Alkoxylated Polycarboxylic Acid Esters

Abstract

Alkoxylated polycarboxylic acid esters are provided obtainable by first reacting an aromatic polycarboxylic acid containing at least three carboxylic acid units or anhydrides derived therefrom, preferably an aromatic polycarboxylic acid containing three or four carboxylic acid units or anhydrides derived therefrom, more preferably an aromatic polycarboxylic acid containing three carboxylic acid units or anhydrides derived therefrom, even more preferably trimellitic acid or trimellitic acid anhydride, most preferably trimellitic acid anhydride, with an alcohol alkoxylate and in a second step reacting the resulting product with an alcohol or a mixture of alcohols, preferably with an alcohol.

Claims

1. Alkoxylated polycarboxylic acid esters, obtainable by first reacting an aromatic polycarboxylic acid containing at least three carboxylic acid units or an anhydride derived therefrom, preferably an aromatic polycarboxylic acid containing three or four carboxylic acid units or an anhydride derived therefrom, more preferably an aromatic polycarboxylic acid containing three carboxylic acid units or an anhydride derived therefrom, even more preferably trimellitic acid or trimellitic acid anhydride, most preferably trimellitic acid anhydride, with an alcohol alkoxylate and in a second step reacting the resulting product with an alcohol or a mixture of alcohols, preferably with an alcohol.

2. The alkoxylated polycarboxylic acid esters according to claim 1, characterised in that the alcohol alkoxylate is described by formula (I), ##STR00005## wherein R1 is a substituted or unsubstituted alkyl or alkenyl group having 1 to 20 carbon atoms, an aryl or alkyl aryl group having 6 to 20 carbon atoms, or H, preferably a substituted or unsubstituted alkyl or alkenyl group having 1 to 12 carbon atoms or an aryl or alkyl aryl group having 6 to 13 carbon atoms, more preferably a substituted or unsubstituted alkyl or alkenyl group having 1 to 6 carbon atoms, and most preferably a methyl group, R2 to R5 are independently of each other hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen or methyl, where the substituents R2 to R5 are chosen such that both of either R2 and R3 or R4 and R5 are hydrogen and at least one of the other substituents is different from hydrogen, preferably such that three of the substituents R2 to R5 are hydrogen, and even more preferably such that three of the substituents R2 to R5 are hydrogen and the other substituent is a methyl group, n and m are independently of each other, based on a molar average, numbers of from 0 to 100 such that n+m is of from 4 to 100, preferably of from 8 to 70, more preferably of from 10 to 60 and even more preferably of from 12 to 50, where in the case that R2 and R3 are both hydrogen, n is a number of from 4 to 100 and m is a number of from 0 to 50, preferably n is from 8 to 70 and m is from 0 to 30, more preferably n is from 10 to 60 and m is from 0 to 25 and even more preferably n is from 12 to 50 and m is from 0 to 20 and when m>0, the ratio of n to m is larger than 1, preferably at least 2, more preferably at least 3 and even more preferably at least 4, where in the case that R4 and R5 are both hydrogen, m is a number of from 4 to 100 and n is a number of from 0 to 50, preferably m is from 8 to 70 and n is from 0 to 30, more preferably m is from 10 to 60 and n is from 0 to 25 and even more preferably m is from 12 to 50 and n is from 0 to 20 and when n>0, the ratio of m to n is larger than 1, preferably at least 2, more preferably at least 3 and even more preferably at least 4, where in the case that both n and m are >0, the units are distributed blockwise, alternating, periodically and/or statistically, R6 and R7 are independently of each other hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen or methyl, and at least one of R6 and R7 is methyl, and Y is OH.

3. The alkoxylated polycarboxylic acid esters according to claim 1 or 2, characterised in that the alcohol alkoxylate is an ethoxylated alcohol or an ethoxylated and propoxylated alcohol, wherein the ratio of ethylene oxide units to propylene oxide units is larger than 1, preferably at least 2, more preferably at least 3 and even more preferably at least 4, and is preferably an ethoxylated and propoxylated alcohol.

4. The alkoxylated polycarboxylic acid esters according to one or more of claims 1 to 3, characterised in that the alcohol alkoxylate of formula (I) is a polyethylene glycol monomethyl ether or an alcohol-terminated methyl-ethoxylated-propoxylated polyether with a molecular mass Mn of 252 to 4900, preferably with a molecular mass Mn of 350 to 4000, even more preferably with a molecular mass Mn of 450 to 3000 and particularly preferably with a molecular mass Mn of 500 to 2500 and is preferably a polyethylene glycol monomethyl ether with a molecular mass Mn of 252 to 4400, preferably with a molecular mass Mn of 350 to 4000, even more preferably with a molecular mass Mn of 450 to 3000 and particularly preferably with a molecular mass Mn of 500 to 2500.

