Care products for dishwashers

Abstract

The present application relates to a care product for an automatic dishwasher having at least one powdered phase and at least one gel phase, as well as to a method for producing this care product and to a method using this care product.

Description

The present invention relates to a care product for automatic dishwashers which is effective against deposits of lime and grease in an automatic dishwasher and can be used together with an automatic dishwasher in a normal dishwasher cycle without adversely affecting the cleaning performance of the dishwasher product, to a production method for this care product, and to a method for cleaning and / or care of a dishwasher using this product.Lime and grease deposits in an automatic dishwasher which are produced by use are nowadays usually removed with special machine care products. These specific caring agents contain lime-removing acids and defat surfactants. Owing to the acid present, such care products have to be used in a separate program, however, since otherwise the cleaning performance of the neutral to alkaline dishwashing products is significantly reduced and the acidic products can have a harmful effect on decor and glasses. The use of such care agents therefore increases the energy and water consumption. Moreover, it is not particularly user-friendly due to the additional time required. Further care products are known which can be used together with an automatic dishwashing product in a normal dishwashing cycle. They are often multi-phase agents, for example a combination of powder and compressed tablet, in order to delay the release of some ingredients compared to others.These multi-phase care products for automatic dishwashers from the prior art have some disadvantages in their production. Thus, the conditions in the production of compositions containing a powdered and a compressed phase in the form of a tablet in a water-soluble casing must be closely monitored in order that optically satisfactory products can be obtained. Only in this way can it be ensured that the tablet is merely inserted into the powder and no powder reaches between tablet film, which would represent an optical shortcoming. This slows down the production process because frequent corrections become necessary.The task of the person skilled in the art was therefore to provide a care product for automatic dishwashers which has a polyphase configuration which is appealing to the consumer and has no optical deficiencies. At the same time, the consumer is to experience the usual high-quality, firm haptics when handling the product. In addition, the product should perform at least the same way during the care of the dishwasher, for example by the release of the active ingredients already taking place completely in the prewash cycle, if present, or at the beginning of the main wash cycle if no prewash cycle is run through.The present object has been achieved by a care composition for automatic dishwashers which contains a pulverulent phase and a gel-like phase:A first subject of the present invention thus relates to a phosphate-free care product for an automatic dishwasher in a water-soluble casing in the form of a pre-portioned single dose comprising at least one pulverulent 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) is 10 to 20% by weight, preferably 12 to 18% by weight, in particular 12.7 to 15.5% by weight of polyvinyl alcohol and / or derivatives thereof, b) is 27 to 35% by weight, preferably 30.5 to 33% by weight, in particular 31 to 32% by weight of 1,3 propanediol, c) is 23 to 29.5% by weight, preferably 25 to 28% by weight of glycerol, d) 12 to 18.5% by weight 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 pulverulent phase comprises at least one organic acid in an amount of 20 to 90% by weight, preferably 50 to 80% by weight, particularly preferably 60 to 75% by weight, based on the total weight of the pulverulent phase, and the pulverulent phase has a pH of 1 to 5 (1% strength at 20° C.), and wherein the at least one gel-like phase is in direct contact with the at least one pulverulent phase.According to the invention, a gel or a gel-like phase, also referred to as gel phase below, is understood to mean a composition (or phase) which 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 agent, 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 are thermoreversible.The care agent can have one, two, three, four or more gels or gel phases. The gels / gel phases may be the same or different. In the case of a plurality of gels or gel phases, these can preferably be distinguished spatially, optically and / or on the basis of their constituents. If the gels / gel phases are different, they can preferably have different dyes and different additions of active substances.The gel is dimensionally stable. In the preparation, the polyvinyl alcohol and / or derivatives thereof is contacted with glycerol. This produces a flowable mixture which can be shaped into a desired shape. After a certain period of time, a gel / gel phase is obtained which remains in the predetermined shape, i.e. is dimensionally stable. This time, the solidification time, is preferably 15 minutes or less, preferably 10 minutes or less, more preferably 5 minutes or less. In order that the production can be carried out more quickly, it is even more preferred if the solidification time is significantly shorter than 5 minutes, in particular 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 rather returns to the initial state after the pressure has ceased. The gel is preferably elastic, in particular linear-elastic.The gel is preferably a shaped body. A molded body is a single body that stabilizes itself in its impressed shape. This dimensionally stable body is formed from a molding compound (e.g. a composition) by bringing this molding compound into a predetermined shape in a targeted manner, e.g. by casting a liquid composition into a casting mold and subsequently curing the liquid composition, e.g. in the context of a sol-gel process.Certain minimum requirements are imposed on formulations of the at least one gel phase. Thus, as already stated, the gel must solidify within the shortest possible time. Long solidification times would lead to a long production time and thus to high costs. According to the invention, solidification time means the period of time during which, during production, the gel changes from a flowable state to a dimensionally stable state which is non-flowable at room temperature. Room temperature is understood to mean a temperature of 20° C.The gel is a solid gel phase. It is preferably cut-resistant. It can be cut, for example, with a knife after solidification without being destroyed further, except at the point of the cut carried out.A phase in the sense of the present invention is a spatial region in which physical parameters and the chemical composition are homogeneous. One phase differs from another phase in terms of different characteristics, for example ingredients, physical properties, external appearance, etc. Preferably, different phases can be visually distinguished. Thus, for the consumer, the at least one powdered phase can be clearly distinguished from the at least one gel phase. In the context of this application, the terms powdery, powdery, in the form of a powder are synonymous. In addition, the transition to granular compositions is smooth. Therefore, within the scope of this application, granular or granular compositions are also understood as being pulverulent. If the care product according to the invention has more than one powdered phase, these can likewise be distinguished from one another in each case with the naked eye, because they differ from one another, for example, in terms of color. The same applies if two or more gel phases are present. In this case too, an optical distinction of the phases is possible, for example on the basis of a difference in color or transparency. Phases within the meaning of the present invention are thus self-contained regions which can be optically distinguished from one another by the consumer with the naked eye. The individual phases can have different properties in use, such as the rate at which the phase dissolves in water and