EP4067469A1 - Cleaning agent - Google Patents

Abstract

The invention relates to cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, comprising a gel, preferably a gel which is solid at room temperature (20° C.), in each case based on the total weight of the gel:a. 4 to 40% by weight, preferably 6 to 30% by weight, in particular 7 to 24% by weight, particularly preferably 8 to 22% by weight, very particularly preferably 12 to 20% by weight PVOH and/or its derivatives; b. 20 to 80% by weight of at least one organic solvent, preferably selected from the group consisting of 1,2-propanediol, 1,3-propanediol, polyethylene glycols and/or alkanetriols, preferably glycerol, 1,1,1-trimethylolpropane, and mixtures from it; c. 0.1 to 30% by weight of at least one polypropylene glycol, preferably having an average molecular weight of 500 to 10,000 g/mol, in particular 1000 to 6000 g/mol.

Description

1. a. 4 bis 40 Gew.-%, bevorzugt 6 bis 30 Gew.-%, insbesondere 7 bis 24 Gew.-%, besonders bevorzugt 8 bis 22 Gew.-%, ganz besonders bevorzugt 12 bis 20 Gew.-% PVOH und/oder dessen Derivate;
2. b. 20 bis 80 Gew.-% mindestens eines organischen Lösungsmittels, bevorzugt ausgewählt aus der Gruppe bestehend aus 1,2-Propandiol, 1,3-Propandiol, Polyethylenglykolen und/oder Alkantriolen, bevorzugt Glycerin, 1,1,1-Trimethylolpropan, sowie Mischungen daraus;
3. c. 0,1 bis 30 Gew.-% mindestens eines Polypropylenglykols, bevorzugt mit einem mittleren Molekulargewicht von 500 bis 10 000 g/mol, insbesondere von 1000 bis 6000 g/mol.

The invention relates to detergents, preferably dishwashing detergents, in particular machine dishwashing detergents, comprising a gel, preferably a gel which is solid at room temperature (20° C.), in each case based on the total weight of the gel:

1. a. 4 to 40% by weight, preferably 6 to 30% by weight, in particular 7 to 24% by weight, particularly preferably 8 to 22% by weight, very particularly preferably 12 to 20% by weight PVOH and/or its derivatives;
2. b. 20 to 80% by weight of at least one organic solvent, preferably selected from the group consisting of 1,2-propanediol, 1,3-propanediol, polyethylene glycols and/or alkanetriols, preferably glycerol, 1,1,1-trimethylolpropane, and mixtures from it;
3. c. 0.1 to 30% by weight of at least one polypropylene glycol, preferably having an average molecular weight of 500 to 10,000 g/mol, in particular 1000 to 6000 g/mol.

Cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, are usually in solid form (for example as tablets) or in liquid form (or else as a flowing gel). Liquid cleaning agents in particular are enjoying increasing popularity with consumers. Pre-portioned forms of presentation are popular with consumers because they are easier to dose. In this context, pre-portioned flowing gels are often problematic because they tend to leak, for example when packaged in single-chamber or multi-chamber bags. At the same time, it is necessary for such gels to have good cleaning and rinsing performance.

The object of the present invention is to provide cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, which can be produced simply and cost-effectively, have good storage stability and also have good cleaning and/or rinsing performance.

1. a. 4 bis 40 Gew.-%, bevorzugt 6 bis 30 Gew.-%, insbesondere 7 bis 24 Gew.-%, besonders bevorzugt 8 bis 22 Gew.-%, ganz besonders bevorzugt 12 bis 20 Gew.-% PVOH und/oder dessen Derivate;
2. b. 20 bis 80 Gew.-% mindestens eines organischen Lösungsmittels, bevorzugt ausgewählt aus der Gruppe bestehend aus 1,2-Propandiol, 1,3-Propandiol, Polyethylenglykolen und/oder Alkantriolen, bevorzugt Glycerin, 1,1,1-Trimethylolpropan, sowie Mischungen daraus;
3. c. 0,1 bis 30 Gew.-% mindestens eines Polypropylenglykols, bevorzugt mit einem mittleren Molekulargewicht von 500 bis 10 000 g/mol, insbesondere von 1000 bis 6000 g/mol.

A first subject matter of the present invention relates to cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, comprising a gel, preferably a gel which is solid at room temperature (20° C.), in each case based on the total weight of the gel:

1. a. 4 to 40% by weight, preferably 6 to 30% by weight, in particular 7 to 24% by weight, particularly preferably 8 to 22% by weight, very particularly preferably 12 to 20% by weight PVOH and/or its derivatives;
2. b. 20 to 80% by weight of at least one organic solvent, preferably selected from the group consisting of 1,2-propanediol, 1,3-propanediol, polyethylene glycols and/or alkanetriols, preferably glycerol, 1,1,1-trimethylolpropane, and mixtures thereof;
3. c. 0.1 to 30% by weight of at least one polypropylene glycol, preferably having an average molecular weight of 500 to 10,000 g/mol, in particular 1000 to 6000 g/mol.

According to the invention, a gel or a gel-like phase, also referred to below as a gel phase, means a composition (or phase) which has an internally structuring network. This internal structuring (spatial) network is formed by the dispersion of a solid but distributed substance with long or highly branched particles and/or gelling agent, here polyvinyl alcohol and/or its derivatives, in at least one liquid (the at least one liquid is liquid at 20° C) formed. Such gel phases behave thermoreversibly.

The cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, can have one, two, three, four or more gels or gel phases. The gels/gel phases can be the same or different. In the case of several gels or gel phases, these can preferably be distinguished spatially, optically or on the basis of their ingredients. If the gels/gel phases are different, they can have different dyes and different additions of active ingredients.

The gel is dimensionally stable. During production, the polyvinyl alcohol and/or its derivatives are brought into contact with glycerol. This gives a flowable mixture which can be brought into a desired shape. After a certain period of time, a gel/a gel phase is obtained which remains in the specified form, i.e. is dimensionally stable. This period of time, the setting time, is preferably 15 minutes or less, preferably 10 minutes or less, particularly preferably 5 minutes or less. The gel gives way under pressure, but does not deform as a result, but returns to its original state after the pressure is removed. The gel is preferably elastic, in particular linear-elastic.

The gel is preferably a shaped body. A molded body is a single body that stabilizes itself in its imposed shape. This dimensionally stable body is formed from a molding compound (e.g. a composition) by deliberately bringing this molding compound into a predetermined shape, e.g. by pouring a liquid composition into a mold and then curing the liquid composition, e.g. as part of a sol-gel process.

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

The gel is a solid gel phase. It is preferably cut-resistant. It can, for example, be cut with a knife after it has solidified without being destroyed further, except at the point where the cut was made.

A phase within the meaning of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous. A phase differs from another phase by various features, for example ingredients, physical properties, external appearance, etc. Various phases can preferably be distinguished visually.

Thus, the at least one gel phase can be clearly distinguished from other solid phases for the consumer. If the cleaning agent according to the invention, preferably dishwashing detergent, in particular machine dishwashing detergent, has more than one gel phase, these can also be distinguished from one another with the naked eye because they differ from one another, for example in terms of color. The same applies if two or more gel phases are present. In this case, too, an optical differentiation of the phases is possible, for example on the basis of a difference in color or transparency. Phases within the meaning of the present invention are therefore self-contained areas which the consumer can visually distinguish from one another with the naked eye. The individual phases can have different properties when used, such as the speed with which the phase dissolves in water and thus the speed and sequence of release of the ingredients contained in the respective phase.

In addition, the gel is preferably translucent (translucent) or transparent, which results in a good optical impression. The transmittance of the gel phase (without dye) is preferably in a range between 100% and 20%, between 100% and 30%, in particular between 100% and 40%. To measure the light transmittance (transmission), the permeability was determined in % at 600 nm against water as a reference at 20 °C. For this purpose, the mass was poured into the 11 mm round cuvettes provided and, after a storage time of 12 h at room temperature, measured in a LICO 300 color measuring system according to Lange.

The cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, contain polyvinyl alcohol and/or derivatives thereof in an amount of from 4 to 40% by weight, in particular from 6 to 30% by weight, particularly preferably in an amount of 8 to 18% by weight, very particularly preferably 12 to 20% by weight, based in each case on the total weight of the gel.

Polyvinyl alcohols are thermoplastics that are usually produced as a white to yellowish powder by the hydrolysis of polyvinyl acetate. Partially hydrolyzed polyvinyl alcohol which still has amounts of up to 30 mol % of non-hydrolyzed acetyl groups is to be understood as polyvinyl alcohol in the context of the invention. Polyvinyl alcohol (PVOH) is resistant to almost all anhydrous organic solvents. Polyvinyl alcohols with a molar mass of 30,000 to 60,000 g/mol are preferred.

Particular preference is given to polyvinyl alcohols, which are available as white-yellowish powders or granules with degrees of polymerization in the range from about 100 to 2500 (molar masses from about 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.

According to a preferred embodiment, the gel comprises PVOH (polyvinyl alcohol). The gels or gel phases produced in this way have a particularly high melting point, are dimensionally stable (even at 40° C.) and do not change their shape, if at all, only insignificantly, even during storage. In particular, they are also not very reactive with regard to a direct negative interaction with components of a granular mixture, in particular an additional powder phase. In particular, PVOH can produce low-water or water-free gel phases. When using PVOH as a polymer for the gel, low-viscosity melts are produced at 110-120 °C, which are particularly easy to process. In particular, the gel phase can be filled into the water-soluble coating quickly and precisely without sticking or the amount is dosed imprecisely. Furthermore, these gel phases adhere particularly well to the water-soluble coating, in particular if this is also made from PVOH. This is also a visual advantage. Due to the rapid solidification of the at least one gel phase with PVOH, the further processing of the gel phases can take place particularly quickly. Furthermore, the good solubility of the gel phases produced is particularly favorable for the overall solubility of the cleaning agent. In addition, gel phases with such short setting times are advantageous in the event that a solid, preferably granular 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 visually unappealing detergent portions.

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

PVOH powders with the properties mentioned above, which are suitable for use in the at least one gel phase, are marketed, for example, by Kuraray under the name ^Mowiol® or ^Poval® . ^Exceval® AQ4104 from Kuraray, for example, is also suitable. 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 by Kuraray.

