Formulations, use thereof as or for the production of dishwashing detergents, and production thereof

Abstract

In a formulation used as or for the production of dishwashing detergents, the formulation includes (A) at least one compound selected from aminocarboxylates, (B) at least one graft copolymer composed of (a) at least one graft base selected from monosaccharides, disaccharides, oligosaccharides and polysaccharides, and side chains obtainable by grafting on of (b) at least one ethylenically unsaturated mono- or dicarboxylic acid and (c) at least one ethylenically unsaturated N-containing monomer with a permanent cationic charge, and (C) at least one inorganic peroxide compound selected from sodium peroxodisulfate, sodium perborate and sodium percarbonate.

Claims

1. A formulation comprising (A) at least one compound selected from methylglycine diacetate (MGDA) and glutamic acid diacetate (GLDA), and salts thereof, (B) at least one graft copolymer composed of (a) at least one graft base selected from monosaccharides, disaccharides, oligosaccharides and polysaccharides, and side chains obtainable by grafting on of (b) at least one ethylenically unsaturated mono- or dicarboxylic acid and (c) at least one ethylenically unsaturated N-containing monomer with a permanent cationic charge, and (C) at least one inorganic peroxide compound selected from sodium peroxodisulfate, sodium perborate and sodium percarbonate.

2. The formulation according to claim 1, wherein it the formulation is free from phosphates and polyphosphates.

3. The formulation according to claim 1, wherein compound (c) is selected from (meth)acrylamidopropyltrimethylammonium chloride.

4. The formulation according to claim 1, wherein compound (A) is selected from the trisodium salt of methylglycine diacetate (MGDA).

5. The formulation according to claim 1, wherein the formulation is solid at room temperature.

6. The formulation according to claim 1, wherein the formulation comprises at least one polymeric builder (D).

7. The formulation according to claim 1, wherein the formulation comprises sodium citrate.

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

9. The formulation according to claim 1, wherein the formulation comprises: in total in the range from 1 to 50% by weight of compound (A), in total in the range from 0.1 to 4% by weight of graft copolymer (B), and in the range from 1 to 20% by weight of peroxide (C), based in each case on solids content of the formulation in question.

10. A process for washing dishes and kitchen utensils, the process comprising washing said dishes and kitchen utensils using the formulation according to claim 1.

11. A process for washing objects which have at least one surface made of glass wherein the glass is one of decorated and undecorated, the process comprising washing said objects using the formulation according to claim 1.

12. The process according to claim 10, wherein the washing comprises washing using a dishwasher.

13. A process for the preparation of formulations according to claim 1, wherein at least one compound (A), at least one graft copolymer (B) and at least one peroxide (C) are mixed together in one or more steps.

14. The process according to claim 13, wherein water is at least partially removed from the formulation after mixing.

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

Description

EXAMPLES

(1) General remarks concerning the experiments relating to deposit inhibition

(2) All of the washing experiments were carried out in a dishwasher from Miele, model G1222 SCL. Here, the program at 65? C. for the wash cycle and 65? C. for the clear-rinse cycle was chosen. The tests were carried out with hardened water with a water hardness of 21? German hardness (Ca/Mg):HCO.sub.3 (3:1):1.35. No separate rinse aid was added and the incorporated water softener (ion exchanger) was not regenerated with regenerating salt. 18 g of the stated formulation according to the invention were dosed in each wash cycle. At the start of each wash cycle, 50 g of a ballast soiling were added, consisting of grease, protein and starch.

(3) To assess the deposit inhibition, a total of 30 successive washing experiments were carried out with the same test ware. The test ware used in each washing experiment was stainless steel knives, blue melamine plates, drinking glasses and porcelain plates. One hour was left between every two washing experiments, for 10 min of which the door of the dishwasher was closed and for 50 min of which the door was open.

(4) In each case 18 g of the stated formulation according to the invention were dosed per washing experiment. At the start of each washing experiment, moreover, 50 g of a ballast soiling were added, consisting of grease, protein and starch.

(5) When the 30th washing experiment was completed, the test ware was inspected visually in a darkened chamber under light behind an aperture plate, and assessed on a grading scale from 1 (=considerable residues) to 10 (=no residues) as regards spots, streaks and film-like deposits.

(6) General remarks concerning the experiments relating to detergency:

(7) The procedure was essentially as described above except that the program at 50? C. was chosen for the wash cycle and 65? C. for the clear-rinse cycle.

