PHOSPHATE-FREE DETERGENT COMPOSITIONS AND THEIR APPLICATIONS

Abstract

Provided herein is a phosphate-free detergent composition including at least one additive with a melting point in the range of from 40 to 60 C. and at least one amide group in the range of from 5 to 150 alkylene oxide groups per molecule.

Claims

1. Phosphate-free detergent composition comprising: (A) at least one additive according to general formula (I)
R.sup.1CONHCH.sub.2CH.sub.2O(AO).sub.xCH.sub.2CH.sub.2NHCOR.sup.2 (I) wherein R.sup.1, R.sup.2 are the same or different and selected from C.sub.5-C.sub.21-alkyl and C.sub.6-C.sub.20-alkenyl, x is in the range of from 5 to 150, and AO is selected from identical or different alkylene oxides, selected from CH.sub.2CH.sub.2O, (CH.sub.2).sub.3O, (CH.sub.2).sub.4O, CH.sub.2CH(CH.sub.3)O, CH(CH.sub.3)CH.sub.2O, and CH.sub.2CH(n-C.sub.3H.sub.7)O, wherein said additive (A) has a melting point in the range of from 40 to 60 C.

2. Detergent composition according to claim 1 wherein all AO in formula (I) are identical and CH.sub.2CH.sub.2O.

3. Detergent composition according to claim 1, wherein, in said additive (A) according to general formula R.sup.1 and R.sup.2 are identical and selected from n-C.sub.6-C.sub.18-alkyl.

4. Detergent composition according to claim 1, wherein said detergent composition further comprises: (B) a chelating agent selected from citric acid and aminocarboxylic acid diacetates and aminosuccinates and their respective alkali metal salts.

5. Detergent composition according to claim 4 wherein chelating agent (B) is selected from alkali metal salts of iminodisuccinic acid (IDS), methylglycine diacetic acid (MGDA), and glutamic acid diacetic acid (GLDA).

6. Detergent composition according to claim 4, wherein said detergent composition comprises: in the range of from 0.5 to 10% by weight of additive (A), and in the range of from 1 to 50% by weight chelating agent (B), the percentages referring to the total solids content of the detergent composition.

7. Detergent composition according to claim 1 wherein said additive (A) is used in combination with at least one non-ionic surfactant according to formula (V) ##STR00006## or (V a)
R.sup.8CH(OH)CH.sub.2O(AO).sub.rA.sup.1O(AO).sub.rCH.sub.2H(OH)R.sup.8 (V a) wherein R.sup.5 is identical or different and selected from hydrogen and linear C.sub.1-C.sub.10-alkyl, R.sup.7 is selected from C.sub.8-C.sub.22-alkyl, branched or linear, R.sup.8 is selected from C.sub.1-C.sub.18-alkyl, m and n are in the range from zero to 300, where the sum of n and m is at least one, r is the same or different and selected from 6 to 50 A.sup.1 is selected from C.sub.2-C.sub.10-alkylene, straight, chain, or branched, and AO is alkylene oxide selected from CH.sub.2CH.sub.2O, (CH.sub.2).sub.3O, (CH.sub.2).sub.4O, CH.sub.2CH(CH.sub.3)O, CH(CH.sub.3)CH.sub.2O, and CH.sub.2CH(n-C.sub.3H.sub.7)O.

8. Method of making a detergent composition according to claim 4, the method comprising mixing (A) at least one additive according to general formula (I) with a melting point in the range of from 40 to 60 C., and (B) at least one chelating agent selected from citric acid and aminocarboxylic and their respective alkali metal salts in the presence or absence of water and removing said water if in the presence of water.

9. Method according to claim 8, wherein the mixing of additive (A) and chelating agent (B) and, optionally, one or more additional substances, takes place in the presence of water followed by removal of 80 to 100% by weight of said water by spray granulating or spray drying.

10. Phosphate-free granule containing: (A) at least one additive according to general formula (I)
CONHCH.sub.2CH.sub.2O(AO).sub.xCH.sub.2CH.sub.2NHCOR.sup.2 (I) wherein R.sup.1, R.sup.2 are the same or different and selected from C.sub.5-C.sub.21-alkyl and C.sub.6-C.sub.20-alkenyl, x is in the range of from 5 to 150, and AO is selected from identical or different alkylene oxides, selected from CH.sub.2CH.sub.2O, (CH.sub.2).sub.3O, (CH.sub.2).sub.4O, CH.sub.2CH(CH.sub.3)O, CH(CH.sub.3)CH.sub.2O, and CH.sub.2CH(n-C.sub.3H.sub.7)O, wherein said additive (A) has a melting point in the range of from 40 to 60 C.

11. Phosphate-free granule according to claim 10, wherein said phosphate-free granule further contains at least one mixing auxiliary selected from silica gel, silicate, and polyethylene glycol.

12. A method of using the phosphate-free granule according to claim 10, the method comprising using the phosphate-free granule in the manufacture of a detergent composition.

13. (canceled)

Description

[0201] The invention is illustrated in more detail by the following working examples.

[0202] General remarks: melting points were determined by DSC with a heat rate of 1 C./min in an open aluminum crucible, peak at second cycle, air flow 3 l/h.

[0203] In the context of the present invention and unless expressly specified otherwise, percentages and ppm refer to % by weight and weight ppm.

