EP3599270A1 - Cleaning composition with silver protection - Google Patents

Abstract

The invention relates to detergents, preferably dishwashing detergents, in particular automatic dishwashing detergents, comprising a gel-like phase which contains fused triazoles and / or their derivatives, in particular unsubstituted benzotriazole and / or benzotriazole-substituted, in particular mono- to trisubstituted alkyl, preferably in each case on the benzene ring linear or branched alkyl radicals with 1 to 4 carbon atoms substituted benzotriazoles, particularly preferably mono-, di- or trimethyl-substituted benzotriazoles on the benzene ring, preferably methylbenzotriazoles (monomethyl-1,2,3-benzotriazole) substituted on the benzene ring, for example 4-methyl-1H -benzotriazole or 5-methyl-1H-benzotriazole, and / or benzotriazole (1,2,3-benzotriazole, 1H-benzotriazole).

Description

The invention relates to detergents, preferably dishwashing detergents, in particular machine dishwashing detergents, comprising a gel phase which contains fused triazoles and / or their derivatives, in particular unsubstituted benzotriazole and / or benzotriazole-substituted, in particular mono- to trisubstituted alkyl, preferably in each case on the benzene ring linear or branched alkyl radicals with 1 to 4 carbon atoms substituted benzotriazoles, particularly preferably mono-, di- or trimethyl-substituted benzotriazoles on the benzene ring, preferably methylbenzotriazoles (monomethyl-1,2,3-benzotriazole) substituted on the benzene ring, for example 4-methyl-1 H- benzotriazole or 5-methyl-1 H -benzotriazole, and / or benzotriazole (1,2,3-benzotriazoles, 1 H -benzotriazole).

In the formulation of cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, fused triazoles, in particular benzotriazoles, are used as silver preservatives. However, the incorporation of triazoles into the particulate phase, as is carried out in the prior art, leads to interactions between the triazole and active substances in the powder, which lead to the yellowing of the powder. This yellowing is also perceived by the consumer and viewed as a reduction in product quality.

The DE19631787 A1 describes granular partial compositions which contain benzotriazole and are suitable for incorporation in automatic dishwashing detergents. The discoloration of the granules was assessed after 4 days (stored open on a crystallizing dish at 30 ° C. and 80% atmospheric humidity).

However, the usual storage time for machine dishwashing detergents is significantly longer, sometimes several months. Detergent portions packaged in water-soluble film, in particular those containing a liquid or gel phase and a powder phase, show yellowing in the powder area after several weeks.

It is therefore an object of the present invention to provide cleaning agents, in particular dishwashing agents, preferably machine dishwashing agents, which contain triazoles, but which, even after storage for more than 7 days, have no yellowing due to the presence of triazoles.

A first object of the present invention thus relates to cleaning agents comprising a gel phase, which fused triazoles and / or its derivatives, in particular unsubstituted benzotriazole and / or substituted on the benzene ring, in particular mono- to trisalkyl-substituted benzotriazoles, preferably in each case on the benzene ring with linear or branched Alkyl radicals with 1 to 4 carbon atoms substituted benzotriazoles, particularly preferably mono-, di- or trimethyl-substituted benzotriazoles on the benzene ring, preferably methylbenzotriazoles (monomethyl-1,2,3-benzotriazole) substituted on the benzene ring, for example 4-methyl-1 H -benzotriazole or 5-methyl-1 H -benzotriazole, and / or benzotriazole (1,2,3-benzotriazole, 1 H -benzotriazole).

According to the invention, methyl-benzotriazole (methyl-1H-benzotriazole) is taken to mean a benzotriazole (methyl-1,2,3-benzotriazole, methyl-1 H -benzotriazole) substituted on the benzene ring with a methyl group (corresponding to a 1H-benzotriazole with a methyl group) one of positions 4, 5, 6 or 7), it also being possible to use isomer mixtures of these methylbenzotriazoles. Especially preferred are 4-methyl-1 H -benzotriazole and / or 5-methyl-1 H- benzotriazole. In particular, tolyltriazole can be used as methylbenzotriazole.

An advantage of the invention is that the incorporation of triazoles into the gel phase is easy to carry out and does not lead to a yellow discoloration of the powder phase when stored, even in indirect or direct contact with a corresponding solid phase. Surprisingly, it was also found that the solid phase does not turn yellow or brown despite the presence of a triazole.

According to the invention, a gel-like phase, hereinafter also referred to as gel phase, is to be understood as a composition / phase which has an internally structuring network. This internally structuring (spatial) network is formed by the dispersion of a solid but distributed substance with long or highly branched particles and / or gel-forming agent in at least one liquid (the at least one liquid is liquid at 20 ° C.). Such gel phases are thermoreversible.

This gel phase can be, for example, flowable or dimensionally stable. According to the invention, however, the gel phase is preferably dimensionally stable at room temperature. In the preparation, the gel former, preferably xanthan, gelatin or polyvinyl alcohol and / or its derivatives, is brought into contact with a solvent, preferably an organic solvent, preferably one or more polyhydric alcohol (s). This gives a flowable mixture which can be brought into a desired shape. After a certain period of time, a gel phase is obtained which remains in the specified form, i.e. is dimensionally stable. This period, the solidification time, is preferably 15 minutes or less, preferably 10 minutes or less, particularly preferably 5 minutes or less. The at least one gel phase yields under pressure, but does not deform as a result, but rather returns to the initial state after the pressure has dropped. The at least one gel phase is preferably elastic, in particular linear-elastic.

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

Certain minimum requirements are imposed on formulations of the at least one gel phase. As already stated, the gel phase must solidify within the shortest possible time. Long solidification times would lead to long production times and thus high costs. According to the invention, solidification time means the period of time during which the at least one gel phase changes from a flowable state to a dimensionally stable state which is not flowable at room temperature. Room temperature is understood to be a temperature of 20 ° C.

The at least one gel phase is preferably a solid gel phase. It is cut-resistant. For example, it can be cut with a knife after solidification without being further destroyed apart from the cut performed.

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

These and other aspects, features and advantages of the invention will become apparent to those skilled in the art upon studying the following detailed description and claims. Each feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it goes without saying that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not restricted to these examples. Unless otherwise stated, all percentages are% by weight. Numerical ranges that are specified in the format "from x to y" include the values mentioned. If several preferred numerical ranges are specified in this format, it goes without saying that all ranges that result from the combination of the different endpoints are also covered.

"At least one" as used herein means 1 or more, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In relation to an ingredient, the information relates to the type of ingredient and not to the absolute number of molecules. "At least one bleaching catalyst" thus means, for example, at least one kind of bleaching catalyst, i.e. that one type of bleaching catalyst or a mixture of several different bleaching catalysts can be meant. Together with the weight information, the information relates to all compounds of the specified type which are contained in the composition / mixture, i.e. that the composition contains no further compounds of this type beyond the stated amount of the corresponding compounds.

If reference is made here to molecular weights, this information always relates to the number-average molecular weight M _n , unless explicitly stated otherwise. The number average molecular weight can be determined, for example, by means of gel permeation chromatography (GPC) according to DIN 55672-1: 2007-08 with THF as the eluent. The weight average molecular weight M _w can also be determined by means of GPC, as described for M _n .

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

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

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

Surprisingly, it was found that detergents, preferably dishwashing detergents, in particular machine dishwashing detergents, which contain triazole (s) in the gel phase, in particular if they contain a further solid phase, even after storage for more than 7 days in a closed vessel at 50 ° C. in Warming cabinet show no yellowing due to the presence of triazoles.

