MULTI-PHASE CLEANING POUCH

Description

[0001] The invention relates to a washing and / or cleaning agent portion which comprises at least one chamber and a water-soluble coating, characterized in that it comprises at least one particulate phase, wherein the at least one particulate phase is brought into direct contact with at least one liquid composition, as well as corresponding production methods.

[0002] Detergents and cleaning agents are typically available in solid form (e.g., tablets) or liquid form (or even as a flowing gel). Liquid detergents and cleaning agents, in particular, are enjoying increasing popularity among consumers.

[0003] Solid detergents and cleaning agents have the advantage that, unlike liquid detergents and cleaning agents, they do not require preservatives. Liquid detergents are becoming increasingly popular on the market, particularly due to their rapid solubility and the associated rapid availability of the active ingredients they contain. This offers consumers the opportunity to use shorter dishwashing cycles while still achieving good cleaning performance.

[0004] Furthermore, consumers have become accustomed to convenient dosing of pre-portioned washing or cleaning agents, such as dishwashing detergents, and use these products in tablet form (solid washing or cleaning agents) or in sachets, usually filled with a liquid washing or cleaning agent. Single-dose sachets in water-soluble sachets are enjoying increasing popularity among consumers not only because they no longer come into contact with the chemical composition, but also because of the attractive appearance of the sachets. The appearance of the dosage form is becoming increasingly important. In addition to good cleaning performance and sufficient storage stability, good appearance is one of the deciding factors for choosing a product.

[0005] Solid detergent formulations with a high surfactant content generally exhibit high stickiness and poor pouring and flow properties. This leads to poor dispensing during production. In particular, lower bulk densities are achieved, meaning that larger volumes must be used to achieve the same cleaning agent performance. Larger cavities, especially in pre-proportioned detergent portions, are then required, which is usually limited by the size of the dispensing chamber.

[0006] JP H05 214398 A discloses a cleaning agent consisting of compositions packaged with a water-soluble film. The composition comprises 5-80 wt% nonionic surfactant(s), 5-60 wt% porous oil-absorbing carrier material(s), and 10-60 wt% crystalline aluminosilicate. EP 1 517 983 A1 discloses a method for depositing fragrance onto a surface, comprising bringing a bag containing fragrance particles into contact with an aqueous solution, whereby the fragrance particles are released into the solution and thereby form a wash liquor, and bringing the surface into contact with the wash liquor thus formed, comprising at least about 0.1 ppm of the fragrance particle, wherein the bag is made of a water-reactive material and contains solids, characterized in that more than 25% by weight of the total amount of the solids are fragrance particles.

[0007] The object of the present invention is therefore to provide washing or cleaning agent portions which are compact and at the same time have good, in particular even improved, washing or cleaning performance.

[0008] A first subject matter of the present invention relates to a washing and / or cleaning agent portion according to claim 1, which comprises at least one chamber and a water-soluble coating, characterized in that it comprises at least one particulate phase, wherein the at least one particulate phase is brought into direct contact with at least one liquid composition.

[0009] The detergent or cleaning agent portions according to the invention are more compact due to the direct contact of the particulate phase with a liquid composition. The particulate phase is, so to speak, impregnated with the liquid phase. The liquid phase is preferentially absorbed into the particulate phase or is otherwise absorbed by it, e.g., by the liquid composition diffusing into the pores of the particulate phase.

[0010] A second aspect of the present invention relates to a production process for detergent or cleaning agent portions, which results in more compact detergent and / or cleaning agent portions with good or even improved cleaning performance. This production process is explained in more detail below.

[0011] The manufacturing process according to the invention also leads to a higher compactness of the cleaning agent in the pouches which are filled with free-flowing formulations by bringing into contact with compositions which would otherwise negatively influence the flowability.

[0012] Advantageously, product changes in production, e.g. to other surfactants or surfactant quantities or perfumes, can also be carried out more easily.

[0013] In particular, with surfactants, a higher surfactant content can be achieved, especially with liquid surfactants, than is possible with normal, particulate formulations, since these should be as free-flowing as possible for better processability.

[0014] A further advantage of the separate dosing of perfume oils is that, in addition to better processability and higher product density, no intensive cleaning of the system is necessary if a change to a new fragrance or perfume is required.

[0015] The detergent and / or cleaning agent portion may have one or more chambers. In at least one chamber, at least one particulate phase is brought into direct contact with at least one liquid phase.

[0016] 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 or spatial separation or arrangement, etc. Different phases can preferably be visually distinguished. In this way, the consumer can clearly distinguish the at least one particulate phase from other phases. If the washing or cleaning agent according to the invention has more than one particulate phase, these can also be distinguished from one another with the naked eye because they differ from one another, for example in their color. The same applies if two or more phases are present. In this case, too, a visual differentiation of the phases is possible, for example due to a difference in color or transparency.Phases within the meaning of the present invention are thus self-contained areas that can be visually distinguished from one another by the consumer with the naked eye. The individual phases can exhibit different properties during use, such as the rate at which the phase dissolves in water and thus the rate and order of release of the ingredients contained in the respective phase.

[0017] For the purposes of the present invention, a particulate phase is understood to be a granular mixture of a solid composition. The particulate phase is formed from a multitude of loose, solid particles, which in turn comprise so-called grains. According to the invention, the term particulate phase encompasses particles, grains, powders, and / or granules.

[0018] A grain is a term for the particulate components of powders (grains are the loose, solid particles), dusts (grains are the loose, solid particles), granules (loose, solid particles are agglomerates of several grains) and other granular mixtures.

[0019] A preferred embodiment of the granular mixture of the particulate phase composition is powder and / or granules. References to "powder" or "granules" here also encompass mixtures of different powders or different granules. Accordingly, powder and granules refer to mixtures of different powders with different granules. The solid particles of the granular mixture preferably have a particle diameter X 50.3 (volume average) of 10 to 1500 µm, more preferably of 200 µm to 1200 µm, and particularly preferably of 600 µm to 1100 µm. These particle sizes can be determined by sieving or using a Camsizer particle size analyzer from Retsch.

[0020] Another advantage is that particulate phases can be more easily modified in their appearance or composition compared to a compressed tablet. In particular, texture differences, such as coarse and fine particles, as well as particles or areas with different colors, either in their entirety or as colored speckles, can be used to enhance a visually appealing appearance. This also offers improved solubility compared to compressed tablets, even without the addition of disintegrants.

[0021] 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. Furthermore, it is 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 indicated. 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 understood that all ranges resulting from the combination of the various endpoints are also encompassed.

[0022] "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 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 may be meant. Together with weight specifications, the statement refers to all compounds of the specified type present in the composition / mixture, i.e., the composition contains no further compounds of this type beyond the specified amount of the corresponding compounds.

[0023] Whenever reference is made to molar masses herein, these figures always refer to the number-average molar mass M n , 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 M w can also be determined by GPC, as described for M n .

[0024] 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.

[0025] According to a preferred embodiment, the detergent and / or cleaning agent portion is characterized in that the at least one particulate phase is free-flowing, preferably at the time of addition. This is important for the production of the detergent or cleaning agent portions, so that such portion packages can be filled evenly with both the same amount and the same composition.

[0026] The granular mixture of the solid composition of the present invention serving as the particulate phase is preferably in free-flowing form (particularly preferably as a free-flowing powder and / or free-flowing granules). The agent of the portion according to the invention thus comprises at least one particulate phase (a phase of a free-flowing, granular mixture of a solid composition).

[0027] The flowability of a granular mixture, particularly the particulate phase, refers to its ability to flow freely under its own weight. Flowability is determined by measuring the flow time of 1000 ml of detergent or cleaning agent powder from a standardized, initially closed, flow test funnel with an outlet of 16.5 mm diameter. The flow time is measured after the outlet is opened, and the flow rate is compared with the flow rate (in seconds) of a standard test sand, whose flow rate is defined as 100%. The defined sand mixture for calibrating the flow apparatus is dry sea sand. Sea sand with a particle diameter of 0.4 to 0.8 mm is used. This sand is available, for example, from Carl Roth, Germany, CAS No. [14808-60-7].For drying, the sea sand is dried for 24 hours at 60 °C in a drying cabinet on a plate with a maximum layer height of 2 cm.

[0028] Preferred embodiments of the particulate phases according to the invention have an angle of repose / angle of repose of 26 to 35, of 27 to 34, of 28 to 33, wherein the angle of repose is determined according to the method mentioned below 24 hours after the preparation of the granular mixture of the solid composition / the particulate phase and storage at 20°C. Such angles of repose have the advantage that the filling of the cavities with the at least one particulate phase can be carried out comparatively quickly and precisely.

[0029] To determine the angle of repose (also called the angle of repose) of at least one particulate phase, a powder funnel with a 400 ml capacity and a 25 mm diameter outlet is suspended vertically on a stand. The funnel is moved upwards using a manually operated knurled wheel at a speed of 80 mm / min, so that the granular mixture, in particular the particulate phase, preferably the powder and / or granules, e.g., the powder, trickles out. This forms a so-called repose cone. The repose cone height and repose cone diameter are determined for the individual particulate phases. The repose angle is calculated from the quotient of the repose cone height and the repose cone diameter * 100.

[0030] Particularly suitable are such granular mixtures of a solid composition, in particular such particulate phases, preferably the powders and / or granules, e.g. the powders which have a flowability in % relative to the above-specified standard test substance of greater than 40%, preferably greater than 50, in particular greater than 55%, particularly preferably greater than 60%, particularly preferably between 63% and 80%, for example between 65% and 75%. Particularly suitable are such granular mixtures of a solid composition, in particular such powders and / or granules which have a flowability in % relative to the above-specified standard test substance of greater than 40%, preferably greater than 45%, in particular greater than 50%, particularly preferably greater than 55%, particularly preferably greater than 60%, wherein the measurement of the flowability is carried out 24 hours after the powder has been produced and stored at 20°C.

[0031] Lower values ​​for flowability are not suitable, since from a process engineering perspective, precise dosing of the granular mixture, in particular the particulate phase, preferably the powder and / or granules, e.g. the powder, is necessary. In particular, values ​​greater than 50%, in particular greater than 55%, preferably greater than 60% (whereby the flowability measurement is carried out 24 hours after the powder has been produced and stored at 20°C) have proven to be advantageous, since the good dosability of the granular mixtures, in particular the particulate phases, preferably the powder and / or granules, e.g. powder, results in only small fluctuations in the dosed amount or composition. The more precise dosing leads to consistent product performance, and economic losses due to overdosing are thus avoided. Furthermore, it is advantageous that the granular mixtures, in particular the particulate phase, preferably the powder and / or granules, e.g.If the powder is easy to dose, the dosing process is faster. Furthermore, such good flowability better prevents the granular mixture, especially the particulate phase, preferably the powder and / or granules, e.g., the powder, from getting onto the part of the water-soluble coating intended for the production of the sealed seam and therefore should remain as free of granules as possible, especially powder-free.

[0032] According to a preferred embodiment, the at least one liquid composition comprises perfume preparations and / or surfactants, preferably non-ionic surfactants.

[0033] The at least one liquid composition is preferably low in water, in particular essentially anhydrous. This has the advantage that the particulate phase, which generally contains washing or cleaning-active substances that can react with water and / or with each other in aqueous solutions, does not undergo these reactions during production and / or storage of the portion. This improves product production and storage stability, and thus generally improves product stability.

[0034] Surprisingly, it has been shown that particularly good storage stability is achieved when at least one liquid composition is low in water.

[0035] Low water content in the context of the present invention means that small amounts of water can be used to produce a phase or composition. The proportion of water in this phase or composition is in particular 20 wt.% or less, preferably 15 wt.% or less, especially 12 wt.% or less, in particular between 10 and 5 wt.%. The data in wt.% refer to the total weight of the respective phase or composition.

[0036] According to a further embodiment, the at least one liquid composition is essentially anhydrous. Anhydrous in the sense of the invention means that the respective phase or composition is preferably essentially free of water. "Essentially free" here means that small amounts of water may be present in the phase or composition. 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, small amounts, in particular no water, are used as a solvent to produce the corresponding phase or composition. The proportion of water in the phase or composition in this embodiment is 4.9 wt.% or less, 4 wt.% or less, preferably 2 wt.% or less, in particular 1 wt.% or less, especially 0.5 wt.% or less, in particular 0.1 wt.% or 0.05 wt.-% or less. The data in wt.% refers to the total weight of the respective phase or composition.

[0037] According to a preferred embodiment, the weight ratio of the total amount of the at least one liquid composition to the total amount of the at least one particulate phase is from 1:800 to 5:1, in particular from 1:600 ​​to 2:1, preferably from 1:500 to 2:1, for example from 1:450 to 1:1.

