Ethoxylated Glycerol Esters And Method For The Production Thereof

Abstract

The invention relates to the use of a specific type of calcium catalyst (C) for the preparation of alkoxylated glycerol esters, alkoxylated glycerol esters prepared in the presence of the catalyst and a process for the preparation of the alkoxylated glycerol esters. It was found that in the presence of the above-mentioned calcium catalyst (C) the alkoxylation reaction requires a significantly smaller amount of time. Furthermore, it has been found that the ethoxylated glycerol esters prepared in the presence of calcium catalyst (C) lead to more homogeneous products with significantly lower hydroxyl values, less decomposition and improved processability.

Claims

1.-8. (canceled)

9. An ethoxylated glycerol ester of formula (I) ##STR00009## prepared from ethylene oxide and one or more triglycerides of formula (II) ##STR00010## in the presence of a calcium catalyst (C), wherein the catalyst (C) is prepared by a reaction involving (A) calcium hydroxide and (B) a carboxylic acid comprising 3 to 40 carbon atoms, wherein the molar ratio of calcium hydroxide (A) and carboxylic acid (B) in the preparation of the catalyst (C) is from 1:1 to 1:5, the carboxylic acid (B) is represented by formula (III), ##STR00011## wherein R.sup.4 is selected from saturated or unsaturated, linear or branched C.sub.1-C.sub.30 alkyl chains; R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are hydrogen, and p is an integer number from 1 to 11, the reaction involving (A) and (B) further involves an acid (AC) having a pK.sub.A value of 3 or less and is selected from the group consisting of acids of sulfur oxides and phosphorus oxides and the molar ratio of (A):(AC) is from 5:1 to 1:1, characterized in that R.sup.1, R.sup.2 and R.sup.3 in formulae (I) and (II) are equal or different and are independently selected from saturated or unsaturated, linear or branched C.sub.7-C.sub.24 alkyl chains; m, n and o in formula (I) are equal or different and are each independently an integer number from 1 to 200 with the proviso that the number-average of the sum of m+n+o is greater than 5.

10. The ethoxylated glycerol ester according to claim 9, characterized in that m, n and o are equal or different and are each independently a number from 1 to 80.

11. The ethoxylated glycerol ester according to claim 9, wherein the ethoxylated glycerol ester has a hydroxyl value smaller than 6 mg KOH/g.

12. A method for preparing an ethoxylated glycerol ester of formula (I), ##STR00012## comprising the steps of i) introducing a catalyst (C), wherein the catalyst (C) is prepared by a reaction involving (A) calcium hydroxide and (B) a carboxylic acid comprising 3 to 40 carbon atoms, wherein the molar ratio of calcium hydroxide (A) and carboxylic acid (B) in the preparation of the catalyst (C) is from 1:1 to 1:5, the carboxylic acid (B) is represented by formula (III), ##STR00013## wherein R.sup.4 is selected from saturated or unsaturated, linear or branched C.sub.1-C.sub.30 alkyl chains; R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are hydrogen, and p is an integer number from 1 to 11, the reaction involving (A) and (B) further involves an acid (AC) having a pK.sub.A value of 3 or less and is selected from the group consisting of acids of sulfur oxides and phosphorus oxides and the molar ratio of (A):(AC) is from 5:1 to 1:1, and one or more triglycerides of formula (II) ##STR00014## into a pressure-resistant reactor; ii) optionally replacing the air in the reactor with nitrogen or other protecting gas; iii) optionally drying the reactor content at a temperature of from 50° C. to 200° C. and/or a pressure below 0.8 bar; iv) heating the content of the reactor to a temperature of from 80° C. to 200° C.; v) optionally pressurizing the reactor with nitrogen or other protecting gas to a pressure of from 0.3 bar to 3.5 bar above atmospheric pressure; vi) pressurizing the reactor with ethylene oxide gas to a pressure of from 1.5 bar to 10 bar above atmospheric pressure with the proviso that the pressure is above the pressure prior to step vi); and vii) allowing the mixture to react until the pressure in the reactor is constant; wherein R.sup.1, R.sup.2 and R.sup.3 in formulae (I) and (II) are equal or different and are independently selected from saturated or unsaturated, linear or branched C.sub.7-C.sub.24 alkyl chains; m, n and o in formula (I) are equal or different and are each independently an integer number from 1 to 200 with the proviso that the number-average of the sum of m+n+o is greater than 5.

