Formulations, their use as or for producing dishwashing detergents and their production

Abstract

Formulation comprising (A) at least one aminocarboxylate selected from methylglycin diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA), and salts thereof, (B) at least one polypropyleneimine which may be alkoxylated.

Claims

1. A formulation comprising (A) at least one aminocarboxylate selected from methylglycin diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA), and salts thereof, wherein the total aminocarboxylate ranges from 1 to 50% by weight based on the solids content of the formulation, (B) at least one polypropyleneimine which is optionally alkoxylated, wherein the total polypropyleneimine ranges from 0.02 to 0.5% by weight based on the solids content of the formulation.

2. The formulation according to claim 1, which is free from phosphates and polyphosphates.

3. The formulation according to claim 1, wherein polypropylenimine (B) is selected from polypropyleneimines which have been reacted with ethylene oxide or propylene oxide.

4. The formulation according to claim 1, which comprises at least one zinc salt.

5. The formulation according to claim 4, which has, apart from zinc, a heavy metal content below 0.05 ppm, based on the solids content of the formulation in question.

6. The formulation according to claim 1, wherein polypropyleneimine (B) is selected from linear polypropyleneimines which is optionally alkoxylated.

7. The formulation according to claim 1, which comprises in the range from 0.1 to 10% by weight of water.

8. The formulation according to claim 1, wherein the polypropyleneimine (B) is alkoxylated, and the molar ratio of nitrogen atoms to alkylene oxide groups in alkoxylated polypropylenimine (B) is in the range from 1:1 to 1:15.

9. The formulation according to claim 1, which comprises: in total in the range from 10 to 25% by weight of aminocarboxylate (A), based on the solids content of the formulation.

10. A method comprising washing dishes and/or kitchen utensils with a formulation according to claim 1, where washing is carried out with water of hardness from 2 to 25 German hardness.

11. The method according to claim 10, wherein the washing is carried out in a dishwasher.

12. The method according to claim 10, wherein said dishes and/or kitchen utensils are drinking glasses, glass vases and/or glass vessels for cooking.

13. A method comprising washing an objects which has at least one surface made of glass, which may be decorated or undecorated, with a formulation according to claim 1.

14. A process for producing formulations according to claim 1, wherein (A) aminocarboxylate selected from methylglycin diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetahte (GLDA), and salts thereof, and (B) at least one polypropyleneimine which is optionally alkoxylated, and optionally further components are mixed in one or more steps with one another in the presence of water and then the water is completely or partially removed.

15. The process according to claim 14, wherein the water is removed by spray-drying or spray-granulation.

Description

(1) The invention is illustrated by working examples.

(2) General: It was ensured that after the first cleaning of the test bodies in the domestic dishwasher until after the weighing and visual inspection of the glasses, the test bodies were handled only with clean cotton gloves so that the weight and/or the visual impression of the test bodies was not falsified.

(3) Data in % are % by weight, unless expressly stated otherwise. Data in German hardness always relate to the permanent hardness.

(4) I. Preparation of Alkoxylated Polypropyleneimines

(5) I.1 Preparation of Polypropyleneimines

(6) I.1.1 Preparation of Linear Polypropyleneimine L-PPI.1

(7) 200 ml of 1,3-propanediamine (1,3-PDA) was poured into a 300 ml steel vessel which was connected to a tubular reactor with an internal diameter of 27 mm. The 1,3-PDA was pumped out of the steel vessel together with 50 l (stp) of hydrogen over a fixed-bed catalyst made of Ni/Co which was supported on ZrO.sub.2 and which was located in the tubular reactor. The reaction temperature was 160 C. At the top of the tubular reactor, gas and liquid phase were separated and the liquid fraction was returned to the steel vessel. From there, it was pumped again over the catalyst. The reaction was carried out for 2 hours. This gave L-PPI.1, the properties of which are listed in table 1.

(8) I.1.2 Preparation of Linear Polypropyleneimine L-PPI.2

(9) 200 ml of 1,3-propanediamine (1,3-PDA) was poured into a 300 ml steel vessel which was connected to a tubular reactor with an internal diameter of 27 mm. The 1,3-PDA was pumped out of the steel vessel together with 50 l (stp) of hydrogen over a fixed-bed catalyst made of Ni/Co which was supported on ZrO.sub.2 and which was located in the tubular reactor. The reaction temperature was 160 C. At the top of the tubular reactor, gas and liquid phase were separated and the liquid fraction was returned to the steel vessel. From there, it was pumped again over the catalyst. The reaction was carried out for 150 minutes. This gave L-PPI.2, the properties of which are listed in table 1.

