WASHING OR CLEANING AGENTS

Description

[0001] The invention relates to washing or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, comprising at least one gel, preferably a gel that is solid at room temperature (20°C), which, based on the total weight of the gel, a) 12.7 to 15.5 wt% PVOH and / or its derivatives, b) 31 to 32 wt% 1,3-propanediol, c) 25 to 28 wt% glycerol, d) 13.5 to 16.5 wt% polyalkylene glycol, and e) < 1 wt% water contains.

[0002] Washing and cleaning products are typically available in solid form (for example, as tablets) or in liquid form (or as a flowing gel). Liquid washing and cleaning products, in particular, are becoming increasingly popular with consumers. Pre-portioned products are popular because they are easier to dose. However, pre-portioned flowing gels are often problematic because they tend to leak, for example, when packaged in single- or multi-chamber pouches.

[0003] The feel and appearance experienced during use also play a role and may determine whether the product is disliked or whether there is an incentive to buy it again.

[0004] German patent application DE102018212204 A1 discloses compositions comprising at least one gel phase containing at least one water-soluble zinc salt. DE102019210893 A1 describes molded bodies comprising polyvinyl alcohol, which may contain glycerin, liquid diols, and water.

[0005] The object of the present invention is to provide washing or cleaning agents, in particular dishwashing detergents, preferably machine dishwashing detergents, which can be produced even more easily and cost-effectively while simultaneously having an appealing feel and appearance.

[0006] A first object of the present invention thus relates to washing or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, comprising a gel, preferably a gel that is solid at room temperature (20 °C), which, based on the total weight of the gel, a) 12.7 to 15.5 wt.% polyvinyl alcohol and / or its derivatives, b) 30.5 to 33 wt.%, in particular 31 to 32 wt.% 1,3-propanediol, c) 25 to 28 wt.% glycerol, d) 13.5 to 16.5 wt.% polyalkylene glycol, and e) contains < 1 wt.% water, where derivatives of polyvinyl alcohol are understood to mean copolymers of polyvinyl alcohol with anionic monomers, as well as polyvinyl alcohols which are acetalized or ketalized with aldehydes or ketones, in particular saccharides or polysaccharides or mixtures thereof.

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

[0008] The washing or cleaning agent can have one, two, three, four, or more gels or gel phases. The gels / gel phases can be identical or different. In the case of multiple gels or gel phases, they are preferably distinguishable spatially, visually, and / or by their ingredients. If the gels / gel phases are different, they preferably contain different dyes and different additions of active ingredients.

[0009] The gel is dimensionally stable. During its production, polyvinyl alcohol and / or its derivatives are brought into contact with glycerin. This yields a flowable mixture that can be shaped as desired. After a certain period, a gel / gel phase is obtained that retains its predetermined shape, i.e., it is dimensionally stable. This period, the solidification time, is preferably 15 minutes or less, more preferably 10 minutes or less, and particularly preferably 5 minutes or less. During this time, the gel yields to pressure but does not deform; instead, it returns to its original state when the pressure is removed. The gel is preferably elastic, particularly linearly elastic.

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

[0011] Certain minimum requirements are placed on formulations of at least one gel phase. As already explained, the gel must solidify within the shortest possible time. Long solidification times would lead to long production times and thus high costs. According to the invention, solidification time means the period during which the gel transitions from a flowable state to a non-flowable, dimensionally stable state at room temperature. Room temperature is defined as a temperature of 20 °C.

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

[0013] A phase, as defined in the present invention, is a spatial region in which physical parameters and chemical composition are homogeneous. A phase differs from another phase by various characteristics, such as ingredients, physical properties, external appearance, etc. Preferably, different phases can be visually distinguished. For example, the consumer can clearly distinguish the at least one solid phase from the at least one gel phase. If the washing or cleaning agent according to the invention has more than one solid phase, these can also be distinguished from one another with the naked eye, for example, because they differ in color. The same applies if two or more gel phases are present. In this case, too, a visual distinction between the phases is possible, for example, based on a difference in color or transparency.Phases within the meaning of the present invention are thus self-contained regions that can be visually distinguished from one another by the consumer with the naked eye. The individual phases can exhibit different properties during use, such as the rate at which the phase dissolves in water and thus the rate and sequence of release of the ingredients contained in the respective phase.

[0014] The gel is preferably translucent or transparent, resulting in a good optical appearance. Preferably, the transmission of the gel phase (without dye) is in the range of 100% to 20%, 100% to 30%, and particularly between 100% and 40%. To measure the light transmittance, the percentage of transmittance at 600 nm against water as a reference at 20 °C was determined. For this purpose, the mixture was poured into the provided 11 mm round cuvettes and, after a 12-hour storage period at room temperature, measured in a Lange LICO 300 color measurement system.

[0015] The washing or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, contain polyvinyl alcohol and / or its derivatives in an amount of 12.7 to 14.6% by weight, based on the total weight of the gel.

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

[0017] According to a preferred embodiment, the gel comprises PVOH (polyvinyl alcohol). These gels or gel phases produced in this way have a particularly high melting point, are dimensionally stable (even at 40 °C), and do not change their shape, or only minimally, during storage. In particular, they are also relatively unreactive with regard to direct negative interactions with components of a granular mixture, especially an additional powder phase. PVOH can, in particular, produce low-moisture or anhydrous gel phases. When PVOH is used as the polymer for the gel, low-viscosity melts are obtained at 110–120 °C, which makes them particularly easy to process. In particular, the gel phase can be filled quickly and precisely into the water-soluble coating without clumping or inaccurate metering.Furthermore, these gel phases adhere particularly well to the water-soluble coating, especially if the coating is also made of PVOH. This is also visually advantageous. The rapid solidification of at least one gel phase with PVOH allows for particularly fast further processing of the gel phases. Moreover, the good solubility of the resulting gel phases is especially beneficial for the overall solubility of the detergent or cleaning agent. In addition, gel phases with such short solidification times are advantageous because the at least one solid phase added to them, comprising granular mixtures, especially powders, does not sink into the not yet fully solidified or too soft gel. This would result in visually unappealing portions of the detergent or cleaning agent.

[0018] Particularly preferred are polyvinyl alcohols in the form of white-yellowish powders or granules with degrees of polymerization in the range of approximately 100 to 2500 (molar masses of approximately 4000 to 100,000 g / mol) and degrees of hydrolysis of 80 to 99 mol%, preferably 85 to 90 mol%, in particular 87 to 89 mol%, for example 88 mol%, which accordingly still contain a residual content of acetyl groups.

[0019] PVOH powders with the aforementioned properties, suitable for use in at least one gel phase, are marketed, for example, under the names Mowiol® or Poval® by Kuraray. Exceval® AQ4104 from Kuraray is also suitable, for example. Particularly suitable are Mowiol C30, the Poval® grades, especially grades 3-83, 3-88, 6-88, 4-85, and particularly preferably 4-88, and most preferably Poval 4-88 S2 and Mowiol® 4-88 from Kuraray.

[0020] For the purposes of the invention, copolymers of polyvinyl alcohol with anionic monomers are preferred as derivatives of PVOH. Preferably suitable anionic monomers are vinylacetic acid, alkyl acrylates, maleic acid and its derivatives, in particular monoalkyl maleates (especially monomethyl maleate), dialkyl maleates (especially dimethyl maleate), maleic anhydride, fumaric acid and its derivatives, in particular monoalkyl fumarate (especially monomethyl fumarate), dialkyl fumarate (especially dimethyl fumarate), fumaric anhydride, itaconic acid and its derivatives, in particular monomethyl itaconate, dialkyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid (methyl maleic acid) and its derivatives, monoalkyl citraconic acid (especially methyl citracana), dialkyl citraconic acid (dimethyl citracana), citraconic anhydride, mesaconic acid (methyl fumaric acid) and its derivatives, monoalkyl mesaconate, dialkyl mesaconate, mesaconic anhydride, glutaconic acid and its derivatives, monoalkyl glutaconate.Dialkylglutaconate, glutaconic anhydride, vinylsulfonic acid, alkylsulfonic acid, ethylenesulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate and combinations thereof, as well as the alkali metal salts or esters of the aforementioned monomers.

[0021] Particularly preferred are derivatives of PVOH selected from copolymers of polyvinyl alcohol with a monomer, in particular selected from the group consisting of monoalkyl maleates (especially monomethyl maleate), dialkyl maleates (especially dimethyl maleate), maleic anhydride, and combinations thereof, as well as the alkali salts or esters of the aforementioned monomers. The values ​​specified for polyvinyl alcohols themselves apply to the suitable molar masses. Within the scope of the present invention, it is preferred that the gel comprises a polyvinyl alcohol and / or its derivatives, preferably a polyvinyl alcohol, whose degree of hydrolysis is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 mol%, and most preferably 82 to 88 mol%.

[0022] The water solubility of polyvinyl alcohol can be modified by post-treatment with aldehydes (acetalization) or ketones (ketalization). These are also derivatives of polyvinyl alcohol. Polyvinyl alcohols that are acetalized or ketalized with the aldehyde or ketone groups of saccharides or polysaccharides, or mixtures thereof, have proven particularly advantageous due to their excellent cold water solubility. The reaction products of polyvinyl alcohol and starch are also extremely beneficial. Furthermore, the water solubility can be modified by complexation with nickel or copper salts or by treatment with dichromates, boric acid, or borax, thus allowing it to be precisely adjusted to desired values.

[0023] The washing or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, contain 31.0 to 32.0 wt% 1,3-propanediol in the gel / gel phase, based on the total weight of the gel.

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

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

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

[0027] Surprisingly, it has been found that the addition of polyethylene glycols, particularly those with average molar masses of 200 to 600 g / mol, to at least one gel phase, especially in gel phases comprising polyvinyl alcohol, accelerates 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, as further processing of the solidified gel phases can be carried out much faster and therefore generally more cost-effectively. Surprisingly, it has been found that the presence of polyethylene glycol(s) with an average molar mass of 200 to 600 g / mol in combination with polyvinyl alcohol and / or its derivatives significantly contributes to reducing the solidification times to less than 1 minute, preferably less than 50 seconds, and particularly preferably less than 40 seconds.Without being bound to the theory, it is assumed that such polyethylene glycols, especially those with a molar mass of 350 to 450 g / mol, particularly those with a molar mass of 400 g / mol, increase the sol-gel temperature.

[0028] In a particularly preferred embodiment, component d) is polyethylene glycols, preferably polyethylene glycol(s) with an average molar mass of 200 to 600, in particular of 350 to 450 g / mol, for example around 400 g / mol, in an amount of 13.5 to 16.5 wt.%.

[0029] According to a further embodiment, in addition to the aforementioned polyethylene glycols with an average molar mass of 200 to 600 g / mol, further polyalkylene glycols, in particular further polyethylene glycols, with an average molar mass between approximately 800 and 8000 g / mol, can be contained in at least one gel phase. These polyethylene glycols are particularly preferably used in amounts of 1 to 10 wt.%, preferably 2 to 5 wt.%, preferably based on the total weight of the gel.

[0030] The gel also includes, as component c), glycerin in an amount of 25 - 28 wt.%, based on the total weight of the gel.

[0031] The gel is essentially anhydrous. This means that the gel is preferably essentially free of water. "Essentially free" here means that small amounts of water may be present in the gel phase. This water can be introduced into the phase, for example, through a solvent, as water of crystallization, or as a result of reactions between components of the phase. However, preferably only small amounts, and in particular no water, are used as a solvent for the preparation of the gel phase. The proportion of water in the gel phase is < 1 wt%, particularly 0.5 wt% or less, especially 0.1 wt% or 0.05 wt% or less. The values ​​given in wt% refer to the total weight of the gel.

