, in the context of this application, granular or grainy compositions are also understood to be powdery.If the care product according to the invention has more than one powdered phase, these can also be distinguished from one another with the naked eye because they differ, for example, in color. The same applies if two or more gel phases are present. In this case, too, a visual 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 therefore self-contained areas 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 speed with which the phase dissolves in water and thus the speed and sequence of release of the ingredients contained in the respective phase.

[0015] The gel is also preferably translucent or transparent, which results in a good visual impression. The transmittance of the gel phase (without dye) is preferably in a range between 100% and 20%, between 100% and 30%, and especially between 100% and 40%. To measure the light transmittance (transmission), the transmittance was determined in % at 600 nm against water as a reference at 20°C. The mass was poured into the designated 11 mm round cuvettes and, after 12 hours of storage at room temperature, measured in a LICO 300 color measurement system according to Lange.

[0016] 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.%, particularly preferably in an amount of 12.7 to 14.6 wt.%, in each case based on the total weight of the gel.

[0017] Polyvinyl alcohols are thermoplastics 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% of unhydrolyzed acetyl groups, is considered polyvinyl alcohol within the meaning of the invention. Polyvinyl alcohol (PVOH) is resistant to almost all anhydrous organic solvents. Polyvinyl alcohols with a molecular weight of 30,000 to 60,000 g / mol are preferred.

[0018] According to a preferred embodiment, the gel comprises PVOH (polyvinyl alcohol). The 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 slightly, upon storage. In particular, they are also less reactive with regard to direct negative interactions with components of a granular mixture, especially an additional powder phase. PVOH can, in particular, produce low-water or anhydrous gel phases. When PVOH is used as the polymer for the gel, low-viscosity melts are produced at 110-120°C, which are therefore particularly easy to process. In particular, the gel phase can be filled into the water-soluble coating quickly and precisely, without sticking or inaccurate metering.Furthermore, these gel phases adhere particularly well to the water-soluble coating, especially if it is also made of PVOH. This is also visually advantageous. Due to the rapid solidification of at least one gel phase with PVOH, further processing of the gel phases can be carried out particularly quickly. Furthermore, the good solubility of the produced gel phases is particularly favorable for the overall solubility of the single dose. Furthermore, gel phases with such short solidification times are advantageous because the at least one powdered phase dosed onto them does not sink into the gel that is not yet fully solidified or is too soft. This leads to visually unappealing care product portions.

[0019] Particularly preferred are polyvinyl alcohols which are in the form of white-yellowish powders or granules with degrees of polymerization in the range from approximately 100 to 2500 (molar masses of approximately 4000 to 100,000 g / mol) and degrees of hydrolysis of 80 to 99 mol%, preferably from 85 to 90 mol%, in particular from 87 to 89 mol%, for example 88 mol%, which accordingly still contain a residual content of acetyl groups.

[0020] PVOH powders with the aforementioned properties, which are suitable for use in at least one gel phase, are marketed, for example, under the name Mowiol® or Poval® by Kuraray. Exceval® AQ4104 from Kuraray is also suitable. Particularly suitable are Mowiol C30, the Poval® grades, in particular grades 3-83, 3-88, 6-88, 4-85, and particularly preferably 4-88, most preferably Poval 4-88 S2, and Mowiol® 4-88 from Kuraray.

[0021] Preferred derivatives of PVOH in the context of the invention are copolymers of polyvinyl alcohol with other monomers, in particular copolymers with anionic monomers. Preferred anionic monomers are vinylacetic acid, alkyl acrylates, maleic acid and its derivatives, in particular monoalkyl maleates (in particular monomethyl maleate), dialkyl maleates (in particular dimethyl maleate), maleic anhydride, fumaric acid and its derivatives, in particular monoalkyl fumarate (in particular monomethyl fumarate), dialkyl fumarate (in particular dimethyl fumarate), fumaric anhydride, itaconic acid and its derivatives, in particular monomethyl itaconate, dialkyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid (methylmaleic acid) and its derivatives, monoalkylcitraconic acid (in particular methylcitraconate), dialkylcitraconic acid (dimethylcitraconate), citraconic anhydride, mesaconic acid (methylfumaric 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 combinations thereof, as well as the alkali metal salts or esters of the aforementioned monomers.

[0022] Particularly preferred PVOH derivatives are those selected from copolymers of polyvinyl alcohol with a monomer, in particular selected from the group of monoalkyl maleates (in particular monomethyl maleate), dialkyl maleates (in particular dimethyl maleate), maleic anhydride, and combinations thereof, as well as the alkali metal salts or esters of the aforementioned monomers. The values ​​given for polyvinyl alcohols themselves apply to suitable molecular weights. Within the scope of the present invention, it is preferred that the gel comprises a polyvinyl alcohol and / or derivatives thereof, preferably 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 above all 82 to 88 mol%.

[0023] The water solubility of polyvinyl alcohol can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization). These are also considered derivatives of polyvinyl alcohol. Polyvinyl alcohols that are acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides, or mixtures thereof, have proven particularly preferred and particularly advantageous due to their exceptionally good cold-water solubility. The reaction products of polyvinyl alcohol and starch are particularly advantageous. Furthermore, the water solubility can be modified by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, or borax, thus specifically adjusting it to desired values.

