Liquid Laundry Detergent Formulation

Abstract

Liquid laundry detergent formulation and washing method. This is a liquid laundry detergent formulation comprising: a liquid carrier; a cleaning surfactant and a cleaning enhancer polymer, wherein the cleaning enhancer polymer has structural units of a monoethylenically unsaturated carboxylic acid monomer; structural units of an ethylenically unsaturated monomer of formula (i), optionally, structural units of an ethylenically unsaturated monomer of formula (iii), and optionally, structural units of an ethylenically unsaturated monomer of formula (iv).

Description

Liquid Laundry Detergent Formulation

[001] 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 polymer having structural units of a monoethylenically unsaturated carboxylic acid monomer; ethylenically unsaturated structural units of formula (I) x a monomer optionally, ethylenically unsaturated units of formula (III) or (I); structural features of a monomer H b (III); and, optionally, ethylenically unsaturated structural units of formula (IV) R8um monomer

[002] o O---R7(IV). Liquid and gel laundry detergents that provide excellent overall cleaning for consumers are desirable. These laundry detergents typically include surfactants, among other components, to deliver cleaning benefits to the consumer. Petition 870260039332, dated 04 / 28 / 2026, page 13 / 22 / 32 desired. However, with increasing environmental sensitivity and rising material costs, there is a growing movement to reduce the use of surfactants in laundry detergents. Consequently, detergent manufacturers are seeking ways to reduce the amount of surfactant per unit dose of laundry detergent while maintaining overall cleaning performance.

[003] One approach to reducing the unit dose of surfactant is to incorporate polymers into liquid detergent formulations, as described by Boutique et al. in US Patent Application Publication No. 20090005288. Boutique et al. disclose a graft copolymer of polyethylene, polypropylene, or polybutylene oxide with vinyl acetate in a weight ratio of about 1:0.2 to about 1:10 for use in liquid or gel laundry detergent formulations with about 2 to about 20% by weight of surfactant.

[004] Nevertheless, there remains a continuing need for liquid laundry detergent formulations that exhibit maintained primary cleaning performance with a reduced surfactant load; preferably, while also providing enhanced anti-redeposition performance.

[005] The present invention provides a liquid laundry detergent formulation comprising: a liquid carrier; a cleaning surfactant and a cleaning enhancer polymer, wherein the cleaning enhancer polymer comprises: (a) 60 to 95% by weight, based on the dry weight of the cleaning enhancer polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer; (b) 5 to 40% by weight, based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (I) Petition 870210103899, dated 10 / 11 / 2021, page 14 / 49 / 32 (I) wherein X is selected from the group consisting of an oxygen atom and a sulfur atom; wherein R1 is a C2-4 alkylene group; wherein R2 is selected from the group consisting of a 2-(2-carboxyacrylamide)ethyl group, a vinyl group, an allyl group, an isopropenyl group, an acryloyl group, a methacryloyl group, a 2-hydroxy-3-(allyloxy)propyl group and a functional group of formula (II) R4-Y-R3- (II) wherein R3 is a C1-5 alkylene group; wherein Y is selected from the group consisting of an -O- and an -NR5-, wherein R5 is selected from the group consisting of a hydrogen and a C1-8 alkyl group; and wherein R4 is selected from the group consisting of a 2-hydroxy-3-(allyloxy)propyl group, a vinyl group, a methacryloyl group, an acryloyl group and a methacryloyloxyacetic group; (c) 0 to 20% by weight, based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (III) b (III) wherein A is selected from the group consisting of an O- and an NR5-; wherein each R6 is independently selected from the group consisting of a -CH2CH2O- group, a -CH2CH(CH3)O- group and a -CH2CH(CH2CH3)O- group; and wherein b is 2 to 20; (d) 0 to 5% by weight, based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (IV) Petition 870210103899, dated 10 / 11 / 2021, page 15 / 49 / 32 R8 R7(IV) wherein each R7 is independently selected from a -C1-4 alkyl group; and wherein each R8 is independently selected from the group consisting of a hydrogen atom and a methyl group.

[006] The present invention provides a liquid laundry detergent formulation comprising: 25 to 97.9% by weight, based on the weight of the liquid laundry detergent formulation, of a liquid carrier; 2 to 60% by weight, based on the weight of the liquid laundry detergent formulation, of a cleaning surfactant; and 0.1 to 15% by weight, based on the weight of the liquid laundry detergent formulation, of a cleaning enhancer polymer, wherein the cleaning enhancer polymer comprises: (a) 60 to 95% by weight, based on the dry weight of the cleaning enhancer polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer; (b) 5 to 40% by weight, based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (I) x (I) wherein X is selected from the group consisting of an oxygen atom and a sulfur atom; wherein R1 is a C2-4 alkylene group; wherein R2 is selected from the group consisting of a 2-(2-carboxyacrylamide)ethyl group, a vinyl group, an allyl group, an isopropenyl group, an acryloyl group, a methacryloyl group, a 2-hydroxy-3-(allyloxy)propyl group and a functional group of formula (II) R4-Y-R3- (II) Petition 870210103899, dated 10 / 11 / 2021, page 16 / 49 / 32 wherein R3 is a C1 5 alkylene group; wherein Y is selected from the group consisting of an -O- and an -NR5-, wherein R5 is selected from the group consisting of a hydrogen and a C1-8 alkyl group; and wherein R4 is selected from the group consisting of a 2-hydroxy-3-(allyloxy)propyl group, a vinyl group, a methacryloyl group, an acryloyl group and a methacryloyloxyacetic group; (c) 0 to 20% by weight, based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (III) o H (III) wherein A is selected from the group consisting of an O- and an NR5-; wherein each R6 is independently selected from the group consisting of a CH2CH2O- group, a CH2CH(CH3)O- group and a CH2CH(CH2CH3)O- group; and wherein b is 2 to 20; (d) 0 to 5% by weight, based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (IV) -----λ R8o < o---R7(IV) wherein each R7 is independently selected from a -C|-4 alkyl group; and wherein each R8 is independently selected from the group consisting of a hydrogen atom and a methyl group.