13. The method according to claim 12, characterized in that the mixture is cooled to a temperature of from 50 to 120° C. and residual ethylene oxide is removed at a pressure below 0.8 bar after carrying out step vii).

14. The method according to claim 12, characterized in that in step i) catalyst (C) is introduced in an amount of 0.1 wt-% to 5 wt-%, based on the total weight of the mixture of triglyceride of formula (II) and ethylene oxide.

15. The method according to claim 12, wherein at least steps ii), iii) and v) are carried out.

16. (canceled)

17. The method according to claim 12, wherein the reaction involving components (A) and (B) further involves an alcohol solvent having 1 to 5 carbon atoms, or a mixture thereof with water.

18. The method according to claim 12, wherein the acid (AC) is selected from the group consisting of sulfuric acid, sulfurous acid, sulfonic acids, phosphorus acid, phosphorous acid and phosphonic acids.

19. The method according to claim 12, wherein the acid (AC) is selected from the group consisting of sulfuric acid, sulfurous acid and methane sulfonic acid.

20. The method according to claim 12, wherein the acid (AC) is sulfuric acid.

21. The method according to claim 17, wherein the alcohol solvents are removed before the catalyst (C) is used for the preparation of the ethoxylated glycerol esters of formula (I).

22. The method according to claim 12, wherein the content of Ca.sup.2+ ions in the catalyst (C) is between 0.5 wt-% and 5 wt-%.

Description

EXAMPLES

Comparative Synthesis Example 1 Preparation of Calcium Catalyst of U.S. Pat. No. 5,386,045

[0072] A mixture of 125 g of alcohol ethoxylate (from C.sub.10/C.sub.12-fatty alcohol and 40 wt-% ethylene oxide; e.g. ALFONIC 1012-40 from Vista Chemical Company), 2 g of 2-ethylhexanoic acid, and 10.9 g of calcium hydroxide was stirred at room temperature under a nitrogen atmosphere in an autoclave, while 2 g of concentrated sulfuric acid were added over a period of 10 min. After complete addition of sulfuric acid, stirring was continued for 5 h. Subsequently, the mixture was heated to 150° C. and volatile components were removed in a stream of nitrogen over 15 min. The mixture was cooled to 125° C. and 17.5 g of aluminum trialkoxide (containing about 6 wt-% Al and with an average alkoxide carbon chain length of 10 carbon atoms) were added.

[0073] The mixture was stirred for additional 2 h at 125° C., after which the temperature was raised to 190° C. and volatile components were removed in a nitrogen stream. After an additional 0.5 hours at 190° C. the mixture was cooled to ambient temperature, providing a catalyst with a Ca.sup.2+ content of around 3 wt-% and an Al.sup.3+ content of around 0.6 wt-% (henceforth “(C-0)”).

Comparative Synthesis Example 2 Preparation of Co-Catalyst (Glycerol Mono-Oleate)

[0074] A mixture of 9.2 g of glycerol and 28.2 g of oleic acid was heated to 175° C. and stirred at this temperature, while removing water with a dean-stark apparatus, until the acid value was <2 mg KOH/g.