According to 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 vinylacetic acid, alkyl acrylates, maleic acid and derivatives thereof, in particular monoalkyl maleates (especially monomethyl maleate), dialkyl maleates (especially dimethyl maleate), maleic anhydride, fumaric acid and derivatives thereof, in particular monoalkyl fumarate (especially monomethyl fumarate), dialkyl fumarate (especially dimethyl fumarate), fumaric anhydride, Itaconic acid and its derivatives, in particular monomethyl itaconate, dialkyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid (methylmaleic acid) and its derivatives, monoalkyl citraconic acid (especially methyl citraconic acid), dialkyl citraconic acid (dimethyl citraconic acid), citraconic acid anhydride, mesaconic acid (methyl fumaric acid) and its derivatives, monoalkyl mesaconate, dialkyl mesaconate, mesaconic acid anhydride, glutaconic acid and their derivatives, monoalkyl glutaconate, dialkyl glutaconate, glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1-methylpropane sulfone acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate and combinations thereof, and the alkali metal salts or esters of the abovementioned monomers.

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

The water solubility of polyvinyl alcohol can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization). Also these are as derivatives of To understand polyvinyl alcohol. 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 of polyvinyl alcohol and starch can be used extremely advantageously. Furthermore, the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus adjusted to desired values.

The gel contains 0.1 to 30% by weight of at least one polypropylene glycol as a further essential component. Mixtures of different polypropylene glycols can of course be used. These are commercially available, for example, under the trade name ^Pluriol® (BASF).

According to a preferred embodiment, the mean molecular weight of the propylene glycol is from 500 to 10,000 g/mol, in particular from 1000 to 6000 g/mol.

According to a particularly preferred embodiment, polypropylene glycol is contained in an amount of 0.6 to 25% by weight, preferably in an amount of 1 to 15% by weight, based in each case on the total weight of the gel.

Surprisingly, it was found that gels with polypropylene glycol(s) with an average molecular weight of the propylene glycol of 500 to 10,000 g/mol, in particular 1000 to 6000 g/mol, work particularly well on stubborn, greasy deposits on hard surfaces, in particular on items to be washed. A particularly positive cleaning performance is achieved with greasy residues and burnt and/or baked-on food residues. An effect on the rinsing performance is also surprisingly found.

The gel or the gel phase contains 20 to 80% by weight of at least one organic solvent. The organic solvents are preferably selected from the group consisting of 1,2-propanediol, 1,3-propanediol, dipropylene glycol, triethylene glycol, polyethylene glycols and/or alkanetriols, preferably glycerol, 1,1,1-trimethylolpropane, and mixtures of the solvents mentioned.

According to a particularly preferred embodiment, the at least one organic solvent in the gel phase in amounts of 30 to 75% by weight, in particular 40 to 70% by weight, is particularly preferred in the cleaning agents according to the invention, preferably dishwashing detergents, in particular automatic dishwashing detergents from 50 to 65% by weight based on the total weight of the gel.

The at least one gel phase preferably comprises at least one polyhydric alcohol. In addition to the production of free-flowing gel phases, the at least one polyhydric alcohol also enables the production of a dimensionally stable, non-flowable gel phase within a short setting time, which is within 15 minutes or less, in particular 10 minutes or less. For the purposes of the present invention, polyhydric alcohols are hydrocarbons in which two, three or more hydrogen atoms have been replaced by OH groups. The OH groups are each attached 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 thus corresponds to the general formula [KW](OH) _x , where KW is a hydrocarbon which 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. HC comprises at least two carbon atoms. The polyhydric alcohol comprises 2, 3 or more OH groups (x=2, 3, 4...), with only one OH group being bonded to each carbon atom of the hydrocarbon. HC particularly preferably comprises 2 to 10, ie 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. In particular, polyhydric alcohols with x=2, 3 or 4 (for example pentaerythritol with x=4) can be used. x=2 (alkanediol) and/or x=3 (alkanetriol) is preferred.

The at least one gel phase particularly preferably comprises at least one alkanetriol and/or at least one alkanediol, in particular at least one C ₃ - to C ₁₀ -alkanetriol and/or at least one C ₃ - to C ₁₀ - alkanediol, preferably at least one C ₃ - to C C ₈ -alkanetriol and/or at least one C ₃ - to C ₈ - alkanediol, particularly at least one C ₃ - to C ₆ -alkanetriol and/or at least one C ₃ - to C ₅ - alkanediol as polyhydric alcohol. It preferably comprises an alkanetriol and an alkanediol as at least one polyhydric alcohol. In a preferred embodiment, the at least gel phase therefore comprises at least one polymer, in particular PVOH or PVOH with gelatin, and at least one alkanediol and at least one alkanetriol, in particular an alkanetriol and an alkanediol. Also preferred is a gel phase which comprises at least one polymer, _PVOH or PVOH with gelatin, and a _C3 to C8 alkanediol and a _C3 to C8 _alkanetriol . A gel phase which comprises at least one polymer, in particular PVOH or PVOH with gelatin, and a C ₃ - to C ₅ -alkanediol and a C ₃ - to C ₆ -alkanetriol is further preferred. According to the invention, the polyhydric alcohols do not include derivatives such as ethers, esters, etc. thereof.

Surprisingly, it has been found that a particularly short solidification time can be achieved when a corresponding triol (alkanetriol) is combined with a corresponding diol (alkanediol). The gel phases obtained are also transparent and have a glossy surface, which is responsible for an attractive visual impression of the invention cleaning agent. The terms diol and alkanediol are used synonymously here. The same applies to triol and alkanetriol.

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 here 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 preferably 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 located 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 is particularly preferably 1,3-propanediol. Surprisingly, it has been shown that particularly good results are achieved with mixtures which comprise glycerol and 1,3-propanediol and/or 1,2-propanediol.

According to a particularly preferred embodiment, the preferred organic solvent is glycerol, preferably in an amount of 5 to 50% by weight, preferably 10 to 45% by weight, particularly preferably 20 to 40% by weight of glycerol, based on the total weight of the gel , contain.

According to a particularly preferred embodiment, the proportion of 1,3-propanediol or 1,2-propanediol, based on the total weight of the gel, is preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight %, especially 20% to 45% by weight. If the gel phase contains 1,3-propanediol, the proportion of 1,3-propanediol, based on the total weight of the gel, is in particular 5% by weight to 50% by weight, in particular 20% by weight to 40% by weight wt%. It is particularly preferably 28 to 35% by weight, based on the total weight of the gel.

The gel phase comprises, in each case based on the total weight of the gel phase, in addition to at least one polypropylene glycol, preferably with an average molecular weight of 1000 to 6000 g/mol, in an amount of 1 to 15% by weight, 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) an alkanetriol, in particular glycerol or 1,1,1-trimethylolpropane, the proportion of alkanetriol, in particular glycerol or 1,1,1-trimethylolpropane, based on that Total weight of the gel phase, between 3 and 75% by weight, preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, particularly 20% by weight to 40% by weight %.

If the gel phase 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% to 65% by weight, especially 20% to 40% by weight.

If glycerol is contained as an alkanetriol in the gel phase, the proportion of glycerol, based on the total weight of the gel phase, is preferably 5% by weight to 50% by weight, in particular 10% by weight to 55% by weight, particularly 20 wt% to 40 wt%. According to a particularly preferred embodiment, the gel contains 23 to 29.5% by weight, particularly preferably 25 to 28% by weight, of glycerol, based on the total weight of the gel phase.

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% to 40% by weight.

If the gel phase contains 2-amino-2-hydroxymethyl-1,3-propanediol, 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% to 65% by weight, particularly 20% 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, particularly 10% to 40% by weight.

In addition to at least one polypropylene glycol, preferably with an average molecular weight of 1000 to 6000 g/mol, the gel phase comprises, based on the total weight of the gel phase, in an amount of 1 to 15% by weight, at least one water-soluble zinc salt, in particular zinc sulfate and/or or zinc acetate, in particular zinc acetate, (preferably in amounts from 0.1 to 2.4% by weight, particularly preferably from 0.2 to 1.0% by weight) at least one alkanediol, in particular 1,3-propanediol or 1 ,2-propanediol, the proportion of alkanediol, in particular 1,3-propanediol or 1,2-propanediol, based on the total weight of the gel phase, is preferably 5 % by weight to 70% by weight, in particular 10% by weight to 65% by weight, particularly 20% by weight to 45% by weight. If the gel phase contains 1,3-propanediol, 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% wt%.

Preference is given to a gel phase which, based on the total weight of the gel-like phase, contains at least one polypropylene glycol, preferably with an average molecular weight of 1000 to 6000 g/mol, in an amount of 1 to 15% by weight, at least one water-soluble zinc salt, in particular Zinc sulphate and/or zinc acetate, in particular zinc acetate (preferably in amounts of from 0.1 to 2.4% by weight, particularly preferably from 0.2 to 1.0% by weight) 20 to 45% by weight 1,3 Propanediol and/or 1,2-propanediol and 10% by weight to 65% by weight of 2-amino-2-hydroxymethyl-1,3-propanediol, based in each case on the total weight of the gel phase. Also preferred is a gel phase containing 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, each based on the 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, based in each case on the total weight of the gel phase, is particularly preferred. It has been shown that in these areas rapid solidification of a gel phase at 20° C. is possible, and the phases obtained are storage-stable and transparent. In particular, the proportion of glycerin has an effect on the curing time.

According to the invention, the gel phase preferably contains at least one polyethylene glycol.

Polyethylene glycols with an average molar mass of between about 100 and 8000 are particularly suitable. Mixtures thereof can also be used. The abovementioned polyethylene glycols are particularly preferably supplied in amounts of 1 to 40% by weight, preferably 2 to 35% by weight, in particular 2.5 to 30% by weight, for example 3 to 20% by weight applied to the total weight of the gel phase or the gel.

The polyethylene glycols used are preferably liquid at 20° C. and 1 bar. According to the invention, preference is given to using polyethylene glycol(s) with an average molar mass of 200 to 600 g/mol in the at least one gel phase or the gel phases. In this case, in combination with polyvinyl alcohol, polyethylene glycols with an average molar mass of between about 200 and about 600 g/mol, preferably between 300 and 500 g/mol, particularly preferably between 350 and 450 g/mol, for example around 400 g/mol INCI: PEG400) deployed. Cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, are thus characterized in that they have polyethylene glycol(s) with an average molar mass of 300 to 500 g/mol, in particular 350 to 450 g/mol.

Surprisingly, it has been shown that the addition of polyethylene glycols, in particular those with an average molar mass 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 of great advantage in particular for the production processes, since the further processing of the gel phases in the solidified state can be carried out much more quickly and therefore generally more cost-effectively. It has surprisingly been found that the presence of polyethylene glycol(s) with an average molar mass of 200 to 600 g/mol in combination with polyvinyl alcohol and/or its derivatives makes a decisive contribution to reducing the solidification times. Without being bound to theory, it is assumed that such polyethylene glycols, in particular those with a molar mass of 350 to 450 g/mol, increase the sol-gel temperature, in particular by 400 g/mol.