thus the rate and the sequence of release of the ingredients contained in the respective phase.The gel is also preferably translucent (translucent) or transparent, which gives a good visual impression. Preferably, the transmission of the gel phase (without dye) is in a range between 100% and 20%, between 100% and 30%, in particular between 100% and 40%. To measure the light transmittance (transmission), the transmittance in % at 600 nm to water was determined as a reference at 20° C. For this purpose, the mass was poured into the 11 mm round cuvettes provided and, after 12 h storage time at room temperature, was measured for a long time in a LICO 300 color measurement system.The care compositions according to the invention comprise polyvinyl alcohol and / or derivatives thereof in an amount of 10 to 20% by weight, in particular 12 to 18% by weight, particularly preferably in an amount of 12.7 to 14.6% by weight, in each case based on the total weight of the gel.Polyvinyl alcohols are thermoplastics which are produced as white to yellowish powders, usually by hydrolysis of polyvinyl acetate. Partially hydrolyzed polyvinyl alcohol which still has amounts of up to 30 mol % of nonhydrolysed acetyl groups is to be understood as polyvinyl alcohol in the sense of the invention. Polyvinyl alcohol (PVOH) is resistant to almost all anhydrous organic solvents. Preference is given to polyvinyl alcohols having a molar mass of from 30 000 to 60 000 g / mol.According to a preferred embodiment, the gel comprises PVOH (polyvinyl alcohol). These gels or gel phases thus produced are particularly high-melting, dimensionally stable (even at 40° C.) and do not change their shape, or change it only insignificantly, even when stored. In particular, they are also poorly reactive with a view to a direct negative interaction with constituents of a granular mixture, in particular an additional powder phase. PVOH can generate in particular low water or anhydrous gel phases. When PVOH is used as polymer for the gel, low viscosity melts are obtained at 110-120° C., which can thereby be processed particularly easily; in particular, the filling of the gel phase into the water-soluble casing can be carried out quickly and accurately without sticking taking place or the quantity being incorrectly dosed. Furthermore, these gel phases adhere particularly well to the water-soluble cladding, in particular if it is likewise made of PVOH. This is also optically advantageous. Due to the rapid solidification of the at least one gel phase with PVOH, the further processing of the gel phases can take place particularly quickly. Furthermore, the good solubility of the gel phases produced is particularly favorable for the overall solubility of the single dose. Gel phases with such short solidification times are also advantageous, so that the at least one pulverulent phase metered thereon does not sink into the gel which has not yet fully solidified or too soft. This leads to visually unappealing care agent portions.Particular preference is given to polyvinyl alcohols which have, as pale yellowish powders or granules with degrees of polymerization in the range from about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol) and degrees of hydrolysis of 80 to 99 mol %, preferably of 85 to 90 mol %, in particular of 87 to 89 mol %, for example 88 mol %, and which accordingly still comprise a residual content of acetyl groups.PVOH powders having the above-mentioned properties which are suitable for use in the at least one gel phase are marketed, for example, under the designation Mowiol® or Poval® by Kuraray. Also suitable is, for example, Exceval® AQ4104, from Kuraray. Particularly suitable are Mowiol C30, the Poval® grades, in particular grades 3-83, 3-88, 6-88, 4-85, and particularly preferably 4-88, very particularly preferably Poval 4-88 S2 and Mowiol® 4-88 from Kuraray.As derivatives of PVOH, copolymers of polyvinyl alcohol with other monomers, in particular copolymers with anionic monomers, are preferred for the purposes of the invention. Suitable anionic monomers are preferably vinylacetic acid, alkyl acrylates, maleic acid and derivatives thereof, in particular monoalkyl maleates (in particular monomethyl maleate), dialkyl maleates (in particular dimethyl maleate), maleic anhydride, fumaric acid and derivatives thereof, in particular monoalkyl fumarate (in particular monomethyl fumarate), dialkyl fumarate (in particular dimethyl fumarate), fumaric anhydride, itaconic acid and derivatives thereof, in particular monomethyl itaconate, dialkyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid (methyl maleic acid) and derivatives thereof, monoalkyl citraconic acid (in particular methyl itraconate), dialkyl citraconic acid (dimethyl itraconate), citraconic anhydride, mesaconic acid (methyl fumaric acid) and derivatives thereof, monoalkylmesaconate, dialkylmesaconate, Mesaconic anhydride, glutaconic acid and derivatives thereof, monoalkyl gluconate, dialkyl gluconate, glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate and combinations thereof and the alkali metal salts or esters of the abovementioned monomers.Particularly preferred derivatives of PVOH 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, and the alkali metal salts or esters of the abovementioned monomers. The values stated for polyvinyl alcohols themselves apply to the suitable molar masses. In the context of the present invention, it is preferred that the gel comprises a polyvinyl alcohol and / or derivatives thereof, preferably polyvinyl alcohol, the degree of hydrolysis of which is preferably 70 to 100 mol %, in particular 80 to 90 mol %, particularly preferably 81 to 89 mol % and in particular 82 to 88 mol %.The water solubility of polyvinyl alcohol can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization). This too is to be understood as derivatives of polyvinyl alcohol. Polyvinyl alcohols have proven to be particularly preferred and particularly advantageous because of their extremely good cold water solubility, which are acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof. The reaction products of polyvinyl alcohol and starch are to be used as extremely advantageous. Furthermore, the water solubility can be changed by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, borax and can thus be adjusted specifically to desired values.The care agents have in the gel / gel phase 27.0 to 35.0 wt % of 1,3-propanediol, preferably 30.5 to 33.0 wt % of 1,3-propanediol, particularly preferably 31.0 to 32.0 wt % of 1,3-propanediol, very particularly preferably 1,3-propanediol, based on the total weight of the gel.According to the invention, the gel phase comprises at least one polyalkylene glycol. Copolymers of ethylene oxide and propylene oxide are not to be considered as included in the polyalkylene glycols according to the invention. The gel preferably comprises at least one polyethylene glycol and / or at least one polypropylene glycol and mixtures thereof.The gel contains 12 to 18.5% by weight, preferably 13.5 to 16.5% by weight, of at least one polyalkylene glycol, based on the total weight of the gel. Preferred polyalkylene glycol is in particular polyethylene glycol and / or polypropylene glycol, and mixtures thereof. Polyethylene glycols having an average molar mass of between about 100 and 8000 are particularly suitable.The polyalkylene glycols used are preferably liquid at 20° C., 1 bar. According to the invention, therefore, polyethylene glycol(s) having an average molar mass of 200 to 600 g / mol are preferably additionally used in the at least one gel phase or the gel phases. Polyethylene glycols having an average molar mass of 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 in combination with polyvinyl alcohol. Care compositions according to the invention are thus characterized in that they comprise polyethylene glycol(s) having an average molar mass of 300 to 500 g / mol, in particular of 350 to 450 g / mol.In a particularly preferred embodiment, polyethylene glycols, preferably polyethylene glycol(s) having an average molar mass 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 %.According to a further embodiment, besides the polyethylene glycols mentioned with an average molar mass of 200 to 