DE102018208651A1 - Process for the time-delayed metering of cleaning compositions in automatic dishwashers - Google Patents

Abstract

The present invention relates to a method for staggered dosing of cleaning compositions when cleaning in an automatic dishwashing machine, the method comprising the steps of: dosing a first cleaning composition, component K1, which comprises at least one enzyme, at a first time T1; thereafter adding a second cleaning composition, component K2, which comprises at least one oxidizing agent, at a second point in time T2, thereby bringing the objects to be cleaned into contact with the component K2, optionally carrying out one or more rinsing steps Water.

Description

The present invention relates to a process for the staggered metering of cleaning compositions when cleaning in an automatic dishwashing machine, the method comprising the steps of: dosing a first cleaning composition, component K1, which comprises at least one enzyme, at a first time T1; thereby bringing the objects to be cleaned into contact with the component K1; thereafter metering in a second cleaning composition, component K2, which comprises at least one oxidizing agent, at a second time T2; thereby bringing the objects to be cleaned into contact with the component K2; optionally carrying out one or more rinsing steps with water.

To increase the cleaning performance of machine dishwashing enzymes have been added to the detergents for a long time. In particular hydrolytic enzymes such as proteases and amylases are constituents of numerous dishwashing detergents. However, it is also known that detergents based only on enzyme-containing compositions, e.g. Remove insufficient coffee and tea stains on the objects to be cleaned.

Bleached cleaning compositions can very well remove this type of soiling. However, these compositions have weaknesses in the removal of stains such as minced meat, egg yolk or spaghetti. Therefore, a combination of enzymes and bleach-containing detergent compositions in detergents is desirable to remove these soils with different requirements in a single machine dishwashing cycle.

However, enzymes are unstable in the presence of oxidants and lose their activity. This is especially true for liquid cleaning compositions. Therefore, the cleaning performance of conventional cleaning compositions combining enzymes and bleaches in a composition is greatly reduced.

It is therefore sought to apply both enzymes and strong oxidizing agents, in particular chlorine-containing oxidizing agents, to the objects to be cleaned in a washing cycle of an automatic dishwashing machine, without reducing the cleaning performance, in particular that of the enzymes.

In order to solve this problem, the inventors have developed a method in which two separately prepared cleaning compositions are dispensed with a time delay in the dishwashing process.

The process according to the invention showed an excellent removal of bleachable stains and at the same time an improved removal of proteinaceous stains during the dishwashing process. Surprisingly, improved mincemeat cleaning performance compared to the individual components could be achieved.

• Zudosieren einer ersten Reinigungszusammensetzung, Komponente K1, welche mindestens ein Enzym umfasst, zu einem ersten Zeitpunkt T1;
• dadurch in Kontakt bringen der zu reinigenden Gegenstände mit der Komponente K1;
• danach Zudosieren einer zweiten Reinigungszusammensetzung, Komponente K2, welche mindestens ein Oxidationsmittel umfasst, zu einem zweiten Zeitpunkt T2;
• dadurch in Kontakt bringen der zu reinigenden Gegenstände mit der Komponente K2; gegebenenfalls Durchführen eines oder mehrerer Klarspülschritte mit Wasser.

In a first aspect, therefore, the invention relates to a process for the staggered metering of cleaning compositions when cleaning in an automatic dishwashing machine, the method comprising the steps:

• Dosing a first cleaning composition, component K1, which comprises at least one enzyme, at a first time T1;
• thereby bringing the objects to be cleaned into contact with the component K1;
• thereafter metering in a second cleaning composition, component K2, which comprises at least one oxidizing agent, at a second time T2;
• thereby bringing the objects to be cleaned into contact with the component K2; optionally carrying out one or more rinsing steps with water.

In a preferred aspect according to the preceding aspect, the component K1 is liquid, in particular in gel form, preferably with a water content of 0.01 to 70 wt .-%, more preferably from 0.1 to 40 wt .-%, and most preferably from 0.5 to 15 wt .-%, based on the total weight of component K1.

In a further preferred aspect according to one of the preceding aspects, the at least one enzyme in component K1 is selected from amylases and proteases or mixtures thereof.

Suitable amylase include Stainzyme® and Stainzyme® Plus (Novozymes) and / or Excellenz® S1000 from (Dupont).

In further preferred aspects according to one of the preceding aspects, the at least one enzyme in component K1 is present in an amount of 0.005 to 1.5% by weight, preferably 0.1 to 0.5% by weight, based on the total weight of Component K1 included. The amounts are based on commercially available enzyme formulations which consist only partially of active protein.

• mindestens ein Tensid, insbesondere mindestens ein nichtionisches Tensid; und/oder
• mindestens einen Verdicker; und/oder
• mindestens ein weiteres Additiv oder einen Zusatzstoff, das von den zuvor genannten Inhaltsstoffen verschieden ist, ausgewählt aus Puffersubstanzen, Gerüststoffen, Korrosionsinhibitoren, Schauminhibitoren, Komplexbildnern, Enzymstabilisatoren, Proteaseinhibitoren, Farbstoffen, Duftstoffen, organischen Lösungsmitteln, antimikrobiellen Wirkstoffen, oder Säuren und Basen zur pH-Einstellung;
• und Wasser.

In further preferred aspects according to any of the preceding aspects, component K1 further comprises

• at least one surfactant, in particular at least one nonionic surfactant; and or
• at least one thickener; and or
• at least one further additive or additive other than the aforementioned ingredients selected from buffer substances, builders, corrosion inhibitors, foam inhibitors, complexing agents, enzyme stabilizers, protease inhibitors, dyes, fragrances, organic solvents, antimicrobial agents, or acids and bases for pH; Attitude;
• and water.

