EP2029719B1 - Cleaning process - Google Patents

Abstract

A method of machine cleaning dishes in a dishwasher, wherein over the course of a cleaning program, having a pre-rinsing operation and a cleaning operation, two liquid cleansers A and B having the following composition: A:—10 to 75 wt % of builder(s); −0.1 to 10 wt % of enzyme(s); −24.9 to 89.9 wt % of solvent; and B: −10 to 74.9 wt % of builder(s); −25 to 89.9 wt % of solvent; are metered into the wash bath at two successive times t1 and t2. The liquid cleanser A has a pH value (20° C.) of between 6 and 9 and is metered in at time t1, while the liquid cleanser B has a pH value (20° C.) of between 9 and 14 and is metered in at time t2.

Description

The present application relates to a method for cleaning dishes. In particular, this application relates to a process for cleaning crockery, in which liquid cleaning agents are dosed with a time delay in the interior of a dishwasher.

Dishwashing detergents are available to the consumer in a variety of forms. In addition to the traditional liquid hand dishwashing detergents, machine dishwashing detergents are particularly important with the spread of household dishwashers. These automatic dishwashing agents are typically offered to the consumer in solid form, for example as a powder or as tablets.

One of the major goals of the machine cleanser manufacturers is to improve the cleaning performance of these agents, with a recent focus on cleaning performance in low temperature or reduced water consumption cleaning cycles.

To solve these objects, the cleaning agents were preferably added new ingredients, for example, more effective surfactants, polymers or bleach. However, since new ingredients are available only to a limited extent and the amount of ingredients used for each cleaning cycle can not be increased to any extent for ecological and economic reasons, this approach has natural limits.

Another approach to improving the performance profile of existing detergents or cleaners is to develop new ready-made forms, for example, in the combination of solid and liquid detergents or cleanser ingredients.

This application was based on the object to provide a detergent for dishwashing, which is distinguished from conventional dishwashing detergents even at low-temperature cleaning cycles or cleaning cycles with low water consumption by improved cleaning performance.

This object has been achieved by a special dishwashing method in which liquid detergents are dispensed with a time delay into the interior of a dishwasher.

• A:
  • 10 bis 75 Gew.-% Gerüststoff(e);
  • 0,1 bis 10 Gew.-% Protease;
  • 24,9 bis 89,9 Gew.-% Lösungsmittel; und
• B:
  • 10 bis 74,9 Gew.% Gerüststoff(e);
  • 25 bis 89,9 Gel.-% Lösungsmittel;
  • weniger als 0,1 Gew.-% Enzym;

in den Innenraum der Geschirrspülmaschine eindosiert werden, wobei das flüssigeA first subject of this application is therefore a method for the automatic cleaning of dishes in a dishwasher, characterized in that in the course of a Cleaning program, which includes a prewash cycle and a cleaning cycle, in this cleaning cycle on two consecutive times t1 and t2 two liquid detergents A and B of the composition:

• A:
  • From 10% to 75% by weight of builder (s);
  • 0.1 to 10% by weight of protease;
  • 24.9 to 89.9% by weight of solvent; and
• B:
  • 10 to 74.9% by weight builder (s);
  • From 25 to 89.9% by weight of solvent;
  • less than 0.1% by weight of enzyme;

be metered into the interior of the dishwasher, wherein the liquid

Detergent A contains from 0.1 to 10 wt .-% enzyme, a pH (20 ° C) between 6 and 9 and is metered at time t1, while the liquid detergent B a pH (20 ° C) between 9 and 14 and is metered at time t2, wherein the pH (20 ° C) of the liquid detergent A from the pH (20 ° C) of the liquid detergent B differs by at least two units, characterized in that the time difference between the times t1 and t2 is 2 to 30 minutes.

The inventive method is carried out in the interior of a commercial dishwasher. The cleaning program can usually be selected and determined by the consumer in a dishwashing machine before the dishwashing process is carried out.

The cleaning program of the dishwasher used in the method according to the invention comprises at least one prewash cycle and one cleaning cycle. According to the invention, cleaning programs which include further cleaning or rinsing operations, for example a rinse cycle, are preferred. The inventive method is therefore not limited to such cleaning programs that consist exclusively of a pre-rinse and a cleaning cycle.

The process according to the invention is particularly preferably part of a cleaning program, comprising a prewash cycle, a cleaning cycle and a rinse cycle. The automatic dishwashing detergent programs may differ in terms of their duration, their water consumption and the temperature of the cleaning liquor. The process of the invention is preferably used in conjunction with such cleaning programs in which the wash liquor is heated in the course of the cleaning cycle.

In a preferred embodiment of the method according to the invention, the cleaning cycle, in the course of which the cleaning agents A and B are metered into the interior of the dishwasher, is characterized in that in its course Temperature of the cleaning liquor to values above 30 ° C, preferably above 40 ° C and especially above 50 ° C increases.

The temperature of the wash liquor at time t1 is in a preferred embodiment between 12 and 45 ° C, preferably between 15 and 40 ° C and in particular between 20 and 35 ° C, while the temperature of the wash liquor at time t2 preferably between 30 and 65 ° C, preferably between 35 and 60 ° C and in particular between 40 and 55 ° C.

At the time of dosing the detergent A and B, the wash liquor may have the same or different temperatures. Preferably, the temperature of the wash liquor at time t1 is different from the temperature of the wash liquor at time t2, wherein the temperature at time t1 may be above or below the temperature at time t2. Particularly advantageous cleaning results could be achieved in methods according to the invention in which the temperature of the wash liquor was below the temperature of the wash liquor at time t 2 at time t 1. Corresponding methods are therefore preferred

To optimize the cleaning performance in the process according to the invention, the temperature of the wash liquor at time t2 is preferably at least 5 ° C, preferably at least 10 ° C and especially between 10 and 40 ° C, but especially between 10 and 20 ° C above the temperature of the wash liquor at time t1.

The metering of the two liquid cleaning agents A and B takes place in the course of the cleaning cycle at two successive times t1 and t2, the cleaning agent A being metered in at time t1 and the cleaning agent B at time t2 and the time t1 being earlier than time t2.

The time t1 is preferably within the first ten minutes after the beginning of the cleaning cycle, preferably within the first eight minutes after the beginning of the cleaning cycle and in particular within the first five minutes after the beginning of the cleaning cycle.

The time difference between the times t1 and t2 is between 2 and 30 minutes, preferably between 4 and 25 minutes and in particular between 6 and 20 minutes.

To optimize the cleaning performance in the method according to the invention, it is further provided to keep the pH values of the cleaning agents A and B within narrow limits. Preferred methods are characterized in that the cleaning agent A has a pH (20 ° C) between 6.5 and 8.5, preferably between 7 and 8, while the pH (20 ° C) of the cleaning agent B between 9 , 5 and 13, preferably between 10 and 12.

The pH (20 ° C) of the liquid detergent A differs from the pH (20 ° C) of the liquid detergent B by at least two units, since achieved in this method particularly good cleaning results can be.

The cleaning agents A and B are preferably conveyed from a self-sufficient dosing device into the interior of the dishwasher. As "self-sufficient" while a dosing device is called, which is not an integral part of the dishwasher used. Such a metering device preferably has its own storage container for the cleaning agents A and B and its own metering device for conveying and metering the cleaning agents A and B into the interior of the dishwasher. In a particularly preferred embodiment, the dosing device is further provided with a stand-alone power supply.

The cleaning agents A and B can each be conveyed via an independent dosing device into the interior of the dishwasher. However, it is preferable to combine the cleaning agents A and B in a common metering device with each other. The liquid detergents A and B are in a preferred embodiment in a water-insoluble two- or multi-chamber reservoir ago. The cleaning agents A and B are preferably spatially separated from each other in this container and are metered from this container into the interior of the dishwasher. By separating the detergents from each other, physical and chemical interactions of the detergents are prevented.

The volume of the respective chambers of the reservoir is preferably sufficient for receiving at least five, preferably at least ten and more preferably at least 20 dosing units of a cleaning agent A or B. Since the dosage amount of the cleaning agent A and B in the course of a cleaning process preferably between 5 and 50 ml, preferably between 10 and 40 ml and in particular between 10 and 30 ml, the preferred volume of the storage chamber for the cleaning agent A and for the cleaning agent B is at least 25 ml, preferably at least 50 and in particular at least 100 ml. Preference is given metering devices, each having a chamber for the cleaning agents A and B, wherein the volume of each of these chambers is between 50 and 1000 ml, preferably between 100 and 800 ml and in particular between 200 and 600 ml.

Surprisingly, it was found that the cleaning performance in the method according to the invention, in addition to the parameters mentioned above, can also be influenced by the metering rate of the metering device. The metering rate of the metering device is preferably between 1 and 40 ml per minute, preferably between 2 and 30 ml per minute and in particular between 4 and 20 ml per minute.

The cleaning agents A and B used in the process according to the invention contain builders in addition to other ingredients which are active in washing or cleaning. Among the builders count in particular, the zeolites, silicates, carbonates, organic cobuilders and -where there are no ecological prejudices against their use- also the phosphates.

Particular preference is given to using crystalline layer-form 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, where especially preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layer-form silicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS -3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, Makatite).

Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O, in which x is 2. In particular, both β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ .yH ₂ O and also, above all, Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O _5, natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3 H ₂ O, kanemite), Na-SKS-11 ( t-Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ).

The liquid detergents A and / or B preferably contain a proportion _by weight of the crystalline layered silicate of the formula NaMSi _x O _{2x + 1} · y H ₂ O of 0.1 to 20 wt .-% of 0.2 to 15 wt .-% and in particular from 0.4 to 10 wt .-%, each based on the weight of the respective cleaning agent A or B, are included.

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, which preferably delayed release and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle ,

Alternatively or in combination with the abovementioned amorphous sodium silicates, X-ray amorphous silicates are used whose silicate particles produce blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such X-ray amorphous silicates also have a dissolution delay compared to conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

In the context of the present invention, it is preferred that these silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous Alkalidisilikate, in the liquid detergent A and / or B in amounts of 2 to 40 wt .-%, preferably from 3 to 30 wt.% And in particular from 5 to 25 wt .-%, each based on the weight of the respective cleaning agent A or B, are included.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Technically particularly important phosphates are the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate). The sodium potassium tripolyphosphates are also preferably used according to the invention.