[0024] The care products contain in the gel / gel phase 27.0 to 35.0 wt.% 1,3-propanediol, preferably 30.5 to 33.0 wt.% 1,3-propanediol, particularly preferably 31.0 to 32.0 wt.% 1,3-propanediol, very particularly preferably 1,3-propanediol, based on the total weight of the gel.

[0025] 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. The gel preferably contains at least one polyethylene glycol and / or at least one polypropylene glycol, as well as mixtures thereof.

[0026] 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 polyalkylene glycol. Polyethylene glycols with an average molecular weight between approximately 100 and 8000 are particularly suitable. The polyalkylene glycols used are preferably liquid at 20°C and 1 bar. Therefore, according to the invention, polyethylene glycol(s) with an average molecular weight of 200 to 600 g / mol are preferably additionally used in the at least one gel phase(s). In combination with polyvinyl alcohol, polyethylene glycols with an average molecular weight between about 200 and about 600 g / mol, preferably between 300 and 500 g / mol, 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 molecular weight of 300 to 500 g / mol, in particular of 350 to 450 g / mol.

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

[0028] According to a further embodiment, in addition to the aforementioned polyethylene glycols having an average molecular weight of 200 to 600 g / mol, further polyalkylene glycols, in particular further polyethylene glycols, having an average molecular weight between approximately 800 and 8000 may be present in the 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 in each case on the total weight of the gel.

[0029] The gel further comprises, as component c), 23 to 29.5 wt.% glycerol, based on the total weight of the gel. Glycerol is particularly preferably 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 small amounts of water may be present in the gel phase. This water can be introduced into the phase, for example, by a solvent or as water of crystallization, or due to reactions between constituents of the phase. However, only small amounts, in particular no water, are preferably used as a solvent to produce the gel phase. The proportion of water in the gel phase in this embodiment 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.%, especially 0.5 wt.% or less, in particular 0.1 wt.% or 0.05 wt.% or less. The data in wt.% refer to the total weight of the gel.According to a particularly preferred embodiment, the invention relates to care products as described above, comprising a gel which is solid at room temperature (20 °C) and which, based on the total weight of the gel, a) 12 to 18% by weight, in particular 12.7 to 15.5% by weight of PVOH, b) 30.5 to 33% by weight, in particular 31 to 32% by weight of 1,3-propanediol, c) 23 to 29.5% by weight, preferably 25 to 28% by weight of glycerol, d) 13.5 to 16.5% by weight of polyethylene glycol(s) with an average molecular weight of 200 to 600 g / mol, in particular of 350 to 450 g / mol, for example around 400 g / mol, and e) < 5% by weight, preferably < 1% by weight of water.

[0031] According to a very particularly preferred embodiment, the invention relates to care products as described above, comprising a gel which 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.% glycerol, d) 13.5 to 16.5 wt.% polyethylene glycol(s) with an average molecular weight of 350 to 450 g / mol, for example around 400 g / mol, and e) < 1 wt.% water.

[0032] These compositions demonstrate particularly good flowability during dosing and, at the same time, an advantageously short setting time after dosing of the gel and cooling, while also exhibiting only minimal syneresis. This means that no large quantities of liquid ingredients escape from the gel. The visible escape of liquid from the gel ("sweating") makes the gel more difficult to handle. Consumers view this as unsightly and as a quality defect. Depending on the packaging of the gel, sweating can also make it difficult to handle the gel safely. The escape of liquid from the gel should be avoided wherever possible, as this can lead to interactions between the liquid and any ingredients contained in a further phase and / or a water-soluble coating in portions of the care product.This can lead to aesthetically undesirable discoloration or inactivation of sensitive ingredients, dissolution or softening of coatings, e.g. coatings or water-soluble coatings.

[0033] Preferably, in particular less than 5 wt.%, preferably less than 3 wt.%, in particular less than 1.5 wt.% of liquid escapes based on the total weight of the gel, measured after one week of storage of the freshly cast gel at a temperature of 20 °C.

[0034] These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. It is understood that any feature of one aspect of the invention may be employed in any other aspect of the invention. Further, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not limited to these examples. All percentages are by weight unless otherwise stated. Numerical ranges given in the format "from x to y" include the stated values. Where multiple preferred numerical ranges are given in this format, it is to be understood that all ranges resulting from the combination of the various endpoints are also included.

[0035] “At least one”, as used herein, means 1 or more, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. When referred to an ingredient, the statement refers to the type of ingredient and not to the absolute number of molecules. “At least one bleach catalyst” thus means, for example, at least one type of bleach catalyst, i.e. one type of bleach catalyst or a mixture of several different bleach catalysts can be meant. Together with weight information, the statement refers to all compounds of the type stated that are present in the composition / mixture, i.e. the composition does not contain any further compounds of this type beyond the stated amount of the corresponding compounds.

[0036] Whenever reference is made to molar masses herein, these data always refer to the number-average molar mass Mn, unless explicitly stated otherwise. The number-average 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-average molar mass Mw can also be determined by GPC, as described for Mn.

[0037] Unless explicitly stated otherwise, all percentages given in connection with the compositions described herein refer to % by weight, in each case based on the mixture or phase in question.