In a further preferred aspect according to any of the preceding aspects, the at least one oxidizing agent in component K2 is a chlorine-based oxidizing agent, preferably the oxidising agent is selected from chlorine dioxide, calcium hypochlorite, potassium hypochlorite, sodium hypochlorite, in particular it is sodium hypochlorite.

In a further preferred aspect according to any of the preceding aspects, the at least one oxidizing agent in component K2 is in an amount of from 0.1 to 8.0% by weight, more preferably in from 0.15 to 3.0% by weight, and most preferably in 0.2 to 1.0% by weight, based on the total weight of component K2.

• mindestens ein Phosphonat; und/oder
• mindestens ein Alkalisierungsmittel; und/oder
• mindestens ein Silikat; und/oder
• mindestens ein weiteres Additiv oder einen Zusatzstoff, das zu den zuvor genannten Inhaltsstoffen verschieden ist, ausgewählt aus Puffersubstanzen, Gerüststoffen, Korrosionsinhibitoren, Schauminhibitoren, Komplexbildnern, Enzymstabilisatoren, Proteaseinhibitoren, Farbstoffen, Duftstoffen, organischen Lösungsmitteln, antimikrobiellen Wirkstoffen, oder Säuren und Basen zur pH-Einstellung;
• und Wasser.

In a further preferred aspect according to one of the preceding aspects, the component K2 further comprises

• at least one phosphonate; and or
• at least one alkalizing agent; and or
• at least one silicate; and or
• at least one further additive or additive other than the aforementioned ingredients, selected from buffer substances, builders, corrosion inhibitors, foam inhibitors, complexing agents, enzyme stabilizers, protease inhibitors, dyes, fragrances, organic solvents, antimicrobial agents, or acids and bases for pH; Attitude;
• and water.

In a further preferred aspect according to one of the preceding aspects, the method is characterized in that component K1 and / or K2 contain a bitter substance.

In a further preferred aspect according to one of the preceding aspects, the metered addition at the first time T1 and the metered addition at the second time T2 take place at a distance of 5 to 30 minutes, more preferably 7 to 20 minutes, most preferably 8 to 14 minutes.

According to the invention, component K1 is preferably substantially free from bleach, where "substantially free of bleach" means that preferably below 0.1 wt%, in particular below 0.01 wt%, and most preferably at all no bleach in Component K1 is included.

Furthermore, component K2 is preferably substantially free of enzyme, wherein "substantially free of enzyme" means that preferably below 0.05 wt%, in particular below 0.001 wt%, and most preferably at all no enzyme in component K2 is included.

"At least one" as used herein refers to 1 or more, for example, 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of constituents of the compound described herein, this indication does not refer to the absolute amount of molecules but to the nature of the constituent. Thus, "at least one enzyme" means, for example, one or more different enzymes, ie one or more different types of enzymes.

Unless indicated otherwise, all amounts stated in connection with the cleaning compositions described herein are based on% by weight, in each case based on the total weight of the respective cleaning composition or component. That is, such amounts, for example, in the context of "at least one enzyme," refer to the total amount of enzymes contained in the particular cleaning composition.

Numbers given herein without decimals refer to the full value, one decimal place, each. For example, "99%" stands for "99.0%".

The term "about" or "about", in the context of a numerical value, refers to a variance of ± 10% based on the given numerical value, preferably ± 5%, more preferably ± 1%.

In the present invention, molecular weights or molecular weights or molecular weights are described, unless explicitly stated otherwise, by the number average molecular weight M _N , which can be determined by gel permeation chromatography using polystyrene standards.

If a "substituted" compound is described, for example a substituted alkyl, then suitable substituents are known to the person skilled in the art, preferably a radical selected from -F, -Cl, -Br, -I, -OH, - NH ₂ , -NHR ¹ , -N (R ¹ ) ₂ , -COOH, -CF ₃ , -SH, -SR ¹ , = O, -OR ¹ , wherein R ^{1 is} an aliphatic hydrocarbon radical having 1 to 10 carbon atoms, which preferably one or more hydrogen atoms, depending on its binding, replaced at the respective compound.

These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention. Further, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular that the invention is not limited to these examples.

In the present invention, the terms cleaning composition, composition and component are used interchangeably and refer to a single component of the process which is metered in at a time of the process.

• Zudosieren einer ersten Reinigungszusammensetzung, Komponente K1, welche mindestens ein Enzym umfasst, zu einem ersten Zeitpunkt T1;
• dadurch in Kontakt bringen der zu reinigenden Gegenstände mit der Komponente K1;
• danach Zudosieren einer zweiten Reinigungszusammensetzung, Komponente K2, welche mindestens ein Oxidationsmittel umfasst, zu einem zweiten Zeitpunkt T2;
• dadurch in Kontakt bringen der zu reinigenden Gegenstände mit der Komponente K2;
• gegebenenfalls Durchführen eines oder mehrerer Klarspülschritte mit Wasser. Die Gegenstände sind dabei bevorzugt Geschirr.

In a first aspect, there is disclosed a method of staggered dosing of cleaning compositions in a machine dishwashing machine. The method comprises the steps:

• Dosing a first cleaning composition, component K1, which comprises at least one enzyme, at a first time T1;
• thereby bringing the objects to be cleaned into contact with the component K1;
• thereafter metering in a second cleaning composition, component K2, which comprises at least one oxidizing agent, at a second time T2;
• thereby bringing the objects to be cleaned into contact with the component K2;
• optionally carrying out one or more rinsing steps with water. The objects are preferably dishes.

The process according to the invention is preferably part of a conventional dishwashing program. Preferably, the first cleaning composition in the pre-rinse, preferably at 20 to 40 ° C, in particular 25 to 35 ° C added. More preferably, the second cleaning composition in the main rinse, preferably at 30 to 50 ° C, in particular at 35 to 45 ° C added. During the automatic dishwashing process, further process steps known to the person skilled in the art may be added or included in addition to the process steps according to the invention.

