EP4345155A1 - Pressed phase gel dish detergent portion unit - Google Patents

Abstract

Cleaning agent portion unit, comprising
a) a dimensionally stable gel body
b) a coating substance in the form of a shaped body, which partially covers the surface of the dimensionally stable gel body, where
i) the gel body occupies from 20 to 45% by volume of the cleaning agent dosage unit, and
ii) the gel body, based on its total weight
- contains a maximum of 30% by weight of surfactant,
- contains 50 to 80% by weight of solvent,
- contains a gelling agent in proportions by weight below 5% by weight

iii) the shell substance, based on its total weight
- contains at least 80% by weight of washing or cleaning active ingredient, process for their production and cleaning process using these cleaning agent portion units.

Description

The present invention relates to a cleaning agent portion unit comprising a gel body and a rigid shell substance which at least partially covers the gel body. Furthermore, the application relates to a method for producing this cleaning agent portion unit and a method for cleaning dishes using such a cleaning agent portion unit.

The packaging and supply of detergents and cleaning agents are constantly changing. For some time now, the main focus has been on the convenient dosing of detergents and cleaning agents by the consumer and the simplification of the work steps required to carry out a washing or cleaning process. One technical solution is pre-portioned detergents or cleaning agents, for example water-soluble containers with one or more receiving chambers for powdered or liquid detergents or cleaning agents. Another technical solution is tablets, which can be designed in one or more phases.

To produce the water-soluble containers, water-soluble polymers are usually formed into receiving chambers, which are then filled with a washing or cleaning agent and finally sealed. The receiving chambers can be made from water-soluble polymer films using a deep-drawing process, for example. In an alternative process, a water-soluble polymer is formed into a receiving container using injection molding.

The water-soluble packaging material used to package the filled cleaning agent portion unit is generally hygroscopic. The tendency and ability of the packaging material to absorb water can, during production, packaging, storage and subsequent use by the consumer, lead to portion units sticking to the surfaces of machines or packaging materials and not being able to be conveyed optimally, or to adjacent portion units sticking together, for example in a shared outer packaging. To avoid this tendency of the water-soluble portion units to stick, it is possible to modify their surface properties by applying a powdering agent. Powdering the water-soluble cleaning agent portion unit requires an additional process step.

Due to the portioning in a water-soluble packaging material, the fragrances added to the detergent or cleaning agent are only very limited or not effective at all in detergent portion units, unlike with conventional solid powders. As a reaction to this situation, products are marketed whose outer cardboard packaging is, for example, provided with adhesives containing fragrances, giving the consumer an impression of the scent of the detergent or cleaning agent contained therein.

The water-soluble packaging materials used are generally not washing or cleaning-active, so they do not contribute to the product's effectiveness. Reducing the proportion of packaging in the total weight of the portion units would therefore not result in any loss of performance and would be welcome at the same time for reasons of sustainability and cost-effectiveness.

Finally, the cleaning performance provided by the cleaning agent portion unit is directly related to the dissolution properties of the portion unit. Especially in view of the increasing use of cold washing processes, it is preferred to keep the thickness of the water-soluble film material contained in the cleaning agent portion unit as small as possible in order to accelerate the dissolution process. However, the reduction in the thickness of the surrounding film material simultaneously results in reduced mechanical stability of the portion units. Overcoming this apparent dichotomy of mechanical stability and dissolution rate using water-soluble film-packaged detergent portion units remains a relevant consideration in the development of water-soluble detergent portion units.

Tablets offer an alternative to the previously described sachets, but in which sufficient mechanical stability and high dissolution speed are incompatible in a similar way as in the case of sachets.

Against the background of the prior art described above, the application was based on the task of providing cleaning agent portion units that can be produced using simplified processes, have a high product and storage stability, can be assembled in a simple manner using minimal amounts of packaging materials and that the consumer can use appealing olfactory, visual and/or haptic appeal. Ultimately, the cleaning agent portion units should have a high product performance and be easy and safe to handle for the consumer.

1. a) einen formstabilen Gelkörper
2. b) eine Hüllsubstanz in Form eines Formkörpers, welche die Oberfläche des formstabilen Gelkörper anteilsweise bedeckt, wobei
   1. i) der Gelkörper von 20 bis 45 Vol.-% der Reinigungsmitteldosiereinheit einnimmt, und
   2. ii) der Gelkörper, bezogen auf sein Gesamtgewicht
      • maximal 30 Gew.-% Tensid enthält,
      • 50 bis 80 Gew.-% Lösungsmittel enthält,
      • einen Gelbildner in Gewichtsanteilen unterhalb 5 Gew.-% enthält
   3. iii) die Hüllsubstanz, bezogen auf ihr Gesamtgewicht
   mindestens 80 Gew.-% wasch- oder reinigungsaktiven Inhaltsstoff enthält.

To solve these tasks, a cleaning agent portion unit is suitable, comprising

1. a) a dimensionally stable gel body
2. b) a coating substance in the form of a shaped body which partially covers the surface of the dimensionally stable gel body, whereby
   1. i) the gel body occupies from 20 to 45 vol.% of the detergent dosing unit, and
   2. (ii) the gel body, based on its total weight
      • contains a maximum of 30% by weight surfactant,
      • Contains 50 to 80 wt.% solvent,
      • contains a gelling agent in weight proportions below 5 wt.%
   3. (iii) the coating substance, based on its total weight
   contains at least 80% by weight of washing or cleaning active ingredient.

The term cleaning agent portion unit describes a form of offer in which a measured portion of a cleaning agent is present. Cleaning agent portion units therefore refer to both types of offers for cleaning hard surfaces such as ceramics, glass, metal or tiles. The cleaning agent portion unit preferably has a weight of 10 g to 35 g, preferably 13 g to 30 g, in particular 15 g to 25 g.

The cleaning agent portion unit according to the invention comprises a dimensionally stable gel and a specific coating substance which at least partially covers this gel.

Gel bodies are bodies that show elastic deformation behavior when force is applied. Bodies that have an inherent shape stability that enables them to assume a non-disintegrating spatial shape under the usual conditions of production, storage, transport and handling by the consumer are considered dimensionally stable, whereby this spatial shape does not change under the conditions mentioned even over a longer period of time, preferably 4 weeks, particularly preferably 8 weeks and in particular 32 weeks, i.e. under the usual conditions of production, storage, transport and handling by the consumer it remains in the spatial-geometric shape determined by the production, i.e. it does not melt.

A "molded body" is an individual body that stabilizes itself in its imprinted shape. This dimensionally stable body is formed from a molding compound (e.g. a composition) by deliberately shaping this molding compound into a predetermined shape, e.g. by pouring a liquid composition into a mold and then hardening the liquid composition or by compressing a particulate premix, for example in a tableting process.

According to the invention, the gel body occupies 20 to 45 vol.% of the cleaning agent portion unit, for example 20, 25, 30, 35, 40 or 45 vol.%. In various embodiments, the gel body occupies 25 to 40 vol.%, for example 30 to 35 vol.%, of the cleaning agent portion unit.

A characteristic feature of the dimensionally stable gel bodies comprised in the cleaning agent portion units according to the invention is their high active substance content, in particular their high proportion by weight of surfactant. Preferred cleaning agent portion units are characterized in that the gel body contains a maximum of 30% by weight of surfactant based on its total weight.

In various embodiments, the gel body contains, based on its total weight, 5 to 25 wt.% and in particular 10 to 20 wt.% surfactant.

The group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants. The compositions according to the invention can comprise one or more of the surfactants mentioned.

In various embodiments, the gel body contains, based on its total weight, less than 5% by weight, preferably less than 1% by weight, preferably no anionic surfactant.

The cleaning agent portion units contain in particular one or more non-ionic surfactants as surfactant. The weight proportion of the total weight of the gel body is preferably 5 to 30 wt.%, preferably 10 to 25 wt.%, even more preferably 10 to 20 wt.%.

All non-ionic surfactants known to the person skilled in the art can be used as non-ionic surfactants.

Examples of nonionic surfactants that can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallow alkyl-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of it.

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

However, low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. The cleaning agent portion units particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols.

Particularly preferred are nonionic surfactants which have a melting point above room temperature. Nonionic surfactants with a melting point above 20°C, preferably above 25°C, particularly preferably between 25 and 60°C and in particular between 26.6 and 43.3°C, are particularly preferred.

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

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder-Alkenylrest steht; jede Gruppe R² bzw. 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.Particularly preferred nonionic surfactants are those which have alternating ethylene oxide and alkylene oxide units. Among these, surfactants with EO-AO-EO-AO blocks are preferred, with one to ten EO or AO groups being bonded to one another before a block of the other groups follows. Here, nonionic surfactants of the general formula

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

Nonionic surfactants which have a C _9-15 alkyl radical with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units are therefore particularly preferred.

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

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

• R ¹ represents a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ² represents H or a linear or branched hydrocarbon radical with 2 to 26 carbon atoms;
• A, A', A" and A‴ independently represent a residue from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH(CH ₃ ), -CH ₂ -CH ₂ - CH ₂ -CH ₂ , -CH ₂ -CH(CH ₃ )-CH ₂ -, - CH ₂ -CH(CH ₂ -CH ₃ ),
• w, x, y and z represent values between 0.5 and 120, where x, y and/or z can also be 0.

Particular preference is given to end-capped, poly(oxyalkylated) nonionic surfactants which, according to the formula R ¹ O[CH ₂ CH ₂ O] _x CH ₂ CH(OH)R ² , are saturated in addition to a radical R ¹ which represents linear or branched or unsaturated, aliphatic or aromatic hydrocarbon radicals with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, furthermore have a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² with 1 to 30 carbon atoms, where x represents values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

Particularly preferred surfactants are those of the formula R ¹ O[CH ₂ CH(CH ₃ )O] _x [CH ₂ CH ₂ O] _y CH ₂ CH(OH)R ² , in which R ¹ is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 1.5 and y is at least 15.

The group of these non-ionic surfactants includes, for example, the C _2-26 fatty alcohol (PO) ₁ -(EO) _15-40 -2-hydroxyalkyl ethers, in particular the C _8-10 fatty alcohol (PO) ₁ -(EO) ₂₂ -2-hydroxydecyl ethers. Particularly preferred are also those end-capped poly(oxyalkylated) nonionic surfactants of the formula R ¹ O[CH ₂ CH ₂ O] _x [CH ₂ CH(R ³ )O] _y CH ₂ CH(OH)R ² , in which R ¹ and R ² independently of one another represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ³ 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 of one another represent values between 1 and 32, with nonionic surfactants with R ³ = -CH ₃ and values for x from 15 to 32 and y from 0.5 to 1.5 being very particularly preferred.

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

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

Particularly preferred end-capped poly(oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is simplified to R ¹ O[CH ₂ CH(R ³ )O] _x CH ₂ CH(OH)CH ₂ OR ² . In the latter formula, R ¹ , R ² and R ³ are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ² have 9 to 14 C atoms, R ³ stands for H and x assumes values from 6 to 15.

• 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.

Finally, the nonionic surfactants of the general formula R ¹ -CH(OH)CH ₂ O-(AO) _w -R ² have proven to be particularly effective, in which

• R ¹ represents a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ² represents a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A represents a radical from the group CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH(CH ₃ ), preferably CH ₂ CH ₂ , and
• w represents values between 1 and 120, preferably 10 to 80, in particular 20 to 40.

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

In various embodiments of the invention, instead of the end-capped hydroxy mixed ethers defined above, the corresponding non-end-capped hydroxy mixed ethers can also be used. These can satisfy the above formulas, but where R ² is hydrogen and R ¹ , R ³ , A, A', A", A‴, w, x, y and z are as defined above.

In various embodiments, the gel body contains at least one nonionic surfactant from the group of hydroxy mixed ethers.

For the manufacturability and the subsequent dissolving power of the gel bodies, it has proven advantageous if they contain, based on their total weight, 55 to 75 wt. %, preferably 60 to 70 wt. % solvent. The solvent systems of the gel bodies are preferably organic or aqueous-organic solvent systems. The Use of 50 to 75 wt.%, preferably 55 to 70 wt.% organic solvent in the gel bodies (each based on the total weight of the gel bodies).

Preferred organic solvents are selected from the group ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerin, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures thereof, preferably from the group Propanediol, glycerin and their mixtures.

In addition to organic solvents, the gel bodies can contain water as a further liquid carrier. The water content of preferred gel bodies, based on their total weight, is less than 20% by weight, preferably between 1 and 15% by weight, in particular between 2 and 14% by weight and very particularly preferably between 3 and 13% by weight.

Another possible component of the cleaning agent portion unit according to the invention are enzyme preparations.

In various embodiments, the cleaning agent portion unit comprises at least one enzyme preparation.

In various embodiments, the cleaning agent portion unit is characterized in that the amount of all amylases, based on the amount of active enzyme protein, in the cleaning agent portion unit is from 1 to 100 mg, preferably 4 to 50 mg, in particular 6 to 25 mg.

In various embodiments, the cleaning agent portion unit is characterized in that the amount of all proteases, based on the amount of active enzyme protein, in the cleaning agent portion unit is 2 to 800 mg, preferably 4 to 200 mg, in particular 6 to 100 mg.

In addition to the actual enzyme protein, an enzyme preparation includes other components such as enzyme stabilizers, carrier materials or fillers. The enzyme protein usually only forms a fraction of the total weight of the enzyme preparation. Preferably used enzyme preparations contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and most preferably between 0.8 and 10% by weight of the enzyme protein. In such compositions, an enzyme stabilizer may be included in an amount of 0.05 to 35% by weight, preferably 0.05 to 10% by weight, based on the total weight in the enzyme composition.

The protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method. In this regard, the active protein concentration is determined by titrating the active centers using a suitable irreversible inhibitor (for proteases, for example phenylmethylsulfonyl fluoride (PMSF)) and determining the residual activity (cf. M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913 ).

As a further preferred optional component, a gel body comprises 0.001 to 5% by weight, preferably 0.01 to 3% by weight, of fragrance preparation.

In addition to the actual fragrances, the fragrance preparation includes, for example, solvents, solid carrier materials or stabilizers.

A fragrance is a chemical substance that stimulates the sense of smell. In order to stimulate the sense of smell, the chemical substance should be at least partially dispersible in the air, i.e. the fragrance should be at least slightly volatile at 25°C. If the fragrance is now very volatile, the odor intensity will quickly subside. However, with a lower volatility, the odor impression is more lasting, i.e. it does not disappear as quickly. In one embodiment, the fragrance therefore has a melting point which is in the range from -100°C to 100°C, preferably from -80°C to 80°C, even more preferably from -20°C to 50°C, in particular from - 30°C to 20°C. In a further embodiment, the fragrance has a boiling point which is in the range from 25°C to 400°C, preferably from 50°C to 380°C, more preferably from 75°C to 350°C, in particular from 100°C to 330°C.

Overall, a chemical substance should not exceed a certain molecular mass in order to function as a fragrance, since if the molecular mass is too high, the required volatility can no longer be guaranteed. In one embodiment, the fragrance has a molecular weight of 40 to 700 g/mol, more preferably 60 to 400 g/mol.

The smell of a fragrance is perceived as pleasant by most people and often corresponds to the smell of, for example, flowers, fruits, spices, bark, resin, leaves, grasses, mosses and roots. Fragrances can also be used to mask unpleasant odors or to give a non-smelling substance a desired smell. Individual fragrance compounds can be used as fragrances, for example synthetic products of the type esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used.

Mixtures of different fragrances are preferably used, which together produce an appealing scent. Such a mixture of fragrances can also be referred to as perfume or perfume oil. Such perfume oils can also contain natural fragrance mixtures such as those available from plant sources.

To prolong the fragrance effect, it has proven advantageous to encapsulate the fragrance. In a corresponding embodiment, at least part of the fragrance is used in encapsulated form (fragrance capsules), in particular in microcapsules. However, the entire fragrance can also be used in encapsulated form. The microcapsules can be water-soluble and/or water-insoluble microcapsules. For example, melamine-urea-formaldehyde microcapsules, melamine-formaldehyde microcapsules, urea-formaldehyde microcapsules or starch microcapsules can be used. "Fragrance precursors" refer to compounds that only release the actual fragrance after chemical conversion/cleavage, typically through the action of light or other environmental conditions, such as pH value, temperature, etc. Such compounds are often also referred to as fragrance storage substances or "pro-fragrance".