A disadvantage would be a change in volume or shrinkage during storage, as this would result in low consumer acceptance of the product. Leakage of liquid or exudation of components from the gel phase is also undesirable. Here, too, the visual impression is relevant. The stability of the gel phase can be influenced by the escape of liquid, such as, for example, solvents, so that the constituents are no longer contained in a stable manner and the washing or cleaning action can also be influenced thereby.

It has also been found that the amount of triazole that must be used for similar silver protection performance in the gel phase can even be reduced. Surprisingly, it was found that when the silver protection was formulated in the gel phase with a lower amount of use, an improvement in the silver protection performance could even be achieved.

Surprisingly, it was also found that the polishability of silver cutlery is also improved in the presence of the same amount of triazole (s) in the gel phase compared to the presence in the solid phase.

Another particular effect of the incorporation of triazole (s) into the gel phase was observed with regard to the inhibition of deposits. The formation of deposits on porcelain, plastic and stainless steel is surprisingly reduced by the presence of triazole (s) in the gel phase.

It was also surprisingly found that the addition of triazole gives the appearance of the gel phase a special sheen.

According to a preferred embodiment, the cleaning agent according to the invention, preferably dishwashing detergent, in particular the automatic dishwashing detergent, contains triazoles and / or derivatives thereof fused in the gel phase, in particular unsubstituted benzotriazole or benzotriazole-substituted, in particular alkyl-substituted, benzotriazoles, preferably with linear or branched alkyl radicals with 1 to 4 carbon atoms substituted, in particular mono- to tri-alkyl-substituted benzotriazoles, particularly preferably methyl-1 H -benzotriazole or benzotriazole (in particular 1,2,3-benzotriazoles, 1 H -benzotriazole) in an amount of 0.1 to 5% by weight .-%, in particular from 0.5 to 4 wt .-%, very particularly preferably from 1 to 3.5 wt .-%, based on the total weight of the gel phase.

Amounts of 0.5 to 4% by weight, in particular 1 to 3.5% by weight, of benzotriazole and / or methyl-1 H -benzotriazole, in particular benzotriazole (preferably 1 H- benzotriazole), in each case based on the Total weight of the gel phase.

According to a further preferred embodiment, the total amount of the fused triazoles and / or their derivatives, in particular of the unsubstituted benzotriazole or of the benzene ring substituted, in particular alkyl substituted, benzotriazoles, preferably with linear or branched alkyl radicals having 1 to 4 C atoms, benzotriazoles, particularly preferably methyl -1 H -benzotriazole and / or benzotriazole (in particular 1,2,3-benzotriazole, 1 H- benzotriazole), based on the weight of the total detergent, preferably dishwashing detergent, in particular automatic dishwashing detergent, 0.01 to 1% by weight, preferably 0.05 to 0.7% by weight, in particular 0.1 to 0.5% by weight.

Particularly preferably, detergents, preferably dishwashing detergents, in particular automatic dishwashing detergents contain 0.05 to 0.7% by weight, in particular 0.1 to 0.5% by weight of benzotriazole and / or methyl-1 H -benzotriazole, in particular benzotriazole (preferred 1 H- benzotriazole, based on the total amount of detergent

According to a further preferred embodiment of the present invention, detergents, preferably dishwashing detergents, in particular machine dishwashing detergents, which are packaged as detergent portions, which preferably contain the active substances necessary for a cleaning cycle, contain the total amount of the fused triazoles and / or their derivatives, in particular the unsubstituted benzotriazole or the benzotriazoles substituted on the benzene ring, in particular alkyl-substituted benzotriazoles, preferably with linear or branched alkyl radicals having 1 to 4 carbon atoms, particularly preferably methyl-1 H -benzotriazole and / or benzotriazole (in particular 1,2,3-benzotriazoles, 1 H -Benzotriazol) in the detergent portion, preferably 0.0004 to 0.5 g, preferably 0.001 to 0.2 g, in particular 0.02 to 0.06 g.

This means that the individual detergent portion which is used to carry out an individual cleaning cycle, in particular is added to a cleaning cycle of a machine dishwasher, 0.0005 to 1 g, preferably 0.01 to 0.5 g, in particular 0.02 to 0 , 1 g of the fused triazole used accordingly.

Particularly preferably, a single portion of detergent according to the invention, which is added in particular to a cleaning cycle in an automatic dishwasher, contains 0.001 to 0.5 g, in particular 0.02 to 0.05 g of benzotriazole and / or methyl-1 H -benzotriazole, in particular benzotriazole (preferred 1 H -benzotriazole, based on the total amount of detergent.

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

According to the invention, the at least one gel phase particularly preferably comprises PVOH (polyvinyl alcohol) and / or their derivatives. Polyvinyl alcohols are thermoplastic materials that are usually produced as white to yellowish powder by hydrolysis of polyvinyl acetate. Polyvinyl alcohol (PVOH) is resistant to almost all anhydrous organic solvents. Polyvinyl alcohols with a molecular weight of 30,000 to 60,000 g / mol are preferred. For the purposes of the invention, preferred PVOH derivatives are copolymers of polyvinyl alcohol with other monomers, in particular copolymers with anionic monomers. Suitable anionic monomers are preferably vinyl acetic acid, alkyl acrylates, maleic acid and their derivatives, in particular monoalkyl maleates (in particular monomethyl maleate), dialkyl maleates (in particular dimethyl maleate), maleic anhydride, fumaric acid and their derivatives, in particular monoalkyl fumarate (in particular monomethyl fumarate), dialkyl fumarate (especially fumarate), dialkyl fumarate itaconic acid and its derivatives, especially monomethyl itaconate, dialkyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid (methylmaleic acid) and derivatives thereof, Monoalkylcitraconsäure (especially Methylcitraconat) Dialkylcitraconsäure (Dimethylcitraconat), citraconic acid, mesaconic acid (methylfumaric) and their derivatives, Monoalkylmesaconat, Dialkylmesaconat, mesaconic, glutaconic and their derivatives, monoalkyl glutaconate, dialkyl glutaconate, glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1 -methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethylacrylate and their combinations as well as the alkali metal salts or esters of the above-mentioned monomers.
Particularly preferred derivatives of PVOH are those which are selected from copolymers of polyvinyl alcohol with a monomer, in particular selected from the group of the monoalkyl maleates (in particular monomethyl maleate), dialkyl maleates (in particular dimethyl maleate), maleic anhydride, and their combinations, and the alkali metal salts or esters of the above mentioned monomers. The values given for polyvinyl alcohols themselves apply to the suitable molar masses. In the context of the present invention, it is preferred that the at least one gel phase comprises a polyvinyl alcohol and / or its derivatives, preferably polyvinyl alcohol, the degree of hydrolysis of which is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 Mol% and especially 82 to 88 mol%.

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

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

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

Surprisingly, it has been shown that PVOH are particularly suitable for producing gel phases which meet the requirements shown above. Particularly preferred is therefore at least one gel phase which, in addition to at least one fused triazole, preferably benzotriazole and / or methyl 1 H -benzotriazole, in particular benzotriazole (preferably 1 H- benzotriazole), in each case based on the total weight of the gel phase, PVOH and at least one has polyhydric alcohol. The at least one gel phase particularly preferably has PVOH and at least one polyhydric alcohol.

According to the invention, the at least one gel phase comprises 0.5 to 4% by weight, in particular 1 to 3.5% by weight, of benzotriazole and / or methyl-1 H -benzotriazole, in particular benzotriazole (preferably 1 H- benzotriazole), PVOH and / or its derivatives in a proportion of about 4% by weight to 40% by weight, in particular from 6% by weight to 30% by weight, preferably from 7 to 24% by weight, particularly preferably between 8% by weight. -% to 22% by weight. Significantly lower proportions of PVOH do not lead to the formation of a stable gel phase. The values are based on the total weight of the gel phase.

