EP3599269B1 - Cleaning agent with protection against glass corrosion - Google Patents

Description

The invention relates to cleaning agents, preferably dishwashing detergents, in particular automatic dishwashing detergents, comprising at least one essentially anhydrous gel-like phase which contains a water-soluble zinc salt, preferably zinc chloride, zinc sulfate and/or zinc acetate, particularly preferably zinc acetate.

When formulating cleaning agents, preferably dishwashing detergents, in particular automatic dishwashing detergents, divalent metal salts, such as bismuth or zinc salts, are used in particular to prevent damage to glasses (glass corrosion). The patent application EP 1797166 describes, for example, water-containing compositions which, in addition to polyvalent metal compounds, contain at least 8% by weight of a nonionic surfactant with a cloud point of less than 32 ° C.

Detergents or cleaning agents are usually in solid form (for example as tablets) or in liquid form (or as a flowing gel). Liquid detergents and cleaning agents in particular are becoming increasingly popular with consumers. Pre-portioned forms are popular with consumers because they are easier to dose. Pre-portioned flowing gels are often problematic because they tend to leak, for example when packaged in single or multi-chamber bags.

The EP 2 230 295 A1 discloses cleaning compositions containing zinc and aluminum salts as glass corrosion inhibitors.

In the DE 10 2013 226301 A1 Liquid gels are described that contain various active ingredients and a thickener.

The US 8,389,458 B2 describes compositions with sulfonated copolymers and zinc salt, which contain a lot of water and xanthan gum as a thickener.

The object of the present invention is to provide cleaning agents, in particular dishwashing detergents, preferably machine dishwashing detergents, which can be produced easily and cost-effectively.

A first subject of the present invention thus relates to cleaning agents comprising a gel phase containing 4.9% by weight or less of water based on the total weight of the gel phase, which contains at least one water-soluble zinc salt with a solubility of above 100 mg/l, preferably above 500 mg/l, particularly preferably above 1 g/l and in particular above 5 g/l at 20° C. in water, preferably zinc sulfate and/or zinc acetate, particularly preferably zinc acetate, and a gelling agent in an amount of 4 to 40 wt. -%, based on the total weight of the gel phase.

The zinc salt to be used according to the invention is water-soluble, which means that it has a solubility in water above 100 mg/l, preferably above 500 mg/l, particularly preferably above 1 g/l and in particular above 5 g/l (all solubilities at 20 ° C water temperature ). The inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate. The organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate, zinc acetylacetonate, zinc 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.

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

The zinc salt is in the gel phase preferably in an amount of 0.05% by weight to 3% by weight, particularly preferably in an amount of 0.1% by weight to 2.4% by weight, in particular in a Amount of 0.2% by weight to 1.0% by weight, based on the total weight of the gel phase.

Zinc salts can also be contained in a solid phase that may be present. In this case, the zinc salt in cleaning agents according to the invention is preferably in an amount of 0.01% by weight to 5% by weight, particularly preferably in an amount of 0.05% by weight to 3% by weight, in particular an amount of 0.1% by weight to 2% by weight, based on the total weight of the cleaning agent.

In addition to the effect of such zinc salts as glass corrosion inhibitors, it was surprisingly found that the presence of zinc salts in the gel phase contributes to stabilizing the gel and improving processability. It proves to be particularly disadvantageous if the gel can no longer be processed within a short time after production. If the gel becomes too viscous within a short time after production, it can no longer be dosed in the usual way. Furthermore, yellowing of the gel is often observed, which visually displeases the end user and leads to them perceiving the product as “no longer fresh” or “no longer usable”. For the production process, this means that the gel only has to be freshly prepared in small quantities and at short time intervals in order to ensure that the gel can be filled into the product. In particular, the time window in which the gel phase can be processed (service life) is significantly extended by adding the zinc salt.

One advantage of the invention is that the gel approaches have a longer service life and a corresponding cleaning agent can therefore be produced more cost-efficiently and in a more resource-saving manner.

Surprisingly, it was found that despite the extended service life due to the addition of zinc salt, the solidification time does not change negatively after dosing the gel into the product, e.g. into the pouch. Surprisingly, it was found that bismuth salts cannot be incorporated into low-water formulations according to the invention.

According to the invention, a gel-like phase, also referred to below as a gel phase, is to be understood as meaning a composition/phase which has an internally structuring network. This internally structuring (spatial) network is created by the dispersion of a fixed but dispersed substance with long or highly branched particles and / or gelling agent, formed in at least one liquid (the at least one liquid is liquid at 20 ° C). Such gel phases behave thermoreversibly.

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

The at least one gel phase is preferably a shaped body. A shaped body is a single body that stabilizes itself in its imposed shape. This dimensionally stable body is formed from a molding compound (e.g. a composition) by specifically bringing this molding compound into a predetermined shape, for example by pouring a liquid composition into a mold and then curing the liquid composition, for example in the context of a sol-gel mold. process.

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

The at least one gel phase is preferably a solid gel phase. It is cut-resistant. For example, it can be cut with a knife after solidification without causing any further destruction other than the cut made.

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

The at least one gel phase is essentially water-free. This means that the gel phase is essentially free of water. “Substantially free” here means that small amounts of water may be contained in the gel phase. This water can be introduced into the phase, for example, through a solvent or as water of crystallization or due to reactions of components of the phase with one another. However, only small amounts, in particular no water, are used as a solvent to produce the gel phase. The proportion of water in the gel phase is 4.9% by weight or less, 4% by weight or less, preferably 2% by weight or less, in particular 1% by weight or less, especially 0.5% by weight. -% or less, in particular 0.1% by weight or 0.05% by weight or less. The information in% by weight refers to the total weight of the gel phase.

It is therefore particularly preferred that the water-soluble zinc salt is used in the gel phase in the form of an anhydrous zinc salt, in particular anhydrous zinc sulfate or zinc acetate, preferably zinc acetate anhydrate.

These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from reading the following detailed description and claims.

Furthermore, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it and in particular the invention is not limited to these examples. Unless otherwise stated, all percentages are% by weight. Numerical ranges specified in the format "from x to y" include the stated values. When multiple preferred numerical ranges are specified in this format, it is understood that any ranges resulting from the combination of the various endpoints will also be captured.

"At least one" as used herein means 1 or more, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In relation to an ingredient, the information refers to the type of ingredient and not to the absolute number of molecules. “At least one bleach catalyst” therefore means, for example, at least one type of bleach catalyst, i.e. that one type of bleach catalyst or a mixture of several different bleach catalysts can be meant. Together with weight information, the information refers to all compounds of the specified type that are contained in the composition/mixture, i.e. that the composition does not contain any other compounds of this type beyond the specified amount of the corresponding compounds.

When reference is made herein to molar masses, this information always refers to the number-average molar mass M _n , unless explicitly stated otherwise. The number average molecular weight can be determined, for example, using gel permeation chromatography (GPC) according to DIN 55672-1:2007-08 with THF as eluent. The weight-average molecular weight M _w can also be determined using GPC, as described for M _n .

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

Furthermore, the gel phase must be storage stable under normal storage conditions. The gel phase according to the invention is part of a cleaning agent. Cleaning products are usually stored in a household for a certain period of time. Storage usually takes place near the washing machine or dishwasher. For such storage, the gel phase should be stable. The gel phase should therefore be stable, especially after a storage period of, for example, 4 to 12 weeks, in particular 10 to 12 weeks or longer at a temperature of up to 40 ° C, especially at 30 ° C, in particular at 25 ° C or at 20 ° C and do not deform or otherwise change in consistency during this time.

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

A change in volume or shrinkage during storage would be disadvantageous, as this would result in low consumer acceptance of the product. A leakage of liquid or the sweating out of components from the gel phase is also undesirable. Here too, the visual impression is relevant. The escape of liquid, such as solvent, can influence the stability of the gel phase so that the components do not are contained more stably and this can also influence the washing or cleaning effect.

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

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

This means that the individual cleaning agent portion, which is used to carry out a single cleaning cycle, is added in particular to a cleaning cycle of an automatic dishwasher, 0.0005 to 1 g, preferably 0.01 to 0.5 g, in particular 0.02 to 0 .06 g of the water-soluble zinc salts, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate.