600 g / mol, further polyalkylene glycols, in particular further polyethylene glycols, with an average molar mass of between about 800 and 8000 can be contained 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 in each case based on the total weight of the gel.The gel further comprises as component c) 23 to 29.5% by weight glycerol, based on the total weight of the gel. Particularly preferably, glycerol is present in the gel in an amount of 25 to 28% by weight, based on the total weight of the gel.The gel is substantially anhydrous. This means that the gel is preferably substantially free of water. "Substantially free" here means that small amounts of water may be contained in the gel phase. This water can be introduced into the phase, for example, by a solvent or as water of crystallization or on the basis of reactions of constituents of the phase with one another. However, it is preferred to use only small amounts, in particular no water, as solvent for preparing the gel phase. The proportion of water in the gel phase is in this embodiment <5% by weight of water, preferably 4.9% by weight or less, 4% by weight or less, preferably 2% by weight or less, in particular 1% by weight or less, preferably <1% by weight, particularly 0.5% by weight or less, in particular 0.1% by weight or 0.05% by weight or less. The data in % by weight are based here on the total weight of the gel.According to a particularly preferred embodiment, the invention relates to care compositions as described above, comprising a gel which is solid at room temperature (20° C.) and which, based on the total weight of the gel, contains 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) having 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) <5% by weight, preferably <1% by weight of water.According to a very particularly preferred embodiment, the invention relates to care compositions as described above, comprising a gel which is solid at room temperature (20° C.) and which, based on the total weight of the gel, contains a) 12.7 to 15.5% by weight of PVOH, b) 31 to 32% by weight of 1,3 propanediol, c) 25 to 28% by weight of glycerol, d) 13.5 to 16.5% by weight of polyethylene glycol(s) having an average molar mass of 350 to 450 g / mol, for example around 400 g / mol, and e) <1% by weight of water.These compositions exhibit a particularly good flowability during the metering and at the same time an advantageously short solidification time after metering of the gel and cooling, wherein they at the same time have only a slight synergism. This means that no larger amounts of liquid ingredients leave the gel. The visible escape of liquid from the gel ("sweating") has the result that the gel is no longer as easy to handle. The consumer sees this as unaesthetic and as a qualitative shortcoming. Depending on the sale form of the gel, sweating also means difficulties in handling the gel without risk. The escape of liquid from the gel is to be avoided as much as possible, since interactions occur in care agent portions between the liquid and any contained ingredients in a further phase and / or a water-soluble coating. This leads to aesthetically undesirable discolorations or inactivation of sensitive ingredients, dissolution or softening of coatings, e.g. coatings or the water-soluble coating. Preferably, in particular less than 5 wt %, preferably less than 3 wt %, in particular less than 1.5 wt % of liquid based on the total weight of the gel, measured after a week storage of the freshly cast gel at a temperature of 20° C., emerges.These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from a study of the present detailed description and claims. Any feature of one aspect of the invention may be used in any other aspect of the invention. Further, it is to be understood that the examples 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 indicated in the format "from x to y" include the above values. When several preferred numerical ranges are specified in this format, it is understood that all ranges arising from the combination of the various endpoints are also detected."At least one" as used herein means 1 or more, i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to an ingredient, the specification 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. that one type of bleach catalyst or a mixture of a plurality of different bleach catalysts may be meant. Together with weight data, the data refer to all compounds of the stated type which are contained 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.Where molecular weights are referred to herein, these data always relate to the number-average molecular weight Mn, unless explicitly stated otherwise. The number average molar mass can be determined, for example, by means of gel permeation chromatography (GPC) in accordance with DIN 55672-1:2007-08 using THF as eluent. The mass average molecular weight Mwcan also be determined by GPC as described for Mn.All percentages given in connection with the compositions described herein relate, unless explicitly stated otherwise, to % by weight, in each case based on the relevant mixture or phase.Furthermore, the gel must be stable on storage, namely under conventional storage conditions. The gel phase is a constituent of a care composition according to the invention. Such products are usually stored in a household for a certain period of time. The storage is usually carried out in the vicinity of the washing or dishwasher. For such storage, the gel should be stable. Thus, the gel should be stable, in particular even after a storage time of, for example, 4 to 12 weeks, in particular 10 to 12 weeks or longer at a temperature of up to 40° C., in particular at 30° C., in particular at 25° C. or at 20° C., and should not deform or otherwise change in consistency during this time.It is preferred that the gel penetrates into the interstices of the immediately adjacent powder phase in the storage period of 4 weeks at 25° C., preferably at most 1 mm.A disadvantage would be a change in volume or shrinkage during storage, since the acceptance of the product by the consumer would be low as a result. Leakage of liquid or sweating of constituents out of the gel phase is also undesirable. Here too, on the one hand, the visual impression is of relevance. The stability of the gel phase can be influenced by the escape of liquid, such as solvent, for example, so that the constituents are no longer contained stably and the care effect can thereby also be influenced.The pulverulent phase comprises at least one organic acid in an amount of from 20 to 90% by weight, preferably from 50 to 80% by weight, particularly preferably from 60 to 75% by weight, based on the total weight of the pulverulent phase. This is the amount of anhydrous acid. In general, polycarboxylic acids are suitable as acids, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. Aminocarboxylic acids are also suitable as acids, such as, for example, aspartic acid, methylglycinediacetic acid (MGDA) and glutaminediacetic acid (GLDA) or ethylenediaminediacetic acid. Iminodisuccinic acid (IDS) and iminodiacetic acid (IDA) are likewise suitable. However, it is preferred that the acids used are not aminocarboxylic acids.