5. The alkoxylated polycarboxylic acid esters according to one or more of claims 1 to 4, characterised in that the alcohol or at least one alcohol from the mixture of alcohols used in step 2 of the reaction is an alkyl aryl alcohol having 7 to 13 carbon atoms or a substituted or unsubstituted alkyl or alkenyl alcohol having 2 to 20 carbon atoms, preferably an alkyl aryl alcohol having 7 to 10 carbon atoms, a substituted or unsubstituted alkyl or alkenyl alcohol having 12 to 18 carbon atoms or a substituted alkyl alcohol having 2 to 4 carbon atoms, more preferably an alkyl aryl alcohol having 7 to 10 carbon atoms, an unsubstituted alkyl or alkenyl alcohol having 12 to 18 carbon atoms, which is preferably straight chain, or an alkyl alcohol having 2 or 3 carbon atoms which is substituted with an ether function, most preferably an unsubstituted alkyl alcohol having 12 to 18 carbon atoms, or an alkyl alcohol with 2 carbon atoms which is substituted with a phenoxy or ethoxyphenoxy group, where the phenyl ring in said phenoxy groups may be further substituted.

6. The alkoxylated polycarboxylic acid amides according to one or more of claims 1 to 5, characterised in that the alcohol or at least one alcohol from the mixture of alcohols used in step 2 of the reaction is selected from the group consisting of lauryl alcohol (dodecanol), myristyl alcohol (tetradecanol), a mixture of lauryl alcohol and myristyl alcohol, cetearyl alcohol (a mixture of hexadecanol and octadecanol), stearyl alcohol (octadecanol) and coconut fatty alcohol (a mixture of C.sub.6 to C.sub.18 alcohols), phenoxyethanol, phenethyl alcohol and benzyl alcohol, and is preferably selected from the group consisting of lauryl/myristyl alcohol, cetearyl alcohol and phenoxyethanol, and is more preferably selected from the group consisting of lauryl/myristyl alcohol and cetearyl alcohol.

7. The alkoxylated polycarboxylic acid esters according to formula (II) ##STR00006## wherein R8, R9 and R10 are selected from (a) and (b) such that at least one of R8, R9 and R10 is (b) and at least one of R8, R9 and R10 is (a), preferably R8 is (a) and one or both of R9 and R10 are (b), more preferably R8 is (a) and one of R9 or R10 is (b) and the other is (a), where: (a) is alkylaryloxy having 7 to 13 carbon atoms or substituted or unsubstituted alkoxy or alkenyloxy having 2 to 20 carbon atoms, preferably alkylaryloxy having 7 to 10 carbon atoms, substituted or unsubstituted alkoxy or alkenyloxy having 12 to 18 carbon atoms or substituted alkoxy having 2 to 4 carbon atoms, more preferably alkylaryloxy having 7 to 10 carbon atoms or unsubstituted alkoxy or alkenyloxy having 12 to 18 carbon atoms, which is preferably straight chain, or alkoxy having 2 or 3 carbon atoms which is substituted with an ether group, most preferably an unsubstituted alkyl alcohol having 12 to 18 carbon atoms, or alkoxy with 2 carbon atoms which is substituted with a phenoxy or ethoxyphenoxy group, where the phenyl ring in said phenoxy groups may be further substituted, and (b) is an alcohol alkoxylate group of formula (I), ##STR00007## wherein R1 is a substituted or unsubstituted alkyl or alkenyl group having 1 to 20 carbon atoms, an aryl or alkyl aryl group having 6 to 20 carbon atoms, or H, preferably a substituted or unsubstituted alkyl or alkenyl group having 1 to 12 carbon atoms or an aryl or alkyl aryl group having 6 to 13 carbon atoms, more preferably a substituted or unsubstituted alkyl or alkenyl group having 1 to 6 carbon atoms, and most preferably a methyl group, R2 to R5 are independently of each other hydrogen, or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen or methyl, where the substituents R2 to R5 are chosen such that both of either R2 and R3 or R4 and R5 are hydrogen and at least one of the other substituents is different from hydrogen, preferably such that three of the substituents R2 to R5 are hydrogen, and even more preferably such that three of the substituents R2 to R5 are hydrogen and the other substituent is a methyl group, n and m are independently of each, based on a molar average, numbers of from 0 to 100 such that n+m is a number of from 4 to 100, preferably of from 8 to 70, more preferably of from 10 to 60 and even more preferably of from 12 to 50, where in the case that R2 and R3 are both hydrogen, n is a number of from 4 to 100 and m is a number of from 0 to 50, preferably n is from 8 to 70 and m is from 0 to 30, more preferably n is from 10 to 60 and m is from 0 to 25 and even more preferably n is from 12 to 50 and m is from 0 to 20 and when m>0, the ratio of n to m is larger than 1, preferably at least 2, more preferably at least 3 and even more preferably at least 4, where in the case that R4 and R5 are both hydrogen, m is a number of from 4 to 100 and n is a number of from 0 to 50, preferably m is from 8 to 70 and n is from 0 to 30, more preferably m is from 10 to 60 and n is from 0 to 25 and even more preferably m is from 12 to 50 and n is from 0 to 20 and when n>0, the ratio of m to n is larger than 1, preferably at least 2, more preferably at least 3 and even more preferably at least 4, where in the case that both n and m are >0, the units can be distributed blockwise, alternating, periodically and/or statistically, R6 and R7 are independently of each other hydrogen, or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen or methyl, and at least one of R6 and R7 is methyl, and Y is O, are preferably in the form of mixtures and are preferably obtainable by the reaction steps described in one or more of claims 1 to 6.