Particularly preferably, a single cleaning agent portion according to the invention, which is added in particular to a cleaning cycle of an automatic dishwasher, contains 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 cleaning agent.

According to the invention, the cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, contain in the gel phase (gel phase) a gelling agent, preferably selected from gelatin, xanthan gum and/or polyvinyl alcohol, in particular gelatin or polyvinyl alcohol, particularly preferably polyvinyl alcohol, in an amount of 4 to 40, in particular from 6 to 30% by weight, particularly preferably in an amount of 7 to 24% by weight, very particularly preferably 8 to 22% by weight, in particular, for example, 14 to 20% by weight, in each case based on the total weight of the gel-like phase.

According to the invention, the at least one gel phase particularly preferably comprises PVOH (polyvinyl alcohol) and/or derivatives thereof. Polyvinyl alcohols are thermoplastics that are usually produced as a white to yellowish powder by hydrolysis of polyvinyl acetate. Polyvinyl alcohol (PVOH) is resistant to almost all anhydrous organic solvents. Polyvinyl alcohols with a molecular weight of 30,000 to 60,000 g/mol are preferred.

For the purposes of the invention, preferred derivatives of PVOH are copolymers of polyvinyl alcohol with other monomers, in particular copolymers with anionic monomers. Suitable anionic monomers are preferably vinyl acetic acid, alkyl acrylates, maleic acid and their derivatives, in particular monoalkyl maleates (in particular monomethyl maleate), dialkyl maleates (in particular dimethyl maleate), maleic anhydride, fumaric acid and their derivatives, in particular monoalkyl fumarate (in particular monomethyl fumarate), dialkyl fumarate (in particular dimethyl fumarate), fumaric anhydride, Itaconic acid and its derivatives, in particular monomethyl itaconate, dialkyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid (methylmaleic acid) and its derivatives, monoalkyl citraconic acid (in particular methyl citraconic acid), dialkyl citraconic acid (dimethyl citraconate), citraconic acid anhydride, mesaconic acid (methyl fumaric acid) and its derivatives, monoalkyl mesacone at, dialkyl mesaconate, mesaconic anhydride, glutaconic acid and their derivatives, monoalkyl glutaconate, dialkyl glutaconate, glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate and their combinations as well as the alkali metal salts or Esters of the above-mentioned monomers.

Particularly preferred derivatives of PVOH are those which are selected from copolymers of polyvinyl alcohol with a monomer, in particular selected from the group of monoalkyl maleates (in particular monomethyl maleate), dialkyl maleates (in particular dimethyl maleate), maleic anhydride, and combinations thereof, as well as the alkali metal salts or esters of the above mentioned monomers. The values given for polyvinyl alcohols apply to the suitable molecular weights. In the context of the present invention, it is preferred that the at least one gel phase comprises a polyvinyl alcohol and/or its derivatives, preferably polyvinyl alcohol, the degree of hydrolysis of which is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 Mol% and especially 82 to 88 mol%.

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

PVOH powders with the above-mentioned properties, which are suitable for use in the at least one gel phase, are known, for example, under the name Mowiol ^® or Poval ^® sold by Kuraray. Exceval ^® AQ4104 from Kuraray is also suitable, for example. Particularly suitable are Mowiol C30, the Poval ^® qualities, in particular the qualities 3-83, 3-88, 6-88, 4-85, and particularly preferably 4-88, very particularly preferably Poval 4-88 S2 and Mowiol ^® 4- 88 from Kuraray.

The water solubility of polyvinyl alcohol can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols which are acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous due to their extremely good solubility in cold water. The reaction products from polyvinyl alcohol and starch are extremely advantageous to use. Furthermore, the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus specifically adjusted to the desired values.

Surprisingly, it has been shown that PVOH are particularly suitable for producing gel phases that meet the requirements shown above. Particular preference is therefore given to at least one gel phase which, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate, has PVOH and at least one polyhydric alcohol. Particularly preferably, the at least one gel phase has PVOH and at least one polyhydric alcohol.

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

According to a particularly preferred embodiment, the at least one gel phase comprises PVOH (polyvinyl alcohol). These 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 change insignificantly during storage. In particular, they are also less reactive with regard to a direct negative interaction with components of the granular mixture, in particular the powder phase. In particular, PVOH can easily produce low-water or water-free gel phases. When using PVOH as a polymer for the at least one gel phase, low-viscosity melts result at 110-120 ° C, which can therefore be processed particularly easily; in particular, the gel phase can be filled into the water-soluble coating quickly and precisely without any Sticking occurs or the amount is dosed inaccurately. Furthermore, these gel phases adhere particularly well to the water-soluble coating, especially if it is also made from PVOH. This is also visually advantageous. Due to the rapid solidification of the at least one gel phase with PVOH, further processing of the gel phases can take place particularly quickly. Furthermore, the good solubility of the gel phases produced is particularly favorable for the overall solubility of the cleaning agent. In addition, gel phases with such short solidification times are advantageous so that the at least one solid phase dosed thereon, comprising granular mixtures, in particular powder, does not sink into the gel that is not yet completely solidified or is too soft. This leads to detergent portions that are visually unappealing.

Particularly in the case of the multi-phase single-use portions according to the invention with at least one solid phase, it is important that the at least one gel phase is dimensionally stable so that as few interactions as possible can take place between the solid and the gel phase. If the at least one gel phase also comprises gelatin in addition to PVOH, the toughness of the gel phase during production is increased.

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

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

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

Surprisingly, it has been shown that particularly short solidification times can be achieved by combining a corresponding triol (alkanediol) with a corresponding diol (alkanediol). The gel phases obtained are also transparent and have a shiny surface, which ensures an attractive visual impression of the cleaning agent according to the invention. The terms diol and alkanediol are used synonymously here. The same applies to triol and alkanetriol.

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

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

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

The C ₃ - to C ₆ -alkanetriol is particularly preferred, glycerol and/or 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (also called 1,1,1-trimethylolpropane). The C ₃ - to C ₅ - alkanediol is, for example, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-butanediol, 1,3-propanediol and/or 1,2-propanediol, preferably 1, 3-propanediol and/or 1,2-propanediol. Surprisingly, it has been shown that the chain length of the diol and in particular the position of the OH groups influence the transparency of the gel phase. The OH groups of the diol are therefore preferably not arranged on immediately adjacent carbon atoms. In particular, there are three or four carbon atoms, in particular 3 carbon atoms, between the two OH groups of the diol. The diol 1,3-propanediol is particularly preferred. Surprisingly, it has been shown that particularly good results are achieved with mixtures which comprise glycerin and 1,3-propanediol and/or 1,2-propanediol.

According to the invention, polyethylene glycol(s) with an average molecular weight of 200 to 600 g/mol are preferably additionally used in the at least one gel phase or gel phases. In combination with polyvinyl alcohol, polyethylene glycols with an average molecular weight between about 200 and about 600 g/mol, preferably between 300 and 500 g/mol, particularly preferably between 350 and 450 g/mol, for example around 400 g/mol (INCI: PEG400) are used. used. Cleaning agent portions according to the invention are therefore characterized in that they contain polyethylene glycol(s) with an average molecular weight of 300 to 500 g/mol, in particular 350 to 450 g/mol.

In particular, it is advantageous that the at least one gel phase or the gel phases, each based on the total weight of the gel phase, comprise at least one water-soluble zinc salt, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2 .4% by weight, particularly preferably from 0.2 to 1.0% by weight, polyvinyl alcohol and at least one polyhydric alcohol, if necessary additionally polyethylene glycols with an average molecular weight of about 200 to 600 g / mol in amounts of 5 to 30% by weight, preferably from 8 to 26% by weight, in particular from 10 to 22% by weight, based on the total weight of the at least one gel phase.

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

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

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

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

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

If glycerin is contained as alkane triol in the gel phase, the proportion of glycerin, based on the total weight of the gel phase, is preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, especially 20 % by weight to 40% by weight.

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

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

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

Based on the total weight of the gel phase, the gel phase comprises in addition to at least one water-soluble zinc salt, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4% by weight, particularly preferably 0.2 up to 1.0% by weight of at least one alkanediol, in particular 1,3-propanediol or 1,2-propanediol, the proportion of alkanediol, in particular 1,3-propanediol or 1,2-propanediol, based on the total weight the gel phase, preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, especially 20% by weight to 45% by weight. If 1,3-propanediol is contained in the gel phase, the proportion of 1,3-propanediol, based on the total weight of the gel phase, is in particular 10% by weight to 65% by weight, in particular 20% by weight to 45 % by weight.