According to a particularly preferred embodiment, 2 to 20% by weight of polyethylene glycol, in particular 3 to 16% by weight of polyethylene glycol, preferably polyethylene glycol with an average molecular weight of 200 to 600, is present as the preferred organic solvent.

In a particularly preferred embodiment, the amount of polyethylene glycol(s) with an average molar mass of 350 to 450 g/mol, for example around 400 g/mol, is 3 to 16% by weight, based on the total weight of the gel.

According to a further embodiment, in addition to the polyethylene glycols mentioned with an average molar mass of 200 to 600 g/mol, further polyethylene glycols, in particular further polyethylene glycols, with an average molar mass between about 800 and 8000 can be contained in the at least one gel phase. The abovementioned polyethylene glycols are particularly preferably used in amounts of 1 to 20% by weight, preferably based in each case on the total weight of the gel.

According to a particularly preferred embodiment, the water content of the gel is less than 30% by weight, less than 20% by weight, preferably less than 15% by weight, in particular less than 10% by weight, particularly preferably less than 5% by weight %, most preferably less than 1% by weight, based on the total weight of the gel.

According to a preferred embodiment, the gel is essentially anhydrous. This means that the gel is preferably essentially free of water. "Essentially free" here means that small amounts of water can be contained in the gel phase. This water can be introduced into the phase, for example, by a solvent or as water of crystallization or as a result of reactions of components of the phase with one another. However, preferably only small amounts, in particular no water, are used as the solvent for the production of the gel phase. The proportion of water in the gel phase is in this Embodiment 4.9% by weight or less, 4% by weight or less, preferably 2% by weight or less, in particular 1% by weight or less, particularly 0.5% by weight or less, in particular 0 .1% by weight or 0.05% by weight or less. The percentages by weight relate to the total weight of the gel.

These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Each feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it should be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not limited to these examples. All percentages are % by weight unless otherwise specified. Numerical ranges given in the format "from x to y" include the stated values. Where multiple preferred numeric ranges are given in this format, it is understood that any ranges resulting from the combination of the different endpoints are also included. "At least one" as used herein means 1 or more, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With regard to an ingredient, the information refers to the type of ingredient and not to the absolute number of molecules. "At least one bleach catalyst" thus means, for example, at least one type of bleach catalyst, i.e. it can mean one type of bleach catalyst or a mixture of several different bleach catalysts. Together with weight information, the information refers to all compounds of the type specified that are contained in the composition/mixture, i.e. 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 relates to the number-average molar mass M _n , unless explicitly stated otherwise. The number average molar mass can be determined, for example, by means of gel permeation chromatography (GPC) in accordance with DIN 55672-1:2007-08 with THF as the eluent. The mass-average molar mass M _w can also be determined by GPC, as described for M _n .

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

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

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

A change in volume or shrinkage during storage would be disadvantageous, since this would result in poor acceptance of the product by consumers. Escape of liquid or exudation of components from the gel phase is also undesirable. On the one hand, the visual impression is also relevant here. The stability of the gel phase can be influenced by the emergence of liquid, such as solvents, so that the components are no longer contained in a stable manner and the washing or cleaning effect can thereby also be influenced.

According to a particularly preferred embodiment, cleaning agents in which at least one other ingredient of the gel is selected from dyes, glass corrosion inhibitors, anionic polymers, nonionic surfactants and other processing aids, in particular perfume, pH adjusters.

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 from 0.05 to 5% by weight, in particular from 0.1 to 2.0% by weight %, most preferably from 0.2 to 1.0% by weight, based on the total weight of the gel.

According to a further preferred embodiment of the present invention, detergents, preferably dishwashing detergents, in particular automatic dishwashing detergents, which are packaged as a detergent portion, preferably dishwashing detergent portion, in particular automatic dishwashing detergent portion, which preferably contain the active ingredients required for a cleaning cycle, are packaged as 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 dishwashing agent portion, in particular machine dishwashing 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 detergent portion, preferably dishwashing detergent portion, in particular automatic dishwashing detergent portion, which is used to carry out a single cleaning cycle, in particular in a cleaning cycle of an automatic dishwasher, is added from 0.0005 to 1 g, preferably from 0.01 to 0.5 g , In particular 0.02 to 0.06 g of water-soluble zinc salts, in particular zinc sulphate and/or zinc acetate, in particular zinc acetate.

Particularly preferably, an individual cleaning agent portion according to the invention, preferably a dishwashing agent portion, in particular an automatic dishwashing agent portion, 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 the cleaning agent, preferably dishwashing agent, in particular machine dishwashing agent.

Very particularly preferred embodiments of the present invention comprise at least one gel phase/or Gel in each case based on the total weight of the gel polypropylene glycol(s), preferably with an average molecular weight of 1000 to 6000 g/mol, in an amount of 1 to 15% by weight, 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% by weight), 8 to 22% by weight PVOH, 20 to 40% by weight glycerol, 5 to 15% by weight polyacrylate copolymer containing sulfonic acid groups, and 1 up to 20% by weight, in particular 3 to 16% by weight, of polyethylene glycol with an average molar mass of 200-600 g/mol, based in each case on the total weight of the gel.

The cleaning agents, preferably dishwashing detergents, in particular automatic dishwashing detergents, preferably dishwashing detergents, in particular automatic dishwashing detergents, are in particular not films. Rather, they represent moldings that have a non-film-like thickness. They therefore have a layer thickness of at least 0.3 mm, preferably at least 0.7 mm, in particular at least 1.0 mm, very particularly preferably at least 1.2 mm. The layer thickness is measured in the plane with the smallest extent.

Furthermore, the gel 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 gel can further comprise anionic polymers or copolymers with builder properties. This is preferably a polycarboxylate. A copolymeric polyacrylate, preferably a sulphopolymer, preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate, is preferably used as the polycarboxylate. The copolymers can have two, three, four or more different monomer units. Contain preferred copolymeric polysulfonates in addition to monomer(s) containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids.

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

The unsaturated carboxylic acid(s) used is/are particularly preferably 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 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH2, -OH or -COOH as defined above or for -COOH or -COOR ⁴ where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

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

In the case of the sulfonic acid group-containing monomers, 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 having 2 to 12 carbon atoms, straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH ₂ , -OH or -COOH or for -COOH or -COOR ⁴ where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is 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 is 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 -.

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

Particularly preferred sulfonic acid group-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water-soluble salts. In the polymers, some or all of the sulfonic acid groups can be present in neutralized form, ie 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 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 in the case of copolymers which only contain carboxylic acid group-containing monomers and sulfonic acid group-containing monomers is preferably 5 to 95% by weight in each case, and the proportion of the sulfonic acid group-containing monomer is particularly preferably 50 to 90% by weight. % and the proportion of the carboxylic acid group-containing monomer is 10 to 50% by weight; the monomers are preferably selected from those mentioned above. The molar mass of the sulfo-copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired application. Preferred cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, are characterized in that the copolymers have molecular weights of 2000 to 200,000 g.mol ^-1 , preferably 4000 to 25,000 g.mol ^-1 and in particular 5000 to 15,000 g.mol ^-1 .

In a further preferred embodiment, the copolymers also comprise at least one nonionic, preferably hydrophobic, monomer in addition to monomer containing carboxyl groups and monomer containing sulfonic acid groups. The use of these hydrophobically modified polymers made it possible in particular to improve the rinsing 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.

The gel particularly preferably also comprises an anionic copolymer, with a copolymer comprising as anionic copolymer

1. i) carboxylic acid group-containing monomers
2. ii) sulfonic acid group-containing monomers
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 is an optionally present spacer group selected from -CH ₂ -, -C(O)O- and -C(O)-NH-, and R ⁴ is a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 ,4-Trimethylpentene-1, 2,4,4-Trimethylpentene-2,2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4 ,4-dimethylhexane-1, ethylcyclohexyne, 1-octene, α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C ₂₂ -α-olefin, 2-styrene, α-Methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N -(Methyl)acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N -(2-ethylhexyl)acrylamide, octyl acrylate, metha octyl acrylate, 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 the material sticking to their hands. There is no material removal even in packaging. The gel therefore preferably comprises PVOH, polyethylene glycol(s) with an average molar mass of 200 to 600 g/mol, glycerol and an anionic copolymer/polymer. The proportion of the anionic polymer is preferably 0.1% by weight to 35% by weight, in particular 3% by weight to 30% by weight, particularly 4% by weight to 25% by weight, preferably 5% by weight % to 20% by weight, for example 10% by weight, based on the total weight of the gel. Sulfopolymers, in particular the preferred copolymeric polysulfonates, which, in addition to sulfonic acid group-containing monomer(s) at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, also ensure excellent surface gloss. In addition, fingerprints are not preserved. Therefore, the proportion of sulfopolymers, in particular the preferred copolymeric polysulfonates, which contain at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, in addition to sulfonic acid group-containing monomer(s), in particular in the sulfopolymers mentioned with AMPS as the sulfonic acid-containing monomer, 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, particularly 4% by weight to 15% by weight, preferably 5% by weight % to 12% by weight based on the weight of the gel phase. They are very particularly preferably used in an amount of from 0.1 to 15% by weight, particularly preferably from 0.5 to 13.0% by weight, based in each case on the total weight of the gel. In a particularly preferred embodiment, the gel therefore comprises PVOH and a sulfopolymer, in particular the preferred copolymeric polysulfonates, which contain at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, and at least one polyfunctional monomer in addition to sulfonic acid group-containing monomer(s). Alcohol.

The zinc salt to be used with preference according to the invention is water-soluble, which means that it has a solubility in water of more than 100 mg/l, preferably more than 500 mg/l, particularly preferably more than 1 g/l and in particular more than 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 of zinc acetate, zinc acetylacetonate, zinc PCA (zinc 5-oxopyrrolidine-2-carboxylate), zinc benzoate, zinc chloride, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate , zinc abietate, zinc valerate and zinc p-toluenesulfonate.

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

The zinc salt is present in the gel phase preferably in an amount of from 0.05% to 3% by weight, more preferably in an amount of from 0.1% to 2.4% by weight, especially in a Amount from 0.2% 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 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 in an amount of from 0.1% by weight to 2% by weight, based on the total weight of the cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent.

