PROCESS FOR CLEANING SOILED METAL SURFACES AND SUBSTANCES USEFUL FOR SUCH PROCESS

Abstract

Process for cleaning soiled metal surfaces characterized in such cleaning is carried out using a composition that comprises at least one alkoxylated polyethylenimine (B) with a polydispersity Q=M.sub.w/M.sub.n of at least 3.5 and an average molecular weight M.sub.w in the range of from 2,500 to 1,500,000 g/mol.

Claims

1. A process for cleaning soiled metal surfaces, the process comprising: cleaning the soiled metal surfaces using a composition that comprises at least one alkoxylated polyethylenimine (B) with a polydispersity Q=M.sub.w/M.sub.n in the range from 3.5 to 10 and an average molecular weight M.sub.w in the range of from 2,500 to 1,500,000 g/mol.

2. The process according to claim 1 wherein such metal surface is soiled with at least one pigment selected from silica, alumina, iron oxide, and soot.

3. The process according to claim 1 wherein such process is being carried out at a temperature in the range from ambient temperature up to 70? C.

4. (canceled)

5. The process according to claim 1 wherein the soil is derived from nature-based pigments.

6. An alkoxylated polyethylenimine (B) with a polydispersity Q=M.sub.w/M.sub.n in the range from 3.5 to 10 and an average molecular weight M.sub.w in the range from 2,500 to 1,500,000 g/mol.

7. (canceled)

8. The alkoxylated polyethylenimine (B) according to claim 6 wherein the molecular weight distribution of said alkoxylated polyethylenimine (B) is bimodal or multimodal.

9. The alkoxylated polyethylenimine (B) according to claim 6 wherein said alkoxylated polyethylenimine (B) has a backbone from a polyethylenimine with a polydispersity Q=M.sub.w/M.sub.n in the range from 3.5 to 10 and an average molecular weight M.sub.w in the range from 2,000 to 1,000,000 g/mol and being alkoxylated with one or more C.sub.2-C.sub.4-alkylene oxides.

10. The alkoxylated polyethylenimine (B) according to claim 6 having an amine value in the range from 10 to 25 mmol/g, determined according to ASTM D2074-07 and refer-ring to primary amines.

11. The alkoxylated polyethylenimine (B) according to claim 6, wherein said alkoxylated polyethylenimine (B) is alkoxylated with ethylene oxide and one or more C.sub.3-C.sub.4-alkylene oxides, and wherein the alkylene oxides are arranged block-wise.

12. A process for making an alkoxylated polyethylenimine (B) according to claim 6 comprising the steps of: (a) making a polyethylenimine (A) semi-discontinuously in one reactor; and (b) reacting polyethylenimine (A) with at least one C.sub.2-C.sub.4-alkylene oxide in the presence of a base.

13. The process according to claim 12, wherein step (a) is being performed by performing the following steps: (a1) charging a reactor with water, an amine or diamine, and an initiator selected from CO.sub.2, Br?nsted acids, and alkyl halides; (a2) adding ethylenimine and at least one substituted aziridine under polymerization conditions but without further addition of initiator, amine, and water; (a3) stopping the addition of ethylenimine and at least one substituted aziridine at a conversion of at least 99% or after 5 to 30 hours; and (a4) maintaining the reaction mixture at reaction conditions for at least 120 minutes.

14. An aqueous composition comprising: (i) at least one alkoxylated polyethylenimine (B) according to claim 6, and at least one further ingredient selected from (ii) at least one cationic surfactant; (iii) at least one non-ionic surfactant selected from polyalkoxylated C.sub.1-C.sub.4-alkanols, polyalkoxylated fatty alkohols, and polyalkoxylated phenols; and (iv) at least one non-ionic surfactant.

15. (canceled)

16. (canceled)

Description

WORKING EXAMPLES

[0179] General remarks:

[0180] Percentages refer to % by unless specifically defined otherwise.