[0038] Furthermore, the gel must be storage-stable under normal storage conditions. The gel phase is a component of a care product according to the invention. Such products are usually 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 be stable even after a storage period of, for example, 4 to 12 weeks, in particular 10 to 12 weeks or longer at a temperature of up to 40°C, particularly at 30°C, in particular at 25°C or 20°C, and should not deform or otherwise change in consistency during this time. It is preferred that the gel penetrates into the spaces between the immediately adjacent powder phase by a maximum of 1 mm during the storage period of 4 weeks at 25°C.

[0039] A change in volume or shrinkage during storage would be disadvantageous, as this would reduce consumer acceptance of the product. Leakage of liquid or the exudation of components from the gel phase is also undesirable. Here, too, the visual impression is important. Leakage of liquid, such as solvents, can affect the stability of the gel phase, so that the components are no longer stable, and this can also impair the care effect.

[0040] 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. This is the amount of anhydrous acid. Generally, polycarboxylic acids are suitable as acids, whereby polycarboxylic acids are understood to be carboxylic acids that carry more than one acid function. Aminocarboxylic acids are also suitable as acids, such as aspartic acid, methylglycinediacetic 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.

[0041] It is preferred according to the invention that the organic acid used is a polycarboxylic acid, preferably selected from the group 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 of these.

[0042] A preferred subject matter is therefore the care product according to the invention, wherein the organic acid is a polycarboxylic acid, preferably selected from the group 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.

[0043] The powdered phase has a pH of 1 to 5 (1% at 20°C). According to the invention, the pH of the powdered phase is preferably from 2 to 4.5, particularly preferably from 2.5 to 4 (1% at 20°C).

[0044] The agent according to the invention is designed such that the at least one gel phase is in direct contact with the at least one powder 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 is used, for example, for the water-soluble coating, is arranged between the at least one gel phase and the at least one powder phase, separating the gel and powder phases from one another. The at least one gel phase and the at least one powder phase are therefore present in the same chamber of the water-soluble coating.

[0045] It is also preferred according to the invention that the care product is present in a water-soluble single-chamber bag.

[0046] 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.

[0047] According to the invention, it is preferred that 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. For example, citrate can be used if citric acid is used as the organic acid. Accordingly, it is preferred that 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.

[0048] It is another preferred object that the powdered phase comprises a base other than 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.

[0049] Additional bases that can be used include carbonates and silicates, which are described further under "Additional Builders." Acetates can also be used. In addition, other ingredients such as sulfates, such as sodium sulfate, other fillers, dyes, and fragrances can be used in the powder phase.

[0050] It is preferred that the amount of organic acid in the care product, especially the amount of organic acid in the powdered phase, is suitable for reducing or eliminating limescale deposits in the dishwasher. In particular, it is preferred that the care product has a pH value of 1 to 5 (1% at 20°C). It is more preferred that the pH of the care product is between 2 and 4.5, particularly preferably between 2.5 and 4 (1% at 20°C).

[0051] In addition to other ingredients, surfactants can also ensure cleaning and care of the automatic dishwasher; these are preferably non-ionic surfactants. It may therefore be preferred for the care product according to the invention to comprise one or more non-ionic surfactants. Non-ionic surfactant can be present in the at least one powdered phase and / or in the at least one gel-like phase. A non-ionic surfactant usable in the care products described herein can be any of the non-ionic surfactants known to the person skilled in the art. In preferred embodiments, however, non-ionic surfactants from the group of alkoxylated alcohols are used.A class of preferred non-ionic surfactants, which can be 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 alcohols.

[0052] In various preferred embodiments, a fatty alcohol alkoxylate, in particular a fatty alcohol ethoxylate, is therefore used. Non-end-capped fatty alcohol alkoxylates are particularly preferred. In preferred embodiments, the fatty alcohol ethoxylate has the formula R 1 -O-(EO)mH , where R 1 is a linear or branched, substituted or unsubstituted alkyl group having 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.

[0053] In particularly preferred embodiments, the fatty alcohol ethoxylate has the formula R 1 -O-(EO) m -H , where R 1 is a linear or branched, substituted or unsubstituted alkyl group having 16 to 18 C atoms; EO is an ethylene oxide unit; and m is 20 to 30, preferably 22 to 27, in particular 25.

[0054] In one embodiment, the alkyl group R 1 a linear, preferably unsubstituted, alkyl group having 16 to 18 C atoms.

[0055] 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.

[0056] In a preferred embodiment, the care product contains less than 1% by weight of nonionic surfactant, based on the total weight of the product. In the same or another preferred embodiment, the powdered solid phase and / or the gel phase contains less than 1.0% by weight of nonionic surfactant, based on the total weight of the respective phase. The nonionic surfactant is preferably a fatty alcohol ethoxylate as described above.

[0057] In another preferred embodiment, the at least one powdered solid phase comprises from 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 agent can be higher than 1 wt. %, based on the total weight of the agent. Preferably, the proportion of nonionic surfactant in the entire agent in these cases is 1 to 5 wt. %. The nonionic surfactant is preferably a fatty alcohol ethoxylate as described above.

[0058] In a further preferred embodiment, the at least one gel-like phase comprises from 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 agent can be higher than 1 wt.%, based on the total weight of the agent. Preferably, the proportion of nonionic surfactant in the entire agent in these cases is 1 to 5 wt.%. The nonionic surfactant is preferably a fatty alcohol ethoxylate as described above.