According to a very particularly preferred embodiment, the at least one gel phase comprises PVOH (polyvinyl alcohol). The gel phases thus produced are particularly high-melting, dimensionally stable (even at 40 ° C) and do not change their shape even during storage or only marginally. In particular, they are also not very reactive with regard to a direct negative interaction with constituents of the granular mixture, in particular the powder phase. In particular, PVOH can also generate water-free or water-free gel phases without difficulty. When using PVOH as a polymer for the at least one gel phase, low-viscosity melts result at 110-120 ° C., which can be processed particularly easily as a result, in particular the gel phase can be poured into the water-soluble coating quickly and accurately without any Gluing takes place or the amount is metered inaccurately. Furthermore, these gel phases adhere particularly well to the water-soluble coating, especially if it is also made from PVOH. This is also visually advantageous. The rapid solidification of the at least one gel phase with PVOH means that the gel phases can be further processed particularly quickly. Furthermore, the good solubility of the gel phases produced is particularly favorable for the overall solubility of the cleaning agent. In addition, gel phases with such short solidification times are advantageous so that the at least one solid phase metered thereon, comprising granular mixtures, in particular powder, does not sink into the gel which has not yet solidified or is too soft. This leads to less appealing detergent portions.

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

The present invention furthermore relates to cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, which in the gel phase are at least one organic solvent, in particular selected from 1,2-propanediol, 1,3-propanediol, glycerol, 1,1,1 -Trimethylolpropane, triethylene glycol, dipropylene glycol, polyethylene glycols and / or mixtures thereof.

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

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

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

According to a particularly preferred embodiment, in the cleaning agents according to the invention, preferably dishwashing agents, in particular machine dishwashing agents, the at least one organic solvent in the gel phase is present in amounts of 1 to 90% by weight, in particular 5 to 85% by weight, particularly preferably of 10 to 80 wt .-%, based on the total weight of the gel phase.

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

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

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

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

It is particularly advantageous that the at least one gel phase or the gel phases, each based on the total weight of the gel phase, in addition to benzotriazole and / or methyl-1 H -benzotriazole, in particular benzotriazole (preferably 1 H -benzotriazole), preferably in amounts of 0.5 to 4 wt .-%, in particular 1 to 3.5 wt .-%, polyvinyl alcohol and at least one polyhydric alcohol, optionally additionally polyethylene glycols with an average molecular weight of about 200 to 600 g / mol in amounts of 5 to 30 wt .-%, preferably from 8 to 26 wt .-%, in particular from 10 to 22 wt .-% based on the total weight of the at least one gel phase.

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

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

A particularly preferred gel phase therefore comprises at least one fused triazole, preferably benzotriazole and / or methyl-1 H -benzotriazole, in particular benzotriazole (preferably 1 H- benzotriazole), PVOH, polyethylene glycol (s) with an average molecular weight of 200 to 600 g / mol and 1,3-propanediol and glycerin or 1,1,1-trimethylolpropane as polyhydric alcohols. Here, within a solidification time of 10 min or less, a non-flowable consistency that is stable at room temperature can be achieved, which remains dimensionally stable even after a long storage period. A corresponding phase is also transparent and has a glossy surface. A particularly preferred gel phase therefore comprises gelatin or PVOH as a polymer and 1,3-propanediol and glycerol or 1,1,1-trimethylolpropane as polyhydric alcohols.

In each case, based on the total weight of the gel phase, the gel phase comprises benzotriazole and / or methyl-1 H -benzotriazole, in particular benzotriazole (preferably 1 H- benzotriazole), preferably in amounts of 0.5 to 4% by weight, in particular 1 to 3.5% by weight, an alkanetriol, in particular glycerol or 1,1,1-trimethylolpropane, the proportion of alkanetriol, in particular glycerol or 1,1,1-trimethylolpropane, based on the total weight of the gel phase, is between 3 and 75% by weight, preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, particularly 20% by weight to 40% by weight.

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

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

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

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

In each case, based on the total weight of the gel phase, the gel phase comprises benzotriazole and / or methyl-1 H -benzotriazole, in particular benzotriazole (preferably 1 H- benzotriazole), preferably in amounts of 0.5 to 4% by weight, in particular 1 to 3.5% by weight, at least one alkanediol, in particular 1,3-propanediol or 1,2-propanediol, the proportion of alkanediol, in particular 1,3-propanediol or 1,2-propanediol, based on the total weight of the Gel phase, preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, particularly 20% by weight to 45% by weight. If 1,3-propanediol is contained in the gel phase, the proportion of 1,3-propanediol, based on the total weight of the gel phase, is in particular 10% by weight to 65% by weight, particularly 20% by weight to 45 wt .-%.

A gel phase is preferred, each based on the total weight of the gel phase in addition to benzotriazole and / or methyl-1 H -benzotriazole, in particular benzotriazole (preferably 1 H- benzotriazole), preferably in amounts of 0.5 to 4% by weight, in particular 1 to 3.5% by weight, 20 to 45% by weight of 1,3 propanediol and / or 1,2-propanediol and 10% by weight to 65% by weight of 2-amino-2-hydroxymethyl 1,3-propanediol, based in each case on the total weight of the gel phase. Also preferred is a gel phase containing 20 to 45% by weight of 1,3 propanediol and / or 1,2-propanediol and 10% by weight to 65% by weight of 1,1,1-trimethylolpropane, based in each case on the Total weight of the gel phase. A gel phase which contains 20 to 45% by weight of 1,3 propanediol and / or 1,2-propanediol and 10% by weight to 65% by weight of glycerol, in each case based on the total weight of the gel phase, is particularly preferred. It has been shown that a rapid solidification at 20 ° C. of a gel phase is possible in these areas, the phases obtained are stable in storage and transparent. The proportion of glycerine in particular has an effect on the curing time.

If the at least one gel phase according to the invention is based on the total weight of the gel phase in addition to benzotriazole and / or methyl-1 H -benzotriazole, in particular benzotriazole (preferably 1 H -benzotriazole), preferably in amounts of 0.5 to 4% by weight, in particular 1 to 3.5% by weight, a C ₃ to C ₆ alkanetriol and a C ₃ to C ₅ alkanediol, their weight ratio is preferably 3: 1 to 1: 2. In particular, the weight ratio is from 2: 1 to 1: 1.5, preferably from 1.5: 1 to 1: 1.2, preferably from 1.3 to 1: 1 if glycerol and 1,3-propanediol are polyhydric alcohols are included. Surprisingly, it has been shown that with these weight ratios, storage-stable, shiny, transparent gel phases can be obtained within 20 minutes or less at 20 ° C. In combination with polyethylene glycols with an average molecular weight of 200 to 600 g / mol, the preferred weight ratios, in particular weight ratios (C ₃ to C ₆ alkanetriol: C ₃ to C ₅ alkanediol) of 1.5: 1 to 1: 1.2, reduce to solidification times of 5 minutes and less.