[0038] The weight proportion of the at least one liquid composition in the total weight of the composition formed from the at least one liquid composition and the at least one particulate composition is preferably 0.0001 to 25 wt.%, in particular 0.005 to 20 wt.%, preferably 0.1 to 18 wt.%, very particularly preferably 0.2 to 15 wt.%.

[0039] It is particularly preferred that, when the at least one liquid composition comprises at least one surfactant, preferably a non-ionic surfactant, the total amount of the at least one liquid composition to the total amount of the at least one particulate phase is from 1:200 to 5:1, in particular from 1:100 to 1:1, preferably from 1:50 to 1:2, for example from 1:20 to 1:5 and / or the weight fraction of the at least one liquid composition in the total weight of the composition formed from the at least one liquid composition and the at least one particulate composition is 0.01 to 25 wt.%, in particular 0.1 to 20 wt.%, preferably 1 to 18 wt.%, very particularly preferably 3 to 15 wt.%.

[0040] The washing or cleaning agent according to the invention comprises at least one surfactant. This surfactant is preferably selected from the group of anionic, nonionic, and cationic surfactants. The washing or cleaning agent according to the invention can also contain mixtures of several surfactants selected from the same group. According to the invention, both the at least one particulate phase and the at least one liquid composition comprise at least one surfactant. However, it is also possible for only the at least one liquid composition to comprise at least one surfactant. However, it is also possible for the phases or preparations to contain different or the same surfactant(s).

[0041] Particulate phases according to the invention and liquid compositions thus preferably comprise at least one surfactant, preferably at least one nonionic surfactant. All nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants. Low-foaming nonionic surfactants are preferred, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. These are specified in more detail below.

[0042] Suitable nonionic surfactants include, for example, alkyl glycosides of the general formula RO(G) x , in which R corresponds to a primary straight-chain or methyl-branched, in particular 2-methyl-branched, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G is the symbol representing a glycose unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably, x is between 1.2 and 1.4.

[0043] Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

[0044] Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably no more than that of the ethoxylated fatty alcohols, in particular no more than half that amount.

[0045] Other suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.

[0046] The washing or cleaning agents according to the invention, in particular cleaning agents for automatic dishwashing, particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, especially primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or, preferably, methyl-branched in the 2-position, or can contain linear and methyl-branched radicals in a mixture, as are usually found in oxo alcohol radicals. However, alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow, or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are particularly preferred.Preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 8-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.

[0047] Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO, or 40 EO.

[0048] Particular preference is given to using ethoxylated nonionic surfactants obtained from C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol, and especially more than 20 mol of ethylene oxide per mol of alcohol. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol, and at least 12 mol, preferably at least 15 mol, and especially at least 20 mol of ethylene oxide. Among these, the so-called "narrow-range ethoxylates" are particularly preferred.

[0049] Preferred surfactants come from the group of alkoxylated nonionic surfactants, especially ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

[0050] Particularly preferred nonionic surfactants for the low-foaming nonionic surfactants in the context of the present invention are those containing alternating ethylene oxide and alkylene oxide units. Among these, surfactants with EO-AO-EO-AO blocks are preferred, with one to ten EO or AO groups bonded to one another before a block of the other groups follows. Here, nonionic surfactants of the general formula preferred, in which R 1< represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2< or R 3< is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH(CH 3 ) 2 and the indices w, x, y, z independently represent integers from 1 to 6.

[0051] Preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1< -OH and ethylene or alkylene oxide. The radical R 1< in the above formula can vary depending on the origin of the alcohol. If native sources are used, the radical R 1< has an even number of carbon atoms and is generally unbranched, with linear radicals from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow, or oleyl alcohol, being preferred. Alcohols accessible from synthetic sources include, for example, Guerbet alcohols or radicals methyl-branched in the 2-position or linear and methyl-branched in a mixture, as are typically found in oxo alcohol radicals.Regardless of the type of alcohol used to produce the nonionic surfactants contained in the compositions, nonionic surfactants are preferred in which R 1< in the above formula represents an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

[0052] In addition to propylene oxide, butylene oxide is particularly suitable as an alkylene oxide unit present alternately with the ethylene oxide unit in the preferred nonionic surfactants. However, other alkylene oxides in which R 2< and R 3< are independently selected from -CH 2 CH 2 -CH 3 or -CH(CH 3 ) 2 are also suitable. Nonionic surfactants of the above formula are preferably used in which R 2< and R 3< are a -CH 3 radical, w and x are independently 3 or 4, and y and z are independently 1 or 2.

[0053] Further preferably used nonionic surfactants are nonionic surfactants of the general formula R 1< O(AlkO) x M(OAlk) y OR 2< , where R 1< and R 2< independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms; Alk stands for a branched or unbranched alkyl radical having 2 to 4 carbon atoms; x and y independently of one another represent values ​​between 1 and 70; and M stands for an alkyl radical from the group CH 2 , CHR 3< , CR 3< R 4< , CH 2 CHR 3< and CHR 3< CHR 4<, where R 3< and R 4< independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms.

[0054] Preferred nonionic surfactants are those of the general formula R 1< -CH(OH)CH 2 -O(CH 2 CH 2 O) x CH 2 CHR(OCH 2 CH 2 ) y -CH 2 CH(OH)-R 2< , where R, R 1< and R 2< independently of one another represent an alkyl radical or alkenyl radical having 6 to 22 carbon atoms; x and y independently of one another represent values ​​between 1 and 40.

[0055] Particularly preferred compounds are those of the general formula R 1< -CH(OH)CH 2 -O(CH 2 CH 2 O) x CH 2 CH R (OCH 2CH 2 ) y O-CH 2 CH(OH)-R 2< , in which R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m, independently of one another, have values ​​from 20 to 30. Corresponding compounds can be obtained, for example, by reacting alkyldiols HO-CHR-CH 2 -OH with ethylene oxide, followed by a reaction with an alkyl epoxide to close the free OH functions to form a dihydroxy ether.

[0056] Preferred nonionic surfactants are those of the general formula R 1< -CH(OH)CH 2 O-(AO) w -(AO) x -(A"O) y -(A"'O) z -R 2< , in which R 1< represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; R 2< represents hydrogen or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A', A" and A‴ independently of one another represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH(CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH(CH 3 )-CH 2 -, -CH 2 -CH(CH 2 -CH 3 ), w, x, y and z represent values ​​between 0.5 and 120, where x, y and / or z can also be 0.

[0057] By adding the above-mentioned non-ionic surfactants of the general formula R 1< -CH(OH)CH 2 O(AO) w -(A'O) x -(A"O y -(A‴) z -R 2< , hereinafter also referred to as "hydroxy mixed ethers", the cleaning performance of preparations according to the invention can surprisingly be significantly improved, both in comparison to surfactant-free systems and in comparison to systems which contain alternative non-ionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

[0058] By using these non-ionic surfactants with one or more free hydroxyl groups on one or both terminal alkyl radicals, the stability of the enzymes contained in the cleaning agent preparations according to the invention can be significantly improved.

[0059] Particularly preferred are those end-capped poly(oxyalkylated) nonionic surfactants which, according to the following formula in addition to a radical R 1< which stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore have a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2< having 1 to 30 carbon atoms, where n stands for values ​​between 1 and 90, preferably for values ​​between 10 and 80 and in particular for values ​​between 20 and 60. Particular preference is given to surfactants of the above formula in which R 1< stands for C 7 to C 13 , n stands for an integer from 16 to 28 and R 2< stands for C 8 to C 12.

[0060] Particularly preferred surfactants are those of the formula R 1< O[CH 2 CH(CH 3 )O] x [CH 2 CH 2 O] y CH 2 CH(OH)R 2< , in which R 1< is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2< is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 1.5 and y is at least 15. The group of these non-ionic surfactants includes, for example, the C 2-26 fatty alcohol (PO) 1 -(EO) 15-40 -2-hydroxyalkyl ethers, in particular also the C 8-10 fatty alcohol (PO) 1 -(EO) 22 -2-hydroxydecyl ethers.

[0061] Particularly preferred are also those end-capped poly(oxyalkylated) nonionic surfactants of the formula R 1< O[CH 2 CH 2 O] x [CH 2 CH(R 3< )O] y CH 2 CH(OH)R 2< , in which R 1< and R 2< independently of one another represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R 3< independently of one another is selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3, -CH(CH 3 ) 2 , but preferably represents -CH 3 , and x and y independently of one another represent values ​​between 1 and 32, with nonionic surfactants with R 3< = -CH 3 and values ​​for x from 15 to 32 and y from 0.5 to 1.5 being very particularly preferred.

[0062] Further nonionic surfactants which can preferably be used are the end-group-capped poly(oxyalkylated) nonionic surfactants of the formula R 1< O[CH 2 CH(R 3< )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2< , in which R 1< and R 2< are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3< is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is between 1 and 30, k and j are between 1 and 12, preferably between 1 and 5. If the value x > 2, each R 3< in the above formula R 1< O[CH 2 CH(R 3< )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2< can be different. R 1< and R 2< are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.For the radical R 3<, H, -CH 3 or -CH 2 CH 3 are particularly preferred. Particularly preferred values ​​for x are in the range from 1 to 20, in particular from 6 to 15.

[0063] As described above, each R 3< in the above formula can be different if x > 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if x is 3, the radical R 3< can be selected to form ethylene oxide (R 3< = H) or propylene oxide (R 3< = CH 3 ) units, which can be joined together in any order, for example (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO). The value 3 for x has been chosen here as an example and can certainly be larger, whereby the range of variation increases with increasing values ​​of x and includes, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa.

[0064] Particularly preferred end-capped poly(oxyalkylated) alcohols of the above formula have values ​​of k = 1 and j = 1, so that the above formula simplifies to R 1< O[CH 2 CH(R 3< )O] x CH 2 CH(OH)CH 2 OR 2<. In the latter formula, R 1< , R 2< and R 3< are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particular preference is given to surfactants in which the radicals R 1< and R 2< have 9 to 14 C atoms, R 3< stands for H and x assumes values ​​from 6 to 15. Finally, the nonionic surfactants of the general formula R 1< -CH(OH)CH 2 O-(AO) w -R 2< have proven to be particularly effective, in which R 1< represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; R 2< represents a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A represents a radical from the group CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH(CH 3 ), preferably CH 2 CH 2 , and w represents values ​​between 1 and 120, preferably 10 to 80, in particular 20 to 40.

[0065] The group of these non-ionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.

[0066] Preferably, the at least one particulate and / or the at least one gel-like phase contains at least one non-ionic surfactant, preferably a non-ionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the non-ionic surfactant in the total weight of the gel-like phase is preferably 0.5 wt.% to 30 wt.%, preferably 5 wt.% to 25 wt.% and in particular 10 wt.% to 20 wt.%.

[0067] In a further preferred embodiment, the non-ionic surfactant of the particulate and / or gel-like phase and / or liquid preparation is selected from non-ionic surfactants of the general formula R 1< -O(CH 2 CH 2 O) x CR 3< R 4< (OCH 2 CH 2 ) y OR 2< , in which R 1< and R 2< independently of one another represent an alkyl radical or alkenyl radical having 4 to 22 carbon atoms; R 3< and R 4< independently of one another represent H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and x and y independently of one another represent values ​​between 1 and 40.

[0068] Particular preference is given to compounds of the general formula R 1< -O(CH 2 CH 2 O) x CR 3< R 4< (OCH 2 CH 2 ) y OR 2< , in which R 3< and R 4< are H and the indices x and y independently of one another assume values ​​from 1 to 40, preferably from 1 to 15. Particular preference is given to compounds of the general formula R 1< -O(CH 2 CH 2 O) x CR 3< R 4< (OCH 2 CH 2 ) y OR 2< , in which the radicals R 1< and R 2< independently of one another represent saturated alkyl radicals having 4 to 14 carbon atoms and the indices x and y independently of one another assume values ​​from 1 to 15 and in particular from 1 to 12. Also preferred are those compounds of the general formula R 1< -O(CH 2 CH 2 O) x CR 3< R 4< (OCH 2 CH 2 ) y OR 2< , in which one of the radicals R 1< and R 2< is branched.Very particular preference is given to compounds of the general formula R 1< -O(CH 2 CH 2 O) x CR 3< R 4< (OCH 2 CH 2 ) y OR 2< , in which the indices x and y independently assume values ​​from 8 to 12.

[0069] The stated carbon chain lengths and degrees of ethoxylation or alkoxylation of the nonionic surfactants represent statistical averages, which can be whole or fractional numbers for a specific product. Due to the manufacturing processes, commercial products of the formulas mentioned usually do not consist of a single representative, but of mixtures, which can result in averages and, consequently, fractional numbers for both the carbon chain lengths and the degrees of ethoxylation or alkoxylation.