Synthesis Example 1

[0075] Preparation of Calcium Catalyst (C) with Carboxylic Acid of Formula (III) [0076] a) A mixture of 1047.0 g of a carboxylic acid of formula (III) under the trade name “Emulsogen COL 050” marketed by Clariant Produkte (Deutschland) GmbH, 55.8 g of Calcium hydroxide and 360.6 g of propan-2-ol was agitated at ambient temperature for 5 min with a batch disperser (Ultra Turrax from IKA Werke GmbH & Co KG). After this, 44.2 g of concentrated sulfuric acid were added over two minutes and the mixture was again agitated for 5 min with the batch disperser, providing a catalyst with a Ca.sup.2+ content of 2.00 wt-% (henceforth “(C-1)”). [0077] Similar results for providing the catalyst with a Ca.sup.2+ content of approximately 2.00 wt-% can be obtained by using methane-sulfonic acid or sulfurous acid instead of sulfuric acid. [0078] b) A mixture of 1047.0 g of a carboxylic acid of formula (III) under the trade name “Emulsogen COL 050” marketed by Clariant Produkte (Deutschland) GmbH, 55.8 g of Calcium hydroxide and 360.6 g of propan-2-ol was agitated at ambient temperature for 5 min with a batch disperser (Ultra Turrax from IKA Werke GmbH & Co KG). After this, 42.9 g of methanesulfonic acid (99 wt.-%) were added over two minutes and the mixture was again agitated for 5 min with the batch disperser, providing a catalyst with a Ca.sup.2+ content of 2.00 wt-% (henceforth “(C-3)”). [0079] c) A mixture of 1047.0 g of a carboxylic acid of formula (III) under the trade name “Emulsogen COL 050” marketed by Clariant Produkte (Deutschland) GmbH, 55.8 g of Calcium hydroxide and 360.6 g of propan-2-ol was agitated at ambient temperature for 5 min with a batch disperser (Ultra Turrax from IKA Werke GmbH & Co KG). After this, 603.7 g of sulfurous acid (6 wt.-%) were added over two minutes and the mixture was again agitated for 5 min with the batch disperser. The solvent mixture was removed under vacuum, providing a catalyst with a Ca.sup.2+ content of approx. 2 wt-% (henceforth “(C-4)”). [0080] Emulsogen COL 050 is a commercial product carboxylic acid (B) comprising, as main component, a carboxylic acid represented by formula (III) wherein R.sup.4 is oleyl; R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are hydrogen; and p is 5.

Synthesis Example 2

[0081] Preparation of Calcium Catalyst (C) with Carboxylic Acid of Formula (IV)

[0082] A mixture of 114 g isononanoic acid, 26.7 g calcium hydroxide, 346.38 g of propan-2-ol and 26.7 g water was agitated for 5 min with a batch disperser (Ultra Turrax from IKA Werke GmbH & Co KG). After this, 10.62 g of concentrated sulfuric acid were added in a single batch and the mixture was again agitated for 5 min with the batch disperser, providing a catalyst with a Ca.sup.2+ content of 2.75 wt-% (henceforth “(C-2)”).

Synthesis Example 3

General Alkoxylation Procedure

[0083] The triglyceride of formula (II), the catalyst and, if applicable, the co-catalyst, were placed into a glass autoclave, which was then flushed with nitrogen by alternatingly applying vacuum and introducing nitrogen (3 cycles). The mixture was dried under aspirator vacuum at 100° C. for 1 hour. The pressure in the autoclave was restored to ambient with nitrogen and heated to 175° C. At this temperature the autoclave was pressurized with nitrogen to a pressure of 0.8 bar above atmospheric pressure, after which pressure controlled dosage of ethylene oxide took place up to a maximum pressure of 4.5 bar above atmospheric pressure.

[0084] The ethoxylation is carried out in a semi-batch process with automated dosage of ethylene oxide within a given temperature window and up to the specified maximum pressure. The pressure is adjusted according to the increased filling volume of the vessel. After introduction of the intended amount of ethylene oxide and closing the ethylene oxide inlet, the reaction was continued until the pressure became constant.

[0085] The reactor content was cooled to 90° C. and aspirator vacuum was applied for 30 min in order to remove residual ethylene oxide. The temperature was reduced to 80° C. and the final product was transferred into storage vessels and analyzed. The typical batch scale was 400 g to 2000 g. The uptake of the intended amount of ethylene oxide is assured by gravimetry and by determination of the saponification value according to DIN EN ISO 3681.

