Title - FORMULATION OF LIQUID LAUNDRY DETERGENT AND METHOD FOR WASHING A FABRIC ARTICLE WITH SAID FORMULATION

Abstract

A liquid laundry detergent is provided, comprising: a liquid carrier; a cleaning surfactant; and a cleaning enhancer of formula (1) wherein b is 0 - 2; wherein c is 2 - 4; wherein R is selected from hydrogen, C₁₋₂₂ alkyl and -CH₂C(=O)R¹⁴; wherein R¹⁴ is from formula (6); wherein R¹ is selected from formula (2) - formula (5); formula (2) wherein R² is from formula (6); formula (3) wherein R³ is from formula (6); and wherein R⁴ is selected from the methyl group and hydrogen; formula (4) wherein R⁵ is from formula (6); wherein f is 1 - 2; and wherein g is 2 - 10; formula (5) wherein R⁶ is from formula (6); formula (6) wherein R⁷ is selected from hydrogen and the C₁₋₂₂ alkyl group; wherein each R⁸ and R⁹ is independently a hydrogen or C₁₋₂₂ alkyl group, with the condition that at least one of R⁸ and R⁹ is a hydrogen in each subunit a; and wherein a is 0 - 30.

Description

84324-AR-NP FORMULATION OF LIQUID LAUNDRY DETERGENT The present invention relates to a liquid laundry detergent formulation. In particular, the present invention relates to a liquid laundry detergent formulation comprising a liquid carrier, a cleaning surfactant, and a cleaning enhancer, wherein the cleaning enhancer is of Formula (I). R1-F(CH2)cN —R' (I) wherein b is 0 to 2; wherein c is 2 to 4; wherein each R is independently selected from the group consisting of a hydrogen, a C1-22 alkyl group, an R1 and a -CH2C(=O)R14 group; wherein each R1 is independently selected from the group consisting of Formula (II), Formula (III), Formula (IV) and Formula (V); wherein R14 is from Formula (VI); R2 r2(II) where the * indicates the point of joining to Formula (I); where each R2 is independent of Formula (VI); 1877122 of 47 84324-AR-NP (III) wherein the * indicates the point of attachment to Formula (I); wherein each R3 is independently in accordance with Formula (VI); and wherein each R4 is independently selected from the group consisting of a hydrogen and a methyl group; either R5--(CH2)f—c—o—(CH2)g--N— *J2 (IV) wherein the * indicates the point of attachment to Formula (I); wherein each R5 is independently in accordance with Formula (VI); wherein f is 1 to 2; and wherein g is 2 to 10; R R6 O (V) where the * indicates the point of joining to Formula (I); and where each R6 is independently in accordance with Formula (VI); 1877122 of 47 84324-AR-NP (VI) wherein the * indicates the point of attachment to the associated base formula; wherein R7 is selected from the group consisting of a hydrogen and a C1-22 alkyl group; wherein each R8 and R9 is independently selected from the group consisting of a hydrogen and a C1-2 alkyl group, with the condition that at least one of R8 and R9 is a hydrogen in each subunit a; and wherein a is 0 to 30. Laundry detergents in liquid and gel forms that provide excellent overall cleaning are desirable to consumers. Such laundry detergents typically include surfactants, among other components, to deliver the desired cleaning benefits. However, with increasing environmental awareness and rising material costs, a movement to reduce surfactant use in laundry detergents is growing. Consequently, detergent manufacturers are seeking ways to reduce the amount of surfactant per unit dose of laundry detergent while maintaining overall cleaning performance. One method for reducing the unit dose of surfactant is to incorporate polymers into liquid detergent formulations, as described by Boutique et al. in U.S. patent application publication no. 20090005288. Boutique et al. describe a graft copolymer of polyethylene oxide, polypropylene, or polybutylene with vinyl acetate in a weight ratio of approximately 1:0.2 to approximately 1:10 for use in 1877122 3 of 47 84324-AR-NP liquid or gel laundry detergent formulations that have approximately 2 to approximately 20% by weight of surfactant. However, there remains a continued need for liquid laundry detergent formulations that exhibit maintained primary cleaning performance with a reduced surfactant load, preferably while also providing improved anti-redeposition performance. There is also a continued need for novel cleaning enhancers with improved biodegradability in accordance with OECD protocol 301F compared to conventional cleaning enhancers. The present invention provides a liquid laundry detergent formulation comprising: a liquid carrier; a cleaning surfactant; and a cleaning enhancer, wherein the cleaning enhancer is of Formula (I) R1T(Ch2)cN (CH2)c R1(I) wherein b is 0 to 2; wherein c is 2 to 4; wherein each R is independently selected from the group consisting of a hydrogen, a C1-22 alkyl group, an R1 and a -CH2C(=O)R14 group; wherein each R1 is independently selected from the group consisting of Formula (II), Formula (III), Formula (IV) and Formula (V); wherein R14 is from Formula (VI); R2 RZ(II) 1877122 of 47 84324-AR-NP where the * indicates the point of joining to Formula (I); where each R2 is independent of Formula (VI); either (III) wherein the * indicates the point of attachment to Formula (I); wherein each R3 is independently in accordance with Formula (VI); and wherein each R4 is independently selected from the group consisting of a hydrogen and a methyl group; R5—(CH2)f—c—o—(CH2) n—* (IV) where the * indicates the point of joining to Formula (I); where each R5 is independently in accordance with Formula (VI); where f is 1 to 2; and where g is 2 to 10; 1877122 of 47 84324-AR-NP R R6(V) where the * indicates the point of joining to Formula (I); and where each R6 is independently in accordance with Formula (VI); (VI) wherein the * indicates the point of attachment to the associated base formula; wherein R7 is selected from the group consisting of a hydrogen and a C1-22 alkyl group; wherein each R8 and R9 is independently selected from the group consisting of a hydrogen and a C1-2 alkyl group, with the condition that at least one of R8 and R9 is a hydrogen in each subunit a; and wherein a is 0 to 30. The present invention provides a liquid laundry detergent formulation comprising: a liquid carrier; a cleaning surfactant; and a cleaning enhancer, wherein the cleaning enhancer is of Formula (I) R1—HCH2)CN (CH2)c R1(I) 1877122 of 47 84324-AR-NP where b is 0 to 2; where c is 2 to 4; where each R is independently selected from the group consisting of a hydrogen, an alkyl group C1-22, an R1 and a -CH2C(=O)R14 group; wherein each R1 is selected independently of the group consisting of Formula (II), Formula (III), Formula (IV) and Formula (V); where R14 is from Formula (VI); R2 R2(II) where the * indicates the point of joining to Formula (I); where each R2 is independent of Formula (VI); Oo nr R4* R4(III) wherein the * indicates the point of attachment to Formula (I); wherein each R3 is independently in accordance with Formula (VI); and wherein each R4 is independently selected from the group consisting of a hydrogen and a methyl group; R5--(CH2)f—C—O—(CH2) N—* (IV) 1877122 of 47 84324-AR-NP where the * indicates the point of joining to Formula (I); where each R5 is independently in accordance with Formula (VI); where f is 1 to 2; and where g is 2 to 10; o(V) where the * indicates the point of joining to Formula (I); and where each R6 is independently in accordance with Formula (VI); (VI) wherein the * indicates the point of attachment to the associated base formula; wherein R7 is selected from the group consisting of a hydrogen and a C1-22 alkyl group; wherein each R8 and R9 is independently selected from the group consisting of a hydrogen and a C1-2 alkyl group, with the condition that at least one of R8 and R9 is a hydrogen in each subunit a; and wherein a is 0 to 30, with the condition that a is 2 to 30 in 70 to 100 mol% of the occurrences of Formula (VI) in the cleaning enhancer. The present invention provides a method for washing a fabric article, comprising: providing a soiled fabric article; providing a formulation 1877122 of 47 84324-AR-NP liquid laundry detergent according to claim 1; providing a wash water; and applying the wash water and the liquid laundry detergent formulation to the soiled fabric to provide a clean