(10) I.1.3 Preparation of Linear Polypropyleneimine L-PPI.3

(11) The reaction from 1.1.2 was repeated, but only over a period of 90 minutes. This gave L-PPI.3.

(12) I.1.4 Preparation of Linear Polypropyleneimine L-PPI.4

(13) 1,3-PDA, together with 10 liters (stp)/h of hydrogen were passed continuously through a tubular reactor with an internal diameter of 27 mm over a cobalt fixed-bed catalyst. The total pressure was 50 bar, the temperature 170 C. The feed of 1,3-PDA was 0.8 kg/l.sub.cat.Math.h. This gave a crude product. Unreacted 1,3-PDA and the corresponding dimer and trimer were distilled off from the crude product, giving L-PPI.4 as a colorless liquid.

(14) I.1.5 Preparation of Linear Polypropyleneimine L-PPI.5

(15) 1,3-PDA, together with 10 liters (stp)/h of hydrogen were passed continuously through a tubular reactor with an internal diameter of 27 mm over a cobalt fixed-bed catalyst. The total pressure was 50 bar, the temperature 160 C. The feed of 1,3-PDA was 0.8 kg/l.sub.cat.Math.h. This gave a crude product. Unreacted 1,3-PDA and the corresponding dimer and trimer were distilled off from the crude product, giving L-PPI.5 as a colorless liquid.

(16) I.1.6 Preparation of Linear Polypropyleneimine L-PPI.6

(17) 1,3-PDA, together with 10 liters (stp)/h of hydrogen were passed continuously through a tubular reactor with an internal diameter of 27 mm over a cobalt fixed-bed catalyst. The total pressure was 50 bar, the temperature 160 C. The feed of 1,3-PDA was 0.6 kg/l.sub.cat.Math.h. This gave a crude product which, according to gas chromatography, had 7% by weight of unreacted 1,3-PDA.

(18) 1,3-PDA and the corresponding dimer and trimer were distilled off, giving L-PPI.6 as a colorless liquid.

(19) M.sub.n: 302 g/mol, M.sub.w: 533 g/mol: M.sub.w/M.sub.n of 1.8.

(20) TABLE-US-00001 TABLE 1 Linear polypropyleneimines and their properties No. PAV SAV PAV/SAV M.sub.n [g/mol] M.sub.w/M.sub.n L-PPI.1 129 923 1:7.15 872 3.4 L-PPI.2 228 826 1:3.6 474 3.4 L-PPI.3 228 482 1:2.1 300 2.5 L-PPI.4 203 816 1:4.0 525 1.6 L-PPI.5 269 786 1:2.9 409 2.3 L-PPI.6 206 841 1:4.1 302 1.8

(21) Primary and secondary amine values are given in mg KOH/g.

(22) PAV: Primary amine value

(23) SAV: Secondary amine value

(24) I.2 Alkoxylation of Polypropyleneimine

(25) I.2.1 Alkoxylation with an EO/NH Molar Ratio of 1:1

(26) 286.3 g of polypropyleneimine L-PPI.1 (tert amine value: 22.1 mg KOH/g) and 14.3 g of water are introduced into a 2 liter autoclave. The autoclave was flushed three times with nitrogen and then heated to 110 C. Over the course of 2 hours, 265.2 g of ethylene oxide were added. In order to complete the reaction, stirring was carried out over a period of 3 hours at 110 C. Then, water and remaining volatile compounds, if present, were removed in vacuo (10 mbar) at 90 C. This gave alkoxylated polypropyleneimine (B.1) according to the invention as a highly viscous yellow oil (522 g).

(27) I.2.2 Alkoxylation with an EO/NH Molar Ratio of 10:1

(28) 75.9 g of (B.1) and 2.6 g of KOH pellets (water content: 50% by weight) are introduced into a 2 liter autoclave. The mixture was heated to 120 C. with stirring and under reduced pressure (10 mbar) and stirred for 2 hours in order to remove the water. The autoclave was then flushed three times with nitrogen and then heated to 140 C. (1 bar). Over the course of 2 hours, 332.8 g of ethylene oxide were added. In order to complete the reaction, the mixture was stirred at 140 C. over a period of 3 hours. Then, water and remaining volatile compounds, if present, were removed in vacuo (10 mbar) at 90 C. This gave alkoxylated polypropyleneimine (B.2) according to the invention as a yellow wax-like solid (399.5 g).