[0070] Of course, the aforementioned non-ionic surfactants (niosurfactants) can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.

[0071] Particularly preferred in the at least one particulate phase or liquid composition are nonionic surfactants that have a melting point above room temperature. Nonionic surfactant(s) with a melting point above 20°C, preferably above 25°C, particularly preferably between 25 and 60°C, and especially between 26.6 and 43.3°C, are particularly preferred.

[0072] Suitable nonionic surfactants that have melting or softening points within the specified temperature range include, for example, low-foaming nonionic surfactants that can be solid or highly viscous at room temperature. If nonionic surfactants that are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pa s, preferably above 35 Pa s, and especially above 40 Pa s. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.

[0073] The nonionic surfactant, which is solid at room temperature, preferably contains propylene oxide units (PO) in the molecule. Such PO units preferably make up to 25% by weight, more preferably up to 20% by weight, and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally contain polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol moiety of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight, and in particular more than 70% by weight of the total molar mass of such nonionic surfactants. Preferred agents are characterized by containing ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule make up to 25% by weight, preferably up to 20% by weight, and in particular up to 15% by weight of the total molar mass of the nonionic surfactant.

[0074] Further nonionic surfactants with melting points above room temperature which are particularly preferably used in the particulate phase or liquid composition contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which contains 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

[0075] In a preferred embodiment, the weight fraction of the nonionic surfactant in the total weight of the particulate phase is from 0.1 to 20 wt.%, particularly preferably from 0.5 to 15 wt.%, in particular from 2.5 to 10 wt.%.

[0076] All anionic surface-active substances are suitable as anionic surfactants in dishwashing detergents. These are characterized by a water-solubilizing anionic group, such as a carboxylate, sulfate, sulfonate, or phosphate group, and a lipophilic alkyl group with approximately 8 to 30 carbon atoms. The molecule may also contain glycol or polyglycol ether groups, ester, ether, and amide groups, as well as hydroxyl groups. Suitable anionic surfactants are preferably in the form of sodium, potassium, and ammonium salts, as well as mono-, di-, and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group. Zinc, manganese(II), magnesium, calcium, or mixtures thereof can also serve as counterions.

[0077] Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

[0078] Instead of the aforementioned surfactants or in combination with them, cationic and / or amphoteric surfactants, such as betaines or quaternary ammonium compounds, can also be used. However, it is preferable that cationic and / or amphoteric surfactants are not used.

[0079] It is particularly preferred if the total amount of the at least one liquid composition, comprising at least one non-ionic surfactant, to the total amount of the at least one particulate phase has a weight ratio of 1:200 to 5:1, in particular from 1:100 to 1:1, preferably from 1:50 to 1:2, for example from 1:20 to 1:5 and / or the weight proportion of the at least one liquid composition in the total weight of the composition formed from the at least one liquid composition and the at least one particulate composition is 0.01 to 25 wt.%, in particular 0.1 to 20 wt.%, preferably 1 to 18 wt.%, very particularly preferably 3 to 15 wt.%.

[0080] According to a further preferred embodiment of the present invention, the surfactant content of the at least one liquid composition is at least 50 wt.%, in particular at least 70 wt.%, preferably at least 80 wt.%, particularly preferably at least 90 wt.%, based on the total weight of the liquid composition. These can be liquid surfactants themselves or mixtures of liquid and / or solid surfactants with solvents, preferably organic solvents, to improve the incorporation of the surfactants.

[0081] The washing or cleaning agent according to the invention comprises, in addition to the at least one particulate phase and the at least one liquid composition, at least one further gel-like phase.

[0082] A gel phase, also referred to below as a gel phase, is understood according to the invention to be a composition / 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 in at least one liquid (the at least one liquid is liquid at 20°C). Such gel phases behave thermoreversibly.

[0083] This gel phase can, for example, be flowable or dimensionally stable. According to the invention, however, the gel-like phase is preferably dimensionally stable at room temperature. During production, the gelling agent, preferably xanthan gum, gelatin or polyvinyl alcohol and / or derivatives thereof, is brought into contact with a solvent, preferably an organic solvent, preferably one or more polyhydric alcohols. This gives rise to a flowable mixture which can be formed into a desired shape. After a certain period of time, a gel phase is obtained which remains in the predetermined shape, i.e. is dimensionally stable. This period of time, the setting time, is preferably 15 minutes or less, preferably 10 minutes or less, particularly preferably 5 minutes or less. The at least one gel phase gives way to pressure but does not deform as a result, but returns to its original state once the pressure is removed.The at least one gel phase is preferably elastic, in particular linear-elastic.

[0084] The at least one gel phase is preferably a shaped body. A shaped 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 molding 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.

[0085] Formulations containing at least one gel phase must meet certain minimum requirements. As already explained, the gel phase must solidify within the shortest possible time. Long solidification times would result in a long production time and thus high costs. According to the invention, solidification time is the period of time during production during which the at least one gel phase 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.

[0086] The at least one gel phase is preferably a solid gel phase. It is cut-resistant. For example, it can be cut with a knife after solidification without further damage other than the cut itself.

[0087] Furthermore, the gel phase must be stable under normal storage conditions. The gel phase according to the invention is a component of a cleaning agent. Cleaning agents are usually stored in a household for a certain period of time. Storage usually takes place near the washing machine or dishwasher. For such storage, the gel phase should be stable. Thus, the gel phase should be stable, in particular 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.

[0088] If the gel phase and a solid, especially a powder phase are in direct contact with each other, the gel phase preferably penetrates a maximum of 1 mm into the spaces of the immediately underlying powder phase during the storage period of 4 weeks at 25 °C.

[0089] 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, which can also impair the washing or cleaning effect.

[0090] The at least one gel-like phase is preferably low in water. This has the advantage that the small amounts of water, in combination with PVOH, can have a structure-forming or gel-forming effect. According to a preferred embodiment, the at least one gel phase is essentially anhydrous.

[0091] Cleaning agents, preferably dishwashing detergents, in particular automatic dishwashing detergents, particularly preferably contain at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate, in an amount of 0.05 to 3 wt.%, in particular 0.1 to 2.4 wt.%, very particularly preferably 0.2 to 1.0 wt.%, based on the total weight of the gel-like phase.

[0092] According to a preferred embodiment, the cleaning agents according to the invention, preferably dishwashing agents, in particular automatic dishwashing agents, contain in the gel phase (gel phase) a gelling agent, preferably selected from gelatin, xanthan and / or polyvinyl alcohol, in particular gelatin or polyvinyl alcohol, particularly preferably polyvinyl alcohol, in an amount of 4 to 40, in particular 6 to 30 wt.%, particularly preferably in an amount of 7 to 24 wt.%, very particularly preferably 8 to 22 wt.%, in particular for example 14 to 20 wt.%, in each case based on the total weight of the gel phase.

[0093] According to the invention, the at least one gel phase particularly preferably comprises PVOH (polyvinyl alcohol) and / or derivatives thereof. Polyvinyl alcohols are thermoplastics which are usually produced as a white to yellowish powder by hydrolysis of polyvinyl acetate. 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. Copolymers of polyvinyl alcohol with other monomers, in particular copolymers with anionic monomers, are preferred as PVOH derivatives within the meaning 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 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 and the alkali metal salts or esters of the above-mentioned monomers.

[0094] 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 molar masses. Within the scope of the present invention, it is preferred that the at least one gel phase 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%.

[0095] 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.

[0096] PVOH powders with the above-mentioned properties, which are suitable for use in at least one gel phase, are marketed, for example, under the name Mowiol® or Poval® by Kuraray. Also suitable is Exceval® AQ4104 from Kuraray. Particularly suitable are Mowiol C30 and 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.

[0097] The water solubility of polyvinyl alcohol can be modified by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols that are acetalized or ketalized with the aldehyde or 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 allowing the desired values ​​to be precisely adjusted.

[0098] Surprisingly, it has been shown that PVOH is particularly suitable for producing gel phases that meet the requirements outlined above. Therefore, at least one gel phase is particularly preferred, which, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate, comprises PVOH and at least one polyhydric alcohol. Particularly preferably, the at least one gel phase comprises PVOH and at least one polyhydric alcohol.

[0099] According to the invention, the at least one gel phase comprises at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate, PVOH and / or its derivatives in a proportion of approximately 4 wt.% to 40 wt.%, in particular from 6 wt.% to 30 wt.%, preferably from 7 to 24 wt.%, particularly preferably between 8 wt.% and 22 wt.%. Significantly lower proportions of PVOH do not lead to the formation of a stable gel phase. The values ​​are based on the total weight of the gel phase.

[0100] According to a particularly preferred embodiment, the at least one gel phase comprises PVOH (polyvinyl alcohol). The 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 the granular mixture, in particular the powder phase. PVOH can also easily produce low-water or anhydrous gel phases. When PVOH is used as the polymer for the at least one gel phase, low-viscosity melts are obtained at 110-120°C, which 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 the 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 cleaning agent. In addition, gel phases with such short solidification times are advantageous because the at least one solid phase dosed onto them, comprising granular mixtures, in particular powder, does not sink into the gel that is not yet fully solidified or is too soft. This leads to visually unappealing cleaning agent portions.

[0101] Particularly in the case of the multi-phase single-dose products according to the invention with at least one solid phase, it is important that the at least one gel phase is dimensionally stable, so that interactions between the solid and gel phases are minimized. If the at least one gel phase also comprises gelatin in addition to PVOH, the viscosity of the gel phase is increased during production.

[0102] A further preferred subject matter of the present invention are cleaning agents, preferably dishwashing agents, in particular automatic dishwashing agents, which contain in the gel phase at least one organic solvent, in particular selected from 1,2-propanediol, 1,3-propanediol, glycerol, 1,1,1-trimethylolpropane, triethylene glycol, dipropylene glycol, polyethylene glycols and / or mixtures thereof.

[0103] The at least one gel phase preferably comprises at least one polyhydric alcohol. In addition to the production of flowable gel phases, the at least one polyhydric alcohol also enables the production of a dimensionally stable, non-flowable gel phase within a short solidification time, which can be within 15 minutes or less, in particular 10 minutes or less. Polyhydric alcohols within the meaning of the present invention are hydrocarbons in which two, three, or more hydrogen atoms are replaced by OH groups. The OH groups are bonded to different carbon atoms. A carbon atom does not have two OH groups. This is in contrast to (simple) alcohols, in which only one hydrogen atom is replaced by an OH group in hydrocarbons. Polyhydric alcohols with two OH groups are called alkanediols, and polyhydric alcohols with three OH groups are called alkanetriols.A polyhydric alcohol therefore corresponds to the general formula [KW](OH) x , where KW stands for a hydrocarbon that is linear or branched, saturated or unsaturated, substituted or unsubstituted. Substitution can occur, for example, with -SH or -NH- groups. KW is preferably a linear or branched, saturated or unsaturated, unsubstituted hydrocarbon. KW comprises at least two carbon atoms. The polyhydric alcohol comprises 2, 3 or more OH groups (x = 2, 3, 4 ...), with only one OH group bonded to each C atom of the KW. KW particularly preferably comprises 2 to 10, i.e. 2, 3, 4, 5, 6, 7, 8, 9, or 10, carbon atoms. In particular, polyhydric alcohols with x = 2, 3 or 4 (for example, pentaerythritol with x = 4) can be used. Preferably x=2 (alkanediol) and / or x=3 (alkanetriol).

[0104] Particularly preferably, the at least one gel phase comprises at least one alkanetriol and / or at least one alkanediol, in particular at least one C 3 to C 10 alkanetriol and / or at least one C 3 to C 10 alkanediol, preferably at least one C 3 to C 8 alkanetriol and / or at least one C 3 to C 8 alkanediol, in particular at least one C 3 to C 6 alkanetriol and / or at least one C 3 to C 5 alkanediol as polyhydric alcohol. It preferably comprises an alkanetriol and an alkanediol as at least one polyhydric alcohol. In a preferred embodiment, the at least one gel phase therefore comprises at least one polymer, in particular PVOH or PVOH with gelatin, and at least one alkanediol and at least one alkanetriol, in particular an alkanetriol and an alkanediol. Also preferred is a gel phase comprising at least one polymer, PVOH or PVOH with gelatin, as well as a C 3 - to C 8 -alkanediol and a C 3 - to C 8 -alkanetriol.Further preferred is a gel phase comprising at least one polymer, in particular PVOH or PVOH with gelatin, as well as a C 3 - to C 5 -alkanediol and a C 3 - to C 6 -alkanetriol. According to the invention, the polyhydric alcohols do not include derivatives thereof, such as ethers, esters, etc.