fabric article. DETAILED DESCRIPTION Surprisingly, liquid laundry detergent formulations with a cleaning enhancer, as described herein, have been found to facilitate improved primary cleaning performance for the removal of sebum soil, while providing good anti-redeposition performance of sebum and clay powder; and also to exhibit desirable biodegradability profiles in accordance with OECD protocol 301F. Unless otherwise stated, proportions, percentages, parts, and the like are by weight. Weight percentages (or % by weight) in the composition are percentages of the dry weight, that is, they exclude any water that may be present in the composition. Preferably, the liquid laundry detergent formulation of the present invention comprises a liquid carrier (preferably, 25 to 97.9% by weight (more preferably, 30 to 95.8% by weight; even more preferably, 40 to 93.5% by weight; even more preferably, 45 to 91.75% by weight; most preferably, 50 to 89% by weight), based on the weight of the liquid laundry detergent formulation of the liquid carrier); and a cleaning surfactant (preferably, 2 to 60% by weight (more preferably, 4 to 50% by weight; even more preferably, 6 to 40% by weight; even more preferably, 7.5 to 35% by weight; most preferably, 10 to 30% by weight), based on the weight of the liquid laundry detergent formulation. 1877122 of 47 84324-AR-NP laundry, of the cleaning surfactant); and a cleaning enhancer (preferably, 0.1 to 15% by weight (more preferably, 0.2 to 12% by weight; even more preferably, 0.5 to 10% by weight; even more preferably, 0.75 to 8% by weight; most preferably 1 to 7.5% by weight), based on the weight of the liquid laundry detergent formulation, of the cleaning enhancer), wherein the cleaning enhancer is of Formula (I) R1—E(CH2)cN (CH2)c R1(I) wherein b is 0 to 2 (preferably 1); wherein c is 2 to 4 (preferably 2); wherein each R is independently selected from the group consisting of a hydrogen, a C1-22 alkyl group and a -CH2C(=O)R14 group (preferably a hydrogen, a C1-5 alkyl group and a -CH2C(=O)R14 group; more preferably a hydrogen, a C1-2 alkyl group and a -CH2C(=O)R14 group; even more preferably a methyl and a -CH2C(=O)R14 group; most preferably a -CH2C(=O)R14 group); wherein R14 is of Formula (VI); and wherein each R1 is selected independently from the group consisting of Formula (II), Formula (III), Formula (IV) and Formula (V) (preferably Formula (II) and Formula (III); with the highest preference, Formula (II)); R2RZ(II) 1877122 of 47 84324-AR-NP where the * indicates the point of joining to Formula (I); where each R2 is independent of Formula (VI) (i.e., individual occurrences of R2 in Formula (II) may be the same or different from each other); oo (III) wherein the * indicates the point of attachment to Formula (I); wherein each R3 is independently in accordance with Formula (VI); and wherein each R4 is independently selected from the group consisting of a hydrogen and a methyl group; R5—(CH2)f—c—o—(CH2) n—* (IV) where the * indicates the point of joining to Formula (I); where each R5 is independently in accordance with Formula (VI); where f is 1 to 2; and where g is 2 to 10; 1877122 of 47 84324-AR-NP (V) where the * indicates the point of joining to Formula (I); and where each R6 is independently in accordance with Formula (VI); (VI) wherein the * indicates the point of attachment to the associated base formula (i.e., Formula (II), Formula (III), Formula (IV), or Formula (V)); wherein R7 is selected from the group consisting of a hydrogen and a C1-22 alkyl group (preferably, a hydrogen and a C1-12 alkyl group; more preferably, a hydrogen and a C1-5 alkyl group; even more preferably, a hydrogen and a C1-4 alkyl group; most preferably, a hydrogen and a C4 alkyl group); wherein each R8 and R9 is independently selected from the group consisting of a hydrogen and a C1-2 alkyl group, provided that at least one of R8 and R9 is a hydrogen in each subunit a; and wherein a is 0 to 30 (preferably, 2 to 25; more preferably, 2 to 17; most preferably, 4 to 30). 12) in 70 to 100 mol% (preferably 80 to 100 mol%; more preferably 90 to 1877122 of 47 84324-AR-NP 100 mol%; with maximum preference, 95 to 100 mol%) of the occurrences of Formula (VI) in the cleaning enhancer). Preferably, the liquid laundry detergent formulation of the present invention comprises a liquid carrier. More preferably, the liquid laundry detergent formulation of the present invention comprises 25 to 97.9% by weight (preferably 30 to 95.8% by weight; more preferably 40 to 93.5% by weight; even more preferably 45 to 91.75% by weight; most preferably 50 to 89% by weight), based on the weight of the liquid laundry detergent formulation, of a liquid carrier. Even more preferably, the liquid laundry detergent formulation of the present invention comprises 25 to 97.9% by weight (preferably 30 to 95.8% by weight; more preferably 40 to 93.5% by weight; even more preferably 45 to 91.75% by weight; most preferably 50 to 89% by weight), based on the weight of the liquid laundry detergent formulation, of a liquid carrier; wherein the liquid carrier comprises water.With the highest preference, the liquid laundry detergent formulation of the present invention comprises 25 to 97.9% by weight (preferably, 30 to 95.8% by weight; more preferably, 40 to 93.5% by weight; even more preferably, 45 to 91.75% by weight; with the highest preference, 50 to 89% by weight), based on the weight of the liquid laundry detergent formulation, of a liquid carrier; wherein the liquid carrier is water. Preferably, the liquid carrier optionally includes a water-miscible liquid, such as C1-3 alkanols, C1-3 alkanediols, and mixtures thereof. More preferably, the liquid carrier optionally includes 0 to 10 wt% (preferably 0.2 to 8 wt%; more preferably 0.5 to 7.5 wt%), based on the weight of the liquid carrier, of water-miscible liquids; wherein the water-miscible liquids are selected from the group consisting of C1-3 alkanols, 1877122 of 47 84324-AR-NP C1-3 alkanediols (e.g., propylene glycol) and mixtures thereof. Most preferably, the liquid carrier optionally includes 0 to 10 wt% (preferably 0.2 to 7.5 wt%; most preferably 0.5 to 7.5 wt%), based on the weight of the liquid carrier, of water-miscible liquids; wherein the water-miscible liquids are selected from the group consisting of ethanol, propylene glycol, and mixtures thereof. Preferably, the liquid laundry detergent formulation of the present invention comprises: a cleaning surfactant. More preferably, the liquid laundry detergent formulation of the present invention comprises: 2 to 60% by weight (preferably, 4 to 50% by weight; more preferably, 6 to 40% by weight; even more preferably, 7.5 to 35% by weight; most preferably, 10 to 30% by weight), based on the weight of the liquid laundry detergent formulation, of a cleaning surfactant.Even more preferably, the liquid laundry detergent formulation of the present invention comprises: 2 to 60% by weight (preferably, 4 to 50% by weight; more preferably, 6 to 40% by weight; even more preferably, 7.5 to 35% by weight; most preferably, 10 to 30% by weight), based on the weight of the liquid laundry detergent formulation, of a cleaning surfactant; wherein the cleaning surfactant is selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and mixtures thereof.Even more preferably, the liquid laundry detergent formulation of the present invention comprises: 2 to 60% by weight (preferably, 4 to 50% by weight; more preferably, 6 to 40% by weight; even more preferably, 7.5 to 35% by weight; most preferably, 10 to 30% by weight), based on the weight of the liquid laundry detergent formulation, of a cleaning surfactant; wherein the cleaning surfactant is selected from the group consisting of a mixture including an anionic surfactant and a nonionic surfactant. 