[0059] The gel / gel-like phase further preferably comprises a further anionic polymer, in particular polycarboxylates. These can act either as builders and / or as thickening polymers. According to the invention, the gel can further comprise anionic polymers or copolymers with builder properties. This is preferably a polycarboxylate. The polycarboxylate used is preferably an acrylate homopolymer and / or a copolymeric polyacrylate, preferably a sulfopolymer, preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate. The copolymers can have two, three, four or more different monomer units. Preferred copolymeric polysulfonates contain, in addition to monomer(s) containing sulfonic acid groups, 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 monomer containing sulfonic acid groups, preferably in addition to sulfonic acid group-containing monomer(s) at least one monomer from the group of unsaturated carboxylic acids.

[0060] As unsaturated carboxylic acid(s), particular preference is given to using unsaturated carboxylic acids of the formula R1 (R2)C=C(R3)COOH, in which R1 to R3 independently of one another represent -H, -CH3, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH2, -OH or -COOH as defined above or represents -COOH or -COOR4, where R4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms. Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, a-chloroacrylic acid, a-cyanoacrylic acid, crotonic acid, a-phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.Of course, unsaturated dicarboxylic acids can also be used. Among the sulfonic acid group-containing monomers, those of the formula R5(R6)C=C(R7)-X-SO3H are preferred, in which R5 to R7 independently of one another represent -H, -CH3, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH2, -OH or -COOH, or -COOH or -COOR4, where R4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group selected from -(CH2)n- where n = 0 to 4, -COO-(CH2)k- where k = 1 to 6, -C(O)-NH-C(CH3)2-, -C(O)-NH- C(CH3)2-CH2- and -C(O)-NH-CH(CH3)-CH2-.Preferred among these monomers 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 optionally present 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-.

[0061] According to a particularly preferred embodiment, the gel / gel phase contains a polymer comprising acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid as monomer containing sulfonic acid groups. Particularly preferred monomers containing sulfonic acid groups 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-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water-soluble salts.In the polymers, the sulfonic acid groups can be present entirely or partially in neutralized form, i.e., the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions, and in particular for sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention. The monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95 wt.% in the case of copolymers containing only carboxylic acid group-containing monomers and sulfonic acid group-containing monomers; 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 are preferably selected from those mentioned above.The molar mass of the sulfo-copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. 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 in particular of 5000 to 15,000 g mol-1. In a further preferred embodiment, the copolymers comprise, in addition to carboxyl group-containing monomer and sulfonic acid group-containing monomer, at least one nonionic, preferably hydrophobic monomer. The use of these hydrophobically modified polymers has made it possible, in particular, to improve the rinse performance of dishwashing detergents according to the invention.

[0062] Particularly preferably, the gel further comprises an anionic copolymer, wherein the anionic copolymer is a copolymer comprising

[0063] 1) Monomers containing carboxylic acid groups ii) Monomers containing sulfonic acid groups iii) Non-ionic monomers, in particular hydrophobic monomers.

[0064] The non-ionic monomers used are preferably monomers of the general formula R1 (R

[0065] 2)C=C(R 3)-X-R4, in which R1 to R 3 independently of one another represent -H, -CH3 or -C2H5, X represents an optionally present spacer group selected from -CH2-, -C(O)O- and -C(O)-NH-, and R4 represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

[0066] Particularly preferred non-ionic 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-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4,4-dimethylhexane-1, ethylcyclohexyne, 1-octene, a-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-Hexadecene, 1-Octadecene and C22- a-olefin, 2-styrene, a-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 methacrylate, N-(2-ethylhexyl)acrylamide,Octyl acrylate, octyl methacrylate, N-(octyl)acrylamide, lauryl acrylate, lauryl methacrylate, N-(lauryl)acrylamide, stearyl acrylate, stearyl methacrylate, N-(stearyl)acrylamide, behenyl acrylate, behenyl methacrylate and N-(behenyl)acrylamide or mixtures thereof, in particular acrylic acid, ethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and mixtures thereof.

[0067] Surprisingly, it has been shown that PVOH and / or its derivatives together with anionic polymers or copolymers, in particular with copolymers containing sulfonic acid groups, lead to the formation of gel phases with insensitive surfaces. Corresponding surfaces can be touched by the end user without material sticking to the hands. Even in packaging, no material is removed. The gel therefore preferably comprises PVOH, polyethylene glycol(s) with an average molecular weight 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.%, in particular 3 wt.% to 30 wt.%, particularly 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 copolymers polysulfonates, which contain at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, in addition to monomer(s) containing sulfonic acid groups, also ensure an excellent surface gloss. In addition, fingerprints are not retained. Therefore, the proportion of sulfopolymers, in particular the preferred copolymers polysulfonates, which contain at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, in addition to monomer(s) containing sulfonic acid groups, in particular of the aforementioned sulfopolymers with AMPS as the monomer containing sulfonic acid groups, 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.%, preferably 5 wt.% to 12 wt.%, based on the weight of the gel phase.In a particularly preferred embodiment, the gel therefore comprises PVOH and a sulfopolymer, in particular the preferred copolymers 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.

