DISHWASHER DETERGENT CONTAINING A COPOLYMER

Abstract

The invention relates to dishwasher detergents which comprise, as component Z1), one or more copolymers containing cationic structural units and macromonomer structural units and, as component Z2), one or more enzymes. The dishwasher detergents have in particular an advantageous rinsing power and an advantageous drying power, in both cases also in phosphate-free compositions.

Claims

1. A dishwasher detergent comprising Z1) at least one copolymer containing a) 0.1 to 99.9 mol % of at least one cationic structural unit (A) and b) 0.1 to 99.9 mol % of at least one macromonomeric structural unit (B), wherein the at least one cationic structural unit (A) is represented by the following formulae (I) and/or (II): ##STR00017## R.sup.1 and R.sup.1a are each identical or different and independently of one another are each hydrogen and/or a methyl radical, R.sup.1b, R.sup.3, R.sup.4 and R.sup.5 are each identical or different and independently of one another are each represented by hydrogen, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, a cycloaliphatic hydrocarbon radical having 5 to 20 carbon atoms, an aryl radical having 6 to 14 carbon atoms and/or polyethylene glycol (PEG), Y is identical or different and is represented by oxygen, NH and/or NR.sup.3, V is identical or different and is represented by (CH.sub.2).sub.x, ##STR00018## x is identical or different and is represented by an integer from 1 to 6, X and X.sub.1 are each identical or different and independently of one another are each represented by a halogen atom, C.sub.1 to C.sub.4 alkyl sulfate and/or C.sub.1 to C.sub.4 alkylsulfonate, and the at least one macromonomeric structural unit (B) is represented by the formula (III): ##STR00019## in which R.sup.x is identical or different and is represented by H and/or methyl, Z is identical or different and is represented by CO and/or O(CH.sub.2).sub.4, l is on molar average a number from 0 to 7, and p is on molar average a number from 1 to 150, and Z2) at least one enzyme.

2. The dishwasher detergent as claimed in claim 1, wherein the at least one cationic structural unit (A) of the at least one copolymers of component Z1) represents the polymerization product of at least one monomer species selected from the group consisting of [2-(acryloyloxy)ethyl]trimethylammonium chloride, [2-(acryloylamino)-ethyl]trimethylammonium chloride, [2-(acryloyloxy)ethyl]trimethylammonium methosulfate, [2-(methacryloyloxy)ethyl]trimethylammonium chloride and methosulfate, [3-(acryloylamino)propyl]trimethylammonium chloride, [3-(methacryloylamino)propyl]trimethylammonium chloride and diallyldimethylammonium chloride (DADMAC).

3. The dishwasher detergent as claimed in claim 1, wherein the at least one macromonomeric structural unit (B) of the formula (III) of the at least one copolymer of component Z1) represents the polymerization product of at least one monomer species selected from the group consisting of polyethylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol vinyloxybutyl ether (in which l is on molar average a number from 1 to 7), polyethylene glycol (meth)acrylate and polyethylene glycol-co-polypropylene glycol (meth)acrylate (in which l is on molar average a number from 1 to 7).

4. The dishwasher detergent as claimed in claim 1, wherein, in the at least one macromonomeric structural unit (B) of the formula (III) of the at least one copolymer of component Z1), i) R.sup.x is H, l is 0, and p is on molar average a number from 1 to 150 if Z is O(CH.sub.2).sub.4 or ii) R.sup.x is identical or different and is represented by H and/or methyl, l is on molar average a number from 1 to 7, and p is on molar average a number from 1 to 150 if Z is CO.

5. The dishwasher detergent as claimed in claim 1, wherein the at least one copolymer of component Z1) comprises not only the structural units (A) and (B) but also at least one structural unit (C) which differ from the structural units (A) and (B), the at least one copolymer containing 0.1 to 99.8 mol % of the at least one structural unit (A), 0.1 to 99.8 mol % of the at least one structural unit (B), and 0.1 to 99.8 mol % of the at least one structural unit (C).

6. The dishwasher detergent as claimed in claim 5, wherein the at least one structural unit (C) of the at least one copolymer of component Z1) represents the polymerization product of at least one monomer species selected from the group consisting of noncationic acrylamides, noncationic methacrylamides, and N-vinyl-substituted lactams having 5 to 7 ring atoms.