[0105] Surprisingly, it has been shown that particularly short setting times can be achieved by combining a corresponding triol (alkanetriol) with a corresponding diol (alkanediol). The resulting gel phases are also transparent and have a glossy surface, which ensures an appealing visual appearance of the cleaning agent according to the invention. The terms diol and alkanediol are used synonymously herein. The same applies to triol and alkanetriol.

[0106] According to a particularly preferred embodiment, the cleaning agents according to the invention, preferably dishwashing agents, in particular automatic dishwashing agents, contain the at least one organic solvent in the gel phase in amounts of 30 to 90 wt.%, in particular 40 to 85 wt.%, particularly preferably 50 to 80 wt.%, based on the total weight of the gel phase.

[0107] The amount of polyhydric alcohol or polyhydric alcohols used in the gel phases according to the invention is preferably at least 45 wt.%, in particular 55 wt.% or more. Preferred ranges are from 45 wt.% to 85 wt.%, in particular from 50 wt.% to 80 wt.%, based on the total weight of the gel phase.

[0108] Preferably, the C 3 - to C 6 -alkanetriol is glycerol and / or 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (also called 1,1,1-trimethylolpropane) and / or 2-amino-2-(hydroxymethyl)-1,3-propanediol (TRIS, trishydroxymethylaminoethane) and / or 1,3,5-pentanetriol.

[0109] The C3- to C6-alkanetriol is particularly preferably glycerol and / or 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (also called 1,1,1-trimethylolpropane). The C3- to C5-alkanediol is, for example, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-butanediol, 1,3-propanediol and / or 1,2-propanediol, preferably 1,3-propanediol and / or 1,2-propanediol. Surprisingly, it has been shown that the chain length of the diol and, in particular, the position of the OH groups influence the transparency of the gel phase. Therefore, the OH groups of the diol are preferably not located on immediately adjacent C atoms. In particular, there are three or four carbon atoms, in particular 3 carbon atoms, between the two OH groups of the diol. The diol is particularly preferred to be 1,3-propanediol. Surprisingly, it has been shown that particularly good results are achieved with mixtures comprising glycerol and 1,3-propanediol and / or 1,2-propanediol.

[0110] 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 this case, polyethylene glycols with an average molecular weight 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. Detergent portions according to the invention are thus characterized by comprising polyethylene glycol(s) with an average molecular weight of 300 to 500 g / mol, particularly between 350 and 450 g / mol.

[0111] In particular, it is advantageous that the at least one gel phase or the gel phases, each comprising, based on the total weight of the gel-like phase, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4% by weight, particularly preferably 0.2 to 1.0% by weight), polyvinyl alcohol and at least one polyhydric alcohol, optionally additionally polyethylene glycols with an average molecular weight of about 200 to 600 g / mol in amounts of 5 to 30% by weight, preferably 8 to 26% by weight, in particular 10 to 22% by weight, based on the total weight of the at least one gel phase.

[0112] Surprisingly, it has been shown that the addition of polyethylene glycols, particularly those with average molecular weights of 200 to 600 g / mol, to the at least one gel phase, especially in the case of gel phases comprising polyvinyl alcohol, leads to an acceleration of the solidification time of the gel phases. Values ​​of a few minutes and even less than one minute can be achieved. This is particularly advantageous for production processes, since further processing of the gel phases in the solidified state can be carried out much more quickly and is therefore generally more cost-effective. Surprisingly, it has been found that the presence of polyethylene glycol(s) with an average molecular weight of 200 to 600 g / mol in combination with polyvinyl alcohol and / or its derivatives contributes significantly to reducing the solidification times.Without being bound by theory, it is assumed that such polyethylene glycols, especially those with a molecular weight of 350 to 450 g / mol, in particular by 400 g / mol, increase the sol-gel temperature.

[0113] In a particularly preferred embodiment, the amount of polyethylene glycol(s) having an average molecular weight of 350 to 450 g / mol, for example around 400 g / mol, is 10 to 22 wt.% based on the total weight of the gel phase.

[0114] A particularly preferred gel phase therefore comprises at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (e.g. zinc acetate anhydrate), PVOH, polyethylene glycol(s) with an average molecular weight of 200 to 600 g / mol and 1,3-propanediol and glycerol or 1,1,1-trimethylolpropane as polyhydric alcohols. Here, a dimensionally stable, non-flowable consistency at room temperature can be achieved within a setting time of 10 minutes or less, which remains dimensionally stable even after prolonged storage. In addition, a corresponding phase is transparent and has a glossy surface. A particularly preferred gel phase therefore comprises gelatin or PVOH as polymer and 1,3-propanediol and glycerol or 1,1,1-trimethylolpropane as polyhydric alcohols.

[0115] If the gel phase comprises, in each case based on the total weight of the gel-like phase, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4% by weight, particularly preferably 0.2 to 1.0% by weight), an alkanetriol, in particular glycerol or 1,1,1-trimethylolpropane, the proportion of alkanetriol, in particular glycerol or 1,1,1-trimethylolpropane, based on the total weight of the gel phase, is between 3 and 75% by weight, preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, particularly 20% by weight to 40% by weight.

[0116] If the gel phase optionally comprises several alkanetriol(s), the total proportion of alkanetriol(s), based on the total weight of the gel phase, is between 3 and 75 wt.%, preferably 5 wt.% to 70 wt.%, in particular 10 wt.% to 65 wt.%, especially 20 wt.% to 40 wt.%.

[0117] If glycerol is present as alkanetriol in the gel phase, the proportion of glycerol, based on the total weight of the gel phase, is preferably 5 wt.% to 70 wt.%, in particular 10 wt.% to 65 wt.%, especially 20 wt.% to 40 wt.%.

[0118] If 1,1,1-trimethylolpropane is present in the gel phase, the proportion of 1,1,1-trimethylolpropane, based on the total weight of the gel phase, is preferably 5 wt.% to 70 wt.%, in particular 10 wt.% to 65 wt.%, particularly preferably 18 to 45 wt.%, particularly preferably 20 wt.% to 40 wt.%.

[0119] If 2-amino-2-hydroxymethyl-1,3-propanediol is contained in the gel phase, the proportion of 2-amino-2-hydroxymethyl-1,3-propanediol, based on the total weight of the gel phase, is preferably 5 wt.% to 70 wt.%, in particular 10 wt.% to 65 wt.%, especially 20 wt.% to 40 wt.%.

[0120] If several alkanediols are present in the gel phase, the proportion of alkanediols, based on the total weight of the gel phase, is preferably 5 wt.% to 70 wt.%, in particular 7 wt.% to 65 wt.%, especially 10 wt.% to 40 wt.%.

[0121] If the gel phase comprises, in each case based on the total weight of the gel-like phase, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4 wt.%, particularly preferably 0.2 to 1.0 wt.%), at least one alkanediol, in particular 1,3-propanediol or 1,2-propanediol, the proportion of alkanediol, in particular 1,3-propanediol or 1,2-propanediol, based on the total weight of the gel phase, is preferably 5 wt.% to 70 wt.%, in particular 10 wt.% to 65 wt.%, particularly 20 wt.% to 45 wt.% If 1,3-propanediol is present in the gel phase, the proportion of 1,3-propanediol, based on the total weight of the gel phase, is in particular 10 wt.% to 65 wt.%, particularly 20 wt.% to 45 wt.%.

[0122] Preference is given to a gel phase which, based on the total weight of the gel phase, contains at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4 wt.%, particularly preferably 0.2 to 1.0 wt.%), 20 to 45 wt.% of 1,3-propanediol and / or 1,2-propanediol and 10 wt.% to 65 wt.% of 2-amino-2-hydroxymethyl-1,3-propanediol, in each case based on the total weight of the gel phase. Also preferred is a gel phase which contains 20 to 45 wt.% of 1,3-propanediol and / or 1,2-propanediol and 10 wt.% to 65 wt.% of 1,1,1-trimethylolpropane, in each case based on the total weight of the gel phase. Particularly preferred is a gel phase which contains 20 to 45 wt.% of 1,3-propanediol and / or 1,2-propanediol and 10 wt.% to 65 wt.% of glycerol, in each case based on the total weight of the gel phase.It has been shown that rapid solidification of a gel phase at 20 °C is possible in these ranges, and the resulting phases are storage-stable and transparent. The glycerin content, in particular, influences the curing time.

[0123] If the at least one gel phase according to the invention comprises, in each case based on the total weight of the gel-like phase, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4 wt. %, particularly preferably 0.2 to 1.0 wt. %), a C 3 - to C 6 -alkanetriol and a C 3 - to C 5 - alkanediol, their weight ratio is preferably 3:1 to 1:2. In particular, the weight ratio is from 2:1 to 1:1.5, preferably from 1.5:1 to 1:1.2, preferably from 1.3 to 1:1, if glycerol and 1,3-propanediol are present as polyhydric alcohols. Surprisingly, it has been shown that at these weight ratios, storage-stable, glossy, transparent gel phases can be obtained within short setting times at 20°C of 10 minutes or less.In combination with polyethylene glycols with an average molecular weight of 200 to 600 g / mol, setting times can be reduced to 5 minutes or less at the preferred weight ratios, in particular weight ratios (C 3 - to C 6 -alkanetriol : C 3 - to C 5 -alkanediol) of 1.5:1 to 1:1.2.

[0124] According to a further preferred embodiment, in addition to the above-mentioned alkanols, triethylene glycol can be present in the at least one gel phase, in particular the gel phases described above as preferred, in particular if this phase contains PVOH and optionally polyethylene glycols with an average molecular weight of 200 to 600 g / mol. Triethylene glycol advantageously accelerates the solidification of the gel phase(s). Furthermore, it leads to the resulting gel phase exchanging liquid with the environment only slightly, if at all, in an unobservable manner. This in particular improves the visual impression of the resulting cleaning agent portions. It is particularly preferred if the at least one gel phase, in each case based on the total weight of the gel-like phase, contains, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4 wt.-%, particularly preferably from 0.2 to 1.0 wt.%) 1,3- and / or 1,2-propanediol, particularly preferably 1 to 3.5 wt.% 1,3-propanediol, and glycerol between 0.1 and 20 wt.%, preferably between 1 and 15 wt.%, in particular between 5 and 12 wt.%, for example 8 to 11 wt.% triethylene glycol.

[0125] Furthermore, the washing or cleaning agent according to the invention preferably comprises, in particular at least the at least one gel phase, preferably both the particulate phase and the gel phase, a further anionic polymer, in particular polycarboxylates. These can act either as builders and / or as thickening polymers. According to the invention, the at least one gel phase can further comprise anionic polymers or copolymers with builder properties. This is preferably a polycarboxylate. The polycarboxylate used is preferably 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.

[0126] According to a particularly preferred embodiment, the low-water gel-like phase contains a polymer comprising at least one monomer containing sulfonic acid groups.

[0127] As unsaturated carboxylic acid(s) it is / are particularly preferred to use unsaturated carboxylic acids of the formula R 1< (R 2< )C=C(R 3< )COOH, in which R 1< to R 3< independently of one another represent -H, -CH 3 , 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 represent -COOH or -COOR 4<, where R 4< is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

[0128] Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid, or mixtures thereof. Unsaturated dicarboxylic acids can, of course, also be used.

[0129] Among the sulfonic acid group-containing monomers, those of the formula R 5< (R 6< )C=C(R 7< )-X-SO 3 H are preferred, in which R 5< to R 7< independently of one another represent -H, -CH 3 , 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 -NH 2 , -OH or -COOH or -COOH or -COOR 4<, where R 4< 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 -(CH 2 ) n - with n = 0 to 4, -COO-(CH 2 ) k - with k = 1 to 6, -C(O)-NH-C(CH 3 ) 2 -, - C(O)-NH-C(CH 3 ) 2 -CH 2 - and -C(O)-NH-CH(CH 3 )-CH 2 -.

[0130] Preferred among these monomers are those of the formulas H 2 C=CH-X-SO 3 H, H 2 C=C(CH 3 )-X-SO 3 H or HO 3 SX-(R 6< )C=C(R 7< )-X-SO 3 H, in which R 6< and R 7< are independently selected from -H, -CH 3 , -CH 2 CH 3 , - CH 2 CH 2 CH 3 and -CH(CH 3 ) 2 and X represents an optionally present spacer group selected from -(CH 2 ) n - with n = 0 to 4, -COO-(CH 2 ) k - with k = 1 to 6, -C(O)-NH-C(CH 3 ) 2 -, - C(O)-NH-C(CH 3 ) 2 -CH 2 - and -C(O)-NH-CH(CH 3 )-CH 2 -.

