DISHWASHING DETERGENT FORMULATIONS COMPRISING POLYASPARTIC ACID AND GRAFT POLYMERS BASED ON OLIGO- AND POLYSACCHARIDES AS FILM INHIBITING ADDITIVES

Abstract

Described herein is a dishwashing detergent formulation, including (a) 1-15% by weight of the total composition of (a1) at least one of polyaspartic acid or modified polyaspartic acid or salts thereof, and (a2) at least one graft copolymer composed of wherein the weight ratio of (a1):(a2) is from 20:1 to 1:12; (b) 0-60% by weight of complexing agent; (c) 0.1-80% by weight of builders and/or cobuilders; (d) 0.1-20% by weight of nonionic surfactants; (e) 0-30% by weight of bleaches and bleach activators; (f) 0-10% by weight of enzymes and enzyme stabilizers; and (g) 0-50% by weight of additives.

Claims

1. A phosphate-free and phosphonate-free dishwashing detergent formulation comprising: (a) 1-15% by weight of the total formulation of (a1) at least one of polyaspartic acid or modified polyaspartic acid or salts thereof, wherein the modified polyaspartic acid is obtainable by polycondensation of (i) 50 to 99 mol % of aspartic acid and (ii) 1 to 50 mol % of at least one carboxyl-containing compound different from aspartic acid and subsequent hydrolysis of co-condensates with an addition of a base, and (a2) at least one graft copolymer composed of (a21) at least one graft base selected from, oligosaccharides and polysaccharides, and side chains obtainable by grafting on of (a22) at least one ethylenically unsaturated mono- or dicarboxylic acid, and (a23) at least one ethylenically unsaturated N-containing monomer with a permanent cationic charge, wherein a weight ratio of (a1):(a2) is from 12:1 to 1:1; (b) 0-60% by weight of complexing agent; (c) 0.1-80% by weight of builders and/or cobuilders; (d) 0.1-20% by weight of nonionic surfactants; (e) 0-30% by weight of bleaches and bleach activators; (f) 0-10% by weight of enzymes and enzyme stabilizers; and (g) 0-50% by weight of additives.

2. The dishwashing detergent formulation according to claim 1, wherein the weight ratio of (a1):(a2) is from 12:1 to 3:1.

3. The dishwashing detergent formulation according to claim 1, wherein (i) is 80 to 95 mol % of aspartic acid and (ii) is 5 to 20 mol % of the at least one carboxyl-containing compound different from aspartic acid.

4. The dishwashing detergent formulation of claim 3, wherein the at least one carboxyl-containing compound (ii) is selected from the group consisting of 1,2,3,4-butanetetracarboxylic acid, citric acid, glycine and glutamic acid.

5. The dishwashing detergent formulation according to claim 1, wherein the at least one ethylenically unsaturated N-containing monomer (a23) is at least one compound of general formula (I), ##STR00007## wherein Z is O or NW.sup.1, R.sup.1 is selected from methyl and hydrogen, A.sup.1 is selected from C.sub.2-C.sub.4-alkylene, R.sup.2 are identical or different and selected from C.sub.1-C.sub.4-alkyl, and X.sup.− is selected from halide, mono-C.sub.1-C.sub.4-alkyl sulfate and sulfate.

6. The dishwashing detergent formulation according to claim 5, wherein the at least one ethylenically unsaturated N-containing monomer (a23) is trimethylaminoethyl(meth)acrylatochloride or methacrylamidopropyltrimethylammonium chloride.

7. The dishwashing detergent formulation according to claim 1, wherein the complexing agent (b) comprises methylglycinediacetic acid (MGDA) and/or glutamic acid diacetic acid (GLDA) or salts thereof.

8. The dishwashing formulation according to claim 1, comprising: (a) 1-15% by weight of the total formulation of (a1) at least one of polyaspartic acid or modified polyaspartic acid, wherein the modified polyaspartic acid is obtainable by polycondensation of (i) 50 to 99 mol % of aspartic acid and (ii) 1 to 50 mol % of at least one carboxyl-containing compound different from aspartic acid and subsequent hydrolysis of the co-condensates with the addition of a base, and (a2) at least one graft copolymer composed of (a21) at least one graft base selected from monosaccharides, disaccharides, oligosaccharides and polysaccharides, and side chains obtainable by grafting on of (a22) at least one ethylenically unsaturated mono- or dicarboxylic acid and (a23) at least one ethylenically unsaturated N-containing monomer with a permanent cationic charge, wherein the weight ratio of (a1):(a2) is from 12:1 to 3:1; (b) 1-50% by weight of methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA) or salts thereof as complexing agent; (c) 3-65% by weight of builders and/or cobuilders; (d) 0.5-10% by weight of nonionic surfactants; (e) 0-30% by weight of bleaches and bleach activators; (f) 0.1-8% by weight of enzymes and enzyme stabilizer; and (g) 0-50% by weight of additives.