8. The alkoxylated polycarboxylic acid esters according to claim 7, where formula (II) is characterised in that R8 is equal to one of R9 or R10 and is an alkylaryloxy having 7 to 13 carbon atoms or a substituted or unsubstituted alkyloxy or alkenyloxy having 2 to 20 carbon atoms, preferably alkylaryloxy having 7 to 10 carbon atoms or substituted or unsubstituted alkyloxy or alkenyloxy having 12 to 18 carbon atoms, more preferably alkylaryloxy having 7 to 10 carbon atoms.

9. The alkoxylated polycarboxylic acid esters according to claim 7 or 8, characterised in that R8 is equal to one of R9 or R10 and is a substituted or unsubstituted ethoxylated aromatic alcohol residue having 8 to 16 carbon atoms, preferably 8 to 12 carbon atoms.

10. The alkoxylated polycarboxylic acid esters according to one or more of claims 7 to 9, where formula (II) is characterised in that (b) is a polyethylene glycol monomethyl ether residue of formula (I) with a molecular mass Mn of 251 to 4400, preferably with a molecular mass Mn of 350 to 4000, even more preferably with a molecular mass Mn of 450 to 3000 and particularly preferably with a molecular mass Mn of 500 to 2500.

11. A process for producing alkoxylated polycarboxylic acid esters according to one or more of claims 1 to 10, comprising the steps of firstly reacting an aromatic polycarboxylic acid containing at least three carboxylic acid units or an anhydride derived therefrom with an alcohol alkoxylate, and secondly reacting the resulting product with an alcohol or a mixture of alcohols, preferably with an alcohol.

12. The process according to claim 11, characterised in that the reaction of step 1 is conducted with 0.7 to 1.5 molar equivalents of the alcohol alkoxylate, preferably 0.8 to 1.4 molar equivalents, more preferably 0.9 to 1.3 molar equivalents and most preferably 1.0 to 1.2 molar equivalents.

13. The process according to claim 11 or 12 characterised in that the reaction of step one is performed at a temperature of 50 to 150 C., preferably at a temperature of 60 to 140 C. even more preferably at a temperature of 70 to 130 C. and most preferably at a temperature of 80 to 120 C.

14. The process according to one or more of claims 11 to 13, characterised in that the reaction of step 2 is conducted with 1.8 to 3.5 molar equivalents of the alcohol or mixture of alcohols, preferably 1.9 to 3.0 molar equivalents and more preferably 2.0 to 2.8 molar equivalents.

Description

EXAMPLES

[0084] The examples below are intended to illustrate the invention in detail without, however, limiting it thereto.

[0085] Trimellitic acid was used as purchased from ACROS Organics. Trimellitic acid anhydride and pyromellitic acid was used as purchased from Alfa Aesar. Phenoxyethanol, para-toluene sulfonic acid and titanium isopropoxide were used as purchased from Merck. Methanesulfonic acid, 4-dodecylbenzenesulfonic acid mixture of isomers and benzyl alcohol were used as purchased from Sigma Aldrich.