[007] The present invention provides a method for washing a cloth article of the present invention comprising: providing a soiled cloth article; providing a liquid laundry detergent formulation according to claim 1; providing wash water; and applying the wash water. Petition 870210103899, dated 10 / 11 / 2021, page 17 / 49 / 32 and the formulation of liquid laundry detergent for soiled cloth in order to provide a clean cloth article. DETAILED DESCRIPTION

[008] Surprisingly, liquid laundry detergent formulations with a cleaning-enhancing polymer, as described in this document, were found to significantly improve primary cleaning performance for powdered tallow, while maintaining good anti-redeposition performance for ground clay.

[009] Unless otherwise indicated, ratios, percentages, parts and the like are by weight. Percentages by weight (or % by weight) in the composition are percentages by dry weight, that is, excluding any water that may be present in the composition.

[0010] As used in this document, unless otherwise indicated, the terms “weight-average molecular weight” and “Mw” are used interchangeably to refer to weight-average molecular weight as measured in a conventional manner with gel permeation chromatography (GPC) and conventional standards such as polystyrene standards. GPC techniques are discussed in detail in Modern Size Exclusion Liquid Chromatography: Practice of Gel Permeation and Gel Filtration Chromatography, Second Edition, Striegel, et al., John Wiley & Sons, 2009. Weight-average molecular weights are reported in this document in Daltons.

[0011] The term structural units, as used in this document and the accompanying claims, refers to the remnant of the indicated monomer; thus, a structural unit of (meth)acrylic acid is illustrated: Petition 870210103899, dated 10 / 11 / 2021, page 18 / 49 / 32 OH where the dashed lines represent the attachment points to the polymer backbone and where R is a hydrogen for acrylic acid structural units and a -CH3 group for methacrylic acid structural units.

[0012] Preferably, the liquid laundry detergent formulation of the present invention comprises a liquid carrier (preferably 25 to 97.9% by weight (more preferably 50 to 94.5% by weight; even more preferably 62.5 to 91.75% by weight; even more preferably 70 to 89.9% by weight; most preferably 76 to 88% by weight), based on the weight of the liquid laundry detergent formulation of the liquid carrier); a cleaning surfactant (preferably 2 to 60% by weight (more preferably 5 to 40% by weight; even more preferably 7.5 to 30% by weight; even more preferably 10 to 25% by weight; most preferably 10 to 20% by weight), based on the weight of the liquid laundry detergent formulation of the cleaning surfactant); and a cleaning enhancer polymer (preferably 0.1 to 15% by weight; more preferably 0.5 to 10% by weight; even more preferably 0.75 to 7.5% by weight; with even more preference, 1 to 5% by weight);most preferably 2 to 4% by weight), based on the weight of the liquid laundry detergent formulation of the cleaning enhancer polymer), wherein the cleaning enhancer polymer comprises: (a) structural units of a monoethylenically unsaturated carboxylic acid monomer; (b) structural units of an ethylenically unsaturated monomer of formula (I); Petition 870210103899, dated 10 / 11 / 2021, page 19 / 49 / 32 wherein X is selected from the group consisting of an oxygen atom and a sulfur atom; wherein R1 is a C2-4-alkylene group; wherein R2 is selected from the group consisting of a 2-(2-carboxyacrylamide)ethyl group, a vinyl group, an allyl group, an isopropenyl group, an acryloyl group, a methacryloyl group, a 2-hydroxy-3-(allyloxy)propyl group and a functional group of formula (II) R4-Y-R3- (II) wherein R3 is a C1-5 alkylene group; wherein Y is selected from the group consisting of an -O- and an -NR5-, wherein R5 is selected from the group consisting of a hydrogen and a C1-8 alkyl group; and wherein R4 is selected from the group consisting of a 2-hydroxy-3-(allyloxy)propyl group, a vinyl group, a methacryloyl group, an acryloyl group and a methacryloyloxyacetic group; (c) optionally, structural units of an ethylenically unsaturated monomer of formula (III) (III) wherein A is selected from the group consisting of an O- and an NR5-; wherein each R6 is independently selected from the group consisting of a CH2CH2O- group, a CH2CH(CH3)O- group and a CH2CH(CH2CH3)O- group; and wherein b is 2 to 20; and (d) optionally, structural units of an ethylenically unsaturated monomer of formula (IV) Petition 870210103899, dated 10 / 11 / 2021, page 20 / 49 / 32 R8 R7(IV) wherein each R7 is independently selected from a -C1-4 alkyl group; and wherein each R8 is independently selected from the group consisting of a hydrogen atom and a methyl group.