9. A method of film inhibition in phosphate-free and phosphonate-free automatic dishwashing detergent formulations, the method comprising: using a phosphate-free and phosphonate-free automatic dishwashing detergent formulation comprising: (a1) at least one of polyaspartic acid or modified polyaspartic acid or salts thereof, wherein the modified polyaspartic acid is obtainable by polycondensation of (i) 50 to 99 mol % of aspartic acid and (ii) 1 to 50 mol % of at least one carboxyl-containing compound different from aspartic acid and subsequent hydrolysis of the co-condensates with the addition of a base, (a2) at least one graft copolymer composed of (a21) at least one graft base selected from monosaccharides, disaccharides, oligosaccharides and polysaccharides, and side chains obtainable by grafting on of (a22) at least one ethylenically unsaturated mono- or dicarboxylic acid and (a23) at least one ethylenically unsaturated N-containing monomer with a permanent cationic charge, wherein the weight ratio of (a1):(a2) is from 12:1 to 1:1.

10.-15. (canceled)

Description

EXAMPLES

Example 1

[0200] Synthesis of Polyaspartic Acid, Sodium Salt (P1)

[0201] In a rotary evaporator, 133.10 g of L-aspartic acid were polycondensed for 2.5 h at a temperature of 220-240° C. The polysuccinimide was obtained as dry powder. In order to prepare the aqueous sodium salt solution of polyaspartic acid, 100 g of polysuccinimide was dispersed into 100 g of water, the mixture was heated to 70° C. and, at this temperature, enough of a 50% strength aqueous sodium hydroxide solution was added for the pH to be in the range of 7-8. During this, the powder dispersed in water gradually dissolved, giving a clear aqueous sodium salt solution of polyaspartic acid. The weight-average molecular weight (Mw) of the modified polyaspartic was 5500 g/mol (determined according to the method described in US 2016/0222322 A).

Example 2

[0202] Preparation of Graft Copolymer (P2)

[0203] Comonomers used:

[0204] (a.I): maltodextrin, commercially available as Cargill C*Dry MDOI 955

[0205] (b.I): acrylic acid

[0206] (c.I): 2-(trimethylamino)ethylmethacrylatochloride (“TMAEMC”)

[0207] In a stirred reactor, 220 g of (a.I) 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:

[0208] a) An aqueous solution of 40.6 g of (c.I) in 149 g of water, over the course of 4 hours.

[0209] 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 a).

[0210] c) A solution of 32.8 g of (b.I) and 36.5 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 a).

[0211] After the complete addition of solutions a) to c), 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 the graft copolymer.

Example 3

[0212] The ASTM D3556 spotting/filming tests are performed as follows:

[0213] Soil

TABLE-US-00001 Blue Bonnet 53% Vegetable Oil Spread 80 wt % Meijer Brans Instant Nonfat Dry Milk 20 wt %

[0214] Water [0215] 300 ppm hardness (2:1 Ca:Mg) [0216] Incoming at 120° F. [0217] Amount of water 16.5 liters

[0218] Machine Type and wash program [0219] Kenmore Dishwasher: Model 587.1401 [0220] Wash program: normal wash [0221] Wash time: 50 minutes [0222] Dry time: 14 minutes

[0223] Procedure [0224] 6 clean glasses (Libbey #53 10 oz highball glasses) are placed in top rackand remain there throughout (plates and silverware are loaded on bottom rack) [0225] 5 duplicate wash cycles (A,B) are performed (+heated dry), with 40 grams of fresh soil added per cycle [0226] Detergent also added per each cycle

[0227] After 5.sup.th cycle, a light box is used to visually assign spot and film scores:

TABLE-US-00002 Spotting Rating None 1.0 Random spots 1.5 ¼ surface spotted 2.0 ½ surface spotted 3.0 ¾ surface spotted 4.0 Totally spotted 5.0

TABLE-US-00003 Filming Rating None 1.0 Barely perceptible 1.5 Slight 2.0 Moderate 3.0 Heavy 4.0 Very heavy 5.0

TABLE-US-00004 TABLE 1 ADW Formulations (Phosphate and phosphonate free) Formulation A Formulation B wt% wt% Na Carbonate 30 Na Carbonate 35 Na Silicate 10 Na Silicate 3 Na Percarbonate 10 Na Percarbonate 10 Na Citrate 4 Na Citrate 0 MGDA 4 MGDA 12 Plurafac SLF 180 3 Plurafac SLF 180 5 EXCELLENZ P1000 0.75 EXCELLENZ P1000 1.5 EXCELLENZ S1000 0.75 EXCELLENZ S1000 1.5 TAED 1.5 TAED 2 Na Sulfate (anhy) 36 Na Sulfate (anhy) 30 SUM 100 SUM 100 MGDA is methylglycine diacetic acid trisodium salt, 80 weight %, rest water Plurafac ® SLF 180 is a low foaming alcohole alkoxylate surfactant (BASF Corporation) EXCELLENZ ™ P1000 is a granular detergent protease enzyme (DuPont) EXCELLENZ ™ S1000 is a granular detergent amylase enzyme (DuPont) TAED = Tetraacetylethylenediamine

[0228] Results Formulation A

TABLE-US-00005 TABLE 2 Average spot/film scores Filming Additive * 3 wt % P1 3 wt % P1 3 wt % P1 3 wt % P1 3 wt % P1 1 wt % P1 0.15 wt % 0.25 wt % 0.50 wt % 3 wt % P2 3 wt % P2 P2 P2 P2 Glass 3.3 2.5 2.3 1.8 2.0 1.8 Rating Filming Additive * 0.5 wt % P1 0.25 wt % P1 3 wt % P2 No additive   3 wt % P2   3 wt % P2 Glass 2.0 2.4 2.8 2.8 Rating * wt % active material Spotting Additive * 3 wt % P1 3 wt % P1 3 wt % P1 3 wt % P1 3 wt % P1 1 wt % P1 0.15 wt % 0.25 wt % 0.50 wt % 3 wt % P2 3 wt % P2 P2 P2 P2 Glass 1.2 1.3 1.3 1.2 1.3 1.2 Rating Spotting Additive * 0.5 wt % P1 0.25 wt % P1 3 wt % P2 No additive   3 wt % P2   3 wt % P2 Glass 1.3 1.3 1.4 1.6 Rating * wt % active material

[0229] Results Formulation B

TABLE-US-00006 TABLE 3 Average spot/film scores Filming Additive* 5 5 wt % 5 wt % P1 5 wt % 3 wt % 1 wt % No wt % P1 0.50 wt % P1 P1 P1 ad- P1 0.25 P2 2 wt % 3 wt % 3 wt % ditive wt % P2 P2 P2 P2 Glass 3.4 2.6 2.0 1.6 1.9 2.3 2.6 Rating Spotting Additive* 5 5 wt % 5 wt % P1 5 wt % 3 wt % 1 wt % No wt % P1 0.50 wt % P1 P1 P1 ad- P1 0.25 P2 2 wt % 3 wt % 3 wt % ditive wt % P2 P2 P2 P2 Glass 1.2 1.3 1.2 1.3 1.2 1.2 1.3 Rating * wt % active material

Example 4

[0230] Aqueous solutions of polyaspartic acid, sodium salt (P1) and graft copolymer (P2) (20 and 40 weight %, based on solid material) were prepared by mixing of predissolved (P1) and (P2). Different (P1):(P2) weight ratio were applied: 20:1, 12:1, 8:1, 6:1, 4:1, 1:1, 1:3, 1:12

[0231] Even after three months storage at 22-25° C. no polymer/polymer incompatibilities were observed.