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, saccharic acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for okological reasons, or mixtures thereof.The present invention therefore preferably provides the care composition, 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, saccharic acids, aminocarboxylic acids, nitrilotriacetic acid or mixtures thereof.The pulverulent phase has a pH of from 1 to 5 (1% strength at 20° C.). It is preferred according to the invention that the pH of the pulverulent phase is from 2 to 4.5, in particular preferably from 2.5 to 4 (1% strength at 20° C.).The agent according to the invention is configured 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 interposed between these two phases. In particular, this also means that no film of water-soluble material, as is used for the water-soluble casing, for example, is arranged between the at least one gel-like phase and the at least one powder-like phase and separates the gel-like and the powder-like phases from one another. The at least one gel phase and the at least one powdered phase are accordingly present in the same chamber of the water-soluble casing.It is also preferred according to the invention that the care agent is present in a water-soluble single-chamber bag.The pulverulent phase comprises, in addition to the organic acid, at least 10% by weight, based on the total weight of the pulverulent phase, of further constituents.According to the invention, it is preferred that the pulverulent phase comprises the corresponding base of the organic acid, preferably in an amount of from 1 to 30% by weight, particularly preferably from 10 to 25% by weight, based on the total weight of the pulverulent phase. For example, citrate can be used when citric acid is used as the organic acid. Accordingly, it is a preferred subject matter that the pulverulent phase comprises the corresponding base of the organic acid, preferably in an amount of from 1 to 30% by weight, particularly preferably from 10 to 25% by weight, based on the total weight of the pulverulent phase.It is another preferred subject matter that the powdered phase has a base different from the corresponding base of the organic acid, preferably in an amount of 1 to 30 wt %, particularly preferably of 10 to 25 wt %, based on the total weight of the powdered phase.Bases which can additionally be used are, in particular, carbonates and silicates which are described further among the builders which can additionally be used; the use of acetates is also possible. In addition, further ingredients such as sulfates, for example sodium sulfate, other fillers, colorants and fragrances can be used in the powdered phase.It is preferred that the amount of organic acid in the care agent, in particular already the amount of organic acid in the powdered phase, is suitable for reducing or eliminating lime-containing soiling in the dishwasher. It is particularly preferred that the care agent has a pH of 1 to 5 (1% strength at 20° C.). It is more preferred that the pH of the care composition is from 2 to 4.5, especially preferably from 2.5 to 4 (1% strength at 20° C.).Among other ingredients, surfactants can also provide for cleaning and care of the automatic dishwasher, preferably nonionic surfactants. It may therefore be preferred for the care composition according to the invention to comprise one or more nonionic surfactants. In this case, nonionic surfactant can be present in the at least one pulverulent phase and / or in the at least one gel phase. A nonionic surfactant that can be used in the care compositions described herein can be any of the nonionic surfactants known to the skilled person. In preferred embodiments, however, nonionic surfactants from the group of alkoxylated alcohols are used. A class of nonionic surfactants which can preferably be used and which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants are accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty alcohols.In various preferred embodiments, therefore, a fatty alcohol alkoxylate, in particular a fatty alcohol ethoxylate, is used. In particular, non end group-terminated fatty alcohol alkoxylates are preferred. In preferred embodiments, the fatty alcohol ethoxylate has the formula R 1- O-(EO) m- H, wherein 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.In particularly preferred embodiments, the fatty alcohol ethoxylate has the formula R 1- O-(EO) m- H, wherein 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.In one embodiment, the alkyl group R 1 is a linear, preferably unsubstituted, alkyl group having 16 to 18 C atoms.The nonionic surfactant is preferably a fatty alcohol ethoxylate which is solid under standard conditions (temperature 25° C., pressure 1013 mbar) and can preferably be used in the form of a powder or granules.In a preferred embodiment, the care composition contains less than 1% by weight of nonionic surfactant, based on the total weight of the composition. In the same or another preferred embodiment, the pulverulent solid phase and / or the gel-like phase comprises 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.In another preferred embodiment, the at least one pulverulent solid phase comprises from 1.0 to 10% by weight of nonionic surfactant, based on the total weight of the respective phase. In these embodiments, the amount of nonionic surfactant in the total composition may be greater than 1% by weight based on the total weight of the composition. Preferably, the proportion of non-ionic surfactant in the total composition in these cases is 1 to 5 wt %. The nonionic surfactant is preferably a fatty alcohol ethoxylate as described above.In a further preferred embodiment, the at least one gel-like phase comprises from 1.0 to 10% by weight of nonionic surfactant, based on the total weight of the respective phase. In these embodiments, the amount of nonionic surfactant in the total composition may be greater than 1% by weight based on the total weight of the composition. Preferably, the proportion of non-ionic surfactant in the total composition in these cases is 1 to 5 wt %. The nonionic surfactant is preferably a fatty alcohol ethoxylate as described above.Further preferably, the gel / gel phase 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 may further comprise anionic polymers or copolymers having builder properties. This is preferably a polycarboxylate. 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 may 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 phase comprises a polymer comprising at least one monomer containing sulfonic acid groups, preferably, in addition to monomer(s) containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids.Unsaturated carboxylic acid(s) used with particular preference is / are unsaturated carboxylic acids of the formula R1(R2)C=C(R3)COOH in which R1to R3independently of one another are -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 are -COOH or -COOR4, where R4is 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, 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. It is of course also possible to use the unsaturated dicarboxylic acids. In the case of the monomers containing sulphonic acid groups, those of the formula R5(R6)C=C(R7)-X-SO3H are preferred in which R5to R7independently 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, where R4is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group which is 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 formulae H2C=CH-X-SO3H, H2C=C(CH3)-X-SO3H or HO3S-X-(R6)C=C(R7)-X-SO3H in which R6and R7are independently selected from -H, -CH3, -CH2CH3, -CH2CH2CH3and -CH(CH3)2and X is 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-.According to a particularly preferred embodiment, the gel / gel phase comprises 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-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or water-soluble salts thereof. In the polymers, the sulfonic acid groups can be present wholly or partly in neutralized form, that is to say that the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by 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 in each case 5 to 95% by weight, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight and the proportion of the monomer containing carboxylic acid groups is 10 to 50% by weight, in the case of copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, the monomers here preferably being selected from the abovementioned. 