(8) In each case, 2 melamine plates DM-21 (egg yolk), DM-93 (triple soiled minced meat), DM-23 (egg yolk 1.5? soiled) (source: Center For Test Materials BV 3130 AC Vlaardingen, NL) and 2 tea cups (soiled according to the method in SOFW Journal, 132, 8-2006, pages 35-49) were placed into the dishwashers. No separate rinse aid was added and the inbuilt water softener (ion exchanger) was not regenerated with regenerating salt. In each case, 18 g of the stated formulation according to the invention and 50 g of IKW ballast soiling (S?F W Journal, 132, 8-2006, 35-49) were metered into the dishwasher at the start of the washing experiment and a washing experiment was carried out.

(9) After drying, the averages from eight reflectance measurements (Elrepho, 460 nm) were formed for each melamine plate. These averages were deducted from the starting reflectance values determined before the start from the melamine plates. Differential values are given in the table. The experiments were carried out as a double determination in two different dishwashers of the type stated above.

(10) The tea cups were assessed visually (grading scale 1 to 10, 1=heavily soiled, 10=clean).

(11) I. Preparation of Graft Copolymers (B), of Formulations According to the Invention and of Comparison Formulations

(12) Comonomers used:

(13) (a.1): maltodextrin, commercially available as Cargill C*Dry MD01910

(14) (a.2): spray-dried glucose syrup, commercially available as Cargill C*Dry GL01924

(15) (a.3): maltodextrin, commercially available as Cargill C*Dry MD01955

(16) (b.1): acrylic acid

(17) (c.1): 3-trimethylammonium propylmethacrylamide chloride (MAPTAC)

(18) (c.2): 3-trimethylammonium propylacrylamide chloride (APTAC)

(19) In the context of the present application, data are in % by weight unless expressly stated otherwise.

(20) The biocide used is always a 9% by weight solution of 1,2-benzisothiazolin-3-one in water/propylene glycol mixture, commercially available as Proxel? XL2 Antimicrobial. Quantitative data are tell qu'elle.

(21) I.1 Preparation of a Graft Copolymer (B.1)

(22) The graft copolymer B.1 was prepared analogously to Ex. 4 from EP 2 138 560 B1.

(23) I.2 Preparation of a Graft Copolymer (B.2)

(24) In a stirred reactor, 220 g of maltodextrin (a.1) in 618 g of water were introduced and heated to 80? C. with stirring. At 80? C., the following solutions were metered in simultaneously and via separate feeds as follows: a) an aqueous solution of 41.6 g of (c.1) in 181 g of water, over the course of 4 hours. b) a solution of 9.85 g of sodium peroxodisulfate in 68.0 g of water over the course of 5 h, simultaneously starting with the metered addition of (c.1). c) a solution of 31.7 g of acrylic acid (b.1) and 35.2 g of sodium hydroxide solution (50% strength in water), diluted with 139 g of water, over the course of 2 hours, starting 2 hours after the start of the metered addition of (c.1).

(25) After the addition of all three solutions was complete, the reaction mixture was stirred for one hour at 80? C. Then, a solution of 0.73 g of sodium peroxodisulfate in 10.0 g of water was added and the mixture was stirred for a further 2 hours at 80? C. The mixture was then cooled to room temperature and 8 g of biocide were added. This gave a 20.8% by weight solution of graft copolymer (B.2).

(26) I.3 Preparation of a Graft Copolymer (B.3)

(27) In a stirred reactor, 220 g of spray-dried glucose syrup (a.2) in 618 g of water were introduced and heated to 80? C. with stirring. At 80? C., the following solutions were metered in simultaneously and via separate feeds as follows: a) an aqueous solution of 41.6 g of (c.1), in 181 g of water, over the course of 4 hours. b) a solution of 9.85 g of sodium peroxodisulfate in 68.0 g of water over the course of 5 h, simultaneously starting with the metered addition of (c.1). c) a solution of 31.7 g of acrylic acid (b.1) and 35.2 g of sodium hydroxide solution (50% strength in water), diluted with 139 g of water, over the course of 2 h, starting 2 h after the start of the metered addition of (c.1).

(28) After the addition of all three solutions was completed, the reaction mixture was stirred for one hour at 80? C. Then, a solution of 0.73 g of sodium peroxodisulfate in 10.0 g of water was added and the mixture was stirred for a further 2 hours at 80? C. The mixture was then cooled to room temperature and 8 g of biocide were added. This gave a 19.8% by weight solution of graft copolymer (B.3).