[0086] Lauryl/myristyl alcohol and cetearyl alcohol were used in technical grade quality and their molecular masses were determined prior to use by measuring the hydroxyl value (OH-value) and subsequently calculating the molecular mass (per hydroxyl function, Gebrauchsmol). In this case the OH-value may be measured according to DIN 53240.

[0087] The acid number (acid value) may be measured according to DIN EN ISO 2114.

[0088] Polyglykols M are mono hydroxy-functional polyethylene glycol monomethyl ethers (M-PEG, CAS-Nr. 9004-74-4).

[0089] Polyglykol M 500 is a linear, mono hydroxy-functional polyethylene glycol monomethyl ether (M-PEG) that has a molecular mass of 470-530 g/mol.

[0090] Polyglykol M 750 is a linear, mono hydroxy-functional polyethylene glycol monomethyl ether (M-PEG) that has a molecular mass of 720-780 g/mol.

[0091] Polyglykol M 1000 is a linear, mono hydroxy-functional polyethylene glycol monomethyl ether (M-PEG) that has a molecular mass of 970-1060 g/mol.

[0092] Polyglykol M 1250 is a linear, mono hydroxy-functional polyethylene glycol monomethyl ether (M-PEG) that has a molecular mass of 1125-1375 g/mol.

[0093] Polyglykol M 2000 is a linear, mono hydroxy-functional polyethylene glycol monomethyl ether (M-PEG) that has a molecular mass of 1800-2200 g/mol.

[0094] The degree of alkoxylation of the used methyl polyglykols may be checked using NMR spectroscopy, for example using .sup.1H-NMR spectroscopy in analogy to the method described in R. Stevanova, D. Rankoff, S. Panayotova, S. L. Spassov, J. Am. Oil Chem. Soc., 65, 1516-1518 (1988). For this purpose, the samples are derivatised by reacting them with trichloro acetyl isocyanate and measured as solutions in deuterated chloroform containing 1 weight-% (1 wt.-%) of tetramethyl silane as an internal standard.

[0095] The esterification reactions were controlled by determining the residual content of alcohol (e.g. benzyl alcohol, phenoxyethanol, lauryl/myristyl alcohol and cetearyl alcohol) by GC-FID. Calibration was performed with pure starting materials. Gas chromatography (GC) was performed using a Hewlett Packard GC 6890 with autosampler, coupled with a flame-ionisation detector (FID).

[0096] For the quantification of benzyl alcohol, samples were separated on a 50 m0.2 mm, 0.33 m film column. The column temperature was initially held at 50 C., then the temperature was raised to 175 C. at a rate of 5 C. per minute and from 175 C. to 300 C. at a rate of 25 C. per minute. The injector temperature was maintained at 250 C. and the injection volume was 1.0 L in the split mode. Helium was used as a carrier gas with a constant pressure of 1.8 bar. The samples were prepared by diluting 500 mg of sample (duplicate analysis) with 5 ml of methanol.

[0097] For the quantification of phenoxyethanol, cetearyl alcohol and lauryl/myristyl alcohol, samples were separated on a 25 m0.32 mm, 0.52 m film column. The column temperature was initially held at 50 C., then the temperature was raised to 250 C. at a rate of 10 C. per minute and held for 6.5 minutes. The injector temperature was maintained at 250 C. and the injection volume was 1.0 L in the split mode. Helium was used as a carrier gas with a constant pressure of 0.9 bar. The samples were prepared by diluting 500 mg of sample (duplicate analysis) with 5 ml of methanol.

[0098] Thin layer chromatography (TLC) was performed using TLC Silica Gel 60 F254 plates from Merck. The aromatic compounds were detected by UV light (254 and 366 nm simultaneously).

[0099] Examples 1 to 22 were performed according to a standard procedure. All reagents and quantities are listed in Table I.

[0100] The alcohol alkoxylate of choice was heated to 80 C. with stirring under nitrogen. The polycarboxylic acid or acid anhydride of choice was then added in portions over 5 minutes. The reaction mixture was then stirred for 2.5 hours at 80 C. The product, henceforth termed precursor, was isolated and the acid number determinedthese are listed in Table I in the column AN1.

[0101] Some amount of the precursor (listed in the column PC of Table I) was mixed with the alcohol and catalyst of choice and heated to the temperature listed in Table I while stirring under nitrogen. The reaction mixture was stirred at the temperature listed for the time denoted in Table I and water was distilled off. For all examples except examples 10 and 11, the product was then isolated after cooling and the acid number of the final product determinedlisted as AN2 in Table I.