If phosphates are used as washing or cleaning substances in the liquid detergents A and / or B in the context of the present application, preferred combination products contain these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate), in amounts of 5 to 60 wt .-%, preferably from 15 to 45 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the respective cleaning agent A or B. , are included.

As organic cobuilders are in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and To name phosphonates. These classes of substances are described below.

Useful organic builders 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 addition to their builder action, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these are particularly preferred call.

The citric acid or salts of citric acid are used with particular preference as builder substance. Combination products, characterized in that the at least one of the cleaning agent A or B contains citric acid or a salt of citric acid and the weight fraction of citric acid or the salt of citric acid, based on the total weight of the cleaning agent, between 0.2 and 12 wt .-% , preferably between 0.2 and 8 wt .-% and in particular between 0.2 and 6 wt .-%, are inventively preferred.

Another particularly preferred builder substance is methylglycine diacid (MGDA). Process according to the invention, characterized in that the cleaning agent contains methylglycinediacetic acid or a salt of methylglycinediacetic acid and that the weight fraction of methylglycinediacetic acid or the salt of methylglycinediacetic acid is preferably between 0.2 and 12% by weight, preferably between 0.2 and 8% by weight and in particular between 0.2 and 6 wt .-%, are preferred according to the invention.

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

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data in which Polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

The content of detergents or cleaners to (co) polymeric polycarboxylates is preferably 0.1 to 10 wt .-%, preferably 0.2 to 8 wt .-%, particularly preferably 0.4 to 6 wt .-% and in particular between 0.4 and 4 wt .-%.

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,

Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are selected from dialdehydes such as glyoxal, Glutaraldehyde, terephthalaldehyde and mixtures thereof and from Palyolcarbonsäuren such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and Welßdextrine with higher molecular weights in the range of 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. Here, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts Further preferred in this context are glycerol disuccinates and glycerol trisuccinates.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as builders.

As a further constituent, the composition used as cleaning agent A in the process according to the invention contains proteases. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 × 10 ^-6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the Bluret method.

Among the proteases, those of the subtilisin type are preferable. Examples thereof are the subtilisins BPN 'and Carlsberg and their further 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.

In addition to proteases, in particular amylases, lipases, hem cellulases, cellulases or oxidoreductases may be present in the composition.

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 nlger and A. oryzae and the further developments of the aforementioned amylases which are improved for use in detergents and cleaners. Furthermore, for this purpose, the α-amylase from Becillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

1. (1) M9L / M202I,
2. (2) M9L / M202I / M323T,
3. (3) M9L / M202I / M323T / M382Y,
4. (4) M9L / M202I / Y295F / A339S,
5. (5) M9L / M202I / Y295F,
6. (6) M9L / M202I / A339S,
7. (7) M9L / M202I / Y295F / A339S,
8. (8) M9L / M202I / Y295F / A339S / E345R,
9. (9) M9L / G149A / M202I / Y295F / A339S / E345R,
10. (10) M9L / M202L,
11. (11) M9L / M202L / M323T,
12. (12) M9L / M202L / M323T / M382Y,
13. (13) M9L / M202L / Y295F / A339S,
14. (14) M9L / M202L / Y295F,
15. (15) M9L / M202L / A339S,
16. (16) M9L / M202L / Y295F / A339S,
17. (17) M9L / M202L / Y295F / A339S, E345R,
18. (18) M9L / G149A / M202L / Y295F / A339S / E345R,
19. (19) M9L / M202T,
20. (20) M9L / M202T / M323T,
21. (21) M9L / M202T / M323T / M382Y,
22. (22) M9L / M202T / Y295F / A339S,
23. (23) M9L / M202T / Y295F,
24. (24) M9L / M202T / A339S,
25. (25) M9L / M202T / Y295F / A339S,
26. (26) M9L / M202T / Y295F / A339S / E345R,
27. (27) M9L / G149A / M202T / Y295F / A339S / E345R,
28. (28) M9L / G149A / M2021 / V214T / Y295F / N299Y / M323T / A339S / E345R,
29. (29) M9L / G149A / M202L / V214I / Y295F / M323T / A339S / E345R / M382Y,
30. (30) M9L / G149A / G182T / G186A / M202I / V214I / Y295F / N299Y / M323T / A339S,
31. (31) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R,
32. (32) M9L / G149A / M202L / V214T / Y295F / N299Y / M323T / A339S / E345R,
33. (33) M9L / G149A / M2021 / V2141 / Y295F / M323T / A339S / E345R / M382Y,
34. (34) M9L / G149A / G182T / G186A / M202L / V214I / Y295F / N299Y / M323T / A339S,
35. (35) M9L / G149A / G182T / G186A / M202I / T257I / Y295F / N299Y / M323T / A339S / E345R,
36. (36) M9L / G 149A / M202I / V214T / Y295F / N299Y / M323T / A339S / E345R / N471 E,
37. (37) M9L / G149A / M202L / V214I / Y295F / M323T / A339S / E345R / M382Y / N471 E,
38. (38) M9L / G149A / G182T / G186A / M202I / V214I / Y295F / N299Y / M323T / A339S / N471 E,
39. (39) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R / N471 E,
40. (40) M202L / M105F / M208F,
41. (41) G133E / M202L / Q361E,
42. (42) G133E / M202L / R444E,
43. (43) M202L / Y295F,
44. (44) M202L / A339S,
45. (45) M202L / M323T,
46. (46) M202L / M323T / M309L,
47. (47) M202L / M323T / M430I,
48. (48) M202L / V214T / R444Y,
49. (49) M202L / N283D / Q361E,
50. (50) M202L / M382Y / K383R,
51. (51) M202L / K446R / N484Q,
52. (52) M202I / Y295F,
53. (53) M202I / A339S,
54. (54) M202I / M105F / M208F,
55. (55) G133E / M2021 / Q361E,
56. (56) G133E / M202I / R444E,
57. (57) M202I / M323T,
58. (58) M202I / M323T / M309L,
59. (59) M202I / M323T / M430I,
60. (60) M202I / V214T / R444Y,
61. (61) M2021 / N283D / Q361E,
62. (62) M202I / M382Y / K383R,
63. (63) M202I / K446R / N484Q,
64. (64) M202V / M105F / M208F,
65. (65) G133E / M202V / Q361E,
66. (66) G133E / M202V / R444E,
67. (67) M202V / M323T,
68. (68) M202V / M323T / M309L,
69. (69) M202V / M323T / M430I,
70. (70) M202V / M323T / M9L,
71. (71) M202V / V214T / R444Y,
72. (72) M202V / N283D / Q361 E,
73. (73) M202V / M382Y / K383R,
74. (74) M202V / K446R / N484Q,
75. (75) M202T / M105F / M208F,
76. (76) G133E / M202T / Q361 E,
77. (77) G133E / M202T / R444E,
78. (78) M202T / Y295F,
79. (79) M202T / A339S,
80. (80) M202T / M323T,
81. (81) M202T / M323T / M309L,
82. (82) M202T / M323T / M430I,
83. (83) M202T / M323T / M9L,
84. (84) M202T / V214T / R444Y,
85. (85) M202T / N283D / Q361E,
86. (86) M202T / A339S,
87. (87) M202T / Y295F
88. (88) M202T / N299F,Y,
89. (89) M202T / M382Y / K383R oder
90. (90) M202T / K446R / N484Q

An α-amylase variant which can be obtained either from an α-amylase AA560-homologizable starting α-amylase via amino acid changes in the following positions has proven to be particularly suitable for use in methods according to the invention: 9, 149, 182, 186, 202, 257, 296, 299, 323, 339, 345 and optionally further (in the count according to the α-amylase AA560) or which can be obtained from the α-amylase AA560 via the following amino acid changes:

1. (1) M9L / M202I,
2. (2) M9L / M202I / M323T,
3. (3) M9L / M202I / M323T / M382Y,
4. (4) M9L / M202I / Y295F / A339S,
5. (5) M9L / M202I / Y295F,
6. (6) M9L / M202I / A339S,
7. (7) M9L / M202I / Y295F / A339S,
8. (8) M9L / M202I / Y295F / A339S / E345R,
9. (9) M9L / G149A / M202I / Y295F / A339S / E345R,
10. (10) M9L / M202L,
11. (11) M9L / M202L / M323T,
12. (12) M9L / M202L / M323T / M382Y,
13. (13) M9L / M202L / Y295F / A339S,
14. (14) M9L / M202L / Y295F,
15. (15) M9L / M202L / A339S,
16. (16) M9L / M202L / Y295F / A339S,
17. (17) M9L / M202L / Y295F / A339S, E345R,
18. (18) M9L / G149A / M202L / Y295F / A339S / E345R,
19. (19) M9L / M202T,
20. (20) M9L / M202T / M323T,
21. (21) M9L / M202T / M323T / M382Y,
22. (22) M9L / M202T / Y295F / A339S,
23. (23) M9L / M202T / Y295F,
24. (24) M9L / M202T / A339S,
25. (25) M9L / M202T / Y295F / A339S,
26. (26) M9L / M202T / Y295F / A339S / E345R,
27. (27) M9L / G149A / M202T / Y295F / A339S / E345R,
28. (28) M9L / G149A / M2021 / V214T / Y295F / N299Y / M323T / A339S / E345R,
29. (29) M9L / G149A / M202L / V214I / Y295F / M323T / A339S / E345R / M382Y,
30. (30) M9L / G149A / G182T / G186A / M202I / V214I / Y295F / N299Y / M323T / A339S,
31. (31) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R,
32. (32) M9L / G149A / M202L / V214T / Y295F / N299Y / M323T / A339S / E345R,
33. (33) M9L / G149A / M2021 / V2141 / Y295F / M323T / A339S / E345R / M382Y,
34. (34) M9L / G149A / G182T / G186A / M202L / V214I / Y295F / N299Y / M323T / A339S,
35. (35) M9L / G149A / G182T / G186A / M202I / T257I / Y295F / N299Y / M323T / A339S / E345R,
36. (36) M9L / G149A / M202I / V214T / Y295F / N299Y / M323T / A339S / E345R / N471E,
37. (37) M9L / G149A / M202L / V214I / Y295F / M323T / A339S / E345R / M382Y / N471E,
38. (38) M9L / G149A / G182T / G186A / M202I / V214I / Y295F / N299Y / M323T / A339S / N471 E,
39. (39) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R / N471 E,
40. (40) M202L / M105F / M208F,
41. (41) G133E / M202L / Q361E,
42. (42) G133E / M202L / R444E,
43. (43) M202L / Y295F,
44. (44) M202L / A339S,
45. (45) M202L / M323T,
46. (46) M202L / M323T / M309L,
47. (47) M202L / M323T / M430I,
48. (48) M202L / V214T / R444Y,
49. (49) M202L / N283D / Q361E,
50. (50) M202L / M382Y / K383R,
51. (51) M202L / K446R / N484Q,
52. (52) M202I / Y295F,
53. (53) M202I / A339S,
54. (54) M202I / M105F / M208F,
55. (55) G133E / M2021 / Q361E,
56. (56) G133E / M202I / R444E,
57. (57) M202I / M323T,
58. (58) M202I / M323T / M309L,
59. (59) M202I / M323T / M430I,
60. (60) M202I / V214T / R444Y,
61. (61) M2021 / N283D / Q361E,
62. (62) M202I / M382Y / K383R,
63. (63) M202I / K446R / N484Q,
64. (64) M202V / M105F / M208F,
65. (65) G133E / M202V / Q361E,
66. (66) G133E / M202V / R444E,
67. (67) M202V / M323T,
68. (68) M202V / M323T / M309L,
69. (69) M202V / M323T / M430I,
70. (70) M202V / M323T / M9L,
71. (71) M202V / V214T / R444Y,
72. (72) M202V / N283D / Q361 E,
73. (73) M202V / M382Y / K383R,
74. (74) M202V / K446R / N484Q,
75. (75) M202T / M105F / M208F,
76. (76) G133E / M202T / Q361 E,
77. (77) G133E / M202T / R444E,
78. (78) M202T / Y295F,
79. (79) M202T / A339S,
80. (80) M202T / M323T,
81. (81) M202T / M323T / M309L,
82. (82) M202T / M323T / M430I,
83. (83) M202T / M323T / M9L,
84. (84) M202T / V214T / R444Y,
85. (85) M202T / N283D / Q361E,
86. (86) M202T / A339S,
87. (87) M202T / Y295F
88. (88) M202T / N299F, Y,
89. (89) M202T / M382Y / K383R or
90. (90) M202T / K446R / N484Q

With particular preference, the α-amylase variant is characterized by additionally one or more amino acid changes in the following positions relative to an α-amylase AA560 homologizable starting α-amylase: 118, 183, 184, 195, 320 and 458 (in Counting according to the α-amylase AA560), wherein the α-amylase variant preferably has in particular the following amino acid position assignments: 118K, 183- (deletion), 184- (deletion), 195F, 320K and / or 458K (in the count according to the α Amylase AA560).

• (10) M9L / M202L,
• (28) M9L / G149A / M202I / V214T / Y295F / N299Y / M323T / A339S / E345R,
• (31) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R,
• (35) M9L / G149A / G182T / G186A / M202I / T257I / Y295F / N299Y / M323T / A339S / E345R,
• (38) M9L / G149A / G182T / G186A / M202I / V214I / Y295F / N299Y / M323T / A339S / N471E,
• (39) M9L / G 149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R / N471E.
• (45) M202L / M323T,
• (46) M202L / M323T / M309L,
• (62) M202I / M382Y / K383R,
• (68) M202V / M323T / M309L,
• (73) M202V / M382Y / K383R
• (82) M202T / M323T / M430I
• (84) M202T / V214T / R444Y.

An α-amylase variant which can be derived from the α-amylase AA560 or a derivative thereof, and preferably derived therefrom, is particularly preferred. Particular preference is given to detergents which are used according to the invention and which contain an α-amylase variant which has one of the following amino acid changes compared to α-amylase AA560:

• (10) M9L / M202L,
• (28) M9L / G149A / M202I / V214T / Y295F / N299Y / M323T / A339S / E345R,
• (31) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R,
• (35) M9L / G149A / G182T / G186A / M202I / T257I / Y295F / N299Y / M323T / A339S / E345R,
• (38) M9L / G149A / G182T / G186A / M202I / V214I / Y295F / N299Y / M323T / A339S / N471E,
• (39) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R / N471E.
• (45) M202L / M323T,
• (46) M202L / M323T / M309L,
• (62) M202I / M382Y / K383R,
• (68) M202V / M323T / M309L,
• (73) M202V / M382Y / K383R
• (82) M202T / M323T / M430I
• (84) M202T / V214T / R444Y.

The above-mentioned preferred α-amylase variants have been distinguished by an above-average storage stability and cleaning performance, in particular during storage and metering by means of automatic metering systems which contain sufficient cleaning agents for several cleaning cycles, which is why these cleaning agents can be stored in these metering systems for a long time.

In addition to the described α-amylase variant, detergents preferably used according to the invention preferably contain a subtilisin protease, the subtilisin protease being a wild-type protease or a protease variant, and the protease variant preferably being one with an amino acid change relative to a starting protease homologizable with the Bacillus lentus alkaline protease in one or more of the following positions: 3, 4, 36, 42, 43, 47, 56, 61, 69, 87, 96, 99, 101, 102, 104, 114, 118, 120, 130, 139, 141, 142, 154, 157, 188, 193, 199, 205, 211, 224, 229, 236, 237, 242, 243, 250, 253, 255 and 268, in the count of the alkaline protease from Bacillus lentus.

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 exchange D96L. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens . It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii .

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

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. 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 in highly different redox potentials between the oxidizing enzymes and the soiling (mediators).

The enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-form compositions, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers. Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

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

A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

A protein and / or enzyme contained in an agent according to the invention can be protected against damage, for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, in particular during storage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Preferred agents according to the invention contain stabilizers for this purpose.

One group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric 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 the 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 97/18287 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. Also, alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and, preferably, are capable of additionally increasing 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 combinatons 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 agent used with particular preference for stabilizing the enzymatic preparations is potassium sulfate (K ₂ SO ₄ ).

As stated at the outset, the weight ratio of the enzymes in the total weight of the liquid cleaning agent A is between 0.1 and 10% by weight. In particularly preferred combination products, the proportion by weight of the enzyme in the total weight of the cleaning agent A is between 0.2 and 9% by weight and in particular between 0.5 and 8% by weight.

The enzyme content of the detergent B was less than 0.1 wt .-%. Particularly preferred methods according to the invention are characterized in that the liquid cleaning agent B contains no enzymes.

Preferably, one or more enzymes and / or enzyme preparations, preferably solid or liquid protease preparations are used. In a particularly preferred embodiment, the liquid cleaning agent A comprises a combination of protease and amylase preparations.

As a further constituent, the cleaning agents A and B used in the process according to the invention contain a solvent. In the simplest embodiment, this solvent is exclusively water. A method, characterized in that the liquid cleaning agent A and / or the liquid cleaning agent B contains water as solvent, are preferred.

Surprisingly, it has been found that the cleaning performance can be improved in a process according to the invention by the addition of organic solvents. The preferred subject matter of the present application is therefore furthermore a process according to the invention in which at least one of the cleaning agents A or B further contains an organic solvent, the organic solvent being used alone, as a mixture of several organic solvents or as a mixture of one or more organic solvents with water can.

Preferred organic solvents are derived, for example, from the groups of monoalcohols, diols, triols or polyclins, ethers, esters and / or amides. Particular preference is given to organic solvents which are water-soluble, "water-soluble" solvents for the purposes of the present application being solvents which are completely miscible with water at room temperature, ie without mixing gap.

Organic solvents which can be used in the process according to the invention are preferably from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the concentration range indicated. Preferably, the solvents are selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, Etheylenglykolmonon-butyl ether, diethylene glycol methyl ether, di-ethylenglykolethylether , Propylenglykolmethyl-, ethyl or propyl ether, Dipropylenglykolmethyl- or ethyl ether, methoxy, ethoxy or Butoxytriglykol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and Mixtures of these solvents.

The organic solvents from the group of the organic amines and / or the alkanolamines have proven to be particularly effective with regard to the cleaning performance and again with regard to the cleaning performance of bleachable soilings, in particular of tea stains.

Particularly preferred organic amines are the primary and secondary alkylamines, the alkyleneamines and mixtures of these organic amines. The group of preferred primary alkylamines include monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine and cyclohexylamine. The group of preferred secondary alkylamines includes in particular dimethylamine.

Preferred alkanolamines are 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.

Particularly powerful process variants are characterized in that the liquid cleaning agent A and / or the liquid cleaning agent B contains a solvent from the group of organic solvents, wherein the organic solvent is preferably an organic amine and / or an alkanolamine, preferably ethanolamine is.

If the cleaning agents A and / or B further comprise water in addition to the organic amine, preference is given to those processes according to the invention in which the weight ratio of water to organic amine and / or alkanolamine in the cleaning agent A or B is more than 1: 1, preferably more than 2: 1 and in particular more than 5: 1.

Another object of this application is the use of organic amines, in particular the aforementioned organic amines and / or alkanolamines in a process according to the invention, for the purification of bleachable stains, preferably for cleaning Teeanschmutzungen on hard surfaces.

Particularly preferred cleaning agents A and / or B contain, based on the total weight of the respective cleaning agent, between 0.1 and 10 wt .-%, preferably between 0.5 and 8 wt .-% and in particular between 1.5 and 6 wt. % of an organic solvent from the group of organic amines and alkanolamines. Particular preference is given to processes according to the invention in which the liquid cleaning agent B, based on the total weight of the cleaning agent B, has a weight fraction of an organic solvent from the group of the organic amine and the alkanolamines between 0.1 and 10% by weight, preferably between 0, 5 and 8 wt .-% and in particular between 1.5 and 6 wt.%, While the weight fraction of organic solvent from the group of organic amines and alkanolamines in the liquid detergent A, based on the total weight of the cleaning agent A, preferred is less than 5 wt .-%, preferably less than 3 wt .-%, more preferably less than 1 wt.% And most preferably less than 0.1 wt .-%, and in particular no organic solvent from the group of organic amines and the alkanolamine is contained in the detergent A.