According to a further preferred embodiment, in addition to the alkanols mentioned above, triethylene glycol can be present in the at least one gel phase, in particular the gel phases described above as preferred, in particular if this phase is PVOH and, if appropriate, polyethylene glycols with an average molecular weight of 200 to 600 g / mol contains. Triethylene glycol advantageously accelerates the solidification of the gel phase (s). It also results in the resulting gel phase, if at all, only slightly, unobservably, exchanging liquid with the environment. In particular, this improves the visual impression of the resulting detergent portions. It is particularly preferred if the at least one gel phase, based in each case on the total weight of the gel phase, in addition to benzotriazole and / or methyl-1 H -benzotriazole, in particular benzotriazole (preferably 1 H -benzotriazole), preferably in amounts of 0.5 to 4 % By weight, in particular 1 to 3.5% by weight, 1,3-and / or 1,2-propanediol, particularly preferably 1 to 3.5% by weight 1,3-propanediol, and glycerol between 0 , 1 and 20 wt .-%, preferably between 1 and 15 wt .-%, in particular between 5 and 12 wt .-%, for example 8 to 11 wt .-% triethylene glycol

Surprisingly, it has been shown that particularly good storage stability is achieved when the gel phase is low in water. Low water in the sense of the present invention means that small amounts of water can be used to produce the at least one gel phase. The proportion of water in the gel phase is in particular 20% by weight or less, preferably 15% by weight or less, particularly 12% by weight or less, in particular between 10 and 5% by weight. The data in% by weight relate to the total weight of the gel phase.

This has the advantage that the small amounts of water in combination with PVOH can have a structure or gel-forming effect.

According to a further embodiment, the at least one gel phase is essentially water-free. This means that the gel phase is preferably essentially free of water. “Essentially free” here means that small amounts of water can be present in the gel phase. This water can, for example, be introduced into the phase by means of a solvent or as water of crystallization or due to reactions of components of the phase with one another. However, no water is used as a solvent for the preparation of the gel phase. The proportion of water in the gel phase in this embodiment is 4.9% by weight or less, 4% by weight or less, preferably 2% by weight or less, in particular 1% by weight or less, particularly 0, 5 wt% or less, especially 0.1 wt% or 0.05 wt% or less. The data in% by weight relate to the total weight of the gel phase.

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

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

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

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H in which R ⁵ to R ⁷ independently of one another are —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 for -COOH or -COOR ⁴ 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 which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO - (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, - C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and - C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Preferred among these monomers are those of the formulas H ₂ C = CH-X-SO ₃ H, H ₂ C = C (CH ₃ ) -X-SO ₃ H or HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H, in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ and -CH (CH ₃ ) ₂ and X represents an optionally available 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-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl sulfopropyl acrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts. The sulfonic acid groups in the polymers can be wholly or partly in neutralized form, that is to say that the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

The monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95% by weight in each case 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 carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are here preferably selected from the aforementioned. The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred cleaning agents are characterized in that the copolymers have molar masses from 2000 to 200,000 g · mol ^-1 , preferably from 4000 to 25,000 g · mol ^-1 and in particular from 5000 to 15,000 g · mol ^-1 .

In a further preferred embodiment, in addition to the monomer containing carboxyl groups and monomer containing sulfonic acid groups, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer. By using these hydrophobically modified polymers, in particular the rinse aid of dishwashing detergents according to the invention could be improved.

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

The at least one gel phase particularly preferably further comprises an anionic copolymer, a copolymer comprising as the anionic copolymer

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

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

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1,2,4,4-trimethylpentene-2,2,3-dimethylhexene-1,2,4-dimethylhexene-1,2,5-dimethylhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, α-olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C ₂₂ -α-otefin, 2-styrene, α-methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid propyl ester, acrylic acid butyl ester, acrylate, acrylate, acrylate, acrylate N - (methyl) acrylamide, 2-ethylhexyl acrylic acid, 2-ethylhexyl methacrylate, N - (2-ethylhexyl) acrylamide, octyl acrylic acid esters, octyl methacrylate, N - (octyl) acrylamide, lauryl acrylate, Methacrylic acid lauryl ester, N - (lauryl) acrylamide, acrylic acid stearyl ester, methacrylic acid stearyl ester, N - (stearyl) acrylamide, acrylic acid behenyl ester, methacrylic acid behenyl ester and N- (behenyl) acrylamide or mixtures thereof, especially acrylic acid, ethyl acrylate, 2-acrylamido-2-methyl propane sulfonic acid their mixtures.

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

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

Very particularly preferred embodiments of the present invention comprise as at least one gel phase, based in each case on the total weight of the gel phase, in addition to benzotriazole and / or methyl-1 H -benzotriazole, in particular benzotriazole (preferably 1 H- benzotriazole), preferably in amounts of 0.5 to 4% by weight, in particular 1 to 3.5% by weight, 8 to 22% by weight PVOH, 15 to 40% by weight 1,3-propanediol, 20 to 40% by weight glycerin, 5 to 15% by weight sulfonic acid group-containing polyacrylate copolymer, and 8 to 22% by weight, in particular 10 to 20% by weight, polyethylene glycol with an average molecular weight of 200-600 g / mol, optionally 2 to 10% by weight 1 , 2-propanediol, and optionally also 2-15% by weight of triethylene glycol, each based on the total weight of the gel phase.

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

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

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

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

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

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

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

In addition to vinyl alcohol, preferred polyvinyl alcohol copolymers comprise dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, itaconic acid being preferred. Also preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester or mixtures thereof.

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

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

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

According to the invention, the water-soluble covering has at least one continuously rotating sealing seam, which lies essentially in one plane. This is favorable in terms of process technology, since only a single sealing step, if necessary using only a single sealing tool, is necessary for a circumferential sealing seam which lies essentially in one plane. The continuous circumferential sealing seam leads to a better seal compared to such wrappings with several sealing seams and an excellent tightness of the sealing seam and thus the wrapping itself. Product escaping from the wrapping, e.g. on the surface of the portion would be disadvantageous since the consumer would then come into contact with the product. This is exactly what should be avoided if possible with a portion of detergent with a water-soluble coating.

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

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

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

The at least one solid phase and the at least one gel phase can be arranged in any combination with one another within the water-soluble coating. A solid phase can be arranged on or next to a gel phase. In this embodiment, the cleaning agent according to the invention has a solid phase and a gel phase. It is also conceivable that a solid phase is surrounded by gel phases. Embedding one phase in another is also included according to the invention. In a further, particularly preferred arrangement, the gel phase is in a cast form, for example in the form of a gel core, which is surrounded by a solid phase. There may also be 2 or more cavities separated from one another which are filled with the at least one gel phase. In this embodiment, the cleaning agent comprises two gel phases, it being possible for the two gel phases to have different compositions.

According to a preferred embodiment there are 3, 4, 5 or 6 or more cavities separated from one another which are filled with one or more of the gel phases. Such cleaning agents preferably comprise 3, 4, 5 or 6 or more gel phases, it being possible for these gel phases to have the same or different compositions.

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

In this context, “solid” means that the composition is in solid form under standard conditions (temperature 25 ° C., pressure 1013 mbar). Suitable solid phases are, on the one hand, granular mixtures of a solid composition, such as powders and / or granules, in particular powdery phases. Also suitable according to the invention are solid compositions / phases which have an increased dimensional stability compared to the loose powder, for example powder or granule preparation which have been compressed by compression before or after being enclosed in the film, for example by restoring forces of the film after deep-drawing or directly compressed compositions such as compresses or tablets. This at least one solid phase can be in direct contact with the gel phase. According to the invention, there are also cleaning agent portions, in particular multi-chamber bags, in which the solid and the gel phase are in spatial proximity, but separate from one another. The two chambers can be made, for example, with a film, in particular a water-soluble film, or also with a sealed seam (preferably from a sealing seam of 3 mm or less). According to the invention are therefore superimposed as well as arranged side by side chambers of a multi-chamber pouch. Furthermore, mixtures of single- or multi-chamber bags, which comprise a gel-like phase according to the invention, comprising BZT, and separate therefrom, comprise at least one solid phase, which can be arranged, for example by folding and fixing a pouch, or by storing at a distance of less than 3 mm come into contact, for example in a packaging bag or a device for portioned dosing, according to the invention.