[0102] In the cases of examples 10 and 11, a vacuum of 500 mbar was applied at 180 C. for 3 h under stirring after completion of stirring for the time listed in Table I.

[0103] In the case of comparative example C1, the alcohol Polyglykol M750 was heated to 80 C. with stirring under nitrogen. Trimellitic acid anhydride was then added in portions over 5 minutes. The reaction mixture was then stirred for 2.5 hours at 80 C. The product, was isolated and the acid number determined.

[0104] In the case of examples 23-27, the alcohol alkoxylate of choice was mixed with the polycarboxylic acid of choice, the alcohol and catalyst of choice and heated to the temperature listed in Table I while stirring under nitrogen. The reaction mixture was stirred at the temperature listed for the time denoted in Table I and water was distilled off. In the cases of examples 25-27, the product was then isolated after cooling and the acid number of the final product determinedlisted as AN2 in Table I. In the case of examples 23-24, a vacuum of 500 mbar was applied at 180 C. for 3 h under stirring after completion of stirring for the time listed in

[0105] Table I. Subsequently, the product was isolated after cooling and the acid number of the final product determinedlisted as AN2 in Table I.

[0106] The abbreviations used in Table I are as follows:

[0107] AA alcohol alkoxylate

[0108] PCA polycarboxylic acid

[0109] PC precursor

[0110] BA benzyl alcohol

[0111] PE phenoxyethanol

[0112] C16/18 cetearyl alcohol

[0113] C12/C14 lauryl/myristyl alcohol

[0114] AN1 acid number of the precursor

[0115] AN2 acid number of the final product

[0116] M500 polyglykol M 500

[0117] M750 polyglykol M 750

[0118] M1000 polyglykol M 1000

[0119] M1250 polyglykol M 1250

[0120] M2000 polyglykol M 2000

[0121] TMA trimellitic acid

[0122] TMAA trimellitic acid anhydride

[0123] PMA pyromellitic acid

[0124] pTsOH p-toluene sulfonic acid

[0125] DDBSA 4-dodecyl benzene sulfonic acid

[0126] MSA methane sulfonic acid

[0127] TIP titanium isopropoxide

TABLE-US-00001 TABLE I Examples of Alkoxylated Polycarboxylic Acid Esters of the Invention Residual PC/ BA/ PE/ C16/ C12/ T/ Time/ AN1/mg AN2/mg Alcohol/ AA PCA g g g 18/g g Cat C. hr KOH/g KOH/g wt.-% 1 M750, TMAA, 130 30.2 pTsOH, 180 36 120.6 34 3.6 450 g 115.3 g 0.16 g 2 M750, TMAA, 130 30.2 pTsOH, 200 36 120.6 26.3 0.6 450 g 115.3 g 0.16 g 3 M750, TMAA, 130 38 pTsOH, 180 37 121.3 24.4 2 450 g 115.3 g 0.17 g 4 M750, TMAA, 130 37.7 pTsOH, 200 44.5 130.6 23.4 1.1 450 g 115.3 g 0.17 g 5 M750, TMAA, 130 30.1 DDBSA, 180 39 120 29.6 6.1 1000 g 256.2 g 0.16 g 6 M750, TMAA, 130 30.1 MSA, 180 39 120 34 3.1 1000 g 256.2 g 0.16 g 7 M750, TMAA, 320 92.5 pTsOH, 180 43 120 26.5 4.2 1000 g 256.2 g 0.41 g 8 M750, TMAA, 131.7 30.5 TIP, 180 25 120 14 1.2 1000 g 256.2 g 0.16 g 9 M750, TMAA, 129.5 29.9 TIP, 200 20 120 25.4 0.5 1000 g 256.2 g 0.16 g 10 M750, TMAA, 127.1 36.7 TIP, 180 21 120 15 9.6 1000 g 256.2 g 0.16 g 11 M750, TMAA, 115.5 40.1 TIP, 180 21 120 6.7 13.8 1000 g 256.2 g 0.16 g 12 M1250, TMAA, 430 64.5 pTsOH, 180 45 78.9 29.1 3 450 g 69.2 g 0.49 g 13 M2000, TMAA, 400 49.4 pTsOH, 180 47 51.2 22.5 6.1 995.1 g 95.6 g 0.45 g 14 M1250, TMAA, 400 75.0 pTsOH, 180 40 80.0 27.0 2.5 1300.0 g 199.8 g 0.48 g 15 M1250, TMAA, 400 95.8 pTsOH, 180 40 80.0 18.8 1.3 1300.0 g 199.8 g 0.50 g 16 M1250, TMAA, 400 146.1 pTsOH, 180 41 79.0 15.6 8.7 2800.0 g 430.4 g 0.55 g 17 M1250, TMAA, 400 108.5 pTsOH, 180 41 79.0 1.7 14.6 2800.0 g 430.4 g 0.51 g 18 M750, TMAA, 320 120.1 pTsOH, 180 43 121.9 17.3 1.1 806.4 g 213 g 0.44 g 19 M750, TMAA, 320 183.1 pTsOH, 180 43 121.9 15.1 7 806.4 g 213 g 0.49 g 20 M750, TMAA, 332.8 134.8 pTsOH, 180 43 121.9 15.9 4.2 806.4 g 213 g 0.50 g 21 M500, TMAA, 333.3 130.2 pTsOH, 180 40 162.1 36.1 2.9 637.8 g 252.7 g 0.46 g 22 M1000, TMAA, 360 85 pTsOH, 180 40 121.9 27.9 4.2 998.9 g 193.3 g 0.45 g 23 M750 PMA, 38.3 TIP, 180 20.5 25.7 2.5 88.5 g 30.0 g 0.16 g 24 M750, TMA, 25.7 TIP, 180 20.5 23.9 1.1 89.2 g 25.0 g 0.14 g 25 M750, TMA, 28.8 pTsOH, 180 42 33.6 3.0 100 g 28.0 g 0.16 g 26 M750, PMA, 43.3 pTsOH, 180 41.5 37.8 3.9 100 g 33.9 g 0.18 g 27 M1250, PMA, 33.4 pTsOH, 180 45 33.1 4.9 125 g 25.4 g 0.18 g C1 M750, TMAA, 2.5 120 1000 g 256.2 g