[0032] According to a particularly preferred embodiment, the invention relates to washing or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, comprising a gel that is solid at room temperature (20 °C) and which, based on the total weight of the gel, a) 12.7 to 15.5 wt% PVOH, b) 30.5 to 33 wt%, in particular 31 to 32 wt% 1,3-propanediol, c) 25 to 28 wt% glycerol, d) 13.5 to 16.5 wt% polyethylene glycol(s) with an average molar mass of 200 to 600 g / mol, in particular of 350 to 450 g / mol, for example around 400 g / mol, and e) < 1 wt% water.

[0033] According to a particularly preferred embodiment, the invention relates to washing or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, comprising a gel that is solid at room temperature (20 °C) and which, based on the total weight of the gel, a) 12.7 to 15.5 wt% PVOH, b) 31 to 32 wt% 1,3-propanediol, c) 25 to 28 wt% glycerol, d) 13.5 to 16.5 wt% polyethylene glycol(s) with an average molar mass of 350 to 450 g / mol, for example around 400 g / mol, and e) < 1 wt% water contains.

[0034] These formulations exhibit particularly good flow properties during dosing and, at the same time, a conveniently short solidification time after dispensing and cooling, while also showing only minimal syneresis. This means that no significant amounts of liquid ingredients leak from the gel. Visible leakage of liquid from the gel ("sweating") makes the gel more difficult to handle. Consumers perceive this as both aesthetically unappealing and a quality defect. Depending on the gel's form of packaging, this seepage can also make it difficult to handle the gel safely.

[0035] Leakage of liquid from the gel should be avoided as much as possible, since in washing or cleaning agent portions, interactions can occur between the liquid and any ingredients contained in a further phase and / or a water-soluble coating. This can lead to aesthetically undesirable discoloration or the inactivation of sensitive ingredients, as well as the dissolution or softening of coatings or the water-soluble coating itself.

[0036] Preferably, less than 5 wt.%, preferably less than 3 wt.%, and in particular less than 1.5 wt.% of liquid escapes, based on the total weight of the gel, measured after one week of storage of the freshly cast gel at a temperature of 20 °C.

[0037] These and other aspects, features, and advantages of the invention will become apparent to the person skilled in the art upon studying the following detailed description and claims. Each feature from one aspect of the invention can be incorporated into any other aspect of the invention. Furthermore, it is understood that the examples contained herein are intended to describe and illustrate the invention, but do not limit it, and in particular, the invention is not limited to these examples. All percentages are weight percentages unless otherwise stated. Numerical ranges specified in the format "from x to y" include the stated values. If several preferred numerical ranges are specified in this format, it is understood that all ranges resulting from the combination of the different endpoints are also included.

[0038] "At least one," as used herein, means one or more, i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, or more. When referring to an ingredient, the statement refers to the type of ingredient and not the absolute number of molecules. Thus, "at least one bleach catalyst," for example, means at least one type of bleach catalyst, i.e., it could refer to one type of bleach catalyst or a mixture of several different bleach catalysts. When used with weight specifications, the statement refers to all compounds of the specified type contained in the composition / mixture, i.e., the composition contains no further compounds of that type beyond the specified quantity of the relevant compounds.

[0039] When reference is made to molar masses herein, these values ​​always refer to the number-mean molar mass Mn, unless explicitly stated otherwise. The number-mean molar mass can be determined, for example, by gel permeation chromatography (GPC) according to DIN 55672-1:2007-08 using THF as the eluent. The mass-mean molar mass Mw can also be determined by GPC, as described for Mn.

[0040] All percentages given in connection with the compositions described herein refer, unless explicitly stated otherwise, to wt%, in each case to the mixture or phase in question.

[0041] Furthermore, the gel must be stable under normal storage conditions. The gel phase according to the invention is a component of a washing or cleaning agent. Washing or cleaning agents are typically stored in a household for a certain period of time. Storage usually takes place near the washing machine or dishwasher. The gel should be stable for such storage. Therefore, the gel should remain stable even after a storage period of, for example, 4 to 12 weeks, particularly 10 to 12 weeks or longer, at temperatures up to 40°C, particularly at 30°C, particularly at 25°C, or at 20°C, and should not deform or otherwise change in consistency during this time.

[0042] If the gel and a solid, in particular a powder phase are in direct contact with each other, the gel penetrates preferably a maximum of 1 mm into the spaces of the immediately underlying powder phase during a storage period of 4 weeks at 25 °C.

[0043] A change in volume or shrinkage during storage would be disadvantageous, as this would reduce consumer acceptance of the product. Leakage of liquid or seepage of components from the gel phase is also undesirable. Here, too, the visual appearance is relevant. Leakage of liquid, such as solvents, can affect the stability of the gel phase, resulting in unstable components and thus potentially impacting the washing or cleaning effect.

[0044] The zinc salt preferably used according to the invention is water-soluble, meaning it has a solubility in water above 100 mg / l, preferably above 500 mg / l, particularly preferably above 1 g / l, and especially above 5 g / l (all solubilities at a water temperature of 20°C). 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 consisting of zinc acetate, zinc acetylacetonate, zinc PCA (zinc 5-oxopyrrolidine-2-carboxylate), zinc benzoate, zinc chloride, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, and zinc p-toluenesulfonate.

[0045] In a particularly preferred embodiment according to the invention, zinc chloride, zinc acetate or zinc sulfate, in particular anhydrous zinc salt (anhydrous), and especially preferably zinc acetate (anhydrous), is used as the water-soluble zinc salt.

[0046] The zinc salt is preferably present in the gel phase in an amount of 0.05 wt.% to 3 wt.%, particularly preferably in an amount of 0.1 wt.% to 2.4 wt.%, and especially in an amount of 0.2 wt.% to 1.0 wt.%, based on the total weight of the gel phase.

[0047] Zinc salts can also be present in any solid phase, preferably a particulate phase or in granular mixtures. In this case, the zinc salt is preferably present in the composition according to the invention in an amount of 0.01 wt.% to 5 wt.%, particularly preferably in an amount of 0.05 wt.% to 3 wt.%, and especially in an amount of 0.1 wt.% to 2 wt.%, based on the total weight of the washing or cleaning agent.

[0048] Besides their effect as glass corrosion inhibitors, zinc salts have surprisingly been found to stabilize the gel and improve its processability. A particular disadvantage arises when the gel becomes unprocessable shortly after preparation. If the gel becomes too viscous soon after production, it can no longer be dispensed in the usual way. Furthermore, yellowing of the gel is frequently observed, which is visually unappealing to the end consumer and leads them to perceive the product as "no longer fresh" or "no longer usable." This means that, in the production process, the gel must be freshly prepared only in small quantities and at short intervals to ensure its dispensing into the final product.In particular, the time window in which the gel can be processed (stand time) is significantly extended by the addition of the zinc salt.

[0049] Particularly preferably, washing or cleaning agents, preferably dishwashing detergents, especially machine dishwashing detergents, 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 5 wt.%, in particular 0.1 to 2.0 wt.%, most preferably 0.2 to 1.0 wt.%, based on the total weight of the gel.

[0050] According to a further preferred embodiment of the present invention, washing or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, which are formulated as washing or cleaning agent portions, preferably containing the active substances necessary for a cleaning cycle, contain as a total amount of the water-soluble zinc salts, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate, in the washing or cleaning agent portion, preferably 0.0004 to 0.5 g, more preferably 0.001 to 0.2 g, in particular 0.02 to 0.06 g.

[0051] This means that the individual portion of washing or cleaning agent used to carry out a single cleaning cycle, in particular when added to a cleaning cycle of a machine dishwasher, contains a total of 0.0005 to 1 g, preferably 0.01 to 0.5 g, in particular 0.02 to 0.06 g of water-soluble zinc salts, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate.

[0052] Particularly preferably, a single portion of washing or cleaning agent according to the invention, which is added in particular to a cleaning cycle of a mechanical dishwasher, contains a total of 0.001 to 0.5 g, in particular 0.02 to 0.05 g of water-soluble zinc salts, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate, based on the total amount of the washing or cleaning agent.

[0053] According to a particularly preferred embodiment, the invention relates to a washing or cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, comprising a gel that is solid at room temperature (20 °C) and which, based on the total weight of the gel, a) 12.7 to 15.5 wt% PVOH, b) 31 to 32 wt% 1,3-propanediol, c) 25 to 28 wt% glycerol, d) 13.5 to 16.5 wt% polyethylene glycol(s) with an average molar mass of 200 to 600 g / mol, in particular of 350 to 450 g / mol, for example around 400 g / mol, e) < 1 wt% water and f) 0.3 to 0.6 wt% of a zinc salt, preferably anhydrous zinc acetate.

[0054] According to a particularly preferred embodiment, the invention relates to a washing or cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, comprising a gel that is solid at room temperature (20 °C), which, based on the total weight of the gel, a) 12.7 to 15.5 wt% PVOH, b) 31 to 32 wt% 1,3-propanediol, c) 25 to 28 wt% glycerol, d) 13.5 to 16.5 wt% polyethylene glycol(s) with an average molar mass of 350 to 450 g / mol, for example around 400 g / mol, e) < 1 wt% water and f) 0.3 to 0.6 wt% of a zinc salt, preferably anhydrous zinc acetate.

[0055] The washing or cleaning agents, preferably dishwashing detergents, especially machine dishwashing detergents, are not films. Rather, they are formed bodies with a non-film-like thickness. They therefore have a layer thickness of at least 0.3 mm, preferably at least 0.7 mm, particularly at least 1.0 mm, and most preferably at least 1.2 mm. The layer thickness is measured in the plane of least extent.

[0056] The gel preferably comprises another anionic polymer, in particular polycarboxylates. These can act either as structural components and / or as thickening polymers. According to the invention, the gel can further comprise anionic polymers or copolymers with structural component properties. Preferably, this is a polycarboxylate. Preferably, an acrylate homopolymer and / or a copolymer polyacrylate, preferably a sulfopolymer, preferably a copolymer polysulfonate, or preferably a hydrophobically modified copolymer polysulfonate is used as the polycarboxylate. The copolymers can have two, three, four, or more different monomer units. Preferred copolymer polysulfonates contain, in addition to sulfonic acid group-containing monomer(s), at least one monomer from the group of unsaturated carboxylic acids.

[0057] According to a particularly preferred embodiment, the gel-like phase contains a polymer comprising at least one sulfonic acid group-containing monomer, preferably in addition to sulfonic acid group-containing monomer(s) at least one monomer from the group of unsaturated carboxylic acids.

[0058] Unsaturated carboxylic acids of the formula R 1< (R 2< )C=C(R 3< )COOH are particularly preferred as unsaturated carboxylic acid(s), in which R 1< to R 3< independently represent -H, -CH 3 , a straight-chain or branched saturated alkyl group with 2 to 12 carbon atoms, a straight-chain or branched, mono- or poly-unsaturated alkenyl group with 2 to 12 carbon atoms, alkyl or alkenyl groups substituted with -NH2, -OH or -COOH as defined above, or -COOH or -COOR 4< , where R 4< is a saturated or unsaturated, straight-chain or branched hydrocarbon group with 1 to 12 carbon atoms.

[0059] 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.