1877122 of 47 84324-AR-NP, most preferably, the liquid laundry detergent formulation of the present invention comprises: 2 to 60% by weight (preferably, 4 to 50% by weight; more preferably, 6 to 40% by weight; even more preferably, 7.5 to 35% by weight; most preferably, 10 to 30% by weight), based on the weight of the liquid laundry detergent formulation, of a cleaning surfactant; wherein the cleaning surfactant includes a mixture of a linear alkylbenzenesulfonate, a sodium laurethoxysulfate, and a nonionic alcohol ethoxylate. Anionic surfactants include alkyl sulfates, alkylbenzene sulfates, alkylbenzene sulfonic acids, alkylbenzene sulfonates, alkyl polyethoxy sulfates, alkoxy alcohols, paraffin sulfonic acids, paraffin sulfonates, olefin sulfonic acids, olefin sulfonates, alpha-sulfocarboxylates, alpha-sulfocarboxylate esters, alkyl glyceryl ether sulfonic acids, alkyl glyceryl ether sulfonates, fatty acid sulfates, fatty acid sulfonates, fatty acid ester sulfonates, alkylphenols, alkyl phenol polyethoxy ether sulfates, 2-acryloxyalkane-1-sulfonic acid, 2-acryloxyalkane-1-sulfonate, beta-alkyloxyalkane sulfonic acid, beta-alkyloxyalkane sulfonate, oxides of amine and mixtures thereof.Preferred anionic surfactants include C8-20 alkylbenzene sulfates, C8-20 alkylbenzene sulfonic acid, C8-20 alkylbenzene sulfonate, paraffin sulfonic acid, paraffin sulfonate, alpha-olefin sulfonic acid, alpha-olefin sulfonate, alkoxylated alcohols, C8-20 alkylphenols, amine oxides, fatty acid sulfonates, fatty acid ester sulfonates, C8-10 alkyl polyethoxy sulfates, and mixtures thereof. More preferred anionic surfactants include C12-16 alkylbenzene sulfonic acid, C12-16 alkylbenzene sulfonate, C12-18 paraffin sulfonic acid, C12-18 paraffin sulfonate, C12-16 alkyl polyethoxy sulfate, and mixtures thereof. 1877122 of 47 84324-AR-NP Nonionic surfactants include alkoxylates (e.g., polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, terminal group-terminated polyglycol ethers, mixed ethers, mixed hydroxy ethers, fatty acid polyglycol esters, and mixtures thereof). Preferred nonionic surfactants include fatty alcohol polyglycol ethers. Further preferred nonionic surfactants include secondary alcohol ethoxylates, ethoxylated 2-ethylhexanol, ethoxylated seed oils, butanol-terminated ethoxylated 2-ethylhexanol, and mixtures thereof. Cationic surfactants include quaternary surface-active compounds. Preferred cationic surfactants include quaternary surface-active compounds that have at least one ammonium group, one sulfonium group, one phosphonium group, one iodonium group, and one arsonium group. The most preferred cationic surfactants include at least one dialkyldimethylammonium chloride and one alkyl dimethylbenzylammonium chloride. Even more preferred cationic surfactants include at least one C16-18 dialkyldimethylammonium chloride, one C8-18 alkyldimethylbenzylammonium chloride, and one disebo dimethylammonium chloride. The most preferred cationic surfactant includes disebo dimethylammonium chloride. Amphoteric surfactants include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amine oxides, acylated amino acids, aliphatic quaternary ammonium compound derivatives, and mixtures thereof. Preferred amphoteric surfactants include aliphatic quaternary ammonium compound derivatives. The most preferred amphoteric surfactants include aliphatic quaternary ammonium compound derivatives with a chain group 1877122 of 47 84324-AR-NP long having 8 to 18 carbon atoms. Even more preferentially, amphoteric surfactants include at least one C-12-14 alkyldimethylamine oxide, 3-(N,N-dimethyl-N-hexadecylammonium)propane-1-sulfonate, 3-(N,N-dimethyl-N-hexadecylammonium)-2-hydroxypropane-1-sulfonate. The most preferred amphoteric surfactants include at least one C-12-14 alkyldimethylamine oxide. Preferably, the liquid laundry detergent formulation of the present invention comprises: 0.1 to 15% by weight (preferably, 0.2 to 12% by weight; more preferably, 0.5 to 10% by weight; even more preferably, 0.75 to 8% by weight; most preferably, 1 to 7.5% by weight), based on the weight of the liquid laundry detergent formulation, of the cleaning enhancer); wherein the cleaning enhancer is of Formula (I) R1-F(CH2)cN (CH2)c R1(I) wherein b is 0 to 2 (preferably 1); wherein c is 2 to 4 (preferably 2); wherein each R is independently selected from the group consisting of a hydrogen, a C1-22 alkyl group and a -CH2C(=O)R14 group (preferably a hydrogen, a C1-5 alkyl group and a -CH2C(=O)R14 group; more preferably a hydrogen, a C1-2 alkyl group and a -CH2C(=O)R14 group; even more preferably a methyl group and a -CH2C(=O)R14 group; most preferably a -CH2C(=O)R14 group); wherein R14 is of Formula (VI); and wherein each R1 is independently selected from the group consisting of the 1877122 of 47 84324-AR-NP Formula (II), Formula (III), Formula (IV) and Formula (V) (preferably, the Formula (II) and Formula (III); with the highest preference, Formula (II)); R2 r2(II) where the * indicates the point of joining to Formula (I); where each R2 is independent of Formula (VI) (i.e., individual occurrences of R2 in Formula (II) may be the same or different from each other); oo (III) wherein the * indicates the point of attachment to Formula (I); wherein each R3 is independently in accordance with Formula (VI); and wherein each R4 is independently selected from the group consisting of a hydrogen and a methyl group; either R5--(CH2)f—C—O—(CH2)g--N— *J2 (IV) 1877122 of 47 84324-AR-NP where the * indicates the point of joining to Formula (I); where each R5 is independently in accordance with Formula (VI); where f is 1 to 2; and where g is 2 to 10; o(V) where the * indicates the point of joining to Formula (I); and where each R6 is independently in accordance with Formula (VI); (VI) wherein the * indicates the point of attachment to the associated base formula (i.e., Formula (II), Formula (III), Formula (IV), or Formula (V); wherein R7 is selected from the group consisting of a hydrogen and a C1-22 alkyl group (preferably a hydrogen and a C1-12 alkyl group; more preferably a hydrogen and a C1-5 alkyl group; still more preferably a hydrogen and a C1-4 alkyl group; most preferably a hydrogen and a C4 alkyl group); wherein each R8 and R9 is independently selected from the group consisting of a hydrogen and a C1-2 alkyl group, provided that at least one of R8 and R9 is a hydrogen in each subunit a; and wherein a is 0 1877122 of 47 84324-AR-NP at 30 (preferably, where a is 2 to 30 (preferably, 2 to 25; more preferably, 2 to 17; most preferably, 4 to 12) in 70 to 100 mol% (preferably, 80 to 100 mol%; more preferably, 90 to 100 mol%; most preferably, 95 to 100 mol%) of the occurrences of Formula (VI) in the cleaning enhancer). Preferably, the cleaning enhancer for cleaning dirty clothes, of the present invention, is of Formula (I); wherein Formula (I) is of Formula (Ia) or R10 R10 River R10(Ia) where x is 0 to 2 (preferably 1); where each R10 is independent of Formula (VI) (VI) where the * indicates the point of attachment to Formula (Ia); where R7 is selected from the group consisting of a hydrogen and a C1-22 alkyl group 1877122 of 47 84324-AR-NP (preferably, a hydrogen and a C1-12 alkyl group; more preferably, a hydrogen and a C1-5 alkyl group; even more preferably, a hydrogen and a C1-4 alkyl group; most preferably, a hydrogen and a C4 alkyl group); wherein each R8 and R9 is independently selected from the group consisting of a hydrogen and a C1-2 alkyl group, provided that at least one of R8 and R9 is a hydrogen in each subunit a; and wherein a is 0 to 30. More preferably, the cleaning enhancer of the present invention is of Formula (I); wherein Formula (I) is of Formula (Ia); wherein an average of 70 to 100 mol% (preferably 80 to 100 mol%; more preferably 90 to 100 mol%; most preferably 95 to 100 mol%) of the R10 groups are of Formula (VI) wherein a is 2 to 30.Even more preferably, the cleaning enhancer for cleaning dirty clothes of the present invention is of Formula (I); wherein Formula (I) is of Formula (Ia); wherein an average of 70 to 100 mol% (preferably, 80 to 100 mol%; more preferably, 90 to 100 mol%; most preferably, 95 to 100 mol%) of the R10 groups are of Formula (VI); wherein Formula (VI) is of Formula (VIa). R11— O—[CH2CH(R12)O] and —* (VIa) wherein the * indicates the point of attachment to Formula (Ia); wherein R11 is selected from the group consisting of a hydrogen and a C1-22 alkyl group (preferably, a hydrogen and a C1-12 alkyl group; more preferably, a hydrogen and a C1-5 alkyl group; still more