Ethoxylated Glycerol Ester-Containing Detergent For Machine Dishwashing

Abstract

A detergent composition for machine dishwashing comprising Z1) one or more ethoxylated glycerol esters of formula (I),

##STR00001##

prepared from ethylene oxide and one or more triglycerides of formula (II) in the presence of a calcium catalyst (C), characterized in that R1, R2 and R3 in formulae (I) and (II) are equal or different and are independently selected from saturated or unsaturated, linear or branched C7-C24 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; and the calcium catalyst (C) is a catalyst obtainable 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) to carboxylic acid (B) in the preparation of the catalyst (C) is from 1:1 to 1:5.

Claims

1. A detergent composition for machine dishwashing comprising Z1) one or more ethoxylated glycerol esters of formula (I), ##STR00015## prepared from ethylene oxide and one or more triglycerides of formula (II) ##STR00016## in the presence of a calcium catalyst (C), 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, proviso that the number-average of the sum of m+n+o is greater than 5; and the calcium catalyst (C) is a catalyst obtainable 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) to carboxylic acid (B) in the preparation of the catalyst (C) is from 1:1 to 1:5.

2. The detergent composition according to claim 1, characterized in that the reaction for preparation of catalyst (C), involving components (A) and (B) further involves the use of an alcohol solvent having 1 to 5 carbon atoms, or a mixture thereof with water.

3. The detergent composition according to claim 1, characterized in that the reaction for preparation of catalyst (C), involves a carboxylic acid (B) which is represented by formula (III) or formula (IV), ##STR00017## wherein R.sup.4 in formula (III) 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 in formula (III) are equal or different and are independently selected from the group consisting of hydrogen, methyl and ethyl; p in formula (III) is an integer number from 0 to 20; and R.sup.9 in formula (IV) is selected from saturated or unsaturated, linear or branched C.sub.5-C.sub.30 alkyl chains.

4. The detergent composition according to claim 1, wherein the reaction for preparation of catalyst (C) involving components (A) and (B) further involves an acid (AC) having a pK.sub.A value of 3 or less, and the molar ratio of (A):(AC) is from 5:1 to 1:1.

5. The detergent composition according to claim 1, wherein the preparation of ethoxylated glycerol esters of formula (I), the volatile components are removed before the catalyst (C) is used for the preparation of the ethoxylated glycerol esters of formula (I).

6. The detergent composition according to claim 1, wherein the content of Ca.sup.2+ ions in the catalyst (C) is between 0.5 wt.-% and 5 wt.-%.

7. The detergent composition according to claim 1, wherein the ethoxylated glycerol ester of formula (I) has a hydroxyl number smaller than 6 mg KOH/g.

8. The detergent composition according to claim 1, which further comprises one or more components selected from the group consisting of: Z2) one or more enzymes; Z3) one or more builders; Z4) one or more bleaching agents; Z5) one or more surfactants Z6) one or more polymers, and Z7) one or more further additives.

9. The detergent composition according to claim 8, the detergent composition comprising from 0.1-15 wt.-% of one or more ethoxylated glycerol esters of formula (I) and from 1×10.sup.−6 to 5 wt.-% of at least one enzyme component Z2), 2 to 50 wt.-% of at least one builder Z3), 1 to 40 wt.-% of at least one bleaching agent Z4), optionally 0 to 15 wt.-% of at least one surfactant Z5), optionally 0-10 wt.-% of at least one polymer Z6) and optionally 0 to 70 wt.-% of at least one further additive Z7), based on the total weight of the detergent composition.