[0131] According to a particularly preferred embodiment, the gel-like phase contains a polymer comprising acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid as sulfonic acid group-containing monomer.

[0132] 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 may be present in completely or partially neutralized form, i.e. the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups may 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.

[0133] The monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95 wt.% in the case of copolymers which contain only carboxylic acid group-containing monomers and sulfonic acid group-containing monomers, particularly preferably 50 to 90 wt.% and 10 to 50 wt.% in the proportion of sulfonic acid group-containing monomers, and the proportion of carboxylic acid group-containing monomers is preferably 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 cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 g mol -1 , preferably of 4000 to 25,000 g mol -1 , and in particular of 5000 to 15,000 g mol -1 .

[0134] In a further preferred embodiment, the copolymers comprise, in addition to the carboxyl-containing monomer and the sulfonic acid-containing monomer, at least one nonionic, preferably hydrophobic monomer. The use of these hydrophobically modified polymers has been shown to improve, in particular, the rinse performance of dishwashing detergents according to the invention.

[0135] Particularly preferably, the at least one gel phase further comprises an anionic copolymer, wherein the anionic copolymer is a copolymer comprising i) monomers containing carboxylic acid groups ii) monomers containing sulfonic acid groups iii) non-ionic monomers, in particular hydrophobic monomers.

[0136] Monomers of the general formula R 1< (R 2< )C=C(R 3< )-XR 4< are preferably used as non-ionic monomers, in which R 1< to R 3< independently of one another represent -H, -CH 3 or - C 2 H 5, X represents an optionally present spacer group selected from -CH 2 -, - C(O)O- and -C(O)-NH-, and R 4< 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.

[0137] 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, α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-Octadecene and C 22 -α-olefin, 2-styrene, α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N -(Methyl)acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N-(2-Ethylhexyl)acrylamide, octyl acrylate, octyl methacrylate, N -(Octyl)acrylamide, acrylic acid lauryl ester, methacrylic acid lauryl ester, N -(Lauryl)acrylamide, stearyl acrylate, stearyl methacrylate, N -(Stearyl)acrylamide, acrylic acid behenyl ester, methacrylic acid behenyl ester and N- (Behenyl)acrylamide or mixtures thereof, in particular acrylic acid, ethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and mixtures thereof.

[0138] 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 phase therefore preferably comprises PVOH, polyethylene glycol(s) with an average molecular weight of 200 to 600 g / mol, at least one polyhydric alcohol and an anionic copolymer / polymer. The proportion of the anionic polymer is preferably 1 wt.% to 35 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 phase.Sulfopolymers, in particular the preferred copolymeric polysulfonates, which contain at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, in addition to sulfonic acid group-containing monomer(s), also ensure an excellent surface gloss. Furthermore, fingerprints are not retained. Therefore, the proportion of sulfopolymers, in particular the preferred copolymeric polysulfonates, which contain at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, in addition to sulfonic acid group-containing monomer(s), in particular of the aforementioned sulfopolymers with AMPS as the sulfonic acid group-containing monomer, for example Acusol 590, Acusol 588, or Sokalan CP50, is preferably 1 wt.% to 25 wt.%, in particular 3 wt.% to 18 wt.%, particularly 4 wt.% to 15 wt.%, preferably 5 wt.% to 12 wt.%, based on the weight of the gel phase.In a particularly preferred embodiment, the at least one gel phase therefore comprises PVOH and a sulfopolymer, in particular the preferred copolymeric polysulfonates, which, in addition to sulfonic acid group-containing monomer(s), contain at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, and at least one polyhydric alcohol.

[0139] 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 can be present in the at least one gel phase. The aforementioned polyethylene glycols are particularly preferably used in amounts of 1 to 40 wt.%, preferably 5 to 35 wt.%, in particular 10 to 30 wt.%, for example 15 to 25 wt.%, preferably in each case based on the total weight of the gel phase.

[0140] Very particularly preferred embodiments of the present invention comprise as at least one gel phase, in each case based on the total weight of the gel-like phase, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.2 to 1.0 wt.%) 8 to 22 wt.% PVOH, 15 to 40 wt.% 1,3-propanediol, 20 to 40 wt.% glycerol, 5 to 15 wt.% sulfonic acid group-containing polyacrylate copolymer, and 8 to 22 wt.%, in particular 10 to 20 wt.%, polyethylene glycol with an average molecular weight of 200-600 g / mol, optionally 2 to 10 wt.% 1,2-propanediol, and optionally additionally also 2-15 wt.% triethylene glycol, in each case based on the total weight of the gel phase. For a good incorporation of the zinc salts, especially zinc sulfate and / or zinc acetate, especially zinc acetate (e.g.in the anhydrous form of the salt) into low-water gel phases which comprise polymers containing carboxylate and / or sulfonic acid groups, it is particularly preferred if the amount of zinc salt in the anhydrous gel phase is selected from 0.2 to 1.0 wt.%, for example 0.5 wt.%.

[0141] According to a further particularly preferred embodiment, the washing or cleaning agents according to the invention, in particular the particulate phase, comprise at least one further ingredient selected from the group consisting of builders, polymers, bleaching agents, bleach activators, bleach catalysts, enzymes, sequestering agents, electrolytes, corrosion inhibitors, glass corrosion inhibitors, foam inhibitors, dyes, additives for improving drainage and drying behavior, disintegration aids, preservatives, pH adjusters, fragrances and perfume carriers.

[0142] The use of builder substances such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids as well as mixtures of these substances, preferably water-soluble builder substances, can be advantageous.

[0143] In a preferred embodiment of the invention, the use of phosphates (including polyphosphates) is largely or completely avoided. In this embodiment, the agent preferably contains less than 5% by weight, particularly preferably less than 3% by weight, and in particular less than 1% by weight of phosphate(s). Particularly preferably, the agent in this embodiment is completely phosphate-free, i.e., the agent contains less than 0.1% by weight of phosphate(s).

[0144] Builders include, in particular, carbonates, citrates, phosphonates, organic builders, and silicates. The weight proportion of the total builders in the total weight of the compositions according to the invention is preferably 15 to 80 wt.% and in particular 20 to 70 wt.%.

[0145] Organic builders suitable for the invention include, for example, polycarboxylic acids (polycarboxylates) usable in the form of their sodium salts. Polycarboxylic acids are understood to be carboxylic acids that carry more than one, in particular two to eight, acid functions, preferably two to six, in particular two, three, four, or five acid functions in the entire molecule. Preferred polycarboxylic acids are therefore dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, and pentacarboxylic acids, in particular di-, tri-, and tetracarboxylic acids. The polycarboxylic acids may also carry additional functional groups, such as hydroxyl or amino groups.Examples include citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example, galactaric acid and glucaric acid), aminocarboxylic acids, especially aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids such as nitrilotriacetic acid (NTA), glutamic-N,N-diacetic acid (also known as N,N-bis(carboxymethyl)-L-glutamic acid or GLDA), methylglycinediacetic acid (MGDA) and their derivatives, as well as mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA, and mixtures thereof.

[0146] Also suitable as organic builders are polymeric polycarboxylates (organic polymers with a large number of (especially more than ten) carboxylate functions in the macromolecule), polyaspartates, polyacetals and dextrins.

[0147] In addition to their builder effect, free acids typically also have the property of an acidifying component. These include citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixtures thereof.

[0148] Particularly preferred washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, contain one or more salts of citric acid, i.e., citrates, as one of their essential builders. These are preferably present in a proportion of 2 to 40 wt.%, in particular 5 to 30 wt.%, especially 7 to 28 wt.%, particularly preferably 10 to 25 wt.%, and very particularly preferably 15 to 20 wt.%, based in each case on the total weight of the agent.

[0149] Particularly preferred is also the use of carbonate(s) and / or bicarbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate (soda), in amounts of 2 to 50% by weight, preferably 4 to 40% by weight and in particular 10 to 30% by weight, very particularly preferably 10 to 24% by weight, in each case based on the weight of the agent.

[0150] Particularly preferred washing or cleaning agents according to the invention, in particular dishwashing agents, preferably automatic dishwashing agents, are characterized in that they contain at least two builders from the group of silicates, phosphonates, carbonates, aminocarboxylic acids and citrates, wherein the weight fraction of these builders, based on the total weight of the cleaning agent according to the invention, is preferably 5 to 70 wt. %, more preferably 15 to 60 wt. % and in particular 20 to 50 wt. %. The combination of two or more builders from the above-mentioned group has proven advantageous for the cleaning and rinsing performance of washing or cleaning agents according to the invention, in particular dishwashing agents, preferably automatic dishwashing agents. In addition to the builders mentioned here, one or more other builders may additionally be present.

[0151] Preferred washing or cleaning agents, in particular dishwashing detergents, preferably automatic dishwashing detergents, are characterized by a builder combination of citrate and carbonate and / or bicarbonate. In a particularly preferred embodiment according to the invention, a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40 wt.%, in particular 10 to 35 wt.%, very particularly preferably 15 to 30 wt.%, and the amount of citrate preferably being from 5 to 35 wt.%, in particular 10 to 25 wt.%, very particularly preferably 15 to 20 wt.%, in each case based on the total amount of the cleaning agent, the total amount of these two builders preferably being 20 to 65 wt.%, in particular 25 to 60 wt.%, preferably 30 to 50 wt.%. In addition, one or more further builders may also be present.

[0152] The washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, can contain, in particular, phosphonates as a further builder. A hydroxyalkane and / or aminoalkanephosphonate is preferably used as the phosphonate compound. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Suitable aminoalkanephosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and their higher homologues. Phosphonates are preferably present in agents according to the invention in amounts of 0.1 to 10 wt. %, in particular in amounts of 0.5 to 8 wt. %, very particularly preferably 2.5 to 7.5 wt. %, in each case based on the total weight of the agent.

[0153] The combined use of citrate, (hydrogen)carbonate, and phosphonate is particularly preferred. These can be used in the amounts stated above. In particular, amounts of 10 to 25 wt.% citrate, 10 to 30 wt.% carbonate (or hydrogen carbonate), and 2.5 to 7.5 wt.% phosphonate are used in this combination, based on the total weight of the agent.

[0154] Further particularly preferred washing or cleaning agents, in particular dishwashing detergents, preferably automatic dishwashing detergents, are characterized in that, in addition to citrate and (hydrogen) carbonate and optionally phosphonate, they contain at least one further phosphorus-free builder. This is particularly selected from the aminocarboxylic acids, with the further phosphorus-free builder preferably being selected from methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS), and ethylenediamine disuccinate (EDDS), particularly preferably from MGDA or GLDA. A particularly preferred combination is, for example, citrate, (hydrogen) carbonate, and MGDA, and optionally phosphonate.

[0155] The wt. % proportion of the further phosphorus-free builder, in particular of MGDA and / or GLDA, is preferably 0 to 40 wt. %, in particular 5 to 30 wt. %, above all 7 to 25 wt. Particular preference is given to using MGDA or GLDA, in particular MGDA, in the form of granules. MGDA granules which contain as little water as possible and / or have lower hygroscopicity (water absorption at 25°C, atmospheric pressure) compared to the non-granulated powder are advantageous. The combination of at least three, in particular at least four builders from the above-mentioned group has proven advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents. In addition, further builders may also be present.

[0156] Polymeric polycarboxylates are also suitable as organic builders. These include, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those with a relative molecular weight of 500 to 70,000 g / mol. Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1,000 to 20,000 g / mol. Due to their superior solubility, the short-chain polyacrylates, which have molecular weights of 1,100 to 10,000 g / mol, and particularly preferably of 1,200 to 5,000 g / mol, may be preferred from this group.

[0157] The content of (homo)polymeric polycarboxylates in the washing or cleaning agents according to the invention, in particular dishwashing agents, preferably automatic dishwashing agents, is preferably 0.5 to 20 wt.%, preferably 2 to 15 wt.% and in particular 4 to 10 wt.%.

[0158] Detergents or cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, can further contain, as builder, crystalline layered silicates of the general formula NaMSi x O 2x+1 y H 2 O, in which M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values ​​for x being 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. Amorphous sodium silicates with a modulus Na 2 O : SiO 2 of 1:2 to 1:3.3, preferably from 1:2 to 1:2.8 and in particular from 1:2 to 1:2.6, which are preferably delayed in dissolution and have secondary washing properties, can also be used.

[0159] In certain washing or cleaning agents according to the invention, in particular dishwashing agents, preferably automatic dishwashing agents, the content of silicates, based on the total weight of the washing or cleaning agent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.