(29) I.2.3 Alkoxylation with an EO/NH Molar Ratio of 20:1

(30) 64.0 g of (B.1) and 2.6 g of KOH pellets (water content: 50% by weight) are introduced into a 2 liter autoclave. The mixture was heated to 120 C. with stirring and under reduced pressure (10 mbar) and stirred for 2 hours in order to remove the water. The autoclave was then flushed three times with nitrogen and then heated to 140 C. (1 bar). Over the course of 4 hours, 584.7 g of ethylene oxide were added. In order to complete the reaction, the mixture was stirred at 140 C. over a period of 3 hours. Then, water and remaining volatile compounds, if present, were removed in vacuo (10 mbar) at 90 C. This gave alkoxylated polypropyleneimine (B.3) according to the invention as a yellow wax-like solid (630.6 g). Amine value: 57.2 mg KOH/g.

(31) I.2.4 Alkoxylation with an EO/PO/NH Molar Ratio of 10:7:1

(32) 225.6 g of (B.2) and 0.8 g of KOH pellets (water content: 50% by weight) are introduced into a 2 liter autoclave. The mixture was heated to 120 C. with stirring and under reduced pressure (10 mbar) and stirred for 2 hours in order to remove the water. The autoclave was then flushed three times with nitrogen and then heated to 140 C. (1 bar). Over the course of 2 hours, 187.9 g of propylene oxide were added. In order to complete the reaction, the mixture was stirred at 140 C. over a period of 3 hours. Then, water and remaining volatile compounds, if present, were removed in vacuo (10 mbar) at 90 C. This gave alkoxylated polypropyleneimine (B.2) according to the invention as a pale yellow wax-like solid (405 g). Amine value: 58.3 mg KOH/g.

(33) I.2.5 Alkoxylation with an EO/PO/NH Molar Ratio of 24:16:1

(34) 242.8 g of (B.3) and 1.1 g of KOH pellets (water content: 50% by weight) are introduced into a 2 liter autoclave. The mixture was heated to 120 C. with stirring and under reduced pressure (10 mbar) and stirred for 2 hours in order to remove the water. Then, the autoclave was flushed three times with nitrogen and then heated to 140 C. (1 bar). 46.1 g of ethylene oxide were added and the mixture was left to react for 3 hours with stirring. Then, over the course of 2 hours, 242.9 g of propylene oxide were added. In order to complete the reaction, the mixture was stirred at 140 C. over a period of 3 hours. Then, water and remaining volatile compounds, if present, were removed in vacuo (10 mbar) at 90 C. This gave alkoxylated polypropyleneimine (B.5) according to the invention as a pale brown solid (506 g). Amine value: 28.6 mg KOH/g.

(35) I.2.6 Alkoxylation with an BuO/NH Molar Ratio of 1:1

(36) 193.7 g of polypropyleneimine L-PPI.1 and 9.7 g of water are introduced into a 2 liter autoclave. The autoclave was flushed three times with nitrogen and then heated to 110 C. Over the course of 2 hours, 293.6 g of 1,2-butylene oxide were added. In order to complete the reaction, the mixture was stirred at 110 C. over a period of 3 hours. Then, water and remaining volatile compounds, if present, were removed in vacuo (10 mbar) at 90 C. This gave alkoxylated polypropyleneimine (B.6) according to the invention as a highly viscous yellow oil (460 g).

(37) I.2.7 Alkoxylation with an EO/NH Molar Ratio of 4:1

(38) 151.8 g of (B.1) and 2.6 g of KOH pellets (water content: 50% by weight) are introduced into a 2 liter autoclave. The mixture was heated to 120 C. with stirring and under reduced pressure (10 mbar) and stirred for 2 hours in order to remove the water. Then, the autoclave was flushed three times with nitrogen and then heated to 140 C. (1 bar). Over the course of 2 hours, 265.6 g of ethylene oxide were added. In order to complete the reaction, the mixture was stirred at 140 C. over a period of 3 hours. Then, water and remaining volatile compounds, if present, were removed in vacuo (10 mbar) at 90 C. This gave alkoxylated polypropyleneimine (B.7) according to the invention as a yellow wax-like solid.