A powdery phase in the sense of the present invention is to be understood as a granular mixture which is formed from a large number of loose, solid particles which in turn comprise so-called grains. According to the invention, the term powder phase comprises powders and / or granules as defined below.

A grain is a term for the particulate constituents of powders (grains are the loose, solid particles), dusts (grains are the loose solid particles), granules (loose, solid particles are agglomerates of several grains) and other granular mixtures. A preferred embodiment of the granular mixture of the composition of the solid phase is the powder and / or the granules, if the term "powder" or "granules" is used here, it is also encompassed that these are also mixtures of different powders or different granules , Accordingly, powder and granules also mean mixtures of different powders with different granules. Said solid particles of the granular mixture again preferably have a particle diameter X _50.3 (volume average) of 10 to 1500 μm, more preferably 200 μm to 1200 μm, particularly preferably 600 μm to 1100 μm. These particle sizes can be determined by sieving or by means of a particle size analyzer Camsizer from Retsch. The granular mixture serving as the solid phase of the solid composition of the present invention is preferably in free-flowing form (particularly preferably as free-flowing powder and / or free-flowing granules). The agent of the portion according to the invention thus comprises at least one solid phase of a free-flowing, granular mixture of a solid composition, in particular a powder, and at least one gel phase as defined above.

A particularly preferred object of the present invention are cleaning agents, in particular cleaning agent portions, in which the gel phase is in direct contact, for example in a chamber, with which at least one solid phase is contained.
Even in such an arrangement, in which the gel-like phase is in direct contact with a solid phase, no discoloration of the powder phase was found after 21 days of storage (at 50 ° C. (not even in those places with direct contact)

Furthermore, it is preferred that the at least one solid phase and the at least one gel phase are in direct contact with one another. In this case there should be no negative interaction between the solid phase and the gel phase. No negative interaction here means, for example, that no ingredients or solvents pass from one phase to the other or that the stability, in particular storage stability, preferably at 4 weeks and 30 ° C. storage temperature, and / or the aesthetics of the product in some form, for example by Color change, formation of wet-looking edges, blurring boundary between the two phases or the like is impaired.

Surprisingly, it has been found that by formulation of a gel phase, preferably dimensionally stable gel phase comprising at least one fused triazole, preferably methyl-1H-benzotriazole and / or benzotriazole, in particular benzotriazole which a granular mixture of a solid-form composition, more particularly a powdery phase combined, this goal can be achieved. It is particularly suitable if the granular mixture of a solid composition, in particular the powdery phase, is free-flowing, since a process-specific filling of the water-soluble coating, in particular when filling a cavity produced by deep drawing, can thus be achieved. In addition, the optical appearance of the granular mixture of a solid composition, in particular of the powder, can be changed better compared to a compressed tablet, in particular texture differences, such as coarse and fine particles, and particles or areas with different colors, as a whole or as colored speckles, can be so can be used to improve a visually appealing appearance. The granular mixture of the solid composition, in particular the powder, also offers improved solubility compared to compressed tablets even without the addition of disintegrants.

A phase in the sense of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous. A phase differs from another phase by different features, for example ingredients, physical properties, external appearance, etc. Different phases can preferably be distinguished optically. For the consumer, the at least one solid phase must be clearly distinguished from the at least one gel phase. If the cleaning agent according to the invention has more than one solid phase, these can also be distinguished from one another with the naked eye, because they differ from one another in terms of color, for example. The same applies if there are two or more gel phases. In this case, too, an optical differentiation of the phases is possible, for example on the basis of a color or transparency difference. Phases in the sense of the present invention are thus self-contained areas that are visually visible to the naked eye from the consumer can be distinguished. When used, the individual phases can have different properties, such as, for example, the rate at which the phase dissolves in water and thus the rate and the order in which the constituents contained in the respective phase are released.

The at least one solid phase of the present invention comprises a granular mixture of a solid composition, in particular it is in powdery and free-flowing form. The cleaning agent according to the invention thus comprises at least one solid powdery and free-flowing phase, and at least one gel phase which contains at least one fused triazole, preferably tolytriazole and / or benzotriazole, in particular benzotriazole, and at least one polyvinyl alcohol, a gel former, in particular gelatin, xanthan and / or PVOH and / or its derivatives, particularly preferably at least PVOH, and at least one polyhydric alcohol.

The pourability of a granular mixture, in particular a powdery solid, the powdery phase, preferably the powder and / or granules, affects its ability to flow freely under its own weight. The flowability is determined by preferring the flow time of 1000 ml of detergent powder from a standardized flow test funnel with a discharge of 16.5 mm in diameter, which is initially closed at its discharge direction, by measuring the time for the granular batch, in particular the powdered phase, to completely flow out of the powder and / or granules, for example of the powder measured after opening the outlet and compared with the outlet speed (in seconds) of a standard test sample whose outlet speed is defined as 100%. The defined sand mixture for the calibration of the trickle equipment is dry sea sand. Sea sand with a particle diameter of 0.4 to 0.8 mm is used, available for example from Carl Roth, Germany CAS no. [14808-60-7]. For drying, the sea sand is dried for 24 hours at 60 ° C in a drying cabinet on a plate with a maximum layer height of 2 cm.

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

To determine the angle of repose (or slope angle) of the at least one solid phase, a powder funnel with a content of 400 ml and a drain with a diameter is used of 25mm just hung on a tripod. The funnel is moved upwards by means of a manually operated knurling wheel at a speed of 80 mm / min, so that the granular mixture, in particular the powdery phase, preferably trickles out the powder and / or granulate, for example the powder. This creates a so-called pouring cone. The height of the cone and the diameter of the cone are determined for the individual solid phases. The slope angle is calculated from the quotient of the cone height and the cone diameter * 100.

Such granular mixtures of a solid composition are particularly suitable, in particular such powdery phases, preferably the powders and / or granules, e.g. the powders which have a flowability in% of the standard test substance specified above of greater than 40%, preferably greater than 50, in particular greater than 55%, particularly preferably greater than 60%, particularly preferably between 63% and 80%, for example between 65% and 75 % exhibit. Particularly suitable are those granular mixtures of a solid composition, in particular those powders and / or granules which have a flowability in% of the standard test substance specified above of greater than 40%, preferably greater than 45%, particularly greater than 50%, particularly preferably greater than 55 %, particularly preferably greater than 60%, the measurement of the pourability being carried out 24 h after the preparation of the powder and storage at 20 ° C.

Lower values for the pourability are rather unsuitable, since from a process engineering point of view an exact dosage of the granular mixture, in particular the powdery phase, preferably the powder and / or granules, e.g. of the powder is necessary. In particular, the values greater than 50%, in particular greater than 55%, preferably greater than 60% (the free-flowing properties being measured 24 hours after the powder has been produced and stored at 20 ° C.) have proven to be advantageous, since the good meterability the granular mixture, in particular the powdery phases, preferably the powder and / or granules, for example Powder only show slight fluctuations in the metered amount or composition. The more precise dosing leads to a constant product performance, economic losses through overdosing are avoided. It is also advantageous that the granular mixture, in particular the powder phase, preferably the powder and / or granules, e.g. the powder can be dosed well, so that the dosing process runs faster. Furthermore, it is better avoided by such good flowability that the granular mixture, in particular the powdery phase, preferably the powder and / or granules, e.g. the powder reaches the part of the water-soluble coating which is intended for the production of the sealed seam and should therefore remain as granule-free as possible, in particular powder-free.