7. The dishwasher detergent as claimed in claim 5, wherein the at least one structural unit (C) of the at least one copolymer of component Z1) is selected from the group consisting of the polymerization product of at least one N-vinyl-substituted lactam having 5 to 7 ring atoms and structural units of the following formulae (IV) and/or (V): ##STR00020## in which R.sup.1 is identical or different and is hydrogen and/or methyl, and R.sup.3 and R.sup.4 are each identical or different and independently of one another are each represented by hydrogen, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, a cycloaliphatic hydrocarbon radical having 5 to 20 carbon atoms, an aryl radical having 6 to 14 carbon atoms, an alkylaryl radical having 7 to 14 carbon atoms, a branched or unbranched C.sub.1-C.sub.5 monohydroxyalkyl group and/or polyethylene glycol (PEG) ##STR00021## in which R.sup.11 is identical or different and is represented by H and/or methyl; X is identical or different and is represented by NH(C.sub.nH.sub.2n) where n=1, 2, 3 or 4; and R.sup.13 is identical or different and is represented by OH, N(CH.sub.3).sub.2, SO.sub.3H, PO.sub.3H.sub.2, OPO.sub.3H.sub.2 and/or para-substituted C.sub.6H.sub.4SO.sub.3H.

8. The dishwasher detergent as claimed in claim 1, wherein the at least one structural unit (C) of the at least one copolymer of component Z1) is selected from the group consisting of the structural units of the formula (IV).

9. The dishwasher detergent as claimed in claim 1, wherein the at least one structural unit (C) of the at least one copolymer of component Z1) represents the polymerization product of at least one monomer species selected from the group consisting of acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N-methylolacrylamide, N-isopropylacrylamide, and N-tert-butylacrylamide.

10. The dishwasher detergent as claimed in claim 5, wherein the at least one copolymer of component Z1) comprise not only the structural units (A), (B), and (C) but also at least one structural unit (D) which differs from the structural units (A), (B), and (C), the at least one copolymer comprises 0.1 to 99.7 mol % of the at least one structural unit (A), 0.1 to 99.7 mol % of the at least one structural unit (B), 0.1 to 99.7 mol % of the at least one structural unit (C), and 0.1 to 99.7 mol % of the at least one structural unit (D).

11. The dishwasher detergent as claimed in claim 10, wherein the at least one copolymer of component Z1) comprises at least one structural unit (D) selected from the qroup consistinq of the structural units of the following formulae (IX) and/or (X): ##STR00022## in which R.sup.11 is identical or different and is represented by H and/or methyl; Z is identical or different and is represented by O and/or NH; ##STR00023## in which R.sup.11 is identical or different and is represented by H and/or methyl; Q is identical or different and is represented by O and/or NH; and R.sup.15 is identical or different and is represented by H, (C.sub.nH.sub.2n)SO.sub.3H where n=0, 1, 2, 3 or 4; (C.sub.nH.sub.2n)OH where n=0, 1, 2, 3 or 4; (C.sub.nH.sub.2n)PO.sub.3H.sub.2 where n=0, 1, 2, 3 or 4; (C.sub.nH.sub.2n)OPO.sub.3H.sub.2 where n=0, 1, 2, 3 or 4; (C.sub.6H.sub.4)SO.sub.3H; (C.sub.6H.sub.4)PO.sub.3H.sub.2; (C.sub.6H.sub.4)OPO.sub.3H.sub.2 and/or (C.sub.mH.sub.2m).sub.eO-(AO).sub.uR.sup.16 where m=0, 1, 2, 3 or 4, e=0, 1, 2, 3 or 4, A=C.sub.xH.sub.2x where x=2, 3, 4 or 5, u=an integer from 1 to 350, and R.sup.16 is identical or different and is represented by an unbranched or branched C.sub.1-C.sub.4 alkyl group.

12. The dishwasher detergent as claimed in claim 10, wherein the structural units (A), (B), and optionally (C) and (D) of the at least one copolymer of component Z1) is present in random, blockwise, alternating or gradientlike distribution in the copolymer.