[0068] According to a particularly preferred embodiment, the invention relates to a care product described herein comprising a gel which 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 molecular weight 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 of 7 to 10.5 wt.-% of a polymer containing sulfonic acid groups, preferably a polymer comprising at least one monomer containing sulfonic acid groups and at least one monomer from the group of unsaturated carboxylic acids, in particular a polyacrylate copolymer with AMPS as the monomer containing sulfonic acid groups, based on the total weight of the gel.

[0069] According to a particularly preferred embodiment, the invention relates to a care product described herein, comprising a gel which 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.% glycerol, d) 13.5 to 16.5 wt.% polyethylene glycol(s) with an average molecular weight of 350 to 450 g / mol, for example around 400 g / mol, e) <1 wt.% water f) 5 to 12 wt.%, in particular from 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.

[0070] The care product according to the invention comprises at least one powdered phase and at least one gel or one gel phase. The care product can have one, two, three or more different powdered phases; likewise, it can have one, two, three, four or more different gel phases. The care product according to the invention preferably comprises a solid phase and a gel phase. The care product particularly preferably comprises two solid phases and one gel phase. It preferably comprises two solid phases and two gel phases. Also preferred is an embodiment 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.

[0071] The weight ratio of the total of the at least one powdered or granular phase to the total of the at least one gel phase (gel phase) is preferably 40:1 to 2:1, particularly preferably 20:1 to 4:1, in particular 14:1 to 6:1, for example 12:1 to 8:1. The total weight of all phases in a care product portion can preferably be between 8 and 30 g, in particular 10 to 25 g, particularly preferably 12 to 21 g, for example 13 to 17 g per care product portion. This weight ratio results in a good concentration of the respective ingredients of the powdered or granular phase or gel phase in a cleaning or care process. A care product is preferred in which 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.

[0072] According to the invention, the at least one solid phase and the gel adjoin one another over their full or partial surface. It is preferred that the two phases adjoin one another directly. If the at least one solid phase and the gel adjoin one another over their full or partial surface, stability is important in addition to the shortest possible setting time for the at least one gel phase. Stability here means that components contained in the gel phase do not pass into the at least one solid phase, but that even after prolonged storage the at least one solid phase and the gel remain optically separate from one another and do not interact with one another, such as, for example, diffusion of liquid components from one phase to the other or reaction of components of one phase with those in the other phase.

[0073] The care products, including the gel phase of the care products, are not films. Rather, they are shaped bodies that have a non-film-like thickness. They therefore have a layer thickness of at least 0.3 mm, preferably at least 0.7 mm, in particular at least 1.0 mm, and most preferably at least 1.2 mm. The layer thickness is measured in the plane of smallest extension.

[0074] The invention also includes a process for producing the care product according to the invention. This process involves the use of one or more water-soluble films that form the water-soluble coating of the single-dose product.

[0075] A further subject matter of the invention is thus a process for producing a care product according to the invention, comprising a) providing a mold with at least one mold cavity; optionally containing a web for dividing the bottom of the mold cavity; b) feeding a water-soluble film onto the mold cavity; c) forming an open chamber in the mold cavity by deforming the water-soluble film; d) filling the open chamber with the 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 can optionally be different from the gel phase according to d); f) optionally allowing the at least one gel phase to solidify; g) subsequently filling the open chamber with the at least one powdery phase; h) providing a second water-soluble film as a lid;i) superimposing the open chamber and the lid to seal the pre-measured single dose at a sealing zone; j) sealing the lid to the open chamber to form a pre-measured single dose comprising a water-soluble coating;

[0076] The water-soluble film may comprise one or more structurally different water-soluble polymers. Particularly suitable water-soluble polymers for the first water-soluble film are polymers from the group of (optionally acetalized) polyvinyl alcohols (PVAL) and their copolymers.

[0077] Water-soluble films for producing the portion unit are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is preferably in the range from 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 in particular from 40,000 to 80,000 gmol-1. Preferred water-soluble films comprise at least 30 wt.%, preferably at least 50 wt.%, and in particular at least 70 wt.% polyvinyl alcohol or polyvinyl alcohol copolymers. The production of the polyvinyl alcohol and polyvinyl alcohol copolymers generally includes 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 in particular 82 to 88 mol%.Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt, or its ester. Particularly preferably, such polyvinyl alcohol copolymers contain, in addition to 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. Other suitable monomers include ethylenically unsaturated dicarboxylic acids, for example, itaconic acid, maleic acid, fumaric acid, and mixtures thereof.

[0078] Suitable water-soluble films for use in the portion units according to the invention are films sold by MonoSol LLC, for example, under the designation M8630, M8720, M8310, C8400, or M8900. Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC, or Solublon® KL from Aicello Chemical Europe GmbH, or the VF-HP films from Kuraray and the Hi-Selon series from Mitsubishi Chemical Corporation.

[0079] The first water-soluble film supplied in step b) preferably has a thickness of 60 to 2000 pm, preferably of 60 to 800 pm and in particular of 60 to 200 pm.

[0080] The second water-soluble film supplied in step h) preferably has a thickness of 80 pm or less, in particular of 65 pm or less, most preferably of 55 pm or less.