I. Manufacture of Polyethylenimines (A)

I.1 Synthesis by Polymerization

[0181] General remarks: the syntheses were performed in a continuously operated tubular reactor, length 18 m, inner diameter 3.5 mm. Said tubular reactor had two reaction zones. In the first reaction zone the temperature was kept at 125 to 130? C., in the second at 150? C. The first reaction zone was in the first 12 m, the second reaction zone in the remaining 6 m of the tubular reactor. The pressure was kept at 0.5 bar above the pressure necessary to keep the reaction mixture liquid, which requires a minimum of 1.5 bar.

[0182] Step (a1) was performed in a so-called mixing chamber, in which water, ethylenimine, aqueous CO.sub.2 solution, and ethylendiamine were mixed through three static mixers. The mixture so obtained was then transferred into the tubular reactor.

[0183] The following starting materials were used:

Aziridine, provided as 25 wt-% aqueous solution
CO.sub.2 as 2.5 wt % aqueous solution
1,2-ethylendiamine

I.1.1 Synthesis of Polyethylenimine (A.1)

[0184] A premix was provided from CO.sub.2 as 2.5 wt % aqueous solution and 1,2-ethylendiamine.

[0185] The tubular reactor described above was fed with a 360 g/h 25 wt-% aqueous solution of aziridine and the above premix in a way that a feed resulted in the addition of 17 g/h 2.5 wt % aqueous solution of CO.sub.2 and 6.2 g/h 1,2-ethylendiamine were introduced into the tubular reactor. The feed had a temperature of 5? C. at the time of mixing. Through exothermic primary polymerization the temperature rose to 80 to 160? C. when entering the first reaction zone. At the end of the tubular reactor, the pressure was adjusted to 5 bar. The conversion of aziridine in the tubular reactor was 99 mol-%.

[0186] After having passed the tubular reactor, the reaction mixture was transferred into a semi-continuously operated tank reactor operated at 160? C. There, the polymerization was completed, step (a3). The average residence time was 2.5 hours in the stirred tank reactor hours. When the tank reactor was full the reaction was stopped by cooling to ambient temperature and pressure release. The water was removed, and polyethylenimine (A.1) was obtained.

I.1.2 Synthesis of Polyethylenimine (A.2)

[0187] A premix was provided from CO.sub.2 as 2.5 wt % aqueous solution and 1,2-ethylendiamine. The tubular reactor described above was fed with a 310 g/h 25 wt-% aqueous solution of aziridine and the above premix in a way that a feed resulted in the addition of 4 g/h 2.5 wt % aqueous solution of CO.sub.2 and 3.0 g/h 1,2-ethylendiamine were introduced into the tubular reactor. The feed had a temperature of 5? C. at the time of mixing. Through exothermic primary polymerization the temperature rose to 80 to 160? C. when entering the first reaction zone. At the end of the tubular reactor, the pressure was adjusted to 5 bar. The conversion of aziridine in the tubular reactor was 99 mol-%.

[0188] After having passed the tubular reactor, the reaction mixture was transferred into a semi-continuously operated tank reactor operated at 160? C. There, the polymerization was completed, step (a3). The average residence time was 4 hours in the stirred tank reactor hours. When the tank reactor was full the reaction was stopped by cooling to ambient temperature and pressure release. The water was removed, and polyethylenimine (A.2) was obtained.

I.1.3 Synthesis of Polyethylenimine (A.3)

[0189] A premix was provided from CO.sub.2 as 2.5 wt % aqueous solution and 1,2-ethylendiamine. The tubular reactor described above was fed with a 285 g/h 25 wt-% aqueous solution of aziridine and the above premix in a way that a feed resulted in the addition of 2.8 g/h 2.5 wt % aqueous solution of CO.sub.2 and 2.1 g/h 1,2-ethylendiamine were introduced into the tubular reactor. The feed had a temperature of 5? C. at the time of mixing. Through exothermic primary polymerization the temperature rose to 80 to 152? C. when entering the first reaction zone. At the end of the tubular reactor, the pressure was adjusted to 5 bar. The conversion of aziridine in the tubular reactor was 99 mol-%.