According to the invention, component K1 is metered in before component K2. Time-delayed means that a certain time elapses between the metered addition of component K1 and the metered addition of component K2, preferably a time between 5 to 30 minutes, more preferably between 7 to 20 minutes, and most preferably between 8 to 14 minutes.

The present invention contains at least two components K1 and K2. Other components, e.g. K3, K4, K5, etc. may additionally be contained in the process and / or added.

Preferably, the metered addition of the cleaning compositions K1 and K2 via a device for single or multiple dosing. The addition of the compositions can be carried out in each case from a water-soluble container. This may also be a water-soluble multi-chamber container in which the time-delayed addition of the preparations K1 and K2 preferably takes place during the wash cycle from separate chambers of this container.

The water-soluble container may in particular be a portion pack for the single-dose dispensing of a dishwashing agent into a dishwasher. Such portion packs are described in detail in the prior art. They can be present, for example, in the form of bags or injection-molded containers, and particularly preferably in the form of thermoformed bodies. Particularly preferred are injection-molded or deep-drawn containers of a water-soluble material such as polyvinyl alcohol, which contain the cleaning compositions K1 and K2 each in separate chambers.

Alternatively, the time-delayed addition of the cleaning compositions in the rinse from at least one, in particular a common, water-insoluble container. In this case, the at least one water-insoluble container is in particular a metering chamber of a dishwasher. The addition of the cleaning compositions into the dishwasher preferably takes place from separate water-insoluble containers.

It may be particularly advantageous if the separate water-insoluble container either component (s) of a mobile dispensing and dispensing system or a fixedly connected to a dishwasher dispensing and dispensing system. Movable in the sense of this application means that the dispensing and dosing is not permanently connected to a dishwasher, but can be removed, for example, from a dishwasher or positioned in a dishwasher.

For the purposes of the present invention, dispensing and metering systems, such as the applicant in her patent application, are particularly suitable WO 2009033828 A1 entitled "Dosing system for dispensing flowable or spreadable preparations" has described.

Further preferred is a dispensing and metering system which is movable in the sense as previously defined, and which in particular is equipped with its own energy source, preferably a source of electrical energy. Consequently, the delivery can be controlled electronically. This can be done by the dishwasher or by a separate, located outside the dishwasher control unit.

It is further preferred if the containers of the dispensing and metering system contain such large quantities of the cleaning compositions K1 and K2 that the dishwashing process can be carried out at least once, preferably several times in succession, without having to refill the containers.

Furthermore, the process according to the invention may be a cleaning process in a batch dishwasher, wherein the water-insoluble containers each have a multiple, preferably 10 to 50 times and especially 20 to 40 times those amounts of the cleaning compositions K1 and K2, as required for cleaning a machine load of dishes under normal operating conditions.

In addition to the aforementioned dispensing and metering systems, any other form of time-delayed metering of cleaning compositions, which is known to the person skilled in the art, can also be used for the method according to the invention.

In a preferred aspect, the cleaning composition K1 is liquid. "Liquid" means that the component at room temperature, ie about 20 ° C, in liquid form and in particular flowable and thus, for example, can be poured out of a container. More preferably, the cleaning composition K1 liquid, in particular thickened in gel form or pasty form, that is not solid, are present. More preferably, a water content in component K1 is from 1 to 95% by weight, more preferably from 10 to 90% by weight, and even more preferably from 20 to 85% by weight, particularly preferably from 60 to 80% by weight. % based on the total weight of the cleaning composition K1.

More preferably, component K2 is also liquid or gel. The terms are defined as for K1.

In addition to the preferably liquid components K1 and K2, it is also possible for further components K3, K4, K5 or K6 to be present in liquid and / or gelatinous and / or solid form in the purification process.

The components, in particular K1 and K2, are spatially separated from each other. The term "spatially separated" as used herein means that the components K1 and K2 can not contact each other prior to use.

In a further preferred aspect according to the preceding aspects, the at least one enzyme in component K1 is selected from amylases and proteases or mixtures thereof.

Among the proteases, those of the subtilisin type are preferable. Examples of these 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 as well as the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids 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 substitution in the positions D96LT213R and / or N233R, particularly preferably all of the exchanges D96L, T213R and N233R.

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

These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents, which are preferably used accordingly. The protein concentration can generally be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method ( Gornall AG, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 ). The determination of the active protein concentration can in this regard via a titration of the active sites using a suitable irreversible inhibitor and determination of the residual activity (see. Bender, M., et al., J. Am. Chem. Soc. 88, 24 (1966), p. 5890-5913 ) respectively.

Furthermore, oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

In a preferred aspect, the at least one enzyme in component K1 is in 0.001 to 1.5% by weight of active enzyme protein, preferably in 0.05 to 0.7% by weight of active enzyme protein, in particular 0.1 to 0, 5 wt .-% based on the total weight of component K1, included. If several enzymes are included, the abovementioned amounts of enzyme apply in each case to the individual enzyme.

In particular, it is preferred if at least one protease, preferably in amounts of 0.1 to 0.8 wt .-% active enzyme protein, and at least one alpha-amylase, preferably in amounts of 0.01 to 0.2 wt .-% active enzyme protein, each based on the total weight of component K1 are included. In addition, other enzymes, such as e.g. Be contained lipases or hemicellulases.

It is possible to assemble two or more enzymes together so that a single cleaning composition has multiple enzyme activities.

In a preferred aspect, the at least one oxidizing agent in component K2 is a chlorine-based oxidizing agent; in particular, the oxidizing agent is selected from chlorine dioxide, calcium hypochlorite, potassium hypochlorite, and sodium hypochlorite, more preferably sodium hypochlorite.

More preferably, the at least one oxidizing agent in component K2 is from 0.1 to 8.0 weight percent, more preferably from 0.15 to 3.0 weight percent, and most preferably from 0.2 to 1.0 Wt .-%, based on the total weight of component K2 included.