[0081] With regard to the mechanical stability of the single-dose care product while at the same time using little packaging, 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, in particular from 2:1 to 1.2:1. The second water-soluble film supplied in step h) is preferably thinner than the first water-soluble film supplied in step b). 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 can be introduced into the receiving chamber. Alternatively, and in order to increase the degrees of freedom in terms of formulation and to improve the product appearance, two gel-like phases or three gel-like phases or four gel-like phases can be introduced into the receiving chamber in step d).The two, three, four or more gel-like phases preferably differ in terms of their composition and comprise, for example, different active ingredients, have different active ingredient contents or different colors. Optionally, the further gel-like phases mentioned can also be introduced in an optional step e). If in steps d) and e) more than one gel-like composition, for example two or three or four gel-like compositions, are introduced into the receiving chamber, these two or 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 one another. 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 introduced into the receiving chamber such that the surface of the gel phase(s) facing the opening of the receiving chamber is completely covered with powder. The filling level of the receiving chamber, which is at least partially filled in step g), is preferably above 20 vol.%, preferably above 50 vol.%, and in particular above 80 vol.%.

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

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

[0085] It is preferred according to the invention that the aforementioned production method comprises the further steps: k) transporting the pre-portioned single-dose comprising a water-soluble coating by means of a transport device through a shrink tunnel and shrinking 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) transporting the pre-shrunk single-dose by means of a transport device through a shrink tunnel and shrinking the water-soluble film of the pre-shrunk single-dose in the shrink tunnel to form a shrunken single-dose.

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

[0087] For process economic reasons, 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, preferably 140 to 260°C, and in particular 175 to 230°C. In step k), the residence time of the single dose in the shrink tunnel is preferably 1 to 10 seconds, preferably 2 to 6 seconds.

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

[0090] To achieve a more uniform shrinking result and a particularly favorable feel and appearance, it has proven helpful to turn the pre-shrunk single-dose product before entering the shrink tunnel in step m). The single-dose product can be turned manually or mechanically. Turning the single-dose product mechanically is preferred.

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

[0092] The heat transfer in step m) can, as in step k), be achieved, for example, by thermal radiation or hot air. Preferably, the water-soluble film is shrunk in step m) by exposure to hot air. In the second shrink tunnel, the hot air preferably has a temperature of 120 to 290°C, preferably 140 to 260°C, and especially 175 to 230°C. The residence time of the single dose in the shrink tunnel in step m) is preferably 1 to 10 seconds, preferably 2 to 6 seconds.

[0093] The shrink tunnels used in step k) and step m) may be identical or different from each other. In other words, the single dose may be transported through the same shrink tunnel in step k) and step m), but the shrink tunnels in step k) and step m) may also be different from each other. Preferred process variants are characterized in that

[0094] - 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

[0095] - 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).

[0096] As already described after step k), the shrunken single-use doses are cooled after step m), preferably using cold air.

[0097] According to the invention, it is preferred that the feel of the care product not only meets the needs of the consumer, 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, which are suitable for quantifying the feel of the product according to the invention, the test product is placed on a holder with a sealed seam facing upwards and pressure is applied 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 lesser, for example, 6 mm, or greater, for example, 10 mm. However, for the comparability of the results obtained, it is crucial to only compare results with the same penetration depth.It is also important that the measurement only begins when the pouch surface is reached, i.e. that any seal seam that protrudes upwards is not part of the measurement, i.e. that both the penetration depth (e.g. 8 mm) and the force measurement to be documented only begin when the pouch surface is reached. In this context, the pouch surface is understood to be the outside of the structure that encloses the care product composition and on the inside of which at least one phase of the care product is located. The pouch surface is not understood to be the seal seam of a single dose. To ensure that the measurement starts in this way, 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 in a short period of time with such measurements. A test speed of 25 mm / sec, for example, is usual.

[0098] Results are obtained for the weight force required in grams per penetration depth tested. The weight force required for the penetration depth achieved can be described with the parameter PF for pouch strength (PF = weight force required 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, particularly preferably 1400 g for 8 mm.

[0099] The present invention also relates to a method for cleaning and / or maintaining an automatic dishwasher, in which, in a normal cleaning cycle for cleaning items to be washed, in particular dirty dishes, with an automatic dishwashing detergent, a care agent formulated separately from the dishwashing detergent is added as described above.

[0100] It is preferred that the care product is dosed into the interior of the automatic dishwasher at the beginning of the cleaning cycle, preferably before the automatic dishwashing detergent.

[0101] It is preferable, both for the care effect and performance of the care product and for the further course of the cleaning cycle or the entire dishwashing process, for the care product to be completely dissolved in the pre-wash cycle. Therefore, methods in which the care product is dosed into the interior of the automatic dishwasher at the beginning of the cleaning cycle, preferably before the automatic dishwashing detergent, and the care product is completely dissolved in the pre-wash cycle are particularly preferred.

[0102] In particular, the invention is described by the following points:

[0103] 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 which 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.% of polyvinyl alcohol and / or its derivatives, b) 27 to 35 wt.%, preferably 30.5 to 33 wt.%, in particular 31 to 32 wt.% of 1,3-propanediol, c) 23 to 29.5 wt.%, preferably 25 to 28 wt.% of glycerol, d) 12 to 18.5 wt.% of polyalkylene glycol, in particular 13.5 to 16.5 wt.% Polyalkylene glycol, and e) < 5 wt.%, preferably < 1 wt.% water and wherein the powdery phase contains at least one organic acid in an amount of 20 to 90 wt.%, preferably 50 to 80 wt.-%, particularly preferably from 60 to 75 wt.%, based on the total weight of the powdery phase, and the powdery 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 powdery phase.