[0086] The materials employed and reaction times to constant pressure in the synthesis example 3 are shown in the following Table 1 (molar equivalents):

TABLE-US-00001 TABLE 1 ethylene oxide Catalyst Co-catalyst Reaction Saponification Example Triglyceride amount amount amount time value No. (1 equivalent) [equivalents] Catalyst [wt- %] [wt- %] [min] [mgKOH/g] Comp. 1 coconut oil 12 C-0 2.0 — 1100 145 Comp. 2 coconut oil 12 KOtBu 1.15 2.0 720 137 Ex. 1 coconut oil 12 C-1 1.8 — 320 142 Comp. 3 coconut oil 22.5 C-0 2.0 1.5 1320 103 Comp. 4 coconut oil 22.5 KOtBu 1.5 5.0 630 96.0 Ex. 2 coconut oil 22.5 C-1 1.3 — 330 104 Comp. 5 coconut oil 60 C-0 1.6 — 1950 55.2 Ex. 3 coconut oil 60 C-1 0.65 — 580 53.0 Ex. 4 coconut oil 45 C-1 0.8 — 440 67.3 Comp. 6 sunflower oil 8 C-0 2.0 1.5 1140 142 Ex. 5 sunflower oil 8 C-1 2.0 — 390 138 Comp. 7 sunflower oil 40 C-0 0.93 0.7 1500 60.1 Comp. 8 sunflower oil 40 KOtBu 1.5 5.0 850 61.7 Ex. 6 sunflower oil 40 C-1 0.53 — 530 62.8 Ex. 7 sunflower oil 12 C-1 0.2 — 390 118 Ex. 8 sunflower oil 60 C-2 0.5 — 300 80.7 Ex. 9 abyssinian oil 60 C-1 0.4 — 500 49.0 Ex. 10 hydrogenated 88 C-1 0.6 — 630 34.9 high eruca rapeseed oil Ex. 11 rapeseed oil 200 C-1 0.5 — 660 17.2 Comp. 9 Trilaurin 35 C-0 2.0 — 2820 79.5 Ex. 12 Trilaurin 35 C-1 2.0 — 580 81.2 Ex. 13 sunflower oil 45 C-3 3.0 — 710 68.1 Ex. 14 sunflower oil 45 C-4 3.0 — 1220 69.0

[0087] An interruption of synthesis example 3 for 15 hours using C-0 resulted in the reaction being re-initiated at a significantly slower rate than the initiation of the reaction in the beginning. An interruption while using C-1 or C-2 resulted in the reaction restarting at essentially the same rate as observed directly before the interruption.

[0088] Furthermore, ethoxylation can also be performed with fatty alcohols, fatty acid alkyl esters, and fatty acid alkylene glycol diesters instead of triglycerides by using the same procedure with catalysts C-1 or C-2. Moreover, it is also possible to perform the ethoxylation of triglycerides, fatty alcohols, fatty acid alkyl esters, and fatty acid alkylene glycol diesters in the presence of additional glycerol, to obtain products with higher polarity due to a larger number of hydroxyl groups in the product.

[0089] From Table 1 it is evident that in the inventive examples, employing catalyst (C-1) or (C-2), the triglycerides reacted at a significantly higher rate than in the comparative examples employing catalyst (C-0) or KOtBu, optionally with glycerol monooleate as co-catalyst. The faster reaction rate is observed with any amount of ethylene oxide introduced and with any triglyceride employed.

[0090] Furthermore, after emptying the autoclave after the reaction employing catalyst (C-0), off-white solids were adhered to the stirrer and temperature sensor as well as in the reaction vessel. These solids were not observed when catalyst (C-1) or catalyst (C-2) were employed in the reaction.

[0091] In Table 2, the appearance of several comparative examples and inventive examples under different conditions is described.