Furthermore, optionally further ingredients may be contained in component K1 and / or component K2 and / or the further components in addition to the ingredients already mentioned.

The group of surfactants which can be used according to the invention comprises the nonionic, the anionic, the cationic and the amphoteric surfactants, but in particular the nonionic surfactants.

Suitable nonionic surfactants are in principle all nonionic surfactants known to the person skilled in the art. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.

in der R für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the formula

wherein R is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula

R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Low-foaming nonionic surfactants are used as preferred surfactants. Cleaning compositions, in particular automatic dishwashing detergent compositions, particularly preferably comprise nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for. From coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 moles of EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. 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 therefore given to ethoxylated nonionic surfactants consisting of C _6-20 -monohydro) cyalkanols 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 mol 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 especially at least 20 mol of ethylene oxide. Of these, the so-called "narrow range ethoxylates" are particularly preferred.

With particular preference surfactants are further used which contain one or more tallow fatty alcohols with 20 to 30 EO in combination with a silicone defoamer.

Particular preference is given to nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred ,

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may 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 which have waxy consistency at room temperature are also preferred.

Nonionic surfactants from the group of alkoxylated alcohols, more preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-Niotenside, are also used with particular preference.

The nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. 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 constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred cleaning compositions are characterized in that they contain ethoxylated and propoxylated nonionic surfactants, in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.

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

More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

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

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

The 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 may vary depending on the origin of the alcohol. When native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of native origin having 12 to 18 C atoms, eg. B. from coconut, palm, tallow or oleyl alcohol, are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions, preference is given to nonionic surfactants in which R ¹ in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.

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

• • - R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• • - R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bei verzweigt 3 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.

Further, the nonionic surfactants of the general formula R ¹ -CH (OH) CHzO- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² , hereinafter also referred to as "Hydroxymix ethers", used in the

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

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

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

The group of these 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.

Preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² in which R ¹ and R ² independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values for x from 15 to 32 and y of 0.5 and 1.5 are 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 ] _x CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 Butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When 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, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when 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 may be joined 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 selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

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

• • - 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, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
• • - w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht

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

• • - R ¹ represents a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 is} 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 ), and
• • - w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40

The group of these nonionic surfactants include, 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 ethers and the C _4-22 fatty alcohol (EO) ₄₀ - ₈₀ 2-hydroxyalkyl ether.

Another preferred surfactant is a surfactant of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _{x [} CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ₂ in which R ^{1 is} a linear or branched one R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x and y is a value between 1 and 40, wherein the alkylene units [CH ₂ CH (CH ₃ ) O] and [CH ₂ CH ₂ O] randomized, ie in the form of a random random distribution.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.

Of course, the aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants. Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,

The cleaning compositions of the process according to the invention, in particular component K1, preferably contain nonionic surfactants based on ethoxylated fatty alcohols. Commercially available surfactants are Emulan® AT9, Emulan® AF, Dehypon® E124-90, Dehypon® E 127, Dehypon® GRA, Dehypon® KE 3447, Dehypon WET, Lutensol® AT 80, Lutensol® AT 25 and Lutensol® AT 50, all available from BASF, and Genapol® EC 50 from Clariant, with Dehypon® E 127 being preferred.

Suitable anionic surfactants are alkyl sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, olefin sulfonates, alkyl sulfonates, alkylbenzenesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates. Also usable in the context of the present invention are fatty acid cyanamides, sulfosuccinates (sulfosuccinic esters), in particular sulfosuccinic mono- and di-alkyl esters having 8 to 18 carbon atoms, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and α-sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glyceryl disulfate.

The anionic surfactants are preferably used as sodium salts, but may also be present as other alkali metal or alkaline earth metal salts, for example potassium or magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder - Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder - Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder-CO-O- und n eine ganze Zahl von 0 bis 5 ist. It is also possible according to the invention to use cationic and / or amphoteric surfactants, for example cationic surfactants of the following formulas:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

Preference is given to surfactants, in particular nonionic surfactants, in amounts of from 0.1 to 25% by weight, more preferably from 0.15 to 10% by weight, even more preferably from 0.2 to 5% by weight, based on the total weight of the respective cleaning composition, in particular in component K1, based on the total weight of component K1 used.

Component K1 preferably contains at least one thickener selected from polyacrylate thickeners, xanthan, gellan, guar, alginate, carrageenan, carboxymethylcellulose, bentonites, welan gum, locust bean gum, agar-agar, tragacanth, gum arabic, pectins, polysaccharides, starch, modified starch, Dextrins, gelatins and casein, modified celluloses, hydroxyethyl ethers and hydroxypropyl ethers, more preferably selected from xanthan, gellan, guar, alginate, carrageenan, carboxymethylcellulose, locust bean gum, agar-agar, tragacanth, gum arabic, pectins, starch, modified starch, dextrins, gelatins and casein, and modified celluloses, most preferably xanthan.

Preferably, at least one thickener in component K1 in amounts of 0.1 to 5 wt .-%, in particular from 0.15 to 1 wt .-%, based on the total weight of component K1, are used.

More preferably, complexing phosphonates may be included in the cleaning compositions, especially in component K2. They include a number of different compounds such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriamine penta (methylenephosphonic acid) (DTPMP). In particular, hydroxyalkane or aminoalkanephosphonates are preferred. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. As the phosphonate, HEDP is preferably used. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferable to use Aminoalkanphosphonate, in particular DTPMP, or to use mixtures of said phosphonates.