[0013] 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 50 to 94.5% by weight; more preferably 62.5 to 91.75% by weight; even more preferably 70 to 89.9% by weight; most preferably 76 to 88% 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 50 to 94.5% by weight; more preferably 62.5 to 91.75% by weight; even more preferably 70 to 89.9% by weight; most preferably 76 to 88% by weight), based on the weight of the liquid laundry detergent formulation, of a liquid carrier; wherein the liquid carrier comprises water. Most preferably, the liquid laundry detergent formulation of the present invention comprises 25 to 97.9% by weight (preferably 50 to 94.5% by weight; more preferably 62.5 to 91.75% by weight; even more preferably 70 to 89.9% by weight; most preferably 76 to 88% by weight), based on the weight of the liquid laundry detergent formulation, of a liquid carrier; wherein the liquid carrier is water.

[0014] Preferably, the liquid carrier may include water-miscible liquids such as C1-3 alkanolamines and C1-3 alkanols. More Petition 870210103899, dated 10 / 11 / 2021, page 21 / 49 / 32 preferably, the liquid carrier includes 0 to 8% by weight (preferably 0.2 to 8% by weight; more preferably 0.5 to 5% by weight), 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 alkanolamines, C1-3 alkanols and mixtures thereof.

[0015] 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 (more preferably, 5 to 40% by weight; even more preferably, 7.5 to 30% by weight; even more preferably, 10 to 25% by weight; most preferably, 10 to 20% by weight), based on the weight of the liquid laundry detergent formulation, of a cleaning surfactant.More preferably, the liquid laundry detergent formulation of the present invention comprises: 2 to 60% by weight (more preferably, 5 to 40% by weight; even more preferably, 7.5 to 30% by weight; even more preferably, 10 to 25% by weight; most preferably, 10 to 20% 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.More preferably, the liquid laundry detergent formulation of the present invention comprises: 2 to 60% by weight (preferably 5 to 40% by weight; even more preferably 7.5 to 30% by weight; even more preferably 10 to 25% by weight; most preferably 10 to 20% 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 that includes an anionic surfactant and a nonionic surfactant. Most preferably, the liquid detergent formulation for... Petition 870210103899, dated 10 / 11 / 2021, page 22 / 49 / 32 The clothes of the present invention comprise: 2 to 60% by weight (more preferably, 5 to 40% by weight; even more preferably, 7.5 to 30% by weight; even more preferably, 10 to 25% by weight; most preferably, 10 to 20% 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 alkylbenzene sulfonate, a sodium lauryl ethoxysulfate and a nonionic ethoxylated alcohol.

[0016] Anionic surfactants include alkyl sulfates, alkylbenzene sulfates, alkylbenzene sulfonates, alkyl polyethoxy sulfates, alkoxylated alcohols, paraffin sulfonates, olefin sulfonates, alpha sulfocarboxylates, alpha sulfocarboxylate esters, glyceryl ether alkyl sulfonates, fatty acid sulfates, fatty acid sulfonates, fatty acid ester sulfonates, alkylphenols, phenol polyethoxy ether alkyl sulfates, 2-acryloxy-alkane-1-sulfonic acid, 2-acryloxy-alkane-1-sulfonate, beta-alkyloxyalkanesulfonic acid, beta-alkyloxyalkanesulfonate, amine oxides and mixtures thereof. Preferred anionic surfactants include C8-20 alkylbenzenesulfates, C8-20 alkylbenzenesulfonic acid, C8-20 alkylbenzenesulfonate, paraffinosulfonic acid, paraffinosulfonate, alpha-olefin sulfonic acid, alpha-olefin sulfonate, alkoxylated alcohols, C8-20 alkylphenols, amine oxides, fatty acid sulfonates, fatty acid ester sulfonates, C8-10 alkylpolyethoxysulfates and mixtures thereof. More preferred anionic surfactants include C12-16 alkylbenzenesulfonic acid, C12-16 alkylbenzenesulfonate, C12-18 paraffinosulfonic acid, C12-18 paraffinosulfonate, C12-16 alkylpolyethoxysulfate and mixtures thereof.

[0017] Nonionic surfactants include alkoxylates (e.g., polyglycol ethers, fatty alcohol polyglycol ethers, ethers of Petition 870210103899, dated 10 / 11 / 2021, page 23 / 49 / 32 alkylphenol polyglycol, terminally capped polyglycol ethers, mixed ethers, hydroxyl-mixed ethers, fatty acid polyglycol esters and mixtures thereof. Preferred nonionic surfactants include fatty alcohol polyglycol ethers. More preferred nonionic surfactants include secondary alcohol ethoxylates, ethoxylated 2-ethylhexanol, ethoxylated seed oils, butanol-capped ethoxylated 2-ethylhexanol and mixtures thereof. More preferred nonionic surfactants include secondary alcohol ethoxylates.

[0018] Cationic surfactants include quaternary surface-active compounds. Preferred cationic surfactants include quaternary surface-active compounds having at least one of an ammonium group, a sulfonium group, a phosphonium group, an iodinium group, and an arsenic group. More preferred cationic surfactants include at least one of dialkyldimethylammonium chloride and alkyldimethylbenzylammonium chloride. Even more preferred cationic surfactants include at least one of C16-18dialkyldimethylammonium chloride, C8-18alkyldimethylbenzylammonium chloride, and dimethyldiseiboammonium chloride. The most preferred cationic surfactant includes dimethyldiseiboammonium chloride.