preferably, a C1-4 alkyl group; most preferably, a C4 alkyl group); in 1877122 of 47 84324-AR-NP wherein each R12 is independently selected from the group consisting of a hydrogen and a C1-2 alkyl group; and wherein y is 2 to 30 (preferably 2 to 25; more preferably 2 to 17; most preferably 4 to 12). Most preferably, the laundry cleaning enhancer of the present invention is of Formula (I); wherein Formula (I) is of Formula (Ia); wherein an average of 70 to 100 mol% (preferably 80 to 100 mol%; more preferably 90 to 100 mol%; most preferably 95 to 100 mol%) of the R10 groups are of Formula (VI); wherein Formula (VI) is of Formula (VIb). R13—O—(EO)h—(PO) i —(EO)j — (VIb) wherein the * indicates the point of attachment to Formula (Ia); wherein R13 is selected from the group consisting of a hydrogen and a C1-12 alkyl group (preferably, a hydrogen and a C1-12 alkyl group; more preferably, a hydrogen and a C1-5 alkyl group; still more preferably, a C14 alkyl group; most preferably, a C4 alkyl group); wherein EO is an ethylene oxide group; wherein PO is a propylene oxide group; wherein h is 0 to 30 (preferably, 0 to 5; more preferably, 0 to 2; most preferably, 0 to 1); wherein i is 0 to 30 (preferably, 0 to 10; more preferably, 0 to 7; most preferably, 2 to 5); where j is 0 to 30 (preferably 2 to 10; most preferably 2 to 8; most preferably 2 to 6); and where h + i + j is 2 to 30 (preferably 2 to 25; most preferably 2 to 17; most preferably 4 to 12). 1877122 of 47 84324-AR-NP Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a structural agent. More preferably, the liquid laundry detergent formulation of the present invention further comprises 0 to 2% by weight (preferably 0.05 to 0.8% by weight; more preferably 0.1 to 0.4% by weight), based on the weight of the liquid laundry detergent formulation, of a structural agent. In the highest preference, the liquid laundry detergent formulation of the present invention further comprises 0 to 2% by weight (preferably 0.05 to 0.8% by weight; more preferably 0.1 to 0.4% by weight), based on the weight of the liquid laundry detergent formulation, of a structural agent; wherein the structural agent is a non-polymeric crystalline hydroxy-functional material capable of forming chain-like structural systems throughout the liquid laundry detergent formulation when crystallized in situ. Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a hydrotrope. More preferably, the liquid laundry detergent formulation of the present invention optionally further comprises: 0 to 15% by weight (preferably, 0.1 to 12% by weight; more preferably, 0.2 to 10% by weight; most preferably, 0.5 to 7.5% by weight), based on the weight of the liquid laundry detergent formulation, of a hydrotrope.More preferably, the liquid laundry detergent formulation of the present invention optionally further comprises: 0 to 15% by weight (preferably, 0.1 to 12% by weight; more preferably, 0.2 to 10% by weight; most preferably, 0.5 to 7.5% by weight), based on the weight of the liquid laundry detergent formulation, of a hydrotrope; wherein the hydrotrope is selected from the group consisting of alkyl hydroxides; glycols; urea; monoethanolamine; diethanolamine; triethanolamine; calcium, sodium, potassium, ammonium and alkanolammon acid salts. 1877122 of 47 84324-AR-NP xylene sulfonic acid, toluene sulfonic acid, ethylbenzene sulfonic acid, naphthalene sulfonic acid, and cumene sulfonic acid; salts thereof and mixtures thereof. Most preferably, the liquid laundry detergent formulation of the present invention further comprises: 0 to 15% by weight (preferably, 0.1 to 12% by weight; more preferably, 0.2 to 10% by weight; most preferably, 0.5 to 7.5% by weight), based on the weight of the liquid laundry detergent formulation, of a hydrotrope; wherein the hydrotrope is selected from the group consisting of ethanol, propylene glycol, sodium toluene sulfonate, potassium toluene sulfonate, sodium xylene sulfonate, ammonium xylene sulfonate, potassium xylene sulfonate, calcium xylene sulfonate, sodium cumene sulfonate, ammonium cumene sulfonate and mixtures thereof. Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a fragrance. More preferably, the liquid laundry detergent formulation of the present invention optionally further comprises: 0 to 10% by weight (preferably, 0.001 to 5% by weight; more preferably, 0.005 to 3% by weight; most preferably, 0.01 to 2.5% by weight), based on the weight of the liquid laundry detergent formulation, of a fragrance. Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises an improver. More preferably, the liquid laundry detergent formulation of the present invention optionally further comprises: 0 to 50% by weight (preferably, 5 to 50% by weight; more preferably, 7.5 to 30% by weight), based on the weight of the liquid laundry detergent formulation, of an improver. Most preferably, the liquid laundry detergent formulation of the present invention comprises 1877122 of 47 84324-AR-NP optionally also: 0 to 50% by weight (preferably 5 to 50% by weight; more preferably 7.5 to 30% by weight), based on the weight of the liquid laundry detergent formulation, of an improver; wherein the improver is selected from the group consisting of inorganic improvers (e.g., tripolyphosphate, pyrophosphate); alkali metal carbonates; borates; bicarbonates; hydroxides; zeolites; citrates (e.g., sodium citrate); polycarboxylates; monocarboxylates; aminotrimethylenephosphonic acid; salts of aminotrimethylenephosphonic acid; hydroxyethanediphosphonic acid; salts of hydroxyethanediphosphonic acid; diethylenetriaminepenta(methylenephosphonic acid); salts of diethylenetriaminepenta(methylenephosphonic acid); ethylenediaminetetraethylenephosphonic acid; salts of ethylenediaminetetraethylenephosphonic acid; oligomeric phosphonates; polymeric phosphonates; mixtures thereof. Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a fabric softener. More preferably, the liquid laundry detergent formulation of the present invention optionally further comprises: 0 to 10% by weight (preferably, 0.5 to 10% by weight), based on the weight of the liquid laundry detergent formulation, of a fabric softener. Most preferably, the liquid laundry detergent formulation of the present invention optionally further comprises: 0 to 10% by weight (preferably, 0.5 to 10% by weight), based on the weight of the liquid laundry detergent formulation, of a fabric softener; wherein the fabric softener is a cationic coacervating polymer (e.g., cationic hydroxyethylcellulose; polyquaternium polymers and combinations thereof). Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a pH adjusting agent. 1877122 of 47 84324-AR-NP Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a pH adjusting agent; wherein the liquid laundry detergent formulation has a pH of 6 to 12.5 (preferably 6.5 to 11; more preferably 7.5 to 10). The pH adjusting bases include mineral bases such as sodium hydroxide (including soda ash) and potassium hydroxide; sodium bicarbonate; sodium silicate; ammonium hydroxide; and organic bases (e.g., mono-, di-, or tri-ethanolamine; and 2-dimethylamino-2-methyl-1-propanol (DMAMP)). The pH adjusting acids include mineral acids (e.g., hydrochloric acid, phosphorous acid, and sulfuric acid) and organic acids (e.g., acetic acid). Preferably, the method for washing a fabric article of the present invention comprises: providing a soiled fabric article (preferably wherein the soiled fabric article is soiled with at least one of tallow oil, dust, and clay dirt; more preferably wherein the soiled fabric article is soiled with tallow oils and clay dirt) (preferably wherein the soiled fabric article is selected from the group consisting of stained cotton fabric, stained cotton interlock fabric, stained cotton terry fabric, stained cotton-polyester blend fabric, stained polyester knit fabric, stained polyester woven fabric, and blends thereof; more preferably wherein the soiled fabric article is at least one of stained cotton fabric and stained cotton interlock fabric); providing a liquid laundry detergent formulation of the present invention; providing wash water;and applying the wash water and the liquid laundry detergent