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 end use. Preferred care agents are characterized in that the copolymers have molar masses of 2000 to 200,000 g·mol-1, preferably of 4000 to 25,000 g·mol-1and 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, also at least one nonionic, preferably hydrophobic monomer. The use of these hydrophobically modified polymers has in particular been able to improve the final rinse performance of dishwashing detergents according to the invention.More preferably, the gel further comprises an anionic copolymer, wherein as anionic copolymer a copolymer comprisingi) Monomers containing carboxylic acid groupsii) Monomers containing sulphonic acid groupsiii) non-ionic monomers, in particular hydrophobic monomersThe compound can be used.The nonionic monomers used are preferably monomers of the general formula R1 (R2)C=C(R 3)-X-R4, in which R1 to R3 independently of one another are -H, -CH3 or -C2H5, X is an optionally present spacer group selected from -CH2-, -C(O)O- and -C(O)-NH-, and R4 is 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.Particularly preferred 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-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4,4-dimethylhexane-1, ethylcyclohexyne, 1-octene, α-olefins having 10 or more carbon atoms, such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, and the like, α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N-(methyl)acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl 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.Surprisingly, it has been found that PVOH and / or derivatives thereof together with anionic polymers or copolymers, in particular with copolymers containing sulphonic acid groups, also leads to the formation of gel phases with insensitive surfaces. Corresponding surfaces can be touched by the end user without material remaining adhering to the hands. No material removal takes place even in a packaging. Preferably, therefore, the gel comprises PVOH, polyethylene glycol(s) having 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% by weight to 20% by weight, in particular 3% by weight to 30% by weight, particularly 4% by weight to 25% by weight, preferably 5% by weight to 20% by weight, for example 10% by weight, based on the total weight of the gel. Sulfopolymers, in particular the preferred copolymeric polysulfonates, which contain not only sulfonic acid group-containing monomer(s) but also at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, additionally ensure an excellent gloss of the surface. In addition, fingerprints are not retained either. Therefore, the proportion of sulfopolymers, in particular the preferred copolymeric polysulfonates, which contain, in addition to sulfonic acid group-containing monomer(s), at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, is, in particular, of the sulfopolymers mentioned with AMPS as sulfonic acid group-containing monomer, for example Acusol 590, Acusol 588 or Sokalan CP50, preferably 1 wt % to 25 wt %, in particular 3 wt % to 18 wt %, in particular 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 copolymeric polysulfonates, which, in addition to sulfonic acid group-containing monomer(s), comprise at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, and at least one polyhydric alcohol.According to a particularly preferred embodiment, the invention relates to a care composition 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% 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) having 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% by weight, preferably <1% by weight of water and f) 5 to 12% by weight, in particular from 7 to 10.5 wt. % of a polymer containing sulfonic acid groups, preferably of 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 monomer containing sulfonic acid groups, based on the total weight of the gel.According to a very particularly preferred embodiment, the invention relates to a care composition described herein, comprising a gel which is solid at room temperature (20° C.) and which, based on the total weight of the gel, comprises a) 12.7 to 15.5% by weight of PVOH, b) 31 to 32% by weight of 1,3-propanediol, c) 25 to 28% by weight of glycerol, d) 13.5 to 16.5% by weight of polyethylene glycol(s) having an average molar mass of 350 to 450 g / mol, for example around 400 g / mol, e) <1% by weight of water f) 5 to 12% by weight, in particular 7 to 10.5% by weight, 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 having AMPS as sulphonic acid group-containing monomer, based on the total weight of the gel.The care composition according to the invention comprises at least one pulverulent phase and at least one gel or one gel phase. The care agent may have one, two, three or more different powdery phases; likewise, it may have one, two, three, four or more different gel phases. The care composition according to the invention preferably comprises a solid phase and a gel phase. Particularly preferably, the care agent comprises two solid phases and one gel phase. Preferably, it comprises two solid phases and two gel phases. Further preferred is an embodiment in which the care agent comprises three solid phases and one or two gel phases. In a preferred embodiment, the care agent comprises three powdered phases and one, two or three gel phases. In another preferred embodiment, the care agent comprises a powdered phase and one, two or three gel phases.The weight ratio of the entirety of the at least one pulverulent or granular phase to the entirety of the at least one gel phase (gel phase) is preferably 40:1 to 2:1, more preferably 20:1 to 4:1, in particular 14:1 to 6:1, for example 12:1 to 8:1. In this weight ratio, a good concentration of the respective ingredients of the powdered or granular phase or gel phase results in a cleaning or care process. A care product is preferred in which the total weight of the one-time 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.According to the invention, the at least one solid phase and the gel are contiguous to one another over the full or partial area. It is preferred that the two phases are immediately adjacent to each other. If the at least one solid phase and the gel directly border one another over their full or partial area, stability is important in addition to the shortest possible solidification time of the at least one gel phase. Stability here means that constituents contained in the gel phase do not pass over into the at least one solid phase, but rather, even after prolonged storage, the at least one solid phase and the gel are present optically separate from one another and do not interact with one another, such as, for example, diffusion of liquid constituents from one phase into the other phase or reaction of constituents of one phase with those in the other phase.The care agents and also the gel-like phase of the care agents are in particular not films. They are rather shaped bodies which have a non-film-like thickness. They therefore have a layer thickness of at least 0.3 mm, preferably of at least 0.7 mm, in particular of at least 1.0 mm, very particularly preferably of at least 1.2 mm. The layer thickness is measured in the plane with the smallest extent.Part of the invention is also a method for producing the care composition according to the invention. This uses one or more water-soluble films which form the water-soluble envelope(s) of the single dose.The invention thus further provides a method for producing a care product according to the invention, comprising a) providing a mold having at least one mold cavity; optionally comprising a web for dividing the base of the mold cavity; b) supplying a water-soluble film to the mold cavity; c) forming an open chamber in the mold cavity by shaping the water-soluble film; d) filling the open chamber with the at least one gel phase; e) optionally filling the open chamber or parts thereof with at least one further gel 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 powder phase; h) providing a second water-soluble film as a lid; i) placing the open chamber and the lid one above the 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 envelope.The water-soluble film may comprise one or more structurally different water-soluble polymer(s). Suitable water-soluble polymer(s) for the first water-soluble film are, in particular, polymers from the group of (optionally acetalized) polyvinyl alcohols (PVAL) and copolymers thereof.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 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 preparation of the polyvinyl alcohol and polyvinyl alcohol copolymers typically 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 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 esters. 