(29) I.4 Preparation of a Graft Copolymer (B.4)

(30) In a stirred reactor, 264 g of maltodextrin (a.3) in 618 g of water were introduced and heated to 80? C. with stirring. At 80? C., the following solutions were metered in simultaneously and via separate feeds as follows: a) an aqueous solution of 16.7 g of (c.1), further diluted with 156 g of water, over the course of 4 h. b) a solution of 3.94 g of sodium peroxodisulfate in 68.0 g of water over the course of 5 h, simultaneously starting with the metered addition of (c.1). c) a solution of 12.7 g of acrylic acid (b.1) and 14.1 g of sodium hydroxide solution (50% strength in water), diluted with 139 g of water, over the course of 2 hours, starting 2 hours after the start of the metered addition of (c.1).

(31) After the addition of all three solutions was completed, the reaction mixture was stirred for one hour at 80? C. Then, a solution of 0.3 g of sodium peroxodisulfate in 10.0 g of water was added and the mixture was stirred for a further 2 hours at 80? C. The mixture was then cooled to room temperature and 8 g of biocide were added. This gave a 21.7% by weight solution of graft copolymer (B.4).

(32) I.5 Preparation of a Graft Copolymer (B.5)

(33) In a stirred reactor, 221 g of maltodextrin (a.3) in 618 g of water were introduced and heated to 80? C. with stirring. At 80? C., the following solutions were metered in simultaneously and via separate feeds as follows: a) an aqueous solution of 55.0 g of (c.1) in 194 g of water, over the course of 4 hours. b) a solution of 9.8 g of sodium peroxodisulfate in 68.0 g of water over the course of 5 h, simultaneously starting with the metered addition of (c.1). c) a solution of 18 g of acrylic acid (b.1) and 20 g of sodium hydroxide solution (50% strength in water), diluted with 139 g of water, over the course of 2 hours, starting 2 hours after the start of the metered addition of (c.1).

(34) After the addition of all three solutions was completed, the reaction mixture was stirred for one hour at 80? C. Then, a solution of 0.73 g of sodium peroxodisulfate in 10.0 g of water was added and the mixture was stirred for a further 2 hours at 80? C. The mixture was then cooled to room temperature and 8 g of biocide were added. This gave a 21.7% by weight solution of graft copolymer (B.5).

(35) I.6 Preparation of a Graft Copolymer (B.6)

(36) The experiment according to I.5 was repeated but metering in, as solution a), an aqueous solution of 59.8 g of (c.1) in 199 g of water and, as solution c), a solution of 13.2 g of acrylic acid (b.1) and 14.7 g of 50% by weight sodium hydroxide solution, diluted with 139.2 g of water.

(37) This gave a 21.8% by weight solution of graft copolymer (B.6).

(38) I.7 Preparation of a Graft Copolymer (B.7)

(39) In a stirred reactor, 230 g of maltodextrin (a.3) in 618 g of water were introduced and heated to 80? C. with stirring. At 80? C., the following solutions were metered in simultaneously and via separate feeds as follows: a) an aqueous solution of 28.9 g of (c.1) in 168 g of water, over the course of 4 hours. b) a solution of 9.85 g of sodium peroxodisulfate in 68.0 g of water over the course of 5 h, simultaneously starting with the metered addition of (c.1). c) a solution of 44.5 g of acrylic acid (b.1) and 49.4 g of sodium hydroxide solution (50% strength in water), diluted with 139 g of water, over the course of 2 hours, starting 2 hours after the start of the metered addition of (c.1).

(40) After the addition of all three solutions was completed, the reaction mixture was stirred for one hour at 80? C. Then, a solution of 0.73 g of sodium peroxodisulfate in 10.0 g of water was added and the mixture was stirred for a further 2 hours at 80? C. Then, the mixture was cooled to room temperature and 8 g of biocide were added. This gave a 22.4% by weight solution of graft copolymer (B.7).

(41) I.8 Preparation of a Graft Copolymer (B.8)

(42) In a stirred reactor, 147 g of maltodextrin (a.3) in 618 g of water were introduced and heated to 80? C. with stirring. At 80? C., the following solutions were metered in simultaneously and via separate feeds as follows: a) an aqueous solution of 83.3 g of (c.1) in 222 g of water, over the course of 4 hours. b) a solution of 19.7 g of sodium peroxodisulfate in 68.0 g of water over the course of 5 h, simultaneously starting with the metered addition of (c.1). c) a solution of 63.5 g of acrylic acid (b.1) and 70.5 g of sodium hydroxide solution (50% strength in water), diluted with 139 g of water, over the course of 2 hours, starting 2 hours after the start of the metered addition of (c.1).