formulation to the soiled fabric to provide a clean fabric article. More preferably, the method for washing a fabric article of the present invention comprises: providing a soiled fabric article (preferably wherein the soiled fabric article is soiled with at least one of tallow oil, powder; 1877122 of 47 84324-AR-NP and clay soiling; more preferably, wherein the soiled cloth article is soiled with tallow oils and clay soiling) (preferably, wherein the soiled cloth article is selected from the group consisting of stained cotton cloth, stained cotton interlock cloth, stained cotton terry cloth, stained cotton-polyester blend cloth, stained polyester knit cloth, stained polyester woven cloth and blends thereof; more preferably, wherein the soiled cloth article is at least one of stained cotton cloth and stained cotton interlock cloth); providing a liquid laundry detergent formulation of the present invention; providing wash water; providing rinse water; applying the wash water and the liquid laundry detergent formulation to the soiled cloth to provide a clean cloth article.and then apply the rinse water to the clean fabric item to remove the liquid laundry detergent formulation from the clean fabric item. Some embodiments of the present invention will now be described in detail in the following examples. The reagents used in the examples are described in Table 1. Table 1 Identifier Description DTPA Diethylenetriamine pentaacetic acid (393.35 g / mol) Available from TCI Ethyl alcohol grade 200 Available from Pharmco / Greenfield Global Ethylene glycol monobutyl ether Available from The Dow Chemical Company under the trade name Butyl Cellosolve™ Sulfuric acid ACS Plus Certified, available from Fisher Scientific AE1 C12-15 ethoxylated alcohol-9 (600 g / mol) available from Stepan Company under the trade name BiO-SOFT® N25-9 AE2 C12-15 ethoxylated alcohol-7 (510 g / mol) available from Stepan Company under the trade name BiO-SOFT® N25-7 1877122 of 47 84324-AR-NP Poly(ethylene glycol) Available from The Dow Chemical Company under the trade name CARBOWAX™ PEG 300 Butylstanoic acid Available from OMC Organometallix under the trade name FASCAT® 9100 EO Ethylene oxide PO Propylene oxide BO Butylene oxide Capryleth-6 carboxylic acid Available from Kao Chemicals under the trade name AKYPO® LF 1 Titanium isopropoxide Available from Sigma Aldrich Dimethyl maleate 97% available from TCI Chemicals Synthesis S1: EO-terminated block PO copolymer Potassium hydride (0.5 g) was dissolved with stirring, under nitrogen, in ethylene glycol monobutyl ether (25 g). From this mixture, 23.6 g was charged using a syringe into a nitrogen-purged reactor. The reactor was sealed and then charged with propylene oxide (41.5 g; 50.0 mL) at 120 °C with a pumping rate of 1 mL / min. An increase in reactor pressure was observed as the propylene oxide was added. The reactor contents were allowed to react with the addition of propylene oxide for 9 hours; during this time, the reactor pressure was observed to decrease and then level off as the propylene oxide was consumed. Ethylene oxide (33.5 g; 38.0 mL) was then charged to the reactor contents at 130 °C with a pumping rate of 1 mL / min. The reactor contents were allowed to react with the addition of ethylene oxide for 4 hours. Afterward, the reactor was vented, purged with nitrogen, and the 15% product was recovered.The yield was quantitative.1H NMR (CDCl3, δ, ppm): 0.90 t (3H, CH3), 1.13 m (8.48 H, CH3 from PO), 1.35 m (2H, CH2), 1.55 m (2H, CH2), 3.55 m (35.93 H, CHCH2 from PO + CH2CH2 from EO). The NMR analysis suggested the following formula for the recovered product: CH3CH2CH2CH2OCH2CH2O(PO)2,83(EO)5,36H. GPC (in THF): Mn = 739, Mw = 859, PDI = 1.16. For the purposes of calculating the. 1877122 of 47 84324-AR-NP stoichiometric reaction in the syntheses referenced to follow, the FW calculated from the empirical formula established above was used from NMR: 519 Daltons. S2 Synthesis: EO-terminated block PO copolymer Potassium hydride (0.4 g) was dissolved with stirring, under nitrogen, in ethylene glycol monobutyl ether (20.75 g). 21.15 g of this mixture was charged with a syringe into a nitrogen-purged reactor. The reactor was sealed and then charged with propylene oxide (41.5 g; 50.0 mL) at 115 °C with a pumping rate of 1 mL / min. An increase in reactor pressure was observed as the propylene oxide was added. The reactor contents were allowed to react with the addition of propylene oxide for 22 hours; during this time, the reactor pressure was observed to decrease and then level off as the propylene oxide was consumed. Ethylene oxide (28.85 g; 33.0 mL) was then charged to the reactor contents at 130 °C with a pumping rate of 1 mL / min. The reactor contents were allowed to react with the addition of ethylene oxide for 4 hours. Afterwards, the reactor was vented, purged with nitrogen, and the product was recovered.The yield was 85.4 g (93%).1H NMR (CDCl3, δ, ppm): 0.90 t (3H, CH3), 1.13 m (11.05 H, CH3 from PO), 1.35 m (2H, CH2), 1.55 m (2H, CH2), 3.55 m (31.02 H, CHCH2 from PO + CH2CH2 from EO). The NMR analysis suggests the following formula: CH3CH2CH2CH2OCH2CH2O(PO)3,68(EO)3,49H. GPC (in THF): Mn = 641, Mw = 761, PDI = 1.19. For the purposes of calculating the stoichiometric reaction in the examples below, the FW calculated from the empirical formula established above from NMR was used: 486 daltons. 1877122 of 47 84324-AR-NP S3 Synthesis: DTPA-ethyl ester using an ethanol and sulfuric acid catalyst DTPA (8.5449 g), ethanol (168.54 g), and sulfuric acid (1.2000 g) were loaded into a 500 mL flask containing a magnetic stir bar under an open atmosphere. The temperature of the flask contents was controlled using a heating mantle connected to a variable transformer, which was connected to a J-KEM temperature controller. The flask was fitted with an adapter connected to a three-way mineral oil bubbler, which was connected to a nitrogen source in one neck. A condenser circulating cold tap water was fitted to another neck of the flask. An alcohol thermometer was placed in another neck of the flask and set to measure the temperature of the empty space. All necks of the flask were sealed with hydrocarbon grease. The loaded and sealed apparatus was placed on top of a heating mantle, which was placed on top of a magnetic stirrer.The flask was purged with nitrogen at a rate of 2–3 bubbles per second for the duration of the reaction, as indicated by an inlet mineral oil bubbler. The seal quality was verified using an outlet mineral oil bubbler connected to the condenser. The contents of the flask were heated to reflux (vapor temperature of the vacuum ~78 °C) and maintained with adequate stirring for a total of 19 hours over several days (with heating and stirring stopped during overnight periods, which were not counted as part of the 19 hours). The contents of the flask were then filtered through filter paper using a vacuum-assisted Buchner funnel. Calcium carbonate (5.0 g) was added to the filtrate, and it was stirred for 30 minutes before being filtered again using vacuum filtration. The filtrate was divided into two aliquots, which were distilled sequentially.Approximately 100-150 ml of sample were placed in a 250 ml round-bottom flask. 1877122 of 47 The 84324-AR-NP apparatus, equipped with a magnetic stir bar and a vacuum distillation head, was placed under a nitrogen atmosphere with a constant nitrogen flow maintained by a bubbler. Distillation with solvent recovery was continued until the solvent recovery rate decreased markedly. After the first half of the filtrate was distilled, the remaining filtrate was added and the distillation was repeated. The product, DTPA-ethyl ester, was obtained as a dark orange-brown viscous liquid.1H NMR (acetone-d6, δ, ppm): 4.91-4.46 (1.87 H), 4.37-4.24 (0.81 H), 4.24-4.10 (5.83 H), 4.01-3.91 (1.69 H), 3.85-3.62 (10.68 H), 3.64-3.54 (0.52 H), 3.46-3.25 (3.55 H), 2.14-1.92 (1.10 H), 1.41-1.16 (13.15 H), 1.16-1.06 (0.58 H). DTPA:ethyl ester groups = 1:4,13. DTPA-ethyl ester active: 98% by weight. S4 Synthesis: DTPA-polyester using an acid catalyst and ethoxylated alcohol The DTPA-ethyl ester prepared according to Synthesis S3 (1.0172 g, 2.0 mmol), AE1 (7.0486 g, 11.8 mmol, 6.0 eq.), and butylstanoic acid (0.0721 g, 0.35 mmol, 18 mol%) were loaded into a 250 mL flask with a magnetic stir bar. The flask was sealed with hydrocarbon grease, purged with nitrogen, and then heated in an OptiTHERM® reaction block attached to an IKA magnetic heating plate at a set point temperature of 150 °C. After reaching 135 °C, a vacuum was applied to the contents of the flask using a mechanical pump with an interposed solvent trap cooled with a dry ice / acetone bath. The mixing speed was adjusted from 50 to 300 rpm, as the flask contents were heated to account for changes in viscosity. The flask contents were maintained at 145–158 °C for six hours under vacuum. 