[0104] Point 2: Care product according to point 1, wherein the organic acid is a polycarboxylic acid, preferably selected from the group 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 of these.

[0105] Point 3:

[0106] Care product according to one of the preceding points, wherein the pre-portioned single dose has a pouch strength of at least 1000 g for 8 mm, preferably of at least 1200 g for 8 mm, particularly preferably of 1400 g for 8 mm.

[0107] Point 4:

[0108] Care product according to one of the previous points, wherein the care product is present in a water-soluble single-chamber bag.

[0109] Point 5:

[0110] Care product according to one of the preceding points, wherein the powdered phase comprises 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.

[0111] Point 6:

[0112] Care product according to one of the preceding points, wherein the weight ratio of the total of the at least one powdery phase to the total 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.

[0113] Point ?:

[0114] Care product according to one of the previous points, whereby the care product has a pH value of 1 to 5 (1% at 20 °C).

[0115] Point 8:

[0116] Care products according to any of the preceding points, wherein the powdered solid phase and / or the gel phase contains less than 1.0 wt.% non-ionic surfactant, based on the total weight of the respective phase. Point 9:

[0117] Care product according to one of points 1 to 7, wherein the at least one powdered solid phase comprises from 1.0 to 10 wt.% of non-ionic surfactant, based on the total weight of the respective phase.

[0118] Point 10:

[0119] Care product according to one of points 1 to 7 and 9, wherein the at least one gel-like phase comprises from 1.0 to 10 wt.% of non-ionic surfactant, based on the total weight of the respective phase

[0120] Point 11:

[0121] Care product according to one of the preceding points, wherein the total weight of the single dose is from 8 to 30 g, in particular from 10 to 25 g, preferably from 12 to 21 g, particularly preferably from 13 to 17 g.

[0122] Point 12:

[0123] A method for producing a care product according to any one of items 1 to 11, comprising a) providing a mold with at least one mold cavity; optionally containing a web for dividing the bottom of the mold cavity; b) feeding a water-soluble film onto the mold cavity; c) forming an open chamber in the mold cavity by deforming the water-soluble film; d) filling the open chamber with the 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 can optionally be different from the gel phase according to d); f) optionally allowing the at least one gel phase to solidify; g) subsequently filling the open chamber with the at least one powdery phase; h) providing a second water-soluble film as a lid;i) superimposing the open chamber and the lid to seal the pre-measured single dose at a sealing zone; j) sealing the lid to the open chamber to form a pre-measured single dose comprising a water-soluble coating;

[0124] Point 13:

[0125] Method according to item 12 comprising the further steps: k) transporting the pre-portioned single-dose comprising a water-soluble coating by means of a transport device through a shrink tunnel and shrinking 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) transporting the pre-shrunk single-dose by means of a transport device through a shrink tunnel and shrinking the water-soluble film of the pre-shrunk single-dose in the shrink tunnel to form a shrunken single-dose.

[0126] Point 14:

[0127] Method for cleaning and / or maintaining an automatic dishwasher, wherein in a normal cleaning cycle for cleaning dishes, in particular dirty dishes, with an automatic dishwashing detergent, a care agent formulated separately from the dishwashing detergent according to one of points 1 to 11 is added.

[0128] Point 15:

[0129] Method according to item 14, wherein the care product is dosed into the interior of the automatic dishwasher at the beginning of the cleaning cycle, preferably before the automatic dishwashing detergent.

[0130] Point 16:

[0131] Process according to point 14 or 15, whereby the care product is completely dissolved in the pre-wash cycle.

[0132] Examples of implementation:

[0133] Compositions:

[0134] A care product according to the invention (E1+G) and a market-known

[0135] Dishwashing product (V1+G) (Somat Excellence 4in1 Caps) manufactured:

[0136] The powdered phases are composed as follows:

[0137] Table 1 : The gel phases G (G1, G2) were composed as follows:

[0138] Table 2:

[0139] * Fatty alcohol alkoxylate, preferably 20-40 EO, endcapped

[0140] The solubility of the gel phases G1 and G2 is almost identical in both cold (approx. 15 °C) and warm water (approx. 45 °C) in terms of quantity and rate.

[0141] For the care product according to the invention (E1+G), 17 g of the powder phase (E1), 2.2 g of the gel phase (G1), and a total of 0 g of the gel phase (G2) were used. The care product according to the invention has a pH of 3.42 (1% solution, 20 °C).

[0142] 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 of 10.50 (1% solution, 20 °C).

[0143] Manufacturing process:

[0144] The care product according to the invention (E1) and the commercially known dishwashing product (V1) were prepared in the same way:

[0145] A water-soluble film was fed into a mold with a mold cavity and molded into the cavity, forming a receiving chamber. The receiving chamber was filled with the gel phases, which flowed upon heating, resulting in an at least partially filled receiving chamber. Upon cooling to room temperature, this solidified. The remaining gel phases were then filled in the same way. 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 sealing it with a heat seal, resulting in a portion unit in a water-soluble coating.The portion 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 treated again in a second shrink tunnel for a period of 6 seconds with hot air at a temperature of 170°C.