TABLE-US-00002 TABLE 2 Example Temperature No. [° C.] State Appearance Homogeneity Ex. 1 25 Liquid turbid liquid homogeneous Comp. 1 25 Liquid turbid liquid, inhomogeneous solid precipitate Ex. 1 65 Liquid almost clear liquid homogeneous Comp. 1 65 Liquid turbid liquid, inhomogeneous solid precipitate Ex. 2 40 Solid colorless solid homogeneous Comp. 3 40 Liquid turbid liquid, inhomogeneous solid precipitate Ex. 2 65 Liquid almost clear homogeneous Comp. 3 65 Liquid almost clear liquid, inhomogeneous solid precipitate Ex. 3 25 Solid colorless solid homogeneous Comp. 5 25 Solid off-white and inhomogeneous colorless solids Ex. 3 65 Liquid clear liquid homogeneous Comp. 5 65 Liquid almost clear liquid, inhomogeneous solid precipitate

[0092] In Table 3, the hydroxyl values and ratios of CH.sub.2OH groups to alkyl-CH.sub.3 groups of several inventive and comparative examples are shown.

[0093] Hydroxyl values were measured according to DIN EN ISO 4629-2. The ratios of CH.sub.2OH groups to alkyl-CH.sub.3 groups were calculated from the integral ratios of the corresponding Proton-NMR signals using a Bruker NMR spectrometer with 400 MHz and CDCl.sub.3 as a solvent.

[0094] The off-white solid residue from comparative examples employing (C-0) as catalyst was insoluble and was not be analyzed.

TABLE-US-00003 TABLE 3 OH-value CH.sub.2OH/Alkyl- Example No. [mg KOH/g] CH.sub.3 ratio Comp. 1 7.6 0.06 Comp. 2 28 0.23 Ex. 1 4.0 0.02 Comp. 3 15 0.13 Comp. 4 41 0.38 Ex. 2 3.1 0.03 Comp. 5 6.6 0.12 Ex. 3 2.7 0.04 Ex. 4 4.6 0.04 Comp. 6 8.9 0.19 Ex. 5 3.1 0.02 Ex. 10 4.6 0.05 Comp. 9 11 0.13 Ex. 12 5.5 0.07

[0095] From the OH values of the comparative and inventive examples it is evident, that the ethoxylated triglycerides of the inventive examples using catalyst (C-1) suffered less decomposition during the synthesis reaction than the ethoxylated triglycerides of the comparative examples using catalysts (C-0) or KOtBu.

[0096] In particular, saponification of the ester groups after ethoxylation appears to have taken place to a lesser extent, which is seen by the ratio of CH.sub.2OH groups derived from polyethoxy-OH, occurring from undesired side reactions (e.g. due to longer reaction times and high reaction temperature), to alkyl-CH.sub.3 groups, derived from fatty acid alkyl.

[0097] The solubility of the ethoxylated triglycerides according to Ex. 2, Comp. 3 and Comp. 4 (each prepared from 1 molar equivalent of coconut oil and 22.5 molar equivalents of ethylene oxide) in water was examined by mixing 0.5 parts by weight of the respective ethoxylated triglyceride with 99.5 parts by weight of deionized water in a glass test tube at 25° C., and a visually evaluation of the clarity was made of the resulting composition, directly after mixing and 1 hour after mixing. In each case, the changes within the 1 hour period were not significant. The visual evaluation was done according to the following rating:

TABLE-US-00004 Clear no suspended matter observed Almost clear traces of suspended matter observed Slightly turbid suspended matter observed, dark background still visible Turbid suspended matter dominant, dark background hardly recognizable Opaque suspended matter very dominant, dark background not recognizable.

[0098] The evaluation is shown in Table 4:

TABLE-US-00005 TABLE 4 Sample obtained from Directly after mixing 1 hour after mixing Ex. 2 slightly turbid slightly turbid Comp. 3 Opaque opaque Comp. 4 almost clear almost clear

[0099] From the above results it can be seen that the ethoxylated glycerol ester of the invention (Ex. 1) prepared with the catalyst C-1 has a significantly better solubility in water than the comparative product prepared with the catalyst C-0 known in the art (Comp. 3). This is important e.g. for the applicability of the product as a surfactant.

[0100] The improved solubility is observed despite the smaller amount of free hydroxyl groups, which is expected to facilitate dissolution in water due to higher polarity.

[0101] The differences are in accord with the formation of insoluble solid residues in the ethoxylation process employing catalyst C-0.