[0128] An aqueous liquid laundry detergent of the following formulation was prepared:

TABLE-US-00002 TABLE II Liquid laundry detergent formulation Ingredient weight-% Mono propylene glycol 2.2 Triethanolamine 1.5 C.sub.12-C.sub.15 alcohol ethoxylate with 7 moles of ethylene oxide 1.2 Linear alkyl benzene sulfonate 4.6 Sodium laureth ether sulphate with 1 mole of ethylene 5.8 oxide Citric acid 2.0 CaCl.sub.2 dihydrate 0.2 NaCl 0.2 Tinopal CBS-X (fluorescer BASF) 0.3 Sodium hydroxide to pH = 8.4 EXEMPLARY alkoxylated polycarboxylic acid esters of see text the invention Water balance

Application Example 1Anti-Redeposition Benefit

[0129] The formulations of Table II were used to wash eight 55 cm knitted cotton cloth pieces in a Tergotometer set at 200 rpm (revolutions per minute). A one hour wash was conducted in 800 ml of water with 26 French hardness at 20 C., with 2.3 g/l of the formulation shown in Table II. To simulate particulate soil that could redeposit, 0.04 g/l of 100% compressed carbon black (ex Alfa Aesar) was added to the wash liquor. To simulate oily sebaceous soil, 7.2 g of an SBL2004 soil strip (ex Warwick Equest) was added to the wash liquor.

[0130] Once the wash had been completed, the cotton swatches were rinsed once in 400 ml clean water, removed, dried and the colour measured on a reflectometer and expressed as the CIE L*a*b* values. The anti-redeposition benefit was expressed as the L value:

L=L*(dispersant)L*(control)

[0131] The larger the L value, the greater the prevention of deposition of the carbon black soil. 95% confidence limits based on the 8 separate cotton swatches were calculated. Formulations were made with and without the addition of 8.7 wt.-% of the dispersants of Table I. The results are given in Table III.

TABLE-US-00003 TABLE III Anti-redeposition benefit Exemplary dispersant L 95% Example 1 3.26 0.20 Example 2 4.01 0.31 Example 3 4.03 0.20 Example 4 4.41 0.25 Example 8 2.84 0.24 Example 9 2.8 0.1 Example 10 2.75 0.27 Example 15 2.52 0.27 Example 16 2.52 0.27 Example 18 3.10 0.15 Example 21 3.41 0.23 Example 22 2.26 0.27 Example C1 0.48 0.26

[0132] The alkoxylated polycarboxylic acid esters of the invention enhance anti-redeposition.