[0204] The following substances were used:

[0205] Additive (A.1):

[0206] Complexing agent (B.1): MGDA-Na.sub.3, racemic

[0207] Melting points were determined by dynamic differential calorimetry (DSC), heating rate of 10 K/min 1 K/min; initial weight 6-7 mg; flushing gas 3 I N.sub.2/h, Al measuring crucible, open

[0208] Components used:

[0209] (A.1): n-C.sub.17H.sub.35CONH(EO).sub.22CH.sub.2CH.sub.2NHCO-n-C.sub.17H.sub.35. The value of x=22 refers to the weight average of the underlying polyethylene glycol

[0210] Further non-ionic surfactant: (V.1), n-C.sub.10H.sub.21CH(OH)CH.sub.2O(EO).sub.40-n-C.sub.10H.sub.21

[0211] (B.1): MGDA-Na.sub.3racemic

[0212] Milling auxiliary1: Precipitated silica, average particle diameter d50: 13.5 m (laser diffraction), surface area according to BET: 190 m.sup.2/g, determined by nitrogen adsorption ISO 92777. (c.1) is commercially available as Sipernat 22 S

[0213] Mixing Auxiliary 2: polyethylene glycol, Mw: 6,000 g/mol

[0214] The solid granule was produced in each case as follows:

[0215] The components (A.1) was melted in a beaker at 70 C. and mixed using a propeller stirrer. Then, the melt was poured onto aluminum foil (20 cm10 cm1 cm) and solidified at room temperature. This gave wax-like plates.

[0216] Pastilles were produced from these wax-like plates using a flake roller. The flake roller used had a diameter of 33 cm, a width of 50 cm and was operated at a speed of 1.2 rpm. The coolant temperature (water) was 16 to 22 C. To produce the pastilles, the procedure in detail involved placing the wax-like plates into a heatable dropping funnel 38 cm in width which was provided on the bottom with 36 holes (diameter 1.5 mm). The melting rate of the plate was adjusted via the funnel temperature of 80 to 100 C. in such a way that defined drops were formed on the cooling surface of the roller, said drops solidifying within one revolution and then being stripped off from the roller by means of a non-flexible knife attached thereto.

[0217] The pastilles produced in this way were ground in an impact mill (knife mill). For this, the mill was operated with 2 knives and a peripheral speed of 14 m/s. The grinding sieve used was a round perforated sieve with a hole diameter of 3.2 mm and a free surface area of 40%. The pastilles, the component (B.1) and above milling auxiliary were metered into this mill simultaneously and milled.

[0218] The following granules according to the invention and comparison granules were obtained, see table 2.

TABLE-US-00002 TABLE 2 Granule All amounts in % by weight Gran.1 Gran.2 Gran.3 (A.1) 97 58 92 (V.1) 39 Milling auxiliary 1 3 3 3 Milling auxiliary 2 5

[0219] The granules had a good appearance and were free-flowable even after several weeks.

[0220] The following mixture was made, Table 3 a.

TABLE-US-00003 TABLE 3 a base mixture [g] (B1.1) racemic MGDA-Na.sub.3 10 Protease 2.5 Amylase 1 Na salt of polyacrylic acid, 5 M.sub.w 4,000 g/mol, completely neutralized Sodium percarbonate 10.2 TAED 4 Na.sub.2Si.sub.2O.sub.5 2 Na.sub.2CO.sub.3 24.5 trisodium citrate dihydrate 5 HEDP 0.8

TABLE-US-00004 TABLE 3 b compositions of test formulations All amounts in g/sample TF-1 C-TF.2 C-TF.3 Base mixture, see Table 3 a 17.1 17.1 17.1 (A.1) 0.72 Non-ionic surfactant 1 0.18 0.9 0.18 Non-ionic surfactant 2 0.72 Nonionic surfactant 1: n-C.sub.10H.sub.21CH(OH)CH.sub.2O(EO).sub.40-n-C.sub.10H.sub.21 Nonionic surfactant 2: n-C.sub.8H.sub.17CH(OH)CH.sub.2O(EO).sub.22CH(CH.sub.3)CH.sub.2O-n-C.sub.10H.sub.21

[0221] A base mixture was made by mixing the ingredients according to Table 3 a.

[0222] Portions of 18 g of base mixture were made by combining base mixture according to Table 3 a with the ingredients according to table 3 b. In accordance with Table 3 b, (A.1) and nonionic surfactant 1 were added as solid granular material. If applicable, nonionic surfactant 2 was molten and then added and added under stirring to distribute it in the mixture homogeneously. Test formulation TF-1according to the inventionand comparative test formulations C-TF.2 and C-TF.3 were obtained.

[0223] Rinsing experiments:

[0224] All dish-wash experiments were carried out in Miele automatic dish wash machines, type G1222 SCL. The program 50 C. (R-time 2, for washing) and 65 for rinsing was selected. No separate rinsing agent was added, no regenerating salt was used. The dish-wash experiments were carried out with water, 21 dH (German hardness), Ca/Mg:HCO.sub.3 (3:1):1.35. In each experiment three knives (stainless steel), three blue melamine resin plates, three drinking glasses and three plates from china were placed in the dishwasher. Before each cycle 100 g of soil, comprising fat, protein and starch in the form of margarine, egg-yolk and starch, were added. In each cycle, 18 g of a formulation according to table 2 were added.

[0225] Between two cycles, a waiting period of one hour was observed, of which 10 minutes were with the door of the dishwashing machine closed and 50 minutes with open door. The dishes were checked by visual assessment of the ware after 6 cycles in a darkened chamber under light behind an aperture diaphragm was awarded using a grading scale from 1 (very poor) to 10 (very good). The results are summarized in Table 4.

TABLE-US-00005 TABLE 4 Rinsing Results Spotting, Spotting, Spotting Spotting, Formulation knives glass melamine china TF.1 10 5.0 5.3 4.7 C-TF.2 2.0 1.3 1.0 2.0 C-TF.3 7.3 4.0 5.3 3.3