[0102] The increased solubility of the product prepared with KOtBu and a co-catalyst (Comp. 4) is a result of the large amount of OH group-bearing decomposition products, which increase the polarity of the mixture and thus the overall solubility of the composition in water.

Application Example 1: Drying Capacity and Clean Dishwasher Interior

[0103] The drying capacity of a detergent composition for machine dishwashing F2 comprising the ethoxylated glycerol ester of Ex. 4 was investigated. As a comparative example, the drying capacity of a comparative formulation F1 comprising a modified fatty alcohol ethoxylate was tested.

Testing Conditions:

[0104] Dishwashing machine: Miele G 1222 SC GSL-2 [0105] Testware dishes: 10 appetizer spoons [0106] 10 appetizer forks [0107] 10 teaspoons [0108] 2 vegetable serving spoons [0109] 12 drinking glasses [0110] 10 porcelain cups [0111] 25 porcelain plates [0112] 3 SAN (poly-styrene-co-acrylonitrile) plates [0113] 3 PP (polypropylene) plates [0114] 6 PP bowls [0115] Dishwashing program: P4R0 without pre-rinsing [0116] main rinse at 50° C. [0117] final rinse at 65° C. [0118] Water hardness: 21° dH [0119] Wasser softening: none [0120] Detergent dosage: 18 g, added into the detergent tablet tray immediately after opening of the dosing chamber [0121] Contamination: 50 g frozen dirt, added immediately after opening of the dosing chamber [0122] Rinse aid: none [0123] Cleaning cycles: 4

[0124] All items were treated once with demineralized water, Neodisher A 8, citric acid, and demineralized water.

Evaluation:

[0125] Evaluation of the testware was begun 30 minutes after the dishwashing cycle was completed. During this time, the dishwasher door was closed. For each test, dishwashing cycles 2 to 4 were evaluated. The assessment was carried out in each case with an illumination of 1000-1500 lux.

[0126] In a fixed order and with a set time limit, the number of adherent drops of residual water was counted for each testware item. Depending on the counted number of drops, the following rating of the drying capacity results for each testware item:

Rating for Porcelain, Stainless Steel and Glass:

[0127] 0 dry, no water drops [0128] 1 1 water drop [0129] 2 2 water drops [0130] 3 3 water drops [0131] 4 4 water drops [0132] 5 5 water drops [0133] 6 more than 5 water drops

Rating for Plastics:

[0134] 0 dry, no water drops [0135] 1 1 water drop [0136] 2 2 water drops [0137] 3 3 water drops [0138] 4 4 water drops [0139] 5 5 water drops [0140] 6 6 water drops [0141] 7 7 water drops [0142] 8 more than 7 water drops.

[0143] In this rating scheme, there is a score of 0 for best performance and a score of 6 for worst performance for each testware dish. For each dishwashing cycle 2, 3 and 4, the sum of the scores of all test dishes was formed. For comparison of the formulations F1 and F2, the average grade of all sums of the dishwashing cycles 2 to 4 was averaged in each case. This leads to a theoretical maximum value with the worst drying performance of 630 and a theoretical minimum value with the best drying performance of 0.

[0144] The results are shown in the following Table 5.

[0145] Furthermore, the fatty residues on plastic parts (filter, rinse aid chamber) of the dishwashing machine were evaluated (on a scale of 1 to 7, with 1 representing a large amount of residues and 7 representing no residues). These results are also shown in Table 5.

Compositions:

[0146] The compositions of the formulations F1 and F2 are shown in the following Table 5.

Application Example 2: Rinse Aiding Performance of Detergent Compositions for Machine Dishwashing

[0147] The rinse aiding performance of the formulation F2 according to the invention was investigated. As comparative example, the rinse aiding performance of the comparative formulation F1 was tested.