[0019] Amphoteric surfactants include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amine oxides, acylated amino acids, derivatives of aliphatic quaternary ammonium compounds, and mixtures thereof. Preferred amphoteric surfactants include derivatives of aliphatic quaternary ammonium compounds. More preferred amphoteric surfactants include derivatives of aliphatic quaternary ammonium compounds with a long-chain group having 8 to 18 carbon atoms. Still more preferred amphoteric surfactants include at least one of C12-14 alkyldimethylamine oxide, 3-(N,N-dimethyl-N-hexadecyl-ammonium)propane-1-sulfonate, Petition 870210103899, dated 10 / 11 / 2021, page 24 / 49 / 32 3-(N,N-dimethyl-N-hexadecylammonium)-2-hydroxypropane-1-sulfonate. Amphoteric surfactants of greatest preference include at least one of C12-14 alkyldimethylamine oxides.

[0020] Preferably, the liquid laundry detergent formulation of the present invention comprises: a cleaning enhancer polymer. More preferably, the liquid laundry detergent formulation of the present invention comprises: 0.1 to 15% by weight (preferably 0.5 to 10% by weight; more preferably 0.75 to 7.5% by weight; even more preferably 1% to 5% by weight; most preferably 2 to 4% by weight), based on the weight of the liquid laundry detergent formulation, of a cleaning enhancer polymer. More preferably, the liquid laundry detergent formulation of the present invention comprises: 0.1 to 15% by weight (preferably 0.5 to 10% by weight; more preferably 0.75 to 7.5% by weight; even more preferably 1 to 5% by weight; most preferably 2 to 4% by weight), based on the weight of the liquid laundry detergent formulation, of a cleaning-enhancing polymer;wherein the cleaning enhancer polymer comprises: (a) 60 to 95% by weight (preferably 70 to 92% by weight; more preferably 75 to 91% by weight; even more preferably 80 to 90% by weight; most preferably 83 to 87% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer; (b) 5 to 40% by weight (preferably 8 to 30% by weight; more preferably 9 to 25% by weight; even more preferably 10 to 20% by weight; most preferably 13 to 17% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (I); Petition 870210103899, dated 10 / 11 / 2021, page 25 / 49 / 32 wherein X is selected from the group consisting of an oxygen atom and a sulfur atom; wherein R1 is a C2-4-alkylene group; wherein R2 is selected from the group consisting of a 2-(2-carboxyacrylamide)ethyl group, a vinyl group, an allyl group, an isopropenyl group, an acryloyl group, a methacryloyl group, a 2-hydroxy-3-(allyloxy)propyl group and a functional group of formula (II) R4-Y-R3- (II) wherein R3 is a C1-5 alkylene group; wherein Y is selected from the group consisting of an -O- and an -NR5-, wherein R5 is selected from the group consisting of a hydrogen and a C1-8 alkyl group; and wherein R4 is selected from the group consisting of a 2-hydroxy-3-(allyloxy)propyl group, a vinyl group, a methacryloyl group, an acryloyl group and a methacryloyloxyacetic group; (c) 0 to 20% by weight (preferably 0 to 15% by weight; more preferably 0 to 10% by weight; even more preferably 0 to 5% by weight; most preferably 0% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (III)(III) b (III) wherein A is selected from the group consisting of an O- and an NR5-; wherein each R6 is independently selected from the group consisting of a CH2CH2O- group, a CH2CH(CH3)O- group and a CH2CH(CH2CH3)O- group; and wherein b is 2 to 20; (d) 0 to 5% by weight Petition 870210103899, of 10 / 11 / 2021, page 26 / 49 / 32 (preferably 0 to 3% by weight; more preferably 0 to 2% by weight; most preferably 0% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (IV) -----λ R8o----( o---R7(IV) wherein each R7 is independently selected from a -C1-4alkyl group; and wherein each R8 is independently selected from the group consisting of a hydrogen atom and a methyl group.

[0021] Preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention has a weight-average molecular weight, MW, of 500 to 100000 Daltons (preferably 2000 to 50000 Daltons; more preferably 5000 to 25000 Daltons; most preferably 10000 to 20000 Daltons).

[0022] Preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 60 to 95% by weight (preferably 70 to 92% by weight; more preferably 75 to 91% by weight; even more preferably 80 to 90% by weight; most preferably 83 to 87% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer. More preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 60 to 95% by weight (preferably 70 to 92% by weight; more preferably 75 to 91% by weight; even more preferably 80 to 90% by weight; most preferably 83 to 87% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of an acid monomer. Petition 870210103899, dated 10 / 11 / 2021, page 27 / 49 / 32 monoethylenically unsaturated carboxylic acid; wherein the monoethylenically unsaturated carboxylic acid monomer is selected from monoethylenically unsaturated monomers containing at least one carboxylic acid group.Even more preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 60 to 95% by weight (preferably 70 to 92% by weight; more preferably 75 to 91% by weight; even more preferably 80 to 90% by weight; most preferably 83 to 87% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer; wherein the monoethylenically unsaturated carboxylic acid monomer is selected from the group consisting of (meth)acrylic acid, (meth)acryloxypropionic acid, itaconic acid, aconitic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, citraconic acid, maleic anhydride, monomethyl maleate, monomethyl fumarate, monomethyl itaconate and other derivatives such as anhydrides, amides and esters.More preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 60 to 95% by weight (preferably 70 to 92% by weight; more preferably 75 to 91% by weight; even more preferably 80 to 90% by weight; most preferably 83 to 87% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer; wherein the monoethylenically unsaturated carboxylic acid monomer is selected from the group consisting of acrylic acid, methacrylic acid and mixtures thereof. Even more preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 60 to 95% by weight (preferably 70 to 92% by weight; more. Petition 870210103899, dated 10 / 11 / 2021, page 28 / 49 / 32 preferably, 75 to 91% by weight; even more preferably, 80 to 90% by weight; most preferably, 83 to 87% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer; wherein the monoethylenically unsaturated carboxylic acid core monomer includes acrylic acid.Most preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 60 to 95% by weight (preferably 70 to 92% by weight; more preferably 75 to 91% by weight; even more preferably 80 to 90% by weight; most preferably 83 to 87% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer; wherein the monoethylenically unsaturated carboxylic acid core monomer is acrylic acid.