10. The detergent composition according to claim 1, wherein it is a solid composition at 20° C.

11. The detergent composition according to claim 1, wherein composition is wrapped in a water-soluble foil.

12. The detergent composition according to claim 1, wherein it is a powder, gel, pod, cap or liquid rinse aid.

13. A method of cleaning dishes in a dishwashing machine, in which contaminated dishes are treated in the dishwashing machine with an aqueous alkaline composition comprising a detergent composition wherein the detergent composition comprises Z1) one or more ethoxylated glycerol esters of formula (I), ##STR00018## prepared from ethylene oxide and one or more triglycerides of formula (II) ##STR00019## in the presence of a calcium catalyst (C), 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; and the calcium catalyst (C) is a catalyst obtainable 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) to carboxylic acid (B) in the preparation of the catalyst (C) is from 1:1 to 1:5.

14. The method according to claim 13, characterized in that the pH value of the aqueous alkaline solution is from 8 to 13.

15. A method of cleaning dishes in a dishwashing machine, in which contaminated dishes are treated in the dishwashing machine with an aqueous composition at a pH ranging from 5.5-8.5 comprising a detergent composition, wherein the detergent composition comprises Z1) one or more ethoxylated glycerol esters of formula (I), ##STR00020## prepared from ethylene oxide and one or more triglycerides of formula (II) ##STR00021## in the presence of a calcium catalyst (C), 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; and the calcium catalyst (C) is a catalyst obtainable 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) to carboxylic acid (B) in the preparation of the catalyst (C) is from 1:1 to 1:5.

16.-19. (canceled)

Description

EXAMPLES

Synthesis Example 1

[0243] Methods of Preparation of calcium catalyst (C) with carboxylic acid of formula (III) [0244] 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)”).

[0245] 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. [0246] 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-% (“(C-3)”). [0247] 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-% (“(C-4)”).

[0248] 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

Synthesis of Ethoxylated Coconut Oil (45 EO)

[0249] The coconut oil (1 molar equivalent) and the catalyst (C-1) (0.8% by weight, based on the total weight of the mixture of coconut oil and ethylene oxide), 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 (45 molar equivalents) took place up to a maximum pressure of 4.5 bar above atmospheric pressure.

[0250] 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. 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.

Comparative Synthesis Example (Glycerol+45 EO+Coconut Fatty Acid)

[0251] Glycerol (1 molar equivalent) and an aqueous potassium hydroxide solution of 40 wt.-% (0.4% by weight, based on the total weight of the mixture of Glycerol and ethylene oxide), 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 160° 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 (45 molar equivalents) took place up to a maximum pressure of 5 bar above atmospheric pressure according to standard alkoxylation procedure.

[0252] After introduction of the intended amount of ethylene oxide, 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 product was isolated.

[0253] In a subsequent reaction step, the Glycerol ethoxylate (1 eq.) was esterified with coconut fatty acid (3 eq.) using a Dean-Stark-Apparatus and 1.0 wt.-% of sulfuric acid (calculated on the total reaction mass) as a catalyst. The reaction was carried out at 170° C. for 8 h, until the calculated amount of water was distilled off and the residual acid value of the product was below 10 mgKOH/g.

Example 1

Drying Capacity and Clean Dishwasher Interior

[0254] The drying capacity of the detergent composition for machine dishwashing F2 according to the invention was investigated. As a comparative example, the drying capacity of the comparative formulations F1 and F3 were tested.

Testing Conditions:

[0255]

TABLE-US-00001 Dishwashing machine: Miele G 1222 SC GSL-2 Testware dishes: 10 appetizer spoons 10 appetizer forks 10 teaspoons 2 vegetable serving spoons 12 drinking glasses 10 porcelain cups 25 porcelain plates 3 SAN (poly-styrene-co- acrylonitrile) plates 3 PP (polypropylene) plates 6 PP bowls Dishwashing program: P4R0 without pre-rinsing main rinse at 50° C. final rinse at 65° C. Water hardness: 21° dH Wasser softening: none Detergent dosage: 18 g, added into the detergent tablet tray immediately after opening of the dosing chamber Contamination: 50 g frozen dirt, added immediately after opening of the dosing chamber Rinse aid: none Cleaning cycles: 4

[0256] All items were treated once with demineralized water, Neodisher A 8, citric acid, and demineralized water.