Testing Conditions:

[0148] Dishwashing machine: Miele G 1222 SC GSL [0149] Testware dishes: 6 drinking glasses (higher quality) [0150] (8 material groups) 6 drinking glasses (lower quality) [0151] 3 PP bowls [0152] 3 melamine plates [0153] 3 buffer dishes+4 knives (stainless steel; lower quality) [0154] 4 knives (stainless steel; higher quality) [0155] 3 porcelain plates (higher quality) [0156] 3 porcelain plates (lower quality) [0157] Dishwashing program: program 4, R=2 without pre-rinsing [0158] main rinse at 50° C. [0159] final rinse at 65° C. [0160] Water hardness: 21° dH [0161] Water softening: none [0162] Detergent dosage: 18 g, added to the dosage chamber before starting the test [0163] Contamination: 100 g frozen dirt, added immediately after the opening of the dosage chamber [0164] Rinse aid: none [0165] Cleaning cycles: 4

[0166] All testware dishes except for the PP bowls were treated once with demineralized water, Neodisher A 8, citric acid and again demineralized water.

Evaluation:

[0167] Evaluation of the testware was begun at least 60 minutes after opening the door of the dishwashing machine after completion of the dishwashing cycle. For each test, dishwashing cycles 2 to 4 were evaluated. The assessment was carried out according to the following rating:

[0168] Rinse aid effects considered for the visual rating:

TABLE-US-00006 Stains Stains of different size and intensity Contact spots Stains resultant from contact points between the testware dishes and parts of the dishwashing machine Stripes Rinse aid stripes Film formation continuous film spread uniformly on the testware dishes Structured film formation Dispersed torn film Solid residues Solid powder or crystalline residues Fatty resudues Fatty drops or fatty film formation Iridescence Shimmering, iridescence

Visual Rating Marks:

[0169] 10 Perfect [0170] 9 Perfect to barely visible [0171] 8 Barely visible [0172] 7 Barely visible to visible [0173] 6 Visible [0174] 5 Visible to disturbing [0175] 4 Disturbing [0176] 3 Disturbing to unacceptable [0177] 2 Unacceptable [0178] 1 Absolutely unacceptable

[0179] The combination of the above listed eight rinse aid effects leads to a rating from 1 to 10 according to the above visual rating marks, wherein a rating of 1 represents the worst performance and a rating of 10 represents the best performance. For each of the above 8 testware material groups in each dishwashing cycle, an average rating was determined, followed by calculating the sum of ratings for all material groups in each individual dishwashing cycle, followed by determining an average rating for the entirety of dishwashing cycles 2 to 4. The resultant average rating was used as the final rinse aiding performance of the formulations F1 and F2. This leads to a theoretical maximum value of 80 for the best performance and a theoretical minimum value of 8 for the worst performance.

Compositions:

[0180] The compositions of the formulation F2 according to the invention and of F1 are shown in the following Table 5. The results are also shown in Table 5.

TABLE-US-00007 TABLE 5 Compositions, drying capacity, fatty residues and rinse aiding performance of formulations F1 and F2 F1 F2 Component wt.-%*.sup.) wt.-%*.sup.) trisodium citrate dihydrate 28.5 28.5 sodium carbonate 19.5 19.5 sodium silicate 2.0 2.0 MGDA-Na.sub.3 15.0 15.0 Polycarboxylate 10.0 10.0 sodium percarbonate 9.0 9.0 TAED 2.0 2.0 HEDP 0.9 0.9 Protease 0.9 0.9 Amylase 0.9 0.9 modified fatty alcohol ethoxylate 3.5 — Coconut oil + 45 EO — 3.5 sodium sulfate 3.2**.sup.) 3.2**.sup.) drying capacity 157 148 rinse aiding performance 56.9 57.3 fatty residues 4.0 6.1 *.sup.)The ingredients were added according to their active component content in wt.-%. **.sup.)Sodium sulfate is added as a filler for a constant mass balance of the detergent composition, without a function and without influence on the preformance of the detergent composition.

[0181] From the results in the above Table 5 it is evident that the use of the detergent composition for machine dishwashing F2 leads to beneficial values of the drying capacity, fatty residues in the machine compartment and rinse aiding performance compared to composition F1.

[0182] Moreover, the formulation F2 shows an excellent cleaning performance and excellent filter cleaning properties.