[0023] Preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 60 to 95% by weight (preferably 70 to 92% by weight; more preferably 75 to 91% by weight; even more preferably 80 to 90% by weight; most preferably 83 to 87% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer; wherein the structural units of the monoethylenically unsaturated carboxylic acid monomer are structural units of formula (V) OH (V) where each R9 is independently selected from a hydrogen and a -CH3 group (preferably a hydrogen). More Petition 870210103899, dated 10 / 11 / 2021, page 29 / 49 / 32 preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 60 to 95% by weight (preferably 70 to 92% by weight; more preferably 75 to 91% by weight; even more preferably 80 to 90% by weight; most preferably 83 to 87% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer; wherein the structural units of the monoethylenically unsaturated monocarboxylic acid monomer are structural units of formula (V), wherein each R9 is independently selected from a hydrogen and a -CH3 group; where R9 is hydrogen in 50 to 100 mol% (preferably 75 to 100 mol%; more preferably 90 to 100 mol%; even more preferably 98 to 100 mol%);with maximum preference, 100% by mol) of the structural units of formula (V) in the cleaning enhancer polymer.;

[0024] Preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 5 to 40% by weight (preferably 8 to 30% by weight; more preferably 9 to 25% by weight; even more preferably 10 to 20% by weight; most preferably 13 to 17% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (I) wherein X is selected from the group consisting of an oxygen atom and a sulfur atom (preferably, an oxygen atom); wherein R1 is a C2-4 alkylene group (preferably, R1 is selected from the group consisting of a -CH2CH2CH2- group, a -CH(CH3)CH2- group and a -CH2CH2- group; more preferably, R1 is Petition 870210103899, of 10 / 11 / 2021, p. 30 / 49 / 32 a group -CH2CH2-); wherein R2 is selected from the group consisting of a 2-(2-carboxyacrylamide)ethyl group, a vinyl group, an allyl group, an isopropenyl group, an acryloyl group, a methacryloyl group, a 2-hydroxy-3-(allyloxy)propyl group and a functional group of formula (II) R4-Y-R3- (II) wherein R3 is a C1-5 alkylene group (preferably a C2-4 alkylene group; more preferably, R3 is selected from the group consisting of a -CH2CH2CH2- group, a -CH(CH3)CH2- group and a CH2CH2- group; most preferably, R3 is a CH2CH2- group); wherein Y is selected from the group consisting of an -O- and an -NR5 (preferably, -O-), wherein R5 is selected from the group consisting of a hydrogen and a C1-8 alkyl group (preferably a C1-4 alkyl group; more preferably, a C1-2 alkyl group; most preferably, a methyl group); and wherein R4 is selected from the group consisting of a 2-hydroxy-3-(allyloxy)propyl group, a vinyl group, a methacryloyl group, an acryloyl group and a methacryloyloxyacetic group.

[0025] Preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 5 to 40% by weight (preferably 8 to 30% by weight; more preferably 9 to 25% by weight; even more preferably 10 to 20% by weight; most preferably 13 to 17% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (I); wherein the structural units of the ethylenically unsaturated monomer of formula (I) are of formula (Ia) Petition 870210103899, dated 10 / 11 / 2021, page 31 / 49 / 32 (Ia) wherein Y is selected from the group consisting of an O- and an -NR5- (preferably an -O-), wherein R5 is selected from the group consisting of a hydrogen and a C1-8 alkyl group (preferably a C1-4 alkyl group, more preferably a group C1-2 alkyl; most preferably, a methyl group); wherein R1 is selected from the group consisting of a -CH2CH2CH2- group, a -CH(CH3)CH2- group and a -CH2CH2- group (preferably, a CH2CH2- group); wherein R3 is a C1-5 alkylene group (preferably, a C2-4 alkylene group; more preferably, R3 is selected from the group consisting of a -CH2CH2CH2- group, a -CH(CH3)CH2- group and a CH2CH2- group; most preferably, R3 is a CH2CH2- group); and wherein X is selected from the group consisting of an oxygen atom and a sulfur atom (preferably, an oxygen atom).

[0026] Preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 0 to 20% by weight (preferably 0 to 15% by weight; more preferably 0 to 10% by weight; even more preferably 0 to 5% by weight; most preferably 0% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (III)(III) (III) where A is selected from the group consisting of a Petition 870210103899, dated 10 / 11 / 2021, page 32 / 49 / 32 O- and an -NR5- (preferably an -O-), wherein R5 is selected from the group consisting of a hydrogen and a C1-8 alkyl group (preferably a C1-4 alkyl group, more preferably a C1-2 alkyl group; most preferably a methyl group); wherein each R6 is independently selected from the group consisting of a -CH2CH2O- group, a -CH2CH(CH3)O- group and a -CH2CH(CH2CH3)O- group (preferably a -CH2CH2O- group and a -CH2CH(CH3)O- group; most preferably a -CH2CH2O- group); and wherein b is 2 to 20 (preferably 2 to 10; more preferably 2 to 7; most preferably 2 to 4).