Preferred gel bodies also contain dye.

In various embodiments, the gel body contains at least one gelling agent in an amount of 0.1 to 5% by weight, particularly preferably 0.1 to 2.5% by weight, based in each case on the total weight of the gel body. For the production and subsequent storage and transport properties of the gel bodies, it has proven to be advantageous to use low molecular weight gel formers with a molar mass of up to 2000 g/mol in the gel body, with their weight proportion to the total weight of the gel body preferably being less than 5% by weight 0.1 to 5% by weight and particularly preferably 0.1 to 2.5% by weight.

In a preferred embodiment, the low molecular weight gelling agent has a solubility in water of less than 0.1 g/L (20° C.). The solubility of the organic gelator compound is determined at 20 ° C in double-distilled, demineralized water.

Furthermore, gel formers are preferably suitable which have a structure containing at least one hydrocarbon structural unit with 6 to 20 carbon atoms (preferably at least one carbocyclic, aromatic structural unit) and additionally an organic structural unit covalently bonded to the aforementioned hydrocarbon unit, which has at least two groups selected from -OH, -NH-, or mixtures thereof.

worin

• *- für eine kovalente Einfachbindung zwischen einem Sauerstoffatom des Alditol-Grundgerüsts und dem vorgesehenen Rest steht,
• n für 0 oder 1, bevorzugt für 1, steht,
• m für 0 oder 1, bevorzugt für 1, steht,
• R¹, R² und R³ unabhängig voneinander steht für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₄-Alkylgruppe, eine Cyanogruppe, eine Nitrogruppe, eine Aminogruppe, eine Carboxylgruppe, eine Hydroxygruppe, eine Gruppe -C(=O)-NH-NH₂, eine Gruppe -NH-C(=O)-(C₂-C₄-Alkyl), eine C₁-C₄-Alkoxygruppe, eine C₁-C₄-Alkoxy-C₂-C₄-alkylgruppe, zwei der Reste gemeinsam mit dem Restmolekül einen 5- oder 6-gliedrigen Ring bilden,
• R⁴, R⁵ und R⁶ unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₄-Alkylgruppe, eine Cyanogruppe, eine Nitrogruppe, eine Aminogruppe, eine Carboxylgruppe, eine Hydroxygruppe, eine Gruppe -C(=O)-NH-NH₂, eine Gruppe -NH-C(=O)-(C₂-C₄-Alkyl), eine C₁-C₄-Alkoxygruppe, eine C₁-C₄-Alkoxy-C₂-C₄-alkylgruppe, zwei der Reste gemeinsam mit dem Restmolekül einen 5- oder 6-gliedrigen Ring bilden.

Particularly preferred gel bodies are characterized in that said gel bodies contain at least one benzylidene alditol compound of the formula (GB-I) as gelling agent

wherein

• *- represents a covalent single bond between an oxygen atom of the alditol backbone and the intended residue,
• n stands for 0 or 1, preferably 1,
• m stands for 0 or 1, preferably 1,
• R ¹ , R ² and R ³ independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxy group, a group -C(=O)-NH-NH ₂ , a group -NH-C(=O)-(C ₂ -C ₄ alkyl), a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkoxy-C ₂ -C ₄ alkyl group, two of the radicals together with the remaining molecule form a 5- or 6-membered ring,
• R ⁴ , R ⁵ and R ⁶ independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxy group, a -C(=O)-NH-NH ₂ group, a -NH-C(=O)-(C ₂ -C ₄ alkyl) group, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkoxy-C ₂ -C ₄ alkyl group, two of the radicals together with the remaining molecule form a 5- or 6-membered ring.

Due to the stereochemistry of the alditols, it should be mentioned that both said benzylidene alditols in the L configuration or in the D configuration or a mixture of both are suitable according to the invention. Due to their natural availability, the benzylidene alditol compounds in the D configuration are preferably used according to the invention. It has been found to be preferred if the alditol basic structure of the benzylidene alditol compound contained in the shaped body according to formula (GB-I) is derived from D-glucitol, D-mannitol, D-arabinitol, D-ribitol, D-xylitol, L-glucitol, L-mannitol, L-arabinitol, L-ribitol or L-xylitol.

• n gemäß Benzylidenalditol-Verbindung der Formel (GB-I) steht bevorzugt für 1.
• m gemäß Benzylidenalditol-Verbindung Formel (GB-I) steht bevorzugt für 1.

Particularly preferred are those gel bodies which are characterized in that R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently of one another according to the benzylideneditol compound of the formula (GB-I). hydrogen atom, methyl, ethyl, chlorine, fluorine or methoxy, preferably a hydrogen atom.

• n according to the benzylidenalditol compound of the formula (GB-I) is preferably 1.
• m according to the benzylidenalditol compound formula (GB-I) is preferably 1.

worin R¹, R², R³, R⁴, R⁵ und R⁶ wie in Formel (I) definiert sind. Am bevorzugtesten stehen gemäß Formel (GB-I1) R¹, R², R³, R⁴, R⁵ und R⁶ unabhängig voneinander für ein Wasserstoffatom, Methyl, Ethyl, Chlor, Fluor oder Methoxy, bevorzugt für ein Wasserstoffatom.Most preferably, the gel body contains as benzylidene alditol compound of formula (GB-I) at least one compound of formula (GB-I1)

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are as defined in formula (I). Most preferably, according to formula (GB-I1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another represent a hydrogen atom, methyl, ethyl, chlorine, fluorine or methoxy, preferably a hydrogen atom.

Most preferably, the benzylidene alditol compound of formula (GB-I) is selected from 1,3:2,4-di-O-benzylidene-D-sorbitol; 1,3:2,4-Di-O-(p-methylbenzylidene)-D-sorbitol; 1,3:2,4-Di-O-(p-chlorobenzylidene)-D-sorbitol; 1,3:2,4-Di-O-(2,4-dimethylbenzylidene)-D-sorbitol; 1,3:2,4-Di-O-(p-ethylbenzylidene)-D-sorbitol; 1,3:2,4-Di-O-(3,4-dimethylbenzylidene)-D-sorbitol or mixtures thereof.

worin

• R¹, R², R³ und R⁴ stehen unabhängig voneinander für ein Wasserstoffatom, eine Hydroxygruppe, eine (C₁-C₆)-Alkylgruppe, eine (C₂-C₆)-Alkenylgruppe, eine (C₂-C₆)-Acylgruppe, eine (C₂-C₆)-Acyloxygruppe, eine (C₁-C₆)-Alkoxygruppe, eine Aminogruppe, eine (C₂-C₆)-Acylaminogruppe, eine (C₁-C₆)-Alkylaminocarbonylgruppe, eine Arylgruppe, eine Aroylgruppe, eine Aroyloxygruppe, eine Aryloxygruppe, eine Aryl-(C₁-C₄)-alkyloxygruppe, eine Aryl-(C₁-C₃)-alkylgruppe, eine Heteroarylgruppe, eine Hetroaryl-(C₁-C₃)-alkylgruppe, eine (C₁-C₄)-Hydroxyalkylgruppe, eine (C₁-C₄)-Aminoalkylgruppe, eine Carboxy-(C₁-C₃)-alkylgruppe, wobei mindestens zwei der Reste R¹ bis R⁴ gemeinsam mit dem Restmolekül einen 5 oder 6-gliedrigen Ring bilden können,
• R⁵ steht für ein Wasserstoffatom, eine lineare (C₁ bis Cs)-Alkylgruppe, eine verzweigte (C₃ bis C₁₀)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂-C₆)-Alkenylgruppe, eine (C₂-C₆)-Alkinylgruppe, eine (C₁-C₄)-Hydroxyalkylgruppe, eine (C₁-C₄)-Alkoxy-(C₁-C₄)-alkylgruppe, eine (C₁-C₄)-Acyloxy-(C₁-C₄)-alkylgruppe, eine Aryloxy-(C₁-C₄)-alkylgruppe, eine O-(Aryl-(C₁-C₄)-alkyl)oxy-(C₁-C₄)-alkylgruppe, eine (C₁-C₄)-Alkylsulfanyl-(C₁-C₄)-alkylgruppe, eine Arylgruppe, eine Aryl-(C₁-C₃)-alkylgruppe, eine Heteroarylgruppe, eine Hetroaryl-(C₁-C₃)-alkylgruppe, eine (C₁-C₄)-Hydroxyalkylgruppe, eine (C₁-C₄)-Aminoalkylgruppe, eine N-(C₁-C₄)-Alkylamino-(C₁-C₄)-alkylgruppe, eine N,N-(C₁-C₄)-Dialkylamino-(C₁-C₄)-alkylgruppe, eine N-(C₂-C₈)-Acylamino-(C₁-C₄)-alkylgruppe, eine N-(C₂-C₈)-Acyl-N-(C₁-C₄)-alkylamino-(C₁-C₄)-alkylgruppe, eine N-(C₂-C₈)-Aroyl-N-(C₁-C₄)-alkylamino-(C₁-C₄)-alkylgruppe, eine N,N-(C₂-C₈)-Diacylamino-(C₁-C₄)-alkylgruppe, eine N-(Aryl-(C₁-C₄)-alkyl)amino-(C₁-C₄)-alkylgruppe, eine N,N-Di(aryl-(C₁-C₄)-alkyl)amino-(C₁-C₄)-alkylgruppe, eine (C₁-C₄)-Carboxyalkylgruppe, eine (C₁-C₄)-Alkoxycarbonyl-(C₁-C₃)-alkylgruppe, eine (C₁-C₄)-Acyloxy-(C₁-C₃)-alkylgruppe, eine Guanidino-(C₁-C₃)-alkylgruppe, eine Aminocarbonyl-(C₁-C₄)-alkylgruppe, eine N-(C₁-C₄)-Alkylaminocarbonyl-(C₁-C₄)-alkylgruppe, eine N,N-Di((C₁-C₄)-Alkyl)aminocarbonyl-(C₁-C₄)-alkylgruppe, eine N-(C₂-C₈)-Acylaminocarbonyl-(C₁-C₄)-alkylgruppe, eine N,N-(C₂-C₈)-Diacylaminocarbonyl-(C₁-C₄)-alkylgruppe, eine N-(C₂-C₈)-Acyl-N-(C₁-C₄)-alkylaminocarbonyl-(C₁-C₄)-alkylgruppe, eine N-(Aryl-(C₁-C₄)-alkyl)aminocarbonyl-(C₁-C₄)-alkylgruppe, eine N-(Aryl-(C₁-C₄)-alkyl)-N-(C₁-C₆)-alkylaminocarbonyl-(C₁-C₄)-alkylgruppe oder eine N,N-Di(aryl-(C₁-C₄)-alkyl)aminocarbonyl-(C₁-C₄)-alkylgruppe.

Preferred gel bodies contain at least one 2,5-diketopiperazine compound of the formula (GB-II) as a gelling agent.

wherein

• R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a hydroxy group, a (C ₁ -C ₆ )alkyl group, a (C ₂ -C ₆ )alkenyl group, a (C ₂ -C ₆ )-acyl group, a (C ₂ -C ₆ )-acyloxy group, a (C ₁ -C ₆ )-alkoxy group, an amino group, a (C ₂ -C ₆ )-acylamino group, a (C ₁ -C ₆ )alkylaminocarbonyl group, an aryl group, an aroyl group, an aroyloxy group, an aryloxy group, an aryl (C ₁ -C ₄ )alkyloxy group, an aryl (C ₁ -C ₃ )alkyl group, an heteroaryl group, a hetroaryl (C ₁ -C ₃ )alkyl group, a (C ₁ -C ₄ )hydroxyalkyl group, a (C ₁ -C ₄ )aminoalkyl group, a carboxy (C ₁ -C ₃ )alkyl group, where at least two of the radicals R ¹ to R ⁴ together with the remaining molecule can form a 5 or 6-membered ring,
• R ⁵ represents a hydrogen atom, a linear (C ₁ to Cs) alkyl group, a branched (C ₃ to C ₁₀ ) alkyl group, a (C ₃ to C ₆ ) cycloalkyl group, a (C ₂ -C ₆ ) alkenyl group, a (C ₂ -C ₆ )-alkynyl group, a (C ₁ -C ₄ )-hydroxyalkyl group, a (C ₁ -C ₄ )-alkoxy-(C ₁ -C ₄ )-alkyl group, a (C ₁ - C ₄ )-acyloxy-(C ₁ -C ₄ )-alkyl group, an aryloxy-(C ₁ -C ₄ )-alkyl group, an O-(aryl-(C ₁ -C ₄ )-alkyl)oxy-(C ₁ -C ₄ )-alkyl group, a (C ₁ -C ₄ )-alkylsulfanyl-(C ₁ -C ₄ )-alkyl group, an aryl group, an aryl-(C ₁ -C ₃ )-alkyl group, a heteroaryl group, a hetroaryl- (C ₁ -C ₃ )-alkyl group, a (C ₁ -C ₄ )-hydroxyalkyl group, a (C ₁ -C ₄ )-aminoalkyl group, an N-(C ₁ -C ₄ )-alkylamino-(C ₁ -C ₄ )-alkyl group, an N,N-(C ₁ -C ₄ )-dialkylamino-(C ₁ -C ₄ )-alkyl group, an N-(C ₂ -C ₈ )-acylamino-(C ₁ -C ₄ ) -alkyl group, an N-(C ₂ -C ₈ )-acyl-N-(C ₁ -C ₄ )-alkylamino-(C ₁ -C ₄ )-alkyl group, an N-(C ₂ -C ₈ )-aroyl -N-(C ₁ -C ₄ )-alkylamino-(C ₁ -C ₄ )-alkyl group, an N,N-(C ₂ -C ₈ )-diacylamino-(C ₁ -C ₄ )-alkyl group, an N -(Aryl-(C ₁ -C ₄ )-alkyl)amino-(C ₁ -C ₄ )-alkyl group, an N,N-di(aryl-(C ₁ -C ₄ )-alkyl)amino-(C ₁ -C ₄ )-alkyl group, a (C ₁ -C ₄ )-carboxyalkyl group, a (C ₁ -C ₄ )-alkoxycarbonyl-(C ₁ -C ₃ )-alkyl group, a (C ₁ -C ₄ )-acyloxy- (C ₁ -C ₃ )-alkyl group, a guanidino-(C ₁ -C ₃ )-alkyl group, an aminocarbonyl-(C ₁ -C ₄ )-alkyl group, an N-(C ₁ -C ₄ )-alkylaminocarbonyl-( C ₁ -C ₄ )-alkyl group, an N,N-di((C ₁ -C ₄ )-alkyl)aminocarbonyl-(C ₁ -C ₄ )-alkyl group, an N-(C ₂ -C ₈ )-acylaminocarbonyl -(C ₁ -C ₄ )-alkyl group, an N,N-(C ₂ -C ₈ )-diacylaminocarbonyl-(C ₁ -C ₄ )-alkyl group, an N-(C ₂ -C ₈ )-acyl-N -(C ₁ -C ₄ )-alkylaminocarbonyl-(C ₁ -C ₄ )-alkyl group, an N-(aryl-(C ₁ -C ₄ )-alkyl)aminocarbonyl-(C ₁ -C ₄ )-alkyl group, one N-(aryl-(C ₁ -C ₄ )-alkyl)-N-(C ₁ -C ₆ )-alkylaminocarbonyl-(C ₁ -C ₄ )-alkyl group or an N,N-di(aryl-(C ₁ -C ₄ )alkyl)aminocarbonyl-(C ₁ -C ₄ )alkyl group.

worin R¹ und R⁵ wie unter Formel (GB-II) (vide supra) definiert sind.It is preferred according to the invention if R ³ and R ⁴ according to formula (GB-II) are a hydrogen atom. It is particularly preferred according to the invention if R ² , R ³ and R ⁴ according to formula (GB-II) are a hydrogen atom. Therefore, very particularly preferred shaped bodies according to the invention contain at least one 2,5-diketopiperazine compound according to formula (GB-IIa)

wherein R ¹ and R ⁵ are as defined under formula (GB-II) (vide supra).

worin R¹ und R⁵ wie zuvor unter Formel (GB-II) (vide supra) definiert sind. Die an den Ringatomen in Formel (GB-Ilb) positionierten Ziffern 3 und 6 markieren zur Veranschaulichung lediglich die Positionen 3 und 6 des Diketopiperazinringes, wie sie generell im Rahmen der Erfindung für die Namensgebung aller erfindungsgemäßen 2,5-Diketopiperazine genutzt werden.It has proven to be preferred if the radical R ¹ binds in the para position of the phenyl ring according to formula (GB-II) and according to formula (GB-Ila). Therefore, for the purposes of the present invention, those shaped bodies according to the invention are preferred which contain at least one 2,5-diketopiperazine compound according to the formula (GB-Ilb),

wherein R ¹ and R ⁵ are as previously defined under formula (GB-II) (vide supra). The numbers 3 and 6 positioned on the ring atoms in formula (GB-Ilb) merely mark positions 3 and 6 of the diketopiperazine ring for illustrative purposes, as they are generally used within the scope of the invention for the naming of all 2,5-diketopiperazines according to the invention.