1877122 of 47 The 84324-AR-NP flasks were then cooled and characterized. The degree of displacement of the ethyl groups was estimated using the integrated peaks in the quantitative 13C NMR spectra for the methyl groups of AE1 (14.4 ppm) and ethyl ester (14.6 ppm). This ratio was 6.7:1, and since the original ethyl:DTPA ratio was 4.13:1 and the AE1:DTPA ratio was 6.0, the ethyl:DTPA ratio in the product was 0.9:1, suggesting that approximately 80% of the ethyl groups had been removed. S5 Synthesis: DTPA-polyester using an acid catalyst, diol and ethoxylated alcohol The DTPA-ethyl ester prepared according to Synthesis S3 (0.9676 g, 1.9 mmol), AE1 (5.3243 g, 8.9 mmol, 4.8 eq.), PEG-300 (0.3712 g, 1.24 mmol, 0.65 eq.), and butylstanoic acid (0.0555 g, 0.27 mmol, 14 molar) were loaded into a 250 mL flask with a magnetic stir bar. The flask was sealed with hydrocarbon grease, purged with nitrogen, and then heated in an OptiTHERM® reaction block attached to an IKA magnetic heating plate at a setpoint temperature of 150 °C. After reaching 133.5 °C, a vacuum was applied to the contents of the flask using a mechanical pump with an interposed solvent trap cooled with a dry ice / acetone bath. The mixing speed was adjusted from 50 to 300 rpm as the flask contents heated up to account for changes in viscosity. The flask contents were maintained at a temperature of 142–149 °C for six hours under vacuum.The contents of the flask were then cooled and characterized. The degree of displacement of the ethyl groups was estimated using the integrated peaks in the quantitative 13C NMR spectra for the methyl groups of AE1 (14.4 ppm) and ethyl ester (14.6 ppm). This ratio was 4.6:1, and since the original ethyl:DTPA ratio was... 1877122 of 47 84324-AR-NP 4.13:1 and the AE1:DTPA ratio was 4.8:1, the ethyl:DTPA ratio in the product was 1:1, suggesting that ~75% of the ethyl groups had been removed. S6 Synthesis: DTPA-polyester using an acid catalyst and ethoxylated alcohol The DTPA-ethyl ester prepared according to Synthesis S3 (1.1378 g, 2.2 mmol), AE1 (6.9510 g, 13.7 mmol, 6.2 eq.), and butylstanoic acid (0.0798 g, 0.38 mmol, 17 mol%) were loaded into a 250 mL flask with a magnetic stir bar. The flask was sealed with hydrocarbon grease, purged with nitrogen, and then heated in an OptiTHERM® reaction block attached to an IKA magnetic heating plate at a set point temperature of 150 °C. After reaching 120 °C, a vacuum was applied to the contents of the flask using a mechanical pump with an interposed solvent trap cooled with a dry ice / acetone bath. The mixing speed was adjusted from 50 to 300 rpm, as the flask contents were heated to account for changes in viscosity. The flask contents were maintained at 121–149 °C for seven hours under vacuum. The contents were then cooled and characterized.The degree of displacement of the ethyl groups was estimated using the integrated peaks in the quantitative 13C NMR spectra for the methyl groups of AE1 (14.4 ppm) and ethyl ester (14.6 ppm). This ratio was 6.5:1, and since the original ethyl:DTPA ratio was 4.13:1 and the AE1:DTPA ratio was 6.2:1, the ethyl:DTPA ratio in the product was 0.94:1, suggesting that approximately 75% of the ethyl groups had been removed. 1877122 of 47 84324-AR-NP S7 Synthesis: DTPA-ethyl pentaester using an ethanol and sulfuric acid catalyst DTPA (5.0008 g), ethanol (177.59 g), and sulfuric acid (1.2118 g) were loaded into a 500 mL flask containing a magnetic stir bar under an open atmosphere. The temperature of the flask contents was controlled using a heating mantle connected to a variable transformer, which was connected to a J-KEM temperature controller. The flask was fitted with an adapter connected to a three-way mineral oil bubbler, which was connected to a nitrogen source in one neck. A condenser circulating cold tap water was fitted to another neck of the flask. An alcohol thermometer was placed in another neck of the flask and set to measure the temperature of the empty space. All necks of the flask were sealed with hydrocarbon grease. The loaded and sealed apparatus was placed on top of a heating mantle, which was placed on top of a magnetic stirrer.The flask was purged for the duration of the reaction with nitrogen at a rate of 2–3 bubbles per second, as indicated by an inlet mineral oil bubbler. The seal quality was verified using an outlet mineral oil bubbler connected to the condenser. The contents of the flask were heated to reflux (vapor temperature of the vacuum ~78 °C) and maintained with adequate mixing for a total of 32 hours over several days (with heating and stirring stopped during overnight periods, which were not counted as part of the 32 hours). The contents of the flask were then filtered through filter paper using a vacuum-assisted Buchner funnel. Calcium carbonate (5.0 g) was added to the filtrate, and it was stirred for 30 minutes before being filtered again using vacuum filtration. The filtrate was divided into two aliquots, which were distilled sequentially. Approximately 100–150 mL of the filtrate was used. 1877122 of 47 Sample 84324-AR-NP was placed in a 250 mL round-bottom flask equipped with a magnetic stir bar and a vacuum distillation head and placed under a nitrogen atmosphere with a constant nitrogen flow maintained by a bubbler. Distillation with solvent recovery was continued until the solvent recovery rate decreased markedly. After the first half of the filtrate was distilled, the remaining filtrate was added and the distillation was repeated. The product, DTPA-ethyl ester, was obtained as a pale yellow, translucent liquid. DTPA:ethyl ester groups = 1:4.17. DTPA-ethyl ester active: 87 wt%. S8 Synthesis: DTPA-polyester using an acid catalyst and alkoxylated butanol The DTPA-ethyl ester prepared according to Synthesis S7 (1.0966 g, 1.86 mmol), EO-terminated block copolymer prepared according to Synthesis S1 (5.6161 g, 10.8 mmol, 5.8 eq.), and butylstanoic acid (0.0718 g, 0.34 mmol, 18 mol%) were loaded into a 250 mL flask with a magnetic stir bar. The flask was sealed with hydrocarbon grease, purged with nitrogen, and then heated in an OptiTHERM® reaction block attached to an IKA magnetic heating plate at a set point temperature of 150 °C. After reaching 133.5 °C, a vacuum was applied to the contents of the flask using a mechanical pump with an interposed solvent trap cooled with a dry ice / acetone bath. The mixing speed was adjusted from 50 to 300 rpm, as the flask contents were heated to account for changes in viscosity. The flask contents were maintained at a temperature of 133–148 °C for five hours under vacuum.The contents of the flask. 