[0060] For 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 represent -H, -CH 3 , a straight-chain or branched saturated alkyl group with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl group with 2 to 12 carbon atoms, alkyl or alkenyl groups substituted with -NH 2 , -OH or -COOH, or -COOH or -COOR 4<, where R 4< is a saturated or unsaturated, straight-chain or branched hydrocarbon group with 1 to 12 carbon atoms, and X represents an optional spacer group selected from -(CH 2 ) n - with n = 0 to 4. -COO-(CH 2 ) k - with k = 1 to 6, -C(O)-NH-C(CH 3 ) 2 -, - C(O)-NH-C(CH 3 ) 2 -CH 2 - and -C(O)-NH-CH(CH 3 )-CH 2 -.

[0061] Among these monomers, preferred are those of the formulas H₂C=CH-X-SO₃H, H₂C=C(CH₃)-X-SO₃H, or HO₃SX-(R₆<)C=C(R₇<)-X-SO₃H, in which R₆< and R₇< are independently selected from -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, and -CH(CH₃)₂, and X represents an optional spacer group selected from -(CH₂)ₙ (n = 0 to 4), -COO-(CH₂)ₖ (k = 1 to 6), -C(O)-NH-C(CH₃)₂, -C(O)-NH-C(CH₃)₂, and -C(O)-NH-CH(CH₃)₂. )-CH 2 -.

[0062] According to a particularly preferred embodiment, the gel / gel phase contains a polymer comprising acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid as a sulfonic acid group-containing monomer.

[0063] Particularly preferred sulfonic acid group-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, metallylsulfonic acid, allyloxybenzenesulfonic acid, metallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, and mixtures of the aforementioned acids or their water-soluble salts. In the polymers, the sulfonic acid groups can be present wholly or partially in neutralized form, meaning that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and especially for sodium ions.The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

[0064] The monomer distribution of the copolymers preferably used according to the invention is, in the case of copolymers containing only carboxylic acid group-containing monomers and sulfonic acid group-containing monomers, preferably 5 to 95 wt.% each, and particularly preferably the proportion of the sulfonic acid group-containing monomer is 50 to 90 wt.% and the proportion of the carboxylic acid group-containing monomer is 10 to 50 wt.%, the monomers being preferably selected from those mentioned above. The molar mass of the sulfo copolymers preferably used according to the invention can be varied to adapt the properties of the polymers to the desired application. Preferred washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 g·mol⁻¹, preferably of 4000 to 25,000 g·mol⁻¹, and particularly of 5000 to 15,000 g·mol⁻¹.

[0065] In a further preferred embodiment, the copolymers comprise, in addition to a carboxyl group-containing monomer and a sulfonic acid group-containing monomer, at least one nonionic, preferably hydrophobic, monomer. The use of these hydrophobically modified polymers has particularly improved the rinsing performance of dishwashing detergents according to the invention.

[0066] The gel preferably further comprises an anionic copolymer, wherein the anionic copolymer is a copolymer comprising i) Monomers containing carboxylic acid groups ii) Monomers containing sulfonic acid groups iii) Non-ionic monomers, especially hydrophobic monomers is used.

[0067] Preferably, nonionic monomers of the general formula R 1< (R 2< )C=C(R 3< )-XR 4< are used, in which R 1< to R 3< independently represent -H, -CH 3 or - C 2 H 5, X represents an optional spacer group selected from -CH 2 -, - C(O)O- and -C(O)-NH-, and R 4< represents a straight-chain or branched saturated alkyl group with 2 to 22 carbon atoms or an unsaturated, preferably aromatic group with 6 to 22 carbon atoms.

[0068] Particularly favored nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4,4-trimethylpentene-1, 2,4,4-trimethylpentene-2,2,3-dimethylhexene-1, 2,4-diemethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4,4-dimethylhexane-1, ethylcyclohexyne, 1-octene, α-olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-Octadecene and C 22-α-olefin, 2-styrene, α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N-(methyl)acrylamide, 2-ethylhexyl acrylate, methacrylic acid 2-ethylhexyl acrylate, N-(2-ethylhexyl)acrylamide, octyl acrylateMethacrylic acid octyl ester, N-(octyl)acrylamide, acrylic acid lauryl ester, methacrylic acid lauryl ester, N-(lauryl)acrylamide, acrylic acid stearyl ester, methacrylic acid stearyl ester, N-(stearyl)acrylamide, acrylic acid behenyl ester, methacrylic acid behenyl ester and N-(behenyl)acrylamide or mixtures thereof, in particular acrylic acid, ethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and mixtures thereof.

[0069] Surprisingly, it has been shown that PVOH and / or its derivatives, together with anionic polymers or copolymers, particularly with copolymers containing sulfonic acid groups, lead to the formation of gel phases with insensitive surfaces. These surfaces can be touched by the end user without any material adhering to their hands. No material loss occurs even within packaging. Therefore, the gel preferably comprises PVOH, polyethylene glycol(s) with an average molar mass of 200 to 600 g / mol, glycerol, and an anionic copolymer / polymer. The proportion of the anionic polymer is preferably 0.5 wt.% to 20 wt.%, particularly 3 wt.% to 30 wt.%, especially 4 wt.% to 25 wt.%, preferably 5 wt.% to 20 wt.%, for example 10 wt.%, based on the total weight of the gel.Sulfopolymers, in particular the preferred copolymeric polysulfonates, which, in addition to sulfonic acid group-containing monomer(s) and at least one monomer from the group of unsaturated carboxylic acids, especially acrylic acid, also ensure an excellent surface gloss. Furthermore, fingerprints do not remain visible. Therefore, the proportion of sulfopolymers, in particular the preferred copolymeric polysulfonates, which, in addition to sulfonic acid group-containing monomer(s) and at least one monomer from the group of unsaturated carboxylic acids, especially acrylic acid, in the aforementioned sulfopolymers with AMPS as the sulfonic acid group-containing monomer, for example Acusol 590, Acusol 588 or Sokalan CP50, is preferably 1 wt.% to 25 wt.%, in particular 3 wt.% to 18 wt.%, particularly 4 wt.% to 15 wt.%, and preferably 5 wt.% to 12 wt.% based on the weight of the gel phase.In a particularly preferred embodiment, the gel therefore comprises PVOH as well as a sulfopolymer, in particular the preferred copolymeric polysulfonates, which, in addition to sulfonic acid group-containing monomer(s), contain at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, and at least one polyhydric alcohol.

[0070] According to a particularly preferred embodiment, the invention relates to a washing or cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, comprising a gel that is solid at room temperature (20 °C) and which, based on the total weight of the gel, a) 12.7 to 15.5 wt% PVOH, b) 31 to 32 wt% 1,3-propanediol, c) 25 to 28 wt% glycerol, d) 13.5 to 16.5 wt% polyethylene glycol(s) with an average molar mass of 200 to 600 g / mol, in particular of 350 to 450 g / mol, for example around 400 g / mol, e < 1 wt% water and f) 5 to 12 wt%, in particular of 7 to 10.5 wt% of a sulfonic acid group-containing polymer, preferably a polymer comprising at least one sulfonic acid group-containing monomer and at least one monomer from the group of unsaturated carboxylic acids, in particular a polyacrylate copolymer with AMPS as the sulfonic acid group-containing monomer, and g) And optionally 0.3 to 0.6 wt% of a zinc salt, preferably anhydrous zinc acetate.

[0071] According to a particularly preferred embodiment, the invention relates to a washing or cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, comprising a gel that is solid at room temperature (20 °C), which, based on the total weight of the gel, a) 12.7 to 15.5 wt% PVOH, b) 31 to 32 wt% 1,3-propanediol, c) 25 to 28 wt% glycerol, d) 13.5 to 16.5 wt% polyethylene glycol(s) with an average molar mass of 350 to 450 g / mol, for example around 400 g / mol, e) < 1 wt% water, f) 5 to 12 wt%, in particular 7 to 10.5 wt% of a sulfonic acid group-containing polymer, preferably a polymer comprising at least one sulfonic acid group-containing monomer and at least one monomer from the group of unsaturated carboxylic acids, in particular a polyacrylate copolymer with AMPS as the sulfonic acid group-containing monomer, and g) 0.3 to 0.6 wt% of a zinc salt, preferably anhydrous zinc acetate.

[0072] According to a further particularly preferred embodiment, the washing or cleaning agent, preferably dishwashing detergent, and especially machine dishwashing detergent, is a portion of washing or cleaning agent in a water-soluble coating with one or more chambers / compartments. The washing or cleaning agent is preferably packaged as a single-use cleaning agent portion, so that it is used to carry out one dishwasher cycle and is (largely) consumed in the process.

[0073] The water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer mixtures. The coating can be formed from one, two, or more layers of the water-soluble film material. The water-soluble film material of the first layer and any subsequent layers can be the same or different.

[0074] 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.

[0075] 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 of 10,000 to 1,000,000 gmol⁻¹, preferably from 20,000 to 500,000 gmol⁻¹, particularly preferably from 30,000 to 100,000 gmol⁻¹ and particularly from 40,000 to 80,000 gmol⁻¹.

[0076] Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, as a direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are produced from polyvinyl acetate copolymers. It is preferred that at least one layer of the water-soluble coating comprises a polyvinyl alcohol with a degree of hydrolysis of 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and especially 82 to 88 mol%.

[0077] In a preferred embodiment, the water-soluble packaging consists of at least 20 wt.%, particularly preferably at least 40 wt.%, most preferably at least 60 wt.% and particularly 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 particularly 82 to 88 mol%.

[0078] A polyvinyl alcohol-containing film material suitable for producing the water-soluble coating may additionally contain a polymer selected from the group comprising (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid, or mixtures of the aforementioned polymers. Polylactic acids are a preferred additional polymer.

[0079] 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. Also preferred are polyvinyl alcohol copolymers comprising, in addition to vinyl alcohol, an ethylene-unsaturated carboxylic acid, its salt, or its ester. Particularly preferred are such polyvinyl alcohol copolymers containing, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, or mixtures thereof.

[0080] It may be preferable for the film material to contain further additives. For example, the film material may contain plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, sorbitol, mannitol, or mixtures thereof. Other additives include, for example, release agents, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-adhesion agents, or mixtures thereof.

[0081] Suitable water-soluble films for use in the water-soluble outer layers of the water-soluble packaging according to the invention are films marketed by MonoSol LLC, for example, under the designations M8720, M8630, M8312, M8440, M7062, C8400, or M8900. Films marketed by Nippon Gohsei under the designations SH2601, SH2504, SH2707, or SH2701 are also suitable. Other suitable films include those designated Solublon®< PT, Solublon®< GA, Solublon®< KC, or Solublon®< KL by Aicello Chemical Europe GmbH, or the VF-HP films by Kuraray.

[0082] The water-soluble coating preferably comprises at least a portion of a bittering agent with a bitterness value between 1,000 and 200,000, in particular one 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 having a bitterness value between 1,000 and 200,000. In this context, it is particularly preferred that the water-soluble coating be coated with the bittering agent having a bitterness value between 1,000 and 200,000 to at least 50%, preferably at least 75%, and most preferably at least 90% of its surface area. The application of the bittering agent, with a bitterness value between 1,000 and 200,000, can be done, for example, by printing, spraying or coating.

[0083] According to the invention, the water-soluble coating preferably has at least one continuous circumferential sealing seam that lies essentially in one plane. This is advantageous from a process engineering perspective, since only a single sealing step, possibly using only a single sealing tool, is necessary for a circumferential sealing seam that lies essentially in one plane. The continuous circumferential sealing seam results in a better seal compared to coatings with multiple sealing seams and excellent sealing tightness of the seam and thus of the coating itself. Leakage of product from the coating, e.g., onto the surface of the portion, would be disadvantageous, as the consumer would then come into contact with the product. This is precisely what should be avoided as far as possible in a portion of washing or cleaning agents with a water-soluble coating.