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 is found 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 also frequently observed, which is visually displeasing to the end user and causes the latter to perceive 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 still be filled into the product. In particular, the time window in which the gel can be processed (service life) is significantly extended by the addition of the zinc salt.

A further object of the present invention relates to a cleaning agent portion, comprising at least one gel as described above, in a water-soluble envelope.

According to a further particularly preferred embodiment, the cleaning agent, preferably dishwashing agent, in particular machine dishwashing agent, is a cleaning agent portion, preferably dishwashing agent portion, in particular machine dishwashing agent portion, in a water-soluble casing. This can have one or more chambers/compartments

The cleaning agent, preferably dishwashing agent, in particular machine dishwashing agent, is preferably packaged as a single portion cleaning agent, so that it is used to carry out a dishwasher cycle and is (largely) essentially or completely consumed.

The water-soluble cover is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures. The cover can be formed from one or from two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if any, 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 containing polyvinyl alcohol or a Contain polyvinyl alcohol copolymer, have good stability with a sufficiently high water solubility, especially cold water solubility.

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

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

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

A polyvinyl alcohol-containing film material suitable for producing the water-soluble casing can also have a polymer selected from the group consisting of (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above Polymers can be added. A preferred additional polymer are 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. Polyvinyl alcohol copolymers which are also preferred include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.

It can be preferred that the film material contains other additives. The film material can contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof. Other additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, antiadhesive agents or mixtures thereof.

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

The water-soluble coating preferably has at least partially a bitter substance with a bitterness 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 casing is at least partially coated with a bitter substance having a bitterness value between 1,000 and 200,000. In this context, it is particularly preferable that the water-soluble casing is coated to at least 50%, preferably at least 75% and most preferably at least 90% with the bitter substance having a bitterness value between 1,000 and 200,000. The application of the bitter substance with a bitter value between 1,000 and 200,000 can be done, for example, by printing, spraying or brushing.

According to the invention, the water-soluble casing preferably has at least one continuous circumferential sealing seam, which essentially lies in one plane. This is favorable 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 such casings with several sealing seams and an excellent tightness of the sealing seam and thus of the casing itself. Leaking of product from the casing, e.g. on the surface of the portion would be disadvantageous, since the consumer would then be exposed to the product came into contact. However, this is precisely what should be avoided as far as possible in the case of a cleaning agent portion, preferably a dishwashing agent portion, in particular a machine dishwashing agent portion, with a water-soluble coating.

The water-soluble casing 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 could then lead to problems in the dishwasher. It is not necessary for the at least two packaging parts to be different. They can be made of the same material and on the preferred be made in the same way. In a preferred embodiment, these are two parts of a water-soluble film, in particular two parts of a water-soluble film of the same composition.

In a further embodiment, the at least two packaging parts can be made from different materials, e.g. from different foils or from material with two different properties (e.g. foil soluble in hot and cold water). In this embodiment, it is preferable that a water-soluble film and another packaging member made by injection molding are combined.

According to a particularly preferred embodiment of the present invention, the water-soluble cover 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 stamping. In particular, the water-soluble covering comprises at least one at least partially plastically deformed film that was produced by deep-drawing.

According to a particularly preferred embodiment, the water-soluble coating has a layer thickness of 30 to 100 μm, in particular 40 to 800 μm.

The at least one solid, preferably granular phase and the gel can be arranged within the water-soluble envelope in any combination with one another. A solid, preferably granular phase can be arranged on or next to a gel phase. In this embodiment, the cleaning agent according to the invention, preferably dishwashing detergent, in particular machine dishwashing detergent, has a solid, preferably granular phase and a gel phase or gel. It is also conceivable that a solid, preferably granular phase is surrounded by gel phases. Embedding one phase in another is also included according to the invention. In a further particularly preferred arrangement, the gel is in cast form, for example in the form of a gel core surrounded by a solid phase. There can also be 2 or more separate cavities that are filled with at least one gel phase. In this embodiment, the cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, comprises two gel phases, it being possible for the two gel phases to 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 dishwashing detergents, in particular machine dishwashing detergents, preferably comprise 3, 4, 5 or 6 or more gel phases, it being possible for these gel phases to have the same or also different compositions.

According to a preferred embodiment, the detergent portion comprises at least one gel or a gel phase at least or more additional phase (s), which is / are selected from a liquid phase, gel phase and / or solid, preferably granular, in particular particulate, preferably free-flowing, solid phase.

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

"Solid" in this context means that the composition is in solid form under standard conditions (temperature 25° C., pressure 1013 mbar). Suitable solid, preferably granular phases are, on the one hand, granular mixtures of a solid composition, such as, for example, powder and/or granules, in particular pulverulent phases. Also suitable according to the invention are solid compositions/phases which have greater dimensional stability than the loose powder, for example powder or granulate preparations which have been compacted by compression before or after being enclosed in the film, e.g. by restoring forces of the film after deep-drawing or directly compressed compositions such as compresses or tablets. This at least one solid, preferably granular phase can be in direct contact with the gel-like phase. Also according to the invention are detergent portions, preferably dishwashing detergent portions, in particular machine dishwashing detergent portions, in particular multi-chamber bags, in which the solid and the gel/the gel phase are present in spatial proximity but separate from one another. The two chambers can be separated, for example, by a film, in particular a water-soluble film, or by a sealed seam (preferably a sealed seam of 3 mm or less). According to the invention, chambers of a multi-chamber pouch are arranged one above the other or next to one another. Furthermore, mixtures of single-chamber or multi-chamber bags, which comprise a gel-like phase according to the invention and, separately from it, at least one solid, preferably granular phase, can be obtained by arrangement, e.g. by folding and fixing a pouch, or by storage at a distance of less than 3 mm come into contact, for example in a packaging bag or a device for portioned dosing, according to the invention.

A granular mixture is to be understood as a powdery phase within the meaning of the present invention, which is formed from a large number of loose, solid particles, which in turn comprise 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 designation 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 granulate, if “powder” or “granulate” is mentioned here, it also includes mixtures of different powders or different granulates . Correspondingly, powder and granules also mean mixtures of different powders with different granules. Said solid particles of the granular mixture in turn preferably have a particle diameter X _50.3 (volume average) of 10 to 1500 μm, more preferably of 200 μm to 1200 μm, particularly preferably of 600 μm to 1100 μm. These particle sizes can be determined by sieving or by means of a Camsizer particle size analyzer from Retsch. The granular mixture of the solid composition of the present invention, which serves as the solid, preferably granular 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, preferably granular 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, preferably dishwashing agents, in particular automatic dishwashing agents, in particular a cleaning agent portion, preferably dishwashing agent portion, in particular automatic dishwashing agent portion, in which the gel / the gel phase is in direct contact, for example in a chamber, with the at least one solid phase is included.

Furthermore, it is preferred that the at least one solid, preferably granular phase and the gel 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 means here, 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 form, for example by Color change, the formation of edges that appear moist, the boundary between the two phases becoming blurred, or the like.

Surprisingly, it has been shown that by formulating a gel phase, preferably dimensionally stable gel phase, comprising at least one polypropylene glycol, preferably having an average molecular weight of 1000 to 6000 g/mol, preferably in an amount of 1 to 15% by weight, which with a granular mixture of a solid composition, in particular combined with a powdered phase, this objective 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 covering can be achieved as a result of 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 and particles or areas with different colors, overall or as colored speckles, can be be used to improve a visually appealing appearance. The granular mixture of the solid composition, in particular the powder, also offers improved solubility compared to compressed tablets, even without the addition of disintegrants.

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 gel is dimensionally stable so that as few interactions as possible can take place between the solid and the gel phase.

The at least one solid, preferably granular phase of the present invention comprises a granular mixture of a solid composition, in particular it is in powdered and free-flowing form. The cleaning agent according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, thus comprises at least one solid, powdery and free-flowing phase, and 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 derivatives thereof, particularly preferably at least PVOH, and glycerol.

The pourability of a granular mixture, in particular of a powdery solid, of the powdery phase, preferably of the powder and/or granulate, relates to its ability to pour freely under its own weight. The pourability is determined by measuring the flow time of 1000 ml cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing powder, from a standardized flow test funnel which is initially closed in its outlet direction and has an outlet diameter of 16.5 mm by measuring the time it takes for the granular mixture to flow out completely , in particular the powdery phase, preferably the powder and/or granulate, eg the powder, is measured after opening the outlet and compared to the outlet speed (in seconds) of a standard test sand whose outlet speed 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 ]. Before the measurement, the sea sand is dried for 24 h at 60° C. in a drying cabinet on a plate with a maximum layer height of 2 cm.

Preferred embodiments of the solid phases according to the invention have an angle of repose/repose of 26 to 35, 27 to 34, 28 to 33, the angle of repose according to the method mentioned below after 24 hours after the preparation of the granular mixture of the solid composition, in particular the powdery solid phase, preferably the powder and/or granules and storage at 20° C., is determined. 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, preferably granular phase, a powder funnel with a capacity of 400 ml and an outlet with a diameter of 25 mm is hung straight on a tripod. The hopper is moved upwards at a speed of 80 mm/min using 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 forms a so-called material cone. The height of the cone of repose and the diameter of the cone of repose are determined for the individual solid phases. The angle of repose is calculated from the quotient of the heap of repose and the diameter of the cone of repose * 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 standard test material specified above 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 those granular mixtures of a solid composition, in particular those powders and/or granules, which have a pourability in % of the standard test substance specified above of greater than 40%, preferably greater than 45%, in particular greater than 50%, particularly preferably greater than 55 %, particularly preferably greater than 60%, the pourability being measured 24 hours after the powder has been produced and stored at 20°C.

Lower values for the pourability are rather unsuitable since, from the point of view of process technology, precise dosing of the granular mixture, in particular the powdered phase, preferably the powder and/or granules, for example the powder, is necessary. In particular, the values greater than 50%, in particular greater than 55%, preferably greater than 60% (the flowability being measured 24 h after the production of the powder and storage at 20° C.) have proven to be advantageous because the good dosability the granular mixture, in particular the powdery phases, preferably the powder and/or granules, eg powder, result in only slight fluctuations in the metered quantity or the composition. The more precise dosing leads to a constant product performance, economic losses due to overdosing are thus avoided. Furthermore, it is advantageous that the granular mixture, in particular the pulverulent phase, preferably the powder and/or granulate, eg the powder, can be easily dosed, so that the dosing process runs more quickly. Furthermore, such a good flowability better prevents the granular mixture, in particular the powdery phase, preferably the powder and/or granules, e.g. the powder, from getting onto the part of the water-soluble cover that is intended for the production of the sealed seam and is therefore possible should remain granule-free, in particular powder-free.

