DETERGENT COMPOSITIONS, POLYMERS AND METHODS OF MANUFACTURING THE SAME

Abstract

Disclosed herein are aqueous detergent compositions including: (A) at least one polymer including: (a) a backbone that is derived from an aliphatic compound with at least 4 amino groups per molecule of which at least one amino group is a (CH.sub.2).sub.aNH.sub.2 group, the variable a being selected from 2 to 4, where at least 40 mol-% of the (CH.sub.2).sub.nNH.sub.2 groups are converted with (b) a sugar based on a mono-, di- or polysaccharide under formation of a secondary amino group of the general formula (CH.sub.2).sub.aNHCH.sub.2.

Claims

1. An aqueous detergent composition comprising: (A) at least one polymer comprising: (a) a backbone that is derived from an aliphatic compound with at least 4 amino groups per molecule of which at least one amino group is a (CH.sub.2).sub.aNH.sub.2 group, the variable a being selected from the group consisting of 2 to 4, wherein at least 40 mol-% of said CH.sub.2(CH.sub.2).sub.aNH.sub.2 groups are converted with (b) a sugar based on a mono-, di- or polysaccharide under formation of a secondary amino group of the general formula (CH.sub.2).sub.aNHCH.sub.2.

2. The composition according to claim 1, wherein said backbone (a) is selected from the group consisting of H.sub.2N(CH.sub.2).sub.3NHCH.sub.2CH.sub.2N(CH.sub.2).sub.3NH.sub.2, polyethylenimine, and (poly) peptides with an average of at least two lysine moieties as building block.

3. The composition according to claim 1, or 2 wherein said backbone (a) is selected from the group consisting of branched polyethylenimines with an average molecular weight M.sub.w in the range of from 500 to 20,000 g/mol.

4. The composition according to claim 1, or 2 wherein said backbone (a) is selected from the group consisting of -polylysine with a molecular weight M.sub.w in the range of from 1,000 to 8,000 g/mol.

5. The composition according to claim 1, wherein polymer (A) has an average molecular weight M.sub.w in the range from 750 to 350,000 g/mol.

6. The composition according to any of the preceding claim 1, wherein sugar (b) is a maltodextrin.

7. The composition according to claim 1, wherein said composition additionally comprises (B) at least one hydrolase.

8. A method of using the composition according to claim 1, the method comprising using the composition for laundry care.

9. A polymer comprising: (a) a backbone that is derived from an aliphatic compound with at least 4 amino groups per molecule of which at least one amino groups is a (CH.sub.2).sub.aNH.sub.2 group, the variable a being selected from the group consisting of 2 to 4, wherein at least 40 mol-% of said (CH.sub.2).sub.aNH.sub.2 groups are converted with (b) with a sugar based on a mono-, di- or polysaccharide under formation of a secondary amino group of the general formula (CH.sub.2).sub.aNHCH.sub.2.

10. The polymer according to claim 9, having an average molecular weight M.sub.w in the range of from 750 to 350,000 g/mol.

11. The polymer according to claim 9, wherein backbone (a) is selected from the group consisting of H.sub.2N(CH.sub.2).sub.3NHCH.sub.2CH.sub.2N(CH.sub.2).sub.3NH.sub.2, polyethylenimine, and (poly) peptides with in an average of at least two lysine moieties as building blocks.

12. The polymer according to claim 9, wherein said backbone (a) is -polylysine with a molecular weight M.sub.w in the range of from 1,000 to 8,000 g/mol.

13. The polymer according to claim 9, wherein sugar (b) is a maltodextrin.

14. Process A process for making the polymer according to claim 9, comprising the steps of; () providing a backbone molecule (a) that is aliphatic compound with at least 4 amino groups per molecule of which at least one amino group is a (CH.sub.2).sub.aNH.sub.2 group, the variable a being selected from the group consisting of 2 to 4, and () reacting said backbone molecule (a) with at least one sugar molecule based on a mono-, di- or polysaccharide in the presence of hydrogen and a catalyst or in the presence of an aminoborane.

15. A method of improving the cleaning performance of a liquid detergent composition, the method comprising adding the polymer according to claim 9 to a detergent composition that comprises at least one lipase (b) and/or at least one protease (D).