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

According to a preferred embodiment, the at least one, preferably all, solid phases are essentially free of 1H-benzotriazole and methyl-1H-benzotriazole, in particular free of fused triazoles, particularly preferably essentially free of triazoles.
“Essentially free” here means that only small amounts of triazoles can be present in the solid phase. The proportion of triazoles in the at least one solid phase, in particular in all solid phases, is in this embodiment 1.5% by weight or less, 1.0% by weight or less, preferably 0.5% by weight or less, in particular 0.1% by weight or less, particularly 0.05% by weight or less, in particular 0.01% by weight or 0.005% by weight or less. The percentages by weight relate to the total weight of the solid phase (s).

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

According to the invention, the at least one solid phase and / or the at least one gel phase comprise at least one surfactant. It is possible that only the at least one solid phase or only the at least one gel phase comprise at least one surfactant. If both phases comprise a surfactant, they are preferably different surfactants. However, it is also possible for the solid and gel phases to have the same surfactant or the same surfactants. At least one solid and / or gel phase according to the invention preferably contain at least one nonionic surfactant. All nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants. Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants, such as alkyl glycosides, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, polyhydroxy fatty acid amides or amine oxides. Particularly preferred nonionic surfactants are specified in more detail below.

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

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

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

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder einbeziehungsweise mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² beziehungsweise R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, -CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.Particularly preferred nonionic surfactants have been found in the context of the present invention for the low-foaming nonionic surfactants 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 follows from the other groups. Here are nonionic surfactants of the general formula

preferred, in which R ^{1 is} a straight-chain or branched, saturated or, 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 represent integers from 1 to 6.

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

In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit. However, other alkylene oxides in which R ² or R ³ are selected independently of one another from —CH ₂ CH ₂ —CH ₃ or —CH (CH ₃ ) ₂ are also suitable. Nonionic surfactants of the above formula are preferably used, in which R ² and R ³ for a radical —CH ₃ , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.

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

Nonionic surfactants of the general formula are preferred

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

wherein R, R ¹ and R ² independently of one another are an alkyl radical or alkenyl radical having 6 to 22 carbon atoms; x and y independently represent values between 1 and 40.

Compounds of the general formula are particularly preferred

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

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

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

Durch den Zusatz der vorgenannten nichtionischen Tenside der allgemeinen Formel R¹-CH(OH)CH₂O-(AO)_w-(A'O)_x-(A"0)_y-(A"'O)_z-R², nachfolgend auch als "Hydroxymischether" bezeichnet, kann überraschenderweise die Reinigungsleistung erfindungsgemäßer Zubereitungen deutlich verbessert werden und zwar sowohl im Vergleich zu Tensid-freien System wie auch im Vergleich zu Systemen, die alternative nichtionischen Tenside, beispielsweise aus der Gruppe der polyalkoxylierten Fettalkohole enthalten.Preferred nonionic surfactants are those of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (AO) _x - (A "O) _y - (A" O) _z -R ² , in which

• R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 represents} hydrogen or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A, A ', A "and A'" independently of one another for a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ),
• w, x, y and z stand for values between 0.5 and 120, where x, y and / or z can also be 0.

By adding the aforementioned nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "0) _y - (A"'O) _z -R ² , hereinafter also referred to as "hydroxy mixed ether", the cleaning performance of preparations according to the invention can surprisingly be significantly improved, both in comparison to a surfactant-free system and in comparison to systems which contain alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

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

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

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

Surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 up to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1.5 and y stands for a value of at least 15. The group of these nonionic surfactants includes, for example, the C _2-26 fatty alcohol (PO) ₁ - (EO) _15-40 -2-hydroxyalkyl ethers, in particular also the C _8-10 fatty alcohol (PO) ₁ - (EO) ₂₂ -2 -hydroxydecylether.

Those end group-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 are also particularly preferred, in which R ¹ and R ² independently of one another for a linear or branched, saturated or mono- or. polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} selected independently of one another from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH3, -CH (CH ₃ ) ₂ , but preferably stands for -CH ₃ , and x and y independently of one another have values between 1 and 32, nonionic surfactants with R ³ = -CH ₃ and values for x from 15 to 32 and y from 0.5 and 1.5 being very particularly preferred.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² , in which R ¹ and R ^{2 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 -Butyl or 2-methyl-2-butyl, x stands for values between 1 and 30, k and j stand for 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 may be} different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

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

• R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-24-Alkyl- oder -Alkenylrest steht;
• R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• A für einen Rest aus der Gruppe CH₂CH₂, CH₂CH₂CH₂, CH₂CH(CH₃), vorzugsweise für CH₂CH₂ steht, und
• w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht.

Particularly preferred end group-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH ) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x 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 carbon atoms, R ^{3 represents} H and x assumes values from 6 to 15. Finally, the nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ^{2 have} proven to be particularly effective in which

• R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical;
• R ^{2 represents} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A is a radical from the group CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH (CH ₃ ), preferably CH ₂ CH ₂ , and
• w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40.

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

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

In a further preferred embodiment, the nonionic surfactant of the solid and / or gel phase is selected from nonionic surfactants of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which R ¹ and R ² independently of one another are an alkyl radical or alkenyl radical having 4 to 22 carbon atoms; R ³ and R ⁴ independently of one another represent H or an alkyl or alkenyl radical having 1 to 18 carbon atoms and x and y independently of one another values between 1 and 40.

Compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² in which R ³ and R ^{4 are} H and the indices x and y are preferred independently of one another assume values from 1 to 40, preferably from 1 to 15. Particularly preferred are particularly compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which the radicals R ¹ and R ² independently of one another are saturated alkyl radicals with 4 to Represent 14 carbon atoms and the indices x and y independently assume values from 1 to 15 and in particular from 1 to 12. Also preferred are those compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _× CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² in which one of the radicals R ¹ and R ^{2 is} branched. Compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _× CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² are very particularly preferred, in which the indices x and y independently assume values from 8 to 12.

The stated C chain lengths and degrees of ethoxylation or alkoxylation of the nonionic surfactants represent statistical mean values which can be an integer or a fraction for a specific product. Because of the manufacturing processes, commercial products of the formulas mentioned usually do not consist of an individual representative, but of mixtures, which can result in mean values and fractional numbers for the C chain lengths as well as for the degrees of ethoxylation or alkoxylation.

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

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

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

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

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

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

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

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

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

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

According to a particularly preferred embodiment, the cleaning agents according to the invention are characterized in that the at least one gel phase is less than 1 % By weight, in particular less than 0.5% by weight, in particular less than 0.1% by weight of anionic surfactant, in each case based on the total weight of the gel phase.
The at least one gel phase is preferably essentially free of anionic surfactants. Essentially free means that the at least one gel phase contains less than 0.05% by weight of anionic surfactant, based in each case on the total weight of the gel phase.

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

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

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

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

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

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

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

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

In addition to their builder action, the free acids typically also have the property of an acidifying component. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

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

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

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

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

The cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents, can contain, in particular, phosphonates as further builders. A hydroxyalkane and / or aminoalkane phosphonate is preferably used as the phosphonate compound. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates in agents according to the invention are preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, very particularly preferably 2.5 to 7.5% by weight, in each case based on the total weight of the agent.

The combined use of citrate, (hydrogen) carbonate and phosphonate is particularly preferred. These can be used in the amounts mentioned above. In particular, in this combination, amounts of 10 to 25% by weight citrate, 10 to 30% by weight carbonate (or bicarbonate), and 2.5 to 7.5% by weight, based in each case on the total weight of the composition. Phosphonate used.