13. The dishwasher detergent as claimed in claim 1, wherein the weight-average molecular weight M.sub.w of the at least one copolymer of component Z1) is from 10 000 to 250 000 g/mol.

14. The dishwasher detergent as claimed in claim 1, wherein it comprises the at least one copolymer of component Z1) in an amount from 0.0005 to 10 wt %, based in each case on the total weight of the dishwasher detergent.

15. The dishwasher detergent as claimed in claim 1, wherein the at least one enzyme of component Z2) is selected from the group consisting of proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases, and oxidoreductases.

16. The dishwasher detergent as claimed in claim 1, wherein it comprises the at least one enzyme of component Z2) in an amount from 110.sup.6 to 5 wt %, based in each case on the total weight of the dishwasher detergent.

17. The dishwasher detergent as claimed in claim 1, wherein it comprises not only the at least one copolymer of component Z1) and the at least one enzyme of component Z2) but also at least one further substance selected from the group consisting of the components Z3), Z4), Z5) and Z6): Z3) at least one builder as component Z3), Z4) a bleaching system as component Z4), Z5) at least one surfactant as component Z5), Z6) at least one further additive, and the pH of the dishwasher detergent at 20 C. from 8 to 14, measured as a 10 wt % solution of the liquid or solid dishwasher detergent in water.

18. The dishwasher detergent as claimed in claim 17, wherein the at least one surfactant of component Z5) is selected from the group of nonionic surfactants.

19. The dishwasher detergent as claimed in claim 17, wherein the at least one surfactant of component Z5) is selected from the group consisting of fatty alcohol alkoxylates, endgroup-capped fatty alcohol alkoxylates, ethylene oxide propylene oxide block copolymers, N-acylglucamides, and epoxy-capped poly(oxalkylated) alcohols.

20. The dishwasher detergent as claimed in claim 17, wherein it contains Z1) 0.0005 to 10 wt % of component Z1), Z2) 110.sup.6 to 5 wt % of component Z2), Z3) 2 to 50 wt % of component Z3), Z4) 1 to 40 wt % of component Z4), Z5) 0.10 to 15 wt % of component Z5), Z6) 0 to 10 wt % of component Z6) based in each case on the total weight of the dishwasher detergent.

21. The dishwasher detergent as claimed in claim 1, wherein it contains no phosphate-based builders.

22. The dishwasher detergent as claimed in claim 1, wherein it is solid at 20 C. and is in the form of a tablet.

23. A method for cleaning dishware in a dishwasher, wherein soiled dishware is treated in a dishwasher with an aqueous alkaline composition comprising a dishwasher detergent as claimed in claim 1.

24. The method as claimed in claim 23, wherein the pH of the aqueous alkaline composition is 8 or more.

25.-28. (canceled)

Description

EXAMPLES

[0285] Abbreviations used are as follows:

TABLE-US-00001 AAPTAC [3-(Acryloylamino)propyl]trimethylammonium chloride (75 wt % active in aqueous solution) AMPS-Na 2-Acryloylamino-2-methylpropanesulfonic acid, Na salt salt (50 wt % % active in aqueous solution) DADMAC Diallyldimethylammonium chloride (65 wt % active in aqueous solution) DMAA N,N-Dimethylacrylamide (100% active) MAPTAC [3-(Methacryloylamino)propyl]trimethylammonium chloride (50 wt % active in aqueous solution) MESNA 2-Mercaptoethanesulfonate sodium (100% active) Meth 1000 Polyethylene glycol-co-polypropylene glycol methacrylate, 1000 g/mol, 4-5 Propylene glycol units (70 wt % active in aqueous solution) Meth 5000 Polyethylene glycol-co-polypropylene glycol methacrylate, 5000 g/mol, 4-5 Propylene glycol units (50 wt % active in aqueous solution) MS-Na Maleic acid, Na salt salt (100% active) NIPAM N-Isopropylacrylamide (100% active) NVP N-Vinylpyrrolidone (100% active) VA-44 2,2-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (100% active) V-PEG Polyethylene glycol vinyloxybutyl ether, 1100 g/mol 1100 (100% active) V-PEG Polyethylene glycol vinyloxybutyl ether, 5000 g/mol 5000 (100% active)