(39) I.2.8 Alkoxylation with an EO/NH Molar Ratio of 7:1

(40) 151.8 g of (B.1) and 2.6 g of KOH pellets (water content: 50% by weight) are introduced into a 2 liter autoclave. The mixture was heated to 120 C. with stirring and under reduced pressure (10 mbar) and stirred for 2 hours in order to remove the water. Then, the autoclave was flushed three times with nitrogen and then heated to 140 C. (1 bar). Over the course of 2 hours, 463.8 g of ethylene oxide were added. In order to complete the reaction, the mixture was stirred at 140 C. over a period of 3 hours. Then, water and remaining volatile compounds, if present, were removed in vacuo (10 mbar) at 90 C. This gave alkoxylated polypropyleneimine (B.8) according to the invention as a yellow solid.

(41) Taking the linear polypropyleneimine L-PPI.4 instead of L-PPI.1 and reacting it with corresponding amounts of ethylene oxide gives the alkoxylated polypropyleneimines M-PPI.4-1 to M-PPI.4-3 according to the invention.

(42) II. Preparation of Formulations According to the Invention

(43) The charge density of modified polypropyleneimines (B) was always determined as follows (see also: Horn, Prog. Colloid & Polym. Sci. 1978, 65, 251):

(44) 1 g of the modified polypropyleneimine (B) in question was dissolved in 100 ml of demineralized water. A buffer solution and aqueous HCl were used to establish a pH of 4.0, determined potentiometrically. Three ml of an aqueous solution of toluidine blue (50 mg/l of water) were added, and N/400-KPVS (potassium polyvinyl sulfate) solution (Wako) with a concentration of 0.0004 meq/ml was titrated until the color changed from blue to pink. The charge density was calculated as follows:
LA=0.4.Math.KV LA: Charge density of the modified polypropyleneimine (B) in question, meq/g (milliequivalent/g) KV: Consumption of the N/400-KPVS solution [ml]

(45) II.1 Preparation of Base Mixtures

(46) Firstly, base mixtures were prepared from the feed materials according to table 2. The feed materials were mixed dry.

(47) TABLE-US-00002 TABLE 2 Base mixtures for experiments with formulations according to the invention and comparison formulations Base-1 Base-2 Base-3 Protease 2.5 2.5 2.5 Amylase 1 1 1 n-C.sub.18H.sub.37(OCH.sub.2CH.sub.2).sub.9OH 5 5 5 Polyacrylic acid M.sub.w 4000 g/mol, as 10 10 10 sodium salt, completely neutralized Sodium percarbonate (D.1) 10.5 10.5 10.5 TAED 4 4 4 Na.sub.2Si.sub.2O.sub.5 2 2 2 Na.sub.2CO.sub.3 19.5 19.5 19.5 Sodium citrate dihydrate (C.1) 5 22.5 30 All data in g.(C.1) is determined as anhydrous sodium citrate. Abbreviations: MGDA: Methylglycineediacetic acid as trisodium salt TAED: N,N,N,N-Tetraacetylethylenediamine

(48) II.2 Preparation of Formulations According to the Invention

(49) II.2.1 Preparation of the Formulations 2 to 8 According to the Invention and of the Comparison Formulations V1

(50) Polypropyleneimines (B) and modified polypropyleneimines (B) according to table 3 were used.

(51) TABLE-US-00003 TABLE 3 Modified polypropyleneimines Alkoxylation of the relevant Abbreviation M.sub.n (g/mol) polypropyleneimine with L-PPI.1 872 L-PPI.4 525 (B.1) 1603 Ethylene oxide (1 EO/NH) (B.7) 3500 Ethylene oxide (4 EO/NH) (B.8) 5200 Ethylene oxide (7 EO/NH) M-PPI.4-1 1510 Ethylene oxide (1 EO/NH) M-PPI.4-2 3330 Ethylene oxide (4 EO/NH) M-PPI.4-3 5100 Ethylene oxide (7 EO/NH)

(52) Procedure:

(53) 20 ml of distilled water was placed in a 100 ml beaker and modified polypropyleneimine (B) or polypropyleneimine (B) according to tables 3 and 4 was added with stirring.

(54) Stirring was then carried out for 10 minutes. MGDA trisodium salt (A.1), dissolved in 30 ml of water, was then added as per table 3. This gave a clearly transparent solution. Base mixture as per table 3 was then added, the mixture was stirred again, and the water was evaporated.