Description

DESCRIPTION OF THE TEST METHOD USED IN THE CONTEXT OF THE PRESENT INVENTION

[0272] Biodegradation in sewage was tested in triplicate using the OECD 301F manometric respirometry method. OECD 301F is an aerobic test that measures biodegradation of a sewage sample by measuring the consumption of oxygen. To a measured volume of sewage. 100 mg/L test substance, which is the nominal sole source of carbon, was added along with the inoculum (aerated sludge taken from the municipal sewage treatment plant, Shanghai, PR China, polymer (A.1) to (A.8), or Mannheim, Germany). This sludge was stirred in a closed flask at a constant temperature (25 C.) for 28 days. The consumption of oxygen is determined by measuring the change in pressure in the closed flask using an Oxi TopC. Carbon dioxide evolved was absorbed in a solution of sodium hydroxide. Nitrification inhibitors were added to the flask to prevent consumption of oxygen due to nitrification. The amount of oxygen taken up by the microbial population during biodegradation of the test substance (corrected for uptake by a blank inoculum run in parallel) is expressed as a percentage of ThOD (theoretical oxygen demand, which is measured by the elemental analysis of the compound). A positive control glucose/glutamic acid is run along with the test samples for each cabinet as reference.

[0273] Calculations: Theoretical oxygen demand: Amount of O.sub.2 required to oxidize a compound to its final oxidation products. This amount is calculated using the elemental analysis data. % Biodegradation

[0274] Experimental O.sub.2 uptake100 and divided by the theoretical oxygen demand

[0275] The results of biodegradability tests are summarized in Table 9.

TABLE-US-00009 TABLE 9 Results of biodegradation tests Polymer 28 days (%) 56 days (%) (A.1) 36 46 (A.4) 46 47 (A.5) 52 55 (A.7) 51 52 (A.8) 69 71 (A.11) 30 33 (A.12) 49 55

IV. Synthesis of Inventive Polymers (A.13) to (A.17)

[0276] The following starting materials were used: [0277] (a.1): linear -polylysine, K-value 19.6, determined in a 1% by weight aqueous solution, commercially available from JNC Corp., Japan [0278] (a.2): branched polylysine, K-value 12.5, synthesis see below [0279] (a.3): N4-amine, commercially available from BASF SE [0280] (a.4): branched polyethyleneimine, Mw=800 g/mol (GPC in water as eluent), commercially available from BASF SE [0281] (a.5): branched polylysine, K-value 9.8, synthesis see below [0282] (a.6): branched polylysine, K-value 10.7, synthesis see below [0283] (a.7): branched polylysine, K-value 11.0, synthesis see below [0284] (b.1): D-maltose [0285] (b.2): maltodextrin, DE 17.8, purchased from Cargill Cpur Series [0286] (b.3): maltodextrin, DE 28.0, purchased from Cargill Cpur Series [0287] (b.4): maltodextrin, DE 37.7, purchased from Cargill Cpur Series [0288] (b.5): D-glucose [0289] (b.6): maltodextrin, DE 9.0, purchased from Roquette Glucidex Series [0290] (b.7): cellulose, DE16.7 purchased from Sigma-Aldrich

Manufacture of (a.2):

Step (.6): branched polylysine K-value 10.7

[0291] A 1000 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with reduced-pressure connection and a Dean-Stark receiver, was charged with 500 g of an aqueous solution of L-lysine (50 wt %). The solution was heated with stirring to an internal temperature of 160 C. with continuous water removal. After a reaction time of 4.0 hours, water was distilled off under reduced pressure (670 mbar). When 260 g of water distillate had been collected, the highly viscous polymer was discharged to a silicone container as fast as possible while it was still hot and flowable. The k-value of the resultant backbone molecule (a.6) was determined as 10.7 in a 1% by weight aqueous solution.

Step (.7): Branched Polylysine K-Value 11.0

[0292] A 1000 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with reduced-pressure connection and a Dean-Stark receiver, was charged with 500 g of an aqueous solution of L-lysine (50 wt %). The solution was heated with stirring to an internal temperature of 160 C. with continuous water removal. After a reaction time of 4.0 hours, water was distilled off under reduced pressure (670 mbar). When 262 g of water distillate had been collected, the highly viscous polymer was discharged to a silicone container as fast as possible while it was still hot and flowable. The k-value of the resultant backbone molecule (a.7) was determined as 11.0 in a 1% by weight aqueous solution.