[0286] Preparation of the Copolymers

[0287] General Protocol for Preparing the Copolymers:

[0288] A multineck flask fitted with a KPG stirrer, reflux condenser, and N.sub.2 connection is used to dissolve the specified amounts of chemicals (apart from the initiator) in the specified amount of distilled water under nitrogen (5 liters/hour) for the examples specified in table 1 for preparing copolymers of component Z1). It should be borne in mind that some of the substances used for preparing the copolymers of component Z1) are employed in aqueous form (see the details of the substances used for preparing the copolymers of component Z1)). The distilled water specified in table 1 is added in addition to the water introduced by way of these substances. In the case of acidic monomers, they are neutralized beforehand with base, such as alkali metal carbonate, as for example potassium carbonate. The aqueous solution is subsequently purged with nitrogen for 30 minutes and heated to 60 C. if using VA-44 as initiator or to 80 C. if using Na.sub.2S.sub.2O.sub.8 as initiator. In the next step, the amount of initiator (VA-44 or Na.sub.2S.sub.2O.sub.8) specified in table 1 is dissolved in 10 g of distilled water and metered in over a period of 90 minutes. After the end of metering, stirring is continued for a further hour at an internal temperature of 60 C. if using VA-44 as initiator or at an internal temperature of 80 C. if using Na.sub.2S.sub.2O.sub.8 as initiator. The conversion in the reaction is checked by a subsequent analysis of the solids, and any unconverted monomers, optionally by slight addition of a 10 wt % aqueous solution of the initiator already employed beforehand, are reacted until complete conversion is achieved. Thereafter the reaction mixture is cooled to room temperature (20-23 C.).

[0289] Table 1 lists synthesis examples of copolymers of component Z1) of the dishwasher detergents of the invention

TABLE-US-00002 TABLE 1 Substances used in preparing the copolymers Co- V-PEG V-PEG Meth Meth polymer 1100 5000 1000 5000 AAPTAC NIPAM DMAA DADMAC MAPTAC # [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] 1 4.816 22.899 61.294 2 4.816 20.060 61.294 3 6.558 14.758 25.777 4 4.816 91.395 30.760 5 4.816 91.395 30.760 6 4.816 80.064 30.760 7 4.816 57.198 46.163 8 4.816 22.899 83.755 9 4.816 50.000 46.000 10 4.816 80.064 30.760 11 29.809 14.758 25.777 12 29.809 14.758 25.777 13 8.750 30.328 55.232 14 34.370 30.328 55.232 15 49.994 27.670 14.758 16 10.000 28.034 17 6.794 27.670 14.758 Co- AMPS MS Na-Hypo- dist. polymer NVP Na salt Na salt phosphite MESNA VA-44 Na.sub.2S.sub.2O.sub.8 H.sub.2O # [mmol] [mmol] [mmol] [g] [g] [g] [g] [g] 1 1.560 136.000 2 1.560 136.000 3 0.120 1.560 146.000 4 0.120 1.560 149.450 5 1.090 1.560 149.450 6 0.120 1.560 144.860 7 1.560 139.500 8 1.560 142.250 9 1.560 697.500 10 1.560 724.300 11 0.120 1.560 80.000 12 1.560 149.500 13 56.235 0.180 1.560 131.670 14 140.543 0.540 1.560 160.700 15 0.180 1.560 138.780 16 9.989 0.180 1.560 105.000 17 0.180 1.150 162.790
The amounts specified in table 1 are based on the active substance

TABLE-US-00003 TABLE 1a relative amounts according to table 1 Co- Total amount Structural poly- of monomers units Structural Structural Structural mer used (A) units (B) units (C) units (D) # [mmol] [mol %] [mol %] [mol %] [mol %] 1 89.009 68.9 5.4 25.7 2 86.170 71.1 5.6 23.3 3 47.093 54.7 13.9 31.3 4 126.971 24.2 3.8 72.0 5 128.061 24.0 3.8 71.4 0.9 6 115.640 26.6 4.2 69.2 7 108.177 42.7 4.5 52.9 8 111.470 75.1 4.3 20.5 9 100.816 45.6 4.8 49.6 10 115.640 26.6 4.2 69.2 11 70.344 36.6 42.4 21.0 12 70.344 36.6 42.4 21.0 13 150.545 20.1 5.8 74.0 14 260.473 11.6 13.2 75.2 15 92.422 29.9 54.1 16.0 16 48.023 58.4 20.8 20.8 17 49.222 56.2 13.8 30.0