[0160] In addition to the aforementioned builders, the detergents or cleaning agents according to the invention may further contain alkali metal hydroxides. These alkali carriers are used in the detergents or cleaning agents, and in particular in the at least one gel-like phase, preferably only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably between 0.1 and 5% by weight, and in particular between 0.5 and 5% by weight, in each case based on the total weight of the detergent or cleaning agent. Alternative detergents or cleaning agents according to the invention are free of alkali metal hydroxides.

[0161] As a further component, cleaning agents according to the invention preferably contain enzyme(s) in the at least one particulate and / or at least one gel phase. These include, in particular, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases, or oxidoreductases, and preferably mixtures thereof. These enzymes are essentially of natural origin; based on the natural molecules, improved variants are available for use in cleaning agents and are therefore preferably used. Cleaning agents according to the invention preferably contain enzymes in total amounts of 1 x 10 -6 wt% to 5 wt%, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

[0162] Among the proteases, those of the subtilisin type are preferred. Examples include subtilisins BPN' and Carlsberg, as well as their more advanced forms, protease PB92, subtilisins 147 and 309, alkaline protease from Bacillus lentus, subtilisin DY, and the enzymes thermitase, proteinase K, and proteases TW3 and TW7, which are classified as subtilases but no longer as subtilisins in the narrower sense.

[0163] Examples of amylases that can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger, and A. oryzae, as well as the improved versions of the aforementioned amylases for use in cleaning agents. Also suitable for this purpose are the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

[0164] Lipases or cutinases can also be used according to the invention, particularly for their triglyceride-cleaving activities, but also for generating peracids in situ from suitable precursors. These include, for example, the lipases originally obtained from Humicola lanuginosa (Thermomyces lanuginosus) or further developed lipases, in particular those with the amino acid substitution at positions D96LT213R and / or N233R, particularly preferably all of the substitutions D96L, T213R, and N233R.

[0165] Enzymes collectively referred to as hemicellulases can also be used. These include, for example, mannanases, xanthan lyases, pectin lyases (=pectinases), pectinesterases, pectate lyases, xyloglucanases (=xylanases), pullulanases, and β-glucanases.

[0166] To increase the bleaching effect, oxidoreductases, for example, oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin-, glucose-, or manganese-peroxidases, dioxygenases, or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention. Advantageously, organic compounds, particularly aromatic ones, that interact with the enzymes are also added to enhance the activity of the oxidoreductases in question (enhancers) or to ensure electron flow in the event of significantly different redox potentials between the oxidizing enzymes and the soils (mediators). A protein and / or enzyme can be protected, particularly during storage, against damage such as inactivation, denaturation, or degradation, for example, due to physical influences, oxidation, or proteolytic cleavage.When proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Cleaning agents may contain stabilizers for this purpose; the provision of such agents represents a preferred embodiment of the present invention.

[0167] Cleaning-active proteases and amylases are generally not supplied in the form of pure proteins, but rather in the form of stabilized, storable, and transportable preparations. These prefabricated preparations include, for example, solid preparations obtained by granulation, extrusion, or lyophilization or, particularly in the case of liquid or gel-like products, solutions of the enzymes, preferably as concentrated as possible, with little water content, and / or containing stabilizers or other additives.

[0168] Alternatively, the enzymes for the at least one particulate and / or the at least one gel-like phase can be encapsulated, for example by spray-drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, for example those in which the enzymes are enclosed as if in a solidified gel, or in those of the core-shell type, in which an enzyme-containing core is coated with a water-, air-, and / or chemical-impermeable protective layer. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers. Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Such granules, for example by applying polymeric film formers, are advantageously low in dust and, due to the coating, stable in storage.

[0169] Furthermore, it is possible to package two or more enzymes together so that a single granulate has multiple enzyme activities.

[0170] As can be seen from the above, the enzyme protein constitutes only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations used according to the invention contain between 0.1 and 40 wt.%, preferably between 0.2 and 30 wt.%, particularly preferably between 0.4 and 20 wt.%, and in particular between 0.8 and 10 wt.% of the enzyme protein. Particularly preferred are cleaning agents which, based on their total weight, contain 0.1 to 12 wt.%, preferably 0.2 to 10 wt.%, and in particular 0.5 to 8 wt.% of the respective enzyme preparations.

[0171] In addition to the components listed above, the at least one particulate and / or at least one gel phase of the washing or cleaning agent according to the invention may contain further ingredients. These include, for example, anionic, cationic and / or amphoteric surfactants, bleaching agents, bleach activators, bleach catalysts, other solvents, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances (particularly in the at least one particulate phase), additives for improving runoff and drying behavior, for adjusting viscosity, for stabilization, UV stabilizers, pearlescent agents, preservatives, antimicrobial agents (disinfectants), and pH adjusters in amounts typically not exceeding 5% by weight.

[0172] As a further solvent, agents according to the invention preferably contain at least one alkanolamine. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanolamine, and propanolamine, and mixtures thereof. The alkanolamine is preferably present in agents according to the invention in an amount of 0.5 to 10 wt.%, in particular in an amount of 1 to 6 wt.%. In a preferred washing or cleaning agent, the at least one gel-like phase is free of alkanolamine, and the alkanolamine is present only in the at least one particulate phase.

[0173] In a preferred embodiment, washing or cleaning agents according to the invention, in particular dishwashing detergents, contain as a further ingredient at least one zinc salt as a glass corrosion inhibitor. The zinc salt can be an inorganic or organic zinc salt. The zinc salt to be used according to the invention preferably has a solubility in water of above 100 mg / l, preferably above 500 mg / l, particularly preferably above 1 g / l, and in particular above 5 g / l (all solubilities at 20°C water temperature). The inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate, and zinc sulfate.The organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate. In a particularly preferred embodiment according to the invention, zinc acetate is used as the zinc salt. The zinc salt is present in cleaning agents according to the invention preferably in an amount of 0.01 wt.% to 5 wt.%, particularly preferably in an amount of 0.05 wt.% to 3 wt.%, in particular in an amount of 0.1 wt.% to 2 wt.%, based on the total weight of the cleaning agent. In addition or alternatively to the above-mentioned salts (in particular the zinc salts), polyethyleneimines, as are available, for example, under the name Lupasol® (BASF), can preferably be used in an amount of 0 to 5 wt.%, in particular 0.01 to 2 wt.-%, as glass corrosion inhibitors.

[0174] Polymers suitable as additives are, in particular, maleic acid-acrylic acid copolymer Na salt (for example Sokalan ®< CP 5 from BASF, Ludwigshafen (Germany)), modified polyacrylic acid Na salt (for example Sokalan ®< CP 10 from BASF, Ludwigshafen (Germany)), modified polycarboxylate Na salt (for example Sokalan ®< HP 25 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example Silwet ®< L-77 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example Silwet ®< L-7608 from BASF, Ludwigshafen (Germany)) and polyethersiloxanes (copolymers of polymethylsiloxanes with ethylene oxide / propylene oxide segments (polyether blocks)), preferably water-soluble linear Polyethersiloxanes with terminal polyether blocks such as Tegopren ®< 5840, Tegopren ®< 5843, Tegopren ®< 5847, Tegopren ®< 5851, Tegopren ®< 5863 or Tegopren ®< 5878 from Evonik,Essen (Germany). Builder substances suitable as additives include, in particular, polyaspartic acid sodium salt, ethylenediamine triacetate cocoalkylacetamide (e.g., Rewopol® CHT 12 from Evonik, Essen (Germany)), methylglycinediacetic acid trisodium salt, and acetophosphonic acid. Mixtures with surfactant or polymeric additives exhibit synergistic effects in the case of Tegopren® 5843 and Tegopren® 5863. However, the use of Tegopren types 5843 and 5863 is less preferred for applications on hard glass surfaces, especially glassware, since these silicone surfactants can be absorbed by the glass. In a particular embodiment of the invention, these additives are omitted.

[0175] A preferred washing or cleaning agent, in particular dishwashing detergent, preferably further comprises a bleaching agent, in particular an oxygen bleaching agent, and optionally a bleach activator and / or bleach catalyst. These, if present, are contained exclusively in the at least one particulate phase.

[0176] As a preferred bleaching agent, cleaning agents according to the invention contain an oxygen bleaching agent from the group consisting of sodium percarbonate, sodium perborate tetrahydrate, and sodium perborate monohydrate. Other useful bleaching agents include, for example, peroxypyrophosphates, citrate perhydrates, and H2O2-yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid, or diperdodecanedioic acid. Furthermore, bleaching agents from the group consisting of organic bleaching agents can also be used. Typical organic bleaching agents are diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxyacids, with particular examples being alkyl peroxyacids and aryl peroxyacids. Due to its good bleaching performance, sodium percarbonate is particularly preferred. A particularly preferred oxygen bleaching agent is sodium percarbonate.

[0177] Bleach activators that can be used are compounds that, under perhydrolysis conditions, yield aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, especially 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those containing O- and / or N-acyl groups with the stated number of carbon atoms and / or optionally substituted benzoyl groups. Polyacylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) having proven particularly suitable.

[0178] The bleach catalysts are bleach-enhancing transition metal salts or transition metal complexes, such as Mn, Fe, Co, Ru, or Mo salen complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V, and Cu complexes with N-containing tripod ligands, as well as Co, Fe, Cu, and Ru ammine complexes, can also be used as bleach catalysts. Particular preference is given to using manganese complexes in oxidation state II, III, IV, or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O, and / or S. Ligands with nitrogen donor functions are preferred.It is particularly preferred to use bleach catalyst(s) in the agents according to the invention which contain 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN) as macromolecular ligands. Suitable manganese complexes are, for example, [Mn III< 2 (µ-O) 1 (µ-OAC) 2 (TACN) 2 ](ClO 4 ) 2 , [Mn III< Mn IV< (µ-O) 2 (µ-OAc) 1 (TACN) 2 ](BPh 4 ) 2 , [Mn IV< 4 (µ-O) 6 (TACN) 4 ](ClO 4 ) 4 , [Mn III< 2 (µ-O) 1 (µ-OA c ) 2 (Me-TACN) 2 ](ClO 4 ) 2 , [Mn III< Mn IV< (µ-O) 1 (µ-OAc) 2 (Me-TACN) 2 ](ClO 4 ) 3 , [Mn IV< 2 (µ-O) 3 (Me-TACN) 2 ](PF 6 ) 2 and [Mn IV< 2 (µ-O) 3 (Me / Me-TACN) 2 ](PF e ) 2 (with OAc = OC(O)CH 3 ).

[0179] When benzoic acid, salicylic acid or lactic acid are used as pH regulators and / or buffer substances, these compounds can support or enhance the antibacterial effect of the silver and / or the silver compound.

[0180] The washing or cleaning agent according to the invention comprises at least one particulate phase and at least one gel-like phase. The washing or cleaning agent can thus have one, two, three or more different particulate phases; likewise, it can have one, two, three or more different gel-like phases. The washing or cleaning agent according to the invention preferably comprises a particulate phase and a gel-like phase. Particularly preferably, the washing or cleaning agent comprises two particulate phases and one gel-like phase. It preferably comprises two particulate phases and two gel-like phases. Further preferred is an embodiment in which the washing or cleaning agent comprises three particulate phases and one or two gel-like phases.

[0181] The weight ratio of the total of the at least one particulate phase to the total of the at least one gel phase is generally 40:1 to 2:1, in particular 20:1 to 4:1, preferably 12:1 to 6:1, for example 10:1 to 8:1. The total weight of all phases in a detergent portion can be between 8 and 30 g, in particular 10 to 25 g, preferably 12 to 21 g, for example 14 to 16 g per detergent or detergent portion. This weight ratio results in a good concentration of the respective ingredients of the particulate or gel phase in a cleaning process.

[0182] According to the invention, the at least one particulate phase and the at least one gel-like phase adjoin one another over their entire or partial surface. It is preferred that the two phases adjoin one another directly.

[0183] If the at least one particulate phase and the at least one gel-like phase border one another directly over their entire or partial surface, stability is important in addition to the shortest possible setting time for the at least one gel-like phase. Stability here means that components contained in the gel-like phase do not pass into the at least one particulate phase, but rather that even after prolonged storage the at least one particulate phase and the gel-like phase 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. Surprisingly, it has been found that this can be achieved by a gel-like phase which comprises polyethylene glycols with an average molecular weight of 200 to 600 g / mol, glycerol, PVOH and at least one C 3 to C 5 alkanediol.