1. a) Aminotrimethylenphosphonsäure (ATMP) und/oder deren Salze;
2. b) Ethylendiamintetra(methylenphosphonsäure) (EDTMP) und/oder deren Salze;
3. c) Diethylentriaminpenta(methylenphosphonsäure) (DTPMP) und/oder deren Salze;
4. d) 1-Hydroxyethan-1,1-diphosphonsäure (HEDP) und/oder deren Salze;
5. e) 2-Phosphonobutan-1,2,4-tricarbonsäure (PBTC) und/oder deren Salze;
6. f) Hexamethylendiamintetra(methylenphosphonsäure) (HDTMP) und/oder deren Salze;
7. g) Nitrilotri(methylenphosphonsäure) (NTMP) und/oder deren Salze.

A preferably used within the scope of this application cleaning composition, in particular component K2, contains one or more phosphonate (s) from the group

1. a) aminotrimethylenephosphonic acid (ATMP) and / or salts thereof;
2. b) ethylenediaminetetra (methylenephosphonic acid) (EDTMP) and / or salts thereof;
3. c) diethylenetriamine penta (methylenephosphonic acid) (DTPMP) and / or salts thereof;
4. d) 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and / or salts thereof;
5. e) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or salts thereof;
6. f) hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and / or salts thereof;
7. g) nitrilotri (methylenephosphonic acid) (NTMP) and / or salts thereof.

Particularly preferred phosphonates are 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylene triamine penta (methylenephosphonic acid) (DTPMP), in particular 2-phosphonobutane-1,2, 4-tricarboxylic acid (PBTC).

Of course, the cleaning compositions may contain two or more different phosphonates.

Preference is given to phosphonates in amounts of 0.1 to 15 wt .-%, more preferably from 0.15 to 7 wt .-%, based on the total weight of the respective cleaning composition, in particular in component K2, based on the total weight of component K2, used.

Particularly suitable as alkalizing agents are the hydroxides, preferably alkali metal hydroxides, the carbonates, bicarbonates or sesquicarbonates, preferably alkali metal carbonates or alkali metal bicarbonates or alkali metal sesquicarbonates, preference being given for the purposes of this invention to the alkali metal hydroxides and alkali metal carbonates, in particular sodium hydroxide, potassium hydroxides, sodium carbonate, sodium bicarbonate or sodium sesquicarbonate Sodium hydroxide, potassium hydroxides, are used.

Preference is given to sodium and / or potassium hydroxide in amounts of 0.1 to 25 wt .-%, in particular from 0.15 to 20 wt .-%, based on the total weight of the respective component, preferably in component K2, based on the total weight of component K2.

Further preferred alkalizing agents are the organic amines, for example the primary and the secondary alkylamines, the alkyleneamines and mixtures of these organic amines. The group of preferred primary alkylamines include monoethylamine, monopropylamine, monobutylamine, monopentylamine and cyclohexylamine. The group of preferred secondary alkylamines includes in particular dimethylamine.

Particularly preferred alkalizing agents from the group of organic amines are the alkanolamines, in particular the primary, secondary and tertiary alkanolamines and mixtures thereof. Particularly preferred primary alkanolamines are monoethanolamine (2-aminoethanol, MEA), monoisopropanolamine, diethylethanolamine (2- (diethylamino) ethanol). Particularly preferred secondary alkanolamines are diethanolamine (2,2'-iminodiethanol, DEA, bis (2-hydroxyethyl) amine), N-methyl-diethanolamine, N-ethyl-diethanolamine. Diisopropanolamine and morpholine. Particularly preferred tertiary alkanolamines are triethanolamine and triisopropanolamine.

Crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, can also be used as builder where particularly preferred values for x are 2, 3 or 4 and y is a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8, and in particular from 1: 2 to 1: 2.6.

Preference is given to containing at least one silicate, in particular selected from sodium, potassium and lithium silicates or hydrates thereof, in particular in component K2. More preferably, sodium silicate is preferably present in amounts of 0.1 to 7 wt .-%, in particular from 1 to 5.5 wt .-%, based on the total weight of the respective component, preferably component K2 included.

The cleaning composition (s) K1 and / or K2 may preferably contain bitter substances. Bitter substances are known to the person skilled in the art and all ordinary bitter substances can be used For example, denatonium benzoate, glycosides, isoprenoids, alkaloids, amino acids and mixtures thereof. Particularly preferred is denatonium benzoate.

Preferred bittering agents have a bitter value of at least 1,000, preferably at least 10,000, more preferably at least 200,000. The standardized method described in the European Pharmacopoeia (5th Edition, Grundwerk, Stuttgart 2005, Volume 1 General Part Monograph Groups, 2.8.15 Bitter Value, p. 278) is used to determine the bitterness value. As a comparison serves an aqueous solution of quinine hydrochloride whose bitterness value is set at 200,000. This means that 1 gram of quinine hydrochloride makes 200 liters of water bitter. The interindividual taste differences in the organoleptic test of bitterness are compensated by a correction factor in this method.

In addition to the ingredients already mentioned, the cleaning compositions may contain at least one further additive or additive other than the aforementioned ingredients, selected from buffer substances, builders, corrosion inhibitors, foam inhibitors, complexing agents, enzyme stabilizers, protease inhibitors, dyes, fragrances, organic solvents, antimicrobial agents, or acids and bases for pH adjustment.

To adjust and / or stabilize the pH, the cleaning composition according to the invention may contain one or more buffer substances (INCI Buffering Agents). Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (chelating agents, INCI chelating agents). Particularly preferred buffer substances are the citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate 2H ₂ O and tripotassium citrate H ₂ O.

Sodium citrate is preferably present in amounts of from 0.1 to 15% by weight, in particular from 0.2 to 12% by weight, based on the total weight of the particular cleaning composition, in particular of component K1.

More preferably, component K1 may contain at least one complexing agent selected from polycarboxylic acids, polycarboxylates, polyacetals, dextrins, phosphates and phosphonates.

Suitable complexing agents are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here. With particular preference is used as a complexing agent, the citric acid or salts of citric acid. Further particularly preferred complexing agents are trisodium nitrilotriacetate, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), glutamic diacetic acid (GLDA) and methylglycine-diacid (MGDA).