Preferred is a gel phase which, based on the total weight of the gel phase, contains at least one water-soluble zinc salt, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4% by weight, particularly preferably 0 .2 to 1.0 wt.%) 20 to 45 wt.% 1,3 propanediol and/or 1,2-propanediol and 10 wt.% to 65 wt.% 2-amino-2-hydroxymethyl 1,3-propanediol, based on the total weight of the gel phase. Also preferred is a gel phase which contains 20 to 45% by weight of 1,3-propanediol and/or 1,2-propanediol and 10% by weight to 65% by weight of 1,1,1-trimethylolpropane, in each case based on that Total weight of the gel phase. A gel phase which contains 20 to 45% by weight of 1,3-propanediol and/or 1,2-propanediol and 10% by weight to 65% by weight of glycerol, in each case based on the total weight of the gel phase, is particularly preferred. It has been shown that in these areas rapid solidification at 20 °C of a gel phase is possible and that the phases obtained are storage-stable and transparent. The proportion of glycerin in particular has an impact on the curing time.

The inventive gel phase has at least one gel phase, based on the total weight of the gel phase, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4% by weight, particularly preferably 0 .2 to 1.0% by weight of a C ₃ to C ₆ alkane triol and a C ₃ to C ₅ alkanediol, their weight ratio is preferably 3:1 to 1:2. In particular, the weight ratio is from 2:1 to 1:1.5, preferably from 1.5:1 to 1:1.2, preferably from 1.3 to 1:1, if glycerin and 1,3-propanediol are contained as polyhydric alcohols. Surprisingly, it has been shown that with these weight ratios, storage-stable, shiny, transparent gel phases can be obtained within short solidification times at 20 ° C of 10 minutes or less. In combination with polyethylene glycols with an average molecular weight of 200 to 600 g/mol, with the preferred weight ratios mentioned, in particular weight ratios (C ₃ - to C ₆ -alkanetriol: C ₃ - to C ₅ -alkanediol) of 1.5: 1 to 1:1.2, reduce to setting times of 5 minutes and less.

According to a further preferred embodiment, in addition to the above-mentioned alkanols, triethylene glycol can be contained in the at least one gel phase, in particular the gel phases described above as preferred, in particular if this phase contains PVOH and possibly polyethylene glycols with an average molecular weight of 200 to 600 g / mol contains. Triethylene glycol advantageously accelerates the solidification of the gel phase(s). In addition, it causes the resulting gel phase to exchange liquid with the environment only slightly, if at all, in an unobservable manner. This particularly improves the visual impression of the resulting cleaning agent portions. It is particularly preferred if the at least one gel phase, based on the total weight of the gel phase, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4% by weight , particularly preferably from 0.2 to 1.0% by weight of 1,3- and / or 1,2-propanediol, particularly preferably 1 to 3.5% by weight of 1,3-propanediol, and glycerol between 0 , 1 and 20% by weight, preferably between 1 and 15% by weight, in particular between 5 and 12% by weight, for example 8 to 11% by weight, of triethylene glycol

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

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

The unsaturated carboxylic acid(s) used with particular preference are unsaturated carboxylic acids of the formula R ¹ (R ² )C=C(R ³ )COOH, in which R ¹ to R ³ independently represent -H, -CH ₃ , one straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH2, -OH or -COOH as defined above or for -COOH or -COOR ⁴ stands, where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical with 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. Of course, the unsaturated dicarboxylic acids can also be used.

Among the monomers containing sulfonic acid groups, preference is given to those of the formula R ⁵ (R ⁶ )C=C(R ⁷ )-X-SO ₃ H, in which R ⁵ to R ⁷ independently represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH ₂ , -OH or -COOH or -COOH or -COOR ⁴ stands, where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical with 1 to 12 carbon atoms, and X stands for an optionally present spacer group which is 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 -.

Preferred among these monomers are those of the formulas H ₂ C=CH-X-SO ₃ H, H ₂ C=C(CH ₃ )-X-SO ₃ H or HO ₃ SX-(R ⁶ )C=C(R ⁷ )-X-SO ₃ H, in which R ⁶ and R ⁷ are independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ and -CH(CH ₃ ) ₂ and X represents an optional spacer group which is 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 -.

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

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxypropanesulfonic acid, Allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene1-sulfonic acid, styrenesulfonic acid, vinyl sulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, Sul fomethylmethacrylamide and mixtures of the above Acids or their water-soluble salts. In the polymers, the sulfonic acid groups can be present entirely or partially in neutralized form, which means that the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

The monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95% by weight for copolymers which only contain monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, and particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight. % and the proportion of the monomer containing carboxylic acid groups 10 to 50% by weight, the monomers are preferably selected from those mentioned above. The molecular weight of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred cleaning agents are characterized in that the copolymers have molecular weights of from 2000 to 200,000 g mol ^-1 , preferably from 4000 to 25,000 g mol ^-1 and in particular from 5000 to 15,000 g mol ^-1 .

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

1. i) Carbonsäuregruppen-haltige Monomere
2. ii) Sulfonsäuregruppen-haltige Monomere
3. iii) nichtionische Monomere, insbesondere hydrophobe Monomere eingesetzt wird.

Particularly preferably, the at least one gel phase further comprises an anionic copolymer, the anionic copolymer comprising a copolymer

1. i) Monomers containing carboxylic acid groups
2. ii) Monomers containing sulfonic acid groups
3. iii) nonionic monomers, in particular hydrophobic monomers, are used.

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

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 ,4-trimethylpentene-1, 2,4,4-trimethylpentene-2,2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4 ,4-Dimethylhexane-1, ethylcyclohexyne, 1-octene, α-olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C ₂₂ -α-olefin, 2-styrene, α-methylstyrol, 3-methylstyren, 4-propylbryol, 4-cycloHexylstyren, 4-dodecylstyren, 2-ethyl-4-benzylstyren, 1-vinylnaphthaline, acrylic acid anhylester, acrylic acid ester, acrynic acry acidic estate Urbutyl ester, acrylic acid pentyl ester, acrylic acid hexylester, methacrylic acid semester, N-(methyl)acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N-(2-ethylhexyl)acrylamide, octyl acrylate, octyl methacrylate, N-(octyl)acrylamide, lauryl acrylate, lauryl methacrylate, N-(lauryl)acrylamide, Stearyl acrylate, stearyl methacrylate, N-(stearyl)acrylamide, behenyl acrylate, behenyl methacrylate and N-(behenyl)acrylamide or mixtures thereof, in particular acrylic acid, ethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and mixtures thereof.

Surprisingly, it has been shown that PVOH and/or its derivatives together with anionic polymers or copolymers, in particular with copolymers containing sulfonic acid groups, also lead to the formation of gel phases with insensitive surfaces. Corresponding surfaces can be touched by the end user without material sticking to their hands. Even in packaging, no material is removed. The gel phase therefore preferably comprises PVOH, polyethylene glycol(s) with an average molecular weight of 200 to 600 g/mol, at least one polyhydric alcohol and an anionic copolymer/polymer. The proportion of anionic polymer is preferably 1% by weight to 35% by weight, in particular 3% by weight to 30% by weight, especially 4% by weight to 25% by weight, preferably 5% by weight. % to 20% by weight, for example 10% by weight, based on the total weight of the gel phase. Sulfopolymers, in particular the preferred copolymeric polysulfonates, which, in addition to monomer(s) containing sulfonic acid groups, contain at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, also ensure an excellent shine of the surface. In addition, fingerprints are not retained. Therefore, the proportion of sulfopolymers, in particular the preferred copolymeric polysulfonates, which, in addition to monomer(s) containing sulfonic acid groups, contains at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, in particular of the sulfopolymers mentioned with AMPS as the monomer containing sulfonic acid groups, for example Acusol 590, Acusol 588 or Sokalan CP50, preferably 1% by weight to 25% by weight, in particular 3% by weight to 18% by weight, especially 4% by weight to 15% by weight, preferably 5 % by weight to 12% by weight based on the weight of the gel phase. In a particularly preferred embodiment, the at least one gel phase therefore comprises PVOH and a sulfopolymer, in particular the preferred copolymeric polysulfonates, which, in addition to monomer(s) containing sulfonic acid groups, contain at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, and at least one polyvalent Alcohol.