TABLE-US-00004 TABLE 2 Measured weight-average molecular weights M.sub.w Copolymer Measured weight-average # molecular weight M.sub.w [g/mol] 1 42 261 2 33 497 3 42 667 5 57 227 6 35 849 7 102 330 8 10 934 9 91 934 10 118 920

Example 1: Rinse Performance of Dishwasher Detergents

[0290] An investigation was made of the rinse performance of the inventive formulations F2-F6. Tested as a comparative example was the rinse performance of formulation F1, which contained only fatty alcohol alkoxylate as rinse surfactant.

[0291] Test Conditions: [0292] Dishwasher: Miele G 1222 SC GSL [0293] Test ware (8 groups): 6 drinking glasses (higher quality) [0294] 6 drinking glasses (lower quality) [0295] 3 polypropylene bowls [0296] 3 melamine plates [0297] 3 butter dishes+4 knives (stainless steel; lower quality) [0298] 4 knives (stainless steel; higher quality) [0299] 3 porcelain plates (higher quality) [0300] 3 porcelain plates (lower quality) [0301] Wash program: program 4, R=2 without prewash [0302] main wash at 50 C. [0303] rinsing at 65 C. [0304] Water hardness: 21 dH [German hardness] [0305] Water softening: none [0306] Detergent metering: 18 g, added to the metering chamber before start of test [0307] Soiling: 100 g of frozen soiling, added immediately after opening of the metering chamber [0308] Rinse aid: none [0309] Cleaning cycles: 4

[0310] All of the items of ware apart from the polypropylene bowls were treated once with demineralized water, Neodisher A 8, citric acid, and demineralized water again.

[0311] Assessment:

[0312] Assessment of the test ware was begun no earlier than 30 minutes after the door of the dishwasher had been opened after the end of the wash. In each test, an assessment was made of washes 2-4. The assessment was made in each case in accordance with the following scoring:

[0313] Rinse Effects Considered in the Visual Scoring: [0314] Spots spots of different size and intensity [0315] Contact points spots resulting from points of contact between ware and components of the dishwasher [0316] Streaks rinsing streaks [0317] Filming continuous film spread uniformly over the test ware [0318] Structural filming scattered, broken film [0319] Solid residues solid powdery or crystalline residues [0320] Grease residues grease drops or formation of a greasy film [0321] Iridescence opalescence, iridescence

[0322] Visual Scoring: [0323] 10 Perfect [0324] 9 Perfect to just visible [0325] 8 Just visible [0326] 7 Just visible to visible [0327] 6 Visible [0328] 5 Visible to nuisance [0329] 4 Nuisance [0330] 3 Nuisance to unacceptable [0331] 2 Unacceptable [0332] 1 Absolutely unacceptable

[0333] The combination of the eight rinse effects set out above results in a score of 1-10 according to the above visual scoring for each item of ware, with a score of 1 representing the worst performance and a score of 10 being the best performance. For each of the above-listed eight test ware groups, the average score for all items of ware in a particular materials group was formed for each wash, after which the sum total of all the materials groups was formed for each wash, and lastly the average was determined for all three washes 2-4 assessed. The resulting average score was used as the total rinse performance for the purpose of comparing the various formulations F1-F6. This leads to a theoretical maximum with the best rinse performance of 80.0 and to a theoretical minimum with the worst rinse performance of 8.0.

[0334] The results are shown in table A hereinafter.

Example 2: Drying Performance of Dishwasher Detergents

[0335] An investigation was made into the drying performance of the inventive formulations F2-F6. As a comparative example, the drying performance of formulation F1, containing only fatty alcohol alkoxylate, was tested.

