MIXED HYDROXYETHER COMPOUNDS, PROCESS FOR MAKING SUCH COMPOUNDS, AND THEIR USE

Abstract

Described herein are compounds according to general formula (I)

R.sup.1—CHR.sup.2—CH.sub.2—O-(AO).sub.x—CH.sub.2—CH(OH)—R.sup.3  (I).

Also described herein are a process to make the compounds according to general formula (I), and a method of using the compounds according to general formula (I) in a composition for automatic dishwashing.

Claims

1. A compound of general formula (I)
R.sup.1—CHR.sup.2—CH.sub.2—O-(AO).sub.x—CH.sub.2—CH(OH)—R.sup.3  (I) wherein R.sup.1 is linear or branched, unsubstituted C.sub.2-C.sub.4-alkyl, R.sup.2 is linear or branched, unsubstituted alkyl group bearing two carbon atoms more than R.sup.1, x is an integer in a range of from 10 to 35, AO is identical or different and selected from the group consisting of CH.sub.2—CH.sub.2—O, (CH.sub.2).sub.3—O, (CH.sub.2).sub.4—O, CH.sub.2CH(CH.sub.3)—O, CH(CH.sub.3)—CH.sub.2—O— and CH.sub.2CH(n-C.sub.3H.sub.7)—O, and R.sup.3 is linear or branched, unsubstituted or substituted C.sub.6-C.sub.18-alkyl.

2. The compound according to claim 1, wherein R.sup.1 is selected from the group consisting of ethyl, n-propyl and iso-propyl.

3. The compound according to claim 1, wherein R.sup.2 is selected from the group consisting of n-butyl, iso-butyl, n-pentyl, iso-pentyl, 3-methylpentyl, n-hexyl, iso-hexyl and mixtures thereof.

4. The compound according to claim 1, wherein R.sup.3 is selected from the group consisting of n-hexyl, n-octyl, n-decyl, n-dodecyl and mixtures thereof.

5. The compound according to claim 1, wherein R.sup.1 is propyl and R.sup.2 is selected from the group consisting of n-pentyl, iso-pentyl and mixtures thereof.

6. The compound according to claim 1, wherein AO is identical and is CH.sub.2—CH.sub.2—O.

7. The compound according to claim 1, wherein AO is (PO).sub.y-(EO).sub.x-y and y is in a range of from 0.2 to 2.

8. The compound according to claim 1, wherein AO is PO-(EO).sub.x-1.

9. A process for preparing the compound of general formula (I) according to claim 1 comprising the steps of (a) reacting an alcohol of the formula R.sup.1—CHR.sup.2—CH.sub.2—OH with one or more C.sub.2-C.sub.4-alkylene oxides, (b) reacting the reaction mixture obtained in step (a) with an epoxide according to formula (II) ##STR00009## wherein R.sup.3 is linear or branched, unsubstituted or substituted C.sub.6-C.sub.18-alkyl.

10. The process according to claim 9 wherein steps (a) and (b) are carried out in bulk.

11. A method of using the compound according to claim 1, the method comprising using the compound in a cleaning composition for automatic dishwashing.

12. A process for cleaning dishware in an automatic dishwasher, the process comprising using a composition that contains at least one compound according to claim 1 for cleaning dishware in the automatic dishwasher.

13. A cleaning composition comprising (A) at least one compound of general formula (I) according to claim 1, and (B) at least one additive.

14. The cleaning composition according to claim 13 comprising (A) 0.5 to 10% by weight of the at least one compound of general formula (I), and (B) 1 to 50% by weight of the at least one additive; by weight of a final weight of the cleaning composition.

15. The cleaning composition according to claim 13, wherein the at least one additive is selected from the group consisting of chelating agents, enzymes, builders, cobuilders, alkali metal carriers, bleaching agents, bleach catalysts, bleach activators, dyes, perfumes, corrosion inhibitors, anti-redeposition agents and fillers.

16. The cleaning composition according to claim 14, wherein the at least one additive is selected from the group consisting of chelating agents, enzymes, builders, cobuilders, alkali metal carriers, bleaching agents, bleach catalysts, bleach activators, dyes, perfumes, corrosion inhibitors, anti-redeposition agents and fillers.

17. A method of using a combination of at least two compounds according to claim 1, the method comprising using the combination of the at least two compounds in a cleaning composition for automatic dishwashing.