According to a further embodiment, in addition to the mentioned polyethylene glycols with an average molecular weight of 200 to 600 g/mol, further polyalkylene glycols, in particular further polyethylene glycols, with an average molecular weight between approximately 800 and 8000 can be contained in the at least one gel phase. The polyethylene glycols mentioned above are particularly preferably used in amounts of 1 to 40% by weight, preferably 5 to 35% by weight, in particular 10 to 30% by weight, for example 15 to 25%, preferably in each case based on the total weight of the gel phase .

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

According to a further particularly preferred embodiment, the cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing detergent, is a cleaning agent portion in a water-soluble coating with one or more chambers/compartments. The cleaning agent is preferably made up as a single-use cleaning agent portion, so that it is used to carry out a dishwasher cycle and is (largely) essentially consumed in the process.

The water-soluble covering is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer mixtures. The wrapping may be formed from one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the additional layers, if present, can be the same or different.

It is preferred that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings that contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with a sufficiently high water solubility, in particular cold water solubility.

Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which is in the range from 10,000 to 1,000,000 gmol ^-1 , preferably from 20,000 to 500,000 gmol ^-1 , particularly preferably from 30,000 to 100,000 gmol ^-1 and in particular from 40,000 to 80,000 gmol ^-1 .

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

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

A polyvinyl alcohol-containing film material suitable for producing the water-soluble coating can 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 above Polymers may be added. A preferred additional polymer is polylactic acids.

In addition to vinyl alcohol, preferred polyvinyl alcohol copolymers include 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 polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated one Carboxylic acid, its salt or its ester. In addition to vinyl alcohol, such polyvinyl alcohol copolymers particularly preferably contain acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.

It may be preferred that the film material contains further additives. The film material can, for example, contain plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, sorbitol, mannitol or mixtures thereof. Other additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, anti-blocking agents, anti-adhesive agents or mixtures thereof.

Suitable water-soluble films for use in the water-soluble wrappings of the water-soluble packaging according to the invention are films sold by MonoSol LLC, for example under the names M8720, M8630, M8312, M8440, M7062, C8400 or M8900. Films that are sold by Nippon Gohsei under the names SH2601, SH2504, SH2707 or SH2701 are also suitable. Other suitable films include films called ^Solublon® PT, ^Solublon® GA, ^Solublon® KC or ^Solublon® KL from Aicello Chemical Europe GmbH or the VF-HP films from Kuraray.

The water-soluble coating preferably has at least partially a bitter substance with a bitter value between 1,000 and 200,000, in particular those selected from quinine sulfate (bitter value = 10,000), naringin (bitter value = 10,000), sucrose octaacetate (bitter 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 bitter substance with a bitterness value between 1,000 and 200,000. In this context, it is particularly preferable that the water-soluble coating is coated to at least 50%, preferably to at least 75% and very particularly preferably at least 90% with the bitter substance with a bitterness value between 1,000 and 200,000. The bitter substance with a bitterness value between 1,000 and 200,000 can be applied, for example, by printing, spraying or brushing.

According to the invention, the water-soluble covering has at least one continuously circumferential sealing seam, which lies essentially in one plane. This is advantageous in terms of process technology, since only a single sealing step, possibly using only a single sealing tool, is necessary for a circumferential sealing seam, which lies essentially in one plane. The continuously circumferential sealing seam leads to a better closure compared to wrappings with multiple sealing seams and an excellent tightness of the sealing seam and thus the wrapping itself. Leaking of product from the wrapping, for example onto the surface of the portion, would be disadvantageous as the consumer would then be left with the product would come into contact. This is exactly what should be avoided if possible with a cleaning agent portion with a water-soluble coating.

The water-soluble covering can preferably be made from at least 2 packaging parts. The at least two packaging parts are preferably water-soluble so that no packaging parts remain in the dishwasher, which can then lead to problems in the dishwasher. It is not necessary that the at least two packaging parts are different. They can preferably be made of the same material and in the same way. In a preferred embodiment, this involves two parts of a water-soluble film, in particular two parts of a water-soluble film of the same composition.

In a further embodiment, the at least two packaging parts can be made from different materials, for example from different films or from material with two different properties (e.g. film that is soluble in warm and cold water). In this embodiment, it is preferred that a water-soluble film and another packaging part made by injection molding are combined.

According to a particularly preferred embodiment of the present invention, the water-soluble covering comprises at least one at least partially plastically deformed film. In particular, this plastic deformation of the film can be produced by methods known to those skilled in the art, such as deep drawing (with and without applying a vacuum), blow molding or stamp molding. In particular, the water-soluble covering comprises at least one at least partially plastically deformed film which was produced by deep drawing.

The at least one solid phase and the at least one gel phase can be arranged within the water-soluble coating in any combination with one another. A solid phase can be arranged on or next to a gel phase. In this embodiment, the cleaning agent according to the invention has a solid phase and a gel phase. 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 phase is in cast form, for example in the form of a gel core which is surrounded by a solid phase. There can also be two or more separate cavities that are filled with the at least one gel phase. In this embodiment, the cleaning agent comprises two gel phases, wherein the two gel phases can have different compositions.

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

A preferred subject matter of the present invention is a cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing detergent, which additionally comprises at least one solid, in particular particulate phase and optionally at least one further liquid/gel or solid phase.

“Solid” in this context means that the composition is in solid form under standard conditions (temperature 25 ° C, pressure 1013 mbar). Suitable solid phases are, on the one hand, granular mixtures of a solid composition, such as powder and/or granules, in particular powdery phases. Also suitable according to the invention are solid compositions/phases which have increased dimensional stability compared to the loose powder, for example powder or granulate preparations which were compacted by compression before or after being enclosed in the film, for example by restoring forces of the film after deep-drawing or directly compressed compositions, such as compresses or tablets. These at least one solid phase can be in direct contact with the gel phase. According to the invention, cleaning agent portions, in particular multi-chamber bags, in which the solid and gel phases are in spatial proximity but separate from one another are also present. The two chambers can be separated, for example, by a film, in particular a water-soluble film, or by a sealing seam (preferably a sealing seam of 3 mm or less). According to the invention, chambers of a multi-chamber pouch are therefore arranged one above the other as well as those arranged next to one another. Furthermore, there are also mixtures of single- or multi-chamber bags which comprise a gel-like phase according to the invention and at least one solid phase separately therefrom, which come into contact by arrangement, for example 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 dosage, according to the invention.

A powdery phase in the context of the present invention is to be understood as a granular mixture which is formed from a large number of loose, solid particles, which in turn include so-called grains. According to the invention, the term powdery phase includes powders and/or granules according to the following definition.

A grain is a name for the particulate components of powders (grains are the loose, solid particles), dusts (grains are the loose, solid particles), granules (loose, solid particles are agglomerates of several grains) and other granular mixtures. A preferred embodiment of the granular mixture of the composition of the solid phase is the powder and/or the granules; when “powder” or “granules” is mentioned here, it also includes that these are also mixtures of different powders or different granules . There are also mixtures with powder and granules different powders with different granules. The said solid particles of the granular _mixture in turn preferably have a particle diameter 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 a solid phase is preferably in a free-flowing form (particularly preferably as a free-flowing powder and/or free-flowing granules). The agent of the portion according to the invention thus comprises at least one solid phase of a free-flowing, granular mixture of a solid composition, in particular a powder, and at least one gel phase as defined above.

A particularly preferred subject of the present invention are cleaning agents, in particular cleaning agent portions, in which the gel-like phase is in direct contact, for example in a chamber, with the at least one solid phase.

Furthermore, it is preferred that the at least one solid phase and the at least one gel phase are in direct contact with one another. 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 pass from one phase to the other or that the stability, in particular storage stability, preferably at 4 weeks and 30 ° C storage temperature, and / or the aesthetics of the product in any way, for example Color change, formation of moist-looking edges, blurred border between the two phases or similar.