The granular mixture of the solid composition of the present invention, which serves as the solid, preferably granular phase, is preferably in a free-flowing form (particularly preferably as a free-flowing powder and/or free-flowing granules). The means of the portion according to the invention thus comprises at least one solid, preferably granular 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 dishwashing detergents, in particular machine dishwashing detergents, 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, preferably dishwashing detergents, in particular machine dishwashing detergents, can also contain mixtures of two or more surfactants selected from the same group.

According to the invention, the at least one solid, preferably granular phase and/or the gel comprise at least one surfactant. It is possible for only the at least one solid, preferably granular phase or only the gel to 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, for example, 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 nonionic surfactants, fatty alcohols can also be used more than 12 EO are 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 obtained from 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, used. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide. Among these, the so-called "narrow range ethoxylates" are particularly preferred.

Surfactants to be used with preference come from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants). Such (PO/EO/PO) nonionic surfactants are also distinguished 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, particularly preferred nonionic surfactants have been found for the low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, preference is in turn given to surfactants with EO-AO-EO-AO blocks, in which case one to ten EO or AO groups are bonded to one another before a block of the other groups follows. Here are nonionic surfactants of the general formula

preferably in which R ¹ is a straight-chain or branched, saturated or partially unsaturated 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 are independent of one another are integers from 1 to 6.

Preferred nonionic surfactants of the above formula can be prepared from the corresponding alcohols R ¹ —OH and ethylene or alkylene oxide by known methods. 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 from alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, are preferred. Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or mixtures of methyl-branched or linear and methyl-branched radicals in the 2-position, see above 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 in which R ¹ in the above formula is an alkyl radical with 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

A suitable alkylene oxide unit, which is present in the preferred nonionic surfactants alternating with the ethylene oxide unit, is, in addition to propylene oxide, in particular butylene oxide. However, other alkylene oxides in which R ² or 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 where ^R.sup.2 or ^R.sup.3 is a --CH.sub.3 radical, w and x are independently ₃ or 4, and y and z are independently 1 or 2.

Other nonionic surfactants preferably used in the solid phase 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 having 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl group having 2 to 4 carbon atoms; x and y independently represent values between 1 and 70; and M is 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 are independently branched or unbranched, saturated or unsaturated alkyl radicals with 1 up to 18 carbon atoms.

Nonionic surfactants of the general formula are preferred here

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

Compounds of the general formula are particularly preferred here

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 is a linear, saturated alkyl radical having 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, which is followed by a reaction with an alkyl epoxide to close the free OH functions with formation of 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 here are those of the general formula R ¹ -CH(OH)CH ₂ O-(AO) _w -(AO) _x -(AʺO) _y -(A‴O) _z -R ² , in which

• R ¹ is a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ² is hydrogen or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A, A', A" and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH 2 , -CH 2 -CH(CH 3 ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH(CH ₃ )-CH ₂ -, -CH ₂ -CH(CH ₂ -CH ₃ ),
• w, x, y and z stand for 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 -(Aʺ0) _y -(A‴O) _z -R ² , hereinafter also referred to as "hydroxy mixed ether", the cleaning performance of preparations according to the invention can surprisingly be significantly improved, both in comparison to surfactant-free systems and in comparison to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

The use of these nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl radicals can significantly improve the stability of the enzymes present in the cleaning compositions according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents.

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.Preference is given in particular to those end-capped poly(oxyalkylated) nonionic surfactants which, according to the following formula

in addition to a radical R ¹ , which is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, also a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² with 1 to 30 carbon atoms, where n is between 1 and 90, preferably between 10 and 80 and in particular between 20 and 60. Particular preference is given to surfactants of the above formula in which R ¹ is C ₇ to C ₁₃ , n is an integer 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 are particularly preferred, in which R ¹ represents a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1.5 and y stands for 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 also the C _8-10 fatty alcohol (PO) ₁ -(EO) ₂₂ -2 -hydroxydecyl ether.

Those end-capped poly(oxyalkylated) nonionic surfactants of the formula R ¹ O[CH ₂ CH ₂ O] _x [CH ₂ CH(R ³ )O] _y CH ₂ CH(OH)R ² , in which R ¹ and R ² independently of one another represents a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 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 represents -CH ₃ , and x and y independently represent values between 1 and 32, where nonionic surfactants with R ³ = -CH ₃ and values for x from 15 to 32 and y of 0.5 and 1.5 are most preferred.

• in der R¹ und R² für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 1 bis 30 Kohlenstoffatomen stehen, R³ für H oder einen Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, 2-Butyl- oder 2-Methyl-2-Butylrest steht, x für Werte zwischen 1 und 30, k und j für Werte zwischen 1 und 12, vorzugsweise zwischen 1 und 5 stehen. Wenn der Wert x > 2 ist, kann jedes R³ in der oben stehenden Formel
• R¹O[CH₂CH(R³)O]_x[CH₂]_kCH(OH)[CH₂]_jOR² unterschiedlich sein. R¹ und R² sind vorzugsweise lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 6 bis 22 Kohlenstoffatomen, wobei Reste mit 8 bis 18 C-Atomen besonders bevorzugt sind. Für den Rest R³ sind H, -CH₃ oder -CH₂CH₃ besonders bevorzugt. Besonders bevorzugte Werte für x liegen im Bereich von 1 bis 20, insbesondere von 6 bis 15.

Other preferably usable nonionic surfactants 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 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ³ is H or a methyl, ethyl, n-propyl, isopropyl, n -butyl, 2-butyl or 2-methyl-2-butyl radical, x has values between 1 and 30, k and j have values between 1 and 12, preferably between 1 and 5. When the value of 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 may be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH ₃ are particularly preferred for the radical R ³ . 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 when x>2. This allows the alkylene oxide unit in the square brackets to be varied. For example, when x is 3, the R ³ group may be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) moieties which may be joined in any order, e.g. (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 selected here as an example and can certainly be larger, with the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .

• 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 endcapped poly(oxyalkylated) alcohols of the above formula have values of k=1 and j=1 such that the above formula translates to R ¹ O[CH ₂ CH(R ³ )O] _x CH ₂ CH(OH )CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ³ is as defined above and x is a number from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Surfactants in which the radicals R ¹ and R ² have 9 to 14 carbon atoms are particularly preferred, R ³ stands for H and x takes values from 6 to 15. Finally, the nonionic surfactants of the general formula R ¹ -CH(OH)CH ₂ O-(AO) _w -R ² have proven to be particularly effective

• R ¹ is 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 is 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 is between 1 and 120, preferably 10 to 80, especially 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 ether and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ether.

Preferably, the at least one solid and/or the gel contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, with the proportion by weight of the nonionic surfactant based on the total weight of the gel 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 group or alkenyl group having 4 to 22 carbon atoms; R ³ and R ⁴ are independently H or an alkyl or alkenyl group having from 1 to 18 carbon atoms and x and y are independently from 1 to 40.

In this connection, 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 assume values from 1 to 40, preferably from 1 to 15, independently of one another. Particular preference is given in particular to compounds of the general formula R ¹ -O(CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which the radicals R ¹ and R ² are independently saturated alkyl radicals having 4 to 14 carbon atoms and the indices x and y independently assume values from 1 to 15 and in particular from 1 to 12.

Also preferred are compounds of the general formula R ¹ —O(CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² in which one of the radicals R ¹ and R ² is branched. Very particular preference is given to compounds of the general formula R ¹ —O(CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which the indices x and y assume values of 8 to 12 independently of one another.

The given carbon chain lengths and degrees of ethoxylation or alkoxylation of the nonionic surfactants represent statistical mean 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 of mixtures, which means that average values and fractional numbers can result both for the C chain lengths and for the degrees of ethoxylation or alkoxylation.

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

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

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferable for them to have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants, 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 molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxy alkanols or alkyl phenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules makes up preferably more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule make up up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight, of the total molar mass of the nonionic surfactant.

Other nonionic surfactants to be used particularly preferably in the solid phase with melting points above room temperature contain 40 to 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend which is 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

In a preferred embodiment, the proportion by weight of the nonionic surfactant in the total weight of the solid, preferably granular 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 the agents. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate or sulfonate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Suitable anionic surfactants are preferably in the form of the sodium, potassium and ammonium and 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 having 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 combination 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.

According to a particularly preferred embodiment, the gel contains at least one further nonionic surfactant, preferably in an amount of 0.1 to 7.5% by weight.

Particularly suitable nonionic surfactants are described above. Substances from the ^Plurafac® LF (BASF) series and the surfactants with or without end groups described above as hydroxy mixed ethers or fatty alcohol polyalkylene glycols are particularly suitable.

Preferred cleaning agents according to the invention, preferably dishwashing detergents, in particular automatic dishwashing detergents, are also characterized in that they contain less than 1.0% by weight and in particular less than 0.1% by weight, preferably no anionic surfactant.

According to a particularly preferred embodiment, the cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, are characterized in that the gel contains less than 1% by weight, in particular less than 0.5% by weight, in particular less than 0.1% by weight. -% anionic surfactant, each based on the total weight of the gel. The gel is preferably essentially free of anionic surfactants. Substantially free means that the gel contains less than 0.05% by weight of anionic surfactant, based on the total weight of the gel.

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 composition as a whole. Furthermore, higher amounts of anionic surfactants have a negative effect on curing. According to a particularly preferred embodiment, the gel 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 gel can contain sugar. According to the invention, sugars include sugar alcohols, monosaccharides, disaccharides and oligosaccharides. In a preferred embodiment, the gel comprises at least one sugar alcohol other than glycerol, preferably at least one monosaccharide or disaccharide sugar alcohol. Mannitol, isomalt, lactitol, sorbitol, threitol, erythritol, arabitol and xylitol are particularly preferred. Particularly preferred monosaccharide sugar alcohols are pentitols and/or hexitols. Xylitol and/or sorbitol is very particularly preferred.

In a further embodiment, the gel 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 higher amounts, the sugar does not completely dissolve in the gel phase and causes the same to become cloudy. The use of sugar, in particular in a proportion of 10% by weight to 5% by weight to 15% by weight, reduces the development of moisture and thus improves adhesion to at least one solid phase.