1877122 of 47 The 84324-AR-NPs were then cooled and characterized. The degree of displacement of the ethyl groups was estimated using the integrated peaks in the quantitative 13C NMR spectra for the methyl groups of the Synthesis product S1 (14.3 ppm) and ethyl ester (14.6 ppm). This ratio was 5.3:1, and since the original ethyl:DTPA ratio was 4.17:1 and the alkoxylate:DTPA ratio was 4.1:1, the ethyl:DTPA ratio in the product was 0.8:1, suggesting that approximately 80% of the ethyl groups had been removed. S9 Synthesis: DTPA-ethyl pentaester using an ethanol and sulfuric acid catalyst DTPA (8.0224 g), ethanol (304.80 g), and sulfuric acid (2.2318 g) were loaded into a 500 mL flask containing a magnetic stir bar under an open atmosphere. The temperature of the flask contents was controlled using a heating mantle connected to a variable transformer, which was connected to a J-KEM temperature controller set at 85 °C. The flask was fitted with an adapter connected to a three-way mineral oil bubbler, which was connected to a nitrogen source in one neck. A condenser circulating cold tap water was fitted to another neck of the flask. An alcohol thermometer was placed in another neck of the flask and set to measure the temperature of the empty space. All necks of the flask were sealed with hydrocarbon grease. The loaded and sealed apparatus was placed on top of a heating mantle, which was placed on top of a magnetic stirrer.The flask was purged with nitrogen for the duration of the reaction at a rate of 2–3 bubbles per second, as indicated by an inlet mineral oil bubbler. The seal quality was verified using an outlet mineral oil bubbler connected to the condenser. The contents of the flask were heated to reflux (vapor temperature of the space). 1877122 of 47 The contents of the flask were heated under vacuum (~79 °C) and kept in a suitable mixing environment for a total of 20 hours over several days (with heating and stirring stopped during overnight periods, which were not counted as part of the 20 hours). The contents of the flask were then filtered through filter paper using a vacuum-assisted Buchner funnel. Calcium carbonate (5.0 g) was added to the filtrate, and the mixture was stirred for 30 minutes before being filtered again using vacuum filtration. The filtrate was placed in a 500 mL round-bottom flask fitted with a magnetic stir bar and a vacuum distillation head and placed under a nitrogen atmosphere with a constant nitrogen flow maintained by a bubbler. Distillation with solvent recovery was continued until the solvent recovery rate decreased markedly. The product, DTPA-ethyl ester, was obtained as a pale yellow, translucent liquid.DTPA:ethyl ester groups = 1:5. DTPA-ethyl ester active: 82% by weight. S10 Synthesis: DTPA-polyester using an acid catalyst and alkoxylated butanol The DTPA-ethyl ester prepared according to Synthesis S9 (4.1987 g, 6.48 mmol), EO-terminated block copolymer prepared according to Synthesis S1 (20.0 g, 38.5 mmol, 5.9 eq.), and titanium isopropoxide (0.3371 g, 1.19 mmol, 18 mol%) were loaded into a 250 mL flask with a magnetic stir bar. The flask was sealed with hydrocarbon grease, purged with nitrogen, and then heated in an OptiTHERM® reaction block attached to an IKA magnetic heating plate at a setpoint temperature of 150 °C. After reaching 129 °C, a vacuum was applied to the contents of the flask using a mechanical pump with an interposed solvent trap cooled with a dry ice / acetone bath. 1877122 of 47 The mixing speed of 84324-AR-NP was adjusted from a parameter of 50 to 300 rpm, as the flask contents were heated to account for changes in viscosity. The flask contents were maintained at a temperature of 150–152 °C for five hours under vacuum. The flask contents were then cooled and characterized. According to NMR, no ethyl groups remained in the 1H NMR spectra, and the 13C NMR showed that the carbonyl region is very simple with two peaks for the two ester types at 168 ppm and 173 ppm. S11 Synthesis: Ester Synthesis Capryleth-6 carboxylic acid (20.8032 g, 46.91 mmol based on a nominal purity of 92%, 4.1 eq.), N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (2.6629 g, 11.4 mmol), and titanium isopropoxide (0.5429 g, 1.9102 mmol, 17 mol%) were loaded into a 250 mL flask with a magnetic stir bar. The flask was sealed with hydrocarbon grease, purged with nitrogen, and then heated in an OptiTHERM® reaction block attached to an IKA magnetic hot plate at a setpoint temperature of 150 °C. After reaching 120 °C, a vacuum was applied to the contents of the flask using a mechanical pump with an interposed solvent trap cooled with a dry ice / acetone bath. The mixing speed was adjusted from 50 to 300 rpm as the flask contents heated up to account for changes in viscosity. The flask contents were maintained at a temperature of 148.3–154.9 °C for 6.5 hours under vacuum.The contents of the flask were then cooled and characterized by NMR to confirm the end of the reaction.1H NMR (acetone-d6, δ, ppm): 4.47-3.87 (15.2 H), 3.87-3.25 (97.8 H), 2.99-2.79 (4.3 H), 2.79-2.35 (4.8 H), 1.74-1.44 (8.1 H), 1.44-1.14 (40.3 H), 1.001877122 of 47. 84324-AR-NP 0.78 (12.0 H).13H NMR (126 MHz, acetone-d6, δ, ppm): 171.06 (2.2 C), 73.3670.07 (35.5 C), 69.02 (2.7 C), 63.49 (2.8 C), 54.26 (2.8 C), 32.66 (3.6 C), 27.01 (3.3 C), 23.39 (4.0 C), 14.46 (4.0 C). S12 Synthesis: Ethylenediamine-methyl acrylate adduct A 40 mL glass vial with a pressure relief cap and magnetic stirrer was charged with methyl acrylate (8.6 g, 100 mmol) and methanol (4 mL). Ethylenediamine (1.5 g, 25 mmol) was slowly added to the vial contents. A slight exothermic reaction was observed during the amine addition. The resulting solution was then placed in a block heater and stirred at 50 °C for seven hours. The progress of the reaction was monitored by 1H NMR spectroscopy. After complete conversion of the amine to a tetrasubstituted adduct, the methanol was distilled on a rotary evaporator to yield 9.3 g (92% molar yield) of a slightly viscous, light yellow adduct. Synthesis S13: Transesterification of methyl acrylate adduct with alkoxylated butanol The EO-terminated block copolymer prepared according to Synthesis S1 (10.3419 g, 13.99 mmol, 3.1 eq.), material prepared according to Synthesis S12 (1.8526 g, 4.58 mmol), and titanium isopropoxide (0.1733 g, 0.61 mmol, 13 mol%) were loaded into a 250 mL flask with a magnetic stir bar. The flask was sealed with hydrocarbon grease, purged with nitrogen, and then heated in an OptiTHERM® reaction block attached to an IKA magnetic heating plate with a setpoint temperature of 120 °C. After reaching 44.4 °C, a vacuum was applied to the contents of the flask using a mechanical pump with a trap. 1877122 of 47 The 84324-AR-NP solvent was intercalated and cooled with a dry ice / acetone bath. The mixing speed was adjusted from 50 to 300 rpm as the flask contents were heated to account for changes in viscosity. The flask contents were maintained at 118.9–122.3 °C for six hours under vacuum. The contents were then cooled and characterized by NMR to confirm reaction completion. Synthesis S14: Methyl acrylate and 3,3'-diamino-n-methyldipropylamine adduct Methyl acrylate (8.6 g, 100 mmol) and methanol (4 mL) were loaded into a glass vial with a magnetic stir bar and a pressure relief cap. N,N-bis(3-aminopropyl)methylamine (3.5 g, 24 mmol) was then slowly added to the vial contents. A slight exothermic reaction was observed during the amine addition. The resulting solution was then placed in a block heater and stirred at 50 °C for 4.5 hours. The progress of the reaction was monitored by 1H NMR spectroscopy. After complete conversion of the amine to a tetrasubstituted adduct, the methanol was distilled on a rotary evaporator to yield 11 g (93.6% molar yield) of a slightly viscous, pale yellow adduct. Synthesis S15: Transesterification of methyl acrylate adduct with alkoxylated butanol The EO-terminated block copolymer prepared according to Synthesis S1 (10.0539 g, 19.3866 mmol, 4.4 eq.), material prepared according to Synthesis S14 (2.1746 g, 4.4 mmol), and titanium isopropoxide (0.1694 g, 0.5960 mmol, 13.6 mol%) were loaded into a 250 mL flask with a magnetic stir bar. 1877122 of 47 The flask 84324-AR-NP was sealed with hydrocarbon grease, purged with nitrogen, and then heated in an OptiTHERM® reaction block attached to an IKA magnetic heating plate with a setpoint temperature of 120 °C. After reaching 86.4 °C, a vacuum was applied to the flask contents using a mechanical pump with an interposed solvent trap cooled with a dry ice / acetone bath. The mixing speed was adjusted from 50 to 300 rpm as the flask contents heated to account for changes in viscosity. The flask contents were held at 117.5–124.7 °C for nine hours under vacuum. The flask contents were then cooled and characterized by NMR to confirm reaction completion. Comparative Examples C1-C2 and Examples 1-4: Liquid laundry detergent The liquid laundry detergent formulations used in the cleaning tests in the following examples were prepared with