Surprisingly, it has been shown that this goal is achieved by a formulation of a gel phase, preferably a dimensionally stable gel phase, comprising at least one water-soluble zinc salt, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate, which is combined with a granular mixture of a solid composition, in particular a powdery phase can be achieved. It is particularly suitable if the granular mixture of a solid composition, in particular the powdery phase, is free-flowing, since a more targeted filling of the water-soluble coating can be achieved due to the process, in particular when filling a cavity produced by deep drawing. In addition, the visual appearance of the granular mixture of a solid composition, in particular the powder, can be changed better compared to a compressed tablet, in particular differences in texture, such as coarse and fine particles as well as particles or areas with different colors, overall or as colored speckles can be used to improve a visually appealing appearance. The grainy mixture of Solid composition, in particular the powder, also offers improved solubility compared to compressed tablets, even without the addition of disintegrants.

A phase in the sense of the present invention is a spatial region in which physical parameters and the chemical composition are homogeneous. One phase differs from another phase by various features, for example ingredients, physical properties, external appearance, etc. Different phases can preferably be distinguished visually. For the consumer, the at least one solid phase can be clearly distinguished from the at least one gel phase. If the cleaning agent according to the invention has more than one solid phase, these can also be distinguished from one another with the naked eye because they differ from one another in color, for example. The same applies if there are two or more gel phases. In this case too, an optical distinction between the phases is possible, for example due to a difference in color or transparency. Phases in the sense of the present invention are therefore self-contained areas that can be visually distinguished from each other by the consumer with the naked eye. The individual phases can have different properties when used, such as the speed at which the phase dissolves in water and thus the speed and sequence of release of the ingredients contained in the respective phase.

The at least one solid phase of the present invention comprises a granular mixture of a solid composition, in particular it is in powdery and free-flowing form. The 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, the 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 gelling agent at least PVOH and / or its derivatives, in particular preferably comprises at least PVOH and at least one polyhydric alcohol.

The flowability of a granular mixture, in particular a powdery solid, the powdery phase, preferably the powder and/or granules, relates to its ability to flow freely under its own weight. The flowability is determined by measuring the flow time of 1000 ml of cleaning agent powder from a standardized trickle test funnel with an outlet of 16.5 mm diameter, initially closed at its outlet direction, by measuring the time for the granular mixture to completely flow out, in particular the powdery phase of the powder and/or granules, e.g. the powder after opening the outlet, is measured and compared with the outlet speed (in seconds) of a standard test sand, the outlet speed of which is defined as 100%. The defined sand mixture for calibrating the trickle 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 ]. To dry, the sea sand is dried for 24 hours at 60 °C in a drying cabinet on a plate with a maximum layer height of 2 cm before the measurement.

Preferred embodiments of the solid phases according to the invention have an angle of repose / angle of repose of 26 to 35, from 27 to 34, from 28 to 33, the angle of repose according to the method mentioned below after 24 hours after the production of the granular mixture of the solid composition, in particular the powdery one solid phase, preferably the powder and/or granules, and storage at 20 °C. Such angles of repose have the advantage that the cavities can be filled with the at least one solid phase comparatively quickly and precisely.

To determine the angle of repose (or also known as the angle of repose) of the at least one solid phase, a powder funnel with a content of 400 ml and a drain with a diameter of 25 mm is hung straight into a tripod. The hopper is moved upwards at a speed of 80 mm/min by means of a manually operated knurled wheel, so that the granular mixture, in particular the powdery phase, preferably the powder and/or granules, e.g. the powder, trickles out. This creates a so-called cone of debris. The cone height and the cone diameter are determined for the individual solid phases. The slope angle is calculated from the quotient of the cone height and the cone diameter * 100.

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

Lower values for the flowability are rather unsuitable since, from a process engineering point of view, precise metering of the granular mixture, in particular the powdery phase, preferably the powder and/or granules, for example the powder, is necessary. In particular, values greater than 50%, in particular greater than 55%, preferably greater than 60% (the measurement of the flowability being carried out 24 hours after the powder has been produced and stored at 20 ° C) have proven to be advantageous because of the good dosability the granular mixture, in particular the powdery phases, preferably the powders and/or granules, for example powders, result in only slight fluctuations in the metered amount or the composition. The more precise dosing leads to consistent product performance, thus avoiding economic losses due to overdosing. Furthermore, it is advantageous that the granular mixtures, in particular the powdery phase, preferably the powder and/or granules, for example the powder, can be easily dosed, so that the dosing process runs more quickly. Furthermore, such good flowability better prevents the granular mixture, in particular the powdery phase, preferably the powder and/or granules, for example the powder, from reaching the part of the water-soluble coating that is intended for producing the sealing seam and therefore as far as possible should remain grain-free, especially powder-free.

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

The cleaning agent according to the invention preferably comprises at least one surfactant. This surfactant is selected from the group of anionic, nonionic and cationic surfactants. The cleaning agent according to the invention can also contain mixtures of several surfactants selected from the same group.

According to the invention, the at least one solid phase and/or the at least one gel phase comprise at least one surfactant. It is possible that only the at least one solid phase or only the at least one gel phase comprise at least one surfactant. If both phases comprise a surfactant, they are preferably different surfactants. However, it is also possible for the solid and gel phases to have the same surfactant or surfactants. At least one solid and/or gel phase according to the invention preferably contains at least one nonionic surfactant. All nonionic surfactants known to those skilled in the art can be used as nonionic surfactants. Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic 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 nonionic surfactants are specified in more detail below.

Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these non-ionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Particular preference is given to ethoxylated nonionic surfactants which consist of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol were won. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol with 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol of ethylene oxide. Of these, the so-called “narrow range ethoxylates” are particularly preferred.

Surfactants to be used preferably come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants). Such (PO/EO/PO) nonionic surfactants are also characterized by good foam control.

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder einbeziehungsweise mehrfach ungesättigten C_6-24-Alkyl- oder-Alkenylrest steht; jede Gruppe R² beziehungsweise R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, -CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.In the context of the present invention, low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred. Among these, surfactants with EO-AO-EO-AO blocks are preferred, with one to ten EO or AO groups bonded to each other before a block from the other groups follows. Here are nonionic surfactants of the general formula

preferred, in which R ¹ represents a straight-chain or branched, saturated or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ³ is independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH(CH ₃ ) ₂ and the indices w, x, y, z independently of one another stand for integers from 1 to 6.

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

As an alkylene oxide unit, which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in addition to propylene oxide, butylene oxide in particular comes into consideration. But other alkylene oxides in which R ² and R ³ are independently selected from -CH ₂ CH ₂ -CH ₃ or -CH(CH ₃ ) ₂ are also suitable. Preference is given to using nonionic surfactants of the above formula in which R ² and R ³ respectively represent a radical -CH ₃ , w and x independently represent values of 3 or 4 and y and z independently represent values of 1 or 2.

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

Nonionic surfactants of the general formula are preferred

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 radical or alkenyl radical with 6 to 22 carbon atoms; x and y independently represent values between 1 and 40.

Compounds of the general formula are particularly preferred

R ¹ -CH(OH)CH ₂ -O(CH ₂ CH ₂ O) _x CH ₂ CHR(OCH ₂ CH ₂ ) _y O-CH ₂ CH(OH)-R ² ,

in which R represents a linear, saturated alkyl radical with 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms and n and m independently have values of 20 to 30. Corresponding compounds can be obtained, for example, by reacting alkyl diols HO-CHR-CH ₂ -OH with ethylene oxide, followed by a reaction with an alkyl epoxide to close the free OH functions to form a dihydroxy ether.

• R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• R² für Wasserstoff oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• A, A', A" und A‴ unabhängig voneinander für einen Rest aus der Gruppe -CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, -CH₂-CH(CH₂-CH₃) stehen,
• w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können.

Preferred nonionic surfactants are those of the general formula R ¹ -CH(OH)CH ₂ O-(AO) _w -(AO) _x -(A"O) _y -(A‴O) _z -R ² , in which

• R ¹ represents a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ² represents hydrogen or a linear or branched hydrocarbon radical 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.