(43) After the addition of all three solutions was completed, the reaction mixture was stirred for one hour at 80? C. Then, a solution of 1.47 g of sodium peroxodisulfate in 10.0 g of water was added and the mixture was stirred for a further 2 hours at 80? C. The mixture was then cooled to room temperature and 8 g of biocide were added. This gave a 21.9% by weight solution of graft copolymer (B.8).

(44) I.9 Preparation of a Graft Copolymer (B.9)

(45) In a stirred reactor, 230 g of maltodextrin (a.3) in 618 g of water were introduced and heated to 80? C. with stirring. At 80? C., the following solutions were metered in simultaneously and via separate feeds as follows: a) an aqueous solution of 40.5 g of (c.2) in 153 g of water, over the course of 4 hours. b) a solution of 9.8 g of sodium peroxodisulfate in 68.0 g of water over the course of 5 h, simultaneously starting with the metered addition of (c.2). c) a solution of 32.9 g of acrylic acid (b.1) and 36.6 g of sodium hydroxide solution (50% strength in water), diluted with 139 g of water, over the course of 2 hours, starting 2 hours after the start of the metered addition of (c.2).

(46) After the addition of all three solutions was completed, the reaction mixture was stirred for one hour at 80? C. Then, a solution of 0.73 g of sodium peroxodisulfate in 10.0 g of water was added and the mixture was stirred for a further 2 hours at 80? C. The mixture was then cooled to room temperature. 8 g of biocide were added and a 25.2% by weight solution of graft copolymer (B.9) was obtained.

(47) I.10 Preparation of a Graft Copolymer (B.10)

(48) In a stirred reactor, 237 g of maltodextrin (a.3) in 618 g of water were introduced and heated to 80? C. with stirring. At 80? C., the following solutions were metered in simultaneously and via separate feeds as follows: a) an aqueous solution of 41.6 g of (c.1) in 181 g of water, over the course of 4 hours. b) a solution of 9.85 g of sodium peroxodisulfate in 68.0 g of water over the course of 5 h, simultaneously starting with the metered addition of (c.1). c) a solution of 31.7 g of acrylic acid (b.1) and 35.2 g of sodium hydroxide solution (50% strength in water), diluted with 139 g of water, over the course of 2 hours, starting 2 hours after the start of the metered addition of (c.1).

(49) After the addition of all three solutions was completed, the reaction mixture was stirred for one hour at 80? C. Then, a solution of 0.73 g of sodium peroxodisulfate in 10.0 g of water was added and the mixture was stirred for a further 2 hours at 80? C. Then, the mixture was cooled to room temperature and 8 g of biocide were added. This gave a 22.7% by weight solution of graft copolymer (B.10).

(50) I.11 Preparation of Formulations According to the Invention (F.1, F.6, F.8.1-F.8.10) and of Comparison Formulations (C-F.2-C-F.5, C-F.7, C-F.9)

(51) Formulations according to the invention F.1, F.6, F.8.1-F.8.10 and comparison formulations C-F.2 to C-F.5 and C-F.7 and C-F.9 were prepared by mixing the components according to table 1with the exception of surfactant 1in the dry state. Nonionic surfactant 1 was melted and stirred into the dry mixture and thereby distributed as homogeneously as possible. If graft copolymer (B) is in the form of an aqueous solution, then the graft copolymer (B) can either be isolated by drying and added in solid form to the other solid components or be added separately to the dishwasher in the form of a solution. The components of formulations according to the invention F.1, F.6, F.8.1-F.8.10 and comparison formulations C-F.2 to C-F.5 and also C-F.7 and C-F.9 can be found in table 1.