[0190] After having passed the tubular reactor, the reaction mixture was transferred into a semi-continuously operated tank reactor operated at 150? C. There, the polymerization was completed, step (a3). The average residence time was 4 hours in the stirred tank reactor hours. When the tank reactor was full the reaction was stopped by cooling to ambient temperature and pressure release. The water was removed, and polyethylenimine (A.3) was obtained.

I.2 Manufacture by Mixing of Two or More Polyethylenimines with a Molecular Weight Distribution Q in the Range of from 1.3 to 3.0

I.2.1 Manufacture of Polyethylenimine (A.7)

[0191] In a 1-litre glass flask, 250 g polyethylenimine (A.1) were mixed with 350 g polyethylenimine C-(A.4) at 80? C. with a propeller stirrer at 1200 rpm for 20 minutes. Polyethylenimine (A.7) was obtained.

I.2.2 Manufacture of Polyethylenimine (A.8)

[0192] In a 1-litre glass flask, 250 g polyethylenimine (A.2) were mixed with 350 g polyethylenimine C-(A.4) at 80? C. with a propeller stirrer at 1200 rpm for 20 minutes. Polyethylenimine (A.8) was obtained.

I.2.3 Manufacture of Polyethylenimine (A.9)

[0193] In a 1-litre glass flask, 400 g polyethylenimine (A.6) were mixed with 280 g polyethylenimine C-(A.4) at 80? C. with a propeller stirrer at 1200 rpm for 20 minutes. Polyethylenimine (A.9) was obtained.

[0194] The polyethylenimines (A) provided are summarized in Table 1.

TABLE-US-00001 TABLE 1 Polyethylenimines and their properties M.sub.w [g/mol] M.sub.n [g/mol] M.sub.w/M.sub.n (A.1) 28,000 6,800 4.1 (A.2) 57,050 12,470 4.6 (A.3) 68,400 13,230 5.2 C-(A.4) 880 620 1.42 C-(A.5) 26,400 13,850 1.9 C-(A.6) 42,040 18,560 2.3 (A.7) 9,770 1,470 6.6 (A.8) 21,480 3,060 7.0 (A.9) 32,400 6,880 4.7

[0195] All molecular weights were determined by GPC with 1.5% by weight aqueous formic acid as eluent and cross-linked poly-hydroxyethylmethacrylate as stationary phase. Internal standard was a 0.05% by weight solution of tert.-butanol in 1.5% by weight aqueous formic acid. The column was calibrated with the aide of pullulan (?-1,4-; ?-1,6-glucan) samples with known molecular weight.

II. Syntheses of Inventive Alkoxylated Polyethylenimines (B)

II.1 Synthesis

II.1.1 Synthesis of Inventive Alkoxylated Polyethylenimine (B1.1.1)

[0196] A 2-I autoclave was charged with 645 g of polyethylenimine (A.1) and 32 g of water and then purged with nitrogen. Then, the autoclave was heated to 90? C. An amount of 555 g of ethylene oxide was added within 10 hours under stirring and allowed to react for additional 12 hours at 90? C. The mixture so obtained was cooled to 80? C., and the volatile ingredients were removed in vacuo. An amount of 1,245 g of a highly viscous yellow liquid was obtained.

[0197] A 2-I autoclave was charged with 330 g of the above highly viscous yellow liquid and 5.6 g of a 50% by weight aqueous KOH solution. The water was removed at 20 mbar. Then, the autoclave was purged with nitrogen and subsequently heated to 120? C. Within 12 hours, 1,000 g of ethylene oxide were added under stirring and allowed to react for additional 12 hours at 120? C. The mixture so obtained was cooled to 80? C., and the volatile ingredients were removed in vacuo. An amount of 1,331 g of a light brown solid was obtained that was inventive alkoxylated polyethylenimine (B1.1.1).

II.1.2 Synthesis of Inventive Alkoxylated Polyethylenimine (B1.1.2)

[0198] A 2-I autoclave was charged with 645 g of polyethylenimine (A.1) and 32 g of water and then purged with nitrogen. Then, the autoclave was heated to 90? C. An amount of 555 g of ethylene oxide was added within 10 hours under stirring and allowed to react for additional 12 hours at 90? C. The mixture so obtained was cooled to 80? C., and the volatile ingredients were removed in vacuo. An amount of 1,245 g of a highly viscous yellow liquid was obtained.