[0146] The portion units in the first shrink tunnel were oriented with the solidified gel-like composition facing upwards and in the second shrink tunnel with the solidified gel-like composition facing downwards.

[0147] Alternatively, some products were not treated in a shrink tunnel, but were manually treated from all sides with hot air (170 °C) for approximately 7 seconds.

[0148] Force-displacement measurements:

[0149] The strength of a care product according to the invention (E1) and a commercially available dishwashing product (V1) was compared. For this purpose, force-displacement measurements were carried out using a Texture Analyser TA.XT plus device (Stable Micro Systems). The test product was placed on a holder with the sealed seam facing upwards and pressure was applied from above using a spherical body (diameter d = 19 mm). The penetration depth was 8 mm. The measurement did not begin until the pouch surface was reached, i.e., the upwardly protruding sealed seam was not part of the measurement (for the example given here, this corresponds to the following release force, which had to be exceeded at the start of the measurement: 10 g). The test speed was 25 mm / sec. 10 repeat measurements were carried out for each product type.

[0150] Table 3:

[0151] It became clear that the product according to the invention required a higher pressure to achieve this penetration depth than the commercially available dishwashing product. The weight force required to achieve the 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 comparative example C1, it is only 402 g for 8 mm. Accordingly, the strength of the product according to the invention is higher, resulting in a higher-quality haptic impression. Solubility:

[0152] The solubility of the care product according to the invention (E1) in cold water was tested. In a BEKO type b300 dishwasher, program: ECO 50°C, it was checked whether residues of the powder and / or gel phase were present in the dishwasher immediately after the end of the pre-wash cycle when the care product according to the invention was placed on the floor of the dishwasher before the start of the wash cycle. No residues of the care product according to the invention were detected after the end of the pre-wash cycle.

Claims

Patent 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 powdered phase and at least one gel-like phase, wherein the gel-like phase is preferably a gel which 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.% of polyvinyl alcohol and / or its derivatives, b) 27 to 35 wt.%, preferably 30.5 to 33 wt.%, in particular 31 to 32 wt.% of 1,3-propanediol, c) 23 to 29.5 wt.%, preferably 25 to 28 wt.% of glycerol, d) 12 to 18.5 wt.% of polyalkylene glycol, in particular 13.5 to 16.5 wt.% Polyalkylene glycol, and e) < 5 wt.%, preferably < 1 wt.% water and wherein the powdery 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 powdery phase, and the powdery 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 powdery phase.

2. Care product according to claim 1, wherein the organic acid is a polycarboxylic acid, preferably selected from the group 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 of at least 1200 g for 8 mm, particularly preferably of 1400 g for 8 mm.

4. Care product according to one of the preceding claims, wherein the care product is present in a water-soluble single-chamber bag.

5. Care product according to one of the preceding claims, wherein the powdered phase comprises the corresponding base of the organic acid, preferably in an amount of 1 to 30 wt.%, particularly preferably from 10 to 25 wt.%, based on the total weight of the powdered phase.

6. Care product according to one of the preceding claims, wherein the weight ratio of the total of the at least one powdery phase to the total 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.

7. Care product according to one of the preceding claims, wherein the care product has a pH value of 1 to 5 (1% at 20 °C).

8. Care product according to one of the preceding claims, wherein the powdered solid phase and / or the gel-like phase comprises less than 1.0% by weight of non-ionic surfactant and / or wherein the at least one powdered solid phase comprises from 1.0 to 10% by weight of non-ionic surfactant and / or wherein the at least one gel-like phase comprises from 1.0 to 10% by weight of non-ionic surfactant, based on the total weight of the respective phase.

9. Care product according to one of the preceding claims, wherein the total weight of the single dose is from 8 to 30 g, in particular from 10 to 25 g, preferably from 12 to 21 g, particularly preferably from 13 to 17 g.

10. A method for producing a care product according to one of claims 1 to 9, comprising a) providing a mold with at least one mold cavity; optionally containing a web for dividing the bottom of the mold cavity; b) feeding a water-soluble film onto the mold cavity; c) forming an open chamber in the mold cavity by deforming the water-soluble film; d) filling the open chamber with the 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 can optionally be different from the gel phase according to d); f) optionally allowing the at least one gel phase to solidify; g) subsequently filling the open chamber with the at least one powdery phase; h) providing 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.

11. A method according to claim 10, comprising the further steps: k) transporting the pre-portioned single-dose comprising a water-soluble coating by means of a transport device through a shrink tunnel and shrinking 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) transporting the pre-shrunk single-dose by means of a transport device through a shrink tunnel and shrinking the water-soluble film of the pre-shrunk single-dose in the shrink tunnel to form a shrunken single-dose.

12. A method for cleaning and / or maintaining an automatic dishwasher, wherein, in a normal cleaning cycle for cleaning dishes, in particular dirty dishes, with an automatic dishwashing detergent, a care agent according to one of claims 1 to 9, formulated separately from the dishwashing detergent, is added.

13. The method according to claim 12, wherein the care agent is dosed into the interior of the automatic dishwasher at the beginning of the cleaning cycle, preferably before the automatic dishwashing detergent.

14. The method according to claim 12 and / or 13, wherein the care agent is completely dissolved in the pre-rinse cycle.

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