Preferably used as a complexing agent in component K1 GLDA and / or MGDA, in particular MGDA or salts thereof, preferably in amounts of 0.1 to 25 wt .-%, in particular from 3 to 22 wt .-%, in particular from 5 to 20 Wt .-% based on the total weight of component K1.

The optionally usable polymers include, in particular, the cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. In general, it is also possible to use cationic, anionic and amphoteric polymers in addition to nonionic polymers.

"Cationic polymers" in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain. Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

For the purposes of the present invention, "amphoteric polymers" furthermore have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.

bei der R¹ und R⁴ unabhängig voneinander für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen steht; R² und R³ unabhängig voneinander für eine Alkyl-, Hydroxyalkyl-, oder Aminoalkylgruppe stehen, in denen der Alkylrest linear oder verzweigt ist und zwischen 1 und 6 Kohlenstoffatomen aufweist, wobei es sich vorzugsweise um eine Methylgruppe handelt; x und y unabhängig voneinander für ganze Zahlen zwischen 1 und 3 stehen. X repräsentiert ein Gegenion, vorzugsweise ein Gegenion aus der Gruppe Chlorid, Bromid, lodid, Sulfat, Hydrogensulfat, Methosulfat, Laurylsulfat, Dodecylbenzolsulfonat, p-Toluolsulfonat (Tosylat), Cumolsulfonat, Xylolsulfonat, Phosphat, Citrat, Formiat, Acetat oder deren Mischungen.Preferred cleaning compositions of the process according to the invention are characterized in that they contain a polymer which has monomer units of the formula R ¹ R ² C =CR ³ R ⁴ , in which each R ¹ , R ² , R ³ , R ^{4 is} independently selected from hydrogen, derivatized hydroxy group, C _1-30 linear or branched alkyl groups, aryl, aryl substituted C _1-30 linear or branched alkyl groups, polyalkoyxylierte alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group having a positive charge in the partial range of the pH range of 2 to 11, or salts thereof, with the proviso that at least one radical R ¹ , R ² , R ³ , R ^{4 is} a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group with a positive La training is. In the context of the present application, particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula

in which R ¹ and R ⁴ are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ^{3 are} independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X represents a counterion, preferably a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula are selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH , -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H.

werden im Falle von X^- = Chlorid auch als DADMAC (Diallyldimethylammonium-Chlorid) bezeichnet.Very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ¹ and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer unit of the formula

in the case of X ^- = chloride, they are also referred to as DADMAC (diallyldimethylammonium chloride).

in der R¹, R², R³, R⁴ und R⁵ unabhängig voneinander für einen linearen oder verzweigten, gesättigten oder ungesättigen Alkyl-, oder Hydroxyalkylrest mit 1 bis 6 Kohlenstoffatomen, vorzugsweise für einen linearen oder verzweigten Alkylrest ausgewählt aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, - CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, und -(CH₂CH₂-O)_nH steht und x für eine ganze Zahl zwischen 1 und 6 steht.Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula

in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of one another are a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , - CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H and x is an integer between 1 and 6.

werden im Falle von X^- = Chlorid auch als MAPTAC (Methyacrylamidopropyl-trimethylammoniumChlorid) bezeichnet. For the purposes of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ^{1 is} H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula

In the case of X ^- = chloride, also referred to as MAPTAC (Methyacrylamidopropyl trimethylammonium chloride).

According to the invention, preference is given to using polymers which contain diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.

The aforementioned amphoteric polymers have not only cationic groups but also anionic groups or monomer units. Such anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.

Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth ) -acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.

Also preferred are amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride. Particularly preferred amphoteric polymers are selected from the group consisting of the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid Copolymers and their alkali metal and ammonium salts. Particular preference is given to amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers as well as their alkali and ammonium salts.

Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference.

Particularly preferred as sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.

In the context of the present invention, unsaturated carboxylic acids of the formula R ¹ (R ² ) C =C (R ³ ) COOH are preferred as monomer in which R ¹ to R ^3, 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 by -NH ₂ , -OH or -COOH, or by -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the above formula are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H, R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) is preferred.

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 by -NH ₂ , -OH or -COOH or -COOH or -COOR ⁴ where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present spacer group which is selected from - (CH ₂ ) - where n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas H ₂ C =CH-X-SO ₃ H, H ₂ C =C (CH ₃ ) -X-SO ₃ H, HO ₃ SX- (R ¹ ) 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 , -CH (CH ₃ ) ₂ 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- and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids.

Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds. The content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers to be used consist only of monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH and monomers of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H.

At least one sulfonic acid group-containing polymer is preferably contained in component K1. More preferably, the commercially available anionic copolymer Acusol 588 from Dow Chemical Company may be contained in component K1.

Preferably, the sulfopolymer in an amount of 0.1 to 10.0 wt .-%, in particular from 1.0 to 5.0 wt .-%, based on the total weight of each component, in particular in component K1, based on the Total weight of component K1 added to the cleaning composition.

An enzyme contained in a preparation according to the invention can be protected especially during storage against damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage. In the case of microbial recovery of the enzymes, inhibition of proteolysis is particularly preferred, especially since the preparations contain proteases. Preferred cleaning compositions of the process according to the invention contain stabilizers for this purpose.

One group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, borinic acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or Salts or esters of the compounds mentioned. Also, peptide aldehydes, that is oligopeptides with a reduced C-terminus, especially those of 2 to 50 monomers are used for this purpose. Among the peptidic reversible protease inhibitors include ovomucoid and leupeptin. Also, specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Certain organic acids used as builders are capable of, as in WO 1997018287 A1 discloses additionally stabilizing a contained enzyme.