[0084] The water-soluble packaging can preferably be made from at least two packaging parts. Preferably, the at least two packaging parts are water-soluble so that no packaging fragments remain in the dishwasher, which could then cause problems. It is not necessary for the at least two packaging parts to be different. They can preferably be made of 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 with the same composition.

[0085] In another embodiment, the at least two packaging parts can be made of different materials, e.g., different films or materials with two different properties (e.g., hot-water and cold-water-soluble film). In this embodiment, it is preferred that a water-soluble film and another packaging part produced by injection molding are combined.

[0086] 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 the application of a vacuum), blow molding, or stamping. In particular, the water-soluble coating comprises at least one at least partially plastically deformed film produced by deep drawing.

[0087] A preferred object of the present invention is a washing or cleaning agent, preferably a dishwashing detergent, in particular a machine dishwashing detergent, which additionally comprises at least one solid, in particular particulate, phase and optionally at least one further liquid / gel-like or solid phase.

[0088] The at least one solid phase and the at least one gel can be arranged within the water-soluble coating in any combination. For example, a solid phase can be arranged on top of or next to a gel phase. In this embodiment, the washing or cleaning agent according to the invention, preferably a dishwashing detergent, particularly a machine dishwashing detergent, comprises a solid phase and a gel phase or gel. It is also conceivable that a solid phase is surrounded by gel phases. Embedding one phase in another is also included according to the invention. In a further, particularly preferred arrangement, the gel is in cast form, for example, in the form of a gel core surrounded by a solid phase. Two or more separate cavities can also be present, which are filled with the at least one gel phase.In this embodiment, the washing or cleaning agent comprises two gel phases, wherein the two gel phases may have different compositions.

[0089] According to a preferred embodiment, 3, 4, 5, or 6 or more separate cavities are provided, which are filled with one or more of the gel phases. Preferably, such washing or cleaning agents comprise 3, 4, 5, or 6 or more gel phases, wherein these gel phases may have the same or different compositions.

[0090] In this context, "solid" means that the composition exists in solid form under standard conditions (temperature 25°C, pressure 1013 mbar). Suitable solid phases include granular mixtures of a solid composition, such as powders and / or granules, particularly powdered phases. Also suitable according to the invention are solid compositions / phases that exhibit increased dimensional stability compared to loose powder, for example, powder or granule preparations that have been compacted by compression before or after being enclosed in the film, e.g., by the film's restoring forces after deep drawing, or directly compressed compositions such as tablets or tablets. This at least one solid phase can be in direct contact with the gel-like phase.According to the invention, portions of washing or cleaning agents, in particular multi-chamber pouches, are further described as follows: the solid phase and the gel phase are spatially close to, but separate from, each other. The two chambers can be separated, for example, by a film, in particular a water-soluble film, or by a seal (preferably a seal of 3 mm or less). Therefore, according to the invention, chambers of a multi-chamber pouch can be arranged both one above the other and side by side. Furthermore, mixtures of single- or multi-chamber pouches, comprising a gel-like phase according to the invention and at least one solid phase separately, which come into contact by arrangement, e.g., by folding and fixing a pouch, or by storage at a distance of less than 3 mm, for example, in a packaging bag or a device for portioned dosing, are also described according to the invention.

[0091] In the context of the present invention, a powdered phase is understood to be a granular mixture composed of a multitude of loose, solid particles, which in turn comprise so-called granules. According to the invention, the term powdered phase includes powders and / or granules as defined below.

[0092] A grain is a term used to describe the particulate components of powders (grains being the loose, solid particles), dusts (grains being the loose, solid particles), granules (loose, solid particles being agglomerates of several grains), and other granular mixtures. A preferred embodiment of the granular mixture in the composition of the solid phase is the powder and / or the granules. The terms "powder" and "granules" used here also include mixtures of different powders or different granules. Similarly, "powder" and "granules" also refer to mixtures of different powders with different granules. The said solid particles of the granular mixture preferably have a particle diameter X 50,3 (volume mean) 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. The granular mixture of the solid composition of the present invention, serving as the solid phase, is preferably in free-flowing form (particularly preferably as free-flowing powder and / or free-flowing granules). The component of the portion according to the invention thus comprises at least one solid phase of a free-flowing, granular mixture of a solid composition, in particular a powder, and at least one gel phase defined as above.

[0093] A particularly preferred object of the present invention is washing or cleaning agents, in particular portions of washing or cleaning agents, special portions of machine dishwashing detergent, in which the gel / the gel phase is in direct contact, for example in a chamber, with which at least one solid, preferably granular, phase is contained.

[0094] Furthermore, it is preferred that the at least one solid phase and the at least one gel are in direct contact with each other. In this case, there should be no negative interaction between the solid phase and the gel phase. No negative interaction here means, for example, that no ingredients or solvents migrate from one phase to the other, or that the stability, in particular storage stability, preferably at a storage temperature of 30 °C for 4 weeks, and / or the aesthetics of the product are not impaired in any way, for example, by color changes, the formation of moist-looking edges, a blurring of the boundary between the two phases, or similar issues.

[0095] The at least one solid phase of the present invention comprises a granular mixture of a solid composition, in particular in powdery and free-flowing form. The washing or cleaning agent according to the invention thus comprises at least one solid, powdery, and free-flowing phase, as well as at least one gel phase comprising at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate, and at least one polyvinyl alcohol, as a gelling agent at least PVOH and / or its derivatives, in particular preferably at least PVOH, as well as glycerin.

[0096] The free-flowing property of a granular mixture, in particular a powdered solid, the powdered phase, preferably the powder and / or granules, relates to its ability to flow freely under its own weight. The free-flowing property is determined by measuring the discharge time of 1000 ml of washing or cleaning agent powder from a standardized, initially closed, flow test funnel with a 16.5 mm diameter outlet. This is done by measuring the time for the complete discharge of the granular mixture, in particular the powdered phase, preferably the powder and / or granules (e.g., the powder), after the outlet has been opened. The discharge rate (in seconds) is then compared to the discharge rate (in seconds) of a standard test sand, whose discharge rate is defined as 100%. The defined sand mixture used to calibrate the flow test apparatus is dry sea sand.Sea sand with a particle diameter of 0.4 to 0.8 mm is used, available, for example, from Carl Roth, Germany, CAS No. [14808-60-7]. For drying, the sea sand is dried for 24 hours at 60 °C in a drying oven on a plate with a maximum layer thickness of 2 cm before measurement.

[0097] Preferred embodiments of the solid phases according to the invention have an angle of repose / slope angle of 26 to 35°, of 27 to 34°, and of 28 to 33°, wherein the angle of repose is determined according to the method described below after 24 hours following the production of the granular mixture of the solid composition, in particular the powdered solid phase, preferably the powder and / or granules, and storage at 20°C. Such angles of repose have the advantage that the filling of the cavities with the at least one solid, preferably granular, phase can be carried out relatively quickly and precisely.

[0098] To determine the angle of repose (or angle of slope) of at least one solid, preferably granular, phase, a powder hopper with a capacity of 400 ml and a 25 mm diameter outlet is suspended vertically in a stand. The hopper is raised at a speed of 80 mm / min using a manually operated knurled wheel, causing the granular mixture, particularly the powdered phase, preferably the powder and / or granules, to trickle out. This forms a so-called cone of repose. The height and diameter of the cone are determined for each solid phase. The angle of repose is then calculated by multiplying the cone height by the cone diameter by 100.

[0099] Particularly suitable are granular mixtures of a solid composition, especially powdered phases, preferably powders and / or granules, e.g., powders exhibiting a free-flowing capacity relative to the aforementioned standard test substance of greater than 40%, preferably greater than 50%, particularly greater than 55%, particularly preferably greater than 60%, and particularly preferably between 63% and 80%, for example, between 65% and 75%. Particularly suitable are granular mixtures of a solid composition, especially powders and / or granules exhibiting a free-flowing capacity relative to the aforementioned standard test substance of greater than 40%, preferably greater than 45%, particularly greater than 50%, particularly preferably greater than 55%, and particularly preferably greater than 60%, wherein the free-flowing capacity is measured 24 hours after the powder has been produced and stored at 20°C.

[0100] Lower flowability values ​​are generally unsuitable, as precise dosing of the granular mixture, particularly the powdered phase, preferably the powder and / or granules, is necessary from a process engineering perspective. Values ​​greater than 50%, especially greater than 55%, and preferably greater than 60% (where flowability is measured 24 hours after powder production and storage at 20°C) have proven particularly advantageous. This is because the good dosing properties of the granular mixture, especially the powdered phases, preferably the powder and / or granules, result in only minor fluctuations in the dosed quantity or composition. More precise dosing leads to consistent product output, thus avoiding economic losses due to overdosing.Furthermore, it is advantageous that the granular mixtures, especially the powdered phase, preferably the powder and / or granules, e.g., the powder, are easily dosable, thus achieving a faster dosing process. Moreover, such good flowability better prevents the granular mixture, especially the powdered phase, preferably the powder and / or granules, e.g., the powder, from coming into contact with the part of the water-soluble coating intended for the formation of the seal, which should therefore remain as free of granules, and especially powder, as possible.

[0101] The granular mixture serving as the solid phase of the solid composition of the present invention is preferably in free-flowing form (particularly preferably as a free-flowing powder and / or free-flowing granules). The component of the portion according to the invention thus preferably comprises at least one solid phase of a free-flowing, granular mixture of a solid composition, in particular a powder, and at least one previously defined gel or gel phase.

[0102] The washing or cleaning agent according to the invention, preferably a dishwashing detergent, particularly a machine dishwashing detergent, preferably comprises at least one surfactant. This surfactant is selected from the group consisting of anionic, nonionic, and cationic surfactants. The washing or cleaning agent according to the invention may also contain mixtures of several surfactants selected from the same group.

[0103] According to the invention, the at least one solid, preferably granular, phase and / or the gel comprise at least one surfactant. It is possible that only the at least one solid, preferably granular, phase or only the gel comprise at least one surfactant. If both phases comprise a surfactant, these are preferably different surfactants. However, it is also possible that the solid and gel phases contain the same surfactant or surfactants. According to the invention, the at least one solid and / or gel phase preferably contains at least one nonionic surfactant. Any nonionic surfactant known to those skilled in the art can be used.Preferably, low-foaming non-ionic surfactants are used, in particular alkoxylated, especially ethoxylated, low-foaming non-ionic surfactants, such as alkyl glycosides, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, polyhydroxy fatty acid amides, or amine oxides. Particularly preferred non-ionic surfactants are specified in more detail below.

[0104] Preferred alcohol ethoxylates exhibit a narrow range of homologs (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohols with 14 EO, 25 EO, 30 EO, or 40 EO.

[0105] Ethoxylated niotenes obtained from C6-20 monohydroxyalkanols, C6-20 alkylphenols, or C16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles, and particularly more than 20 moles of ethylene oxide per mole of alcohol are particularly preferred. A particularly preferred niotene is obtained from a straight-chain fatty alcohol with 16 to 20 carbon atoms (C16-20 alcohol), preferably a C18 alcohol, and at least 12 moles, preferably at least 15 moles, and particularly at least 20 moles of ethylene oxide. Among these, the so-called "narrow-range ethoxylates" are particularly preferred.

[0106] Preferred surfactants come from the groups of alkoxylated niotonic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) niotonic surfactants are also characterized by good foam control.