By adding the aforementioned nonionic 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 which contain alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

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

neben einem Rest R¹, welcher für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 2 bis 30 Kohlenstoffatomen, vorzugsweise mit 4 bis 22 Kohlenstoffatomen steht, weiterhin einen linearen oder verzweigten, gesättigten oder ungesättigten, aliphatischen oder aromatischen Kohlenwasserstoffrest R² mit 1 bis 30 Kohlenstoffatomen aufweisen, wobei n für Werte zwischen 1 und 90, vorzugsweise für Werte zwischen 10 und 80 und insbesondere für Werte zwischen 20 und 60 steht. Insbesondere bevorzugt sind Tenside der vorstehenden Formel, in denen R¹ für C₇ bis C₁₃, n für eine ganze natürliche Zahl von 16 bis 28 und R²für C₈ bis C₁₂ steht.Particularly preferred are those end-capped poly(oxyalkylated) nonionic surfactants which have the following formula

in addition to a radical R ¹ , which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, further a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² with 1 to 30 carbon atoms, where n stands for values between 1 and 90, preferably for values between 10 and 80 and in particular for values between 20 and 60. Particularly preferred are surfactants of the above formula in which R ¹ is C ₇ to C ₁₃ , n is an integer natural number from 16 to 28 and R ² is C ₈ to C ₁₂ .

Surfactants of the formula R ¹ O[CH ₂ CH(CH ₃ )O] _x [CH ₂ CH ₂ O] _y CH ₂ CH(OH)R ² , in which R ¹ represents a linear or branched aliphatic hydrocarbon radical with 4, are particularly preferred up to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical 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. The group of these nonionic surfactants includes, for example, the C _2-26 fatty alcohol (PO) ₁ -(EO) _15-40 -2-hydroxyalkyl ethers, in particular the C _8-10 fatty alcohol (PO) ₁ -(EO) ₂₂ -2 -hydroxydecyl ether.

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

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

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

• R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C 6-24-Alkyl- oder -Alkenylrest steht;
• R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• A für einen Rest aus der Gruppe CH₂CH₂, CH₂CH₂CH₂, CH₂CH(CH₃), vorzugsweise für CH₂CH₂ steht, und
• w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht.

Particularly preferred end-capped poly(oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula becomes R ¹ O[CH ₂ CH(R ³ )O] _x CH ₂ CH(OH )CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ³ are as defined above and x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ² has 9 to 14 carbon atoms, R ³ is H and x has values of 6 to 15. As special Finally, the nonionic surfactants of the general formula R ¹ -CH(OH)CH ₂ O-(AO) _w -R ² have proven to be effective, in which

• R ¹ represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical;
• R ² represents a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A represents a radical from the group CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH(CH ₃ ), preferably CH ₂ CH ₂ , and
• w represents values between 1 and 120, preferably 10 to 80, in particular 20 to 40.

The group of these nonionic surfactants includes, for example, the C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, in particular the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ethers and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ether.

The at least one solid and/or the at least one gel phase preferably contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, the proportion by weight of the nonionic surfactant in the total weight of the gel phase preferably being 0.5% by weight to 30% by weight. -%, preferably 5% by weight to 25% by weight and in particular 10% by weight to 20% by weight.

In a further preferred embodiment, the nonionic surfactant of the solid and/or gel phase is selected from nonionic 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 radical or alkenyl radical having 4 to 22 carbon atoms; R ³ and R ⁴ independently represent H or an alkyl radical or alkenyl radical with 1 to 18 carbon atoms and x and y independently represent values between 1 and 40.

Particular preference is given to compounds of the general formula R ¹ -O(CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which R ³ and R ⁴ are H and the indices x and y independently assume values from 1 to 40, preferably from 1 to 15.

Compounds of the general formula R ¹ -O(CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² in which the radicals R ¹ and R ² independently of one another are saturated alkyl radicals with 4 to Represent 14 carbon atoms and the indices x and y independently assume values from 1 to 15 and in particular from 1 to 12.

Further preferred are those compounds of the general formula R ¹ -O(CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² in which one of the radicals R ¹ and R ² is branched. Compounds of the general formula R ¹ -O(CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which the indices x and y independently assume values of 8 to 12, are very particularly preferred.

The specified C chain lengths and degrees of ethoxylation or alkoxylation of the nonionic surfactants represent statistical average values, which can be a whole or a fractional number for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned usually do not consist of an individual representative, but rather of mixtures, which means that average values and the resulting fractional numbers can result for both the C chain lengths and the degrees of ethoxylation or alkoxylation.

Of course, the aforementioned nonionic surfactants (niotensides) can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.

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

Suitable nonionic surfactants that have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants that can be solid or highly viscous at room temperature. If nonionic surfactants are used that are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa s, preferably above 35 Pa s and in particular above 40 Pa s. Niotensides, which have a waxy consistency at room temperature, are also preferred.

The nonionic surfactant, which is solid at room temperature, preferably has propylene oxide units (PO) in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule account for up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic identify surfactants. Further nonionic surfactants with melting points above room temperature, which are particularly preferably used in the solid phase, contain 40 to 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend, which contains 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

In a preferred embodiment, the proportion by weight of the nonionic surfactant in the total weight of the solid phase is from 0.1 to 20% by weight, particularly preferably from 0.5 to 15% by weight, in particular from 2.5 to 10% by weight. .

All anionic surface-active substances are suitable as anionic surfactants in dishwashing detergents. These are characterized by a water-soluble, anionic group such as: B. a carboxylate, sulfate or sulfonate group and a lipophilic alkyl group with about 8 to 30 carbon atoms. In addition, the molecule may 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 the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group, but also zinc, manganese (II), magnesium, calcium or Mixtures of these can serve as counterions. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

Instead of the surfactants mentioned or in conjunction with them, 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.

Surfactants influence the opacity of the gel phase. In another embodiment, the gel phase is therefore free of nonionic surfactants, in particular free of surfactants. “Free from” means that the gel phase contains less than 1.0% by weight and in particular less than 0.1% by weight, preferably no surfactant or no nonionic surfactant).

Preferred cleaning agents according to the invention are further characterized in that they contain less than 1.0% by weight and in particular less than 0.1% by weight in the at least one solid and/or the at least one gel phase, in particular in the solid phase. preferably contain no anionic surfactant.

According to a particularly preferred embodiment, the cleaning agents according to the invention are characterized in that the at least one gel phase contains less than 1% by weight, in particular less than 0.5% by weight, in particular less than 0.1% by weight of anionic surfactant to the total weight of the gel phase.

Preferably, the at least one gel phase is essentially free of anionic surfactants. Essentially free means that the at least one gel phase contains less than 0.05% by weight of anionic surfactant, based on the total weight of the gel phase.

In this context, it has been shown that the presence of 1% by weight of anionic surfactant in the at least one gel phase leads to poorer foaming behavior and poorer rinsing behavior of the overall composition. Furthermore, higher amounts of anionic surfactants have a negative effect on curing. According to a particularly preferred embodiment, the gel phase contains less than 1% by weight, preferably less than 0.5% by weight, in particular less than 0.05% by weight, of fatty acid salts or soaps.

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

In a further embodiment, the gel phase can comprise disaccharides, in particular sucrose. The proportion of sucrose is 0% by weight to 30% by weight, in particular 5% by weight to 25% by weight, particularly preferably 10% by weight to 20% by weight, based on the weight of the gel phase . In larger quantities, the sugar does not completely dissolve in the gel phase and causes it to become cloudy. The use of sugar, in particular in a proportion of 10% to 5% to 15% by weight, reduces the development of moisture and thus improves the adhesion to at least one solid phase.

The use of builder substances (builders) 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.

In a particularly preferred embodiment according to the invention, the use of phosphates (including polyphosphates) is largely or completely dispensed with. In this embodiment, the agent preferably contains less than 5% by weight, particularly preferably less than 3 % by weight, in particular less than 1% by weight of phosphate(s). In this embodiment, the agent is particularly preferably completely phosphate-free, ie the agent contains less than 0.1% by weight of phosphate(s).

The builders include, in particular, carbonates, citrates, phosphonates, organic builders and silicates. The proportion by weight of the total builders in the total weight of agents according to the invention is preferably 15 to 80% by weight and in particular 20 to 70% by weight.

Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which have more than one, in particular two to eight acid functions, preferably two to six, in particular two, three, four or five acid functions carried throughout the molecule. Dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids, are preferred as polycarboxylic acids. The polycarboxylic acids can carry additional functional groups, such as hydroxyl or amino groups. For example, these are 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 referred to as N,N-bis(carboxymethyl)-L-glutamic acid or GLDA), methylglycinediacetic acid (MGDA) and their derivatives and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures of these.

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

In addition to their builder effect, the free acids typically also have the properties of an acidifying component. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned.

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

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

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

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

The cleaning agents according to the invention, in particular dishwashing detergents, preferably machine dishwashing detergents, can contain, in particular, phosphonates as a further builder. 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. The preferred aminoalkane phosphonates are ethylenediaminetetramethylene phosphonate (EDTMP), diethylenetriaminepentamethylene phosphonate (DTPMP) and their higher homologues. Phosphonates in agents according to the invention are preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8 % by weight, very particularly preferably from 2.5 to 7.5% by weight, based on the total weight of the agent.

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 contains amounts of, based on the total weight of the agent, 10 to 25% by weight of citrate, 10 to 30% by weight of carbonate (or bicarbonate), and 2.5 to 7.5% by weight. Phosphonate used.

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

The percentage by weight of the further phosphorus-free builder, in particular MGDA and/or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 25% by weight. The use of MGDA or GLDA, in particular MGDA, as granules is particularly preferred. MGDA granules that contain as little water as possible and/or have lower hygroscopicity (water absorption at 25 ° C, normal pressure) compared to non-granulated powder are advantageous. The combination of at least three, in particular at least four builders from the group mentioned above has proven to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents. In addition, other builders may also be included.

Polymeric polycarboxylates are also suitable as organic builders; these are, for example, 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. Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g/mol. Due to their superior solubility, the short-chain polyacrylates, which have molecular weights of 1,100 to 10,000 g/mol, and particularly preferably of 1,200 to 5,000 g/mol, may be preferred from this group.

The content of (homo)polymeric polycarboxylates in the cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, is preferably 0.5 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight.

Cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, can also contain _, as a builder, crystalline layered silicates of _the general _formula NaMSi from 1.9 to 4, particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20. Amorphous sodium silicates with a modulus Na ₂ O:SiO ₂ of 1:2 to 1:3.3, preferably from 1:2 to 1:2.8 and in particular from 1:2 to 1:2.6, which can also be used preferably have delayed dissolution and have secondary washing properties.

In addition to the aforementioned builders, the cleaning agents according to the invention can also contain alkali metal hydroxides. These alkali carriers are used in the cleaning agents and in particular in the at least one gel phases preferably only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably between 0. 1 and 5% by weight and in particular between 0.5 and 5% by weight, each based on the total weight of the cleaning agent. Alternative cleaning agents according to the invention are free of alkali metal hydroxides.

As a further component, 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; Based on the natural molecules, improved variants are available for use in cleaning agents and are therefore preferred. Cleaning agents according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 % by weight to 5% by weight, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the Biuret method.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN' and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, which can be assigned to the subtilases but no longer to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.

Examples of amylases that can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the aforementioned amylases that have been improved for use in cleaning agents. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) should be highlighted.

Lipases or cutinases can also be used according to the invention, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally available or further developed from Humicola lanuginosa (Thermomyces lanuginosus), in particular those with the amino acid exchange in the positions D96LT213R and / or N233R, particularly preferably all of the exchanges D96L, T213R and N233R.

Enzymes can also be used, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (=pectinases), pectin esterases, pectate lyases, xyloglucanases (=xylanases), pullulanases and β-glucanases.

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

Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations. These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or mixed with stabilizers or other aids.

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

Furthermore, it is possible to assemble two or more enzymes together so that a single granulate has several enzyme activities.

As can be seen from the previous statements, the enzyme protein only forms a fraction of the total weight of common enzyme preparations. Protease and amylase preparations used according to the invention contain between 1 and 40% by weight, preferably between 2 and 30% by weight, particularly preferably between 3 and 25% by weight of the enzyme protein. Particular preference is given to cleaning agents which, based on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of the respective enzyme preparations contain.

In addition to the components listed so far, the at least one solid and/or the at least one gel phase of the cleaning agent according to the invention can contain further ingredients. These include, for example, anionic, cationic and/or amphoteric surfactants, bleaches, bleach activators, bleach catalysts, other solvents, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver preservatives, glass corrosion inhibitors, foam inhibitors, dyes, fragrances (particularly in the at least one solid phase), additives to improve the drainage and drying behavior, to adjust the viscosity, for stabilization, UV stabilizers, preservatives, antimicrobial active ingredients (disinfectants), pH adjusters in amounts of usually not more than 5% by weight.

Agents according to the invention preferably contain at least one alkanolamine as a further solvent. The alkanolamine is preferably selected from the group consisting of Mono-, di-, triethanol and propanolamine and mixtures thereof. The alkanolamine is contained in agents according to the invention preferably in an amount of 0.5 to 10% by weight, in particular in an amount of 1 to 6% by weight. In preferred cleaning agents, the at least one gel phase is essentially free of alkanolamine, ie the at least one gel phase contains less than 1% by weight, in particular less than 0.5% by weight, preferably less than 0.1% by weight, particularly preferably less than 0.05% by weight of alkanolamine and the alkanolamine is only contained in the at least one solid phase.

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

Polymers suitable as additives are, in particular, maleic acid-acrylic acid copolymer Na salt (for example ^Sokalan® CP 5 from BASF, Ludwigshafen (Germany)), modified polyacrylic acid Na salt (for example ^Sokalan® CP 10 from BASF, Ludwigshafen (Germany). )), modified polycarboxylate Na salt (for example ^Sokalan® HP 25 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example ^Silwet® L-77 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example Silwet ^® L-7608 from BASF, Ludwigshafen (Germany)) and polyether siloxanes (copolymers of polymethyl siloxanes with ethylene oxide/propylene oxide segments (polyether blocks)), preferably water-soluble linear polyether siloxanes with terminal polyether blocks such as Tegopren ^® 5840, Tegopren ^® 5843, Tegopren ^® 5847, ^Tegopren® 5851, ^Tegopren® 5863 or ^Tegopren® 5878 from Evonik, Essen (Germany). Builder substances suitable as additives are, in particular, polyaspartic acid Na salt, ethylenediamine triacetate, coconut alkyl acetamide (for example Rewopol ^® CHT 12 from Evonik, Essen (Germany)), methylglycinediacetic acid triNa salt and acetophosphonic acid. Mixtures with surfactant or polymeric additives show synergisms in the case of Tegopren ^® 5843 and Tegopren ^® 5863. However, the use of Tegopren types 5843 and 5863 is less preferred when applied to hard glass surfaces, especially glass tableware, as these can absorb silicone surfactants onto glass. In a special embodiment of the invention, the additives mentioned are dispensed with.

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

As a preferred bleaching agent, cleaning agents according to the invention contain an oxygen bleaching agent from the group consisting of sodium percarbonate, sodium perborate tetrahydrate and Sodium perborate monohydrate. Other useful bleaching agents include, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -providing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminooperic acid or diperdodecanedioic acid. Bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxyacids, with alkylperoxyacids and arylperoxyacids being particularly mentioned as examples. Sodium percarbonate is particularly preferred because of its good bleaching performance. A particularly preferred oxygen bleach is sodium percarbonate.

Compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid can be used as bleach activators. Substances which carry O- and/or N-acyl groups of the stated number of carbon atoms and/or optionally substituted benzoyl groups are suitable. Multiply acylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) proving to be particularly suitable.

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 N-containing tripod ligands as well as Co, Fe, Cu and Ru ammine complexes can also be used as bleaching catalysts. Manganese complexes in the oxidation state II, III, IV or IV are particularly preferably used, which preferably contain one or more macrocyclic ligand(s) with the donor functions N, NR, PR, O and/or S. Ligands which have nitrogen donor functions are preferably used. It is particularly preferred to use bleaching catalyst(s) in the agents according to the invention which have 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN) as macromolecular ligands ), 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 ).