[0184] According to a particularly preferred embodiment, the washing or cleaning agents according to the invention are characterized in that the at least one gel-like phase comprises less than 1 wt. %, in particular less than 0.5 wt. %, in particular less than 0.1 wt. % anionic surfactant, based in each case on the total weight of the gel-like phase. Preferably, the at least one gel-like phase is substantially free of anionic surfactants. Substantially free means that the at least one gel-like phase contains less than 0.05 wt. % anionic surfactant, based in each case on the total weight of the gel-like phase. In this context, it has been shown that the presence of 1 wt. % anionic surfactant in the at least one gel-like phase leads to poorer foaming behavior and poorer rinsing behavior of the overall composition. Furthermore, higher amounts of anionic surfactants negatively influence curing.

[0185] In addition to the surfactants, the agent according to the invention, in particular the at least one gel phase, can also contain sugar. According to the invention, sugars include sugar alcohols, monosaccharides, disaccharides, and oligosaccharides. In a preferred embodiment, the at least one gel phase comprises at least one sugar alcohol, preferably mannitol, isomalt, lactitol, sorbitol, threitol, erythritol, arabitol, and xylitol. Xylitol is particularly preferred.

[0186] In a further embodiment, the agent according to the invention, in particular the at least one gel-like phase, can comprise disaccharides, in particular sucrose. The proportion of sucrose is 0 wt.% to 30 wt.%, in particular 5 wt.% to 25 wt.%, particularly preferably 10 wt.% to 20 wt.%, based on the weight of the gel-like phase. In higher amounts, the sugar does not dissolve completely in the gel-like phase and leads to clouding of the same. The use of sugar, in particular in a proportion of 10 wt.% to 15 wt.%, reduces moisture development and thus improves adhesion to the at least one particulate phase.

[0187] The washing or cleaning agent portion according to the invention preferably comprises a washing or cleaning agent according to the invention in a water-soluble casing. The water-soluble casing is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer mixtures. The casing can be formed from one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, can be the same or different.

[0188] It is preferred that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer exhibit good stability with sufficiently high water solubility, particularly cold water solubility.

[0189] Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is 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<.

[0190] Polyvinyl alcohol is typically produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and especially 82 to 88 mol%.

[0191] In a preferred embodiment, the water-soluble packaging consists of at least 20 wt.%, particularly preferably at least 40 wt.%, very particularly preferably at least 60 wt.% and in particular at least 80 wt.% of a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol.%, preferably 80 to 90 mol.%, particularly preferably 81 to 89 mol.% and in particular 82 to 88 mol.%.

[0192] A polymer selected from the group comprising (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, or mixtures of the above polymers can additionally be added to a polyvinyl alcohol-containing film material suitable for producing the water-soluble wrapping. A preferred additional polymer is polylactic acid.

[0193] Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid, and mixtures thereof, with itaconic acid being preferred. Likewise 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, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, or mixtures thereof.

[0194] It may be preferred for the film material to contain further additives. The film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, sorbitol, mannitol, or mixtures thereof. Further additives include, for example, release agents, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-adhesive agents, or mixtures thereof.

[0195] Suitable water-soluble films for use in the water-soluble wrappers of the water-soluble packaging according to the invention are films sold by MonoSol LLC, for example, under the designation M8720, M8630, M8312, M8440, M7062, C8400, or M8900. Also suitable are films sold under the designation SH2601, SH2504, SH2707, or SH2701 by Nippon Gohsei. Other suitable films include films with the designation Solublon®< PT, Solublon®< GA, Solublon®< KC, or Solublon®< KL from Aicello Chemical Europe GmbH, or the VF-HP films from Kuraray.

[0196] The water-soluble coating preferably comprises at least partially a bittering agent with a bitterness value between 1,000 and 200,000, in particular those selected from quinine sulfate (bitterness value = 10,000), naringin (bitterness value = 10,000), sucrose octaacetate (bitterness value = 100,000), quinine hydrochloride, and mixtures thereof. In particular, the outer surface of the water-soluble coating is at least partially coated with a bittering agent with a bitterness value between 1,000 and 200,000. In this context, it is particularly preferred that the water-soluble coating is coated to at least 50%, preferably to at least 75%, and most preferably to at least 90% with the bittering agent with a bitterness value between 1,000 and 200,000. The bittering substance with a bitterness value between 1,000 and 200,000 can be applied, for example, by printing, spraying or coating.

[0197] According to the invention, the water-soluble wrapping has at least one continuous, circumferential seal seam that lies essentially in one plane. This is advantageous from a process engineering perspective, since for a circumferential seal seam that lies essentially in one plane, only a single sealing step is necessary, possibly using only a single sealing tool. The continuous, circumferential seal seam leads to a better closure than wrappings with multiple seal seams and excellent tightness of the seal seam and thus of the wrapping itself. Leakage of product from the wrapping, e.g., onto the surface of the portion, would be disadvantageous, as the consumer would then come into contact with the product. However, this is precisely what should be avoided as far as possible in a washing or cleaning agent portion with a water-soluble wrapping.

[0198] The water-soluble wrapping can preferably be made from at least two packaging parts. The at least two packaging parts are preferably water-soluble, so that no packaging parts remain in the dishwasher, which could then cause problems in the dishwasher. It is not necessary for the at least two packaging parts to be different. They can preferably be made from the same material and in the same way. In a preferred embodiment, these are two parts of a water-soluble film, in particular two parts of a water-soluble film of the same composition.

[0199] In a further embodiment, the at least two packaging parts can be made of different materials, e.g., different films or materials with two different properties (e.g., hot and cold water-soluble films). In this embodiment, it is preferred that a water-soluble film and another packaging part produced by injection molding are combined.

[0200] According to a particularly preferred embodiment of the present invention, the water-soluble coating comprises at least one at least partially plastically deformed film. In particular, this plastic deformation of the film can be produced by methods known to those skilled in the art, such as deep drawing (with and without applying a vacuum), blow molding, or stamp molding. In particular, the water-soluble coating comprises at least one at least partially plastically deformed film produced by deep drawing. The at least one particulate phase and the at least one gel-like phase can be arranged in any desired combination within the water-soluble coating. For example, a particulate phase can be arranged on or next to a gel-like phase. In this embodiment, the washing or cleaning agent according to the invention has a particulate phase and a gel-like phase.It is also conceivable for a particulate phase to be surrounded by gel-like phases. Embedding one phase in another is also encompassed by the invention. In a further, particularly preferred arrangement, the gel-like phase is present in cast form, for example in the form of a gel core surrounded by the particulate phase. Two or more separate cavities may also be present, which are filled with the at least one gel-like phase. In this embodiment, the washing or cleaning agent comprises two gel-like phases, wherein the two gel-like phases may have different compositions.

[0201] According to a preferred embodiment, there are 3, 4, 5, or 6 or more separate cavities filled with one or more of the gel phases. Such washing or cleaning agents preferably comprise 3, 4, 5, or 6 or more gel phases, whereby these gel phases may have the same or different compositions.

[0202] According to a particularly preferred embodiment, the washing or cleaning agent portion according to the invention is characterized in that it contains a dishwashing agent, in particular a dishwashing agent for machine cleaning of dishes.

[0203] Another object of the present invention is a process for the production of washing and / or cleaning agent portions containing a product with at least one particulate phase, comprising: a) Providing a mold with at least one mold cavity; optionally containing at least one web for dividing the bottom of the mold cavity; b) Feeding a water-soluble film onto the mold cavity; c) Forming at least one open chamber in the mold cavity by deforming the water-soluble film; d) Optionally filling the open chamber with at least one gel-like phase; e) Filling the open chamber with at least one particulate phase; f) Optionally filling the open chamber with at least one further composition; g) Providing a second water-soluble film as a lid; h) Placing the open chamber and the lid on top of each other to seal the portion pack at a sealing area;i) sealing the lid with the open chamber, characterized in that before or after step e) the chamber is filled with at least one liquid composition, preferably containing perfume preparations and / or surfactants, in particular non-ionic surfactants. ;

[0204] The mold comprises at least one cavity (molding cavity). The mold can be provided, for example, as a single mold or as part of a series of molds in the form of a conveyor belt, as is known from the conveyor belt process and the drum process. The mold comprises an area onto which the film can be placed, e.g. a sealing area which is typically defined around the opening of a mold cavity. The mold cavity can have various geometries; if edges are present, it is advantageous for them to be rounded. Rounded edges and / or dome-shaped cavities ensure that when the film is pulled into the cavity, the film is pulled more homogeneously, thus ensuring that the film thickness remains uniform and that no breaks or tears are created, which in turn leads to a more stable portion pack.

[0205] Optionally, but according to a particular embodiment, preferably, the mold contains at least one mold cavity having at least one web for subdividing the bottom of the mold cavity. This creates one or more, preferably 2, 3, 4, 5, or 6, bulges or pockets in the molded chamber, creating a visually pleasing appearance. In particular, if only the areas of these bulges are completely or partially, preferably almost completely, filled with the gel-like phase(s), this area is once again clearly separated from the granular mixture, in particular the particulate phase, creating a particularly pleasing visual appearance.

[0206] The water-soluble film can be fed from a roll and guided onto the mold cavity. The film is positioned and held on the mold. The holding can take place by suction holes on the mold surface, which is not part of the mold cavity. However, the film can also be held on the mold by mechanical means, such as clamps. For example, the film can be held in place by a punch that presses on the sealing area. In continuous production processes, such as drum processes and conveyor belt processes, it is preferable that the speed of the film is matched to the speed of the conveyor belt formed from the molds, so that the film is not unnecessarily drawn thinner by holding on to a moving mold.

[0207] After the film is held in place relative to the mold cavity, a chamber is formed in the mold cavity area by at least partially adapting the film to the mold cavity. The adaptation is achieved by elastic and / or plastic deformation. Preferably, the film deformation has a greater plastic than elastic component. The deformation of the water-soluble film is achieved, for example, by deep drawing or using suitable stamps. A preferred variant is deep drawing, by applying negative pressure (forming pressure) in the mold cavity. For this purpose, the mold cavity preferably comprises small openings, preferably in the base area, which are connected to a vacuum pump by means of appropriate lines.

[0208] In subsequent steps, the open chamber is now filled. Filling, in this context, means adding quantities of the respective particulate or gel phases or liquid compositions to the open chamber. This implies that the open chamber is only partially filled by adding one of the compositions / phases. This leaves space in the open chamber for the addition of additional phases or compositions.

[0209] After forming the open chamber, in step d), this chamber or parts thereof are optionally but preferably filled with the at least one gel phase of the product. Once the at least one gel phase has solidified, possibly after an additional period of time necessary for solidification, further product components can then be added to the chamber. After a first gel phase in step d), one or more further gel phases can be added.

[0210] Subsequently, in step e), at least one particulate phase can be introduced, the specifications and compositions of which have already been described in detail above. The at least one particulate phase according to step e) is preferably a solid comprising a granular mixture; in particular, it is particulate, especially particulate and free-flowing.

[0211] In the aforementioned manufacturing process, it is preferred that the open chamber, which contains at least one gel-like and at least one particulate phase, is not completely filled with the gel-like phase(s). The chamber can preferably be filled only partially, preferably only in the lower region or only in the region of or just above the region of the bulges or pockets of the chamber formed by the optional web according to a).

[0212] During filling with product, the deformed film is preferably held in the cavity during filling. For example, when applying negative pressure, the negative pressure is only broken after sealing. However, the negative pressure after the chamber has been formed may be of a lower intensity (higher pressure) compared to the forming pressure, which only serves a holding function.

[0213] It is important that the sealing area remains free of product. For example, if the chamber is at least partially elastically deformed, this elastic deformation must not decrease after filling and before sealing to such an extent that the product flows over and out of the open chamber, thus contaminating the sealing area.

[0214] According to a particular embodiment, the lid is positioned over the open chamber so that in the next step, the lid can be applied to the sealing area. The position of the lid is generally determined relative to the position of the chamber. If the chamber moves with a moving mold on a conveyor belt, the lid must move in the same direction to maintain the same position relative to the chamber.

[0215] The lid is then applied to the open chamber, thus sealing it. Contact between the lid and the film in the sealing area thus closes the chamber.

[0216] A preferred sealing method is a fusion of the film and lid, for example, by partially dissolving the film before applying the lid, or by melting the film and / or lid in the sealing area. Alternatively, the seal can be achieved by gluing or welding.

[0217] Positioning, application, and sealing can take place either in separate steps or simultaneously.

[0218] The mold may also comprise at least a second mold cavity, so that at least two open chambers are created by process steps a) to d). The at least two chambers are formed in the same plane. It is preferred that the lid is positioned over the at least two open chambers in process step h) and that the lid is applied to at least both chambers in process step i) to seal the portion pack at a sealing area. Since the at least two chambers are connected by the same lid, the chambers remain in a specific position relative to one another, in contrast to the prior art, where adjacent chambers are connected by the web formed by the thin films of the packaging. It is easily possible to design three, four, five or more chambers next to one another, which are filled with a corresponding number of gel-like phases (with the same or different composition).