Description

EMBODIMENTS

[0252] 1. A compound of general formula (I)

R.sup.1—CHR.sup.2—CH.sub.2—O-(AO).sub.x—CH.sub.2—CH(OH)—R.sup.3  (I) [0253] wherein [0254] R.sup.1 is linear or branched, unsubstituted C.sub.2-C.sub.4-alkyl, [0255] R.sup.2 is linear or branched, unsubstituted alkyl group bearing two carbon atoms more than R.sup.1, [0256] x is an integer in the range of from 10 to 35, [0257] AO is identical or different and selected from CH.sub.2—CH.sub.2—O, (CH.sub.2).sub.3—O, (CH.sub.2).sub.4—O, CH.sub.2CH(CH.sub.3)—O, CH(CH.sub.3)—CH.sub.2—O— and CH.sub.2CH(n-C.sub.3H.sub.7)—O, and [0258] R.sup.3 is linear or branched, unsubstituted or substituted C.sub.6-C.sub.18-alkyl. [0259] 2. The compound according to embodiment 1, wherein R.sup.1 is selected from the group consisting of ethyl, n-propyl and iso-propyl. [0260] 3. The compound according to embodiment 1, wherein R.sup.2 is selected from the group consisting of n-butyl, iso-butyl, n-pentyl, iso-pentyl, 3-methylpentyl, n-hexyl, iso-hexyl and mixtures thereof. [0261] 4. The compound according to embodiment 1, wherein R.sup.3 is selected from the group consisting of n-hexyl, n-octyl, n-decyl, n-dodecyl and mixtures thereof. [0262] 5. The compound according to one or more of embodiments 1 to 4, wherein R.sup.1 is propyl and R.sup.2 is selected from the group consisting of n-pentyl, iso-pentyl and mixtures thereof. [0263] 6. The compound according to one or more of embodiments 1 to 5, wherein AO is identical and is CH.sub.2—CH.sub.2—O. [0264] 7. The compound according to embodiment 1, wherein AO is (PO).sub.y-(EO).sub.x-y and y is in the range of from 0.2 to 2. [0265] 8. The compound according to one or more of embodiments 1 to 5 or 7 wherein AO is PO-(EO).sub.x-1. [0266] 9. A process for preparing compound of general formula (I) as defined in one or more of embodiments 1 to 8, comprising the steps of [0267] (a) reacting an alcohol of the formula R.sup.1—CHR.sup.2—CH.sub.2—OH with one or more C.sub.2-C.sub.4-alkylene oxides, [0268] (b) reacting the reaction mixture obtained in step (a) with an epoxide according to formula (II)

##STR00008## [0269] wherein R.sup.3 is linear or branched, unsubstituted or substituted C.sub.6-C.sub.18-alkyl. [0270] 10. The process according to embodiment 9, wherein in step (a) the temperature is in the range of 70° C. to 250° C. [0271] 11. The process according to embodiment 9 or 10, wherein the reaction time of step (a) is in the range of 0.5 hour to 12 hours. [0272] 12. The process according to embodiment 9, wherein in step (b) the temperature is in the range of 120° C. to 200° C. [0273] 13. The process according to embodiment 9 or 12, wherein the reaction time of step (b) is in the range of from 1 hour to 6 hours. [0274] 14. The process according to one or more of embodiments 9 to 13, further comprising at least one solvent. [0275] 15. The process according to embodiment 14, wherein the at least one solvent is selected from the group consisting of hexane, cyclohexane, toluene and xylene, tetrahydrofuran, 1,4-dioxane, dimethylformamide, dimethylacetamide and N-methylpyrrolidone. [0276] 16. The process according to one or more of embodiments 9 to 15 wherein steps (a) and (b) are carried out in bulk. [0277] 17. Use of a compound according to any of embodiments 1 to 8 or of a combination of at least two compounds according to any of embodiments 1 to 8 in a cleaning composition for automatic dishwashing. [0278] 18. A process for cleaning dishware in an automatic dishwasher by using a composition that contains at least one compound of formula (I) according to one or more of embodiments 1 to 8. [0279] 19. A cleaning composition comprising [0280] (A) at least one compound of general formula (I) according to one or more of embodiments 1 to 8, and [0281] (B) at least one additive. [0282] 20. The cleaning composition according to embodiment 19 comprising [0283] (A) 0.5 to 10% by weight of at least one compound of general formula (I) according to one or more of embodiments 1 to 8, and [0284] (B) 1 to 50% by weight of at least one additive; [0285] by weight of the final weight of the cleaning composition. [0286] 21. The cleaning composition according to embodiment 19 or 20, wherein the at least one additive is selected from the group consisting of chelating agents, enzymes, builders, cobuilders, alkali metal carriers, bleaching agents, bleach catalysts, bleach activators, dyes, perfumes, corrosion inhibitors, anti-redeposition agents and fillers.