[0027] Preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 0 to 5% by weight (preferably 0 to 3% by weight; more preferably 0 to 2% by weight; most preferably 0% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (IV) -----λ R8o----( o---R7(IV) wherein each R7 is independently selected from a -C1-4 alkyl group (preferably a methyl group, an ethyl group and a butyl group; more preferably, an ethyl group and a butyl group; most preferably, an ethyl group) and wherein each R8 is independently selected from the group consisting of a hydrogen atom and a methyl group (preferably, a hydrogen). More preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 0 to 5% by weight (preferably 0 to 3% by weight; more preferably 0 to 2% Petition 870210103899, dated 10 / 11 / 2021, page 33 / 49 / 32 in weight; most preferably 0% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (IV), wherein R7 is an ethyl group in 75 to 100 mol% (preferably 90 to 100 mol%; more preferably 98 to 100 mol%, most preferably 100 mol%) of structural units of formula (IV) in the cleaning enhancer polymer and wherein R8 is a hydrogen in 75 to 100 mol% (preferably 90 to 100 mol%; more preferably 98 to 100 mol%; most preferably 100 mol%) of the structural units of formula (IV) in the cleaning enhancer polymer.

[0028] Preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention contains <1% by weight (preferably, <0.5% by weight; more preferably, <0.2% by weight; even more preferably, <0.1% by weight; most preferably, <0.01% by weight; most preferably, <o limite detectável), com base no peso seco do aditivo líquido para roupas, de um polímero de álcool vinílico (PVA).More preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention contains <1% by weight (preferably, <0.5% by weight; more preferably, <0.2% by weight; even more preferably, <0.1% by weight; even more preferably, <0.01% by weight; most preferably, <o limite detectável), com base no peso seco do aditivo líquido para roupas, de um polímero de álcool vinílico (PVA); em que o polímero de álcool vinílico tem um grau de saponificação de 80 a 100% em mol (determinado usando-se o método especificado em JIS K 6726 (1994)). Com máxima preferência, o polímero intensificador de limpeza usado na formulação de detergente líquido para roupas da presente invenção contém <1% em peso (preferencialmente, <0,5% em peso; mais preferencialmente, <0,2% em peso; ainda mais preferencialmente, <0,1% em. Petition 870210103899, dated 10 / 11 / 2021, page 34 / 49 / 32 weight; with even greater preference, <0.01% by weight; with maximum preference, <o limite detectável), com base no peso seco do aditivo líquido para roupas, de um polímero de álcool vinílico (PVA); em que o polímero de álcool vinílico pode incluir um polímero de álcool vinílico modificado. O polímero de álcool vinílico modificado inclui PVA modificado com ânion (por exemplo, PVA modificado com grupo de ácido sulfônico e PVA modificado com grupo de ácido carboxílico); PVA modificado com cátion (por exemplo, PVA modificado com grupo amina quaternária); PVA modificado com amida; PVAs modificados com grupo acetoacetila; PVA modificado com diacetona acrilamida e PVA modificado com etileno.

[0029] Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a structuring 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 structuring agent.Most 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 structuring agent; wherein the structuring agent is composed of non-polymeric crystalline hydroxyfunctional materials capable of forming thread-like structuring systems throughout the liquid laundry detergent formulation when crystallized in situ.

[0030] 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 10% in Petition 870210103899, dated 10 / 11 / 2021, page 35 / 49 / 32 weight (preferably 0.1 to 7.5% by weight; more preferably 0.2 to 5% by weight; most preferably 0.5 to 2.5% by weight), based on the weight of the liquid laundry detergent formulation, from a hydrotrope.More preferably, the liquid laundry detergent formulation of the present invention optionally further comprises: 0 to 10% by weight (preferably 0.1 to 7.5% by weight; more preferably 0.2 to 5% by weight; most preferably 0.5 to 2.5% 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 alkanol ammonium salts of xylenesulfonic acid, toluenesulfonic acid, ethylbenzenesulfonic acid, naphthalenesulfonic acid and cumenesulfonic acid; salts thereof and mixtures thereof.Most preferably, the liquid laundry detergent formulation of the present invention further comprises: 0 to 10% by weight (preferably 0.1 to 7.5% by weight; more preferably 0.2 to 5% by weight; most preferably 0.5 to 2.5% 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.

[0031] 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 Petition 870210103899, dated 10 / 11 / 2021, page 36 / 49 / 32 weight of the liquid laundry detergent formulation, of a fragrance.

[0032] Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a booster. 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 a booster. Most 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 a booster; wherein the booster is selected from the group consisting of inorganic boosters (e.g., tripolyphosphate, pyrophosphate); alkali metal carbonates; borates; bicarbonates; hydroxides; zeolites;citrates (e.g., sodium citrate); polycarboxylates; monocarboxylates; aminotrismethylenephosphonic acid; salts of aminotrismethylenephosphonic 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.

[0033] 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 Petition 870210103899, dated 10 / 11 / 2021, page 37 / 49 / 32 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 coacervation polymer (for example, cationic hydroxyethylcellulose; polyquaternary polymers and combinations thereof).