The 2,5-diketopiperazine compounds of the formula (GB-II) have chiral centers at least at the carbon atoms of positions 3 and 6 of the 2,5-diketopiperazine ring. The numbering of ring positions 3 and 6 was illustrated by way of example in formula (GB-IIb). The 2,5-diketopiperazine compound of the formula (GB-II) of the compositions according to the invention is preferably, based on the stereochemistry of the carbon atoms at positions 3 and 6 of the 2,5-diketopiperazine ring, the configuration isomer 3S,6S, 3R,6S, 3S,6R, 3R,6R or mixtures thereof, particularly preferably 3S,6S.

Preferred gel bodies contain at least one 2,5-diketopiperazine compound of the formula (GB-II) as gelling agent, selected from 3-benzyl-6-carboxyethyl-2,5-diketopiperazine, 3-benzyl-6-carboxymethyl-2,5-diketopiperazine, 3-benzyl-6-(p-hydroxybenzyl)-2,5-diketopiperazine, 3-benzyl-6-iso-propyl-2,5-diketopiperazine, 3-benzyl-6-(4-aminobutyl)-2,5-diketopiperazine, 3,6-di(benzyl)-2,5-diketopiperazine, 3,6-di(p-hydroxybenzyl)-2,5-diketopiperazine, 3,6-di(p-(benzyloxy)benzyl)-2,5-diketopiperazine, 3-Benzyl-6-(4-imidazolyl)methyl-2,5-diketopiperazine, 3-benzyl-6-methyl-2,5-diketopiperazine, 3-benzyl-6-(2-(benzyloxycarbonyl)ethyl)-2,5-diketopiperazine or mixtures thereof. In this case, compounds with the aforementioned configuration isomers are preferred for selection.

worin

• X⁺ unabhängig voneinander für Wasserstoffatom oder ein äquivalent eines Kations steht,
• R¹, R², R³ und R⁴ unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₄-Alkylgruppe, eine C₁-C₄-Alkoxygruppe, eine C₂-C₄-Hydroxyalkylgruppe, eine Hydroxylgruppe, eine Aminogruppe, eine N-(C₁-C₄-Alkyl)aminogruppe, eine N,N-Di(C₁-C₄-Alkyl)aminogruppe, eine N-(C₂-C₄-hydroxyalkyl)aminogruppe, eine N,N-Di(C₂-C₄-hydroxyalkyl)aminogruppe oder R¹ mit R² oder R³ mit R⁴ einen 5- oder 6-gliedrigen annelierten Ring bildet, der wiederum jeweils mit mindestens einer Gruppe aus C₁-C₄-Alkylgruppe, C₁-C₄-Alkoxygruppe, C₂-C₄-Hydroxyalkylgruppe, Hydroxylgruppe, Aminogruppe, N-(C₁-C₄-Alkyl)aminogruppe, N,N-Di(C₁-C₄-Alkyl)aminogruppe, N-(C₂-C₄-hydroxyalkyl)aminogruppe, N,N-Di(C₂-C₄-hydroxyalkyl)aminogruppe substituiert sein kann.

It is also possible for the gel bodies according to the invention to contain as gelling agents a) at least one diarylamidocystin compound of the formula (GB-III)

wherein

• X ⁺ independently represents hydrogen atom or an equivalent of a cation,
• R ¹ , R ² , R ³ and R ⁴ independently of one another represent a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, a C ₂ -C ₄ hydroxyalkyl group, a hydroxyl group, an amino group, an N-(C ₁ -C ₄ alkyl)amino group, an N,N-di(C ₁ -C ₄ alkyl)amino group, an N-(C ₂ -C ₄ hydroxyalkyl)amino group, an N,N-di(C ₂ -C ₄ hydroxyalkyl)amino group or R ¹ with R ² or R ³ with R ⁴ forms a 5- or 6-membered fused ring which in turn is each fused to at least one group from C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group, C ₂ -C ₄ hydroxyalkyl group, hydroxyl group, amino group, N-(C ₁ -C ₄ -alkyl)amino group, N,N-di(C ₁ -C ₄ -alkyl)amino group, N-(C ₂ -C ₄ -hydroxyalkyl)amino group, N,N-di(C ₂ -C ₄ -hydroxyalkyl)amino group.

Each of the stereocenters contained in the compound of formula (GB-III) can independently represent the L or D stereoisomer. According to the invention, it is preferred if said cystine compound of the formula (GB-III) is derived from the L-stereoisomer of cysteine.

Said gel bodies can contain at least one compound of the formula (GB-III) in which R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl group, a C ₁ - C ₄ alkoxy group, a C ₂ -C ₄ hydroxyalkyl group, a hydroxyl group, or R ¹ with R ² or R ³ with R ⁴ forms a 5- or 6-membered fused ring, which in turn is each with at least one group from C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group, C ₂ -C ₄ hydroxyalkyl group, hydroxyl group can be substituted. Particularly suitable are those shaped bodies which, as a diarylamidocystine compound of the formula (GB-III), are N,N'-dibenzoylcystine (R ¹ = R ² = R ³ = R ⁴ = hydrogen atom; X ⁺ = independently of one another for hydrogen atom or a equivalent to a cation), in particular N,N'-dibenzoyl-L-cystine.

wobei

• n 2 bis 4, vorzugsweise 3 oder 4, insbesondere 4, ist;
• R¹ ausgewählt wird aus Wasserstoff, C₁-C₁₆ Alkylresten, C₁-C₃ Hydroxy- oder Methoxyalkylresten, vorzugsweise C₁-C₃ Alkyl-, Hydroxyalkyl- oder Methoxyalkylresten, besonders bevorzugt Methyl;
• R² ausgewählt wird aus C₈-C₂₄-Alkylresten, C₈-C₂₄-Monoalkenylresten, C₈-C₂₄-Dialkenylresten, C₈-C₂₄-Trialkenylresten, C₈-C₂₄-Hydroxyalkylresten, C₈-C₂₄-Hydroxyalkenylresten, C₁-C₃ Hydroxyalkylresten oder Methoxy-C₁-C₃-alkylresten, vorzugsweise C₈-C₁₈ Alkylresten und Mischungen davon, noch bevorzugter C₈, C₁₀, C₁₂, C₁₄, C₁₆ und C₁₈-Alkylresten und Mischungen davon, am meisten bevorzugt C₁₂ und C₁₄ Alkylresten oder einer Mischung davon.

The N-(C ₈ -C ₂₄ )-hydrocarbylglyconamide compounds suitable as gel formers a) preferably have the formula (GB-IV)

where

• n is 2 to 4, preferably 3 or 4, especially 4;
• R ¹ is selected from hydrogen, C ₁ -C ₁₆ alkyl radicals, C ₁ -C ₃ hydroxy or methoxyalkyl radicals, preferably C ₁ -C ₃ alkyl, hydroxyalkyl or methoxyalkyl radicals, particularly preferably methyl;
• R ² is selected from C ₈ -C ₂₄ alkyl radicals, C ₈ -C ₂₄ monoalkenyl radicals, C ₈ -C ₂₄ dialkenyl radicals, C ₈ -C ₂₄ trialkenyl radicals, C ₈ -C ₂₄ hydroxyalkyl radicals, C ₈ -C ₂₄ hydroxyalkenyl radicals, C ₁ -C ₃ hydroxyalkyl radicals or methoxy-C ₁ -C ₃ alkyl radicals, preferably C ₈ -C ₁₈ alkyl radicals and mixtures thereof, more preferably C ₈ , C ₁₀ , C ₁₂ , C ₁₄ , C ₁₆ and C ₁₈ alkyl radicals and mixtures thereof, most preferably C ₁₂ and C ₁₄ alkyl radicals or a mixture thereof.

ein von einer Glycuronsäure, insbesondere der Glycuronsäure einer Hexose (n=4), abgeleiteter Rest. Hierbei ist insbesondere Glucuronsäure als bevorzugter Rest zu nennen. R¹ ist vorzugsweise H oder ein kurzkettiger Alkylrest, insbesondere Methyl. R² ist vorzugsweise ein langkettiger Alkylrest, beispielsweise eine C₈-C₁₈ Alkylrest.In particularly preferred embodiments, the remainder is

a residue derived from a glycuronic acid, in particular the glycuronic acid of a hexose (n=4). In particular, glucuronic acid should be mentioned as a preferred residue. R ¹ is preferably H or a short-chain alkyl radical, especially methyl. R ² is preferably a long-chain alkyl radical, for example a C ₈ -C ₁₈ alkyl radical.

wobei R² die für Formel (GB-IV) angegebenen Bedeutungen hat.Particularly preferred are therefore compounds of the formula (GB-IV1)

where R ² has the meanings given for formula (GB-IV).

In a particularly preferred embodiment, the at least one low molecular weight gelling agent is selected from the group consisting of the group of cyclic dipeptides, cyclic dipeptide derivatives and dibenzylidene sorbitol. In various embodiments, the gelling agent is selected from the group of low molecular weight gelling agents with a molar mass of up to 2000 g/mol, in particular from the group of cyclic dipeptides, cyclic dipeptide derivatives and dibenzylidene sorbitol. Due to its technical effect, the at least one gelling agent dibenzylidene sorbitol (DBS) is particularly preferred.

A cleaning agent portion according to the invention contains, in some embodiments, at least one water-soluble and/or water-insoluble, organic and/or inorganic builder (builder).

The general builders that can be used include, in particular, aminocarboxylic acids and their salts, zeolites, silicates, carbonates, organic (co)builders and - where there are no ecological prejudices against their use - also phosphates. However, according to preferred embodiments, the agents according to the invention are phosphate-free.

Phosphonates are also suitable as builders. A hydroxyalkane and/or aminoalkane phosphonate is preferably used as the phosphonate compound. Of the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues are preferably used as aminoalkane phosphonates. Phosphonates are preferably contained in the cleaning agent portion units in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, in each case based on the total weight of the cleaning agent portion unit.

In various embodiments, the cleaning agent portion unit contains at least one phosphonate as described above. In various embodiments, the at least one phosphonate is contained in the gel body.

Also suitable according to the invention are the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which have more than one, in particular two to eight, acid functions, preferably two to six, in particular two, three, four or five acid functions in total carry molecule. Dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids, are preferred as polycarboxylic acids. The polycarboxylic acids can carry additional functional groups, such as hydroxyl or amino groups. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and glucaric acid), aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids, such as nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA) , aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), and their derivatives and mixtures of these, whereby glutamine-N,N-diacetic acid (also as N,N-bis(carboxymethyl)-L -glutamic acid or GLDA) is preferably excluded as described above. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, MGDA and mixtures of these.

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

In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof should be mentioned.

Other suitable polymeric polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g/mol. Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g/mol. Due to their superior solubility, the short-chain polyacrylates from this group, which have molecular weights of 2,000 to 10,000 g/mol, and particularly preferably of 3,000 to 5,000 g/mol, may be preferred. For the purposes of this document, the molecular weights stated are weight-average molecular weights Mw, which were generally determined by means of gel permeation chromatography (GPC) using a UV detector. The measurement was carried out against an external standard, which provides realistic molecular weight values due to its structural similarity to the polymers examined.

The builders suitable according to the invention also include crystalline layered silicates of the general formula NaMSi _x O _2x+i · yH ₂ O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values for x being 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. Amorphous sodium silicates with a Na ₂ O : SiO ₂ modulus of 1:2 to 1:3.3, preferably from 1:2 to 1:2.8 and in particular from 1:2 to 1:2.6, which are preferably delayed in dissolution and have secondary washing properties, can also be used.

Crystalline or amorphous alkali aluminosilicates can be used in particular as water-insoluble, water-dispersible inorganic builder materials. Among these, crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, P and optionally X, are preferred.

Carbonate(s) and bicarbonate(s) are also suitable as builders, with alkali metal carbonate(s) being preferred, in particular sodium carbonate (soda). Typical amounts are in the range from 5 to 50% by weight, preferably 10 to 40% by weight, in particular 15 to 30% by weight, based in each case on the total weight of the cleaning agent portion unit.

In various embodiments, the cleaning agent portion unit comprises at least one active substance from the group of builders, in particular at least one active substance from the group of zeolites, silicates and carbonates, preferably from the group of carbonates.

In various embodiments, the cleaning agent portion unit comprises, based on its total weight, at least one active substance from the group of builders in weight proportions of 5 to 70 wt. %, preferably 10 to 50 wt. %, in particular at least one active substance from the group of zeolites, silicates and carbonates, preferably from the group of Carbonates, in particular carbonates in weight proportions of 5 to 70 wt.%, preferably 10 to 50 wt.%.

In various embodiments, a cleaning agent portion unit according to the invention contains at least one sulfopolymer. The weight proportion of the sulfopolymer in the total weight of the cleaning agent portion unit according to the invention is preferably from 0.1 to 20 wt. %, in particular from 0.5 to 18 wt. %, particularly preferably from 1.0 to 15 wt. %, in particular from 4 to 14 wt. %, above all from 6 to 12 wt. %. The sulfopolymer is usually used in the form of an aqueous solution, with the aqueous solutions typically containing 20 to 70 wt. %, in particular 30 to 50 wt. %, preferably about 35 to 40 wt. % sulfopolymers.

The sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.

The copolymers can have two, three, four or more different monomer units. Preferred copolymeric polysulfonates contain, in addition to monomer(s) containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids.

As unsaturated carboxylic acid(s) it is particularly preferred to use unsaturated carboxylic acids of the formula R ¹ (R ² )C=C(R ³ )COOH, in which R ¹ to R ³ independently of one another represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or represent -COOH or -COOR ⁴ , where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

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

The monomers containing sulfonic acid groups are those of the formula

R ⁵ (R ⁶ )C=C(R ⁷ )-X-SO ₃ H

preferred, in which R ⁵ to R ⁷ independently represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, with - NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical with 1 to 12 carbon atoms, and X represents 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

HO ₃ SX-(R ⁶ )C=C(R ⁷ )-X-SO ₃ H,

in which R ⁶ and R ⁷ are independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ and -CH(CH ₃ ) ₂ and X represents an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO-(CH ₂ ) _k - with k = 1 to 6, -C(O)-NH-C(CH ₃ ) ₂ -, - C(O)-NH-C(CH ₃ ) ₂ -CH ₂ - and -C(O)-NH-CH(CH ₃ )-CH ₂ -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene1-sulfonic acid, styrenesulfonic acid, vinyl sulfonic acid, 3-sulfopropyl acrylate, 3-sulfo propyl methacrylate , sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water-soluble salts.

In the polymers, the sulfonic acid groups can be present in completely or partially neutralized form, i.e. the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

The monomer distribution of the copolymers preferably used is preferably 5 to 95% by weight in copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight and the proportion of the monomer containing carboxylic acid groups Monomers 10 to 50 wt.%, the monomers are preferably selected from those mentioned above.

The molecular weight of the sulfo copolymers preferably used can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred cleaning agent portion units are characterized in that the copolymers have molecular weights of from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

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

Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention. The nonionic monomers used are preferably monomers of the general formula R(R ² )C=C(R ³ )-XR ⁴ , in which R to R ³ independently of one another represent -H, -CH ₃ or -C ₂ H ₅ , X represents an optionally present spacer group selected from -CH ₂ -, -C(O)O- and -C(O)-NH-, and R ⁴ represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

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, alpha-olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22 alpha-olefin, 2-styrene, alpha -Methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2,vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N -(Methyl)acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N-(2-ethylhexyl)acrylamide, octyl acrylate, octyl methacrylate, N-(octyl)acrylamide, lauryl acrylate, lauryl methacrylate, N-(lauryl) acrylamide, stearyl acrylate , stearyl methacrylate, N-(stearyl)acrylamide, behenyl acrylate, behenyl methacrylate and N-(behenyl)acrylamide or mixtures thereof.

The monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably 5 to 80% by weight in relation to the monomer containing sulfonic acid groups, the hydrophobic monomer and the monomer containing carboxylic acid groups, particularly preferably the proportion of the monomer containing sulfonic acid groups and the hydrophobic monomer is 5 to 30% by weight and the proportion of monomer containing carboxylic acid groups is 60 to 80% by weight; the monomers are preferably selected from those mentioned above.

In various embodiments, the gel body contains, based on its total weight, 0 to 12 wt. %, preferably 1 to 10 wt. %, more preferably 2 to 8 wt. % of a washing or cleaning-active polymer, preferably a washing or cleaning-active polymer from the group of polycarboxylates, preferably polymers which comprise acrylate and/or methacrylate, in particular polymers which additionally comprise monomers containing sulfonic acid groups.

Such washing and cleaning active polymers have been described previously.

In various embodiments, the cleaning agent portion unit contains washing or cleaning active ingredients from the group of sodium salts of organic and inorganic acids and at least 80% by weight, preferably at least 90% by weight and particularly preferably at least 95% by weight of this sodium salt is present as a component of the coating substance.

In various embodiments, the cleaning agent portion unit comprises citrate in weight proportions of 0.5 to 25 wt.%, preferably 5 to 15 wt.%, each based on the total weight of the cleaning agent portion unit.

In various embodiments, the cleaning agent portion unit comprises aminocarboxylates, in particular selected from the group MGDA, GLDA, EDDS and/or their salts.

In various embodiments, the cleaning agent portion unit comprises MGDA, GLDA, EDDS and/or their salts in proportions by weight of 0.5 to 25% by weight, preferably from 5 to 15% by weight, in each case based on the total weight of the cleaning agent portion unit.

In various embodiments, the detergent portion unit comprises MGDA and/or its salt in weight proportions of 0.5 to 25 wt.%, preferably 5 to 15 wt.%, each based on the total weight of the detergent portion unit
In various embodiments, the detergent portion unit as described herein comprises at least one bleaching agent.

Bleaching agents are substances that have washing or cleaning properties. Among the compounds that serve as bleaching agents and provide H ₂ O ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -providing peracidic salts or peracids such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. All other inorganic or organic peroxy bleaching agents known to the person skilled in the art from the prior art can also be used. According to the invention, percarbonates and in particular sodium percarbonate are particularly preferred as bleaching agents.

According to the invention, cleaning agent portion units are preferred which contain 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably 3.5 to 20% by weight and in particular 5 to 15% by weight of bleach, preferably sodium percarbonate.

In various embodiments of the invention, the cleaning agent portion units additionally contain at least one bleach activator. Compounds which, under perhydrolysis conditions, yield aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and/or optionally substituted perbenzoic acid, can be used as bleach activators. Of all the bleach activators known to the person skilled in the art from the prior art, particularly preferred bleach activators are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS). Combinations of conventional bleach activators can also be used. According to the invention, TAED is very particularly preferred as the bleach activator, in particular in combination with a percarbonate bleach, preferably sodium percarbonate.

These bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight, in each case based on the total weight of the cleaning agent portion unit.

Furthermore, the cleaning agent portion units can contain bleach catalysts. The bleaching catalysts that can be used include, but are not limited to, the group of bleach-enhancing transition metal salts and transition metal complexes, preferably the Mn, Fe, Co, Ru or Mo complexes, particularly preferably from the group of manganese and/or Cobalt salts and/or complexes, in particular the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate and the complexes of manganese with 1,4 ,7-trimethyl-1,4,7-triazacyclononane (Mn ₃ -TACN) or 1,2,4,7-tetramethyl-1,4,7-tri-azacyclononane (Mn ₄ -TACN).

Cleaning agent portion units are preferred which contain 0.001 to 1% by weight, preferably 0.01 to 0.1% by weight, of bleach catalyst, preferably an Mn complex, in particular a complex of manganese with 1,4,7-trimethyl-1, 4,7-triazacyclononane (Mns-TACN) or 1,2,4,7-tetramethyl-1,4,7-tri-azacyclononane (Mn ₄ -TACN).

In various embodiments, the cleaning agent portion unit contains at least one glass corrosion inhibitor, preferably in an amount of 0.05 to 5% by weight, preferably between 0.2 to 4% by weight and in particular between 0.4 to 3% by weight, respectively based on the total weight of the cleaning agent portion unit.

Glass corrosion inhibitors prevent the appearance of clouding, streaks and scratches, as well as the iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and/or zinc salts and/or magnesium and/or zinc complexes.

The spectrum of zinc salts preferred according to the invention, preferably organic acids, particularly preferably organic carboxylic acids, ranges from salts that are sparingly or insoluble in water, i.e. a solubility below 100 mg/l, preferably below 10 mg/l, in particular below 0.01 mg/l, up to those salts which have a solubility in water above 100 mg/l, preferably above 500 mg/l, particularly preferably above 1 g/l and in particular above 5 g/l (all solubilities at 20 ° C water temperature). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate; the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

It is particularly preferred to use at least one zinc salt of an organic carboxylic acid as the glass corrosion inhibitor, particularly preferably a zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and/or zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

Soluble inorganic zinc salts, especially zinc sulfate, zinc nitrate and zinc chloride, are also suitable for glass corrosion protection.

In various embodiments, the at least one glass corrosion inhibitor is selected from the group consisting of zinc salts of organic carboxylic acid, zinc salts being particularly preferred from the group consisting of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate, zinc citrate, zinc ricinoleate, zinc abietate, and/or zinc oxalate; and/or from the group consisting of soluble inorganic zinc salts, zinc sulfate, zinc nitrate and zinc chloride being particularly preferred.

Corrosion inhibitors serve to protect the items to be washed or the machine, with silver protection agents being particularly important in the area of automatic dishwashing. The known substances from the prior art can be used, in particular cysteine and/or cystine. Silver protective agents are usually used in an amount of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04% by weight, based on the total weight of the respective agent, in the context of the present invention, therefore based on the total weight of the cleaning agent portion unit.

In various embodiments, the cleaning agent portion unit contains at least one silver protective agent, preferably in an amount of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04% by weight, in each case based on the total weight of the cleaning agent portion unit.

In various embodiments, a cleaning agent portion unit according to the invention comprises at least one silver protective agent selected from the group consisting of cysteine, cystine and mixtures thereof.

Furthermore, silver protective agents selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used. Benzotriazole and/or alkylaminotriazole represent commonly used silver protective agents. 3-Amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts represent further examples, with these substances usually in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight. -%, particularly preferably 0.01 to 0.04% by weight can be used. In this context, preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulfurous acid, organic carboxylic acids such as acetic, glycolic, citric and succinic acid. 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-versatic-10-acid alkyl-3-amino-1,2,4-triazoles and mixtures are particularly effective of these substances.

In addition, cleaning formulations often contain active chlorine-containing agents, which can significantly reduce the corrosion of the silver surface. In chlorine-free cleaning agents, organic redox-active compounds containing oxygen and nitrogen, such as di- and trivalent phenols, e.g. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds are used. Salt and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are also frequently used. Preference is given to transition metal salts selected from the group of manganese and/or cobalt salts and/or complexes, particularly preferably cobalt (ammine) complexes, cobalt (acetate) complexes, cobalt (carbonyl) complexes, chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion of the items being washed.

Instead of or in addition to the silver protective agents described above, for example the benzotriazoles, redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and/or complexes, the metals preferably being in one of the oxidation states II, III, IV, V or VI are present.

The metal salts or metal complexes used should be at least partially soluble in water. The counterions suitable for salt formation include all usual one-, two- or three-fold negatively charged inorganic anions, for example oxide, sulfate, nitrate, fluoride, but also organic anions such as stearate.

Particularly preferred metal salts and/or metal complexes are selected from the group MnSO ₄ , Mn(II) citrate, Mn(II) stearate, Mn(II) acetylacetonate, Mn(II)-[1-hydroxyethane-1,1-diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co(NO ₃ ) ₂ , Ce(NO ₃ ) ₃ , and mixtures thereof, so that the metal salts and/or metal complexes are selected from the group MnSO ₄ , Mn(II) citrate, Mn(II) stearate, Mn(II) acetylacetonate, Mn(II)-[1-hydroxyethane-1,1-diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co(NO ₃ ) ₂ , Ce(NO ₃ ) ₃ are used with particular preference.

The inorganic redox-active substances, in particular metal salts or metal complexes, are preferably coated, i.e. completely covered with a waterproof material that is easily soluble at cleaning temperatures, in order to prevent their premature decomposition or oxidation during storage. Preferred coating materials, which are applied using known methods, such as Sandwik melt coating methods from the food industry, are paraffins, micro waxes, waxes of natural origin such as carnauba wax, candelilla wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids.

Preferred gel bodies are transparent. Gel bodies are referred to as "transparent" if they are transparent in the wavelength range from 410 to 800 nm at at least one wavelength, preferably at 600 nm, have a transmission above 20%, preferably above 30% and in particular above 35%. The transmission is determined using VIS spectrometry at a sample temperature of 20°C and a cuvette length of 10 mm.

The spatial shape of the gel body is fundamentally freely selectable; its side surfaces can, for example, be designed to be convex, concave or flat. At the same time, however, certain spatial configurations have proven to be particularly advantageous in terms of the producibility, storage and use of the gel bodies.

In the case of correspondingly advantageous cleaning agent portion units, the gel body has a flat underside, the largest diagonal of which is greater than the height of the gel body. These bodies are not only easy to produce, for example by means of a casting process, they can also be packaged easily and in a space-saving manner and are suitable for dosing via the dosing or dispensing chambers of electronic cleaning devices. It is preferred if the gel body has a flat underside, the largest diagonal of which is more than 1.5 times, preferably more than 2 times, the height of the gel body.

For manufacturability, for example in relation to the removal of the gel body from a mold, it has proven to be advantageous if the underside of the gel body has no corners. Preferred gel bodies are therefore characterized by oval undersides or alternatively by ellipsoidal or round, preferably round undersides. Corresponding gel bodies with a non-square bottom are also preferred by many consumers due to their appearance. For example, gel bodies that have a bottom and a top that are connected to one another by a cylindrical lateral surface are preferred.

Advantages in terms of space utilization during production and packaging are achieved by square bottoms. If the gel bodies are cast in the form of plates, for example, which are subsequently cut into gel bodies, square bottoms are advantageous because such gel bodies can be cut without leaving any residue and can be packaged in a space-saving manner. In an alternative embodiment, preferred gel bodies therefore have square bottoms, in particular triangular, square or hexagonal bottoms.

With regard to the production, packaging and use of the cleaning agent portion units, it has also proven advantageous if the gel bodies have an upper side that is plane-parallel to the lower side.

In a first preferred geometric embodiment, the gel body has a bottom and a top that have the same geometric shape, the bottom and the top having the same area size. Corresponding gel bodies can be used, as already mentioned previously described, can be produced in a simple manner, for example by casting plates and then cutting the plates into individual gel bodies. These gel bodies can also be spatially aligned more easily than gel bodies with less body symmetry in any subsequent process steps, during packaging or use by the user, due to the geometric identity of the bottom and top. This applies in particular to gel bodies, which at the same time have a top side that is plane-parallel to the underside. Examples of such gel bodies are circular cylinders, elliptical cylinders, parallelepipeds, rhombohedrons, straight or oblique prisms, cuboids or cubes. The group of circular cylinders and elliptical cylinders includes the vertical circular cylinders and elliptical cylinders as well as the oblique circular cylinders and elliptical cylinders. Because they are easy to produce by separating them from a plate, gel bodies in the form of vertical circular cylinders, vertical elliptical cylinders, straight prisms, straight cuboids or cubes are preferred.

In an alternative embodiment, the gel body has a bottom and a top that have the same geometric shape, with the bottom and the top having different surface sizes. Corresponding gel bodies can be preferred due to their attractive appearance or their optimized fit while being comparatively easy to produce. Examples of such gel bodies are circular cylinders or elliptical cylinders with a convex or concave bottom and a flat top. Other examples are truncated cones or truncated pyramids.

In summary, preferred application subjects can be characterized as cleaning agent portion units, comprising a gel body with a bottom and a top, the area of the top being 80 to 100%, preferably 90 to 100% and in particular 98 to 100% of the bottom.

In addition to the gel body, the cleaning agent portion unit comprises, as a further essential component, a water-soluble coating substance which partially covers the gel body.

For reasons of simplified production, reduced packaging and improved aesthetics, cleaning agent portion units are preferred in which the gel body forms at least 10%, preferably at least 15% and in particular at least 20% of the total surface of the cleaning agent portion unit. For the same reasons, it is preferred if the coating substance covers 20 to 90%, preferably 30 to 80% and in particular 40 to 75% of the surface of the gel body.

It is also preferred if the water-soluble coating substance covers the surface of the gel body on two opposite sides of the gel body, since in this way the handling of the cleaning agent portion unit by the consumer can be simplified.

In addition, this type of surface covering has advantages with regard to the packaging of the detergent portion units, in particular when packaging several detergent portion units together, for example when the detergent portion units are stacked in an outer packaging.

For the reasons mentioned above, cleaning agent portion units are particularly preferred in which the gel body has a bottom and a top and the water-soluble coating substance at least partially covers both the bottom and the top of the gel body. Preferably, both the bottom and the top of the gel body are covered by at least 40%, preferably by at least 60% and in particular by at least 80%.

In a special embodiment, the gel body has a bottom and a top and the water-soluble coating substance covers both the bottom and the top of the gel body over the entire surface.

In the cleaning agent portion unit, the coating substance can be formed as a single shaped body or in the form of several shaped bodies.

In a first embodiment, the enveloping substance is in the form of a single shaped body which has n = 2 points on its surface, the surface normals of which coincide.

1. a) einen formstabilen Gelkörper, umfassend eine Unterseite, eine Oberseite und eine die Unterseite und die Oberseite verbindende zylindrische Mantelfläche,
2. b) eine Hüllsubstanz in Form eines einzelnen Formkörpers, welche die Unterseite und die Mantelfläche des formstabilen Gelkörper bedeckt, wobei
   1. i) die Hüllsubstanz auf ihrer äußeren Oberfläche n > 1 Punkte aufweist, deren Flächennormalen sowohl durch die Hüllsubstanz als auch durch den formstabilen Gelkörper verlaufen und sich in einem Winkel 360°/n treffen und
   2. ii) das Längenverhältnis der von diesen Flächennormalen innerhalb der Hüllsubstanz verlaufenden Strecke zu der von diesen Flächennormalen innerhalb des Gelkörpers verlaufenden Strecke 1:3 bis 1:14, vorzugsweise 1:4 bis 1:10 beträgt.

Correspondingly preferred cleaning agent portion units include

1. a) a dimensionally stable gel body, comprising a bottom, a top and a cylindrical lateral surface connecting the bottom and the top,
2. b) a shell substance in the form of a single molded body, which covers the underside and the lateral surface of the dimensionally stable gel body, where
   1. i) the shell substance has n > 1 points on its outer surface, the surface normals of which run through both the shell substance and the dimensionally stable gel body and meet at an angle of 360 ° / n and
   2. ii) the length ratio of the distance running from these surface normals within the shell substance to the distance running from these surface normals within the gel body is 1:3 to 1:14, preferably 1:4 to 1:10.

Cleaning agent portion units in which the coating substance is in the form of two shaped bodies whose surface normals coincide have proven to be an alternative embodiment.

1. a) einen formstabilen Gelkörper, umfassend eine Unterseite, eine Oberseite und eine die Unterseite und die Oberseite verbindende zylindrische Mantelfläche,
2. b) eine Hüllsubstanz in Form von zwei Formkörpern, welche die Unterseite und die Oberseite des formstabilen Gelkörper bedecken, wobei
   1. i) die Flächennormalen der Formkörper sowohl durch die Hüllsubstanz als auch durch den formstabilen Gelkörper verlaufen und sich in einem Winkel von 180° treffen und
   2. ii) das Längenverhältnis der von diesen Flächennormalen innerhalb der Hüllsubstanz verlaufenden Strecke zu der von diesen Flächennormalen innerhalb des Gelkörpers verlaufenden Strecke 1:3 bis 1:14, vorzugsweise 1:4 bis 1:10 beträgt.