With regard to their meterability in the course of the cleaning process according to the invention, those cleaning agents have proven advantageous which have a viscosity of more than 10,000 mPas, preferably more than 50,000 mPas and in particular more than 100,000 mPas.

Preference according to the invention is therefore given to those processes in which the viscosity (Brookfield LVT-II viscosimeter at 20 rpm and 20 ° C., spindle 3) of at least one of the cleaning agents A or B is between 200 and 10,000 mPas, preferably between 500 and 7,000 mPas and in particular between 1000 and 4000 mPas. The viscosity (Brookfield viscometer LVT-II at 20 rpm and 20 ° C., spindle 3) of particularly preferred detergents or cleaners is above 500 mPas, preferably above 1000 mPas and in particular above 2000 mPas.

In order to achieve the desired viscosity of the cleaning agents, these agents are preferably thickening agents, especially thickeners from the group agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein , Carboxymethylcellulose, terminal flour ethers, polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, Polyethers, polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonites, zeolites and silicic acids added, wherein it has proved to be particularly advantageous if the detergent, the thickener in amounts between 0.1 and 8 wt .-%, preferably between 0.2 and 6 wt .-% and particularly preferably between 0.4 and 4 wt .-% based on the total weight of the cleaning agent.

Natural-derived polymers used as thickening agents in the present invention are, as described above, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein.

Modified natural products come mainly from the group of modified starches and celluloses, examples which may be mentioned here carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose and core flour ethers.

A large group of thickeners, which find wide use in a variety of applications, are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes. Thickening agents from these classes of compounds are widely available commercially and are sold for example under the trade name Acusol ^® -820 (methacrylic acid (stearyl alcohol 20 EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ^®-GT-282 -S (alkyl polyglycol ethers, Akzo), DEUTEROL ^® polymer-11 (dicarboxylic acid copolymer, Schoner GmbH) deuteron ^® -xg (anionic heteropolysaccharide based on β-D-glucose, D-mannose, D-glucuronic acid, Schoner GmbH) , deuteron ^® -XN (nonionic polysaccharide Schoner GmbH), DICRYLAN ^® -Verdicker-O (ethylene oxide adduct, 50% solution in water / isopropanol, Pfersse Chemie), EMA ^® -81 and EMA ^® -91 (ethylene-maleic anhydride copolymer, Monsanto), thickener QR-1001 (polyurethane emulsion, 19-21% in water / diglyme, Rohm & Haas), Mirox ^® -AM (anionic acrylic acid-acrylate copolymer dispersion, 25% in water, Stockhausen ), SER-AD FX 1100 (hydrophobic urethane polymer, servo Delden), Shellflo ^® -S (high molecular weight Polysaccharide, stabilized with formaldehyde, Shell), and Shellflo XA ^® (xanthan biopolymer, stabilized with formaldehyde, Shell) is.

The detergents according to the invention may furthermore contain bleaches, but with regard to the bleach content of the detergents A and B it is possible to distinguish between two preferred variants.

In a first preferred embodiment, the bleach content of the liquid detergents A and B is low and is preferably less than 2% by weight. Surprisingly, by the process control according to the invention by the Use of bleach-poor detergents can be achieved a cleaning performance that is comparable to the cleaning performance bleach-containing Reinger. By dispensing with bleaching agents, however, it was possible at the same time to increase the reciprocal freedom with decreasing production costs.

Inventive method, characterized in that the bleach content of the cleaning agents A and B are each less than 2 wt .-%, preferably less than 1 wt .-%, preferably less than 0.5 wt .-% and in particular less than 0.1 wt .-%, are therefore preferred. Particular preference is given to processes according to the invention in which the cleaning agents A and B contain no bleaching agents.

In a second preferred embodiment, the cleaning agents A and / or B contain bleaching agents, with particular preference being given to those processes in which the cleaning agent B has a bleaching agent content of between 0.1 and 15% by weight. Preferred processes are characterized in that the bleach content of the cleaning agent B, in each case based on the total weight of the cleaning agent B, between 0.5 and 15 wt .-%, preferably between 2.0 and 15 wt .-%, particularly preferably between 3 and 12 wt .-% and in particular between 5 and 10 wt .-% is. The bleach content of the cleaning agent A in this embodiment is preferably less than 2 wt .-%, preferably less than 1 wt .-%, preferably less than 0.5 wt .-% and in particular less than 0.1 wt .-%. Particularly preferred methods are characterized in that the cleaning agent A contains no bleaching agents.

In addition to H ₂ O ₂ , the group of bleaches includes, for example, the compounds H ₂ O _{2 which} supply water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate. Further bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaliminoperoxyhexanoic acid (PAP)] , o-Carboxybenzamidoperoxycaproic acid, N-Nonenylamidoperadipinsäure and N-Nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-Diperoxyazelainsäure, Diperocysebacinsäure, Diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronate).

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -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, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist.If the cleaning agents A and / or B contain bleaching agents, bleach activators are preferably additionally used in order to achieve an improved bleaching action when cleaning at temperatures of 60 ° C. and below. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran. Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula

in the R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C _1-24 -alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -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 , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion.

in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁶ = -CH₃ und insbesondere R⁴ = R⁵ = R⁶ = -CH₃ gilt und Verbindungen der Formeln (CH₃)₃N⁽⁺⁾CH₂-CN X^-, (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^-, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂-CN X^-, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂-CN X^-, oder (HO-CH₂-CH₂)₃N⁽⁺⁾CH₂-CN X^- besonders bevorzugt sind, wobei aus der Gruppe dieser Substanzen wiederum das kationische Nitril der Formel (CH₃)₃N⁽⁺⁾CH₂-CN X^-, in welcher X^- für ein Anion steht, das aus der Gruppe Chlorid, Bromid, Iodid, Hydrogensulfat, Methosulfat, p-Toluolsulfonat (Tosylat) oder Xylolsulfonat ausgewählt ist, besonders bevorzugt ist.Particularly preferred is a cationic nitrile of the formula

in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , wherein R ⁴ additionally also -H may be and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ( CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{- are} particularly preferred, wherein from the group of these substances turn the cationic Nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- in which X ^{- represents} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is particularly preferred.

As bleach activators it is also possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methylsulfate (MMA) and also acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl-fructose, tetraacetyl-xylose and octaacetyl lactose as well as acetylated, optionally N- alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used.

If, in addition to the nitrile quats, further bleach activators are to be used, preference is given to bleach activators from the group of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (US Pat. n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA).

In addition to, or in place of, the conventional bleach activators, so-called bleach catalysts can also be used. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Also, Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are useful as bleach catalysts,

Bleach-enhancing transition metal complexes, in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) Complex, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate used.

The chlorine bleaches have proved to be particularly effective for use in a process according to the invention. The group of these bleaching agents includes, for example, heterocyclic N-bromo- and N-chloroamides such as trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin also belong to the group of these bleaching agents.

• A:
  • 10 bis 75 Gew.-% Gerüststoff(e);
  • 0,1 bis 10 Gew.-% Protease;
  • 24,9 bis 89,9 Gew.-% Lösungsmittel; und
• B:
  • 10 bis 74,8 Gew.% Gerüststoff(e);
  • 25 bis 89,9 Gew.-% Lösungsmittel;
  • 0,1 bis 15 Gel.-% Chlorbleichmittel;
  • weniger als 0,1 Gew.-% Enzym;

Processes according to the invention in which the cleaning agent B contains from 0.1 to 20% by weight of a chlorine bleach are preferred. A preferred subject matter of the present application is therefore also a method for machine dishwashing in a dishwasher, comprising a prewash and a cleaning cycle, characterized in that in the cleaning cycle at two successive times t1 and t2 two liquid detergents A and B of the composition:

• A:
  • From 10% to 75% by weight of builder (s);
  • 0.1 to 10% by weight of protease;
  • 24.9 to 89.9% by weight of solvent; and
• B:
  • 10 to 74.8% by weight builder (s);
  • From 25 to 89.9% by weight of solvent;
  • 0.1 to 15 gel .-% chlorine bleach;
  • less than 0.1% by weight of enzyme;

Are metered into the interior of the dishwasher, wherein the liquid detergent A from 0.1 to 10 wt .-% enzyme, a pH (20 ° C) between 6 and 9 and is metered at time t1, while the liquid Detergent B has a pH (20 ° C) between 9 and 14 and is metered at time t2, wherein the pH (20 ° C) of the liquid detergent A from the pH (20 ° C) of the liquid Reinlgungsmittels B differs by at least two units, characterized in that the time difference between the times t1 and t2 is 2 to 30 minutes.

In addition to the ingredients described above, the compositions according to the invention described above may contain further washing and cleaning-active substances, preferably washing and cleaning-active substances from the group of surfactants, polymers, bleach activators, Glass corrosion inhibitors, corrosion inhibitors, disintegrating agents, fragrances and perfume carriers, dyes and preservatives. These preferred ingredients will be described in more detail below.

The group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.

As nonionic surfactants, it is possible to use 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 the symbol is that which represents 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. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

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 propxylierte 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. With particular preference, washing or cleaning agents, in particular automatic dishwashing detergents, contain 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 natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred. 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 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 mol of ethylene oxide per mol Alcohol was used. A particularly preferred nonionic surfactant is a straight-chain one 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. 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 agents 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 to each other before a block of the other groups follows. Here are nonionic 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. If 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 natural origin having 12 to 18 C atoms, for example 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 of one another for values of 3 or 4 and y and z independently of one another are values of 1 or 2.

In summary, particularly preferred are nonionic surfactants having a C _9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

Surfactants of the general formula

R ^{1 is} -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² ,

in whichR ¹ and R ² independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 -alkyl or -alkenyl radical; A, A ', A "and A"' independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), - CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which are of 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 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having from 1 to 30 carbon atoms, where x is between 1 and 90, preferably between 40 and 80, and especially between 40 and 60.