(55) If, in the test, the corresponding fractions of base mixture are metered in separately from aqueous solution of (A.1), (B), sodium citrate (C.1) or (D.1), the same results are obtained as when the dried formulation was tested with identical amounts of active ingredient. The order of the metered addition is therefore of no consequence.

(56) III. Use of Formulations According to the Invention and Comparison Formulations for the Machine Cleaning of Glasses

(57) General: It was ensured that after the first cleaning of the test bodies in the domestic dishwasher until after the weighing and visual inspection of the glasses, the test bodies were handled only with clean cotton gloves so that the weight and/or the visual impression of the test bodies was not falsified.

(58) The testing of formulations according to the invention and comparison formulations was carried out as follows.

(59) III.1 Test Method for Dishwasher with Continuous Operation

(60) Dishwasher: Miele G 1222 SCL

(61) Program: 65 C. (with prewash)

(62) Ware: 3 GILDE champagne glasses, 3 INTERMEZZO brandy glasses

(63) For the cleaning, the glasses were arranged in the upper crockery basket of the dishwasher. The dishwashing detergent used was in each case 25 g of formulation according to the invention or 25 g of comparison formulation according to table 4, table 4 specifying in each case individually the active components (A.1), base mixture and (B) of formulation according to the invention. The water hardness was in each case in the range from zero to 2 German hardness. Washing was carried out in each case for 100 wash cycles, i.e. the program was left to run 100. Evaluation was carried out gravimetrically and visually after 100 wash cycles.

(64) The weight of the glasses was determined before the start of the first wash cycle and after drying after the last wash cycle. The weight loss is the difference in the two values.

(65) Besides the gravimetric evaluation, a visual assessment of the ware after 100 cycles in a darkened chamber with light behind a perforated plate was carried out using a grading scale from 1 (very poor) to 5 (very good). In this connection, grades were awarded in each case for patchy corrosion/clouding and/or line corrosion.

(66) Experimental Procedure:

(67) Firstly, for the purposes of pretreatment, the test bodies were washed in a domestic dishwasher (Bosch SGS5602) with 1 g of surfactant (n-C.sub.18H.sub.37(OCH.sub.2CH.sub.2).sub.10OH) and 20 g of citric acid in order to remove any soilings. The test bodies were dried, their weight was determined and they were fixed to the grid base insert.

(68) To assess the gravimetric abrasion, the dry test bodies were weighed. The visual assessment of the test bodies was then made. For this, the surface of the test bodies was assessed with regard to line corrosion (score lines) and clouding corrosion (patchy clouding).

(69) The assessments were carried out according to the following scheme.

(70) Line Corrosion:

(71) L5: no lines evident

(72) L4: slight line formation in a very few areas, fine line corrosion

(73) L3: line corrosion in some areas

(74) L2: line corrosion in a number of areas

(75) L1: pronounced line corrosion

(76) Glass Clouding

(77) L5: no clouding evident

(78) L4: slight clouding in a very few areas

(79) L3: clouding in some areas

(80) L2: clouding in a number of areas

(81) L1: pronounced clouding over virtually the entire glass surface

(82) In the case of the inspection, interim grades (e.g. L3-4) were also allowed.

(83) If water with 2 German hardness was used for the tests, then formulations according to the invention were likewise always superior to the corresponding comparison formulations as far as inhibiting the glass corrosion is concerned.

(84) III.2 Results

(85) The results are summarized in table 4.

(86) TABLE-US-00004 TABLE 4 Results of the test with dishwasher (continuous operation) Visual Visual Base Weight loss Weight loss assessment assessment Example mixture: (A.1) (B) champagne brandy champagne brandy No. [g] [g] [mg] glass [mg] glass [mg] glass glass V-1 Base-3: 17 3 42.6 22.7 L1-2, T1-2 L2, T2 2 Base-3: 17 3 12 (L-PPI.1) 10 8 L4-5, T5.sup. L5, T5 3 Base-3: 17 3 12 (L-PPI.4) 14 11 .sup.L4, T4-5 L4-5, T4-5 4 Base-3: 17 3 6 (L-PPI.1) 10 9 L4, T5 L4-5, T5.sup. 5 Base-3: 17 3 12 (B.7) 18 13 L3, T4 L3, T4 6 Base-3: 17 3 12 (B.1) 15 13 L3-4, T4.sup. L4, T4 7 Base-2: 17 3 24 (B.1) 14 12 L3-4, T4-5 .sup.L4, T4-5

(87) When using formulations according to the invention, only slight or even no glass corrosion was always found.