[0107] Particularly preferred niotenes for low-foaming niotenes within the scope of the present invention have proven to be those comprising alternating ethylene oxide and alkylene oxide units. Among these, surfactants with EO-AO-EO-AO blocks are preferred, wherein one to ten EO or AO groups are bonded together before a block of the other groups follows. Here, nonionic surfactants of the general formula are used. preferably, in which R 1< represents a straight-chain or branched, saturated or, in particular, polyunsaturated C 6-24 -alkyl or -alkenyl group; each group R 2< or R 3< is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH(CH 3 ) 2 and the indices w, x, y, z independently represent integers from 1 to 6.

[0108] Preferred niotenes of the above formula can be prepared from the corresponding alcohols R1-OH and ethylene or alkylene oxide by known methods. The R1 group in the above formula can vary depending on the origin of the alcohol. If native sources are used, the R1 group has an even number of carbon atoms and is generally unbranched, with linear groups from native alcohols with 12 to 18 carbon atoms, for example, from coconut, palm, tallow, or oleyl alcohol, being preferred. Alcohols accessible from synthetic sources include, for example, the Guerbet alcohols or methyl-branched groups at the 2-position, or linear and methyl-branched groups in the mixture, as are commonly found in oxo alcohol groups.Regardless of the type of alcohol used to produce the niotenes contained in the agents, niotenes are preferred in which R 1< in the above formula represents an alkyl group with 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and particularly 9 to 11 carbon atoms.

[0109] In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit, which alternates with the ethylene oxide unit in the preferred niotenes. However, other alkylene oxides are also suitable, where R2 and R3 are independently selected from -CH2CH2-CH3 or -CH(CH3)2, respectively. Niotenes of the above formula are preferably used, where R2 and R3 represent a residue of -CH3, w and x independently represent values ​​of 3 or 4, and y and z independently represent values ​​of 1 or 2.

[0110] Other preferably used non-ionic surfactants of the solid phase are non-ionic surfactants of the general formula R 1< O(AlkO) x M(OAlk) y OR 2< , where R 1< and R 2< independently represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl group with 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl group with 2 to 4 carbon atoms; x and y independently represent values ​​between 1 and 70; and M represents an alkyl group from the group CH 2 , CHR 3< , CR 3< R 4< , CH 2 CHR 3< and CHR 3< CHR 4< , where R 3< and R 4< independently represent a branched or unbranched, saturated or unsaturated alkyl group with 1 to 18 carbon atoms.

[0111] Preferably nonionic surfactants of the general formula R 1< -CH(OH)CH 2 -O(CH 2 CH 2 O) x CH 2 CHR(OCH 2 CH 2 ) y -CH 2 CH(OH)-R 2< , where R, R 1< and R 2< independently represent an alkyl or alkenyl group with 6 to 22 carbon atoms; x and y independently represent values ​​between 1 and 40.

[0112] Particularly preferred are compounds of the general formula R1 -CH(OH)CH2 -O(CH2CH2O)xCH2CHR(OCH2CH2)yO-CH2CH(OH)-R2, in which R represents a linear, saturated alkyl group with 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently have values ​​of 20 to 30. Such compounds can be obtained, for example, by reacting alkyldiols HO-CHR-CH2-OH with ethylene oxide, followed by a reaction with an alkyl epoxide to seal the free OH groups and form a dihydroxy ether.

[0113] Preferred nonionic surfactants are those of the general formula R 1< -CH(OH)CH 2 O-(AO) w -(AO) x -(A"O) y -(A‴O) z -R 2< , in which R 1< represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl residue; R 2< represents hydrogen or a linear or branched hydrocarbon residue with 2 to 26 carbon atoms; A, A', A" and A‴ independently represent a residue from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH(CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH(CH 3 )-CH 2 -, -CH 2 -CH(CH 2 -CH 3 ), w, x, y and z represent values ​​between 0.5 and 120, where x, y and / or z can also be 0.

[0114] By adding the aforementioned non-ionic surfactants of the general formula R 1< -CH(OH)CH 2 O-(AO) w -(A'O) x -(A"O) y -(A‴O) z -R 2< , hereinafter also referred to as "hydroxy mixed ether", 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 containing alternative non-ionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

[0115] The use of these non-ionic surfactants with one or more free hydroxyl groups on one or both terminal alkyl groups can significantly improve the stability of the enzymes contained in the washing or cleaning agent preparations according to the invention.

[0116] Particularly preferred are end-group-capped poly(oxyalkylated) niosurfactants which, according to the following formula In addition to a residue R1<, which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, the compound further comprises a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residue R2< with 1 to 30 carbon atoms, where n represents values ​​between 1 and 90, preferably values ​​between 10 and 80, and particularly values ​​between 20 and 60. Surfactants of the above formula in which R1< represents C7 to C13, n represents a natural number from 16 to 28, and R2< represents C8 to C12 are particularly preferred.

[0117] Particularly preferred are surfactants of the formula R1< O[CH2CH(CH3)O] x [CH2CH2O] y CH2CH(OH)R2< , where R1< represents a linear or branched aliphatic hydrocarbon residue with 4 to 18 carbon atoms or mixtures thereof, R2< represents a linear or branched hydrocarbon residue with 2 to 26 carbon atoms or mixtures thereof, and x represents values ​​between 0.5 and 1.5 and y represents a value of at least 15. Examples of these nonionic surfactants include the C2-26 fatty alcohol (PO)1-(EO)15-40-2-hydroxyalkyl ethers, and in particular the C8-10 fatty alcohol (PO)1-(EO)22-2-hydroxydecyl ethers.

[0118] Particularly preferred are end-group-capped poly(oxyalkylated) niotenes of the formula R 1< O[CH 2 CH 2 O] x [CH 2 CH(R 3< )O] y CH 2 CH(OH)R 2< , in which R 1< and R 2< independently represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon residue with 2 to 26 carbon atoms, R 3< is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3, -CH(CH 3 ) 2 , preferably, however, represents -CH 3, and x and y independently represent values ​​between 1 and 32, wherein niotenes with R 3< = -CH 3 and values ​​for x from 15 to 32 and y from 0.5 and 1.5 are particularly preferred.

[0119] Other preferably usable niotenes are the end-capped poly(oxyalkylated) niotenes of the formula R 1< O[CH 2 CH(R 3< )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2< , in which R 1< and R 2< represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues with 1 to 30 carbon atoms, R 3< represents H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl residue, x represents values ​​between 1 and 30, k and j represent values ​​between 1 and 12, preferably between 1 and 5.

[0120] If the value x > 2, each R 3< in the formula above R 1< O[CH 2 CH(R 3< )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2< can be different. R 1< and R 2< are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues with 6 to 22 carbon atoms, residues with 8 to 18 carbon atoms being particularly preferred. For the residue R 3<, H, -CH 3 or -CH 2 CH 3 are particularly preferred. Particularly preferred values ​​for x are in the range of 1 to 20, especially from 6 to 15.

[0121] As described above, each R3< in the formula above can be different if x > 2. This allows the alkylene oxide unit within the square brackets to be varied. For example, if x represents 3, the R3< group can be chosen to form ethylene oxide (R3<= H) or propylene oxide (R3<= CH3) units, which can be joined together in any order, such as (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO), and (PO)(PO)(PO). The value 3 for x is chosen here as an example and can certainly be larger, with the range of variation increasing with increasing x values ​​and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa.

[0122] Particularly preferred end-capped poly(oxyalkylated) alcohols of the formula above have values ​​of k = 1 and j = 1, so that the above formula simplifies to R1< O[CH2CH(R3< )O] x CH2CH(OH)CH2OR2<. In the latter formula, R1<, R2<, and R3< are defined as above, and x represents numbers from 1 to 30, preferably from 1 to 20, and particularly from 6 to 18. Surfactants in which the R1< and R2< substituents have 9 to 14 carbon atoms, R3< represents hydrogen, and x takes on values ​​from 6 to 15 are particularly preferred. Finally, the nonionic surfactants of the general formula R1< -CH(OH)CH2O-(AO) w -R2< have proven to be particularly effective, in which R 1< represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or -alkenyl residue; R 2< represents a linear or branched hydrocarbon residue with 2 to 26 carbon atoms; A represents a residue from the group CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH(CH 3 ), preferably for CH 2 CH 2 , and w represents values ​​between 1 and 120, preferably 10 to 80, in particular 20 to 40.

[0123] Examples of these non-ionic surfactants include the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.

[0124] Preferably, the at least one solid and / or the gel 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 is preferably 0.5 wt.% to 30 wt.%, preferably 5 wt.% to 25 wt.% and in particular 10 wt.% to 20 wt.%.

[0125] In a further preferred embodiment, the non-ionic surfactant of the solid and / or gel phase is selected from non-ionic surfactants of the general formula R 1< -O(CH 2 CH 2 O) x CR 3< R 4< (OCH 2 CH 2 ) y OR 2< , in which R 1< and R 2< independently represent an alkyl or alkenyl group with 4 to 22 carbon atoms; R 3< and R 4< independently represent H or an alkyl or alkenyl group with 1 to 18 carbon atoms; and x and y independently represent values ​​between 1 and 40.

[0126] Particularly preferred are 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< stand for H and the indices x and y independently take values ​​from 1 to 40, preferably from 1 to 15.

[0127] Particularly preferred are 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 R 1< and R 2< groups are independently saturated alkyl groups with 4 to 14 carbon atoms and the indices x and y independently take values ​​of 1 to 15 and in particular of 1 to 12.

[0128] Compounds of the general formula R 1< -O(CH 2 CH 2 O) x CR 3< R 4< (OCH 2 CH 2 ) y OR 2< are also preferred, in which one of the residues R 1< and R 2< is branched.

[0129] Compounds of the general formula R 1< -O(CH 2 CH 2 O) x CR 3< R 4< (OCH 2 CH 2 ) y OR 2< are particularly preferred, in which the indices x and y independently take values ​​from 8 to 12.

[0130] The specified carbon chain lengths and degrees of ethoxylation or alkoxylation of the niotenes represent statistical averages, which may be whole numbers or fractions for a specific product. Due to the manufacturing processes, commercial products of the aforementioned formulas usually do not consist of a single individual compound, but rather of mixtures. This can result in average values ​​for both the carbon chain lengths and the degrees of ethoxylation or alkoxylation, and consequently, fractions.

[0131] Of course, the aforementioned non-ionic surfactants (niotenes) can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.

[0132] Particularly preferred in the at least one solid phase are nonionic surfactants having a melting point above room temperature. Nonionic surfactant(s) with a melting point above 20°C, preferably above 25°C, particularly preferably between 25 and 60°C, and especially between 26.6 and 43.3°C, is / are particularly preferred.

[0133] Suitable nonionic surfactants with melting or softening points within the specified temperature range include, for example, low-foaming nonionic surfactants that can be solid or highly viscous at room temperature. If nonionic surfactants that are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pa·s, preferably above 35 Pa·s, and particularly above 40 Pa·s. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.

[0134] The niotenoid, which is solid at room temperature, preferably contains propylene oxide (PO) units in the molecule. Preferably, such PO units constitute up to 25 wt.%, particularly preferably up to 20 wt.%, and especially up to 15 wt.% of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols that additionally contain polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol portion of such niotenoid molecules preferably constitutes more than 30 wt.%, particularly preferably more than 50 wt.%, and especially more than 70 wt.% of the total molar mass of such niotenoids. Preferred compositions are characterized in that they contain ethoxylated and propoxylated niotenoids in which the propylene oxide units constitute up to 25 wt.%, preferably up to 20 wt.%, and especially up to 15 wt.% of the total molar mass of the nonionic surfactant.