The resulting preferred detergent portion units comprise

1. a) a dimensionally stable gel body comprising a bottom side, a top side and a cylindrical surface connecting the bottom side and the top side,
2. b) a coating substance in the form of two shaped bodies which cover the bottom and the top of the dimensionally stable gel body, wherein
   1. i) the surface normals of the shaped bodies pass through both the shell substance and the dimensionally stable gel body and meet at an angle of 180° and
   2. ii) the length ratio of the distance running from these surface normals within the shell substance to the distance running from these surface normals within the gel body is 1:3 to 1:14, preferably 1:4 to 1:10.

To the extent that the course of the surface normals characterizing the subject matter of the claim and running through the shell substance has proven to be advantageous for the handling of the cleaning agent portion units, the appearance of the cleaning agent portion units can be improved by a molded body structure which provides a gel body on its outer side , from the surface uncovered by the shell substance has at least one point, the surface normal of which connects it to another point on the outer surface of the gel body uncovered by the shell substance. These optical advantages arise in particular in the case of the transparent gel bodies described above.

The gel body and the coating substance are preferably adhesively bonded to each other.

The covering substance can be manufactured in different ways. The use of cast bodies has proven to be technically simpler to implement. The production of the shell substance by casting processes has the advantage that a wide variety of geometries can be produced. The casting bodies are particularly preferably solidified melts.

Due to their ease of large-scale production, pressed bodies, especially tablets, are particularly preferred as coating substances.

Regardless of the process used to produce it, the coating substance preferably has a breaking strength of 50 N to 300 N, in particular 70 N to 200 N. This breaking strength ensures, on the one hand, sufficient stability of the coating substance during production, transport and handling by the consumer and, on the other hand, ensures satisfactory dissolution behavior of the coating substance in an aqueous liquor. The hardness of the shell substance is measured by deformation until fracture, whereby the force acts on the side surfaces of the shell substance and the maximum force that it can withstand is determined. A tablet testing device from Sotax, for example, is suitable for determining the hardness of the shell substance.

In a preferred embodiment of the cleaning agent portion units, their coating substance also contributes to the washing and cleaning effect. Corresponding cleaning agent portion units comprise a coating substance which, based on their total weight, contains at least 82% by weight, preferably at least 85% by weight, particularly preferably at least 90% by weight of washing or cleaning active ingredient.

In various embodiments, the coating substance contains one or more washing or cleaning-active ingredients from the group of builders, bleaching agents, bleach activators, bleaching catalysts, and silver protective agents.

The first group of washing or cleaning active ingredients integrated into the coating substance are the fragrances. Their incorporation into the coating substance ensures a fragrance experience that is perceptible to the consumer, which cannot be guaranteed in the same way when the fragrances are incorporated into the gel body.

Another group of detergent or cleaning-active ingredients preferably incorporated into the shell substance is the builders, in particular the zeolites, silicates and carbonates, particularly preferably the zeolites or carbonates.

The weight proportion of these active substances in the total weight of the coating substance is preferably 5 to 60% by weight, in particular 10 to 50% by weight. Coating substances which contain 5 to 60% by weight, in particular 10 to 50% by weight of zeolite based on their total weight are particularly preferred. These active substances not only contribute to the intended washing and cleaning effect, but also improve the contour sharpness and durability of the printed image if the surface of the coating substance is printed on. In an alternative embodiment, coating substances which contain 5 to 60% by weight, in particular 10 to 50% by weight of carbonate based on their total weight are preferred. These active substances not only increase the intended washing and cleaning effect, but also improve the compressibility of the coating substance.

To improve the printed image, preferred coating substances contain less than 10% by weight, preferably less than 5% by weight and in particular less than 1% by weight of an organic acid based on their total weight. Organic acids are those active substances which are contained in the coating substance in acid form, i.e. not in the form of their salt.

In a preferred embodiment, the coating substance is non-transparent. Coating substances that have a transmission of less than 10% in the wavelength range from 410 to 800 nm at at least one wavelength, preferably at 600 nm, are referred to as "non-transparent". preferably below 5% and in particular below 1%. The transmission is determined using VIS spectrometry at a sample temperature of 20°C and a cuvette length of 10 mm.

The use of non-transparent coating substances, particularly when used in combination with transparent gel bodies, creates a product appearance that enables the consumer to distinguish between the surfaces covered by the coating substance and those not covered by the coating substance and to specifically grip the cleaning agent portion unit, for example when removing it from a container that contains several cleaning agent portion units, at the surfaces covered by the coating substance and in this way to avoid direct contact with the gel body.

For the reasons mentioned above, the gel body and the shell substance preferably have a color difference ΔE above 20, preferably above 40.

Due to their optical properties and their ease of production, preferred coating substances are white, i.e. not colored. The white color of the coating substance is particularly suitable for printing.

As an alternative to a preferably non-transparent white design of the coating substance, it can also be colored. The colored design of the coating substance enables, for example, the optical communication of specific product properties, for example in relation to its effect or smell. In order to ensure that the gel body and the coating substance can be visually distinguished, the colored coating substance preferably does not have the same color as the gel body. Of course, colored fiber materials can also be printed.

In various embodiments, the covering substance is printed.

To improve the integrity of the detergent portion unit, it can have a film packaging, wherein it is particularly preferred if each of the detergent portion units has a separate film packaging.

If film packaging is used, film packaging made of a water-soluble film material is preferred. The water-soluble film material may comprise one or more structurally different water-soluble polymer(s). Particularly suitable water-soluble polymer(s) are polymers from the group of (possibly acetalized) polyvinyl alcohols (PVAL) and their copolymers.

Water-soluble film materials are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol ^-1 , preferably from 20,000 to 500,000 gmol ^-1 , particularly preferably from 30,000 to 100,000 gmol ^-1 and in particular from 40,000 to 80,000 gmol ^-1 .

The production of polyvinyl alcohol and polyvinyl alcohol copolymers generally includes the hydrolysis of intermediate polyvinyl acetate. Preferred polyvinyl alcohols and polyvinyl alcohol copolymers have a degree of hydrolysis of 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. Particularly preferably, such polyvinyl alcohol copolymers contain, in addition to vinyl alcohol, sulfonic acids such as 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof; among the esters, C _1-4 alkyl esters or hydroxyalkyl esters are preferred. Other monomers that can be considered are ethylenically unsaturated dicarboxylic acids, for example itaconic acid, maleic acid, fumaric acid and mixtures thereof.

Due to their availability, ease of processing and biodegradability, film packaging is preferred which consists of at least 40% by weight, preferably at least 60% by weight and in particular at least 80% by weight of polyvinyl alcohol.

To increase the stability of the cleaning agent portion units and to ensure a sufficient fill level in the outer packaging, it is preferable to shrink the film packaging onto the cleaning agent portion units.

For reasons of sustainable design of the cleaning agent portion units, it may be advisable to forego foil packaging. Particularly preferred cleaning agent portion units therefore do not have an outer packaging made of a water-soluble or a water-insoluble film material.

The problem-free removal of the cleaning agent portion units from the outer packaging can also be facilitated by the orientation of the cleaning agent portion units in the outer packaging. In this context, it has proven advantageous if the cleaning agent portion unit is arranged together with at least one further cleaning agent portion unit in a common outer packaging in such a way that the coating substance of at least one cleaning agent portion unit is in direct contact with the gel body or the coating substance, preferably the coating substance of another cleaning agent portion unit.

To produce the cleaning agent portion units according to the invention, a gel and a water-soluble coating substance are connected to one another to form a cleaning agent dosage unit.

1. i) Bereitstellen eines Hüllmaterials;
2. ii) Bereitstellen eines Gelkörpers;
3. iii) Aufbringen eines Hüllmaterials auf die Oberfläche des Gelkörpers.

A preferred method variant includes the steps:

1. i) providing a wrapping material;
2. ii) providing a gel body;
3. iii) applying a shell material to the surface of the gel body.

To provide the shell material in step i) of the process, it is preferred to press a particulate premix with a pressure of 5 to 30 kN. In contrast, the gel body in step ii) is preferably provided by solidification of a flowable composition. It is particularly preferred to apply a flowable composition to a shell material in step ii), the gel body being formed by subsequent solidification of the flowable composition and being adhesively bonded to the water-soluble shell material.

After applying a water-soluble coating material, the gel body can be divided into cleaning agent portion units.

A final subject matter of the application is a method for cleaning dishes, in which a previously described detergent portion unit is introduced into the dosing chamber or the interior of a dishwasher.

1. 1. Reinigungsmittelportionseinheit, umfassend
   1. a) einen formstabilen Gelkörper
   2. b) eine Hüllsubstanz in Form eines Formkörpers, welche die Oberfläche des formstabilen Gelkörper anteilsweise bedeckt, wobei
      1. i) der Gelkörper von 20 bis 45 Vol.-% der Reinigungsmitteldosiereinheit einnimmt, und
      2. ii) der Gelkörper, bezogen auf sein Gesamtgewicht
         • maximal 30 Gew.-% Tensid enthält,
         • 50 bis 80 Gew.-% Lösungsmittel enthält,
         • einen Gelbildner in Gewichtsanteilen unterhalb 5 Gew.-% enthält iii) die Hüllsubstanz, bezogen auf ihr Gesamtgewicht
         • mindestens 80 Gew.-% wasch- oder reinigungsaktiven Inhaltsstoff enthält.
2. 2. Reinigungsmittelportionseinheit nach Punkt 1, wobei die Portionseinheit ein Gewicht von 10 g bis 35 g, vorzugsweise von 13 g bis 30 g, insbesondere von 15 g bis 25 g aufweist.
3. 3. Reinigungsmittelportionseinheit nach einem der Punkte 1 bis 2, wobei der Gelkörper 25 bis 40 Vol.-%, beispielsweise 30 bis 35 Vol.-%, der Reinigungsmittelportionseinheit einnimmt.
4. 4. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper, bezogen auf sein Gesamtgewicht, 5 bis 25 Gew.-% und insbesondere 10 bis 20 Gew.-% Tensid enthält.
5. 5. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper, bezogen auf sein Gesamtgewicht, weniger als 5 Gew.-%, vorzugsweise weniger als 1 Gew.-%, bevorzugt kein anionisches Tensid enthält.
6. 6. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper, bezogen auf sein Gesamtgewicht, 5 bis 30 Gew.-%, vorzugsweise 10 bis 25 Gew.-%, noch bevorzugter 10 bis 20 Gew.-%, ein oder mehrere nichtionische Tenside enthält.
7. 7. Reinigungsmittelportionseinheit nach Punkt 6, wobei der Gelkörper nichtionisches Tensid aus der Gruppe der endgruppenverschlossenen poly(oxyalkylierten) Niotenside der Formel
   