[0199] A 2-I autoclave was charged with 82.6 g of the above highly viscous yellow liquid and 5.5 g of a 50% by weight aqueous KOH solution. The water was removed at 20 mbar. Then, the autoclave was purged with nitrogen and subsequently heated to 120? C. Within 12 hours, 1,195 g of ethylene oxide were added under stirring and allowed to react for additional 12 hours at 120? C. The mixture so obtained was cooled to 80? C., and the volatile ingredients were removed in vacuo. An amount of 1,273 g of a light brown solid was obtained that was inventive alkoxylated polyethylenimine (B1.1.2).

II.1.3 Synthesis of Inventive Alkoxylated Polyethylenimine (B1.1.3)

[0200] A 2-1 autoclave was charged with 645 g of polyethylenimine (A.1) and 32 g of water and then purged with nitrogen. Then, the autoclave was heated to 90? C. An amount of 730 g of propylene oxide was added within 10 hours under stirring and allowed to react for additional 12 hours at 90? C. The mixture so obtained was cooled to 80? C., and the volatile ingredients were removed in vacuo. An amount of 1,356 g of a highly viscous yellow liquid was obtained.

[0201] A 2-I autoclave was charged with 155 g of the above highly viscous yellow liquid and 5.5 g of a 50% by weight aqueous KOH solution. The water was removed at 20 mbar. Then, the autoclave was purged with nitrogen and subsequently heated to 130? C. Within 12 hours, 1,126 g of propylene oxide were added under stirring and allowed to react for additional 12 hours at 130? C. The mixture so obtained was cooled to 80? C., and the volatile ingredients were removed in vacuo. An amount of 1,282 g of a light brown solid was obtained that was inventive alkoxylated polyethylenimine (B1.1.3).

II.1.4 Synthesis of Inventive Alkoxylated Polyethylenimine (B1.1.4)

[0202] A 2-I autoclave was charged with 645 g of polyethylenimine (A.1) and 32 g of water and then purged with nitrogen. Then, the autoclave was heated to 90? C. An amount of 555 g of ethylene oxide was added within 10 hours under stirring and allowed to react for additional 12 hours at 90? C. The mixture so obtained was cooled to 80? C., and the volatile ingredients were removed in vacuo. An amount of 1,245 g of a highly viscous yellow liquid was obtained.

[0203] A 2-I autoclave was charged with 124 g of the above highly viscous yellow liquid and 5.3 g of a 50% by weight aqueous KOH solution. The water was removed at 20 mbar. Then, the autoclave was purged with nitrogen and subsequently heated to 120? C. Within 12 hours, 560 g of ethylene oxide were added under stirring and allowed to react for additional 12 hours at 120? C. Then, 569 g of propylene oxide were added under stirring within 12 hours and allowed to react for additional 12 hours at 120? C. The mixture so obtained was cooled to 80? C., and the volatile ingredients were removed in vacuo. An amount of 1,295 g of a light brown solid was obtained that was inventive alkoxylated polyethylenimine (B1.1.4).

II.1.5 Synthesis of Inventive Alkoxylated Polyethylenimine (B1.1.5)

[0204] A 2-1 autoclave was charged with 645 g of polyethylenimine (A.1) and 32 g of water and then purged with nitrogen. Then, the autoclave was heated to 90? C. An amount of 555 g of ethylene oxide was added within 10 hours under stirring and allowed to react for additional 12 hours at 90? C. The mixture so obtained was cooled to 80? C., and the volatile ingredients were removed in vacuo. An amount of 1,245 g of a highly viscous yellow liquid was obtained.

[0205] A 2-I autoclave was charged with 66 g of the above highly viscous yellow liquid and 5.3 g of a 50% by weight aqueous KOH solution. The water was removed at 20 mbar. Then, the autoclave was purged with nitrogen and subsequently heated to 120? C. Within 12 hours, 759 g of ethylene oxide were added under stirring and allowed to react for additional 12 hours at 120? C. Then, 692 g of propylene oxide were added under stirring within 12 hours and allowed to react for additional 12 hours at 120? C. The mixture so obtained was cooled to 80? C., and the volatile ingredients were removed in vacuo. An amount of 1,295 g of a light brown solid was obtained that was inventive alkoxylated polyethylenimine (B1.1.5).