[0034] Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a pH adjusting agent. More 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 sodium carbonate) and potassium hydroxide; sodium bicarbonate; sodium silicate; ammonium hydroxide; and organic bases (e.g., mono-, di- or triethanolamine; and 2-dimethylamino-2-methyl-1-propanol (DMAMP)). The pH adjusting acids include mineral acids (e.g., hydrochloric acid, phosphoric acid and sulfuric acid) and organic acids (e.g., acetic acid).

[0035] Preferably, the liquid laundry detergent formulation of the present invention contains <1% by weight (preferably, <0.5% by weight; more preferably, <0.2% by weight; even more preferably, <0.1% by weight; with even greater preference, <0.01% by weight; most preferably, <o limite detectável), com base no peso seco do aditivo líquido para roupas, de um polímero de álcool vinílico (PVA).

[0036] Preferably, the method for washing a cloth article of the present invention comprises: providing a soiled cloth article (preferably, wherein the soiled cloth article is soiled with at least one of clay and used motor oil; more preferably, wherein the Petition 870210103899, dated 10 / 11 / 2021, page 38 / 49 / 32 soiled cloth article is soiled with used motor oil) (preferably, wherein the soiled cloth article is stained cotton; more preferably, wherein the soiled cloth article is cotton stained with used motor oil); provide a liquid laundry detergent formulation of the present invention; provide washing water; and apply the washing water and the liquid laundry detergent formulation to the soiled cloth in order to provide a clean cloth article.More preferably, the method for washing a cloth article of the present invention comprises: providing a soiled cloth article (preferably, wherein the soiled cloth article is soiled with at least one of clay and used motor oil; more preferably, wherein the soiled cloth article is soiled with used motor oil) (preferably, wherein the soiled cloth article is a stained cotton; more preferably, wherein the soiled cloth article is cotton stained with used motor oil); providing a liquid laundry detergent formulation of the present invention; providing washing water; providing rinsing water; applying the washing water and the liquid laundry detergent formulation to the soiled cloth to provide a clean cloth article; and then applying the rinsing water to the clean cloth article to remove the liquid laundry detergent formulation from the clean cloth article.

[0037] Some embodiments of the present invention will, for now, be described in detail in the following Examples. SYNTHESIS S1: POLYMER 1

[0038] A two-liter round-bottom flask, equipped with a mechanical stirrer, heating mantle, thermocouple, condenser, and inlets for the addition of monomer (or monomers), initiator, and chain regulator, was charged with deionized water (206.25 g). The contents of the flask were then stirred and heated to 72 °C. Once the contents of the flask reached the reaction temperature of 72 °C, 0.15% of an aqueous ferrous sulfate heptahydrate promoter solution (2.5 g) was added, followed by Petition 870210103899, dated 10 / 11 / 2021, page 39 / 49 / 32 Sodium metabisulfite (SMBS) (0.84 g) dissolved in deionized water (5.25 g) as a pre-charge. Then, separate feeds were made to the flask as follows: Co-feeding of the primer: feed the flask with sodium persulfate (0.96 g) dissolved in deionized water (22.5 g) for 95 minutes.

[0039] Chain transfer agent (CTA) co-feeding: feed the flask with sodium metabisulfite (19.42 g) dissolved in deionized water (45 g) for 80 minutes.

[0040] Monomer 1 co-feeding: feed the bottle with a monomer solution containing glacial acrylic acid (240 g) and polyethylene glycol methacrylate (PEGMA 360) (30 g) for 90 minutes.

[0041] Monomer 2 co-feeding: feed the flask with dimethylaminoethyl methacrylate (DMAEMA) (30 g) for 90 minutes.

[0042] After the completion of the co-feedings, deionized water (17 g) was added as a rinse. The contents of the vial were held at 72 °C for 10 minutes. At the end of the holding time, two sequential injection solutions were added to the vial with a 5-minute holding time between injection additions. Both injections comprised sodium persulfate (0.39 g) in deionized water (5.25 g) and were added over 10 minutes. After the second injection addition, the contents of the vial were then held at 72 °C for 20 minutes. At the end of the final holding time, the contents of the vial were cooled below 50 °C. Then, 50% of an aqueous sodium hydroxide solution (110 g) was added to the contents of the vial slowly through an addition funnel, while maintaining the temperature below 60 °C.After the addition of the aqueous sodium hydroxide solution, 35% of an aqueous hydrogen peroxide scavenging solution (2.9 g) was added to the contents of the vial. No residual bisulfite was detected, followed by 50% of a sodium hydroxide solution. Petition 870210103899, dated 10 / 11 / 2021, page 40 / 49 / 32 aqueous (100 g) were added to the contents of the flask, maintaining the temperature below 60 °C. A final rinse with deionized water (20 g) was then added through the addition funnel to the contents of the flask. The contents of the flask were then cooled to <35 °C. The polymeric product had a solids content of 45.1%, a pH of 6.46, and a Brookfield viscosity of 1030 mPa·s (1030 cps). The residual monomer was measured below 25 ppm. The final weight-average molecular weight, Mw, as measured by Gel Permeation Chromatography was 6783 Daltons. S2 SYNTHESIS: POLYMER 2

[0043] A two-liter round-bottom flask, equipped with a mechanical stirrer, heating mantle, thermocouple, condenser, and inlets for the addition of monomer(s), initiator, and chain regulator, was charged with deionized water (206.25 g). The contents of the flask were then adjusted to be stirred and heated to 72 °C. Once the contents of the flask reached the reaction temperature of 72 °C, 0.15% of an aqueous ferrous sulfate heptahydrate promoter solution (2.5 g) was added to the contents of the flask, followed by the addition of sodium metabisulfite (SMBS) (1.13 g) dissolved in deionized water (5.25 g) as a precharge. Separate feeds were then made into the flask as follows: Co-feeding of the initiator: feed the flask with sodium persulfate (1.55 g) dissolved in deionized water (30 g) for 95 minutes.