            R¹O[CH₂CH(R³)O]_x[CH₂]_kCH(OH)[CH₂]_jOR²,
   
   wobei 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; wobei, wenn der Wert x > 2 ist, jedes R³ unterschiedlich sein kann.
8. 8. Reinigungsmittelportionseinheit nach Punkt 7, wobei R¹ und R² vorzugsweise lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 6 bis 22 Kohlenstoffatomen sind, wobei Reste mit 8 bis 18 C-Atomen besonders bevorzugt sind, und wobei für den Rest R³ H, -CH₃ oder -CH₂CH₃ besonders bevorzugt sind, wobei besonders bevorzugte Werte für x im Bereich von 1 bis 20, insbesondere von 6 bis 15 liegen.
9. 9. Reinigungsmittelportionseinheit nach einem der Punkte 7 und 8, wobei besonders bevorzugte endgruppenverschlossene poly(oxyalkylierte) Alkohole der oben stehenden Formel Werte von k = 1 und j = 1 aufweisen, so dass sich die vorstehende Formel zu R¹O[CH₂CH(R³)O]_xCH₂CH(OH)CH₂OR² vereinfacht, wobei in dieser Formel R¹, R² und R³ wie oben definiert sind und x für Zahlen von 1 bis 30, vorzugsweise von 1 bis 20 und insbesondere von 6 bis 18 steht, wobei besonders bevorzugt Tenside sind, bei denen die Reste R¹ und R² 9 bis 14 C-Atome aufweisen, R³ für H steht und x Werte von 6 bis 15 annimmt.
10. 10. Reinigungsmittelportionseinheit nach einem der Punkte 6 bis 9, wobei ein oder mehrere nichtionische Tenside ausgewählt sind aus nichtionischen Tensiden der allgemeinen Formel R¹-CH(OH)CH₂O-(AO)_w-R², wobei
    • 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.
11. 11. Reinigungsmittelportionseinheit nach Punkt 10, wobei ein oder mehrere nichtionische Tenside ausgewählt sind aus der Gruppe bestehend aus C_4-22 Fettalkohol-(EO)_10-80-2- hydroxyalkylethern, C_8-12 Fettalkohol-(EO)₂₂-2-hydroxydecylethern und C_4-22 Fettalkohol-(EO)_40-80-2-hydroxyalkylethern.
12. 12. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper mindestens ein nichtionisches Tensid aus der Gruppe der Hydroxymischether enthält.
13. 13. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper, bezogen auf sein Gesamtgewicht, 55 bis 75 Gew.-%, vorzugsweise 60 bis 70 Gew.-% Lösungsmittel enthält.
14. 14. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper, bezogen auf sein Gesamtgewicht, 50 bis 75 Gew.-%, vorzugsweise 55 bis 70 Gew.-% organisches Lösungsmittel enthält.
15. 15. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper organisches Lösungsmittel ausgewählt aus der Gruppe Ethanol, n-Propanol, i-Propanol, Butanolen, Glykol, Propandiol, Butandiol, Methylpropandiol, Glycerin, Diglykol, Propyldiglycol, Butyldiglykol, Hexylenglycol, Ethylenglykolmethylether, Ethylenglykolethylether, Ethylenglykolpropylether, Ethylenglykolmono-n-butylether, Diethylenglykolmethylether, Diethylenglykolethylether, Propylenglykolmethylether, Propylenglykolethylether, Propylenglykolpropylether, Dipropylenglykolmonomethylether, Dipropy-lenglykolmonoethylether, Methoxytriglykol, Ethoxytriglykol, Butoxytriglykol, 1-Butoxyethoxy-2-propanol, 3-Methyl-3-methoxybutanol, Propylen-glykol-t-butylether, Di-n-octylether sowie deren Mischungen, vorzugsweise aus der Gruppe Propandiol, Glycerin und deren Mischungen enthält.
16. 16. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper, bezogen auf sein Gesamtgewicht, weniger als 20 Gew.-%, bevorzugt von 1 und 15 Gew.-%, insbesondere von 2 bis 14 Gew.-% und ganz besonderes bevorzugt von 3 und 13 Gew.-% Wasser enthält.
17. 17. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper, bezogen auf sein Gesamtgewicht 0,1 bis 5 Gew.-%, besonders bevorzugt 0,1 bis 2,5 Gew.-% Gelbildner enthält.
18. 18. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelbildner ausgewählt ist aus der Gruppe der niedermolekularen Gelbildner mit einer molaren Masse bis 2000 g/mol, insbesondere aus der Gruppe der cyclischen Dipeptide, der cyclischen Dipeptidderivate und Dibenzylidensorbitol.
19. 19. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei als Gelbildner Dibenzylidensorbitol eingesetzt wird.
20. 20. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper, bezogen auf sein Gesamtgewicht, 0 bis 12 Gew.-%, vorzugsweise 1 bis 10 Gew.-%, noch bevorzugter 2 bis 8 Gew.-% eines wasch- oder reinigungsaktiven Polymers, vorzugsweise eines wasch- oder reinigungsaktiven Polymers aus der Gruppe der Polycarboxylate (Builderpolymere; 0-15 Gew.-%), bevorzugt Polymere, welche Acrylat und/oder Methacrylat umfassen, insbesondere Polymere, die zusätzlich Sulfonsäuregruppenhaltige Monomere umfassen, enthält.
21. 21. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Reinigungsmittelportionseinheit mindestens eine Enzymzubereitung umfasst.
22. 22. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Menge aller Amylasen, bezogen auf die Menge an aktivem Enzymprotein, in der Reinigungsmittelportionseinheit von 1 bis 100 mg, bevorzugt 4 bis 50 mg, insbesondere 6 bis 25 mg beträgt.
23. 23. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Menge aller Proteasen, bezogen auf die Menge an aktivem Enzymprotein, in der Reinigungsmittelportionseinheit 2 bis 800 mg, bevorzugt 4 bis 200 mg, insbesondere 6 bis 100 mg beträgt.
24. 24. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper, bezogen auf sein Gesamtgewicht, 0,001 bis 5 Gew.-%, vorzugsweise 0,01 bis 3 Gew.-% Duftstoffzubereitung enthält.
25. 25. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Hüllsubstanz bezogen auf ihr Gesamtgewicht, mindestens 82 Gew.-%, vorzugsweise mindestens 85 Gew.-%, besonders bevorzugt mindestens 90 Gew.-% wasch- oder reinigungsaktiven Inhaltsstoff enthält.
26. 26. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Hüllsubstanz einen oder mehrere wasch- oder reinigungsaktive Inhaltsstoffe aus der Gruppe der Gerüststoffe, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, Silberschutzmittel enthält.
27. 27. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Reinigungsmittelportionseinheit mindestens einen Aktivstoff aus der Gruppe der Gerüststoffe, insbesondere mindestens einen Aktivstoff aus der Gruppe der Zeolithe, Silikate und Carbonate, vorzugsweise aus der Gruppe der Carbonate umfasst.
28. 28. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Reinigungsmittelportionseinheit, bezogen auf ihr Gesamtgewicht, mindestens einen Aktivstoff aus der Gruppe der Gerüststoffe in Gewichtsanteilen von 5 bis 70 Gew.-%, vorzugsweise von 10 bis 50 Gew.-% umfasst, insbesondere mindestens einen Aktivstoff aus der Gruppe der Zeolithe, Silikate und Carbonate, vorzugsweise aus der Gruppe der Carbonate, insbesondere Carbonate in Gewichtsanteilen von 5 bis 70 Gew.-%, vorzugsweise von 10 bis 50 Gew.-% umfasst.
29. 29. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Reinigungsmittelportionseinheit wasch- oder reinigungsaktive Inhaltsstoffe aus der Gruppe der Natriumsalze organischer und anorganischer Säuren enthält und mindestens 80 Gew.-%, vorzugsweise mindestens 90 Gew.-% und insbesondere bevorzugt mindestens 95 Gew.-% dieses Natriumsalzes als Bestandteil der Hüllsubstanz vorliegt.
30. 30. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Reinigungsmittelportionseinheit Citrat in Gewichtsanteilen von 0,5 bis 25 Gew.-%, vorzugsweise von 5 bis 15 Gew.-% umfasst, jeweils bezogen auf das Gesamtgewicht der Reinigungsmittelportionseinheit.
31. 31. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Reinigungsmittelportionseinheit Aminocarboxylate, insbesondere ausgewählt aus der Gruppe MGDA, GLDA, EDDS und/oder deren Salzen umfasst.
32. 32. Reinigungsmittelportionseinheit nach Punkt 31, wobei die Reinigungsmittelportionseinheit MGDA, GLDA, EDDS und/oder deren Salze in Gewichtsanteilen von 0,5 bis 25 Gew.-%, vorzugsweise von 5 bis 15 Gew.-% umfasst, jeweils bezogen auf das Gesamtgewicht der Reinigungsmittelportionseinheit.
33. 33. Reinigungsmittelportionseinheit nach einem der Punkte 31 bis 32, wobei die Reinigungsmittelportionseinheit MGDA und/oder deren Salz in Gewichtsanteilen von 0,5 bis 25 Gew.-%, vorzugsweise von 5 bis 15 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Reinigungsmittelportionseinheit.
34. 34. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Reinigungsmittelportionseinheit mindestens ein Bleichmittel, vorzugsweise in einer Menge von 1 bis 35 Gew.-%, noch bevorzugter 2,5 bis 30 Gew.-%, besonders bevorzugt 3,5 bis 20 Gew.-%, und insbesondere 5 bis 15 Gew.-%, jeweils basierend auf dem Gesamtgewicht der Reinigungsmittelportionseinheit, enthält; wobei das mindestens eine Bleichmittel vorzugsweise ausgewählt ist aus der Gruppe bestehend aus Natriumpercarbonat; Natriumperborattetrahydrat; Natriumperboratmonohydrat; Peroxypyrophosphaten; Citratperhydraten; und H₂O₂ liefernden persauren Salzen oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure, Phthaloiminopersäure oder Diperdodecandisäure.
35. 35. Reinigungsmittelportionseinheit nach Punkt 34, wobei die Reinigungsmittelportionseinheit zusätzlich mindestens einen Bleichaktivator, vorzugsweise in Mengen bis 10 Gew.-%, insbesondere 0,1 Gew.-% bis 8 Gew.-%, besonders 2 bis 8 Gew.-% und besonders bevorzugt 2 bis 6 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Reinigungsmittelportionseinheit, enthält; wobei der mindestens eine Bleichaktivator vorzugsweise ausgewählt ist aus der Gruppe bestehend aus Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, noch bevorzugter aus der Gruppe bestehend aus mehrfach acylierten Alkylendiaminen, insbesondere Tetraacetylethylendiamin (TAED), acylierten Triazinderivaten, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), acylierten Glykolurilen, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimiden, insbesondere N-Nonanoylsuccinimid (NOSI), acylierten Phenolsulfonaten, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso-NOBS); wobei der mindestens eine Bleichaktivator besonders bevorzugt TAED ist, insbesondere in Kombination mit einem Percarbonat-Bleichmittel, vorzugsweise Natriumpercarbonat.
36. 36. Reinigungsmittelportionseinheit nach einem der Punkte 34 bis 35, wobei die Reinigungsmittelportionseinheit zusätzlich mindestens einen Bleichkatalysator, vorzugsweise in einer Menge von 0,001 bis 1 Gew.-%, bevorzugt 0,01 bis 0,1 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Reinigungsmittelportionseinheit enthält; wobei der mindestens einen Bleichkatalysator vorzugsweise ausgewählt ist aus der Gruppe bestehend aus bleichverstärkenden Übergangsmetallsalzen und Übergangsmetallkomplexen, vorzugsweise der Mn-, Fe-, Co-, Ru - oder Mo-Komplexe, besonders bevorzugt aus der Gruppe der Mangan und/oder Cobaltsalze und/oder - komplexe, insbesondere der Cobalt(ammin)-Komplexe, der Cobalt(acetat)-Komplexe, der Cobalt(Carbonyl)-Komplexe, der Chloride des Cobalts oder Mangans, des Mangansulfats und der Komplexe des Mangans mit 1,4,7-trimethyl-1,4,7-triazacyclononan (Mns-TACN) oder 1,2,4,7-tetramethyl-1,4,7-tri-azacyclononan (Mn₄-TACN), wobei es sich bei dem mindestens einen Bleichmittel insbesondere um einen Mn-Komplex, insbesondere einen Komplex des Mangans mit 1,4,7-trimethyl-1,4,7-triazacyclononan (Mns-TACN) oder 1,2,4,7-tetramethyl-1,4,7-tri-azacyclononan (Mn₄-TACN) handelt.
37. 37. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Reinigungsmittelportionseinheit mindestens ein Phosphonat, vorzugsweise in einer Menge von 0,1 bis 10 Gew.-%, insbesondere von 0,5 bis 8 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Reinigungsmittelportionseinheit, enthält, wobei das mindestens eine Phosphonat vorzugsweise ausgewählt ist aus der Gruppe bestehend aus Hydroxyalkan- und Aminoalkanphosphonaten, wobei unter den Hydroxyalkanphosphonaten das 1-Hydroxyethan-1,1-diphosphonat (HEDP) besonderws bevorzugt ist und unter den Aminoalkanphosphonaten das Ethylendiamintetramethylenphosphonat (EDTMP), das Diethylentriaminpentamethylenphosphonat (DTPMP) sowie deren höhere Homologe besonders bevorzugt sind.
38. 38. Reinigungsmittelportionseinheit nach Punkt 37, wobei das mindestens eine Phosphonat in dem Gelkörper enthalten ist.
39. 39. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Reinigungsmittelportionseinheit mindestens ein Sulfopolymer, vorzugsweise in einer Menge von 0,1 bis 20 Gew.-%, insbesondere von 0,5 bis 18 Gew.-%, besonders bevorzugt 1,0 bis 15 Gew.-%, insbesondere von 4 bis 14 Gew.-%, vor allem von 6 bis 12 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Reinigungsmittelportionseinheit, enthält.
40. 40. Reinigungsmittelportionseinheit nach Punkt 39, wobei es sich bei dem mindestens einen Sulfopolymer um ein copolymeres Polysulfonat, insbesondere um ein hydrophob modifiziertes copolymeres Polysulfonat handelt, wobei die Copolymere zwei, drei, vier oder mehr unterschiedliche Monomereinheiten aufweisen können.
41. 41. Reinigungsmittelportionseinheit nach Punkt 40, wobei copolymere Polysulfonate neben Sulfonsäuregruppen-haltigem(n) Monomer(en) wenigstens ein Monomer aus der Gruppe der ungesättigten Carbonsäuren enthalten, bevorzugt aus der Gruppe der ungesättigten Carbonsäuren der Formel R¹(R²)C=C(R³)COOH, wobei R¹ bis R³ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist.
42. 42. Reinigungsmittelportionseinheit nach einem der Punkte 39 bis 41, wobei Sulfonsäuregruppenhaltige Monomere ausgewählt sind aus der Gruppe bestehend aus Monomeren der Formel R⁵(R¹)C=C(R¹)-X-SO₃H, wobei R⁵ bis R⁷ unabhängig voneinander für-H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, OH oder -COOH substituierte Alkyl- oder Alkenylreste oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, COO-(CH₂)_k- mit k = 1 bis 6, C(O)-NH-C(CH₃)₂-, C(O)-NH-C(CH₃)₂-CH₂- und -C(O)-NH-CH(CH₃) CH₂-,
43. 43. Reinigungsmittelportionseinheit nach Punkt 42, wobei Sulfonsäuregruppen-haltige Monomere ausgewählt sind aus der Gruppe bestehend aus 1-Acrylamido-1-propansulfonsäure, 2-Acrylamido-2-propansulfonsäure, 2-Acrylamido-2-methyl-1-propansulfonsäure, 2-Methacrylamido-2-methyl-1-propansulfonsäure, 3-Methacrylamido-2-hydroxy-propansulfonsäure, Allylsulfonsäure, Methallylsulfonsäure, Allyloxybenzolsulfonsäure, Methallyloxybenzolsulfonsäure, 2-Hydroxy-3-(2-propenyl-oxy)propansulfonsäure, 2-Methyl-2-propen1-sulfonsäure, Styrolsulfonsäure, Vinylsulfonsäure, 3-Sulfopropylacrylat, 3-Sulfopropylmethacrylat, Sulfomethacrylamid, Sulfomethylmethacrylamid sowie Mischungen der genannten Säuren oder deren wasserlöslichen Salzen.
44. 44. Reinigungsmittelportionseinheit nach einem der Punkte 39 bis 43, wobei die Sulfonsäuregruppen ganz oder teilweise in neutralisierter Form vorliegen, wobei teil- oder vollneutralisierte sulfonsäuregruppenhaltige Copolymere bevorzugt sind.
45. 45. Reinigungsmittelportionseinheit nach einem der Punkte 40 bis 44, wobei die Monomerenverteilung bei Copolymeren, die nur Carbonsäuregruppen-haltige Monomere und Sulfonsäuregruppen-haltige Monomere enthalten, jeweils 5 bis 95 Gew.-% beträgt, wobei bevorzugt der Anteil des Sulfonsäuregruppen-haltigen Monomers 50 bis 90 Gew.-% und der Anteil des Carbonsäuregruppen-haltigen Monomers 10 bis 50 Gew.-% beträgt.
46. 46. Reinigungsmittelportionseinheit nach einem der Punkte 40 bis 45, wobei die Molmasse der Sulfo-Copolymere von 2000 bis 200.000 gmol^-1, vorzugsweise von 4000 bis 25.000 gmol^-1 und insbesondere von 5000 bis 15.000 gmol^-1 beträgt.
47. 47. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Reinigungsmittelportionseinheit mindestens einen Glaskorrosionsinhibitor enthält, vorzugsweise in einer Menge von 0,05 bis 5 Gew.-%, bevorzugt zwischen 0,2 bis 4 Gew.-% und insbesondere zwischen 0,4 bis 3 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Reinigungsmittelportionseinheit.
48. 48. Reinigungsmittelportionseinheit nach Punkt 47, wobei der mindestens eine Glaskorrosionsinhibitor ausgewählt ist aus der Gruppe bestehend aus Zinksalzen organischer Carbonsäure, wobei besonders bevorzugt Zinksalze aus der Gruppe bestehend aus Zinkstearat, Zinkoleat, Zinkgluconat, Zinkacetat, Zinklactat, Zinkcitrat, Zinkricinoleat, Zinkabietat, und/oder Zinkoxalat sind; und/oder aus der Gruppe bestehend aus löslichen anorganischen Zinksalzen, wobei besonders bevorzugt Zinksulfat, Zinknitrat und Zinkchlorid sind.
49. 49. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Reinigungsmittelportionseinheit mindestens ein Silberschutzmittel enthält, vorzugsweise in einer Menge von 0,001 bis 10 Gew.-%, bevorzugt 0,0025 bis 2 Gew.-%, besonders bevorzugt 0,01 bis 0,04 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Reinigungsmittelportionseinheit.
50. 50. Reinigungsmittelportionseinheit nach Punkt 49, wobei das Silberschutzmittel ausgewählt ist aus der Gruppe bestehend aus Cystein, Cystin und Mischungen davon.
51. 51. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper eine flache Unterseite aufweist, deren größte Diagonale größer ist als die Höhe des Gelkörpers.
52. 52. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper eine flache Unterseite aufweist, deren größte Diagonale mehr als das 1,5-fache, vorzugsweise mehr als das 2-fache der Höhe des Gelkörpers beträgt.
53. 53. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper eine ovale Unterseite aufweist.
54. 54. Reinigungsmittelportionseinheit nach einem der Punkte 1 bis 52, wobei der Gelkörper eine ellipsoide oder runde, vorzugsweise eine runde Unterseite aufweist.
55. 55. Reinigungsmittelportionseinheit nach einem der Punkte 1 bis 52, wobei der Gelkörper eine eckige, Unterseite aufweist.
56. 56. Reinigungsmittelportionseinheit nach Punkt 55, wobei der Gelkörper eine dreieckige, viereckige oder sechseckige Unterseite aufweist.
57. 57. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper eine zur Unterseite planparallele Oberseite aufweist.
58. 58. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper eine Unterseite und eine Oberseite aufweist, welche die gleiche geometrische Form aufweisen und wobei die Unterseite und die Oberseite die gleiche Flächengröße aufweisen.
59. 59. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper eine Unterseite und eine Oberseite aufweist, welche die gleiche geometrische Form aufweisen und wobei die Unterseite und die Oberseite unterschiedliche Flächengrößen aufweisen.
60. 60. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper eine Unterseite und eine Oberseite aufweist, welche durch eine zylindrische Mantelfläche miteinander verbunden sind.
61. 61. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper eine Unterseite und eine Oberseite aufweist und die Fläche der Oberseite 80 bis 100%, vorzugsweise 90 bis 100% und insbesondere 98 bis 100% der Unterseite beträgt.
62. 62. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Hüllsubstanz als Gießkörper vorliegt.
63. 63. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Hüllsubstanz als Presskörper, vorzugsweise als Tablette vorliegt.
64. 64. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Hüllsubstanz eine Bruchfestigkeit von 50 N bis 300 N, insbesondere von 70 N bis 200 N aufweist.
65. 65. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper und die Hüllsubstanz haftend miteinander verbunden sind.
66. 66. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper wenigstens 10%, vorzugsweise wenigstens 15% und insbesondere wenigstens 20% der Gesamtoberfläche der Reinigungsmittelportionseinheit ausbildet.
67. 67. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Hüllsubstanz 20 bis 90%, vorzugsweise 30 bis 80% und insbesondere 40 bis 75% der Oberfläche des Gelkörpers bedeckt.
68. 68. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper einen Farbstoff enthält.
69. 69. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper transparent ist.
70. 70. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Hüllsubstanz intransparent ist.
71. 71. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Hüllsubstanz weiß ist.
72. 72. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Hüllsubstanz farbig ist.
73. 73. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper und die Hüllsubstanz eine Farbdifferenz ΔE oberhalb 20, vorzugsweise oberhalb 40 aufweisen.
74. 74. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Hüllsubstanz bedruckt ist.
75. 75. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die wasserlösliche Hüllsubstanz die Oberfläche des Gelkörpers auf zwei einander gegenüberliegenden Seiten des Gelkörpers bedeckt.
76. 76. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper eine Unterseite und eine Oberseite aufweist und die wasserlösliche Hüllsubstanz sowohl die Unterseite als auch die Oberseite des Gelkörpers wenigstens anteilsweise bedeckt.
77. 77. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper eine Unterseite und eine Oberseite aufweist und die wasserlösliche Hüllsubstanz sowohl die Unterseite als auch die Oberseite des Gelkörpers zu wenigstens 40 %, vorzugsweise zu wenigstens 60% und insbesondere zu wenigstens 80% bedeckt.
78. 78. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper eine Unterseite und eine Oberseite aufweist und die wasserlösliche Hüllsubstanz sowohl die Unterseite als auch die Oberseite des Gelkörpers vollflächig bedeckt.
79. 79. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Hüllsubstanz in Form eines einzelnen Festkörpers vorliegt, welcher auf seiner Oberfläche n = 2 Punkte aufweist, deren Flächennormalen zusammenfallen.
80. 80. Reinigungsmittelportionseinheit, umfassend
    1. a) einen formstabilen Gelkörper, umfassend eine Unterseite, eine Oberseite und eine die Unterseite und die Oberseite verbindende zylindrische Mantelfläche,
    2. b) eine Hüllsubstanz in Form eines einzelnen Festkörpers, welche die Unterseite und die Mantelfläche des formstabilen Gelkörper bedeckt, wobei
       1. i) die Hüllsubstanz auf ihrer äußeren Oberfläche n > 1 Punkte aufweist, deren Flächennormalen sowohl durch die Hüllsubstanz als auch durch den formstabilen Gelkörper verlaufen und sich in einem Winkel 360°/n treffen und
       2. ii) das Längenverhältnis der von diesen Flächennormalen innerhalb der Hüllsubstanz verlaufenden Strecke zu der von diesen Flächennormalen innerhalb des Gelkörpers verlaufenden Strecke 1:3 bis 1:14, vorzugsweise 1:4 bis 1:10 beträgt.
81. 81. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Hüllsubstanz in Form von zwei Festkörpern vorliegt deren Flächennormalen zusammenfallen.
82. 82. Reinigungsmittelportionseinheit, umfassend
    1. a) einen formstabilen Gelkörper, umfassend eine Unterseite, eine Oberseite und eine die Unterseite und die Oberseite verbindende zylindrische Mantelfläche,
    2. b) eine Hüllsubstanz in Form von zwei Festkörpern, welche die Unterseite und die Oberseite des formstabilen Gelkörper bedecken, wobei
       1. i) die Flächennormalen der Festkörper sowohl durch die Hüllsubstanz als auch durch den formstabilen Gelkörper verlaufen und sich in einem Winkel von 180° treffen und
       2. ii) das Längenverhältnis der von diesen Flächennormalen innerhalb der Hüllsubstanz verlaufenden Strecke zu der von diesen Flächennormalen innerhalb des Gelkörpers verlaufenden Strecke 1:3 bis 1:14, vorzugsweise 1:4 bis 1:10 beträgt.
83. 83. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei der Gelkörper auf seiner äußeren, von der Hüllsubsubstanz unbedeckten Oberfläche mindestens einen Punkt aufweist, dessen Flächennormale ihn mit einem weiteren Punkt auf der äußeren, von der Hüllsubsubstanz unbedeckten Oberfläche des Gelkörpers verbindet.
84. 84. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Reinigungsmittelportionseinheit keine Umverpackung aus einem wasserlöslichen Filmmaterial aufweist.
85. 85. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Reinigungsmittelportionseinheit keine Umverpackung aus einem wasserunlöslichen Filmmaterial aufweist.
86. 86. Reinigungsmittelportionseinheit nach einem der vorherigen Punkte, wobei die Reinigungsmittelportionseinheit gemeinsam mit mindestens einer weiteren Reinigungsmittelportionseinheit derart in einer gemeinsamen Umverpackung angeordnet ist, dass die Hüllsubstanz mindestens einer Reinigungsmittelportionseinheit in direktem Kontakt zum Gelkörper oder zur Hüllsubstanz, vorzugsweise zur Hüllsubstanz einer weiteren Reinigungsmittelportionseinheit steht.
87. 87. Verfahren zur Herstellung einer Reinigungsmittelportionseinheit, wobei ein Gel und eine wasserlösliche Hüllsubstanz miteinander zu einer Reinigungsmitteldosiereinheit nach einem der Punkte 1 bis 86 verbunden werden.
88. 88. Verfahren nach Punkt 87, umfassend die Schritte:
    1. i) Bereitstellen eines Hüllmaterials;
    2. ii) Bereitstellen eines Gelkörpers;
    3. iii) Aufbringen eines Hüllmaterials auf die Oberfläche des Gelkörpers.
89. 89. Verfahren zur Herstellung einer Reinigungsmittelportionseinheit nach Punkt 88, wobei die Hüllsubstanz in Schritt i) durch Verpressen eines teilchenförmigen Vorgemisches mit einem Pressdruck von 5 bis 30 KN erhalten wird.
90. 90. Verfahren zur Herstellung einer Reinigungsmittelportionseinheit nach einem der Punkte 88 bis 89, wobei der Gelkörper in Schritt ii) durch Erstarrung einer fließfähigen Zusammensetzung erhalten wird.
91. 91. Verfahren nach einem der Punkte 88 bis 90, wobei in Schritt ii) eine fließfähige Zusammensetzung auf ein Hüllmaterial aufgetragen wird und der Gelkörper durch nachfolgende Erstarrung der fließfähigen Zusammensetzung gebildet und haftend mit dem wasserlöslichen Hüllmaterial verbunden wird.
92. 92. Verfahren nach einem der Punkte 87 bis 91, wobei der Gelkörper nach dem Aufbringen eines wasserlöslichen Hüllmaterials in Reinigungsmittelportionseinheiten zerteilt wird.
93. 93. Verfahren zur Geschirrreinigung, bei welchem eine Reinigungsmittelportionseinheit nach einem der Punkte 1 bis 86 in die Dosierkammer oder den Innenraum einer Geschirrspülmaschine eingebracht wird.