[0219] It is particularly preferred that the lid be provided as part of a belt, by feeding / transferring a belt comprising at least one lid. The separation of the lid can take place before positioning, after positioning but before application, during application, or after application to the chamber.

[0220] If the lid is separated before positioning, it is preferable to punch it out.

[0221] The lid and film can also be separated simultaneously with the sealing process. The device that creates the sealing by melting consists of at least two parts: one is the mold itself, and the other part is a counter-punch that presses against the mold from the lid side. It is preferable that during the sealing step, the pressure exerted by the mold and the other part in the sealing area be lower than the pressure exerted in the separation area. The separation area surrounds the sealing area.

[0222] In the case of separation after sealing, the lid and film are preferably separated from the belt in the same step, thus separating the portion packs.

[0223] According to a preferred embodiment, there are 2, 3, 4, 5, or 6 or more separate cavities, which are filled with one or more of the gel phases. Such washing or cleaning agents preferably comprise 3, 4, 5, or 6 or more gel phases, whereby these gel phases may have the same or different compositions.

[0224] Before or after step e), the chamber is filled with at least one liquid composition, preferably containing perfume preparations and / or surfactants, in particular non-ionic surfactants. This has advantages with regard to the more compact and simpler production of the particulate phases brought into contact with the liquid composition. The at least one liquid composition can be filled into the open chamber, which optionally contains the already solidified at least one gel-like phase, before the particulate phase is introduced. Preferred methods include that in step d), after the open chamber has been filled with the at least one gel-like phase, the gel-like phase solidifies or solidifies.

[0225] Preferably, the liquid composition is applied to the gel-like and already solidified phase introduced according to step c) so that the composition does not mix with the not yet solidified gel-like phase. Thus, the at least one liquid composition, in particular comprising a perfume preparation and / or at least one surfactant, in particular a nonionic surfactant, is brought into direct contact with the at least one particulate phase by the subsequent introduction of the particulate phase. The composition can then impregnate the particulate phase or be absorbed into it.

[0226] It is equally preferred that the at least one particulate phase be applied before the liquid composition (preferably onto the gel-like and already solidified phase introduced according to step c). Subsequently, the at least one liquid phase is then at least partially applied to the surface of the particulate phase and is thus in direct contact with it. The liquid composition can thus impregnate the particulate composition or absorb it into it. This results in an open chamber containing more compact compositions of detergents or cleaning agents.

[0227] In both cases, the particulate phase in the open chamber can also be compacted by the application of pressure.

[0228] According to a further preferred embodiment of the invention, the open chamber in step f) can be filled with at least one further composition.

[0229] The further composition according to step f) can be at least one further liquid composition for further impregnation, as well as at least one further particulate phase and / or at least one further gel-like phase, as already described above. Preferably, a solidifying composition can also be introduced according to step f) (alternatively or additionally, such a solidifying composition can also be introduced after step c). Suitable solidifying compositions (in addition to the gel-like phases already mentioned) include, for example, compositions such as those disclosed in DE102015213938 A1 or DE102015213939 A1. The disclosure contained therein is hereby incorporated by reference in its entirety.

[0230] According to the above-mentioned production methods, multi-chamber pouches can also be produced which contain at least one chamber comprising at least one particulate phase according to the invention and at least one liquid composition, in particular additionally at least one gel-like phase according to the invention, in direct contact with one another, and furthermore have at least one further, for example two, three or more further separate chambers.

[0231] For the at least one particulate phase comprising granular mixtures of a solid composition, in particular the at least one particulate phase, the above-described conditions for the cleaning agents according to the invention apply. It is preferred that the at least one particulate phase be particulate and free-flowing, preferably as described above.

[0232] The above-mentioned statements regarding the washing or cleaning agent portion also apply to the liquid compositions, gel phases, and particulate phases to be used in the processes according to the invention, to which explicit reference is hereby made. A particular suitability of the above-described gel phases for the process mentioned lies in the fact that the rapid setting times of the gel phases, in particular the phases containing PVOH, at least one polyhydric alcohol, and polyethylene glycol with an average molecular weight of 200 to 600 g / mol, greatly shorten the step of allowing the gel phase(s) to solidify and may even make it unnecessary, since such phases cool and solidify particularly quickly, without the need for additional cooling, long production lines, or prolonged downtimes or waiting times.

[0233] In this context, very particularly preferred embodiments of the present invention comprise, as at least one gel-like phase, 8 to 22 wt.% PVOH, 15 to 30 wt.% 1,3-propanediol, 30 to 40 wt.% glycerol, 5 to 15 wt.% sulfonic acid group-containing polyacrylate copolymer, 10-22 wt.% polyethylene glycol(s) with an average molecular weight of 200-600 g / mol), and optionally zinc salts, data in wt.% in each case based on the total weight of the gel-like phase.

[0234] Depending on the manufacturing process, the gel-like phase(s) can be located significantly above or below the seal seam level (first-mentioned process) or approximately at the level of the seal seam level (latter-mentioned process).

[0235] The present invention further relates to washing or cleaning agent portions as obtainable by one of the processes described above.

[0236] A further subject matter of the present application, not according to the invention, is a method for cleaning hard surfaces, in particular tableware, in which the surface is treated in a conventional manner using a cleaning agent according to the invention. In particular, the surface is brought into contact with the washing or cleaning agent according to the invention. Cleaning is carried out in particular using a cleaning machine, preferably a dishwasher.

[0237] The present invention also further relates to the use of a detergent portion according to the invention for cleaning dishes in automatic dishwashers. Another non-inventive subject of the invention is the use of a detergent portion for the automatic cleaning of laundry or textiles.

[0238] In a preferred embodiment, the present application relates to automatic dishwashing detergents. According to this application, automatic dishwashing detergents are defined as compositions that can be used to clean soiled dishes in an automatic dishwashing process. The automatic dishwashing detergents according to the invention thus differ, for example, from automatic rinse aids, which are always used in combination with automatic dishwashing detergents and do not exhibit any cleaning action of their own.

[0239] In the following exemplary embodiment, the washing or cleaning agent according to the invention is described in a non-limiting manner. Examples of implementation:

[0240] Cleaning agents according to the invention were produced, comprising a solid phase and a gel phase. Different geometries were realized. Furthermore, cleaning agents were produced comprising two solid phases and a gel phase. Cleaning agents comprising a solid phase and three, four, and five gel phases (of the same or different composition) were also produced. The following data refer to the wt. % active ingredient based on the total weight of the respective phase (unless otherwise stated). Table 1: The solid granular mixtures of a solid composition, in particular powdery and free-flowing phases, had the following preferred composition: % by weight Citrate, sodium salt 15-20 Phosphonate (e.g. HEDP) 2,5-7,5 MGDA, sodium salt 0-25 Disilicate, sodium salt 5-35 soda 10-25 Silver protection (e.g. cysteine) 0,0 - 1,0 Percarbonate, sodium salt 10-15 Bleach catalyst (preferably Mn-based) 0,02-0,5 Bleach activator (e.g. TAED) 1-3 Non-ionic surfactant(s), e.g. fatty alcohol alkoxylate, preferably 20-40 EO, if necessary endcapped 2,5-10 Polycarboxylate 4 - 10 Cationic copolymer 0 - 0,75 Disintegrant - (e.g. Crosslinked PVP) 0 -1,5 Protease preparation (tq) 1,5-5 Amylase preparation (tq) 0,5-3 perfume 0,05-0,25 Dye solution 0,0-1 Zn salt (e.g. acetate) 0,1-0,3 Sodium sulfate 0,0 - 10 Water 0,0-1,5 pH adjuster (e.g. citric acid) 0-1,5 Process aids 0-5 Table 2: The gel phases used had the following compositions (data based on the total amount of gel phase): % by weight Water-soluble zinc salt (preferably zinc acetate anhydrate) 0,1-2,4 glycerin 10-50 Propanediol (preferably 1,3-propanediol) 10-50 Polycarboxylate copolymer with sulfonic acid-containing groups 0- 30 Non-ionic surfactant(s), e.g. fatty alcohol alkoxylate, preferably 20-40 EO, if necessary endcapped 0-40 Polyethylene glycol average Mr 200-600, (e.g. PEG 400 (INCI) 8-26 PVOH 8-22 Process aids 0 - 10 Dye solution 0,0 - 1,5 Misc., other active ingredients, organic solvents, perfume, Add 100

[0241] The solid and gel phases could be combined as desired. The spatial configuration of the gel phase, which was liquid after mixing the ingredients and dimensionally stable within a setting time of a maximum of 10 minutes, was determined by the spatial configuration of the solid phase as well as by commercially available or self-designed molds. A water-soluble enclosure in the form of an open pouch was produced by deep drawing a PVOH-containing film. A liquid composition was poured into this open cavity, which formed the gel phase after curing. Solid phases in the form of a free-flowing solid in a pouch containing polyvinyl alcohol were then filled onto it. 1.0 g of the liquid non-ionic surfactant Genapol EC 50 was dosed onto the resulting particulate surface. The proportion of non-ionic surfactants could thus be significantly increased without altering other phases.The open pouch was then sealed by applying a second film and heat-sealing it. The resulting cleaning agent portions were characterized by their appealing aesthetics.

Claims

1. Washing and / or cleaning agent portion comprising at least one chamber and a water-soluble envelope, characterized in that it comprises at least one particulate phase, the at least one particulate phase being brought into direct contact with at least one liquid composition in such a way that it is impregnated with the at least one liquid composition, wherein the at least one liquid composition comprises surfactants and, in addition to the at least one particulate phase and the at least one liquid composition, at least one further gel-like phase is contained.

2. Washing and / or cleaning agent portion according to claim 1, characterized in that the at least one particulate phase is free-flowing, preferably at the time of addition.

3. Washing and / or cleaning agent portion according to claim 1 or 2, characterized in that the at least one liquid composition comprises surfactants, preferably nonionic surfactants, and / or perfume preparations, wherein the proportion of water in the liquid composition is 20% by weight or less, preferably 15% by weight or less, in particular 12% by weight or less, based on the total weight of the liquid composition.

4. Washing and / or cleaning agent portion according to claim 3, characterized in that the weight ratio of the total amount of the at least one liquid composition to the total amount of the at least one particulate phase is from 1:800 to 5:1, in particular from 1:600 to 2:1, preferably from 1:500 to 2:1, for example from 1:450 to :1, and / or the weight proportion of the at least one liquid composition to the total weight of the composition formed from the at least one liquid composition and the at least one particulate composition is 0.0001 to 25 wt., in particular 0.005 to 20 wt.%, preferably 0.1 to 18 wt.%, most preferably 0.2 to 15 wt.%.

5. Washing and / or cleaning agent portion according to one of claims 3 or 4, characterized in that the surfactant content of the at least one liquid composition is at least 50% by weight, in particular at least 70% by weight, preferably at least 80% by weight, in particular preferably at least 90% by weight, based on the total weight of the liquid composition.

6. Washing and / or cleaning agent portion according to one of the preceding claims, characterized in that the particulate phase contains at least one ingredient selected from the group consisting of builders, polymers, bleaching agents, bleach activators, bleach catalysts, enzymes, sequestering agents, electrolytes, corrosion inhibitors, glass corrosion inhibitors, foam inhibitors, dyes, additives to improve the flow and drying behavior, disintegration aids, preservatives, pH adjusters, fragrances, and perfume carriers.

7. Method for producing washing and / or cleaning agent portions containing a product with at least one particulate phase, comprising: a) providing a mold with at least one mold cavity; optionally containing at least one web for dividing the bottom of the mold cavity; b) feeding a water-soluble film onto the mold cavity; c) forming at least one open chamber in the mold cavity by deforming the water-soluble film; d) optionally filling the open chamber with at least one gel-like phase e) filling the open chamber with at least one particulate phase; f) optionally filling the open chamber with at least one further composition; g) providing a second water-soluble film as a lid; h) placing the open chamber and the lid on top of each other to seal the portion pack at a sealing area; i) sealing the lid to the open chamber, characterized in that, before or after step e), the chamber is filled with at least one liquid composition, preferably containing perfume preparations and / or surfactants, in particular nonionic surfactants.

8. Method according to claim 9, characterized in that in step d), after filling the open chamber with the at least one gel-like phase, the gel-like phase solidifies or hardens.

9. Method according to claim 7 or 8, characterized in that in step f), the open chamber is filled with at least one further composition, preferably a solidifying composition.

10. Washing or cleaning agent portion, obtainable by one of the methods according to one of claims 7 to 9.

11. Use of a cleaning agent portion according to one of claims 1 to 6 or 10 for machine cleaning of dishes.