Particularly preferred are 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 having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.

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

Other 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 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, so that the above formula zu

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the latter formula, R ¹ , R ² and R ^{3 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.

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 ,

Inventive method, characterized in that the cleaning agent A further contains 0.2 to 10 wt .-%, preferably 0.4 to 7 wt .-% and in particular 0.6 to 4 wt .-% nonionic surfactants, are preferred.

Instead of the surfactants mentioned or in conjunction with them, it is also possible to use cationic and / or amphoteric surfactants.

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.As cationic active substances, for example, cationic compounds of the following formulas can be used:

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.

The group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can be used in detergents or cleaners 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" further comprise, 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.

Preferred washing or cleaning agents, in particular preferred automatic dishwashing agents, are characterized in that they contain a polymer a) which has monomer units of the formula R ¹ R ² C =CR ³ R ⁴ in which each R ¹ , R ² , R ⁴ radical ³ , R ^{4 is} independently selected from hydrogen, derivatized hydroxy, C _1-30 linear or branched alkyl groups, aryl, aryl substituted C _1-30 linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen , at least one quaternized nitrogen 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 Aminogr uppe with a positive charge is.

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, Iodid, Sulfat, Hydrogensulfat, Methosulfat, Laurylsulfat, Dodecylbenzolsulfonat, p-Toluolsulfonat (Tosylat), Cumolsulfonat, Xylolsulfonat, Phosphat, Citrat, Formiat, Acetat oder deren Mischungen.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 from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, lauryl sulfate, 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.

Preferred zwitterionic polymers are 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 from the group of the Methacrylamidoalkyl-trialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the Methacrylamidoalkyltrialkylammoniumchlorid / 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 and their alkali and ammonium salts.

• Beschichtungsmittel, vorzugsweise mittels wasserlöslicher oder wasserdispergierbarer natürlicher oder synthetischer Polymere;
• die Verkapselung der Polymere mittels wasserunlöslicher, schmelzbarer Beschichtungsmittel, vorzugsweise mittels wasserunlöslicher Beschichtungsmittel aus der Gruppe der Wachse oder Paraffine mit einem Schmelzpunkt oberhalb 30°C;
• die Cogranulation der Polymere mit inerten Trägermaterialien, vorzugsweise mit Trägermaterialien aus der Gruppe der wasch- oder reinigungsaktiven Substanzen, besonders bevorzugt aus der Gruppe der Builder (Gerüststoffe) oder Cobuilder.

In a particularly preferred embodiment of the present invention, the polymers are present in prefabricated form. For the preparation of the polymers is suitable inter alia

• Coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;
• the encapsulation of the polymers by means of water-insoluble, meltable coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C;
• the co-granulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing- or cleaning-active substances, more preferably from the group of builders or cobuilders.

Preferred cleaning agents preferably contain the abovementioned cationic and / or amphoteric polymers in amounts of between 0.01 and 8% by weight, based in each case on the total weight of the combination product. Within the scope of the present application, however, preference is given to those combination products in which the weight fraction of the cationic and / or amphoteric polymers is between 0.01 and 6% by weight, preferably between 0.01 and 4% by weight, more preferably between 0 and 01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the cleaning agent is.

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 are as unsaturated monomer carboxylic acids of the formula

R ¹ (R ² ) C = C (R ³ ) COOH

in which R ¹ to R ³ independently of one another 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, NH ₂ , -OH or -COOH are substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 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 sulfonic acid-containing monomers are 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, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group , which is selected from - (CH ₂ ), - 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 ) -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H,

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

1. i) ungesättigten Carbonsäuren der Formel R¹(R²)C=C(R³)COOH
   in der R¹ bis R³ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, einoder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
2. ii) Sulfonsäuregruppen-haltigen Monomeren der Formel R⁵(R⁶)C=C(R⁷)-X-SO₃H in der R⁵ bis R⁷ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, einoder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
3. iii) gegebenenfalls weiteren ionogenen oder nichtionogenen Monomeren besonders bevorzugt.

In summary, copolymers are made of

1. i) unsaturated carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH
   in the 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, with -NH ₂ , - OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
2. ii) sulfonic acid group-containing monomers of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H in the 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 as defined above 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 optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -
3. iii) optionally further ionic or nonionic monomers are particularly preferred.

1. i) einer oder mehreren ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
2. ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln:
   
           H₂C=CH-X-SO₃H
   
           H₂C=C(CH₃)-X-SO₃H
   
           HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H,
   
   in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n-mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
3. iii) gegebenenfalls weiteren ionogenen oder nichtionogenen Monomeren.

Further particularly preferred copolymers consist of

1. i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid
2. ii) one or more sulfonic acid group-containing monomers of the formulas:
   
   H ₂ C = CH-X-SO ₃ H
   
   H ₂ C = C (CH ₃ ) -X-SO ₃ H
   
   HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H,
   
   in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -
3. iii) optionally further ionogenic or nonionic monomers.

The copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii). Particularly preferred polymers have certain structural units, which are described below.

For example, copolymers which are structural units of the formula are preferred

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. When the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred. The corresponding copolymers contain the structural units of the formula

- [CH ₂ -C (CH ₃ ) COOH] _m -CH ₂ -CHC (O) -Y-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, copolymers which are structural units of the formula

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) -, as preferred as copolymers, the structural units of the formula

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred. Also preferred according to the invention are copolymers which contain structural units of the formula

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ )- stands.

In summary, such copolymers are preferred according to the invention, the structural units of the formulas

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p -

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p -

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

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

The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.

In the case of terpolymers, particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,

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 end use. Preferred washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

Combination products, characterized in that the cleaning agent A and / or the cleaning agent B further based on the total weight of the cleaning agent A or B 0.01 to 15 wt .-%, preferably 0.02 to 12 wt .-% and in particular 0.1 to 8 wt .-% of one or more washing or cleaning active polymers containing, are inventively preferred.

Glass corrosion inhibitors prevent the occurrence of haze, 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.

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

With particular preference, the glass corrosion inhibitor used is at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

Also suitable for glass corrosion protection are the soluble inorganic zinc salts, in particular the zinc sulfate, zinc nitrate and zinc chloride.

Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. According to the invention, preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts, these substances preferably being present in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2 Wt .-%, particularly preferably 0.01 to 0.04 wt .-% are used. Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid. Especially effective are 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-versatic-10-alkyl-3-amino-1,2,4-triazole and mixtures of these substances.

In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds used. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

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

The metal salts or metal complexes used should be at least partially soluble in water. The counterions suitable for salt formation include all conventional mono-, di-, or tri-negatively charged inorganic anions, e.g. Oxide, sulfate, nitrate, fluoride, but also organic anions such as e.g. Stearate.

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

The inorganic redox-active substances, in particular metal salts or metal complexes are preferably coated, ie completely coated with a waterproof material which is readily soluble in the cleaning temperatures, in order to prevent their premature decomposition or oxidation during storage. Preferred coating materials, which are applied by known methods, such as Sandwik melt coating process from the food industry, are Paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids.

As perfume oils or perfumes, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type 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, patchouly, rose or ylang-ylang oil.

In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note", "middle note" or "body note" ) and "base note" (end note or dry out). Since odor perception is also largely due to odor intensity, the top note of a perfume does not consist solely of volatile compounds, while the base note consists largely of less volatile, i. adherent fragrances. For example, in the composition of perfumes, more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly. In the subsequent classification of the fragrances in "more volatile" or "adherent" fragrances so nothing about the olfactory impression and whether the corresponding fragrance is perceived as a head or middle note, nothing said.

The fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.

Preferred dyestuffs, the choice of which presents no difficulty to a person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, as well as no pronounced substantivity to those with the dye-containing Agents to be treated substrates such as textiles, glass, ceramics or plastic dishes, so as not to stain them.

When choosing the colorant, it must be remembered that the colorants have a high storage stability and insensitivity to light as well as not too strong affinity for glass, ceramic or plastic dishes. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, colorant concentrations in the range of a few 10 ^-2 to 10 ^-3 % by weight are typically selected. By contrast, in the case of the particularly preferred, but less readily water-soluble, pigment dyes due to their brilliance, the suitable concentration of the colorant in detergents or cleaners is typically about 10 ^-3 to 10 ^-4 % by weight.

Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable are, for example, anionic colorants, e.g. anionic nitrosofarads.

The detergents of the invention may further contain preservatives. Preservatives from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives are suitable according to the invention such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides , Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2- Benzyl 4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- ( 3,4-dichlorophenyl) urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4- Chlorophenyl) -3,12-diimino-2,4,11,13-tetraazatetradecandiimidamide, antimicrobial quaternary surface active compounds, guanidines. However, particularly preferred preservatives are selected from the group comprising salicylic acid, quaternary Surfactants, especially benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.