Lower aliphatic alcohols, but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers. Di-glycerol phosphate also protects against denaturation due to physical influences. Likewise, calcium and / or magnesium salts are used, such as calcium acetate or calcium formate.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polyamine N-oxide containing polymers act simultaneously as enzyme stabilizers and as dye transfer inhibitors. Other polymeric stabilizers are linear C ₈ -C ₁₈ polyoxyalkylenes. Alkyl polyglycosides can also stabilize and preferably increase the enzymatic components of the cleaning composition according to the invention in their performance. Crosslinked N-containing compounds preferably perform a dual function as soil release agents and as enzyme stabilizers. Hydrophobic, nonionic polymer stabilizes in particular an optionally contained cellulase.

Reducing agents and antioxidants increase the stability of the enzymes to oxidative degradation; For example, sulfur-containing reducing agents are familiar. Other examples are sodium sulfite and reducing sugars.

Particular preference is given to using combinations of stabilizers, for example of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The effect of peptide-aldehyde stabilizers is favorably enhanced by the combination with boric acid and / or boric acid derivatives and polyols, and still further by the additional action of divalent cations, such as calcium ions.

Another particularly preferred agent used to stabilize the enzymatic preparations is potassium sulfate (K ₂ SO ₄ ).

The cleaning compositions may additionally contain builders in component K1 and / or component K2 and / or in further components.

Suitable builders include aminocarboxylic acids and their salts, carbonates, organic cobuilders and silicates.

Aminocarboxylic acids and / or their salts represent another important class of builders. Particularly preferred members of this class are methylglycinediacetic acid (MGDA) or its salts, and glutamic diacetic acid (GLDA) or its salts or ethylenediamine diacetic acid or its salts (EDDS). Also suitable are iminodisuccinic acid (IDS) and iminodiacetic acid (IDA).

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals and dextrins.

Glutamic diacetic acid (GLDA) is preferably used, in particular N, N-bis (carboxymethyl) -L-glutamic acid or its salts, particularly preferably tetrasodium-N, N-bis (carboxymethyl) -L-glutamate. This substance is e.g. under the trade name Dissolvine GL 47S from AkzoNobel.

Possible, but not preferred, for example, is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate. Alkali carbonates, especially sodium carbonate, can also be used as pH adjusters.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a weight-average molecular weight of 500 to 70,000 g / mol.

Suitable polymers are in particular polyacrylates, which preferably have a weight-average molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have a weight-average molecular weight of from 2,000 to 10,000 g / mol, and particularly preferably from 3,000 to 5,000 g / mol, may in turn be preferred from this group. Preferably, the weight average molecular weight is determined by gel permeation chromatography using polystyrene standards.

Examples of particularly preferred substances to be used are Acusol 587D (polyacrylic sulfonate, Rohm & Haas / Dow Chemical), Acusol 445N (polycarboxylate sodium salt, Rohm & Haas / Dow Chemical Company), Acusol 590 (polyacrylate copolymer, Rohm & Haas / Dow Chemical), Acusol 916 (polyacrylate sodium salt, Rohm & Haas / Dow Chemical Co.), Sokalan CP42 (modified polycarboxylate sodium salt, BASF), Sokalan PA 30CL (polycarboxylate sodium salt, BASF), Dequest P 9000 (polymaleic acid, Thermphos), alginic acid, poly -2-acrylamido-2-methyl-1-propanesulfonic acid, poly-4-styrene-sulfonic acid co-maleic acid sodium salt, poly-acrylamido-co-acrylic acid sodium salt, poly-methacrylic acid sodium salt, poly-methyl vinyl ether-old maleic acid or polyvinylsulfonic acid sodium salt.

More preferably, a polyacrylate compound in amounts of 0.1 to 5 wt .-%, in particular from 0.15 to 3 wt .-%, based on the total weight of the respective cleaning composition, in particular in component K2, based on the total weight of Component K2, are used.

Suitable acids for pH adjustment are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid, most preferably citric acid. In addition, however, it is also possible to use the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof.

Furthermore, citric acid is preferably present in amounts of from 0.1 to 15% by weight, in particular from 0.15 to 5% by weight, based on the total weight of the respective cleaning composition, in particular in component K1, based on the total weight of component K1, contain.

Suitable bases are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal carbonates, of which sodium carbonate is preferred.

As perfume oils or perfumes, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

Furthermore, the cleaning compositions may contain corrosion inhibitors. (Glass) corrosion inhibitors prevent the occurrence of turbidity, streaks and scratches but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and / or zinc salts and / or magnesium and / or zinc complexes.

Preferably, the composition may also contain dyes. Dyes are known to those skilled in the art and any of the ordinary dyes can be used so long as they have no negative interaction with the other components of the composition.

Likewise, it is preferred that drugs with antimicrobial activity before or / and after the cleaning compositions of the main wash cycle are used. The use of active ingredients with antimicrobial action in the pre-rinse cycle has the advantage that the spread and multiplication of microbes in the main rinse cycle is prevented or at least reduced. However, the active ingredient is then washed away with the rinsing liquor.

For their antimicrobial efficacy, e.g. cationic surfactants, in particular with a sulfonium, phosphonium, iodonium or arsonium group.

The products of the Acticide® family from Thor GmbH are optionally usable as suitable antimicrobial agents.

In a further preferred aspect, the metered addition is carried out at the first time T1 and the metered addition at the second time T2 at a distance of 5 to 30 minutes, preferably 7 to 20 minutes, more preferably 8 to 14 minutes.

The total weight of the respective cleaning composition is preferably between 3 and 35 g, in particular between 5 and 10 g.