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 esters, methacrylic esters or mixtures thereof; among the esters, C1-4-alkyl esters or hydroxyalkyl esters are preferred. Other suitable monomers are ethylenically unsaturated dicarboxylic acids, for example itaconic acid, maleic acid, fumaric acid and mixtures thereof.Suitable water-soluble films for use in the portion units according to the invention are films which are sold by the company MonoSol LLC, for example under the name M8630, M8720, M8310, C8400 or M8900. Other suitable films include Solublon® PT, Solublon® GA, Solublon® KC, or Solublon® KL films from Aicello Chemical Europe GmbH, or Kuraray's VF-HP films, as well as the Hi-Selon Series from Mitsubishi Chemical Corporation.The first water-soluble film supplied in step b) preferably has a thickness of 60 to 2000 μm, preferably 60 to 800 μm, and more preferably 60 to 200 μm.The second water-soluble film supplied in step h) preferably has a thickness of 80 μm or less, more preferably of 65 μm or less, most preferably of 55 μm or less.With regard to the mechanical stability of the care agent single portion with at the same time little use of packaging agents, 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. Preferably, the second water-soluble film supplied in step h) is thinner than the first water-soluble film supplied in step b).The number of gel compositions introduced into the receiving chamber may vary. For example, in step d) of the method, only a single gel phase can be introduced into the receiving chamber. Alternatively and because of the increase in the compositional degrees of freedom and the improved product optics, in step d) two gel-like phases or three gel-like phases or four gel-like phases can be introduced into the receiving chamber. The two, three, four or more gel phases preferably differ in terms of their composition and comprise, for example, different active substances, have different active substance 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) a total of more than one gel-like composition, i.e. if, for example, two or three or four gel-like compositions are introduced into the receiving chamber, then 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 undesired reactions between individual active ingredients contained in the different gel-like compositions and improves the optical properties of the product.In step g), the powder is preferably introduced into the receiving chamber in such a way that the surface of the gel-like phase(s) facing the opening of the receiving chamber is completely covered with powder. The filling degree of the receiving chamber at least partially filled in step g) is preferably above 20% by volume, preferably above 50% by volume and in particular above 80% by volume.With regard to the later optical and haptic properties of the care agent portion unit, it is particularly preferred if the at least partially filled receiving chamber in step g) has a filling degree of 60 to 120 vol. %, preferably of 80 to 110 vol. % and in particular of 90 to 100 vol. %.The at least partially filled receiving chamber is sealed in step j) of the method. The sealing is preferably effected under the influence of solvent or under the influence of heat.It is preferred according to the invention that the above-mentioned method for production has the further steps:k) transporting the pre-portioned single dose comprising a water-soluble wrapping by means of a transport device through a shrink tunnel and shrinking the water-soluble wrapping of the single dose in the shrink tunnel to form a pre-shrunk single dose;l) cooling the pre-shrunk single-use dose on a cooling section outside the first shrink tunnel;m) transporting the pre-shrunk single dose by means of a transporting device through a shrink tunnel and shrinking the water-soluble film of the pre-shrunk single dose in the shrink tunnel to form a shrunk single dose.When steps k) to m) are carried out, the shrinkage of the water-soluble film takes place in a device which is set up for this purpose and is referred to as a shrink tunnel. A shrink tunnel enables the targeted heating of the water-soluble film enclosing the disposable care agent dose. The shrink tunnel has a conveying system with the aid of which the single dose is transported through the shrink tunnel. This conveying system can be, for example, a revolving conveyor belt. The heat transfer in the shrink tunnel can be effected, for example, by heat radiation or hot air. In such processes, the water-soluble film in step k) is preferably shrunk by exposure to hot air.For reasons of process economy, it is preferred if the single dose in step k) rests with the first water-soluble film on the transport device.In the first shrink tunnel, the hot air preferably has a temperature of 120 to 290° C., preferably of 140 to 260° C. and in particular of 175 to 230° C. In step k), the dwell time of the single dose in the shrink tunnel is preferably 1 to 10 seconds, preferably 2 to 6 seconds.After exiting from the shrink tunnel, the pre-shrunk single dose is cooled in step I). The cooling is preferably effected by means of cold air, wherein the cold air preferably has a temperature of 5 to 35° C., particularly preferably of 10 to 30° C., and in particular of 15 to 25° C. The cooling serves to stabilize the shrinkage result, allows the single dose to be processed further rapidly and thus prepares the subsequent method steps. In step I), the dwell time of the pre-shrunk single dose on the cooling section is 1 to 60 seconds, preferably 5 to 30 seconds.In order to achieve a more uniform shrinkage result and a particularly advantageous haptics and optics, it has proven to be helpful to turn the pre-shrunk single dose before entering the shrinkage tunnel in step m). The single dose can be turned manually or mechanically. It is preferred to turn the single dose mechanically.Preferably, the single dose in step m) with the second water-soluble film is deposited on the transport device. It is particularly preferred if the single dose, as described above, rests on the transport device with the first water-soluble film in step k) and with the second water-soluble film in step m).The heat transfer in step m) can, as already in step k), take place, for example, by heat 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 of 140 to 260° C. and in particular of 175 to 230° C. The dwell time of the single dose in the shrink tunnel in step m) is preferably 1 to 10 seconds, preferably 2 to 6 seconds.The shrink tunnels used in step k) and in step m) may be identical or different from each other. In other words, the single dose in step k) and in step m) can be transported through the same shrink tunnel, but the shrink tunnels in step k) and step m) can also be shrink tunnels different from one another. Preferred process variants are characterized in thatthe dwell time of the single dose in the first shrink tunnel in step k) differs from the dwell time in the second shrink tunnel in step m), and / orthe hot air temperature in the first shrinking tunnel in step k) differs from the hot air temperature in the second shrinking tunnel in step m).As already following step k), the shrunk disposable doses following step m) are preferably cooled by means of cold air.It is preferred according to the invention that the haptics of the care product not only meet the requirements of the consumers, but also that this haptic impression can be quantified and the production process can be monitored in this way by checking as regular. Such quantification is possible by determining the strength with the aid of force-displacement measurements. In force-displacement measurements which are suitable for quantifying the haptics of the product according to the invention, the test product is placed with a seal seam upwards on a holder and is pressurized from above by means of a ball body (diameter d=19 mm). In suitable measurements, the penetration depth is, for example. 8 mm. The penetration depth can also be smaller, for example. 6 mm or higher, for example. 10 mm. However, for the comparative nature of the results obtained, it is important to compare only results of the same depth of penetration with one another. It is also important that the measurement is started only when the pouch surface is reached, i.e. that a sealing seam which may protrude upward is not part of the measurement, i.e. that both the penetration depth (for example. 