EXAMPLES

[0287] Compounds

[0288] Compound of general formula (I), (A.1):

n-C.sub.5H.sub.11—CH(n-C.sub.3H.sub.7)—CH.sub.2—O-(EO).sub.21—CH.sub.2—CH(OH)-n-C.sub.10H.sub.21  (1)

n-C.sub.5H.sub.11—CH(n-C.sub.3H.sub.7)—CH.sub.2—O-(EO).sub.23—CH.sub.2—CH(OH)-n-C.sub.10H.sub.21  (II)

[0289] Compounds used in Comparative examples, (B.1):

iso-C.sub.11H.sub.23—O-(EO).sub.21—CH.sub.2—CH(OH)-n-C.sub.10H.sub.21  (III)

iso-C.sub.9H.sub.19—O-(EO).sub.20—CH.sub.2—CH(OH)-n-C.sub.10H.sub.21  (IV)

iso-C.sub.13H.sub.27—O-(EO).sub.26—CH.sub.2—CH(OH)-n-C.sub.10H.sub.21  (V)

iso-C.sub.11H.sub.23—O-(EO).sub.22—CH.sub.2—CH(OH)-n-C.sub.8H.sub.17  (VI)

[0290] Additives

[0291] Chelating agent 1: Trisodium salt of methyl glycinediacetic acid (MGDA-Na.sub.3)

[0292] Chelating agent 2: Trisodium citrate dihydrate

[0293] Enzyme 1: Protease

[0294] Enzyme 2: Amylase

[0295] Builder 1: Polyacrylic acid M.sub.w 4000 g/mol as sodium salt, completely neutralized.

[0296] Builder 2: Polycarboxylate polymer of 2-Acrylamido-2-methylpropane sulfonic acid and acrylic acid

[0297] Builder 3: Na.sub.2Si.sub.2O.sub.5

[0298] Cobuilder: 1-hydroxyethane-1,1-diphosphonate (HEDP)

[0299] Bleaching agent: Sodium percarbonate

[0300] Filler: Sodium sulfate

[0301] Bleach activator: tetraacetylethylenediamine (TAED)

[0302] Alkali metal carrier: Na.sub.2CO.sub.3

[0303] The cleaning composition for automatic dishwashing are prepared according to table 1.

TABLE-US-00001 TABLE 1 All amounts in g/ sample ADW.1 ADW.2 ADW.3 ADW.4 ADW.5 ADW.6 ADW.7 Chelating agent 1 40.0 10.0 0.0 0.0 25.0 35.0 40.0 Enzyme 1 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Enzyme 2 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Compound according 3.0 to 3.0 to 3.0 to 3.0 to 3.0 to 3.0 to 3.0 to to general formula (I), 5.0 5.0 5.0 5.0 5.0 5.0 5.0 (A.1) Builder 1 5.0 5.0 0.0 0.0 0.0 0.0 0.0 Builder 2 0.0 0.0 5.0 5.0 5.0 5.0 5.0 Bleaching agent 15.0 10.2 10.2 10.2 10.2 10.2 15.0 Filler 1.0 0.0 0.0 9.5 9.5 0.0 1.0 Bleach activator 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Builder 3 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Alkali metal carrier 23.7 24.5 34.5 35.0 35.0 34.5 23.7 Chelating agent 2 0.0 35.0 30.0 25.0 0.0 0.0 0.0 Cobuilder 0.8 0.8 5.8 0.8 0.8 0.8 0.8

[0304] Cleaning compositions prepared according to Table-1 are excellent in rinsing, especially when used as automatic dishwashing compositions.

Example I

[0305] Rinse Performance

[0306] Rinsing Experiments:

[0307] The rinsing experiments of example I were carried out in Miele automatic dish wash machines, type G1223 GSL2. The program 50° C. (“R-time 2”, for washing) and 65° for rinsing was selected.