[0135] Further niotenes, particularly preferred for use in the solid phase and with melting points above room temperature, contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend comprising 75 wt% of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol ethylene oxide and 44 mol propylene oxide, and 25 wt% of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 mol ethylene oxide and 99 mol propylene oxide per mol trimethylolpropane.

[0136] In a preferred embodiment, the weight fraction of the non-ionic surfactant in relation to the total weight of the solid phase(s) is 0.1 to 20 wt.%, particularly preferably 0.5 to 15 wt.%, and especially 2.5 to 10 wt.%.

[0137] In a preferred embodiment, the weight fraction of the non-ionic surfactant in relation to the total weight of the gel phase(s) is 0.1 to 20 wt.%, particularly preferably 0.5 to 15 wt.%, and especially 2.5 to 10 wt.%.

[0138] According to a particularly preferred embodiment, the invention relates to a washing or cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, comprising a gel that is solid at room temperature (20 °C) and which, based on the total weight of the gel, a) 12.7 to 15.5 wt% PVOH, b) 31 to 32 wt% 1,3-propanediol, c) 25 to 28 wt% glycerol, d) 13.5 to 16.5 wt% polyethylene glycol(s) with an average molar mass of 200 to 600 g / mol, in particular of 350 to 450 g / mol, for example around 400 g / mol, e) < 1 wt% water, and f) 0.4 to 2.3 wt%, particularly preferably 0.5 to 1.5 wt% nonionic surfactant(s), g) 5 to 12 wt%, in particular 7 to 10.5 wt% of a sulfonic acid group-containing polymer, preferably a polymer comprising at least one sulfonic acid group-containing monomer and at least one monomer from the group of unsaturated carboxylic acids, in particular a polyacrylate copolymer with AMPS as sulfonic acid group-containing monomer, as well as h) And optionally 0.3 to 0.6 wt.% of a zinc salt, preferably anhydrous zinc acetate.

[0139] According to a particularly preferred embodiment, the invention relates to a washing or cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, comprising a gel that is solid at room temperature (20 °C), which, based on the total weight of the gel, a) 12.7 to 15.5 wt% PVOH, b) 31 to 32 wt% 1,3-propanediol, c) 25 to 28 wt% glycerol, d) 13.5 to 16.5 wt% polyethylene glycol(s) with an average molar mass of 350 to 450 g / mol, for example around 400 g / mol, e) < 1 wt% water, and f) 0.5 to 1.5 wt% nonionic surfactant(s), g) Optionally 5 to 12 wt%, in particular 7 to 10.5 wt%, of a sulfonic acid group-containing polymer, preferably a polymer comprising at least one sulfonic acid group-containing monomer and at least one monomer from the group of unsaturated carboxylic acids, in particular a polyacrylate copolymer with AMPS as the sulfonic acid group-containing monomer, and h) And optionally 0.3 to 0.6 wt% of a Zinc salt, preferably anhydrous zinc acetate.

[0140] All anionic surfactants are suitable for use in these products. These are characterized by a water-soluble anionic group, such as a carboxylate, sulfate, or sulfonate group, and a lipophilic alkyl group with approximately 8 to 30 carbon atoms. The molecule may also contain glycol or polyglycol ether groups, ester, ether, and amide groups, as well as hydroxyl groups. Suitable anionic surfactants are preferably in the form of sodium, potassium, and ammonium salts, as well as mono-, di-, and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group. However, zinc, manganese(II), magnesium, calcium, or mixtures thereof can also serve as counterions. 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.

[0141] Instead of or in combination with the surfactants mentioned, cationic and / or amphoteric surfactants, such as betaines or quaternary ammonium compounds, can also be used. However, it is preferred that no cationic and / or amphoteric surfactants are used.

[0142] Surfactants influence the opacity of the gel phase. In another embodiment, the gel is therefore free of nonionic surfactants, in particular free of surfactants. "Free of" means that the gel contains less than 1.0 wt% and in particular less than 0.1 wt%, preferably no surfactant or no nonionic surfactant.

[0143] Preferred washing or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, are further characterized in that they contain less than 1.0 wt.% and in particular less than 0.1 wt.%, preferably no anionic surfactant, in the at least one solid and / or the at least one gel phase, in particular in the solid phase.

[0144] According to a particularly preferred embodiment, the washing or cleaning agents according to the invention, especially the machine dishwashing detergents, are characterized in that the gel comprises less than 1 wt.%, in particular less than 0.5 wt.%, in particular less than 0.1 wt.% anionic surfactant, in each case based on the total weight of the gel. Preferably, the gel is substantially free of anionic surfactants. Substantially free means that the gel contains less than 0.05 wt.% anionic surfactant, in each case based on the total weight of the gel.

[0145] In this context, it has been shown that the presence of 1 wt% anionic surfactant in at least one gel phase leads to poorer foaming and rinsing properties of the overall composition. Furthermore, higher amounts of anionic surfactants negatively affect curing. According to a particularly preferred embodiment, the gel contains less than 1 wt%, preferably less than 0.5 wt%, and especially less than 0.05 wt% fatty acid salts or soaps.

[0146] According to another embodiment, the gel can contain sugars. According to the invention, sugars include sugar alcohols, monosaccharides, disaccharides, and oligosaccharides. In a preferred embodiment, the gel comprises at least one sugar alcohol other than glycerol, preferably at least one monosaccharide or disaccharide sugar alcohol. Mannitol, isomalt, lactitol, sorbitol, threitol, erythritol, arabitol, and xylitol are particularly preferred. Pentitols and / or hexitols are particularly preferred monosaccharide sugar alcohols. Xylitol and / or sorbitol are especially preferred.

[0147] In another embodiment, the gel can comprise disaccharides, in particular sucrose. The proportion of sucrose is 0 wt.% to 30 wt.%, in particular 5 wt.% to 25 wt.%, and most preferably 10 wt.% to 20 wt.%, based on the weight of the gel phase. In higher quantities, the sugar does not dissolve completely in the gel phase and leads to clouding. By using sugar, in particular in a proportion of 10 wt.% to 5 wt.% to 15 wt.%, moisture development is reduced and thus the adhesion to the at least one solid, preferably particulate, phase is improved.

[0148] The use of builder substances (structural materials) such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids, and mixtures of these substances, preferably water-soluble builder substances, can be advantageous.

[0149] In a particularly preferred embodiment according to the invention, the use of phosphates (including polyphosphates) is largely or completely omitted. In this embodiment, the composition preferably contains less than 5 wt.%, more preferably less than 3 wt.%, and particularly less than 1 wt.% phosphate(s). Most preferably, in this embodiment, the composition is completely phosphate-free, i.e., it contains less than 0.1 wt.% phosphate(s).

[0150] The framework materials include, in particular, carbonates, citrates, phosphonates, organic framework materials, and silicates. The weight fraction of the total framework materials in the total weight of the composition according to the invention is preferably 15 to 80 wt.% and particularly 20 to 70 wt.%.

[0151] Suitable organic framework materials according to the invention are, for example, polycarboxylic acids (polycarboxylates) that can be used in the form of their sodium salts. Polycarboxylic acids are understood to be those carboxylic acids that carry more than one, in particular two to eight, preferably two to six, in particular two, three, four, or five acid functions in the entire molecule. Dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, and pentacarboxylic acids, in particular di-, tri-, and tetracarboxylic acids, are thus preferred as polycarboxylic acids. The polycarboxylic acids may also carry further 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, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids such as nitrilotriacetic acid (NTA), glutamine-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.

[0152] Other suitable organic framework materials include polymeric polycarboxylates (organic polymers with a large number of carboxylate functional groups in the macromolecule, especially more than ten), polyaspartates, polyacetals and dextrins.

[0153] In addition to their building block effect, free acids typically also possess the property of an acidifying component. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixtures thereof are particularly noteworthy in this regard.

[0154] Particularly preferred washing or cleaning agents according to the invention, especially dishwashing detergents, preferably machine dishwashing detergents, contain one or more salts of citric acid, i.e., citrates, as one of their essential building blocks. These are preferably contained in a proportion of 2 to 40 wt.%, particularly 5 to 30 wt.%, particularly 7 to 28 wt.%, particularly preferably 10 to 25 wt.%, and most preferably 15 to 20 wt.%, in each case based on the total weight of the agent.

[0155] Particularly preferred is the use of carbonate(s) and / or hydrogen carbonate(s), preferably alkali carbonate(s), particularly preferably sodium carbonate (soda), in amounts of 2 to 50 wt.%, preferably 4 to 40 wt.% and particularly 10 to 30 wt.%, most preferably 10 to 24 wt.%, in each case based on the weight of the agent.

[0156] Particularly preferred washing or cleaning agents according to the invention, especially dishwashing detergents, preferably machine dishwashing detergents, are characterized in that they contain at least two builder materials from the group consisting of silicates, phosphonates, carbonates, aminocarboxylic acids, and citrates, wherein the weight fraction of these builder materials, based on the total weight of the washing or cleaning agent according to the invention, is preferably 5 to 70 wt.%, preferably 15 to 60 wt.%, and particularly 20 to 50 wt.%. The combination of two or more builder materials from the aforementioned group has proven advantageous for the cleaning and rinsing performance of washing or cleaning agents according to the invention, especially dishwashing detergents, preferably machine dishwashing detergents. In addition to the builder materials mentioned here, one or more other builder materials may also be included.

[0157] Preferred washing or cleaning agents, in particular dishwashing detergents, preferably machine 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, wherein the amount of carbonate is preferably 5 to 40 wt.%, in particular 10 to 35 wt.%, most preferably 15 to 30 wt.%, and the amount of citrate is preferably 5 to 35 wt.%, in particular 10 to 25 wt.%, most preferably 15 to 20 wt.%, each based on the total amount of the washing or cleaning agent, wherein the total amount of these two builders is preferably 20 to 65 wt.%, in particular 25 to 60 wt.%, more preferably 30 to 50 wt.%. Furthermore, one or more additional builders may be included.

[0158] The washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably machine dishwashing detergents, may contain, as a further building block, in particular phosphonates, insofar as permitted by regulations. A hydroxyalkane and / or aminoalkane phosphonate is preferably used as the phosphonate compound. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance.

[0159] Significance. Suitable aminoalkane phosphonates include preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and their higher homologs. Phosphonates are present in compositions according to the invention, to the extent permitted by regulations, preferably in amounts of 0.1 to 10 wt.%, particularly in amounts of 0.5 to 8 wt.%, and most preferably in amounts of 2.5 to 7.5 wt.%, in each case based on the total weight of the composition.

[0160] The combined use of citrate, (hydrogen) carbonate, and phosphonate is particularly preferred. These can be used in the quantities mentioned above. In particular, this combination uses amounts of 10 to 25 wt% citrate, 10 to 30 wt% carbonate (or hydrogen carbonate), and 2.5 to 7.5 wt% phosphonate, each based on the total weight of the product.

[0161] Further particularly preferred washing or cleaning agents, especially dishwashing detergents, preferably machine dishwashing detergents, are characterized in that, in addition to citrate and (hydrogen) carbonate and optionally phosphonate, they contain at least one further phosphorus-free structural component. In particular, this component is selected from the aminocarboxylic acids, wherein the further phosphorus-free structural component is preferably selected from methylglycine diacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyl iminodiacetate (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.

[0162] The wt.% proportion of the further phosphorus-free builder material, in particular MGDA and / or GLDA, is preferably 0 to 40 wt.%, particularly 5 to 30 wt.%, and especially 7 to 25 wt.%. The use of MGDA or GLDA, in particular MGDA, as granules is particularly preferred. MGDA granules containing as little water as possible and / or exhibiting lower hygroscopicity (water absorption at 25 °C, normal pressure) compared to the non-granulated powder are advantageous. The combination of at least three, in particular at least four, builders from the group mentioned above has proven advantageous for the cleaning and rinsing performance of washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably machine dishwashing detergents. Additional builders may also be included.