Evaluation:

[0257] 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.

[0258] 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:

[0259] Rating for porcelain, stainless steel and glass:

TABLE-US-00002 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

Rating for Plastics:

[0260]

TABLE-US-00003 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 6 water drops 7 7 water drops 8 more than 7 water drops.

[0261] 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, F2 and F3, 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.

[0262] The results are shown in the following table A.

[0263] 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 A.

Compositions:

[0264] The compositions of the formulations F1,F2 and F3 are shown in the following Table A.

Example 2

Rinse Aiding Performance of Detergent Compositions for Machine Dishwashing

[0265] The rinse aiding performance of the formulation F2 according to the invention was investigated. As comparative examples, the rinse aiding performance of the comparative formulations F1 and F3 was tested.

Testing Conditions:

[0266]

TABLE-US-00004 Dishwashing machine: Miele G 1222 SC GSL Testware dishes: 6 drinking glasses (higher quality) (8 material groups) 6 drinking glasses (lower quality) 3 PP bowls 3 melamine plates 3 butter dishes + 4 knives (stainless steel; lower quality) 4 knives (stainless steel; higher quality) 3 porcelain plates (higher quality) 3 porcelain plates (lower quality) Dishwashing program: program 4, R = 2 without pre-rinsing main rinse at 50° C. final rinse at 65° C. Water hardness: 21° dH Water softening: none Detergent dosage: 18 g, added to the dosage chamber before starting the test Contamination: 100 g frozen dirt, added immediately after the opening of the dosage chamber Rinse aid: none Cleaning cycles: 4

[0267] All testware dishes except for the PP bowls were treated once with demineralized water, Neodisher A 8, citric acid and again demineralized water.

Evaluation:

[0268] 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:

Rinse Aid Effects Considered for the Visual Rating:

[0269]

TABLE-US-00005 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 Dispersed torn film formation Solid residues Solid powder or crystalline residues Fatty resudues Fatty drops or fatty film formation Iridescence Shimmering, iridescence

Visual Rating Marks:

[0270]

TABLE-US-00006 10 Perfect 9 Perfect to barely visible 8 Barely visible 7 Barely visible to visible 6 Visible 5 Visible to disturbing 4 Disturbing 3 Disturbing to unacceptable 2 Unacceptable 1 Absolutely unacceptable

[0271] 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, F2 and F3. 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:

[0272] The compositions of the formulation F2 according to the invention and of F1 and F3 are shown in the following table A. The results are also shown in table A.

TABLE-US-00007 TABLE A Compositions, drying capacity, fatty residues and rinse aiding performance of formulations F1, F2, and F3 F1 F2 F3 Component wt.-% wt.-%.sup.*) wt.-% trisodium citrate dihydrate 28.5 28.5 28.5 sodium carbonate 19.5 19.5 19.5 sodium silicate 2.0 2.0 2.0 MGDA-Na.sub.3 15.0 15.0 15.0 polycarboxylate 10.0 10.0 10.0 sodium percarbonate 9.0 9.0 9.0 TAED 2.0 2.0 2.0 HEDP 0.9 0.9 0.9 protease 0.9 0.9 0.9 amylase 0.9 0.9 0.9 modified fatty alcohol ethoxylate 3.5 — — Coconut oil + 45 EO — 3.5 — Glycerol + 45 EO + coconut 3.5 fatty acid sodium sulfate 3.2.sup.**) 3.2.sup.**) 3.2.sup.**) drying capacity 157 148 175 rinsing aiding performance 56.9 57.3 n.d. fatty residues 4.0 6.1 5.3 .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.

[0273] From the results in the above table A it is evident that the use of the detergent composition for machine dishwashing F2 leads to beneficial values of the drying capacity and fatty residues in the machine compartment compared to compositions F1 and F3 and further beneficial values for the rinse aiding performance compared to F1.

[0274] Moreover, the formulation F2 shows an excellent cleaning performance and excellent filter cleaning properties.