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

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

Polymeric polycarboxylates are also suitable as organic builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol. Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 1100 to 10000 g / mol, and particularly preferably from 1200 to 5000 g / mol, can in turn be preferred from this group.

The content of (homo) polymeric polycarboxylates in the cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents, is preferably 0.5 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight. Cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents, can furthermore contain crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably of 1.9 to 4, with particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20. Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are preferably delayed release and have secondary washing properties.

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

As a further constituent, cleaning agents according to the invention preferably contain enzyme (s) in the at least one solid and / or the at least one gel phase. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents, which are accordingly preferred. Cleaning agents according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 % by weight to 5% by weight, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

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

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae and the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, the α-amylase from Bacillus sp. A 7-7

(DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

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

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

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

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

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

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

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

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

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

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

Polymers suitable as additives are, in particular, maleic acid-acrylic acid copolymer Na salt (for example Sokalan® CP 5 from BASF, Ludwigshafen (Germany)), modified polyacrylic acid Na salt (for example Sokalan® CP 10 from BASF, Ludwigshafen (Germany )), modified polycarboxylate Na salt (for example Sokalan® HP 25 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example Silwet® L-77 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example Silwet® L-7608 from BASF, Ludwigshafen (Germany)) and polyether siloxanes (copolymers of polymethylsiloxanes with ethylene oxide / propylene oxide segments (polyether blocks)), preferably water-soluble linear polyether siloxanes with terminal polyether blocks such as Tegopren® 5840, Tegopren® 5843 5847, Tegopren® 5851, Tegopren® 5863 or Tegopren® 5878 from Evonik, Essen (De lish land). Builder substances suitable as additives are, in particular, polyaspartic acid sodium salt, ethylenediamine triacetate coconut alkylacetamide (for example Rewopol® CHT 12 from Evonik, Essen (Germany)), methylglycinediacetic acid tri-sodium salt and acetophosphonic acid. Mixtures with surfactant or polymeric additives show synergisms in the case of Tegopren® 5843 and Tegopren® 5863. The use of the Tegoprene types 5843 and 5863 is however with the Use on hard surfaces made of glass, especially glass dishes, less preferred, as these can pull silicone surfactants onto glass. In a particular embodiment of the invention, the additives mentioned are dispensed with.

A preferred cleaning agent, in particular machine dishwashing agent, preferably further comprises a bleaching agent, in particular an oxygen bleaching agent and optionally a bleach activator and / or bleaching catalyst. Where available, these are only contained in the at least one solid phase.

As a preferred bleaching agent, cleaning agents according to the invention contain an oxygen bleaching agent from the group sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Sodium percarbonate is particularly preferred for its good bleaching performance. A particularly preferred oxygen bleach is sodium percarbonate.

Bleach activators which can be used are 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. Substances which carry 0- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable. Multi-acylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) having proven to be particularly suitable.

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

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

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

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

If the at least one solid phase and the at least one gel phase border one another directly over the full or partial area, stability is important in addition to the shortest possible solidification time of the at least one gel phase. Stability here means that constituents contained in the gel phase do not pass into the at least one solid phase but, even after prolonged storage, the at least one solid phase and the gel phase are optically separate from one another and do not interact with one another, such as diffusion of liquid constituents of one in the other phase or reaction of components of one phase with those in the other phase. Surprisingly, it has been shown that this is achieved by a gel phase which, in addition to fused triazoles, preferably benzotriazole and / or methyl-1 H- benzotriazole, in particular benzotriazole, also polyethylene glycols with an average molecular weight of 200 to 600 g / mol, glycerol, PVOH and at least a C ₃ - to C ₅ alkanediol, can be made possible.

Another object of the present invention is the use of triazoles and / or their derivatives, in particular benzotriazole and / or methyl-1 H -benzotriazole, particularly preferably benzotriazole, to improve the gloss of a gel detergent.

Another object of the present invention is the use of triazoles and / or their derivatives, in particular benzotriazole and / or methyl-1 H -benzotriazole, particularly preferably benzotriazole, for reducing and / or inhibiting deposits on the wash ware, in particular on porcelain, plastic and / or stainless steel.

The present application also relates to a method for cleaning hard surfaces, in particular dishes, in which the surface is processed in a manner known per se using a cleaning agent according to the invention. In particular, the surface is brought into contact with the cleaning agent according to the invention. The cleaning is carried out in particular with a cleaning machine, preferably with a dishwasher.

Another object of the present invention is also the use of a cleaning agent, as described above, for cleaning hard surfaces, in particular dishes, in particular in automatic dishwashers.

The use of the method and the method that has been specifically disclosed for the cleaning agents apply accordingly.

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

EXAMPLES

Cleaning agents according to the invention were produced which comprised a solid phase and a gel phase. Different geometries were realized. Cleaning agents were also produced which comprised two solid phases and one gel phase. Cleaning agents were also produced, which comprised a solid phase as well as 3, 4 and 5 gel phases (of the same or different composition). The following information relates to% by weight of active substance based on the total weight of the respective phase (unless stated otherwise). Table 1: The solid granular mixtures of a solid composition, in particular powdery and free-flowing phases, had the following preferred composition: Wt .-% Citrate, Na salt 15-20 Phosphonate (e.g. HEDP) 2.5-7.5 MGDA, Na salt 0-25 Disilicate, sodium salt 5-35 soda 10-25 Percarbonate, Na salt 10-15 Bleaching catalyst (preferably Mn-based) 0.02-0.5 Bleach activator (e.g. TAED) 1-3 Non-ionic surfactant (s), for example fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 2.5-10 polycarboxylate 4 - 10 Cationic copolymer 0 - 0.75 Disintegrant - (e.g. Crosslinked PVP) 0 -1.5 Protease preparation (tq) 1.5-5 Amylase preparation (tq) 0.5-3 Perfume 0.05-0.25 dye solution 0.0 to 1 Zn salt (e.g. acetate) 0.1-0.3 sodium sulphate 0.0 - 10 water 0.0 to 1.5 pH adjusting agent (e.g. citric acid) 0-1.5 processing aids 0-5 Wt .-% Benzotriazole and / or methyl-1 H -benzotriazole 0.5-4.0 glycerin 10-50 Propanediol (preferably 1,3-propanediol) 10-50 Polycarboxylate copolymer with sulfonic acid groups 0-30 Non-ionic surfactant (s), for example fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 0-40 Polyethylene glycol average Mr 200-600, (e.g. PEG 400 (INCI) 8-26 PVOH 8-22 processing aids 0-10 dye solution 0.0 - 1.5

The solid and the gel phases could be combined with one another as desired. The spatial configuration of the gel phase, which was liquid after the ingredients had been mixed and had a stable shape within a solidification time of a maximum of 10 minutes, was determined by the spatial configuration of the solid phase and by commercially available or self-designed shapes. A water-soluble envelope in the form of an open pouch was produced by deep-drawing a PVOH-containing film. A liquid composition was poured into this open cavity, which gave the gel phase after curing, then solid phases in the form of a free-flowing solid were filled in a pouch comprising polyvinyl alcohol and the open pouch was then sealed by placing a second film and sealing by means of heat sealing. Table 3: Compositions V1, V2, E1, E2 In% by weight V1 V2 E1 E2 gel phase Polymer comprising acrylic acid and AMPS monomers 1.5 1.5 1.5 0.7 glycerin 5 5 5 5 1,3 propanediol 5 5 5 5 PEG 400 1.3 1.3 1.3 1.3 PVOH (Mowiol 4-88) 3 3 3 3 citric acid 1 1 1 1 benzotriazole - - 0.3 0.15 powder phase Citrate, Na salt 24 24 24 24 Phosphonate (e.g. HEDP) 7 7 7 7 Disilicate, sodium salt 2.5 2.5 2.5 2.5 soda 16 16 16 16 Percarbonate, Na salt 15 15 15 15 Bleaching catalyst (preferably Mn-based) 0,002 0,002 0,002 0,002 Bleach activator (e.g. TAED) 2 2 2 2 Fatty alcohol alkoxylate, 20-40 EO, possibly endcapped 4 4 4 4 Polymer comprising acrylic acid and AMPS monomers 7 7 7 7 benzotriazole 0.3 Protease preparation (tq) 2.8 2.8 2.8 2.8 Amylase preparation (tq) 0.5 0.5 0.5 0.5 Misc (including process aids, pH adjusting agents, perfume, dye) Add 100 Add 100 Add 100 Add 100

Corresponding formulations were prepared in accordance with Table 3 and packaged in single portions with a total weight of 18.5 g as described in Table 2.