According to a particularly preferred embodiment, the at least one additional phase contains at least one, preferably comprises several ingredients, which are selected from which are selected from the group formed from builders (preferably carbonates, citrate, aminopolycarboxylates and/or aminocarboxylates, preferably MGDA and/or GLDA or their salts, and/or bleaches (especially percarbonate), and/or bleach activators and/or bleach catalysts, and/or silver protectants, and/or enzymes (preferably protease(s) and/or amylase(s)), and/or nonionic surfactants and/or other processing aids.

The use of builders (builders) such as silicates, aluminum silicates (in particular zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builders, can be advantageous.

In an embodiment which is particularly preferred 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, i.e. the agents contain 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 as meaning 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 carry throughout the molecule. Dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids, are therefore preferred as polycarboxylic acids. The polycarboxylic acids can also carry other 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), methylglycine diacetic 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 of (especially 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 property of an acidifying component. Particular mention should be made here of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these.

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

Particular preference is also given to using 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, based in each case on the weight of the agent.

Particularly preferred cleaning agents according to the invention, preferably dishwashing agents, in particular machine dishwashing agents, 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, preferably dishwashing detergent, in particular machine dishwashing detergent, 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, preferably dishwashing agents, in particular machine dishwashing agents. In addition to the builders mentioned here, one or more other builders can also be present.

Preferred cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, are characterized by a builder combination of citrate and carbonate and/or hydrogen carbonate. In a very 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 from 10 to 35% by weight, very particularly preferably from 15 to 30% by weight. and the amount of citrate preferably from 5 to 35% by weight, in particular 10 to 25% by weight, most preferably 15 to 20% by weight, in each case on the total amount of the cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, is, the total amount of these two builders preferably being 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 can also be included.

The cleaning agents according to the invention, preferably dishwashing detergents, in particular automatic dishwashing detergents, can contain, in particular phosphonates, as a further builder, to the extent permitted by regulations. A hydroxyalkane and/or aminoalkane phosphonate is preferably used as the phosphonate compound. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. Phosphonates are present in agents according to the invention, to the extent permitted by regulations, preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, very particularly preferably 2.5 to 7.5% by weight %, based in each case 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 amounts mentioned above. In this combination, in particular, amounts of, in each case 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, preferably dishwashing detergents, in particular machine dishwashing detergents, are characterized in that they contain at least one further phosphorus-free builder in addition to citrate and (hydrogen) carbonate and, if appropriate, phosphonate. In particular, this is selected from the aminocarboxylic acids, with the further phosphorus-free builder preferably being selected from methylglycine diacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), particularly preferably from MGDA or GLDA. A particularly preferred combination is, for example, citrate, (hydrogen) carbonate and MGDA and optionally phosphonate.

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

Polymeric polycarboxylates are also suitable as organic builders, 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. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 1100 to 10000 g/mol, and particularly preferably from 1200 to 5000 g/mol, may in turn be preferred from this group.

The content of (homo)polymeric polycarboxylates in the cleaning agents according to the invention, preferably dishwashing detergents, in particular machine 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, preferably dishwashing detergents, in particular machine dishwashing detergents, can also contain crystalline layered silicates of the general formula NaMSi _x O _2x+1 y H ₂ O as a builder, in which M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20. Amorphous sodium silicates with an Na ₂ O:SiO ₂ modulus of 1:2 to 1:3.3, preferably of 1:2 to 1:2.8 and in particular of 1:2 to 1:2.6, can also be used are preferably delayed in dissolution and have secondary washing properties.

In addition to the aforementioned builders, the cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, can also contain alkali metal hydroxides. These alkali carriers are present in the cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents and in particular in the at least one gel phase, preferably only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight. %, particularly preferably between 0.1 and 5% by weight and in particular between 0.5 and 5% by weight, based in each case on the total weight of the cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing detergent. Alternative cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, are free from alkali metal hydroxides.

Cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, preferably contain enzyme(s) as a further component 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, preferably dishwashing agents, in particular machine dishwashing agents, which are correspondingly preferably used. Cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, 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 which 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 and the further developments of the aforementioned amylases improved for use in detergents, preferably dishwashing detergents, in particular automatic dishwashing detergents . Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

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

It is also possible to use enzymes which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (=pectinases), pectinesterases, pectate lyases, xyloglucanases (=xylanases), pullulanases and β-glucanases.

According to the invention, 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 to increase the bleaching effect. Advantageously, preferably organic, particularly preferably aromatic, compounds that interact with the enzymes are additionally added in order to increase the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons in the case of greatly differing redox potentials between the oxidizing enzymes and the soiling (mediators). A protein and/or enzyme can be protected against damage such as, for example, inactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage. In the case of microbial production of the proteins and/or enzymes, inhibition of proteolysis is particularly preferred, particularly if the agents also contain proteases. Cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, can contain stabilizers for this purpose; 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 preparations that can be stored and transported. These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like preparations, solutions of the enzymes, advantageously as concentrated as possible, low in water and/or mixed with stabilizers or other auxiliaries.

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

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

As can be seen from the above, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations used according to the invention contain between 1 and 40% by weight, preferably between 2 and 30% by weight, particularly preferably between 3 and 25% by weight, of the enzyme protein. Preference is given in particular to cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, 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 included.

In addition to the ingredients mentioned so far, the at least one solid and/or the gel of the cleaning agent according to the invention, preferably dishwashing detergent, in particular automatic dishwashing detergent, can contain other 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 protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances (in particular 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 agents (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 preferably contained in agents according to the invention 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, preferably dishwashing detergents, in particular machine dishwashing detergents, the gel is essentially free of alkanolamine, i.e. the gel 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 contained only in the at least one solid phase.

In addition to the zinc salts mentioned above, polyethyleneimines, such as those available under the name ^Lupasol® (BASF), can be used as glass corrosion inhibitors, preferably 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 sodium salt (for example Sokalan ^® HP 25 from the company BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example ^Silwet® L-77 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example ^Silwet® L-7608 from BASF, Ludwigshafen (Germany)) and Polyethersiloxanes (copolymers of polymethylsiloxanes with ethylene oxide/propylene oxide segments (polyether blocks)), preferably water-soluble linear polyethersiloxanes with terminal polyether blocks such as Tegopren ^® 5840, Tegopren ^® 5843, Tegopren ^® 5847, Tegopren ^® 5851, Tegopren ^® 5863 or Tegopren ^® 5878 from Evonik, Essen (Germany). Builder substances suitable as additives are, in particular, sodium polyaspartic acid salt, ethylenediamine triacetate coconut alkylacetamide (for example ^Rewopol® CHT 12 from Evonik, Essen (Germany)), sodium trimethylglycine diacetic acid salt and acetophosphonic acid. In the case of Tegopren ^® 5843 and Tegopren ^® 5863, mixtures with surfactant or polymer additives show synergisms. However, the use of Tegopren types 5843 and 5863 is less preferred when used on hard surfaces made of glass, in particular glassware, since these silicone surfactants can be absorbed by glass. In a particular embodiment of the invention, the additives mentioned are omitted.

A preferred cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, preferably also comprises a bleach, in particular an oxygen bleach and optionally a bleach activator and/or bleach catalyst. If present, these are contained exclusively in the at least one solid phase.

Cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, contain an oxygen bleaching agent from the group consisting of sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate as a preferred bleaching agent. Examples of other bleaches which can be used are peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which supply H ₂ O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. Bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples being the alkylperoxyacids and the arylperoxyacids. Sodium percarbonate is particularly preferred because of its good bleaching performance. A particularly preferred oxygen bleach is sodium percarbonate.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid. Substances which carry 0- and/or N-acyl groups with the number of carbon atoms mentioned and/or optionally substituted benzoyl groups are suitable. Polyacylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) having proven to be particularly suitable.

The bleach catalysts are bleach-boosting transition metal salts or transition metal complexes such as, for example, 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 and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts. Complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligand(s) with the donor functions N, NR, PR, O and/or S, are particularly preferably used. Ligands which have nitrogen donor functions are preferably used. It is particularly preferred to use bleach catalyst(s) in the agents according to the invention which contain 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane (Me/Me-TACN ) and/or 2-methyl-1,4,7-triazacyclononane (Me/TACN). Examples of suitable manganese complexes are [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(OCH ₃ ).

According to a preferred embodiment, the detergent portion comprises at least one gel or a gel phase at least or more additional phase (s), which is / are selected from a liquid phase, gel phase and / or solid, preferably granular, in particular particulate, preferably free-flowing, solid phase.

The cleaning agent according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, preferably comprises at least one gel or one gel phase and at least one solid, preferably granular phase. The cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, can have one, two, three or more solid, preferably granular phases; it can also have one, two, three, four or more different gel phases. The cleaning agent according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, preferably comprises a solid, preferably granular phase and a gel phase. The cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, particularly preferably comprises two solid, preferably granular phases and a gel phase. It preferably comprises two solid, preferably granular, phases and two gel phases. Also preferred is an embodiment in which the cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, comprises three solid, preferably granular phases and one or two gel phases.

The weight ratio of all of the at least one solid phase to all of the at least one gel phase phase is generally 40:1 to 2:1, in particular 20:1 to 4:1, preferably 14:1 to 6:1, for example 12:1 to 8:1. The total weight of all phases in a cleaning agent portion, preferably dishwashing agent portion, in particular machine dishwashing 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, preferably dishwashing agent portion, in particular machine dishwashing 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, preferably granular phase and the gel adjoin one another over the whole or part of the surface. It is preferred that the two phases directly adjoin one another.

If the at least one solid, preferably granular phase and the gel directly adjoin one another over the whole or part of the surface, the stability is important in addition to the shortest possible setting time of the at least one gel phase. Stability here means that the components contained in the gel phase do not migrate into the at least one solid, preferably granular phase, but rather that the at least one solid, preferably granular phase and the gel are optically separate from one another even after prolonged storage and do not interact with one another, such as diffusion of liquid components from one phase to another or reaction of components in one phase with those in the other phase.

Another subject of the present application is a method for cleaning hard surfaces, in particular dishes, in which the surface is treated in a manner known per se using a cleaning agent according to the invention, preferably dishwashing detergent, in particular machine dishwashing detergent. In particular, the surface is brought into contact with the cleaning agent according to the invention, preferably dishwashing detergent, in particular machine dishwashing detergent. The cleaning takes place in particular with a cleaning machine, preferably with a dishwasher.

A further subject of the present invention is also the use of a cleaning agent, preferably a dishwashing detergent, in particular an automatic dishwashing detergent, as described above, for cleaning hard surfaces, in particular dishes, in particular in automatic dishwashers.

For the use or the process, the specific disclosures made above for the cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, apply accordingly.