[0308] No separate rinsing agent was added, no regenerating salt was used. The dishwash experiments were carried out with water, 21° dH (German hardness), (Ca:Mg):HCO.sub.3 (3:1):1.35. In each experiment eight tea cups and nine dinner plates were placed in the dishwasher as base load. For evaluation in each experiment three knives (stainless steel), three blue melamine resin plates, three drinking glasses and three plates from china were placed in the dishwasher. Before each cycle 100 g of soil, comprising fat, protein and starch in the form of margarine, egg-yolk and starch, were added. In each cycle, 18 g of the detergent compositions for automatic dishwashing ADW.3 according to table 1 were added into the dosing chamber of the machine.

[0309] Between two cycles, a waiting period of one hour was hold, of which 10 minutes were with the door of the dishwashing machine closed and 50 minutes with open door. The dishes for the evaluation were checked by visual assessment of the ware after 6 cycles in a darkened chamber under light behind an aperture diaphragm was awarded using a grading scale from 1 (very poor) to 10 (very good). The grades for each type of table ware (knives (stainless steel), blue melamine resin plates, drinking glasses, plates from china) were summed up and divided by the number (3) of tableware. Results are found in table 2. Σ Spotting is the sum of the values for all 4 different tableware types. The standard deviation of the grades in the comparative test is ±0.5.

[0310] The 18 g portions of the detergent compositions for automatic dishwashing ADW.3 according to table 1 were made by mixing the solid ingredients except (A.1) and weighing portions of 17.1 g of this base mixture. To each portion the associated quantity found in table 2 of molten (A.1) in case of inventive examples and molten (B.1) in case of comparative examples was added and distributed (A.1) or (B.1) homogeneously in the mixture before adding into the dosing chamber of the dishwashing machine.

TABLE-US-00002 TABLE 2 Rinsing Test base Spotting, Spotting, Spotting Spotting, Formulation mixture (A.1) (B.1) knives glass melamine china Σ Example no. (ADW.3) [g] [g] [g] (scale) (scale) (scale) (scale) Spotting Comparative (B.1) (III) 17.10 0.90 10.0 3.7 2.7 7.3 23.7 ex. 1 Comparative (B.1) (III) 17.10 0.54 1.0 1.0 1.7 1.0 4.7 ex. 2 Inventive (A.1) (II) 17.10 0.90 10.0 8.7 5.7 8.7 33.1 example 1 Inventive (A.1) (II) 17.10 0.54 8.7 3.0 2.0 3.3 17.0 example 2 Comparative (B.1) (IV) 17.10 0.90 9.0 4.3 4.3 6.0 23.6 ex. 3 Comparative (B.1) (IV) 17.10 0.54 5.0 2.0 1.3 2.0 10.3 ex. 4 Comparative (B.1) (V) 17.10 0.90 10.0 4.7 1.7 6.7 23.1 ex. 5 Comparative (B.1) (V) 17.10 0.54 10.0 2.0 1.3 2.7 16.0 ex. 6

[0311] As is evident from Table 2, the spotting results for knives, glass, melanin and china were higher when the cleaning composition comprised the inventive compounds of general formula (I) compared to the comparative examples. The compounds of the present invention provide a better spotting effect on different materials varying from steel, glass, plastic and china.

Example II

[0312] Rinsing Experiments:

[0313] The rinsing experiments of example 11 were carried out in Miele automatic dish wash machines, type G1223 GSL2. The program 50° C. (“R-time 2”, for washing) and 65′ for rinsing was selected. No separate rinsing agent was added, no regenerating salt was used. The dish-wash experiments were carried out with water, 21° dH (German hardness), (Ca:Mg):HCO.sub.3 (3:1):1.35. In each experiment eight tea cups and nine dinner plates were placed in the dishwasher as base load. For evaluation in each experiment three knives (stainless steel), three blue melamine resin plates, three drinking glasses and three plates from china were placed in the dishwasher. Before each cycle 100 g of soil, comprising fat, protein and starch in the form of margarine, egg-yolk and starch, were added. In each cycle, 18 g of the detergent compositions for automatic dishwashing ADW.2 according to table 1 were added into the dosing chamber of the machine.