[0206] Further inventive alkoxylated polyethylenimines were synthesized accordingly. The properties are summarized in Table 2.

TABLE-US-00002 TABLE 2 Properties of inventive alkoxylated polyethylenimines (B) molar ratio Starting amine value (A) (B) alkylene Sample material [mmol/g] M.sub.w/M.sub.n AO 1 AO 2 M.sub.w/M.sub.n oxide/NH (B.1.1) (A.1) 19.1 4.1 EO 3.9 7 (B.1.2) (A.1) 19.1 4.1 EO 3.7 20 (B.1.3) (A.1) 19.1 4.1 PO 4.0 12 (B.1.4) (A.1) 19.1 4.1 EO PO 3.9 10/7 (B.1.5) (A.1) 19.1 4.1 EO PO 4.3 24/16 (B.2.1) (A.2) 18.7 4.6 EO 4.5 7 (B.2.2) (A.2) 18.7 4.6 EO 4.2 20 (B.2.3) (A.2) 18.7 4.6 PO 4.1 12 (B.3.1) (A.3) 18.5 5.2 EO 4.7 7 (B.3.2) (A.3) 18.5 5.2 EO 5.0 20 (B.3.3) (A.3) 18.5 5.2 EO PO 5.0 10/7 (B.3.4) (A.3) 18.5 5.2 EO PO 5.5 24/16 C-(B.4.1) C-(A.4) 20.5 1.4 EO 1.4 7 C-(B.4.2) C-(A.4) 20.5 1.4 EO 1.3 20 C-(B.4.3) C-(A.4) 20.5 1.4 PO 1.4 12 C-(B.4.4) C-(A.4) 20.5 1.4 EO PO 1.5 10/7 C-(B.4.5) C-(A.4) 20.5 1.4 EO PO 1.7 24/16 C-(B.5.1) C-(A.5) 19.3 1.9 EO 1.9 7 C-(B.5.2) C-(A.5) 19.3 1.9 EO 2.0 20 C-(B.5.3) C-(A.5) 19.3 1.9 PO 2.2 12 C-(B.6.1) C-(A.6) 19.0 2.3 EO 2.4 20 C-(B.6.2) C-(A.6) 19.0 2.3 EO PO 2.6 24/16 (B.7.1) (A.7) 19.6 6.6 EO 5.3 7 (B.7.2) (A.7) 19.6 6.6 EO 5.0 20 (B.7.3) (A.7) 19.6 6.6 EO PO 5.7 10/7 (B.7.4) (A.7) 19.6 6.6 EO PO 5.9 24/16 (B.8.1) (A.8) 19.4 7.0 EO 6.0 20 (B.8.2) (A.8) 19.4 7.0 EO PO 6.4 10/7 (B.8.3) (A.8) 19.4 7.0 EO PO 6.7 24/16 (B.8.4) (A.8) 19.4 7.0 EO 6.0 7 (B.8.5) (A.8) 19.4 7.0 PO 6.2 12 (B.9.1) (A.9) 19.5 4.7 EO 4.3 7 (B.9.2) (A.9) 19.5 4.7 EO 4.2 20 (B.9.3) (A.9) 19.5 4.7 PO 4.5 12 C-(B.6.3) C-(A.6) 19.1 2.3 PO 2.4 24 (B.3.5) (A.3) 18.5 5.2 PO 4.9 24
Explanations with respect to Table 2:
AO: alkylene oxide
Alkoxylated polyethylenimines C-(B.4.1), C-(B.4.2) and so forth are comparison materials. The amine value is the primary amine value und refers to the respective polyethylenimine (A).