Insofar as it is stated in the present application that the cleaning agent according to the invention, preferably dishwashing detergents, in particular automatic dishwashing detergents, in Entirely or in the gel, something included is also to be regarded as disclosed that cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, or the respective phase can consist of it. In the exemplary embodiment below, the cleaning agent according to the invention, preferably a dishwashing agent, in particular an automatic dishwashing agent, is described in a non-limiting manner.

1. 1. Reinigungsmittel, umfassend ein Gel, bevorzugt ein bei Raumtemperatur (20 °C) festes Gel, umfassend, jeweils bezogen auf das Gesamtgewicht des Gels:
   1. a) 4 bis 40 Gew.-%, bevorzugt 6 bis 30 Gew.-%, insbesondere 7 bis 24 Gew.-%, besonders bevorzugt 8 bis 22 Gew.-%, ganz besonders bevorzugt 12 bis 20 Gew.-% PVOH und/oder dessen Derivate;
   2. b) 20 bis 80 Gew.-% mindestens eines organischen Lösungsmittels, bevorzugt ausgewählt aus der Gruppe bestehend ausgewählt aus der Gruppe bestehend aus 1,2-Propandiol, 1,3-Propandiol, Dipropylenglykol, Triethylenglykol, Polyethylenglykole und/oder Alkantriolen, bevorzugt Glycerin, 1,1,1-Trimethylolpropan, sowie Mischungen daraus;
   3. c) 0,1 bis 30 Gew.-% mindestens eines Polypropylenglykol mit einem mittleren Molekulargewicht von 500 bis 10 000 g/mol, insbesondere von 1000 bis 6000 g/mol.
2. 2. Reinigungsmittel nach Punkt 1, dadurch gekennzeichnet, dass das Polypropylenglykol in einer Menge von 0,6 bis 25 Gew.-%, bevorzugt in einer Menge von 1 bis 15 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Gels, enthalten ist.
3. 3. Reinigungsmittel nach Punkt 1 oder 2, dadurch gekennzeichnet, dass als ein bevorzugtes organisches Lösungsmittel Glycerin, bevorzugt in einer Menge 5 bis 50 Gew.-%, bevorzugt 10 bis 45 Gew.-%, besonders bevorzugt 20 bis 40 Gew.-% Glycerin, bezogen auf das Gesamtgewicht des Gels, enthalten ist.
4. 4. Reinigungsmittel nach einem der Punkte 1 bis 3, dadurch gekennzeichnet, als ein bevorzugtes organisches Lösungsmittel 2 bis 20 Gew.-% Polyethylenglykol, insbesondere 3 bis 16 Gew.-% Polyethylenglykol, bevorzugt Polyethylenglykol mit einem mittleren Molekulargewicht von 200 bis 600 enthalten ist.
5. 5. Reinigungsmittel nach Punkt 1 bis 4, dadurch gekennzeichnet, dass als bevorzugtes organisches Lösungsmittel 1,3-Propandiol, bevorzugt in einer Menge 5 bis 50 Gew.-%, bevorzugt 20 bis 40 Gew.-%, besonders bevorzugt 28 bis 35 Gew.-%, bezogen auf das Gesamtgewicht des Gels, enthalten ist.
6. 6. Reinigungsmittel nach einem der Punkte 1 bis 5, dadurch gekennzeichnet, dass der Wassergehalt des Gels weniger als 30 Gew.-%, weniger als 20 Gew.-%, bevorzugt weniger als 15 Gew.-%, insbesondere weniger als 10 Gew.-%, besonders bevorzugt weniger als 5 Gew.-%, ganz besonders bevorzugt weniger als 1 Gew.-%, bezogen auf das Gesamtgewicht des Gels, beträgt.
7. 7. Reinigungsmittel nach einem der Punkte 1 bis 6, dadurch gekennzeichnet, dass mindestens ein weiterer Inhaltsstoff des Gels ausgewählt ist aus Farbstoffen, Glaskorrosionsinhibitoren, anionischen Polymeren, nichtionischen Tensiden sowie weiteren Prozesshilfsmittel, insbesondere Parfüm, pH-Stellmittel.
8. 8. Reinigungsmittel nach einem der Punkte 1 bis 7, dadurch gekennzeichnet, dass mindestens ein Zinksalz, bevorzugt Zinkchlorid, Zinksulfat und/oder Zinkacetat, insbesondere Zinkacetat, besonders bevorzugt Zinkacetat-Anhydrat, in einer Menge von 0,05 bis 3 Gew.-%, bevorzugt in einer Menge von 0,1 bis 2,4 Gew.-%, insbesondere 0,2 bis 1 Gew.-%, bezogen auf das Gesamtgewicht des Gels, enthalten ist.
9. 9. Reinigungsmittel nach einem der Punkte 1 bis 8, dadurch gekennzeichnet, dass das Gel mindestens ein anionisches Polymer, insbesondere Acrylathomo- oder Copolymer, insbesondere ein Polyacrylatcopolymer mit mindestens einem sulfonsäuregruppenhaltigen Monomer, insbesondere einem Monomer ausgewählt aus Acrylamidopropansulfonsäuren, Methacrylamidomethylpropansulfonsäuren oder Acrylamidomethylpropansulfonsäure, umfasst, bevorzugt in einer Menge von 0,1 bis 15 Gew.-%, insbesondere bevorzugt von 0,5 bis 13,0 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Gels.
10. 10. Reinigungsmittel nach einem der Punkte 1 bis 9, dadurch gekennzeichnet, dass mindestens ein weiteres nichtionisches Tensid, bevorzugt in einer Menge von 0,1 bis 7,5 Gew.-% enthalten ist.
11. 11. Reinigungsmittelportion, umfassend mindestens ein Gel gemäß einem der Punkten 1 bis 10 in einer wasserlöslichen Umhüllung.
12. 12. Reinigungsmittelportion nach Punkt 11, dadurch gekennzeichnet, dass die wasserlösliche Umhüllung Polyvinylalkohol umfasst, wobei die Umhüllung bevorzugt eine Schichtdicke von 30 bis 100 µm, insbesondere von 40 bis 800 µm aufweist.
13. 13. Reinigungsmittelportion nach Punkt 11 oder 12, dadurch gekennzeichnet, dass sie mindestens oder mehr zusätzliche Phase(n) umfasst, die ausgewählt ist/sind aus einer flüssigen Phase, gelförmigen Phase und/oder festen, bevorzugt körnigen, insbesondere partikulären, bevorzugt rieselfähigen, festen Phase.
14. 14. Reinigungsmittelportion nach Punkt 13, dadurch gekennzeichnet, dass wenigstens eine zusätzliche Phase mindestens einen, bevorzugt mehrere Inhaltsstoffe umfasst, welche ausgewählt sind aus der Gruppe gebildet aus Gerüststoffe (bevorzugt Carbonate, Citrat, Aminopolycarboxylate und/oder Aminocarboxylate, bevorzugt MGDA und/oder GLDA bzw. deren Salze, und/oder Bleichmittel (insbesondere Percarbonat), und/oder Bleichaktivatoren und/oder Bleichkatalysatoren, und/oder Silberschutzmittel, und/oder Enzyme (bevorzugt Protease(n) und/oder Amylase(n)), und/oder nichtionische Tenside und/oder weitere Prozesshilfsmitteln.
15. 15. Reinigungsmittelportion nach einem der Punkte 11 bis 14, dadurch gekennzeichnet, dass die Gelphase und optional auch die zusätzliche Phase weniger als 1 Gew.-%, insbesondere weniger als 0,5 Gew.-%, insbesondere weniger als 0,1 Gew.-% Aniontensid, jeweils bezogen auf das Gesamtgewicht des Gels bzw. ggf. das Gesamtgewicht der zusätzlichen Phase, umfasst.
16. 16. Reinigungsmittel nach einem der Punkte 1 bis 15, dadurch gekennzeichnet, dass es ein Geschirrspülmittel, insbesondere ein Geschirrspülmittel zur maschinellen Reinigung von Geschirr ist.
17. 17. Verwendung eines Gels gemäß Punkt 1 bis 10, oder einer Reinigungsmittelportion nach einem der Punkte 11 bis 17 zur maschinellen Reinigung von Geschirr, insbesondere von hartnäckigen und/oder fettigen Speiseresten.
18. 18. Verfahren zur maschinellen Reinigung von Geschirr, dadurch gekennzeichnet, dass ein Gel gemäß Punkt 1 bis 10 bzw. eine Reinigungsmittelportion nach einem der Punkte 11 bis 17 in einer Geschirrspülmaschine zum Einsatz kommt.

Items provided by this application include:

1. 1. Cleaning agent, comprising a gel, preferably a gel that is solid at room temperature (20° C.), comprising, in each case based on the total weight of the gel:
   1. a) 4 to 40% by weight, preferably 6 to 30% by weight, in particular 7 to 24% by weight, particularly preferably 8 to 22% by weight, very particularly preferably 12 to 20% by weight, PVOH and /or its derivatives;
   2. b) 20 to 80% by weight of at least one organic solvent, preferably selected from the group consisting of 1,2-propanediol, 1,3-propanediol, dipropylene glycol, triethylene glycol, polyethylene glycols and/or alkanetriols, preferably glycerol , 1,1,1-trimethylolpropane, and mixtures thereof;
   3. c) 0.1 to 30% by weight of at least one polypropylene glycol having an average molecular weight of 500 to 10,000 g/mol, in particular 1000 to 6000 g/mol.
2. 2. Cleaning agent according to point 1, characterized in that the polypropylene glycol is contained in an amount of 0.6 to 25% by weight, preferably in an amount of 1 to 15% by weight, based in each case on the total weight of the gel .
3. 3. Cleaning agent according to point 1 or 2, characterized in that glycerol, preferably in an amount of 5 to 50% by weight, preferably 10 to 45% by weight, particularly preferably 20 to 40% by weight, is used as a preferred organic solvent. Glycerin, based on the total weight of the gel, is included.
4. 4. Cleaning agent according to one of points 1 to 3, characterized in that 2 to 20% by weight of polyethylene glycol, in particular 3 to 16% by weight of polyethylene glycol, preferably polyethylene glycol with an average molecular weight of 200 to 600, is present as a preferred organic solvent .
5. 5. Cleaning agent according to points 1 to 4, characterized in that the preferred organic solvent is 1,3-propanediol, preferably in an amount of 5 to 50% by weight, preferably 20 to 40% by weight, particularly preferably 28 to 35% by weight % based on the total weight of the gel.
6. 6. Cleaning agent according to one of points 1 to 5, characterized in that the water content of the gel is less than 30% by weight, less than 20% by weight, preferably less than 15% by weight, in particular less than 10% by weight. -%, particularly preferably less than 5% by weight, very particularly preferably less than 1% by weight, based on the total weight of the gel.
7. 7. Cleaning agent according to one of points 1 to 6, characterized in that at least one other ingredient of the gel is selected from dyes, glass corrosion inhibitors, anionic polymers, nonionic surfactants and other processing aids, in particular perfume, pH adjusters.
8. 8. Cleaning agent according to one of points 1 to 7, characterized in that at least one zinc salt, preferably zinc chloride, zinc sulfate and/or zinc acetate, in particular zinc acetate, particularly preferably zinc acetate anhydrate, in an amount of 0.05 to 3% by weight , preferably in an amount of 0.1 to 2.4% by weight, in particular 0.2 to 1% by weight, based on the total weight of the gel.
9. 9. Cleaning agent according to one of points 1 to 8, characterized in that the gel comprises at least one anionic polymer, in particular acrylate homo- or copolymer, in particular a polyacrylate copolymer with at least one monomer containing sulfonic acid groups, in particular a monomer selected from acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid, preferably in an amount of 0.1 to 15% by weight, particularly preferably 0.5 to 13.0% by weight, based in each case on the total weight of the gel.
10. 10. Cleaning agent according to one of points 1 to 9, characterized in that at least one further nonionic surfactant is present, preferably in an amount of 0.1 to 7.5% by weight.
11. 11. Cleaning agent portion, comprising at least one gel according to one of points 1 to 10 in a water-soluble envelope.
12. 12. Detergent portion according to item 11, characterized in that the water-soluble coating comprises polyvinyl alcohol, the coating preferably having a layer thickness of 30 to 100 μm, in particular 40 to 800 μm.
13. 13. Detergent portion according to item 11 or 12, characterized in that it comprises at least or more additional phase(s) which is/are selected from one liquid phase, gel phase and/or solid, preferably granular, in particular particulate, preferably free-flowing, solid phase.
14. 14. Detergent portion according to point 13, characterized in that at least one additional phase comprises at least one, preferably several ingredients, which are selected from the group consisting of builders (preferably carbonates, citrate, aminopolycarboxylates and/or aminocarboxylates, preferably MGDA and/or GLDA or their salts, and/or bleaches (in particular percarbonate), and/or bleach activators and/or bleach catalysts, and/or silver protectants, and/or enzymes (preferably protease(s) and/or amylase(s)), and/or nonionic surfactants and/or other processing aids.
15. 15. Detergent portion according to one of points 11 to 14, characterized in that the gel phase and optionally also the additional phase contain less than 1% by weight, in particular less than 0.5% by weight, in particular less than 0.1% by weight. -% anionic surfactant, based in each case on the total weight of the gel or optionally the total weight of the additional phase.
16. 16. Cleaning agent according to one of points 1 to 15, characterized in that it is a dishwashing detergent, in particular a dishwashing detergent for machine cleaning of dishes.
17. 17. Use of a gel according to items 1 to 10, or a detergent portion according to one of items 11 to 17 for machine cleaning of dishes, in particular of stubborn and/or greasy food residues.
18. 18. Method for machine cleaning of dishes, characterized in that a gel according to points 1 to 10 or a detergent portion according to one of points 11 to 17 is used in a dishwasher.

Examples:
Cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, were produced which comprised a solid, preferably granular phase and a gel phase. Different geometries were realized here. Furthermore, detergents, preferably dishwashing detergents, in particular machine dishwashing detergents, were produced which comprised two solid, preferably granular phases and a gel phase. Cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, were also produced, which comprised a solid, preferably granular phase and 3, 4 and 5 gel phases (of the same or different composition). The following information relates to % by weight of active substance, based on the total weight of the phase in question (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: wt% citrate, sodium salt 15-20 Phosphonate (e.g. HEDP) 0; 2.5-7.5 MGDA, Na salt 0-25 Disilicate, Na salt 5-35 soda 10-25 SILVER PROTECTION (e.g. cysteine) 0.0 - 1.0 Percarbonate, Na salt 10-15 Bleach catalyst (preferably Mn-based) 0.02-0.5 Bleach activator (e.g. TAED) 1-3 Nonionic surfactant(s), eg fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 2.5-10 polycarboxylate 4-10 cationic copolymer 0 - 0.75 Disintegrant - (ex. 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 wt% wt% wt% Water-soluble zinc salt (preferably zinc acetate anhydrate) 0-3 0.1-2.4 0.2-1.0 glycerin 5-50 10-40 20-35 Propanediol (esp. 1,3-propanediol) 0-40 20-40 28-35 Polycarboxylate copolymer with sulfonic acid containing groups 0-20 1-15 4-12 Polypropylene glycol medium Mr (e.g. Pluriol ^® 2000, Pluriol ^® 4000 (BASF) 0.1-30 0.6-26 1-15 polyethylene glycol average Mr 200-600, (e.g. PEG 400 (INCI) 0-26 2-20 3-16 PVOH 4-40 7-22 8-22 dye solution 0.0-1.5 0.0-1.5 0.0-1.5 water <5 <1 <1 Misc., Other Actives, Organic Solvents, Perfume, Processing Aids add 100 add 100 add 100

The solid granular phases and the gel could be combined with one another as desired. The spatial configuration of the gel phase, which was liquid after mixing the ingredients and dimensionally stable within a maximum setting time of 5 minutes, was determined by the spatial configuration of the solid phase and by commercially available or self-designed forms. A water-soluble cover 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 gave the gel after curing, then solid phases in the form of a free-flowing solid were filled into a pouch comprising polyvinyl alcohol and the open pouch was then sealed by placing a second film and sealing by heat sealing. Table 3: Gel phase compositions In % by weight (active ingredient) E1 E2 E3 Zinc acetate anhydrous 0.5 0.5 0.5 Polymer comprising acrylic acid and amidopropylsulfonic acid containing monomers 11 5 11 glycerin 27 38 28 1,3-propanediol 32 29 31 PEG 400 9.5 7.5 12 Pluriol 2000 5 5 2.5 PVOH (Mowiol 4-88) 15 15 15 Misc (including processing aids, pH adjusters, perfume, dye) add 100 add 100 add 100

Corresponding formulations were prepared according to Table 3.

The gel was stirred at temperatures of 110°C.

These gel phases were then packaged as described under Table 2 together with solid granular 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 setting times of less than 5 minutes, had particularly good processing properties.

Claims (13)

Cleaning agent, comprising a gel, preferably a gel that is solid at room temperature (20° C.), comprising, in each case based on the total weight of the gel: a. 4 to 40% by weight, preferably 6 to 30% by weight, in particular 7 to 24% by weight, particularly preferably 8 to 22% by weight, very particularly preferably 12 to 20% by weight PVOH and/or its derivatives; b. 20 to 80% by weight of at least one organic solvent, preferably selected from the group consisting of 1,2-propanediol, 1,3-propanediol, polyethylene glycols and/or alkanetriols, preferably glycerol, 1,1,1-trimethylolpropane, and mixtures from it; c. 0.1 to 30% by weight of at least one polypropylene glycol having an average molecular weight of 500 to 10,000 g/mol, in particular 1000 to 6000 g/mol. Cleaning agent according to Claim 1, characterized in that the polypropylene glycol is contained in an amount of 0.6 to 25% by weight, preferably in an amount of 1 to 15% by weight, based in each case on the total weight of the gel. Cleaning agent according to Claim 1 or 2, characterized in that glycerol, preferably in an amount of 5 to 50% by weight, preferably 10 to 45% by weight, particularly preferably 20 to 40% by weight of glycerol, is used as a preferred organic solvent. based on the total weight of the gel. Cleaning agent according to one of Claims 1 to 3, characterized in that 2 to 20% by weight of polyethylene glycol, in particular 3 to 16% by weight of polyethylene glycol, preferably polyethylene glycol with an average molecular weight of 200 to 600, is present as a preferred organic solvent. Cleaning agent according to Claims 1 to 4, characterized in that 1,3-propanediol, preferably in an amount of 5 to 50% by weight, preferably 20 to 40% by weight, particularly preferably 28 to 35% by weight, is used as the preferred organic solvent. % based on the total weight of the gel. Cleaning agent according to one of Claims 1 to 5, characterized in that the water content of the gel is less than 30% by weight, less than 20% by weight, preferably less than 15% by weight, in particular less than 10% by weight , particularly preferably less than 5% by weight, very particularly preferably less than 1% by weight, based on the total weight of the gel. Cleaning agent according to one of Claims 1 to 6, characterized in that at least one zinc salt, preferably zinc chloride, zinc sulfate and/or zinc acetate, in particular zinc acetate, particularly preferably zinc acetate anhydrate, in an amount of 0.05 to 3% by weight is preferred in an amount of 0.1 to 2.4% by weight, in particular 0.2 to 1% by weight, based on the total weight of the gel. Cleaning agent according to one of Claims 1 to 7, characterized in that the gel comprises at least one anionic polymer, in particular acrylate homo- or copolymer, in particular a polyacrylate copolymer with at least one monomer containing sulfonic acid groups, in particular a monomer selected from acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid, preferably in an amount of 0.1 to 15% by weight, particularly preferably 0.5 to 13.0% by weight, based in each case on the total weight of the gel. Detergent portion comprising at least one gel according to any one of Claims 1 to 8 in a water-soluble coating. Cleaning agent portion according to Claim 9, characterized in that the water-soluble coating comprises polyvinyl alcohol, the coating preferably having a layer thickness of 30 to 100 µm, in particular 40 to 800 µm. Detergent portion according to Claim 9 or 10, characterized in that it comprises at least or more additional phase(s) which is/are selected from a liquid phase, gel phase and/or solid, preferably granular, in particular particulate, preferably free-flowing, solid phase . Detergent portion according to Claim 11, characterized in that at least one additional phase comprises at least one, preferably several ingredients which are selected from the group formed from builders (preferably carbonates, citrate, aminopolycarboxylates and/or aminocarboxylates, preferably MGDA and/or GLDA or their salts, and/or bleaches (in particular percarbonate), and/or bleach activators and/or bleach catalysts, and/or silver protectants, and/or enzymes (preferably protease(s) and/or amylase(s)), and/or nonionic surfactants and/or other processing aids. Use of a gel as claimed in claims 1 to 8, or of a detergent portion as claimed in any of claims 9 to 12, for machine cleaning of dishes, in particular of stubborn and/or greasy food residues.