[0163] Suitable organic framework materials include polymeric polycarboxylates, such as the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those with a relative molecular mass of 500 to 70,000 g / mol. Particularly suitable polymers are polyacrylates, preferably with a molecular mass of 1,000 to 20,000 g / mol. Due to their superior solubility, short-chain polyacrylates from this group, with molar masses of 1,100 to 10,000 g / mol, and especially preferably 1,200 to 5,000 g / mol, are particularly advantageous.

[0164] The content of (homo)polymeric polycarboxylates in the washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably machine dishwashing detergents, is preferably 0.5 to 20 wt.%, preferably 2 to 15 wt.% and in particular 4 to 10 wt.%.

[0165] Washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably machine dishwashing detergents, can further utilize as a framework material crystalline layered silicates of the general formula NaMSi x O 2x+1 · y H 2 O, where M represents 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 particularly from 1:2 to 1:2.6, which are preferably retardant and exhibit secondary washing properties, can also be used.

[0166] In addition to the aforementioned base materials, the washing or cleaning agents according to the invention may further contain alkali metal hydroxides. These alkali carriers are preferably used in the washing or cleaning agents, and in particular in the at least one gel phase, only in small quantities, preferably in quantities below 10 wt.%, more preferably below 6 wt.%, more preferably below 5 wt.%, particularly preferably between 0.1 and 5 wt.%, and especially between 0.5 and 5 wt.%, in each case based on the total weight of the washing or cleaning agent. Alternative washing or cleaning agents according to the invention are free of alkali metal hydroxides.

[0167] As a further component, washing or cleaning agents according to the invention preferably contain enzyme(s) in the at least one solid and / or the at least one gel phase. These include, in particular, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases, or oxidoreductases, and preferably mixtures thereof. These enzymes are, in principle, of natural origin; starting from the natural molecules, improved variants are available for use in washing or cleaning agents and are therefore preferably employed. Washing or 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.

[0168] Among the proteases, those of the subtilisin type are preferred. Examples include the subtilisins BPN' and Carlsberg, as well as their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY, and the enzymes thermitase, proteinase K, and the proteases TW3 and TW7, which are classified as subtilases but no longer as subtilisins in the strict sense.

[0169] 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 developments of the aforementioned amylases for use in detergents or cleaning agents. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) are particularly noteworthy for this purpose.

[0170] Lipases or cutinases can also be used according to the invention, particularly because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtained from Humicola lanuginosa (Thermomyces lanuginosus) or further developed from it, especially those with the amino acid substitution at positions D96LT213R and / or N233R, most preferably all of the substitutions D96L, T213R and N233R.

[0171] Furthermore, enzymes collectively known as hemicellulases can be used. These include, for example, mannanases, xanthan lyases, pectin lyases (=pectinases), pectinesterases, pectate lyases, xyloglucanases (=xylanases), pullulanases, and β-glucanases.

[0172] To enhance 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, preferably organic, and especially aromatic, compounds that interact with the enzymes are added to enhance the activity of the respective oxidoreductases (enhancers) or to ensure electron flow in cases of significantly different redox potentials between the oxidizing enzymes and the contaminants (mediators). A protein and / or enzyme can be protected, particularly during storage, against damage such as inactivation, denaturation, or degradation, for example, by physical influences, oxidation, or proteolytic cleavage.When proteins and / or enzymes are produced microbially, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Washing or cleaning agents can contain stabilizers for this purpose; the provision of such agents represents a preferred embodiment of the present invention.

[0173] Cleaning-active proteases and amylases are generally not supplied as pure proteins, but rather as stabilized preparations suitable for storage and transport. These pre-prepared formulations include, for example, solid preparations obtained by granulation, extrusion, or lyophilization, or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with low water content, and / or containing stabilizers or other additives.

[0174] Alternatively, the enzymes can be encapsulated in at least one solid and / or gel, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, such as those in which the enzymes are enclosed as if in a solidified gel, or in core-shell type capsules in which an enzyme-containing core is coated with a protective layer impermeable to water, air, and / or chemicals. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers. Such capsules are produced using methods known per se, for example by shake or roll granulation or in fluid-bed processes. Advantageously, such granules are low in dust, for example by applying polymeric film formers, and are stable during storage due to the coating.

[0175] Furthermore, it is possible to combine two or more enzymes so that a single granule has multiple enzyme activities.

[0176] As can be seen from the preceding explanations, 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 1 and 40 wt.%, preferably between 2 and 30 wt.%, and particularly preferably between 3 and 25 wt.% of the enzyme protein. Washing or cleaning agents containing, based on their total weight, 0.1 to 12 wt.%, preferably 0.2 to 10 wt.%, and particularly 0.5 to 8 wt.% of the respective enzyme preparations are especially preferred.

[0177] In addition to the components already mentioned, the at least one solid and / or the gel 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, bleaching activators, bleaching catalysts, further solvents, thickeners, sequestrants, electrolytes, corrosion inhibitors, in particular silver preservatives, glass corrosion inhibitors, foam inhibitors, dyes, fragrances (especially in the at least one solid phase), additives for improving flow and drying properties, for adjusting viscosity, for stabilization, UV stabilizers, preservatives, and antimicrobial agents.

[0178] (Disinfectant), pH adjuster in quantities not usually exceeding 5% by weight.

[0179] As a further solvent, compositions according to the invention preferably contain at least one alkanolamine. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanololamine, and ethanololamine, and mixtures thereof. The alkanolamine is preferably present in compositions according to the invention in an amount of 0.5 to 10 wt.%, in particular in an amount of 1 to 6 wt.%. In preferred washing or cleaning agents, the gel is essentially free of alkanolamine, i.e., the gel contains less than 1 wt.%, in particular less than 0.5 wt.%, preferably less than 0.1 wt.%, and in particular preferably less than 0.05 wt.% alkanolamine, and the alkanolamine is contained only in the at least one solid phase.

[0180] In addition to the zinc salts mentioned above, polyethyleneimines, such as those available under the name Lupasol® (BASF), can preferably be used as glass corrosion inhibitors in an amount of 0 to 5 wt.%, in particular 0.01 to 2 wt.%.

[0181] Suitable polymers as additives include, in particular, maleic acid-acrylic acid copolymer sodium salt (e.g., Sokalan® < CP 5 from BASF, Ludwigshafen (Germany)), modified polyacrylic acid sodium salt (e.g., Sokalan® < CP 10 from BASF, Ludwigshafen (Germany)), modified polycarboxylate sodium salt (e.g., Sokalan® < HP 25 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (e.g., Silwet® < L-77 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (e.g., 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). Suitable additive building blocks include, in particular, polyaspartic acid sodium salt, ethylenediamine triacetate cocosalkylacetamide (for example, Rewopol® < CHT 12 from Evonik, Essen (Germany)), methylglycine diacetic acid trisodium salt, and acetophosphonic acid. Mixtures with surfactant or polymeric additives show synergistic effects in the case of Tegopren® < 5843 and Tegopren® < 5863. However, the use of Tegopren types 5843 and 5863 is less preferred for application on hard glass surfaces, especially glassware, because these silicone surfactants can adhere to glass. In a particular embodiment of the invention, the aforementioned additives are omitted.

[0182] A preferred washing or cleaning agent, in particular a machine dishwashing detergent, preferably further comprises a bleaching agent, in particular an oxygen bleaching agent, and optionally a bleaching activator and / or bleaching catalyst. These, if present, are contained exclusively in the at least one solid phase.

[0183] As a preferred bleaching agent, washing or 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 suitable bleaching agents include, for example, peroxypyrophosphates, citrate perhydrates, and pericy salts or peracids that provide H₂O₂, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid, or diperdodecanedioic acid. Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are the peroxy acids, with alkyl peroxy acids and aryl peroxy acids being particularly examples. Sodium percarbonate is especially preferred because of its good bleaching performance. A particularly preferred oxygen bleaching agent is sodium percarbonate.

[0184] Suitable bleaching activators include compounds that, under perhydrolysis conditions, yield aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, particularly 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances bearing O- and / or N-acyl groups of the specified number of carbon atoms and / or optionally substituted benzoyl groups are suitable. Multiply acylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) proving particularly suitable.

[0185] The bleaching 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 nitrogen-containing tripod ligands, as well as Co, Fe, Cu, and Ru ammine complexes, can also be used as bleaching catalysts. Manganese complexes in oxidation states II, III, IV, or IV are particularly preferred, preferably containing one or more macrocyclic ligand(s) with the donor functions N, NR, PR, O, and / or S. Ligands with nitrogen donor functions are especially favored.It is particularly preferred to use bleaching catalyst(s) in the compositions according to the invention, which contain as macromolecular ligands 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). 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-OAc) 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 6 ) 2 (with OAc = OC(O)CH 3 ). Portion:

[0186] The washing or cleaning agent according to the invention preferably comprises at least one solid, preferably granular, phase and at least one gel or gel phase. The washing or cleaning agent can have one, two, three, or more distinct solid phases; likewise, it can have one, two, three, four, or more distinct gel phases. Preferably, the washing or cleaning agent according to the invention comprises one solid phase and one gel phase. Particularly preferably, the washing or cleaning agent comprises two solid phases and one gel phase. More preferably, it comprises two solid phases and two gel phases. A further preferred embodiment is one in which the washing or cleaning agent comprises three solid phases and one or two gel phases.

[0187] The weight ratio of the totality of the at least one solid, preferably granular, phase to the totality of the at least one gel phase is generally 40:1 to 2:1, in particular 20:1 to 4:1, preferably 14:1 to 6:1, for example 12:1 to 8:1. The total weight of all phases in a portion of washing or cleaning agent can be between 8 and 30 g, in particular 10 to 25 g, preferably 12 to 21 g, for example 13 to 17 g per portion of washing or cleaning agent. This weight ratio results in a good concentration of the respective ingredients of the solid and gel phases in a cleaning process.

[0188] According to the invention, the at least one solid phase and the gel are fully or partially adjacent to each other. It is preferred that the two phases are directly adjacent to each other.

[0189] If the at least one solid phase and the gel are in direct, full- or partial-surface contact, stability is important in addition to the shortest possible solidification time of the at least one gel phase. Stability here means that components contained in the gel phase do not migrate into the at least one solid phase, but rather that even after prolonged storage, the at least one solid phase and the gel remain optically separate and do not interact with each other, such as through diffusion of liquid components from one phase to the other or reaction of components of one phase with those in the other phase.

[0190] Also disclosed is a method for cleaning hard surfaces, in particular dishes, in which the surface is treated in a manner known per se using a washing or cleaning agent according to the invention. In particular, the surface is brought into contact with the washing or cleaning agent according to the invention. The cleaning is carried out in particular with a cleaning machine, preferably a dishwasher.

[0191] Also disclosed is the use of a washing or cleaning agent, as described above, for cleaning hard surfaces, in particular dishes, especially in machine dishwashers.

[0192] The use and / or method is subject to the provisions specified above for washing or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents.