The cleaning agent according to the invention preferably comprises at least one solid phase and at least one gel phase. The cleaning agent can therefore have one, two, three or more different solid phases; it can also have one, two, three or more different gel phases. The cleaning agent according to the invention preferably comprises a solid phase and a gel phase. This particularly preferably includes Cleaning agent two solid phases and a gel phase. It preferably comprises two solid phases and two gel phases. Also preferred is an embodiment in which the cleaning agent comprises three solid phases and one or two gel phases.

The weight ratio of the total of the at least one solid phase to the total of the at least one gel phase is generally 40:1 to 2:1, in particular 20:1 to 4:1, preferably 14:1 to 6:1, for example 12:1 up to 8:1. The total weight of all phases in a cleaning agent portion 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 cleaning agent portion. This weight ratio results in a good concentration of the respective ingredients of the solid or gel phase in a cleaning process.

According to the invention, the at least one solid phase and the at least one gel phase border one another over the entire or partial area. It is preferred that the two phases directly border one another.

If the at least one solid phase and the at least one gel phase border one another directly over the entire or partial area, stability is important in addition to the shortest possible solidification time of the at least one gel phase. Stability here means that components contained in the gel phase do not pass into the at least one solid phase, but even after prolonged storage the at least one solid phase and the gel phase are optically separated from one another and do not interact with one another, such as, for example, diffusion of liquid components one into the other phase or reaction of components in one phase with those in the other phase. Surprisingly, it has been shown that this is achieved by a gel phase which, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate, also contains polyethylene glycols with an average molecular weight of 200 to 600 g/mol, glycerol, PVOH and at least one _C3 - up to C ₅ alkanediol can be made possible.

Another subject of the present invention is also the use of a cleaning agent, as described above, for the automatic cleaning of dishes.

For the use or the method, what was specifically disclosed above for the cleaning agents applies accordingly.

Insofar as it is stated in the present application that the cleaning agent according to the invention comprises something as a whole or in the at least one solid phase or in the at least one gel phase, it is also to be regarded as disclosed that the cleaning agent or the respective phase can consist of it. In the following exemplary embodiment, the cleaning agent according to the invention is described in a non-limiting manner.

Examples:

Cleaning agents according to the invention were produced which comprised a solid phase and a gel phase. Different geometries were realized here. Furthermore, cleaning agents were produced which comprised two solid phases and a gel phase. Cleaning agents were also produced that included a solid phase and 3, 4 and 5 gel phases (of the same or different composition). The following information refers to% by weight of active substance based on the total weight of the respective phase (unless otherwise stated). Table 1: The solid granular mixtures of a solid composition, in particular powdery and free-flowing phases, had the following preferred composition: % by weight Citrate, sodium salt 15-20 Phosphonate (e.g. HEDP) 2.5-7.5 MGDA, sodium salt 0-25 Disilicate, sodium salt 5-35 soda 10-25 SILVER PROTECTION (e.g. cysteine) 0.0 - 1.0 Percarbonate, sodium salt 10-15 Bleach catalyst (preferably Mn-based) 0.02-0.5 Bleach activator (e.g. TAED) 1-3 Non-ionic surfactant(s), e.g. fatty alcohol alkoxylate, preferably 20-40 EO, 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 Zn salt (e.g. acetate) 0.1-0.3 Sodium sulfate 0.0 - 10 Water 0.0-1.5 pH adjusting agent (e.g. citric acid) 0-1.5 Process aids 0-5 % by weight Water-soluble zinc salt (preferably zinc acetate anhydrate) 0.1-2.4 glycerin 10-50 Propanediol (preferably 1,3-propanediol) 10-50 Polycarboxylate copolymer with sulfonic acid-containing groups 0-30 Non-ionic surfactant(s), e.g. fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 0-40 Polyethylene glycol medium Mr 200-600, (for example PEG 400 (INCI) 8-26 PVOH 8-22 Process aids 0-10 dye solution 0.0 - 1.5 Mixture, other active ingredients, organic solvents, perfume, Add 100

The solid and gel phases could be combined with each other as desired. The spatial configuration of the gel phase, which was liquid after mixing the ingredients and remained dimensionally stable within a solidification time of a maximum of 10 minutes, was dictated by the spatial configuration of the solid phase as well as by commercially available or self-designed shapes. A water-soluble covering in the form of an open pouch was produced by deep drawing a film containing PVOH. A liquid composition was poured into this open cavity, which after hardening resulted in the gel phase, then solid phases in the form of a free-flowing solid were poured into a pouch comprising polyvinyl alcohol and the open pouch was then sealed by placing a second film and sealing using heat sealing. Table 3: Compositions of the gel phase In wt.% E1 E2 E3 V1 Zinc acetate anhydrous 0.5 1.0 2.0 0 Polymer comprising monomers containing acrylic acid and amidopropylsulfonic acid 11 11 0 11 Glycerin 25 25 25 25 1,3 propanediol 30 30 30 30 PEG 400 15 15 15 15 PVOH (Mowiol 4-88) 15 15 15 15 Misc (including processing aids, pH adjusters, perfume, dye) Add 100 Add 100 Add 100 Add 100

Corresponding formulations were prepared according to Table 3.

The gel phases were stirred at temperatures of 110 °C. After 16 h, the flowability of the gel phases was examined. E1, E2 and E3 showed good incorporation ability of the zinc acetate and formed a homogeneous, transparent gel phase. Compared to V1, E1 showed significantly better flowability even after 16 hours.

These gel phases were then prepared as described in Table 2 together with solid phases according to Table 1 in single portions with a total weight of 18.5 g. It was found that the gel phases produced in this way with solidification times of less than 1 minute had particularly good processing properties.

Claims (11)

1. Cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing detergent, comprising at least one gel phase containing 4.9 % by weight or less of water, based on the total weight of the gel phase, which comprises at least one water-soluble zinc salt, having a solubility of above 100 mg/l, preferably above 500 mg/l, particularly preferably above 1 g/l and especially above 5 g/l at 20°C in water, preferably zinc sulfate and/or zinc acetate, particularly preferably zinc acetate, and a gelling agent in an amount of from 4 to 40 % by weight, based on the total weight of the gel phase.
2. Cleaning agent according to claim 1, characterized in that the gel phase contains 4% by weight or less, preferably 2 % by weight or less, in particular 1 % by weight or less, especially 0.5 % by weight or less, in particular 0.1 % by weight or 0.05 % by weight or less water, based on the total weight of the gel phase.
3. Cleaning agent according to one of the preceding claims, characterized in that the gel phase contains the zinc salt in an amount of from 0.05 to 3 % by weight, in particular from 0.1 to 2.4 % by weight, very preferably from 0.2 to 1.0 % by weight, based on the total weight of the gel phase.
4. Cleaning agent according to one of the preceding claims, characterized in that it contains a gelling agent, preferably selected from gelatin, xanthan and/or polyvinyl alcohol, in particular gelatin or polyvinyl alcohol, particularly preferably polyvinyl alcohol, in an amount of 6 to 30 % by weight, particularly preferably in an amount of 7 to 24 % by weight, most preferably 8 to 22 % by weight, in each case based on the total weight of the gel phase.
5. Cleaning agent according to one of the preceding claims, characterized in that the gel phase contains at least one organic solvent, in particular selected from 1,2-propanediol, 1,3-propanediol, glycerol, 1,1,1-trimethylolpropane, triethylene glycol, dipropylene glycol, polyethlene glycols and/or mixtures thereof.
6. Cleaning agent according to claim 5, characterized in that the at least one organic solvent is present in the gel phase in amounts of from 30 to 90 % by weight, in particular from 40 to 85 % by weight, particularly preferably from 50 to 80 % by weight, based on the total weight of the gel phase.
7. Cleaning agent according to any one of the preceding claims, characterized in that the gel phase contains a polymer comprising sulfonic acid group-containing monomer, in particular a monomer selected from acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid.
8. Cleaning agent according to one of the preceding claims, characterized in that it additionally comprises at least one solid, in particular particulate, phase and optionally at least one further liquid/gel or solid phase.
9. Cleaning agent according to any one of the preceding claims, characterized in that it is a detergent portion in a water-soluble envelope having one or more chambers/compartments.
10. Cleaning agent according to any one of claims 8 or 9, characterized in that the gel phase is contained in direct contact, for example in a chamber, with the at least one solid phase.
11. Use of a cleaning agent according to any one of claims 1 to 10 for machine cleaning of tableware.