• Verfahren zur maschinellen Reinigung von Geschirr in einer Geschirrspülmaschine, dadurch gekennzeichnet, dass im Verlauf eines Reinigungsprogramms, welches einen Vorspülgang und
• einen Reinigungsgang umfasst, In diesem Reinigungsgang an zwei aufeinander folgenden Zeitpunkten t1 und t2 zwei flüssige Reinigungsmittel A und B der Zusammensetzung:
  • A: gemäß nachfolgender Tabelle
  • B: gemäß nachfolgender Tabelle

in den Innenraum der Geschirrspülmaschine eindosiert werden, wobei das flüssige Reinigungsmittel A 0,1 bis 10 Gew.-% Proteasen enthält, einen pH-Wert (20°C) zwischen 6 und 9 aufweist und zum Zeitpunkt t1 eindosiert wird, während das flüssige Reinigungsmittel B weniger als 0,1 Gew.-% Enzym enthält, einen pH-Wert (20°C) zwischen 9 und 14 aufweist und zum Zeitpunkt t2 eindosiert wird, wobei sich der pH-Wert (20°C) des flüssigen Reinigungsmittels A vom pH-Wert (20°C) des flüssigen Reinigungsmittels B um mindestens zwei Einheiten unterscheidet, dadurch gekennzeichnet, dass die zeitliche Differenz zwischen den Zeitpunkten t1 und t2 2 bis 30 Minuten beträgt, sind aus diesem Grunde erfindungsgemäß bevorzugt. Lfd. Nummer Reinigungsmittel A, enthaltend Reinigungsmittel B, enthaltend 1 10 bis 75 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,9 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel 2 10 bis 74,9 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,8 Gew.-% Wasser, 0,1 bis 15 Gew.-% Bleichmittel 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltigas Polymer 3 10 bis 74,8 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,7 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel 0,2 bis 10,0 nichtionisches Tensid 4 10 bis 74,7 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89, 6 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel 0,2 bis 10,0 nichtionisches Tensid; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 5 10 bis 75 Gew.% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89,9 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 6 10 bis 74,9 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89,8 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 7 10 bis 74,8 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89,7 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,2 bis 10,0 nichtionisches Tensid 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 8 10 bis 74,7 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89, 6 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,2 bis 10,0 nichtionisches Tensid; 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 9 10 bis 75 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89,9 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel 0,1 bis 10 Gew.-% Alkanolamin 10 10 bis 74,9 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89,8 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,1 bis 10 Gew.-% Alkanolamin 11 10 bis 74,8 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89,7 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel 0,2 bis 10,0 nichtionisches Tensid 0,1 bis 10 Gew.-% Alkanolamin 12 10 bis 74,7 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89, 6 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel 0,2 bis 10,0 nichtionisches Tensid; 0,1 bis 10 Gew.-% Alkanolamin 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 13 10 bis 75 Gew.-% Gerüststoff(e); 10 bis 74,7 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,7 Gew.-% Wasser; 24,9 bis 89,9 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer; 0,1 bis 10 Gew.-% Alkanolamin 14 10 bis 74,9 Gew.-% Gerüststoff(e); 10 bis 74,7 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,7 Gew.-% Wasser; 24,9 bis 89,8 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer; 0,1 bis 10 Gew.-% Alkanolamin 15 10 bis 74,8 Gew.-% Gerüststoff(e); 10 bis 74,7 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,7 Gew.-% Wasser; 24,9 bis 89,7 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,2 bis 10,0 nichtionisches Tensid 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer; 0,1 bis 10 Gew.-% Alkanolamin 16 10 bis 74,7 Gew.-% Gerüststoff(e); 10 bis 74,7 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,7 Gew.-% Wasser; 24,9 bis 89, 6 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,2 bis 10,0 nichtionisches Tensid; 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,1 bis 10 Gew.-% Alkanolamin 17 10 bis 75 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89,9 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 18 10 bis 74,9 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89,8 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 19 10 bis 74,8 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89,7 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,2 bis 10,0 nichtionisches Tensid 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 20 10 bis 74,7 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89, 6 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,2 bis 10,0 nichtionisches Tensid; 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 21 10 bis 75 Gew.-% Gerüststoff(e); 10 bis 74,7 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,7 Gew.-% Wasser; 24,9 bis 89,9 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer; 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 22 10 bis 74,9 Gew.-% Gerüststoff(e); 10 bis 74,7 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,7 Gew.-% Wasser; 24,9 bis 89,8 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer; 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 23 10 bis 74,8 Gew.-% Gerüststoff(e); 10 bis 74,7 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,7 Gew.-% Wasser; 24,9 bis 89,7 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,2 bis 10,0 nichtionisches Tensid 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer; 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 24 10 bis 74,7 Gew.-% Gerüststoff(e); 10 bis 74,7 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,7 Gew.-% Wasser; 24,9 bis 89, 6 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,2 bis 10,0 nichtionisches Tensid; 0,01 bis 15 Gew.% Sulfonsäuregruppen- 0,01 bis 15 Gew.% haltiges Polymer; Sulfonsäuregruppen-haltiges Polymer 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 25 10 bis 75 Gew.-% Gerüststoff(e); 10 bis 74,7 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,7 Gew.-% Wasser; 24,9 bis 89,9 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel 0,1 bis 10 Gew.-% Alkanolamin; 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 26 10 bis 74,9 Gew.-% Gerüststoff(e); 10 bis 74,7 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,7 Gew.-% Wasser; 24,9 bis 89,8 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel 0,01 bis 15 Gew.% 0,1 bis 10 Gew.-% Alkanolamin; Sulfonsäuregruppen-haltiges Polymer 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 27 10 bis 74,8 Gew.-% Gerüststoff(e); 10 bis 74,7 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,7 Gew.-% Wasser; 24,9 bis 89,7 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel 0,2 bis 10,0 nichtionisches Tensid 0,1 bis 10 Gew.-% Alkanolamin; 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 28 10 bis 74,7 Gew.-% Gerüststoff(e); 10 bis 74,7 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,7 Gew.-% Wasser; 24,9 bis 89, 6 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel 0,2 bis 10,0 nichtionisches Tensid; 0,1 bis 10 Gew.-% Alkanolamin; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 29 10 bis 75 Gew.-% Gerüststoff(e); 10 bis 74,6 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,6 Gew.-% Wasser; 24,9 bis 89,9 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer; 0,1 bis 10 Gew.-% Alkanolamin; 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 30 10 bis 74,9 Gew.-% Gerüststoff(e); 10 bis 74,6 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,6 Gew.-% Wasser; 24,9 bis 89,8 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer; 0,1 bis 10 Gew.-% Alkanolamin; 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 31 10 bis 74,8 Gew.-% Gerüststoff(e); 10 bis 74,6 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,6 Gew.-% Wasser; 24,9 bis 89,7 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,2 bis 10,0 nichtionisches Tensid 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer; 0,1 bis 10 Gew.-% Alkanolamin; 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 32 10 bis 74,7 Gew.-% Gerüststoff(e); 10 bis 74,6 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,6 Gew.-% Wasser; 24,9 bis 89, 6 Gew.-% Wasser; 0,1 bis 15 Gew.-% Bleichmittel; 0,2 bis 10,0 nichtionisches Tensid; 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,1 bis 10 Gew.-% Alkanolamin; 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 33 10 bis 75 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,9 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkanolamin 34 10 bis 75 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,9 Gew.-% Wasser; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 35 10 bis 74,9 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,8 Gew.-% Wasser; 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 36 10 bis 75 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89,9 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkanolamin; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 37 10 bis 74,9 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,8 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkanolamin; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 38 10 bis 74,8 Gew.% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,7 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkanolamin 0,2 bis 10,0 nichtionisches Tensid 39 10 bis 74,8 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89, 7 Gew.-% Wasser; 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer 0,2 bis 10,0 nichtionisches Tensid 40 10 bis 74,7 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89, 6 Gew.-% Wasser; 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer 0,2 bis 10,0 nichtionisches Tensid; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 41 10 bis 74,8 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89, 7 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkanolamin; 0,2 bis 10,0 nichtionisches Tensid 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 42 10 bis 74,7 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,6 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkanolamin; 0,2 bis 10,0 nichtionisches Tensid; 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 43 10 bis 75 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,9 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkalihydroxid 44 10 bis 75 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89,9 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkalihydroxid; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 45 10 bis 74,9 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,8 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkalihydroxid; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 46 10 bis 74,8 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,7 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkalihydroxid 0,2 bis 10,0 nichtionisches Tensid 47 10 bis 74,8 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89, 7 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkalihydroxid; 0,2 bis 10,0 nichtionisches Tensid 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 48 10 bis 74,7 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,6 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkalihydroxid; 0,2 bis 10,0 nichtionisches Tensid; 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 49 10 bis 75 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,9 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkanolamin 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 50 10 bis 75 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,9 Gew.-% Wasser; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 51 10 bis 74,9 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,8 Gew.-% Wasser; 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 52 10 bis 75 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89,9 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkanolamin; 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer 53 10 bis 74,9 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,8 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkanolamin; 0,01 bis 15 Gew.% 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer Sulfonsäuregruppen-haltiges Polymer 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 54 10 bis 74,8 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,7 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkanolamin 0,2 bis 10,0 nichtionisches Tensid 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 55 10 bis 74,8 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89, 7 Gew.-% Wasser; 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer 0,2 bis 10,0 nichtionisches Tensid 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 56 10 bis 74,7 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89, 6 Gew.-% Wasser; 0,01 bis 15 Gew.% Sulfonsäuregruppen- 0,2 bis 10,0 nichtionisches Tensid; haltiges Polymer 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 57 10 bis 74,8 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89, 7 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkanolamin; 0,2 bis 10,0 nichtionisches Tensid 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 58 10 bis 74,7 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,6 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkanolamin; 0,2 bis 10,0 nichtionisches Tensid; 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 59 10 bis 75 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,9 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkalihydroxid 60 10 bis 75 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89,9 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkalihydroxid; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 61 10 bis 74,9 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,8 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkalihydroxid; 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 62 10 bis 74,8 Gew.-% Gerüststoff(e); 10 bis 74,9 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,7 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkalihydroxid 0,2 bis 10,0 nichtionisches Tensid 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 63 10 bis 74,8 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,8 Gew.-% Wasser; 24,9 bis 89, 7 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkalihydroxid; 0,2 bis 10,0 nichtionisches Tensid 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere 64 10 bis 74,7 Gew.-% Gerüststoff(e); 10 bis 74,8 Gew.% Gerüststoff(e); 0,1 bis 10 Gew.-% Enzym(e); 25 bis 89,9 Gew.-% Wasser; 24,9 bis 89,6 Gew.-% Wasser; 0,1 bis 10 Gew.-% Alkalihydroxid; 0,2 bis 10,0 nichtionisches Tensid; 0,01 bis 15 Gew.% Sulfonsäuregruppenhaltiges Polymer 0,01 bis 15 Gew.% Sulfonsäuregruppen-haltiges Polymer 0,01 bis 8 Gew.-% kationische und/oder amphotere Polymere In terms of their performance and storage stability, a number of cleaning agents have proven to be particularly advantageous:

• Method for machine cleaning dishes in a dishwasher, characterized in that in the course of a cleaning program, which a pre-wash and
• comprises a cleaning cycle, in this cleaning cycle on two consecutive times t1 and t2, two liquid cleaning agents A and B of the composition:
  • A: according to the following table
  • B: according to the following table

are metered into the interior of the dishwasher, wherein the liquid detergent A contains 0.1 to 10 wt .-% proteases, a pH (20 ° C) between 6 and 9 and is metered at time t1, while the liquid detergent B contains less than 0.1% by weight of enzyme, has a pH (20 ° C.) between 9 and 14 and is metered in at time t2, the pH (20 ° C.) of the liquid cleaning agent A being from pH value (20 ° C) of the liquid detergent B differs by at least two units, characterized in that the time difference between the times t1 and t2 is 2 to 30 minutes are, for this reason, preferred according to the invention. Ser. number Detergent A, containing Detergent B containing 1 From 10% to 75% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.9% by weight of water; 0.1 to 15% by weight of bleach 2 10 to 74.9% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.8% by weight of water, 0.1 to 15% by weight of bleach 0.01 to 15% by weight of sulfonic acid group-containing polymer 3 From 10 to 74.8% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.7% by weight of water; 0.1 to 15% by weight of bleach 0.2 to 10.0 nonionic surfactant 4 10 to 74.7% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89, 6 wt .-% water; 0.1 to 15% by weight of bleach 0.2 to 10.0 nonionic surfactant; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 5 From 10 to 75% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89.9% by weight of water; 0.1 to 15% by weight of bleach; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 6 10 to 74.9% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89.8% by weight of water; 0.1 to 15% by weight of bleach; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 7 From 10 to 74.8% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89.7% by weight of water; 0.1 to 15% by weight of bleach; 0.2 to 10.0 nonionic surfactant 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 8th 10 to 74.7% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89, 6 wt .-% water; 0.1 to 15% by weight of bleach; 0.2 to 10.0 nonionic surfactant; 0.01 to 15 wt.% Sulfonsäuregruppenhaltiges polymer 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 9 From 10% to 75% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89.9% by weight of water; 0.1 to 15% by weight of bleach 0.1 to 10 wt .-% alkanolamine 10 10 to 74.9% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89.8% by weight of water; 0.1 to 15% by weight of bleach 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.1 to 10 wt .-% alkanolamine 11 From 10 to 74.8% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89.7% by weight of water; 0.1 to 15% by weight of bleach 0.2 to 10.0 nonionic surfactant 0.1 to 10 wt .-% alkanolamine 12 10 to 74.7% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89, 6 wt .-% water; 0.1 to 15% by weight of bleach 0.2 to 10.0 nonionic surfactant; 0.1 to 10 wt .-% alkanolamine 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 13 From 10% to 75% by weight of builder (s); 10 to 74.7% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.7% by weight of water; 24.9 to 89.9% by weight of water; 0.1 to 15% by weight of bleach; 0.01 to 15% by weight of sulfonic acid group-containing polymer; 0.1 to 10 wt .-% alkanolamine 14 10 to 74.9% by weight of builder (s); 10 to 74.7% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.7% by weight of water; 24.9 to 89.8% by weight of water; 0.1 to 15% by weight of bleach; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.01 to 15% by weight of sulfonic acid group-containing polymer; 0.1 to 10 wt .-% alkanolamine 15 From 10 to 74.8% by weight of builder (s); 10 to 74.7% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.7% by weight of water; 24.9 to 89.7% by weight of water; 0.1 to 15% by weight of bleach; 0.2 to 10.0 nonionic surfactant 0.01 to 15% by weight of sulfonic acid group-containing polymer; 0.1 to 10 wt .-% alkanolamine 16 10 to 74.7% by weight of builder (s); 10 to 74.7% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.7% by weight of water; 24.9 to 89, 6 wt .-% water; 0.1 to 15% by weight of bleach; 0.2 to 10.0 nonionic surfactant; 0.01 to 15% by weight of sulfonic acid group-containing polymer; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.1 to 10 wt .-% alkanolamine 17 From 10% to 75% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89.9% by weight of water; 0.1 to 15% by weight of bleach; 0.01 to 8 wt .-% cationic and / or amphoteric polymers 18 10 to 74.9% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89.8% by weight of water; 0.1 to 15% by weight of bleach; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.01 to 8 wt .-% cationic and / or amphoteric polymers 19 From 10 to 74.8% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89.7% by weight of water; 0.1 to 15% by weight of bleach; 0.2 to 10.0 nonionic surfactant 0.01 to 8 wt .-% cationic and / or amphoteric polymers 20 10 to 74.7% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89, 6 wt .-% water; 0.1 to 15% by weight of bleach; 0.2 to 10.0 nonionic surfactant; 0.01 to 8 wt .-% cationic and / or amphoteric polymers 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 21 From 10% to 75% by weight of builder (s); 10 to 74.7% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.7% by weight of water; 24.9 to 89.9% by weight of water; 0.1 to 15% by weight of bleach; 0.01 to 15% by weight of sulfonic acid group-containing polymer; 0.01 to 8 wt .-% cationic and / or amphoteric polymers 22 10 to 74.9% by weight of builder (s); 10 to 74.7% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.7% by weight of water; 24.9 to 89.8% by weight of water; 0.1 to 15% by weight of bleach; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.01 to 15% by weight of sulfonic acid group-containing polymer; 0.01 to 8 wt .-% cationic and / or amphoteric polymers 23 From 10 to 74.8% by weight of builder (s); 10 to 74.7% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.7% by weight of water; 24.9 to 89.7% by weight of water; 0.1 to 15% by weight of bleach; 0.2 to 10.0 nonionic surfactant 0.01 to 15% by weight of sulfonic acid group-containing polymer; 0.01 to 8 wt .-% cationic and / or amphoteric polymers 24 10 to 74.7% by weight of builder (s); 10 to 74.7% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.7% by weight of water; 24.9 to 89, 6 wt .-% water; 0.1 to 15% by weight of bleach; 0.2 to 10.0 nonionic surfactant; 0.01 to 15% by weight of sulfonic acid group 0.01 to 15% by weight containing polymer; Sulfonic acid group-containing polymer 0.01 to 8 wt .-% cationic and / or amphoteric polymers 25 From 10% to 75% by weight of builder (s); 10 to 74.7% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.7% by weight of water; 24.9 to 89.9% by weight of water; 0.1 to 15% by weight of bleach 0.1 to 10% by weight of alkanolamine; 0.01 to 8 wt .-% cationic and / or amphoteric polymers 26 10 to 74.9% by weight of builder (s); 10 to 74.7% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.7% by weight of water; 24.9 to 89.8% by weight of water; 0.1 to 15% by weight of bleach 0.01 to 15% by weight 0.1 to 10% by weight of alkanolamine; Sulfonic acid group-containing polymer 0.01 to 8 wt .-% cationic and / or amphoteric polymers 27 From 10 to 74.8% by weight of builder (s); 10 to 74.7% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.7% by weight of water; 24.9 to 89.7% by weight of water; 0.1 to 15% by weight of bleach 0.2 to 10.0 nonionic surfactant 0.1 to 10% by weight of alkanolamine; 0.01 to 8 wt .-% cationic and / or amphoteric polymers 28 10 to 74.7% by weight of builder (s); 10 to 74.7% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.7% by weight of water; 24.9 to 89, 6 wt .-% water; 0.1 to 15% by weight of bleach 0.2 to 10.0 nonionic surfactant; 0.1 to 10% by weight of alkanolamine; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.01 to 8 wt .-% cationic and / or amphoteric polymers 29 From 10% to 75% by weight of builder (s); From 10 to 74.6% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.6% by weight of water; 24.9 to 89.9% by weight of water; 0.1 to 15% by weight of bleach; 0.01 to 15% by weight of sulfonic acid group-containing polymer; 0.1 to 10% by weight of alkanolamine; 0.01 to 8 wt .-% cationic and / or amphoteric polymers 30 10 to 74.9% by weight of builder (s); From 10 to 74.6% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.6% by weight of water; 24.9 to 89.8% by weight of water; 0.1 to 15% by weight of bleach; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.01 to 15% by weight of sulfonic acid group-containing polymer; 0.1 to 10% by weight of alkanolamine; 0.01 to 8 wt .-% cationic and / or amphoteric polymers 31 From 10 to 74.8% by weight of builder (s); From 10 to 74.6% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.6% by weight of water; 24.9 to 89.7% by weight of water; 0.1 to 15% by weight of bleach; 0.2 to 10.0 nonionic surfactant 0.01 to 15% by weight of sulfonic acid group-containing polymer; 0.1 to 10% by weight of alkanolamine; 0.01 to 8 wt .-% cationic and / or amphoteric polymers 32 10 to 74.7% by weight of builder (s); From 10 to 74.6% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.6% by weight of water; 24.9 to 89, 6 wt .-% water; 0.1 to 15% by weight of bleach; 0.2 to 10.0 nonionic surfactant; 0.01 to 15% by weight of sulfonic acid group-containing polymer; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.1 to 10% by weight of alkanolamine; 0.01 to 8 wt .-% cationic and / or amphoteric polymers 33 From 10% to 75% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.9% by weight of water; 0.1 to 10 wt .-% alkanolamine 34 From 10% to 75% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.9% by weight of water; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 35 10 to 74.9% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.8% by weight of water; 0.01 to 15 wt.% Sulfonsäuregruppenhaltiges polymer 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 36 From 10% to 75% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89.9% by weight of water; 0.1 to 10% by weight of alkanolamine; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 37 10 to 74.9% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.8% by weight of water; 0.1 to 10% by weight of alkanolamine; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 38 10 to 74.8% by weight builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.7% by weight of water; 0.1 to 10 wt .-% alkanolamine 0.2 to 10.0 nonionic surfactant 39 From 10 to 74.8% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89, 7 wt .-% water; 0.01 to 15 wt.% Sulfonsäuregruppenhaltiges polymer 0.2 to 10.0 nonionic surfactant 40 10 to 74.7% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89, 6 wt .-% water; 0.01 to 15 wt.% Sulfonsäuregruppenhaltiges polymer 0.2 to 10.0 nonionic surfactant; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 41 From 10 to 74.8% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89, 7 wt .-% water; 0.1 to 10% by weight of alkanolamine; 0.2 to 10.0 nonionic surfactant 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 42 10 to 74.7% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.6% by weight of water; 0.1 to 10% by weight of alkanolamine; 0.2 to 10.0 nonionic surfactant; 0.01 to 15 wt.% Sulfonsäuregruppenhaltiges polymer 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 43 From 10% to 75% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.9% by weight of water; 0.1 to 10 wt .-% alkali hydroxide 44 From 10% to 75% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89.9% by weight of water; 0.1 to 10% by weight of alkali hydroxide; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 45 10 to 74.9% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.8% by weight of water; 0.1 to 10% by weight of alkali hydroxide; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 46 From 10 to 74.8% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.7% by weight of water; 0.1 to 10 wt .-% alkali hydroxide 0.2 to 10.0 nonionic surfactant 47 From 10 to 74.8% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89, 7 wt .-% water; 0.1 to 10% by weight of alkali hydroxide; 0.2 to 10.0 nonionic surfactant 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 48 10 to 74.7% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.6% by weight of water; 0.1 to 10% by weight of alkali hydroxide; 0.2 to 10.0 nonionic surfactant; 0.01 to 15 wt.% Sulfonsäuregruppenhaltiges polymer 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 49 From 10% to 75% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.9% by weight of water; 0.1 to 10 wt .-% alkanolamine 0.01 to 8 wt .-% cationic and / or amphoteric polymers 50 From 10% to 75% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.9% by weight of water; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.01 to 8 wt .-% cationic and / or amphoteric polymers 51 10 to 74.9% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.8% by weight of water; 0.01 to 15 wt.% Sulfonsäuregruppenhaltiges polymer 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.01 to 8 wt .-% cationic and / or amphoteric polymers 52 From 10% to 75% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89.9% by weight of water; 0.1 to 10% by weight of alkanolamine; 0.01 to 15 wt.% Sulfonsäuregruppenhaltiges polymer 53 10 to 74.9% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.8% by weight of water; 0.1 to 10% by weight of alkanolamine; 0.01 to 15% by weight 0.01 to 15 wt.% Sulfonsäuregruppenhaltiges polymer Sulfonic acid group-containing polymer 0.01 to 8 wt .-% cationic and / or amphoteric polymers 54 From 10 to 74.8% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.7% by weight of water; 0.1 to 10 wt .-% alkanolamine 0.2 to 10.0 nonionic surfactant 0.01 to 8 wt .-% cationic and / or amphoteric polymers 55 From 10 to 74.8% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89, 7 wt .-% water; 0.01 to 15 wt.% Sulfonsäuregruppenhaltiges polymer 0.2 to 10.0 nonionic surfactant 0.01 to 8 wt .-% cationic and / or amphoteric polymers 56 10 to 74.7% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89, 6 wt .-% water; 0.01 to 15% by weight of sulfonic acid group 0.2 to 10.0 nonionic surfactant; containing polymer 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.01 to 8 wt .-% cationic and / or amphoteric polymers 57 From 10 to 74.8% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89, 7 wt .-% water; 0.1 to 10% by weight of alkanolamine; 0.2 to 10.0 nonionic surfactant 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.01 to 8 wt .-% cationic and / or amphoteric polymers 58 10 to 74.7% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.6% by weight of water; 0.1 to 10% by weight of alkanolamine; 0.2 to 10.0 nonionic surfactant; 0.01 to 15 wt.% Sulfonsäuregruppenhaltiges polymer 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.01 to 8 wt .-% cationic and / or amphoteric polymers 59 From 10% to 75% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.9% by weight of water; 0.1 to 10 wt .-% alkali hydroxide 60 From 10% to 75% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89.9% by weight of water; 0.1 to 10% by weight of alkali hydroxide; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.01 to 8 wt .-% cationic and / or amphoteric polymers 61 10 to 74.9% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.8% by weight of water; 0.1 to 10% by weight of alkali hydroxide; 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.01 to 15 wt.% Sulfonsäuregruppenhaltiges polymer 0.01 to 8 wt .-% cationic and / or amphoteric polymers 62 From 10 to 74.8% by weight of builder (s); 10 to 74.9% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.7% by weight of water; 0.1 to 10 wt .-% alkali hydroxide 0.2 to 10.0 nonionic surfactant 0.01 to 8 wt .-% cationic and / or amphoteric polymers 63 From 10 to 74.8% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.8% by weight of water; 24.9 to 89, 7 wt .-% water; 0.1 to 10% by weight of alkali hydroxide; 0.2 to 10.0 nonionic surfactant 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.01 to 8 wt .-% cationic and / or amphoteric polymers 64 10 to 74.7% by weight of builder (s); 10 to 74.8% by weight builder (s); 0.1 to 10% by weight of enzyme (s); From 25 to 89.9% by weight of water; 24.9 to 89.6% by weight of water; 0.1 to 10% by weight of alkali hydroxide; 0.2 to 10.0 nonionic surfactant; 0.01 to 15 wt.% Sulfonsäuregruppenhaltiges polymer 0.01 to 15 wt.% Sulfonsäuregruppen-containing polymer 0.01 to 8 wt .-% cationic and / or amphoteric polymers