[0314] Between two cycles, a waiting period of one hour was hold, of which 10 minutes were with the door of the dishwashing machine closed and 50 minutes with open door. The dishes for the evaluation were checked by visual assessment of the ware after 6 cycles in a darkened chamber under light behind an aperture diaphragm was awarded using a grading scale from 1 (very poor) to 10 (very good). The grades for each type of table ware (knives (stainless steel), blue melamine resin plates, drinking glasses, plates from china) were summed up and divided by the number (3) of tableware. Results are found in table 3. E Spotting is the sum of the values for all 4 different tableware types. The standard deviation of the grades in the comparative test is ±0.5.

[0315] The 18 g portions of the detergent compositions for automatic dishwashing ADW.2 according to table 1 were made by mixing the solid ingredients except (A.1) and weighing portions of 17.1 g of this base mixture. To each portion the associated quantity found in table 3 of molten (A.1) in case of inventive examples and molten (B.1) in case of comparative examples was added and distributed (A.1) or (B.1) homogeneously in the mixture before adding into the dosing chamber of the dishwashing machine.

TABLE-US-00003 TABLE 3 Rinsing Test base Formulation mixture (A.1) (B.1) Spotting, Spotting, Spotting Spotting, Σ Example (ADW.2) [g] [g] [g] knives glass melamine china Spotting Comparative (B.1) (III) 17.10 0.90 10.0 5.7 4.0 8.3 28.0 ex. 7 Comparative (B.1) (III) 17.10 0.54 2.3 2.0 3.3 2.3 9.9 ex. 8 Inventive (A.1) (II) 17.10 0.90 10.0 7.0 8.0 10.0 35.0 example 3 Inventive (A.1) (II) 17.10 0.54 10.0 8.0 4.3 9.7 32.0 example 4 Comparative (B.1) (IV) 17.10 0.90 10.0 9.0 5.7 10.0 34.7 ex. 9 Comparative (B.1) (IV) 17.10 0.54 8.7 5.3 5.0 5.0 24.0 ex. 10 Comparative (B.1) (V) 17.10 0.90 10.0 9.0 4.0 10.0 33.0 ex. 11 Comparative (B.1) (V) 17.10 0.54 7.0 2.0 3.3 4.7 17.0 ex. 12

[0316] The composition comprising the compound of the presently claimed invention exhibit an improved spotting as shown by the higher value on the grading scale for all the types of material compared to the comparative compositions.

Example III

[0317] Rinsing Experiments:

[0318] The rinsing experiments of example Ill were carried out in Miele automatic dishwash machines, type G1223 GSL2. The program 45° C. (“R-time 2”, for washing) and 550 for rinsing was selected. No separate rinsing agent was added, no regenerating salt was used. The dishwash experiments were carried out with water, 21° dH (German hardness), (Ca:Mg):HCO.sub.3 (3:1):1.35. In each experiment eight tea cups and nine dinner plates were placed in the dishwasher as base load. For evaluation in each experiment three knives (stainless steel), three blue melamine resin plates, three drinking glasses and three plates from china were placed in the dishwasher. Before each cycle 100 g of soil, comprising fat, protein and starch in the form of margarine, egg-yolk and starch, were added. In each cycle, 18 g of the detergent compositions for automatic dishwashing ADW.1 and ADW.7 according to table 1 were added into the dosing chamber of the machine.

[0319] Between two cycles, a waiting period of one hour was hold, of which 10 minutes were with the door of the dishwashing machine closed and 50 minutes with open door. The dishes for the evaluation were checked by visual assessment of the ware after 6 cycles in a darkened chamber under light behind an aperture diaphragm was awarded using a grading scale from 1 (very poor) to 10 (very good). The grades for each type of table ware (knives (stainless steel), blue melamine resin plates, drinking glasses, plates from china) were summed up and divided by the number (3) of tableware. Results are found in table 4. Σ Spotting is the sum of the values for all 4 different tableware types. The standard deviation of the grades in the comparative test is ±0.5.

[0320] The 18 g portions of the detergent compositions for automatic dishwashing ADW.1 and ADW.7 according to table 1 were made by mixing the solid ingredients except (A.1) and weighing portions of 17.1 g of this base mixture. To each portion the associated quantity found in table 4 of molten (A.1) in case of inventive examples and molten (B.1) in case of comparative examples was added and distributed (A.1) or (B.1) homogeneously in the mixture before adding into the dosing chamber of the dishwashing machine.