8 mm) as well as the force measurement to be documented only starts when the pouch surface is reached. In this context, a pouch surface is understood to mean the outer side of the structure which encloses the care agent composition and on the inner side of which at least one phase of the care agent is located. The pouch surface is not understood to mean the sealed seam of a single dose. In order to ensure such a start of the measurement, a triggering force can be defined, for example, which must be exceeded before the start of the measurement (for example. 10 g). The depth of penetration of the ball body is achieved in a short period of time in such measurements. A test speed of 25 mm / sec is customary, for example.Results are obtained for the weight force to be applied in grams per tested penetration depth. The weight to be applied for the penetration depth carried out can be described with the parameter PF for pouch resistance (PF=weight to be applied for penetration depth). It is preferred according to the invention that the preportioned single dose has a pouch resistance 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.The present invention likewise relates to a method for cleaning and / or caring for an automatic dishwasher, in which a caring agent formulated separately from the dishwasher agent is metered in as described above in a normal cleaning cycle for cleaning washware, in particular dirty dishes, with an automatic dishwasher agent.It is preferred that the care agent is metered into the interior of the automatic dishwasher at the beginning of the cleaning cycle, preferably before the automatic dishwasher agent.It is preferred both for the care effect and performance of the care agent and for the further course of the cleaning cycle or the entire rinsing process if the care agent is completely dissolved in the pre-rinsing cycle. Therefore, in particular methods are preferred in which the care agent is dosed into the interior of the automatic dishwasher at the beginning of the cleaning cycle, preferably before the automatic dishwasher detergent, and the care agent is completely dissolved in the prewash cycle.In particular, the invention is described by the following points:Item 1: Phosphate-free care product for an automatic dishwasher in a water-soluble casing in the form of a pre-sized single dose comprising at least one pulverulent 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) is 10 to 20% by weight, preferably 12 to 18% by weight, in particular 12.7 to 15.5% by weight, of polyvinyl alcohol and / or derivatives thereof, b) is 27 to 35% by weight, preferably 30.5 to 33% by weight, in particular 31 to 32% by weight, of 1,3 propanediol, c) is 23 to 29.5% by weight, preferably 25 to 28% by weight, of glycerol, d) is 12 to 18.5% by weight of polyalkylene glycol, in particular 13.5 to 16.5 wt % polyalkylene glycol, and e) <5 wt %, preferably <1 wt % water, and wherein the pulverulent phase comprises at least one organic acid in an amount of 20 to 90 wt %, preferably of 50 to 80 wt %, particularly preferably of 60 to 75 wt %, based on the total weight of the pulverulent phase, and the pulverulent 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 pulverulent phase.Item 2: Care agent according to item 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, saccharic acids, aminocarboxylic acids, nitrilotriacetic acid or mixtures thereof.Item 3: Care agent according to one of the preceding items, wherein the pre-portioned single dose has a pouch resistance 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.Item 4: The care agent according to any one of the preceding items, wherein the care agent is present in a water-soluble single chamber bag.Item 5: Care agent according to one of the preceding items, wherein the pulverulent phase comprises the corresponding base of the organic acid, preferably in an amount of from 1 to 30% by weight, particularly preferably from 10 to 25% by weight, based on the total weight of the pulverulent phase.Item 6: Care agent according to one of the preceding items, wherein the weight ratio of the entirety of the at least one pulverulent phase to the entirety 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.Item 7: The care agent according to any one of the preceding items, wherein the care agent has a pH of 1 to 5 (1% at 20° C.).Item 8: Care composition according to one of the preceding items, wherein the pulverulent solid phase and / or the gel-like phase comprises less than 1.0% by weight of nonionic surfactant, based on the total weight of the respective phase.Item 9: The care composition according to any one of items 1 to 7, wherein the at least one pulverulent solid phase comprises from 1.0 to 10% by weight of nonionic surfactant, based on the total weight of the respective phase.Item 10: Care composition according to any of Items 1 to 7 and 9, wherein the at least one gel-like phase comprises from 1.0 to 10% by weight of nonionic surfactant, based on the total weight of the respective phaseItem 11: Care agent according to one of the preceding items, 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.Item 12: Method for producing a care product according to one of Items 1 to 11 comprising a) providing a mold having at least one mold cavity; optionally containing a web for dividing the base of the mold cavity; b) supplying a water-soluble film onto the mold cavity; c) forming an open chamber in the mold cavity by shaping 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 powder-like phase; h) providing a second water-soluble film as a lid; i) placing the open chamber and the lid one above the 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 envelope.Item 13: The method according to item 12 comprising the further steps:k) transporting the pre-portioned single dose comprising a water-soluble wrapping by means of a transport device through a shrink tunnel and shrinking the water-soluble wrapping of the single dose in the shrink tunnel to form a pre-shrunk single dose;l) cooling the pre-shrunk single-use dose on a cooling section outside the first shrink tunnel;m) transporting the pre-shrunk single dose by means of a transporting device through a shrink tunnel and shrinking the water-soluble film of the pre-shrunk single dose in the shrink tunnel to form a shrunk single dose.Item 14: Method for cleaning and / or caring for an automatic dishwasher, wherein in a normal cleaning cycle for cleaning washware, in particular dirty dishes, with an automatic dishwasher product, a caring product formulated separately from the dishwasher product is metered in according to one of Items 1 to 11.Item 15: Method according to item 14, wherein the care agent is metered into the interior of the automatic dishwasher at the beginning of the cleaning cycle, preferably before the automatic dishwasher agent.Item 16: Method according to item 14 or 15, wherein the care agent is completely dissolved in the pre-rinse cycle.Exemplary Embodiments:Compositions:A care composition according to the invention (E1+G) and a commercially known dishwashing product (V1+G) (Somatostatin Excess 4in1 Caps) were produced:The powder phases were composed as follows: Table 1: Table 1:In % by weightE1V1Na citrate, anhydrate18,915-20Phosphonate (e.g. HEDP)2,5-7,5MGDA, Na salt0-25Disilicate, Na salt5-35Soda Soda Soda3,810-25SILVER PROTECTION (e.g. cysteine)0,0 - 1,0Percarbonate, Na salt10-15Bleach catalyst (preferably Mn-based)0,02-0,5Bleach activator (e.g. TAED)1-3Nonionic surfactant(s) such as fatty alcohol alkoxylate, preferably 20-40 EO, optionally end-capped2,5-10Polycarboxylate Resin Polycarboxylate Products4 - 10Cationic copolymer0-0,75Disintegrant - (e.g. Crosslinked PVP)0-1,5Protease Preparation (tq)1,5-5Amylase Preparation (tq)0,5-3Perfume0,05-0,25Dye0,0-10,0-1Zn salt (e.g., acetate)0,1-0,3Sodium Sulfate100,0 - 10Water0,0-1,5pH adjusters (e.g., citric acid)0-1,5Process Aid0-5Citric acid, anhydrate67The gel-like phases G (G1, G2) were composed as follows: Table 2: Table 2:In % by weightG1G2A polymer comprising acrylic acid- and amido propyl sulfonic acid-containing monomers10101,3-Propanediol3229Glycerol2624Nonionic Surfactant*07PEG 4001514PVOH (Mowiol 4-88)1514Misc (inter alia processing aid, pH adjuster, perfume, dye, residual water)100 add100 addFatty alcohol alkoxylate, preferably 20-40 EO, endcappedThe solubility of the gel phases G1 and G2 is