Synthesis of Inventive Polymers (A)

Synthesis of Inventive Copolymers with -Picoline Borane as Reducing Agent

Inventive Polymer (A.13)

[0293] In a 250 ml round-bottom flask equipped with a magnetic stirrer, a condenser and a gas bubbler, 3.0 g of (a.6) were dissolved in 70 g of water: acetic acid 10:1 wt. under stirring. Then, 20.8 g of (b.2) were added to the solution followed by dropwise addition of a solution of 2.20 g of -picoline borane in 5 ml methanol. The pH value at the beginning of the reaction was between 3.5-4.5. Gas evolution was observed. The reaction was allowed to proceed at 85 C. for 24 h. After work-up as above, inventive polymer (A.13) was obtained, DM: 72%, Mn: 5,426 g/mol. Mw: 6,974 g/mol.

Inventive Polymer (A.14)

[0294] In a 250 ml round-bottom flask equipped with a magnetic stirrer, a condenser and a gas bubbler, 3.0 g of (a.6) were dissolved in 90 g of water: acetic acid 10:1 wt. under stirring. Then, 42.0 g of (b.6) were added to the solution followed by dropwise addition of a solution of 2.25 g of -picoline borane in 5 ml methanol. The pH value at the beginning of the reaction was between 3.5-4.5. Gas evolution was observed. The reaction was allowed to proceed at ambient temperature until the reaction mixture was transparent and no visible gas bubbles were generated any more. After work-up as above, inventive polymer (A.14) was obtained, DM: 48%, Mn: 6,913 g/mol, Mw: 17,322 g/mol.

Inventive Polymer (A.15)

[0295] In a 250 ml round-bottom flask equipped with a magnetic stirrer, a condenser and a gas bubbler, 2.7 g of (a.2) were dissolved in 90 g of water: acetic acid 10:1 wt. under stirring. Then, 42.0 g of (b.6) were added to the solution followed by dropwise addition of a solution of 2.25 g of -picoline borane in 5 ml methanol. The pH value at the beginning of the reaction was between 3.5-4.5. Gas evolution was observed. The reaction was allowed to proceed at 85 C. for 24 h. After work-up as above, inventive polymer (A.15) was obtained, DM: 44%, Mn: 12,252 g/mol, Mw: 50,844 g/mol.

Inventive Polymer (A.16)

[0296] In a 250 ml round-bottom flask equipped with a magnetic stirrer, a condenser and a gas bubbler, 4.0 g of (a.1) were dissolved in 90 g of water: acetic acid 10:1 wt. under stirring. Then, 47.4 g of (b.2) were added to the solution followed by dropwise addition of a solution of 3.34 g of -picoline borane in 5 ml methanol. The pH value at the beginning of the reaction was between 3.5-4.5. Gas evolution was observed. The reaction was allowed to proceed at 60 C. for 24 h. After work-up as above, inventive polymer (A.16) was obtained, DM: 86%, Mn: 50,570 g/mol, Mw: 61,292 g/mol.

Inventive Polymer (A.17)

[0297] In a 250 ml round-bottom flask equipped with a magnetic stirrer, a condenser and a gas bubbler, 3.0 g of (a.7) were dissolved in 70 g of water: acetic acid 10:1 wt. under stirring. Then, 18.50 g of (b.7) were added to the solution followed by dropwise addition of a solution of 2.25 g of -picoline borane in 5 ml methanol. The pH value at the beginning of the reaction was between 3.5-4.5. Gas evolution was observed. The reaction was allowed to proceed at at 60 C. for 24 h. After work-up as above, inventive polymer (A.17) was obtained, DM: 66%, Mn: 5,166 g/mol, Mw: 8,594 g/mol.