[0193] Also disclosed is a method for producing portion packs of washing and / or cleaning agents as described above, which contain a product with at least one solid gel phase as described above, comprising: a) Providing a mold with at least one mold cavity; optionally including a ridge for dividing the bottom of the mold cavity; b) Feeding a water-soluble film onto the mold cavity; c) Forming an open chamber in the mold cavity by deforming the water-soluble film; d) Filling the open chamber with at least one gel phase according to the foregoing embodiments (in particular according to any one of claims 1 to 6); e) optionally filling the open chamber or parts thereof with at least one further gel phase as described above, wherein this second gel phase may optionally differ from the gel phase according to d); f) optionally allowing the at least one gel phase to solidify; g) optionally subsequently filling the open chamber with at least one further phase, which preferably comprises a granular mixture of a solid composition, in particular a powdered phase, which differs from the at least one gel phase;h) Providing a second water-soluble film as a lid; i) Aligning the open chamber and the lid to seal the portion pack at a sealing area; ii) Sealing the lid to the open chamber.

[0194] Also disclosed is a method for producing portion packs of washing and / or cleaning agents, as described above, comprising a product with at least one first phase and at least one second phase different from the first phase: a) Providing a mold with at least one cavity; optionally including a ridge for dividing the base of the cavity; b) Applying a water-soluble film to the cavity; c) Forming an open chamber in the cavity by deforming the water-soluble film; d) Filling the open chamber with at least one phase comprising a granular mixture of a solid composition, in particular a first powdered phase; e) Providing a second mold with at least one second cavity; optionally including a ridge for dividing the base of the cavity; f) Applying a second water-soluble film to the second cavity; g) Forming a second open chamber in the second cavity by deforming the water-soluble film; h) Filling the second open chamber or parts thereof with at least one gel phase, according to any one of claims 1 to 6;i) Optionally, filling the second open chamber or parts thereof from step h) with at least one further gel phase according to any one of claims 1 to 6, wherein this at least one further gel phase is optionally different from the gel phase according to h); j) Optionally, allowing the gel phase(s) to solidify; k) Stacking the two open chambers on top of each other to seal the portion pack at a sealing area, wherein the filled areas face each other; l) Sealing the open chambers together.

[0195] Insofar as the present application states that the washing or cleaning agent according to the invention comprises something, either as a whole or as a gel, it is also considered disclosed that the washing or cleaning agent, or the respective phase thereof, can consist of something. In the following exemplary embodiment, the washing or cleaning agent according to the invention is described in a non-limiting manner. Examples of implementation:

[0196] Washing and cleaning agents were produced that comprised a gel phase or a solid phase and a gel phase. Various geometries were implemented. Furthermore, washing and cleaning agents were produced that comprised two solid phases and a gel phase. Also produced were washing and cleaning agents that comprised a solid phase and three, four, or five gel phases (of the same or different composition). The following data refers to wt% active substance based on the total weight of the respective phase (unless otherwise specified). Table 1: Gels not conforming to the invention had the following compositions (values ​​given in each case based on the total amount of the gel phase): % by weight % by weight Water-soluble zinc salt (preferably anhydrous zinc acetate) 0 0,3-0,6 Glycerin 23,0-29,5 25-28 1,3-Propanediol 27 - 35 30,5-33 Polycarboxylate copolymer with sulfonic acid-containing groups 5-10,5 7-10,5 Non-ionic surfactant(s), e.g. fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 0-2,3 0,5-1,5 Polyethylene glycol medium MR 200-600, (e.g. PEG 400 (INCI) 12-18,5 12-18,5 PVOH 12-18 12,7-15,5 dye solution 0,0 - 1,5 0,0 - 1,5 Misc., other active ingredients, organic solvents, perfume, processing aids Add 100 Add 100

[0197] The solid phases and the gel could be combined in any desired way. The spatial configuration of the gel phase, which was liquid after mixing the ingredients and dimensionally stable within a solidification time of a maximum of 1 minute, was determined by the spatial configuration of the solid phase as well as by commercially available or custom-designed molds. A water-soluble, open-pouch envelope was produced by deep drawing a PVOH-containing film (Monosol M8630). A liquid composition was poured into this open cavity, which, after hardening, formed the gel. The open pouch was then sealed by applying a second film and heat-sealing.

[0198] For the syneresis measurement, ellipsoids (casts) were made from the gel under test (dimensions: b=16.6, I=23 mm, h=5 mm + 2 mm bridge). These casts were stored for one and seven days at room temperature (20 °C). To determine the mass ratios, the ellipsoids (15 pieces per measurement) were dabbed with an absorbent cloth, and the proportion of absorbent liquid compared to the mass of the remaining cast was determined.

[0199] A device with two different ramps is used to measure the solidification time. The front ramp section is 300 mm long, has an angle of 28°, and a width tapering from 100 mm to 80 mm; the rear ramp section is 200 mm long, has an angle of 110°, and a width tapering from 80 mm to 65 mm. The device is kept at a temperature of 25°C ±2°C. 50 g of the gel to be tested is poured onto the ramp at a temperature of 125°C, and the time it takes for the gel to solidify as it flows down the ramp is measured. Table 2: Compositions of the gel phase according to the invention in wt.% E1 E2 E2 Zinc acetate anhydrous 0,5 0,5 0,5 Polymer comprising monomers containing acrylic acid and amidopropylsulfonic acid 10 10 10 1,3-Propanediol 32 32 32 Glycerin 26 26 26 Non-ionic surfactant* 0 1,5 0,8 PEG 400 15 15 15 PVOH (Mowiol 4-88) 15 15 15 Misc (including process aids, pH adjusters, perfume, dye, residual water) Add 100 Add 100 Add 100 Gelling time / min < 30 s < 30 s < 30 s * Fatty alcohol alkoxylate, preferably 20-40 EO, endcapped

[0200] Alternatively, fatty alcohol ethoxylate can also be used, preferably 20-40 EO without endcap.

[0201] According to Table 2, corresponding formulations were prepared. Formulations E1 and E2 showed a syneresis of less than 1.5% after 7 days of storage at room temperature. Table 3: 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) 0; 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 Bleaching catalyst (preferably Mn-based) 0,02-0,5 Bleach activator (e.g. TAED) 1-3 Non-ionic surfactant(s), e.g. fatty alcohol alkoxylate, preferably 20-40 EO, optionally 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 Zinc salt (e.g. acetate) 0,1-0,3 Sodium sulfate 0,0 - 10 Water 0,0-1,5 pH adjusters (e.g. citric acid) 0-1,5 Process aids 0-5

[0202] 1.0 g of the gel phases according to Table 2 were filled into a pouch containing polyvinyl alcohol (as described above). Additionally, 17.5 g of free-flowing solid phases according to Table 3 were applied and sealed as described above. Despite the addition of the particulate phase to the gel, no mixing of the gel and particulate phase occurred only 30 seconds after the dissolved gel was placed into the corresponding wells of the thermoformed film.

Claims

1. A detergent or cleaning agent, preferably a dishwashing detergent, in particular a machine dishwashing detergent, comprising a gel, preferably a gel that is solid at room temperature (20 °C), which, based on the total weight of the gel, a) 12.7 to 15.5 wt% polyvinyl alcohol and / or its derivatives, b) 31 to 32 wt% 1,3-propanediol, c) 25 to 28 wt% glycerin, d) 13.5 to 16.5 wt% polyalkylene glycol, and e) < 1 wt% water, wherein the derivatives of polyvinyl alcohol are understood to be copolymers of polyvinyl alcohol with anionic monomers, as well as polyvinyl alcohols which are acetalized or ketalized with aldehydes or ketones, in particular saccharides or polysaccharides or mixtures thereof.

2. A detergent or cleaning agent according to claim 1, characterized in that component d) comprises polyethylene glycols, preferably polyethylene glycol(s) with an average molecular weight of 200 to 600 g / mol, in particular of 350 to 450 g / mol, for example around 400 g / mol, are used in an amount of 13.5 to 16.5 wt%.

3. A detergent or cleaning agent according to any of claims 1 or 2, characterized in that the gel contains at least one additional ingredient, preferably two, three, four, or more ingredients, which are preferably selected from dyes, glass corrosion inhibitors, anionic polymers, nonionic surfactants, silver protection, perfumes, salts, pH adjusters, and other processing aids.

4. A detergent or cleaning agent according to claim 3, characterized in that it contains at least one zinc salt, in particular zinc acetate, preferably zinc acetate anhydrous, in an amount of 0.001 to 0.8 wt.%, preferably in an amount of 0.3 to 0.6 wt.%.

5. A detergent or cleaning agent according to any of claims 3 or 4, characterized in that it contains at least one anionic polymer, in particular a polyacrylate copolymer, preferably a polyacrylate terpolymer, in an amount of 5 to 12 wt.%, in particular 7 to 10.5 wt.%.

6. A detergent or cleaning agent according to any one of claims 1 to 5, characterized in that it contains at least one nonionic surfactant, preferably in an amount of 0.1 to 7.5% by weight, more preferably in an amount of 0.4 to 2.3% by weight, and most preferably in an amount of 0.5 to 1.5% by weight.

7. A detergent or cleaning agent according to any one of claims 1 to 6, characterized in that the anionic monomers in the polyvinyl alcohol copolymers are selected from vinylacetic acid, alkyl acrylates, maleic acid, monoalkyl maleates (in particular monomethyl maleate), dialkyl maleates (in particular dimethyl maleate), maleic anhydride, fumaric acid, monoalkyl fumarate (in particular monomethyl fumarate), dialkyl fumarate (in particular dimethyl fumarate), fumaric anhydride, itaconic acid, monomethyl itaconate, dialkyl itaconate, dimethyl itaconate, itaconic anhydride, citracon acid (methyl maleic acid), monoalkyl citracon acid (in particular methyl citraconate), dialkyl citracon acid, citracon anhydride, mesacon acid (methyl fumaric acid), monoalkyl mesaconate, dialkyl mesaconate, mesaconic acid anhydride, glutaconic acid, monoalkylglutaconate, dialkylglutaconate, glutaconic acid anhydride, vinylsulfonic acid, alkylsulfonic acid, ethylene sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, as well as combinations thereof, and the alkali metal salts or esters of the aforementioned monomers, wherein the anionic monomers are preferably selected from the group consisting 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.

8. A detergent or cleaning agent portion comprising at least one gel according to any one of claims 1 to 7 in a water-soluble coating.

9. A detergent or cleaning agent portion according to claim 8, characterized in that the water-soluble coating comprises polyvinyl alcohol.

10. A detergent or cleaning agent portion according to claim 8 or 9, characterized in that it contains, as at least one additional phase, a granular mixture of a solid composition, which is preferably in powder form, in particular in powder form and free-flowing.

11. A detergent or cleaning agent portion according to claim 10, characterized in that, as at least the additional phase, it comprises at least one, preferably several, ingredients selected from the group consisting of structuring agents (preferably carbonates and / or citrates), complexing agents (in particular aminocarboxylates, preferably MGDA and / or GLDA or their salts), bleaching agents (in particular percarbonate), bleaching activators, bleaching catalysts, silver protection agents, enzymes (preferably protease(s) and / or amylase(s)), nonionic surfactants, and process aids, as well as mixtures thereof.

12. A detergent or cleaning agent portion according to any of claims 8 to 11, characterized in that the gel phase comprises less than 1 wt.%, in particular less than 0.5 wt.%, in particular less than 0.1 wt.%, of anionic surfactant, in each case based on the total weight of the second phase.

13. A detergent or cleaning agent portion according to any one of claims 8 to 12, characterized in that it is a dishwashing detergent, in particular a dishwashing detergent for the machine cleaning of dishes.

14. Use of a gel according to claims 1 to 7, or a cleaning agent portion according to any of claims 8 to 13, for the machine cleaning of dishes.

15. A method for the machine cleaning of dishes, characterized in that a gel according to claim 1 to 7 or a cleaning agent portion according to one of claims 8 to 13 is used in a dishwasher.