III. Tests as Demulgators

[0207] In a 2-liter vessel, 35 ppm (mass) of inventive polyalkoxylated polyethylenimine (B) according to table 3 were dissolved in the 10-fold amount of toluene and then mixed with 1 liter of crude oil/water emulsion (oil in water) under vigorous stirring, conditions: anchor stirrer, 1200 rpm, for 5 minutes at 40? C. The crude oil/water emulsion stemmed from North Africa (samples II, III) or Western Africa (sample (I), see Table 3. Then, three 100 ml-aliquots of the respective emulsion were transferred into 3 graduated cylinders and allowed to settle. The kinetics were determined by measuring the volume of the aqueous phase after 3, 5, 8, 15 und 30 minutes. The results are summarized in Table 3. As further comparsons, the tests were repeated without the addition of any alkoxylated polyethylenimines (B).

TABLE-US-00003 TABLE 3 kinetics of crude oil/water emulsion (oil in water) separation crude oil/water 3 min 5 min 8 min 15 min 30 min (B) emulsion [ml] [ml] [ml] [ml] [ml] I 2 2 4 C-(B.6.2) I 4 10 15 25 (B.1.5) I 2 6 12.5 17 30 (B.3.4) I 2 6 14 20 35 (B.8.3) I 4 8 18 25 40 C-(B.6.3) I 2 5 10 17 27.5 (B.3.5) I 5 10 15 25 38 II 4 6 10 17 C-(B.6.2) II 2 6 10 20 35 (B.1.5) II 2 8 15 25 40 (B.3.4) II 2 10 20 30 45 (B.8.3) II 4 15 25 40 47 C-(B.6.3) II 2 5 13 20 33 (B.3.5) II 5 8 17.5 25 40 III 4 9 14 C-(B.6.2) III 2 4 8 18 28 (B.1.5) III 3 7.5 14 21 32 (B.3.4) III 3 8 16 25 36 (B.8.3) III 4 8.5 21 30 44 C-(B.6.3) III 2 6.5 13 21 27.5 (B.3.5) III 5 10 15 25 38

IV. Test in Laundry Detergent Compositions

[0208] The anti-greying abilities of alkoxylated polyethylenimines (B) were tested by preparing wash solutions using water of 14? dH hardness (2.5 mmol/L; Ca:Mg:HCO.sub.3 4:1:8) containing 5 g/L of the test detergent T (see Table 5) and 1.0-2.5% of the alkoxylated polyethylenimines (B) (see Table 1)

TABLE-US-00004 TABLE 5 Composition of Test Detergent T Liquid laundry base formulation n-C.sub.10-C.sub.13-Alkylbenzene sulfonic acid 5.7% C.sub.13/.sub.15-Oxoalkohol ethoxylated with 7 moles of ethylene 5.4% 1,2-propylenglycol .sup.6% ethanol .sup.2% Potassium coconut soap 2.4% KOH 3.1% Lauryl ether sulphate 7.7% Polyalkylenalkoxylate according to Table 6 1 or 2%.sup. Water to 100%

[0209] As test fabrics 10 cm?10 cm squares of different cotton were selected (wfk10A as standard cotton, wfK12A as cotton terry cloth, wfk80A as cotton knit, EMPA 221 as cotton fabric, cretonne, bleached without optical brightener, T-shirt from Brantic, Kapart brand) and synthetic fabrics (wfk20A, wfk30A, EMPA406). The test was performed in a launder-O-meter (LP2 type from SDL Atlas, Inc.) with beakers of 1 L size. Soil was a mixture of two 2.5 g EMPA 101 (olive oil/carbon black on cotton, purchased at EMPA Testmaterials, St Gallen, Switzerland) and of two 2,5 g SBL 2004 fabrics (soil ballast fabric Formula 2004 that simulates sebum grease stains, purchased from wfk Testgewebe GmbH, Br?ggen, Germany). As an additional ballast soil 300 mg of a pigment-oil paste were added to the washing liquor (see below, Table 6).

[0210] The first cycle was run using the launder-O-meter beakers containing the test wash solution (0.25 L) plus test fabrics and ballast soil, at 40? C. for 20 min (fabric to liquor ratio of 1:10). After the wash, the test fabrics and ballast soil were separated. The process was repeated using the washed test fabrics and effectuating 3 cycles in total. New ballast soil was used for each cycle. After the 3 cycles, the test fabrics were rinsed in water, followed by drying at ambient room temperature overnight.