[0232] A build-up test was performed as follows [0233] Dishwasher: Miele G 1222 SCL [0234] Program: 65° C. in main cycle (with prewash), 65° C. rinse temperature, no rinse aid was used, no regenerating salt for ion exchange resin was used [0235] Dishes: 3 knives (WMF Tafelmesser Berlin, monobloc) [0236] 3 Amsterdam 0.2 L drinking glasses [0237] 3 “OCEAN BLAU” breakfast plates (MELAMINE) [0238] 3 porcelain plates: 19 cm plates with rims flat [0239] Ballast dishes 8 tea cups, 8 porcelain plates [0240] Arrangement: Knives in the cutlery drawer, glasses in the upper baskets, plates in the lower basket [0241] Dosage: 18 g of dishwashing detergent [0242] Ballast soil: 50 g of ballast soil is added with the formulation after the prewash; for composition see below [0243] Water hardness: 21° German hardness (Ca/Mg):HCO3 (3:1):1.35 [0244] Wash cycles: 30; break in between for 1 h in each case (10 min with door open, 50 min with door closed) [0245] Evaluation: Visually after 30 wash cycles

[0246] The evaluation of the dishes was carried out after 30 cycles in a darkened chamber under light behind an aperture diaphragm using a grading scale from 10 (very good) to 1 (very poor). Grades from 1-10 for filming (1=very severe filming, 10=no filming) were awarded.

[0247] Composition of the Ballast Soil: [0248] Starch: 0.5% potato starch, 2.5% gravy [0249] Fat: 10.2% margarine [0250] Protein: 5.1% egg yolk, 5.1% milk [0251] Others: 2.5% tomato ketchup, 2.5% mustard, 0.1% benzoic acid, 71.4% water

[0252] The following base detergent compositions were used:

TABLE-US-00007 TABLE 4 (weight %) F1 F2 F3 Citric acid trisodiumsalt dihydrate 35 35 0 MGDA 10 10 45 Natriumpercarbonate, 2Na.sub.2CO.sub.3 .Math. 3H.sub.2O.sub.2 10.19 10.19 10.19 Nonionic surfactant 1 4 4 4 Nonionic surfactant 2 1 1 1 Protease 2.5 2.5 2.5 Amylase 1 1 1 Na.sub.2Si.sub.2O.sub.5 2 2 2 TAED 4 4 4 Na.sub.2CO.sub.3 24.5 24.5 24.5 HEDP 0.81 Gap 0.81 0.81 Polymer 5 5 5 MGDA: Methylglycine diacetic acid trisodium salt, 80 weight-%, rest water Nonionic surfactant 1: n-C.sub.8H.sub.17—CH(OH)—CH.sub.2—O—(EO).sub.22—CH(CH.sub.3)—CH.sub.2—O-n-C.sub.10H.sub.21 Nonionic surfactant 2: n-C.sub.10H.sub.2 —CH(OH)—CH.sub.2—O—(EO).sub.40-n-C.sub.10H.sub.21 Na.sub.2Si.sub.2O.sub.5: commercially available as Britesil ® H 265 LC HEDP: 1-Hydroxyethane-1,1-diphosphonate disodium salt TAED: Tetraacetylethylenediamine Polymer: P1, P2, M1, M2, M3, M4 (active material) M1 = aqueous mixture (40 weight %) of P1 and P2 (P1:P2 weight ratio 4:1) M2 = aqueous mixture (40 weight %) of P1 and P2 (P1:P2 weight ratio 8:1) M3 = aqueous mixture (40 weight %) of P1 and P2 (P1:P2 weight ratio 12:1) M4 = aqueous mixture (40 weight %) of P1 and P2 (P1:P2 weight ratio 1:1)

[0253] Filming Results on Glass

TABLE-US-00008 TABLE 5 Average film scores Detergent composition F1 F1 F1 F1 F1 F1 Additive * 5 wt % P1 5 wt % M1 5 wt % M2 5 wt % M3 5 wt % M4 5 wt % P2 Glass 3.0 5.0 4.7 4.3 4.3 3.3 Rating * wt % active material Detergent composition F2 F2 F2 F2 F2 F2 Additive * 5 wt % P1 5 wt % M1 5 wt % M2 5 wt % M3 5 wt % M4 5 wt % P2 Glass 3.0 4.3 4.3 4.0 3.7 2.7 Rating * wt % active material Detergent composition F3 F3 F3 F3 F2 F3 Additive * 5 wt % P1 5 wt % M1 5 wt % M2 5 wt % M3 5 wt % M4 5 wt % P2 Glass 4.0 5.3 5.0 4.7 4.3 3.7 Rating * wt % active material