(52) TABLE-US-00001 TABLE 1 Composition of formulation according to the invention F.1, F.6 and F.8.1, and of comparison formulations C-F.2 to C-F.5, C-F.7 and C-F.9 Constituent [g] F.1 C-F.2 C-F.3 C-F.4 C-F.5 F.6 C-F.7 F.8.1 C-F.9 C-F.10 (A.1) 35 35 35 35 35 10 10 10 Citric acid as 35 35 35 35 35 trisodium salt dihydrate (B.1) 1 1 1 1 1 1 Polymeric 4 5 4 4 4 5 9 10 9 builder (D.1) Polymeric 4 builder (D.2) Polymeric 1 builder C- (D.3) (C.1) 10.2 10.2 10.2 10.2 10.2 10.2 10.2 10.2 Nonionic 4 4 4 4 4 4 4 4 4 4 surfactant 1 Nonionic 1 1 1 1 1 1 1 1 1 1 surfactant 2 Protease 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Amylase 1 1 1 1 1 1 1 1 1 1 Na.sub.2Si.sub.2O.sub.5 2 2 2 2 2 2 2 2 2 2 TAED 4 4 4 4 4 4 4 4 4 4 Na.sub.2CO.sub.3 34.5 34.5 34.5 34.5 34.5 34.5 34.5 19.5 19.5 19.5 HEDP 0.81 0.81 0.81 0.81 0.81 0.8 0.8 0.8 0.8 0.8 Explanation: (A.1): MGDA-Na.sub.3, 78% by weight, remainder is water (C.1): Sodium percarbonate, 2Na.sub.2CO.sub.33H.sub.2O.sub.2 Nonionic surfactant 1: n-C.sub.8H.sub.17CH(OH)CH.sub.2O(EO).sub.22CH(CH.sub.3)CH.sub.2On-C.sub.10H.sub.21 Nonionic surfactant 2: n-C.sub.10H.sub.21CH(OH)CH.sub.2O(EO).sub.40n-C.sub.10H.sub.21 Na.sub.2Si.sub.2O.sub.5: commercially as Britesil? H 265 LC HEDP: 1-Hydroxyethane-1,1-diphosphonate disodium salt Polymeric builder (D.1): polyacrylic acid M.sub.w 4000 g/mol as sodium salt, completely neutralized Polymeric builder (D.2): random copolymer acrylic acid/2-acrylamido-2-methylpropanesulfonic acid as sodium salt, completely neutralized, comonomer ratio 70:30 (% by weight), K value 40. Polymeric builder C-(D.3): alternating copolymer of maleic acid and diisobutene, sodium salt, M.sub.w 12 000 g/mol, completely neutralized

(53) In formulation F.8.2 according to the invention, (B.1) was replaced by an identical amount of (B.2), i.e. 1 g. In formulation F.8.3 according to the invention, (B.1) was replaced by 1 g of (B.3). In formulation F.8.4 according to the invention, (B.1) was replaced by 1 g of (B.4). For the formulations according to the invention F.8.5 to F.8.10, mutatis mutandis applies.

(54) II. Experiments Relating to Deposit Inhibition

(55) Per experiment in the dishwasher, in each case 18 g of formulation according to the invention F.1, F.6, F.8.1 or one of the comparison formulations C-F.2, C-F.4, C-F.7, C-F.9 or C-F.10 were used.

(56) TABLE-US-00002 TABLE 2 Results of the film formation Filming on knives Filming on glass Filming on melamine F.1 5.7 6.3 6.3 C-F.2 5.0 4.0 5.7 F.6 6.0 5.0 5.3 C-F.7 4.0 4.0 4.3 C-F.4 3.0 5.0 n.d. F.8.1 6.3 5.0 5.0 C-F.9 6.3 4.0 4.0 C-F.10 4.3 4.0 4.3

(57) Formulations according to the invention exhibit on glass always at least grade 5 or better and consequently less of a build-up than the comparison formulations in question. This can be seen particularly clearly when comparing the filming on glass of F.8.1 and C-F.9 or C-F.10 and also of F.1 and C-F.2.

(58) III. Experiments Relating to Detergency

(59) Per experiment in the dishwasher, in each case 18 g of formulation according to the invention F.1 or one of the comparison formulations C-F.2 to C-F.5 were used.

(60) The result of the detergency is summarized in tables 3 and 4 below.

(61) TABLE-US-00003 TABLE 3 Result of detergency on melamine plates by differential reflectance Formulation DM-21 DM-23 DM-93 F.1 29.6 17.2 26.9 C-F.2 25.0 16.1 n.d. C-F.3 21.1 10.8 19.1 C-F.4 19.4 12.7 24.4 C-F.5 16.1 10.8 21.8

(62) Of the listed formulations, F.1 thus cleans the selected melamine plates the best. n.d.: not determined.

(63) TABLE-US-00004 TABLE 4 Result of detergency on tea cups made of porcelain Formulation Grade tea F.1 8 C-F.3 6.25 C-F.4 5.25 C-F.5 3.5