In summary, this application provides, among others, the following items:

1. 1. Detergent portion unit comprising
   1. a) a dimensionally stable gel body
   2. b) a coating substance in the form of a shaped body which partially covers the surface of the dimensionally stable gel body, whereby
      1. i) the gel body occupies from 20 to 45 vol.% of the detergent dosing unit, and
      2. (ii) the gel body, based on its total weight
         • contains a maximum of 30% by weight surfactant,
         • Contains 50 to 80 wt.% solvent,
         • contains a gelling agent in a weight proportion of less than 5% by weight iii) the coating substance, based on its total weight
         • contains at least 80% by weight of washing or cleaning active ingredient.
2. 2. Cleaning agent portion unit according to item 1, wherein the portion unit has a weight of 10 g to 35 g, preferably 13 g to 30 g, in particular 15 g to 25 g.
3. 3. Detergent portion unit according to one of items 1 to 2, wherein the gel body occupies 25 to 40 vol.%, for example 30 to 35 vol.%, of the detergent portion unit.
4. 4. Cleaning agent portion unit according to one of the preceding points, wherein the gel body contains, based on its total weight, 5 to 25 wt.% and in particular 10 to 20 wt.% surfactant.
5. 5. Cleaning agent portion unit according to one of the preceding points, wherein the gel body, based on its total weight, contains less than 5 wt.%, preferably less than 1 wt.%, preferably no anionic surfactant.
6. 6. Cleaning agent portion unit according to one of the preceding points, wherein the gel body contains, based on its total weight, 5 to 30 wt.%, preferably 10 to 25 wt.%, more preferably 10 to 20 wt.%, of one or more nonionic surfactants.
7. 7. Cleaning agent portion unit according to item 6, wherein the gel body contains nonionic surfactant from the group of 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 ,
   