The cleaning agents A and B designated by the serial numbers 33 to 64 preferably have a bleaching agent content below 2% by weight, preferably below 1% by weight, more preferably below 0.5% by weight and most preferably do not contain any bleaching agents.

The inventive method is particularly suitable for the removal of bleachable soils, such as tea contaminants and for the cleaning of dried soils.

The use of the method according to the invention for removing bleachable soils, preferably for removing contaminated soils, on hard surfaces or for cleaning dried and / or burned soiling, in particular for cleaning dried and / or burnt soils in automatic dishwashing are therefore further objects of the present application.

The group of dried-on or burnt-on soils includes, for example, dried starch soils, for example oatmeal, or baked residues of casseroles which, for example, in addition to starch components such as noodles or potatoes, also include meat residues.

Claims (16)

1. A method for the automatic cleaning of dishes in a dishwashing machine, characterised in that, in the course of a cleaning programme which comprises a prewash cycle and a cleaning cycle, at two successive points in time t1 and t2 in said cleaning cycle two liquid cleaning agents A and B of the composition:

   A:

   - 10 to 75 wt.% of builder(s);

   - 0.1 to 10 wt.% of protease;

   - 24.9 to 89.9 wt.% of solvent; and

   B:

   - 10 to 74.9 wt.% of builder(s);

   - 25 to 89.9 wt.% of solvent;

   - less than 0.1 wt.% of enzyme;

   are dispensed into the interior of the dishwashing machine, wherein liquid cleaning agent A contains from 0.1 to 10 wt.% of enzyme, has a pH value (20°C) of between 6 and 9 and is dispensed at point in time t1, while liquid cleaning agent B has a pH value (20°C) of between 9 and 14 and is dispensed at point in time t2, wherein the pH value (20°C) of liquid cleaning agent A differs from the pH value (20°C) of the liquid cleaning agent B by at least two units, characterised in that the time difference between points in time t1 and t2 amounts to 2 to 30 minutes.
2. A method according to claim 1, characterised in that the time difference between points in time t1 and t2 amounts to 4 to 25 minutes and in particular to 6 to 20 minutes.
3. A method according to either of the preceding claims, characterised in that the temperature of the washing liquor at point in time t1 amounts to between 12 and 45°C, preferably between 15 and 40°C and in particular between 20 and 35°C.
4. A method according to any one of the preceding claims, characterised in that the temperature of the washing liquor at point in time t2 amounts to between 30 and 65°C, preferably between 35 and 60°C and in particular between 40 and 55°C.
5. A method according to any one of the preceding claims, characterised in that the liquid cleaning agent A and/or the liquid cleaning agent B contains water as solvent.
6. A method according to any one of the preceding claims, characterised in that the liquid cleaning agent A and/or the liquid cleaning agent B contain(s) a solvent from the group of organic solvents, wherein the organic solvent is preferably an organic amine and/or an alkanolamine, preferably ethanolamine.
7. A method according to any one of the preceding claims, characterised in that cleaning agent A has a pH value (20°C) of between 6.5 and 8.5, preferably between 7 and 8.
8. A method according to any one of the preceding claims, characterised in that cleaning agent B has a pH value (20°C) of between 9.5 and 13, preferably between 10 and 12.
9. A method according to any one of the preceding claims, characterised in that cleaning agent B contains from 0.1 to 20 wt.% of a chlorine bleaching agent.
10. A method according to any one of claims 1 to 8, characterised in that the bleaching agent content of cleaning agents A and B in each case amounts to less than 2 wt.%, preferably less than 1 wt.%, preferably less than 0.5 wt.% and in particular less than 0.1 wt.%.
11. A method according to any one of claims 1 to 8, characterised in that cleaning agents A and B contain no bleaching agent.
12. A method according to any one of the preceding claims, characterised in that cleaning agent A furthermore contains 0.2 to 10 wt.%, preferably 0.4 to 7 wt.% and in particular 0.6 to 4 wt.% of nonionic surfactants.
13. A method according to any one of the preceding claims, characterised in that the cleaning agent contains methylglycinediacetic acid or a methylglycinediacetic acid salt and in that the proportion by weight of methylglycinediacetic acid or of methylglycinediacetic acid salt preferably amounts to between 0.2 and 12 wt.%, preferably between 0.2 and 8 wt.% and in particular between 0.2 and 6 wt.%.
14. A method according to any one of the preceding claims, characterised in that the viscosity (Brookfield LVT-II viscometer at 20 rpm and 20°C, spindle 3) of at least one of cleaning agents A or B amounts to between 200 and 10000 mPa·s, preferably between 500 and 7000 mPa·s and in particular between 1000 and 4000 mPa·s.
15. A method according to any one of the preceding claims, characterised in that liquid cleaning agents A and B are present in a water-insoluble two-or multi-chamber reservoir.
16. Use of a method according to any one of the preceding claims for cleaning dried on and/or burnt on soiling, in particular for cleaning dried on and/or burnt on soiling in automatic dishwashing.