Examples

Cleaning compositions which can be used in the process according to the invention are summarized in the following tables (Table 1: EG1-4 and Table 2: FC 1-4). Table 1: Component K1: Enzyme-containing gel (EC) (all data, unless otherwise stated, based on active substance in% by weight). EC1 EC2 EC3 EC4 Wt .-% sodium citrate 9.5 9.5 9.5 9.5 citric acid 1.2 1.2 1.2 1.2 MGDA (40% in water) 18.5 18.5 18.5 18.5 calcium chloride 0.2 0.2 0.2 0.2 Xanthan gum 0.4 0.4 0.4 0.4 Sulfonic acid group-containing acrylate copolymer 4.5 4.5 4.5 4.5 Nonionic surfactant * 2.0 2.0 2.0 2.0 Cationic acrylate copolymer ** (20% in water) 6.7 6.7 6.7 6.7 Protease (wt% of active enzyme) 0.13 0.3 0.35 0.05 Amylase (wt% of active enzyme) 0.02 0.1 0.02 0.1 water Ad 100 Ad 100 Ad 100 Ad 100 * ethoxylated fatty alcohol ** rinse aid polymer Table 2: Component K2: Liquid chlorine bleach (FC) (all data, unless otherwise stated, based on active substance in% by weight). FC1 FC2 FC3 FC4 Wt .-% 2-phosphonobutane-1,2,4-tricarboxylic acid 4.0 4.0 4.0 4.0 potassium hydroxide 10.0 10.0 10.0 10.0 sodium hydroxide 5.0 5.0 5.0 5.0 Sodium hypochlorite (15% in water) 3.1 1.5 5.5 2.1 water glass 3.2 3.2 3.2 3.2 sodium polyacrylate 2.3 2.3 2.3 2.3 water Ad 100 Ad 100 Ad 100 Ad 100

In a Miele GSL 2 dishwasher at 45 ° C (R45 ° / 8 '/ KL55 ° C) and 21 ° dH crockery was rinsed with various stains and after each rinse cycle visually determines the cleaning performance according to IKW (2016) (evaluation of 1-10 the higher the value, the better the performance, differences of at least 1 are significant). The individual cleaners were introduced via the metering chamber. When combining both cleaners, EG1 was added directly via the dosing chamber and the cleaner FC1 10 minutes later. For this purpose, various cleaning compositions were dosed. The results for the recipes tested are listed in Table 3 as arithmetic mean (n = 3). Table 3: Cleaning performance on stubborn stains. tea minced meat egg yolk spaghetti EG1, 29g 1.7 1.2 1.7 4.4 FC1, 25g 7.7 1.0 0.3 1.4 EG1 + FC1, 54g 6.2 4.6 1.3 2.1

The results make it clear that the combination of enzyme-containing gel and liquid chlorine bleach, which are metered time-delayed, results in a good cleaning performance of tea and even an improved cleaning performance of minced meat soils.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2009033828 A1 [0037]
• WO 1997018287 A1 [0142]

Cited non-patent literature

• Gornall, C.S. Bardawill and M.M. David, J. Biol. Chem., 177 (1948), pp. 751-766 [0051]
• Bender, M., et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913 [0051]

Claims (10)

A method of staggered dosing of cleaning compositions when cleaned in an automatic dishwashing machine, the method comprising the steps of: Dosing a first cleaning composition, component K1, which comprises at least one enzyme, at a first time T1; thereby bringing the objects to be cleaned into contact with the component K1; thereafter metering in a second cleaning composition, component K2, which comprises at least one oxidizing agent, at a second time T2; thereby bringing the objects to be cleaned into contact with the component K2; optionally carrying out one or more rinsing steps with water. Method according to Claim 1 wherein the component K1 is liquid, in particular in gel form, preferably with a water content of 1 to 95 wt .-%, more preferably from 10 to 90 wt .-%, even more preferably from 20 to 85 wt .-%, in particular preferably from 60 to 80 wt .-%, based on the total weight of component K1. Method according to one of the preceding claims, wherein the at least one enzyme in component K1 is selected from amylases and proteases or their mixture. Method according to one of the preceding claims, wherein the at least one enzyme in component K1 in 0.001 to 1.5 wt .-%, preferably 0.05 to 0.7 wt .-%, in particular 0.1 to 0.5 wt. -% of active enzyme protein based on the total weight of component K1 is included. Method according to one of the preceding claims, wherein the component K1 further at least one surfactant, in particular at least one nonionic surfactant; and or at least one thickener; and or at least one further additive or additive other than the aforementioned ingredients, selected from buffer substances, builders, corrosion inhibitors, foam inhibitors, complexing agents, enzyme stabilizers, protease inhibitors, dyes, fragrances, organic solvents, antimicrobial agents, or acids and bases for pH; Attitude; and water includes. A process according to any one of the preceding claims, wherein the at least one oxidant in component K2 is a chlorine based oxidant, preferably the oxidant is selected from chlorine dioxide, calcium hypochlorite, potassium hypochlorite, sodium hypochlorite, in particular it is sodium hypochlorite. A process according to any one of the preceding claims, wherein the at least one oxidizing agent in component K2 is present in 0.1 to 8.0 wt.%, Preferably in 0.15 to 3.0 wt.%, And more preferably in 0.2 to 1.0 wt .-%, based on the total weight of component K2, is included. Method according to one of the preceding claims, wherein the component K2 further at least one phosphonate; and or at least one alkalizing agent; and or at least one silicate and or hydrates thereof; and or at least one further additive or additive other than the aforementioned ingredients, selected from buffer substances, builders, corrosion inhibitors, foam inhibitors, complexing agents, enzyme stabilizers, protease inhibitors, dyes, fragrances, organic solvents, antimicrobial agents, or acids and bases for pH; Attitude; and water includes. Method according to one of the preceding claims, characterized in that component K1 and / or K2 contain a bitter substance. Method according to one of the preceding claims, wherein the metering takes place at the first time T1 and the metered addition at the second time T2 at a distance of 5 to 30 minutes, preferably 7 to 20 minutes, in particular 8 to 14 minutes.