TABLE-US-00004 TABLE 4 Rinsing Test base Example Formulation mixture (A.1) (B.1) Spotting, Spotting, Spotting Spotting, Σ no. (ADW.1) [g] [g] [g] knives glass melamine china Spotting Comparative (B.1) (I) 17.10 0.63 10.0 8.0 2.7 7.3 28.0 ex. 13 Inventive (A.1) (II) 17.10 0.63 10.0 8.0 3.3 9.0 30.3 example 5 base Formulation mixture (A.1) (A.1) Spotting, Spotting, Spotting Spotting, Σ (ADW.7) [g] [g] [g] knives glass melamine china Spotting Comparative (B.1) (III) 17.10 0.63 2.3 4.3 3.0 4.3 13.9 ex. 14 Inventive (A.1) (II) 17.10 0.63 10.0 7.7 3.7 8.7 30.1 example 6

Example IV

[0321] Rinsing Experiments:

[0322] The rinsing experiments of example IV were carried out in Miele automatic dishwash machines, type G1223 GSL2. The program 50° C. (“R-time 2”, for washing) and 65° for rinsing was selected. No separate rinsing agent was added, no regenerating salt was used. The dishwash experiments were carried out with water, 21° dH (German hardness), (Ca:Mg):HCO.sub.3 (3:1):1.35. In each experiment eight tea cups and nine dinner plates were placed in the dishwasher as base load. For evaluation in each experiment three knives (stainless steel), three blue melamine resin plates, three drinking glasses and three plates from china were placed in the dishwasher. Before each cycle 100 g of soil, comprising fat, protein and starch in the form of margarine, egg-yolk and starch, were added. In each cycle, 18 g of the detergent compositions for automatic dishwashing ADW.4, ADW.5 and ADW.6 according to table 1 were added into the dosing chamber of the machine.

[0323] Between two cycles, a waiting period of one hour was hold, of which 10 minutes were with the door of the dishwashing machine closed and 50 minutes with open door. The dishes for the evaluation were checked by visual assessment of the ware after 6 cycles in a darkened chamber under light behind an aperture diaphragm was awarded using a grading scale from 1 (very poor) to 10 (very good). The grades for each type of table ware (knives (stainless steel), blue melamine resin plates, drinking glasses, plates from china) were summed up and divided by the number (3) of tableware. Results are found in table 5. Σ Spotting is the sum of the values for all 4 different tableware types. The standard deviation of the grades in the comparative test is ±0.5.

[0324] The 18 g portions of the detergent compositions for automatic dishwashing ADW.4, ADW.5 and ADW.6 according to table 1 were made by mixing the solid ingredients except (A.1) and weighing portions of 17.1 g of this base mixture. To each portion the associated quantity found in table 5 of molten (A.1) in case of inventive examples and molten (B.1) in case of comparative examples was added and distributed (A.1) or (B.1) homogeneously in the mixture before adding into the dosing chamber of the dishwashing machine.

TABLE-US-00005 TABLE 5 Rinsing Test base Formulation mixture (A.1) (B.1) Spotting, Spotting, Spotting Spotting, Σ Example no. (ADW.4) [g] [g] [g] knives glass melamine china Spotting Comparative (B.1) (III) 17.10 0.72 10.0 3.7 2.7 3.7 20.1 ex. 15 Inventive (A.1) (II) 17.10 0.72 10.0 4.3 8.7 7.3 30.3 example 7 base Formulation mixture (A.1) (B.1) Spotting, Spotting, Spotting Spotting, Σ (ADW.5) [g] [g] [g] knives glass melamine china Spotting Comparative (B.1) (III) 17.10 0.72 10.0 2.7 4.3 3.7 20.7 ex. 16 Inventive (A.1) (II) 17.10 0.72 10.0 6.7 6.0 7.0 29.7 example 8 base Formulation mixture (A.1) (B.1) Spotting, Spotting, Spotting Spotting, Σ (ADW.6) [g] [g] [g] knives glass melamine china Spotting Comparative (B.1) (III) 17.10 0.72 8.0 6.0 3.7 5.0 22.7 ex. 17 Inventive (A.1) (II) 17.10 0.72 10.0 5.3 6.0 10.0 31.3 example 9

Example V

[0325] Drying Experiments

[0326] The drying experiments of example V were carried out in Miele automatic dishwash machines, type G1223 GSL2. The program 45° C. (“R-time 2”, for washing) and 550 for rinsing was selected. No separate rinsing agent was added, no regenerating salt was used. The dishwash experiments were carried out with water, 21° dH (German hardness), (Ca:Mg):HCO.sub.3 (3:1):1.35.