approximately identical in terms of quantity and velocity both in cold (about 15° C.) and in warm water (about 45° C.).For the care composition (E 1+G) according to the invention, 17 g of the pulverulent phase (E 1), 2.2 g of the gel phase (G 1) and a total of 0 g of the gel phase (G 2) were used. The care composition according to the invention has a pH of 3.42 (1%, 20° C.).For the commercially known dishwashing product (V1+G), 17 g of the pulverulent phase (V1), 1.4 g of the gel phase (G1) and a total of 0.8 g of the gel phase (G2) were used. The conventional dishwashing product on the market has a pH of 10.50 (1%, 20° C.).Production Method:The care composition (E1) according to the invention and the conventional dishwashing product (V1) were prepared in the same way:A water soluble film was supplied to a mold having a mold cavity and molded into the mold cavity, thereby forming a receiving chamber. The receiving chamber was filled with the gel phases that were flowable by heating, whereby an at least partially filled receiving chamber was obtained. On cooling to room temperature, this solidified. Subsequently, the further gel phases were introduced in the same way. The solidified phases were completely covered with the powder phase. Subsequently, the partially filled receiving chamber was sealed by placing a second PVOH-containing film thereon and sealing by heat sealing, whereby a portion unit in a water-soluble casing was obtained. Subsequently, the portion unit was treated repeatedly with hot air: i) in a first shrink tunnel for a period of 6 seconds with hot air having a temperature of 210° C.; ii) after passing through a cooling section outside the first shrink tunnel, the pre-shrunk disposable doses were treated again in a second shrink tunnel for a period of 6 seconds with hot air having a temperature of 170° C.The portion units were oriented upward in the first shrink tunnel with the consolidated gel-like composition and downward in the second shrink tunnel with the consolidated gel-like composition.Alternatively, some products were not treated in a shrink tunnel, but were treated manually from all sides with hot air (170° C.) for about 7 seconds.Force-Travel Measurements:The strength of a care composition (E1) according to the invention and a conventional dishwashing product (V1) was compared. For this purpose, force-displacement measurements were carried out in a Texture Analyzer TA.XT plus (Stable Micro Systems). The test product was placed with a sealed seam at the top on a holder and pressurized from the top by means of a ball body (diameter d=19 mm). The penetration depth was 8 mm. The measurement was started only when the pouch surface was reached, i.e. the upwardly protruding sealing seam was not part of the measurement (for the example mentioned here, this corresponds to the following triggering force which had to be exceeded at the beginning of the measurement: 10 g). The test speed was 25 mm / sec. 10 repeat measurements were carried out per product type. Table 3: Table 3: Table 3: Table 3:E1V1Weight force applied in grams (g) (mean (n=1))1610402It became clear that a higher pressure was necessary in the product according to the invention in order to achieve this penetration depth than in the commercially available dishwashing product. The weight to be applied for the penetration depth carried out can be described with the parameter PF for pouch resistance (PF=weight to be applied for penetration depth). For example E1, it is 1610 g for 8 mm, for comparative example V1 only 402 g for 8 mm. Accordingly, the strength of the product according to the invention is higher, and therefore the haptic impression is higher.Solubility:The solubility of the care composition (E1) according to the invention in cold water was checked. In a BEKO type b300 dishwasher, program: ECO 50°C, it was checked whether residues of the powdered and / or the gel phase were present in the machine directly after the end of the prewash cycle, when the care agent according to the invention was placed on the bottom of the machine before the start of the wash cycle. After the end of the prewash cycle, no residues of the care composition according to the invention were found.References included in the specificationThis list of documents cited by the applicant has been produced in an automated manner and is only included for the better information of the reader. The list is not part of the German patent application or utility model application. The DPMA does not take any adhesion for any faults or omissions.Cited Non-Patent LiteratureDIN 55672-1:2007-08

[0035]

Claims

Phosphate-free care composition for an automatic dishwasher in a water-soluble casing in the form of a pre-portioned single dose comprising at least one pulverulent 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) is 10 to 20% by weight, preferably 12 to 18% by weight, in particular 12.7 to 15.5% by weight, of polyvinyl alcohol and / or derivatives thereof, b) is 27 to 35% by weight, preferably 30.5 to 33% by weight, in particular 31 to 32% by weight, of 1,3 propanediol, c) is 23 to 29.5% by weight, preferably 25 to 28% by weight, of glycerol, d) is 12 to 18.5% by weight of polyalkylene glycol, in particular 13.5 to 16.5 wt % polyalkylene glycol, and e) <5 wt %, preferably <1 wt % water, and wherein the pulverulent phase comprises at least one organic acid in an amount of 20 to 90 wt %, preferably of 50 to 80 wt %, particularly preferably of 60 to 75 wt %, based on the total weight of the pulverulent phase, and the pulverulent 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 pulverulent phase.Care composition 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, saccharic acids, aminocarboxylic acids, nitrilotriacetic acid or mixtures thereof.Care composition according to any of the preceding claims, wherein the pre-portioned single dose has a pouch resistance 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.Care composition according to any of the preceding claims, wherein the pulverulent phase comprises the corresponding base of the organic acid, preferably in an amount of from 1 to 30% by weight, particularly preferably from 10 to 25% by weight, based on the total weight of the pulverulent phase.Care composition according to any of the preceding claims, wherein the weight ratio of the entirety of the at least one pulverulent phase to the entirety 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.The care composition according to any one of the preceding claims, wherein the care composition has a pH of 1 to 5 (1% at 20°C).Care composition according to any of the preceding claims, wherein the pulverulent solid phase and / or the gel-like phase comprises less than 1.0% by weight of nonionic surfactant and / or wherein the at least one pulverulent solid phase comprises from 1.0 to 10% by weight of nonionic surfactant and / or wherein the at least one gel-like phase comprises from 1.0 to 10% by weight of nonionic surfactant, based on the total weight of the respective phase.A method for producing a care product according to any one of claims 1 to 7 comprising a) providing a mould having at least one mould cavity; optionally containing a web for dividing the bottom of the mould cavity; b) supplying a water-soluble film onto the mould cavity; c) forming an open chamber in the mould cavity by shaping 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 powder-like phase; h) providing a second water-soluble film as a lid; i) placing the open chamber and the lid one above the 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 envelope.Method according to claim 8, comprising the further steps: k) transporting the pre-portioned single dose comprising a water-soluble wrapping by means of a transport device through a shrink tunnel and shrinking the water-soluble wrapping 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) 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 shrunk single dose.Method for cleaning and / or caring for an automatic dishwasher, wherein in a normal cleaning cycle for cleaning washware, in particular dirty dishes, with an automatic dishwasher detergent, a caring agent formulated separately from the dishwasher detergent is metered in according to one of Claims 1 to 7.