[0336] Test Conditions: [0337] Dishwasher: Bosch SMS86 [0338] Test ware: 10 starter knives [0339] 10 starter forks [0340] 10 starter spoons [0341] 10 coffee spoons [0342] 2 vegetable spoons [0343] 12 drinking glasses [0344] 10 porcelain cups [0345] 25 porcelain plates [0346] 3 SAN plates [0347] 3 polypropylene plates [0348] 6 polypropylene bowls [0349] Wash program: Eco 50 Variospeed Plus without prewash [0350] main wash at 50 C. [0351] rinsing at 65 C. [0352] drying phase at 70 C. [0353] Water hardness: 21 dH [German hardness] [0354] Water softening: none [0355] Detergent metering: 18 g, added to the tablet collection tray immediately after opening the metering chamber [0356] Soiling: 100 g of frozen soiling, added immediately after opening of the metering chamber [0357] Rinse aid: none [0358] Cleaning cycles: 4

[0359] All the articles were treated once with demineralized water, Neodisher A 8, citric acid, and demineralized water again.

[0360] Assessment:

[0361] Assessment of the test ware was begun 30 minutes after the end of the wash. During this time, the door of the dishwasher remained closed. In each test, an assessment was made of washes 2-4. The assessment was made in each case under illumination of 1000-1500 lux.

[0362] In a set order and with a set time limit, a count was made of the number of adhering residual water drops for each item of test ware. Depending on the number of drops counted, the scoring for each item of test ware is as follows:

[0363] Scoring:

TABLE-US-00005 0 dry, no water drops 1 1 water drop 2 2 water drops 3 3 water drops 4 4 water drops 5 5 water drops 6 more than 5 water drops

[0364] In this assessment scheme, a score of 0 represents the best performance and a score of 6 the worst performance for each item of test ware. For each wash 2, 3 and 4, the sum total of the scores of all the items of test ware was formed. For comparison of the various formulations F1-F6, the average score of all sum totals of the washes 2-4 was averaged in each case. This leads to a theoretical maximum with the poorest drying performance of 606, and a theoretical minimum with the best drying performance of 0.

[0365] The results are shown in table A hereinafter.

[0366] Compositions:

[0367] The compositions of the formulations F1-F6 and also the values for the rinse performance and for the drying performance are specified in table A below.

TABLE-US-00006 TABLE A Compositions, rinse performance, and drying performance for formulations F1-F6 F1 F2 F3 F4 F5 F6 Component wt %*.sup.) wt %*.sup.) wt %*.sup.) wt %*.sup.) wt %*.sup.) wt %*.sup.) Trisodium citrate 30.0 30.0 30.0 30.0 30.0 30.0 dihydrate Sodium carbonate 20.0 20.0 20.0 20.0 20.0 20.0 Sodium silicate 2.0 2.0 2.0 2.0 2.0 2.0 MGDANa.sub.3 15.0 15.0 15.0 15.0 15.0 15.0 Polycarboxylate 10.0 10.0 10.0 10.0 10.0 10.0 Sodium percarbonate 9.0 9.0 9.0 9.0 9.0 9.0 TAED 2.0 2.0 2.0 2.0 2.0 2.0 HEDP 0.9 0.9 0.9 0.9 0.9 0.9 Protease 0.5 0.5 0.5 0.5 0.5 0.5 Amylase 0.5 0.5 0.5 0.5 0.5 0.5 C.sub.12/15 Oxo-process 3.5 3.5 3.5 3.5 3.5 3.5 alcohol alkoxylate Copolymer 1 0.1 Copolymer 2 0.1 Copolymer 3 0.1 Copolymer 4 0.1 Copolymer 5 0.1 Water ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 2 Sodium sulfate 2.4**.sup.) 1.9**.sup.) 1.9**.sup.) 1.9**.sup.) 1.9**.sup.) 1.9**.sup.) Overall rinse 25.9 28.8 29.5 29.1 31.1 30.1 performance Drying performance 225 111 103 128 101 107 *.sup.)The ingredients are added according to their active substance content in wt %. **.sup.)Sodium sulfate is added as a filler for a constant mass balance of the dishwasher detergent, without function and without influence on the performance of the dishwasher detergent.

[0368] From the results in table A above it is apparent that the use of the inventive dishwasher detergents F2-F6 leads to advantageous values for the rinse performance and for the drying performance, in comparison to the use of the comparative formulation F1.

[0369] Furthermore, the inventive dishwasher detergents F2-F6 in the above example exhibit very good cleaning performance.