[0327] A full load of tableware with items of different material were used (metal, glass, porcelain, plastic). For each cycle the detergent according to table 6 and 50 g of ballast soil were added to the machine. The first three cycles are used to condition the dishwasher. After these 3 conditioning cycles the next three cycles were evaluated. For the evaluation cycles, the machine is opened 30 minutes after end of machine program and residual water drops on all items are counted within about 10 minutes. Number of drops are counted from best 0=no water drops to 8=8 or more water drops left. Average value for each tableware group is calculated per cycle and average values of three evaluation cycles are calculated. In addition a average of all tableware groups is calculated. The standard deviation of the average values in the comparative test is ±0.5.

[0328] Machine Load:

[0329] 11 Dinner plates (tableware group porcelain)

[0330] 3 blue SAN plates (tableware group plastics)

[0331] 3 red PP plates (tableware group plastics)

[0332] 8 Soup plates (tableware group porcelain)

[0333] 7 dessert plates (tableware group porcelain)

[0334] 6 Tupperware boxes (tableware group plastics)

[0335] 6 beakers (tableware group gasses)

[0336] 10 cups (tableware group porcelain)

[0337] 6 drinking glasses (tableware group gasses)

[0338] 12 knives (tableware group cutlery)

[0339] 6 forks (tableware group cutlery)

[0340] 6 soup spoons (tableware group cutlery)

[0341] 6 desert forks (tableware group cutlery)

[0342] 6 coffee spoons (tableware group cutlery)

TABLE-US-00006 TABLE 6 Drying Test Average of base Average of Average of Average of Average of droplets on Formulation mixture (A.1) (B.1) droplets on droplets on droplets on droplets on all table- Example no. (ADW.2) [g] [g] [g] porcelain plastics glasses cutlery ware groups Comparative (B.1) (I) 17.10 0.54 3.40 7.28 2.39 0.98 3.51 ex. 18 Inventive (A.1) (I) 17.10 0.54 3.21 4.33 1.33 0.70 2.40 example 10 Comparative (B.1) (III) 17.10 0.72 2.95 3.44 1.14 0.50 2.01 ex. 19 Inventive (A.1) (I) 17.10 0.72 2.37 2.72 0.78 0.44 1.58 example 11 Comparative (B.1) (III) 17.10 0.90 2.30 2.97 0.97 0.29 1.38 ex. 20 Inventive (A.1) (I) 17.10 0.90 1.77 0.75 0.78 0.00 0.79 example 12

Example VI

[0343] Fat Residue

[0344] The determination of fat residues of example VI was carried out in Miele automatic dish wash machines, type G 1223 SC GSL2. The program 45° C. (“R-time 2”, for washing) and 55° for rinsing was selected. No separate rinsing agent was added, no regenerating salt was used. The dish-wash experiments were carried out with water, 21° dH (German hardness), (Ca:Mg):HCO.sub.3 (3:1):1.35.

[0345] In each experiment three stainless steel knives eight tea cups and nine dinner plates were placed in the dishwasher as base load. Before each cycle, 5 g of Biskin Gold®, a solid vegetable fat, and 5 g of margarine were added into the machine. For each cycle the detergent formulation according to table 7 were added to the machine, consisting of base mixture and (A.1) in case of inventive examples and molten (B.1) in case of comparative examples. 5 cycles were run without drying times between cycles. After the 5.sup.th cycles the filters from the bottom of the machines were taken out of the machine and dried for 18 h at ambient conditions. The weights of the filters were determined and the differences to their weights before the first cycle were calculated (fat residue [g]=weight of filter before test [g]−weight of filter after test). The standard deviation of the fat residue is ±0.2 g.

[0346] The results are summarized in table 7.

TABLE-US-00007 TABLE 7 Fat residue test base Fat Formulation mixture (A.1) residue Example no. (ADW.2) [g] [g] B.1 [g] Comparative ex. 21 (B.1) (VI) 17.10 — 0.54 3.37 Comparative ex. 22 (B.1) (VI) 17.10 — 0.72 5.12 Inventive example (A.1) (I) 17.10 0.54 — 2.48 13 Inventive example (A.1) (I) 17.10 0.72 — 3.27 14

[0347] As seen in Table 7, the amount of fat residue in case of formulations containing the compounds of the inventive examples is less compared to the comparative examples.