[0211] The greying of the cotton and synthetic test fabrics was measured by determining the degree of whiteness (reflectance values) after washing using a sphere reflectance spectrometer (SF 500 type from Datacolor, USA, wavelength range 360-700 nm, optical geometry d/8?) with a UV cutoff filter at 460 nm.

[0212] The anti-greying properties of the detergents tested were then quantified after addition of 1.0 to 2% of the respective alkoxylated polyethylenimines (B) (see Table 6). Reflectance values decrease with the visible greying of the fabrics, the higher the reflectance value, the better the anti-greying performance of the detergent. For simplicity, cotton delta reflectance values (?R) are represented in Table 3. Cotton ?R values represent the difference between the reflectance after wash of the test detergent T containing the corresponding alkoxylated polyethylenimines (B) (R1) and the reflectance after wash of the test detergent without the alkoxylated polyethylenimines (B) for the summation of the 5 different cotton fabrics. An ?R value>10 means a clearly visible contribution and effect of the inventive substances and a ?R value>5 is already significant above the standard deviation. Correspondingly a broad molecular weight contribution shows improved and very stable effects in the avoidance of greying and deposition of dirt of a huge variety.

[0213] As shown in Table 3, inventive alkoxylated polyethylenimines (B) (1 to 8) have a positive effect on the secondary-washing action, preventing the re-deposition of the soil removed from the wash liquor to the fabrics.

[0214] In summary, alkoxylated polyethylenimines (B) according to the present invention outperform comparative alkoxylated polyethylenimines with a narrow molecular weight distribution. Without wishing to be bound by any bound to any theory, this can be explained with a superior dispersion profile that has to match a huge variety of dust/clay and soils that a detergent formulation has to cope with.

Selections of Clay/Soil Pigments:

[0215] For test purposes, each 23% by weight of 4 different nature-based clay samples (crude kaolin) as well as 3% bauxite from Jamaica and 3% ash from a tennis court were milled in a ball mill for a period of 30 minutes. Then, olive oil was added in a ratio of ? by weight. A paste was obtained.

[0216] The clays had been selected as follows:

a) Kaolin/(Tonerde) from Germany, Kaolin Mine Hirschau-Schnaittenbach,
b) Kaolin from the USA (CE Minerals Inc, Georgia),
c) Kaolin from the USA (English Indian Clays Ltd, Kerala),
d) Kaolin from Brasil (Fa. Omnia, MIRAGLOSS 90 DRY).

[0217] Then, the test detergents according to Table 5 were tested on said soiled cottons, vide supra. The cleaning efficacy was determined photometrically by determination of the reflectance. The results are summarized in Table 6.

TABLE-US-00005 TABLE 6 test results on inventive laundry detergent compositions and comparative laundry detergents Cotton, Delta Cotton, Delta Reflectance (%) Reflectance (%), Entry (B) (Table 2) 1.0% by weight (B) 2% by weight (B) C-IV-1 C-(B.4.2) 8 13 C-IV-2 C-(B.5.1) 10 13 C-IV-3 C-(B.5.2) 7 12 C-IV-4 C-(B.5.3) 5 9 C-IV-5 C-(B.6.1) 9 12 C-IV-6 C-(B.6.2) 12 16 IV-7 (B.2.1) 14 19 IV-8 (B.2.2) 17 23 IV-9 (B.2.3) 13 17 IV-10 (B.3.1) 17 22 IV-11 (B.3.2) 17 25 IV-12 (B.3.3) 19 27 IV-13 (B.3.4) 19 29 IV-14 (B.8.1) 22 31 IV-15 (B.8.2) 25 30 IV-16 (B.8.3) 24 31 IV-17 (B.8.4) 22 29 IV-18 (B.8.5) 18 25

[0218] The pH value of the liquid test detergents formulations was approx. 8.5.

[0219] Delta Reflectance cotton is represented as the average of a 2 times replication.