the generic formulation as described in Table 2 with the cleaning enhancer as indicated in Table 3 neutralized to a pH of 8.5, and were prepared using standard liquid laundry formulation preparation procedures. Table 2 Ingredient Trade Name % by Weight Linear Alkylbenzene Sulfonate . . ____* Nacconal 90G 16.0 Sodium Laurethoxysulfate . . * Steol CS-460 4.0 Propylene Glycol — 5.0 Ethanol — 2.0 Sodium Citrate — 5.0 Non-ionic Surfactant Biosoft N25-7 5.0 Sodium Xylenesulfonate Stepanate SXS-93 5.5 Fatty Acid Prifac 7908a 3.0 1877122 of 47 84324-AR-NP Cleaning Booster — 5.0 Deionized Water — QS at 100 * ru · i λ xu Available from Stepan Company Available from Croda Table 3 Example Cleaning Enhancer Comparative Example C1 None Comparative Example C2 Alcohol Ethoxylate1 Example 1 Synthesis S5 Example 2 Synthesis S11 Example 3 Synthesis S10 Example 4 Synthesis S15 1 Available from Stepan Company under the trade name BIO-SOFT® N25-9 Primary cleaning performance The primary cleaning performance of the liquid laundry detergent formulations from Comparative Examples C1-C2 and Examples 1-4 was evaluated in a Launder-Ometer (SDL Atlas, model M228AA) at a set test temperature of 22°C using an 18-minute wash cycle. Twenty 1.2-liter containers were filled with 500 ml of water with a hardness adjusted to 100 ppm by mass and a molar ratio of 2:1 Ca:Mg for each run. The washed fabrics were rinsed in 300 ml of water with a hardness adjusted to 100 ppm (2:1 Ca / Mg) at room temperature for 5 minutes at 260 oscillations per minute in an Eberbach E6000 reciprocating agitator. The stained fabrics and soiling materials used in the tests were Testfabrics' PCS-S15 132 high-discrimination tallow BEY pigments and PCS-S-94 ASTM tallow / powder dyes sewn onto a pre-shrunk cotton interlock fabric. The cotton interlock size was 5 x 5 cm.The stained fabric samples were 2.5 x 3 cm. A 5 x 5 cm SBL-CFT soil ballast was added to each container. 1877122 of 47 84324-AR-NP provided reference soil to the washing solution. The total surfactant concentration in the washing solution was 200 ppm. Reflectance measurement and stain removal index (SRI) The Stain Removal Index (SRI) for each of the liquid laundry detergent formulations evaluated in the primary cleaning performance test was determined using the ASTM D4265-14 method. The average SRI taken from 8 fabric samples per condition (two samples per container, 4 containers) is provided in Table 4. The L*, a*, and b* values ​​of the stained fabrics were measured before and after washing using a Mach 5 Colour Consult spectrophotometer. The L*, a*, and b* values ​​for the unwashed, unstained polycotton fabric were calculated using the SRI calculations as follows: SRI = (AE(US-UF) ^(WS-UF) ΛΡ* ^pUS-UF) x 100 where US is the unwashed stained area, UF is the unwashed (unstained) fabric area, WS is the washed stained area, ΔE*(US.UF) is the color difference ΔE* between the unwashed stain and the unwashed fabric, and ΔE*(WS.UF) is the color difference ΔE* between the washed stain and the unwashed fabric. The value of ΔE* is calculated as AE* = (AL2+ Aa2+ Ab2 / 1877122 of 47 84324-AR-NP The ASRI values ​​provided in Table 4 give the difference between the SRI measured for the indicated example with respect to the SRI measured for Comparative Example C1. A positive value indicates an increase in dirt removal with respect to Comparative Example C1. Table 4 Example Cleaning Enhancer ΔSRI PCS-94 PCS-132 Comparative Example C2 Alcohol Ethoxylate1 4.37 2.65 Example 1 Synthesis S5 4.46 — Example 2 Synthesis S11 2.24 2.09 Example 3 Synthesis S10 2.58 1.76 Example 4 Synthesis S15 5.69 3.99 1Available from Stepan Company under the trade name BIO-SOFT® N25-9 Comparative Examples C3-C4 and Examples 5-7: Liquid laundry detergent The liquid laundry detergent formulation used in the cleaning tests in the following examples was prepared by combining 0.5 g of a standard liquid laundry detergent formulation with an adjusted pH of 8.5 as described in Table 5 with 1.5 g of a 1% by weight aqueous solution of the cleaning enhancer indicated in Table 6. Table 5 Ingredient Trade Name % by Weight Linear Alkylbenzene Sulfonate . . ____* Nacconal 90G 12 Sodium Laurethoxysulfate . . * Steol CS-460 2 Propylene Glycol — 3.5 Ethanol — 1.5 Deionized Water — QS a 100 * · i zs zk Available from Stepan Company a Available from The Dow Chemical Company 1877122 of 47 84324-AR-NP Table 6 Example Cleaning Enhancer Comparative Example C3 None Comparative Example C4 Alcohol Ethoxylate1 Example 5 Synthesis S8 Example 6 Synthesis S11 Example 7 Synthesis S10 1 Available from Stepan Company under the trade name BIO-SOFT® N25-9 Anti-redeposit The anti-redeposit performance of the combination of standard liquid laundry detergent + cleaning booster from Comparative Examples C3-C4 and Examples 5-7 was evaluated in a Terg-o-tometer Model 7243ES agitated at 90 cycles per minute under the conditions indicated in Table 7. Table 7 Parameter Settings Temperature 50 °C Water hardness 300 ppm, Ca2+ / Mg2+ = 2 / 1 Fabric types Cotton (C) Cotton interlock (CI) Cotton terry (CT) Polyester: cotton blend (PB) Polyester knit (PK) Polyester woven (PW) Two fabrics of each type in each container Wash time 60 minutes Rinse time 3 minutes Liquid laundry detergent dosage 0.5 g Cleaning booster 1.5 g of 1% wt aqueous solution Anti-redeposit soil 2.5 g / l of tallow powder 0.63 g / l of Redart clay Drying After the final rinse, the fabrics were dried in a food dehydrator at 50 °C for 2 hours and minutes. 1877122 of 47 84324-AR-NP The anti-redeposition performance was determined by calculating the ΔE measured with a MACH 5+ instrument (L, a & b). The results are shown in Table 8, where ΔE* agrees with the equation ΔE* = ΔEaw - ΔEbw where ΔEaw is measured from the fabrics after washing, and ΔEbw is measured from the fabrics before washing. A higher ΔE* corresponds to better anti-redeposition performance. Table 8 Example ΔE* CT CI CT PB PK PW Comparison of C3 9.61 18.80 16.56 12.61 24.62 16.87 Comparison of C4 10.22 19.15 21.06 12.27 23.80 14.99 Example 5 9.55 16.82 13.33 13.17 25.05 15.39 Example 6 7.48 15.68 15.27 13.28 24.03 17.17 Example 7 8.18 16.67 14.19 14.03 28.66 18.64 1877122 of 47 Alejandra Aoun - 27184140328 Digitally signed by PORTALTRAM ITES - INPI Date: 2022.07.14 17:51:27 -03:00 Reason: Digitally Signed by the INPI Location: Buenos Aires, Argentina 1877122

Claims

1. A liquid laundry detergent formulation, characterized in that it comprises: a liquid carrier; a cleaning surfactant; and a cleaning enhancer, wherein the cleaning enhancer is of Formula (I) (FORMULA 1) wherein b is 0 to 2; wherein c is 2 to 4; wherein each R is independently selected from the group consisting of a hydrogen, a C1-22 alkyl group, an R1, and a -CH2C(=O)R14 group; wherein R14 is of Formula (VI); and wherein each R1 is independently selected from the group consisting of Formula (II), Formula (III), Formula (IV), and Formula (V); (FORMULA 2) wherein the * indicates the point of attachment to Formula (I); wherein each R2 is independently selected from Formula (VI); (FORMULA 3) wherein the * indicates the point of attachment to Formula (I); wherein each R3 is independently in accordance with Formula (VI); and wherein each R4 is independently selected from the group consisting of a hydrogen and a methyl group;(FORMULA 4) wherein the * indicates the point of attachment to Formula (I); wherein each R 5 is independently according to Formula (VI); wherein f is 1 to 2; and wherein g is 2 to 10; (FORMULA 5) wherein the * indicates the point of attachment to Formula (I); and wherein each R 6 is independently according to Formula (VI); (FORMULA 6) wherein the * indicates the point of attachment to the associated base formula; wherein R 7 is selected from the group consisting of a hydrogen and a C1-22 alkyl group; wherein each R 8 and R 9 is independently selected from the group consisting of a hydrogen and a C1-2 alkyl group, provided that at least one of R 8 and R 9 is a hydrogen in each subunit a; and wherein a is 0 to 30, provided that a is 2 to 30 in a molar percentage of 70 to 100 of the occurrences of Formula (VI) in the cleaning enhancer. Eight claims follow;