V. Biodegradability of Inventive Polymers (A.13) to (A.17)

TABLE-US-00010 TABLE 10 Results of biodegradation tests Polymer 28 days (%) 56 days (%) (A.13) 68 68 (A.14) 72 79 (A.15) 69 72 (A.16) 69 69 (A.17) 63 68

VI. Wash Performance of Inventive Polymers (A.13) to (A.17)

Anti-Greying Performance

Test 1 Yellow Clay Asian Conditions

[0298] A laundering process was simulated in lab using a Terg-o-meter (RHLG-IV, from Shanghai Bank Equipment Co. Ltd, China), which includes 12 barrels with respective rotor blades as washing units, generally following GBT 13174-2008. The washing units were operated at the same stirring speed of 120 rotation per minute (rpm) and each contained 1 L washing liquor. White test fabrics were washed in the same barrel together with together with 10 g yellow clay and oil mixtures at 30 C., in a wash liquor comprising a detergent formulation as shown in Table xx. After the washing, the fabrics were removed from the washing units, drained and rinsed twice in 10 L tap water for 30 seconds and dried in air. The details of the wash cycles are summarized in Table xx.

[0299] The anti-greying performance was characterized by Remission R value of the soiled fabric after wash and determined by measuring the fabric with the spectrophotometer Elrepho 2000 from Datacolor at 457 nm. The higher the Remission R value, the better is the performance. Results were summarized in Table xx.

TABLE-US-00011 TABLE 11 Ingredients for liquid detergent formulation. Detergent Formulation CN, L.3 Amount, Ingredient wt % Linear alkylbenzene sulfonate (C.sub.10-C.sub.13), Na salt 4.0 Lauryl ether sulphate (C.1), 2 EO 8.0 C13/C15-oxoalkohol reacted with 7 mol of ethylene oxide 4.0 Potassium cocoate 1.0 Sodium citrate 1.5 1,2 propylene glycol 0.5 Sodium sulfate 0.1 Sodium chloride 0.6 Additive as shown in Table 2 1.0 Water up to 100 Adjust pH to 8

TABLE-US-00012 TABLE 12 Details of laundering experiments Equipment Terg-O-meter Detergent dosage 2 g/L Detergent Formulation as shown in Table xx Water hardness 2.5 mmol/L Ca:Mg 3:2 Washing temperature 30 C. Wash cycles 3 (30 min) Wash liquor 1000 ml White test fabric Cotton: WFK 10A, WFK 80A, WFK 12A; PES/ (3 pieces for each, Cotton blend: WFK 20A; Polyester: WFK 30A each 6 6 cm) Test soil 10 g/L yellow clay and oil mixtures (WFK soil oily mixture) Rinsing conditions Tap water directly, max water level (10 L) Drying sonditions Naturally

TABLE-US-00013 TABLE 13 Laundering results Additive R, Sum of all fabrics Blank 344.20 PA25 357.98 HP20 355.92 Maltodextrin-g-PAA Graft Bio Bverde 790 354.69 (A.8) 350.20 (A.13) 352.51 (A.14) 354.33 (A.15) 354.32 (A.16) 361.42 (A.17) 350.40
Compatibility with Liquid Laundry Detergent Formulations

TABLE-US-00014 TABLE 14 Ingredients for liquid detergent formulations L.1, L.2, L.3, L.4, Ingredient wt % wt % wt % wt % Linear alkylbenzene 15.1 5.5 4.0 5.0 sulfonate (C.sub.10-C.sub.13), Na salt Lauryl ether sulphate 23.8 5.5 8.0 19.6 (C.1), 2 EO C13/C15-oxoalkohol reacted 1.6 5.5 4.0 6.7 with 7 mol of ethylene oxide Potassium cocoate 2.4 1.0 2.7 KOH 1.6 Sodium citrate 2.5 1.5 4.1 1,2 propylene glycol 6.0 0.5 2.7 Glycerol 0.4 Sodium sulfate 0.3 0.1 Sodium chloride 0.1 0.6 Ethanol 4.0 2.0 0.8 Additive As shown in Table 15 Water up to 100 Adjust pH to 8

TABLE-US-00015 TABLE 15 Compatibility of additives in liquid detergent formulations Formulation L.1 L.2 L.3 L.4 Additive 5.4% wt. 1% wt. 1% wt. 1% wt. 3% wt. (A.1) n.a. (A.2) n.a. (A.3) n.a. (A.4) n.a. n.a. (A.5) n.a. n.a. (A.6) n.a. (A.7) n.a. n.a. (A.8) n.a. n.a. x (A.13) n.a. n.a. x (A.16) n.a. n.a. : Transparent, : Turbid, x: Phase-separate