Storage test:

To determine the product stability or discoloration, the recipes according to Table 3 are stored in screw-top jars for 7 days, 2 weeks and 3 weeks at 50 ° C. The discoloration of the powder phase is assessed visually by several people.

The formulation which contains benzotriazole in the powder formula (V1) shows a light yellow color after 7 days and a strong yellow color after 3 weeks, while the formulations E1 and E2 according to the invention show no change in the color of the powder phase.

Silver protection:

The silver protection was determined in Miele household dishwashers in a 65 ° C program after 25 and 50 cycles with a water hardness of 21 ° dH. 50 g of dirt are added per wash cycle to simulate a normally soiled load on the dishwasher. After completing the 25 or 50 cycles, the silver cutlery was in a black box a D6500 daylight lamp was assessed visually according to a rating scale of 1-5 (grade 1 = very strongly tarnished to grade 5 = not to very low tarnish) (Table 4). Table 4: Discoloration / start: V1 V2 E1 E2 Assessment after 25 cycles 2.8 2.8 2.8 3.3 Assessment after 50 cycles 2.5 1.8 2.3 2.8

The use of the BZT in the gel phase in E1 according to Table 4 shows the same performance as V1. If less BZT is used in the gel phase (E2), there is even better silver protection performance after 50 cycles.

polishing:

The polishability was determined using old silver cutlery in Miele household dishwashers in a 65 ° C program after 50 cycles with a water hardness of 21 ° dH. 50 g of dirt are added per wash cycle to simulate a normally soiled load on the dishwasher. After completion of the 25 or 50 cycles, the silver cutlery was assessed visually in a black box with a D6500 daylight lamp on the rating scale of 1-6 (see Table 5) (Table 6). Table 5: Evaluation scheme of the polishability Note 1 Cannot be polished out, very severe surface damage across the entire surface Grade 2 Cannot be polished out, significant surface damage in the entire area Note 3 Not fully polishable, slight surface damage in specific areas, heavy polishing required Grade 4 Fully polishable, strong polishing work required Grade 5 Fully polishable, medium level polishing required Grade 6 Fully polishable, little polishing work required polishing V1 V2 E1 50 cycles 4.3 2.8 4.8

The formulation E1 with BZT in the gel phase shows an improvement in the polishability of old silver cutlery in comparison to the formulation V1.

Surface Test:

The coating test was carried out in a Miele endurance running machine in a 65 ° C operation (10 min 65 ° CKS) program at 21 ° dH. In order to simulate a normally soiled load, 50 g of ballast dirt was dosed per rinse cycle. After 30 rinsing cycles, the test dishes (porcelain, plastic and stainless steel) in the black box (D6500 daylight lamp and outside of the black box under artificial light) were assessed visually according to Table 7, where 1 means very thick coating and 10 means no coating. Table 7: Evaluation scheme for coverings grade Appearance under artificial daylight: Note 1 Very strong Grade 2 Strong / very strong Note 3 strongly Grade 4 Medium / strong Grade 5 medium Grade 6 Low / medium Note 7 Low Note 8 Very low / low Note 9 Very little Grade 10 Nothing coverings stainless steel porcelain plates plastic V1 5.4 4.3 5 E1 6.2 5.3 6

The formulation E1 with BZT in the gel phase shows a significantly better coating result on porcelain, plastic and stainless steel than the formulation V1.

Claims (12)

Detergents, preferably dishwashing detergents, in particular machine dishwashing detergents, comprising a gel phase which contains fused triazoles and / or their derivatives, in particular unsubstituted benzotriazole and / or benzotriazole-substituted, in particular mono- to tri-alkyl-substituted, preferably in each case on the benzene ring with linear or branched alkyl radicals Benzotriazoles substituted with 1 to 4 carbon atoms, particularly preferably mono-, di- or trimethyl-substituted benzotriazoles on the benzene ring, preferably methylbenzotriazoles (monomethyl-1,2,3-benzotriazole) substituted on the benzene ring, for example 4-methyl-1 H- benzotriazole or 5-methyl-1 H -benzotriazole, and / or benzotriazole (1,2,3-benzotriazoles, 1H-benzotriazole). Cleaning agent according to claim 1, characterized in that the gel phase triazole and / or its derivatives, in particular benzotriazole and / or methyl-1 H- benzotriazole, particularly preferably benzotriazole, in an amount of 0.1 to 5 wt .-%, in particular from 0.5 to 4% by weight, very particularly preferably from 1 to 3.5% by weight, based on the total weight of the gel phase. Cleaning agent according to one of the preceding claims, characterized in that it is a gel former, preferably selected from gelatin, xanthan and / or polyvinyl alcohol, in particular gelatin or polyvinyl alcohol, particularly preferably polyvinyl alcohol, in an amount of 4 to 40, in particular 6 to 30,% by weight. -%, particularly preferably in an amount of 7 to 24 wt .-%, very particularly preferably 8 to 22 wt .-%, each based on the total weight of the gel phase. Cleaning agent according to one of the preceding claims, characterized in that the gel phase contains at least one organic solvent, in particular selected from 1,2-propanediol, 1,3-propanediol, glycerol, 1,1,1-trimethylolpropane, triethylene glycol, dipropylene glycol , Polyethylene glycols and / or mixtures thereof. Cleaning agent according to claim 4, characterized in that the at least one organic solvent in the gel phase in amounts of 1 to 90 wt .-%, in particular from 5 to 85 wt .-%, particularly preferably from 10 to 80 wt .-%, based on the total weight of the gel phase. Cleaning agent according to one of the preceding claims, characterized in that it additionally comprises at least one solid, in particular particulate phase and optionally at least one further liquid / gel-like or solid phase. Detergent according to one of the preceding claims, characterized in that it is a detergent portion in a water-soluble envelope with one or more chambers / compartments. Detergent according to one of claims 1 to 6, characterized in that the gel phase is in direct contact, for example in a chamber, with the at least one solid phase. Detergent according to one of the preceding claims, characterized in that at least one, preferably all, solid phases are essentially free, essentially free of benzotriazole and / or methyl-1 H -benzotriazole, in particular essentially free of triazoles. Use of a cleaning agent according to one of claims 1 to 9 for the mechanical cleaning of dishes. Use of triazoles and / or their derivatives, in particular benzotriazole and / or methyl-1 H -benzotriazole, particularly preferably benzotriazole, to improve the gloss of a gel-like cleaning agent. Use of triazoles and / or their derivatives, in particular benzotriazole and / or methyl-1 H -benzotriazole, particularly preferably benzotriazole, for reducing and / or inhibiting deposits on the wash ware, in particular on porcelain, plastic and / or stainless steel.