   where 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 are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5; where, if the value x is > 2, each R ³ can be different.
8. 8. Cleaning agent portion unit according to item 7, wherein R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 C atoms being particularly preferred, and wherein H, -CH ₃ or -CH ₂ CH ₃ are particularly preferred for the radical R ³ , with particularly preferred values for x being in the range from 1 to 20, in particular from 6 to 15.
9. 9. Cleaning agent portion unit according to one of points 7 and 8, wherein particularly preferred end-capped poly(oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is simplified to R ¹ O[CH ₂ CH(R ³ )O] _x CH ₂ CH(OH)CH ₂ OR ² , wherein in this formula R ¹ , R ² and R ³ are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, wherein particularly preferred surfactants are those in which the radicals R ¹ and R ² have 9 to 14 C atoms, R ³ stands for H and x assumes values from 6 to 15.
10. 10. Cleaning agent portion unit according to one of items 6 to 9, wherein one or more nonionic surfactants are selected from nonionic surfactants of the general formula R ¹ -CH(OH)CH ₂ O-(AO) _w -R ² , wherein
    • R ¹ represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical;
    • R ² represents a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
    • A represents a radical from the group CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH(CH ₃ ), preferably CH ₂ CH ₂ , and
    • w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40.
11. 11. Cleaning agent portion unit according to item 10, wherein one or more nonionic surfactants are selected from the group consisting of C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ethers and C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ethers.
12. 12. Cleaning agent portion unit according to one of the preceding points, wherein the gel body contains at least one non-ionic surfactant from the group of hydroxy mixed ethers.
13. 13. Cleaning agent portion unit according to one of the preceding points, wherein the gel body contains, based on its total weight, 55 to 75 wt.%, preferably 60 to 70 wt.% solvent.
14. 14. Cleaning agent portion unit according to one of the preceding points, wherein the gel body contains, based on its total weight, 50 to 75 wt.%, preferably 55 to 70 wt.% of organic solvent.
15. 15. Cleaning agent portion unit according to one of the preceding points, wherein the gel body contains organic solvent selected from the group ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerin, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, Di-n-octyl ether and mixtures thereof, preferably from the group propanediol, glycerin and mixtures thereof.
16. 16. Cleaning agent portion unit according to one of the preceding points, wherein the gel body, based on its total weight, contains less than 20 wt. %, preferably from 1 to 15 wt. %, in particular from 2 to 14 wt.% and very particularly preferably from 3 to 13 wt.% water.
17. 17. Cleaning agent portion unit according to one of the preceding points, wherein the gel body contains, based on its total weight, 0.1 to 5 wt.%, particularly preferably 0.1 to 2.5 wt.% gelling agent.
18. 18. Cleaning agent portion unit according to one of the preceding points, wherein the gelling agent is selected from the group of low molecular weight gelling agents with a molar mass of up to 2000 g/mol, in particular from the group of cyclic dipeptides, cyclic dipeptide derivatives and dibenzylidene sorbitol.
19. 19. Detergent portion unit according to one of the preceding points, wherein dibenzylidene sorbitol is used as gelling agent.
20. 20. Cleaning agent portion unit according to one of the preceding points, wherein the gel body, based on its total weight, contains 0 to 12 wt.%, preferably 1 to 10 wt.%, more preferably 2 to 8 wt.% of a washing or cleaning-active polymer, preferably a washing or cleaning-active polymer from the group of polycarboxylates (builder polymers; 0-15 wt.%), preferably polymers which comprise acrylate and/or methacrylate, in particular polymers which additionally comprise monomers containing sulfonic acid groups.
21. 21. Detergent portion unit according to one of the preceding points, wherein the detergent portion unit comprises at least one enzyme preparation.
22. 22. Detergent portion unit according to one of the preceding points, wherein the amount of all amylases, based on the amount of active enzyme protein, in the detergent portion unit is from 1 to 100 mg, preferably 4 to 50 mg, in particular 6 to 25 mg.
23. 23. Detergent portion unit according to one of the preceding points, wherein the amount of all proteases, based on the amount of active enzyme protein, in the detergent portion unit is 2 to 800 mg, preferably 4 to 200 mg, in particular 6 to 100 mg.
24. 24. Cleaning agent portion unit according to one of the preceding points, wherein the gel body contains, based on its total weight, 0.001 to 5 wt.%, preferably 0.01 to 3 wt.% fragrance preparation.
25. 25. Detergent portion unit according to one of the preceding points, wherein the coating substance contains, based on its total weight, at least 82% by weight, preferably at least 85% by weight, particularly preferably at least 90% by weight of washing or cleaning active ingredient.
26. 26. Detergent portion unit according to one of the preceding points, wherein the coating substance contains one or more washing or cleaning active ingredients from the group of builders, bleaching agents, bleach activators, bleach catalysts, silver preservatives.
27. 27. Cleaning agent portion unit according to one of the preceding points, wherein the cleaning agent portion unit comprises at least one active substance from the group of builders, in particular at least one active substance from the group of zeolites, silicates and carbonates, preferably from the group of carbonates.
28. 28. Cleaning agent portion unit according to one of the preceding points, wherein the cleaning agent portion unit, based on its total weight, comprises at least one active substance from the group of builders in weight proportions of 5 to 70 wt.%, preferably 10 to 50 wt.%, in particular at least one active substance from the group of zeolites, silicates and carbonates, preferably from the group of carbonates, in particular carbonates in weight proportions of 5 to 70 wt.%, preferably 10 to 50 wt.%.
29. 29. Detergent portion unit according to one of the preceding points, wherein the detergent portion unit contains washing or cleaning active ingredients from the group of sodium salts of organic and inorganic acids and at least 80% by weight, preferably at least 90% by weight and particularly preferably at least 95% by weight of this sodium salt is present as a component of the coating substance.
30. 30. Detergent portion unit according to one of the preceding points, wherein the detergent portion unit comprises citrate in weight proportions of 0.5 to 25 wt.%, preferably 5 to 15 wt.%, in each case based on the total weight of the detergent portion unit.
31. 31. Detergent portion unit according to one of the preceding points, wherein the detergent portion unit comprises aminocarboxylates, in particular selected from the group MGDA, GLDA, EDDS and/or their salts.
32. 32. Detergent portion unit according to item 31, wherein the detergent portion unit comprises MGDA, GLDA, EDDS and/or their salts in weight proportions of 0.5 to 25 wt.%, preferably 5 to 15 wt.%, in each case based on the total weight of the detergent portion unit.
33. 33. Detergent portion unit according to one of items 31 to 32, wherein the detergent portion unit contains MGDA and/or its salt in weight proportions of 0.5 to 25 wt.%, preferably 5 to 15 wt.%, in each case based on the total weight of the detergent portion unit.
34. 34. Detergent portion unit according to one of the preceding points, wherein the detergent portion unit contains at least one bleaching agent, preferably in an amount of 1 to 35 wt.%, more preferably 2.5 to 30 wt.%, particularly preferably 3.5 to 20 wt.%, and in particular 5 to 15 wt.%, each based on the total weight of the detergent portion unit; wherein the at least one bleaching agent is preferably selected from the group consisting of sodium percarbonate; sodium perborate tetrahydrate; sodium perborate monohydrate; peroxypyrophosphates; citrate perhydrates; and H ₂ O ₂ -yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
35. 35. Detergent portion unit according to item 34, wherein the detergent portion unit additionally contains at least one bleach activator, preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight, each based on the total weight of the detergent portion unit; wherein the at least one bleach activator is preferably selected from the group consisting of compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and/or optionally substituted perbenzoic acid, even more preferably from the group consisting of multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS); wherein the at least one bleach activator is particularly preferably TAED, in particular in combination with a percarbonate bleach, preferably sodium percarbonate.
36. 36. Cleaning agent portion unit according to one of items 34 to 35, wherein the cleaning agent portion unit additionally contains at least one bleach catalyst, preferably in an amount of 0.001 to 1% by weight, preferably 0.01 to 0.1% by weight, in each case based on the total weight of the cleaning agent portion unit; wherein the at least one bleach catalyst is preferably selected from the group consisting of bleach-enhancing transition metal salts and transition metal complexes, preferably the Mn, Fe, Co, Ru or Mo complexes, particularly preferably from the group of manganese and/or cobalt salts and/or - complexes, in particular cobalt (ammine) complexes, cobalt (acetate) complexes, cobalt (carbonyl) complexes, chlorides of cobalt or manganese, manganese sulfate and complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Mns-TACN) or 1,2,4,7-tetramethyl-1,4,7-tri-azacyclononane (Mn ₄ -TACN), wherein the at least one bleaching agent is in particular a Mn complex, in particular a complex of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Mns-TACN) or 1,2,4,7-tetramethyl-1,4,7-tri-azacyclononane (Mn ₄ -TACN).
37. 37. Cleaning agent portion unit according to one of the preceding points, wherein the cleaning agent portion unit contains at least one phosphonate, preferably in an amount of 0.1 to 10% by weight, in particular 0.5 to 8% by weight, in each case based on the total weight of the cleaning agent portion unit, wherein the at least one phosphonate is preferably selected from the group consisting of hydroxyalkane and aminoalkane phosphonates, wherein among the hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly preferred and among the aminoalkane phosphonates ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues are particularly preferred.
38. 38. Detergent portion unit according to item 37, wherein the at least one phosphonate is contained in the gel body.
39. 39. Detergent portion unit according to one of the preceding points, wherein the detergent portion unit contains at least one sulfopolymer, preferably in an amount of 0.1 to 20 wt.%, in particular 0.5 to 18 wt.%, particularly preferably 1.0 to 15 wt.%, in particular 4 to 14 wt.%, especially 6 to 12 wt.%, in each case based on the total weight of the detergent portion unit.
40. 40. Detergent portion unit according to item 39, wherein the at least one sulfopolymer is a copolymeric polysulfonate, in particular a hydrophobically modified copolymeric polysulfonate, wherein the copolymers can have two, three, four or more different monomer units.
41. 41. Cleaning agent portion unit according to item 40, wherein copolymeric polysulfonates contain, in addition to sulfonic acid group-containing monomer(s), at least one monomer from the group of unsaturated carboxylic acids, preferably from the group of unsaturated carboxylic acids of the formula R ¹ (R ² )C=C(R ³ )COOH, wherein R ¹ to R ³ independently of one another represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH ₂ , -OH or -COOH such as as defined above or represents -COOH or -COOR ⁴ , where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
42. 42. Cleaning agent portion unit according to one of items 39 to 41, wherein monomers containing sulfonic acid groups are selected from the group consisting of monomers of the formula R ⁵ (R ¹ )C=C(R ¹ )-X-SO ₃ H, wherein R ⁵ to R ⁷ independently of one another represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH ₂ , OH or -COOH or represent -COOH or -COOR ⁴ , wherein R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group selected from -(CH ₂ ) _n - with n = 0 to 4, COO-(CH ₂ ) _k - with k = 1 to 6, C(O)-NH-C(CH ₃ ) ₂ -, C(O)-NH-C(CH ₃ ) ₂ -CH ₂ - and -C(O)-NH-CH(CH ₃ ) CH ₂ -,
43. 43. Cleaning agent portion unit according to item 42, wherein monomers containing sulfonic acid groups are selected from the group consisting of 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyl-oxy)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.
44. 44. Cleaning agent portion unit according to one of items 39 to 43, wherein the sulfonic acid groups are completely or partially in neutralized form, with partially or fully neutralized copolymers containing sulfonic acid groups being preferred.
45. 45. Cleaning agent portion unit according to one of items 40 to 44, wherein the monomer distribution in copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is in each case 5 to 95 wt.%, wherein preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90 wt.% and the proportion of the monomer containing carboxylic acid groups is 10 to 50 wt.%.
46. 46. Detergent portion unit according to one of items 40 to 45, wherein the molecular weight of the sulfo copolymers is from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .
47. 47. Cleaning agent portion unit according to one of the preceding points, wherein the cleaning agent portion unit contains at least one glass corrosion inhibitor, preferably in an amount of 0.05 to 5 wt.%, preferably between 0.2 to 4 wt.% and in particular between 0.4 to 3 wt.%, in each case based on the total weight of the cleaning agent portion unit.
48. 48. Cleaning agent portion unit according to item 47, wherein the at least one glass corrosion inhibitor is selected from the group consisting of zinc salts of organic carboxylic acid, particularly preferred zinc salts are from the group consisting of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate, zinc citrate, zinc ricinoleate, zinc abietate, and/or zinc oxalate; and/or from the group consisting of soluble inorganic zinc salts, particularly preferred zinc sulfate, zinc nitrate and zinc chloride.
49. 49. Cleaning agent portion unit according to one of the preceding points, wherein the cleaning agent portion unit contains at least one silver protective agent, preferably in an amount of 0.001 to 10 wt.%, more preferably 0.0025 to 2 wt.%, particularly preferably 0.01 to 0.04 wt.%, in each case based on the total weight of the cleaning agent portion unit.
50. 50. The cleaning agent portion unit of item 49, wherein the silver protecting agent is selected from the group consisting of cysteine, cystine and mixtures thereof.
51. 51. Detergent dispensing unit according to any one of the preceding points, wherein the gel body has a flat bottom whose largest diagonal is greater than the height of the gel body.
52. 52. Detergent portion unit according to one of the preceding points, wherein the gel body has a flat bottom whose largest diagonal is more than 1.5 times, preferably more than 2 times the height of the gel body.
53. 53. Detergent portion unit according to one of the preceding points, wherein the gel body has an oval bottom.
54. 54. Detergent portion unit according to one of items 1 to 52, wherein the gel body has an ellipsoidal or round, preferably a round, bottom.
55. 55. Detergent portion unit according to one of items 1 to 52, wherein the gel body has a square bottom side.
56. 56. Detergent dispensing unit according to item 55, wherein the gel body has a triangular, square or hexagonal bottom.
57. 57. Detergent portion unit according to one of the preceding points, wherein the gel body has an upper side plane-parallel to the lower side.
58. 58. Detergent portion unit according to one of the preceding points, wherein the gel body has a bottom and a top which have the same geometric shape and wherein the bottom and the top have the same surface area.
59. 59. Detergent portion unit according to one of the preceding points, wherein the gel body has a bottom and a top which have the same geometric shape and wherein the bottom and the top have different surface sizes.
60. 60. Detergent portion unit according to one of the preceding points, wherein the gel body has a bottom side and a top side which are connected to one another by a cylindrical outer surface.
61. 61. Detergent portion unit according to one of the preceding points, wherein the gel body has a bottom side and a top side and the area of the top side is 80 to 100%, preferably 90 to 100% and in particular 98 to 100% of the bottom side.
62. 62. Detergent portion unit according to one of the preceding points, wherein the coating substance is present as a cast body.
63. 63. Detergent portion unit according to one of the preceding points, wherein the coating substance is in the form of a pressed body, preferably a tablet.
64. 64. Detergent portion unit according to one of the preceding points, wherein the coating substance has a breaking strength of 50 N to 300 N, in particular of 70 N to 200 N.
65. 65. Detergent portion unit according to one of the preceding points, wherein the gel body and the coating substance are adhesively bonded to one another.
66. 66. Detergent portion unit according to one of the preceding points, wherein the gel body forms at least 10%, preferably at least 15% and in particular at least 20% of the total surface of the detergent portion unit.
67. 67. Detergent portion unit according to one of the preceding points, wherein the coating substance covers 20 to 90%, preferably 30 to 80% and in particular 40 to 75% of the surface of the gel body.
68. 68. Detergent portion unit according to one of the preceding points, wherein the gel body contains a dye.
69. 69. Detergent portion unit according to any one of the preceding items, wherein the gel body is transparent.
70. 70. Detergent portion unit according to one of the preceding points, wherein the coating substance is non-transparent.
71. 71. Detergent portion unit according to any one of the preceding items, wherein the coating substance is white.
72. 72. Detergent portion unit according to any one of the preceding items, wherein the coating substance is coloured.
73. 73. Detergent portion unit according to one of the preceding points, wherein the gel body and the coating substance have a color difference ΔE above 20, preferably above 40.
74. 74. Detergent portion unit according to one of the preceding items, wherein the shell substance is printed.
75. 75. Detergent portion unit according to one of the preceding points, wherein the water-soluble coating substance covers the surface of the gel body on two opposite sides of the gel body.
76. 76. Detergent portion unit according to one of the preceding points, wherein the gel body has a bottom side and a top side and the water-soluble coating substance at least partially covers both the bottom side and the top side of the gel body.
77. 77. Detergent portion unit according to one of the preceding points, wherein the gel body has a bottom side and a top side and the water-soluble coating substance covers both the bottom side and the top side of the gel body to at least 40%, preferably to at least 60% and in particular to at least 80%.
78. 78. Detergent portion unit according to one of the preceding points, wherein the gel body has a bottom side and a top side and the water-soluble coating substance completely covers both the bottom side and the top side of the gel body.
79. 79. Detergent portion unit according to one of the preceding points, wherein the coating substance is in the form of a single solid body which has n = 2 points on its surface whose surface normals coincide.
80. 80. Detergent portion unit comprising
    1. a) a dimensionally stable gel body comprising a bottom side, a top side and a cylindrical surface connecting the bottom side and the top side,
    2. b) a coating substance in the form of a single solid body which covers the underside and the outer surface of the dimensionally stable gel body, wherein
       1. i) the shell substance has n > 1 points on its outer surface, the surface normals of which pass through both the shell substance and the dimensionally stable gel body and meet at an angle of 360°/n and
       2. ii) the length ratio of the distance running from these surface normals within the shell substance to the distance running from these surface normals within the gel body is 1:3 to 1:14, preferably 1:4 to 1:10.
81. 81. Detergent portion unit according to one of the preceding points, wherein the coating substance is in the form of two solid bodies whose surface normals coincide.
82. 82. Detergent portion unit comprising
    1. a) a dimensionally stable gel body comprising a bottom side, a top side and a cylindrical surface connecting the bottom side and the top side,
    2. b) a coating substance in the form of two solid bodies covering the bottom and the top of the dimensionally stable gel body, wherein
       1. i) the surface normals of the solid bodies pass through both the shell substance and the dimensionally stable gel body and meet at an angle of 180° and
       2. ii) the length ratio of the distance running from these surface normals within the shell substance to the distance running from these surface normals within the gel body is 1:3 to 1:14, preferably 1:4 to 1:10.
83. 83. Detergent portion unit according to one of the preceding points, wherein the gel body has on its outer surface uncovered by the shell sub-substance at least one point whose surface normal connects it to another point on the outer surface of the gel body uncovered by the shell sub-substance.
84. 84. Detergent portion unit according to one of the preceding points, wherein the detergent portion unit does not have an outer packaging made of a water-soluble film material.
85. 85. Detergent portion unit according to one of the preceding points, wherein the detergent portion unit does not have an outer packaging made of a water-insoluble film material.
86. 86. Detergent portion unit according to one of the preceding points, wherein the detergent portion unit is arranged together with at least one further detergent portion unit in a common outer packaging such that the coating substance of at least one detergent portion unit is in direct contact with the gel body or the coating substance, preferably with the coating substance of a further detergent portion unit.
87. 87. A method for producing a detergent portion unit, wherein a gel and a water-soluble coating substance are combined with one another to form a detergent dosing unit according to one of items 1 to 86.
88. 88. Procedure according to item 87, comprising the steps:
    1. (i) providing a wrapping material;
    2. ii) providing a gel body;
    3. iii) Applying a coating material to the surface of the gel body.
89. 89. A process for producing a detergent portion unit according to item 88, wherein the coating substance in step i) is obtained by compressing a particulate premix with a compression pressure of 5 to 30 KN.
90. 90. Process for producing a cleaning agent portion unit according to one of items 88 to 89, wherein the gel body in step ii) is obtained by solidification of a flowable composition.
91. 91. Process according to one of items 88 to 90, wherein in step ii) a flowable composition is applied to a coating material and the gel body is formed by subsequent solidification of the flowable composition and is adhesively bonded to the water-soluble coating material.
92. 92. Method according to one of items 87 to 91, wherein the gel body is divided into cleaning agent portion units after the application of a water-soluble coating material.
93. 93. Method for cleaning dishes, in which a detergent portion unit according to one of items 1 to 86 is introduced into the dosing chamber or the interior of a dishwasher.

Claims (15)

Cleaning agent portion unit, comprising a) a dimensionally stable gel body b) a coating substance in the form of a shaped body, which partially covers the surface of the dimensionally stable gel body, where i) the gel body occupies from 20 to 45% by volume of the cleaning agent dosage unit, and ii) the gel body, based on its total weight - contains a maximum of 30% by weight of surfactant, - contains 50 to 80% by weight of solvent, - contains a gelling agent in proportions by weight below 5% by weight iii) the shell substance, based on its total weight - contains at least 80% by weight of washing or cleaning active ingredient. Detergent portion unit according to claim 1, wherein the portion unit has a weight of 10 g to 35 g, preferably 13 g to 30 g, in particular 15 g to 25 g. Detergent portion unit according to one of the preceding claims, wherein the gel body, based on its total weight, contains less than 5 wt.%, preferably less than 1 wt.%, preferably no anionic surfactant. Cleaning agent portion unit according to one of the preceding claims, wherein the gel body, based on its total weight, contains 5 to 30% by weight, preferably 10 to 25% by weight, more preferably 10 to 20% by weight, of one or more nonionic surfactants. Detergent portion unit according to one of the preceding claims, wherein the gel body, based on its total weight, contains 55 to 75 wt.%, preferably 60 to 70 wt.% of solvent.
5. Cleaning agent portion unit according to one of the preceding claims, wherein the gel body, based on its total weight, contains less than 20 wt. %, preferably from 1 to 15 wt. %, in particular from 2 to 14 wt. %, and very particularly preferably from 3 to 13 wt. % of water. Detergent portion unit according to one of the preceding claims, wherein the gel body contains, based on its total weight, 0.1 to 5 wt.%, particularly preferably 0.1 to 2.5 wt.% gelling agent. Detergent portion unit according to one of the preceding claims, wherein the gel body, based on its total weight, contains 0 to 12 wt.%, preferably 1 to 10 wt.%, more preferably 2 to 8 wt.% of a washing or cleaning-active polymer, preferably a washing or cleaning-active polymer from the group of polycarboxylates (builder polymers; 0-15 wt.%), preferably polymers which comprise acrylate and/or methacrylate, in particular polymers which additionally comprise monomers containing sulfonic acid groups. Detergent portion unit according to one of the preceding claims, wherein the detergent portion unit comprises at least one enzyme preparation. Cleaning agent portion unit according to one of the preceding claims, wherein the gel body, based on its total weight, contains 0.001 to 5% by weight, preferably 0.01 to 3% by weight, of fragrance preparation. Detergent portion unit according to one of the preceding claims, wherein the coating substance contains, based on its total weight, at least 82% by weight, preferably at least 85% by weight, particularly preferably at least 90% by weight of washing or cleaning active ingredient. Cleaning agent portion unit according to one of the preceding claims, wherein the cleaning agent portion unit comprises at least one active substance from the group of builders, in particular at least one active substance from the group of zeolites, silicates and carbonates, preferably from the group of carbonates. Detergent portion unit according to one of the preceding claims, wherein the detergent portion unit comprises citrate in weight proportions of 0.5 to 25 wt.%, preferably 5 to 15 wt.%, in each case based on the total weight of the detergent portion unit. Cleaning agent portion unit according to one of the preceding claims, wherein the gel body has a bottom and a top and the water-soluble coating substance covers both the bottom and the top of the gel body over the entire surface. Method for producing a cleaning agent portion unit, wherein a gel and a water-soluble coating substance are connected to one another to form a cleaning agent dosage unit according to one of claims 1 to 13. Method for cleaning dishes, in which a detergent portion unit according to one of claims 1 to 13 is introduced into the dosing chamber or the interior of a dishwasher.