[0044] Co-feeding of the chain transfer agent (CTA): feed the flask with sodium metabisulfite (25.87 g) dissolved in deionized water (60 g) for 80 minutes.

[0045] Monomer co-feeding: the flask was fed with a monomer solution containing glacial acrylic acid (255 g) and 2-(2-oxoimidazolidin-1-yl)ethyl methacrylate (90 g) for 90 minutes.

[0046] After completion of co-feeding, deionized water (15 g) Petition 870210103899, dated 10 / 11 / 2021, page 41 / 49 / 32, was added as a rinse. The contents of the vial were kept at 72°C for 10 minutes. At the end of the holding time, two sequential injection solutions were added to the vial with a 5-minute holding time between injection additions. Both injections comprised sodium persulfate (0.39 g) in deionized water (8.0 g) and were added over 10 minutes. After the second injection addition, the contents of the vial were then kept at 72°C for 20 minutes. At the end of the final holding time, the contents of the vial were cooled below 50°C. Then, 50% of an aqueous sodium hydroxide solution (105 g) was added to the contents of the vial slowly through an addition funnel, while maintaining the temperature below 60°C. After the addition of the aqueous sodium hydroxide solution, 30% of an aqueous hydrogen peroxide scavenging solution (5.2 g) was added to the contents of the flask.With no residual bisulfite detected, 50% of an aqueous sodium hydroxide solution (106 g) was added to the contents of the flask, maintaining the temperature below 60 °C. A final rinse with deionized water (15 g) was then added through the addition funnel to the contents of the flask. The contents of the flask were then cooled to <35 °C. The polymeric product had a solids content of 42.5%, a pH of 6.16, and a Brookfield viscosity of 1170 mPa·s (1170 cps). Residual monomer was measured below 50 ppm. The final weight-average molecular weight, Mw, as measured by Gel Permeation Chromatography was 15488 Daltons; and the number-average molecular weight, Mn, was 4520 Daltons. COMPARATIVE EXAMPLES C1-C2 AND EXAMPLE 1: LIQUID LAUNDRY DETERGENT

[0047] The liquid laundry detergent formulations used in the cleaning tests in the subsequent Examples were prepared with the generic formulation, as described in TABLE 1, and with the cleaning enhancer polymer, as observed in Table 2, and were Petition 870210103899, dated 10 / 11 / 2021, page 42 / 49 / 32 prepared by standard clothing liquid formulation preparation procedures. TABLE 1 Ingredient Trade Name % by weight Linear alkylbenzene sulfonate Nacconal 90G* 8.0 Sodium lauryl ethoxysulfate Steol CS-460* 2.0 Non-ionic surfactant Biosoft N25-7* 4.0 Cleaning enhancer polymer -- 3.0 Deionized water -- QS a 100 * available from Stepan Company TABLE 2 Example Cleaning Enhancer Polymer Comparative Example C1 ethoxylated poly(ethyleneimine)1 Comparative Example C2 Polymer 1 1 Polymer 2 1 available from BASF under the trade name Sokolan™ HP-20 PRIMARY CLEANING PERFORMANCE

[0048] The primary cleaning performance of the liquid laundry detergent formulations from Comparative Examples C1-C2 and Example 1 was evaluated in a Model TOM-52-A Tergotometer, available from SR Lab Instruments (6 x 1 l wells) agitated at 90 cycles per minute under the conditions observed in Table 3. TABLE 3 Parameter Context Temperature 15 °C Water hardness 200 ppm, Ca / Mg = 2 / 1 Cloth types (3 in each well) Stained cotton 400 Stains Clay, motor oil and tallow powder (purchased from Scientific Services S / D, Inc.) Washing time 16 minutes Rinsing time 3 minutes Liquid laundry detergent dosage 0.5 g / l

[0049] The soil removal index (SRI) was calculated using the ASTM D4265-14 method. The ΔSRI was determined with reference to a control detergent with the same surfactant concentrations, without the cleaning enhancer. The results are provided in Table 4. TABLE 4 Petition 870210103899, dated 10 / 11 / 2021, page 43 / 49 / 32 Example ASRI stain: Ground clay, Motor oil, Tallow powder. Ex. Comp. C1 +8 +5 +1 Ex. Comp. C2 +8 +5 +3 Ex. 1 +7 +1 +5

Claims

1. Liquid laundry detergent formulation, characterized in that it comprises: a liquid carrier; a cleaning surfactant; and a cleaning enhancer polymer, wherein the cleaning enhancer polymer comprises: (a) 60 to 95% by weight, based on the dry weight of the cleaning enhancer polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer; (b) 5 to 40% by weight, based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (I) (I) wherein X is selected from the group consisting of an oxygen atom and a sulfur atom; wherein R1 is a C 2-4 alkylene group;wherein R2 is selected from the group consisting of a 2-(2-carboxyacrylamide)ethyl group, a vinyl group, an allyl group, an isopropenyl group, an acryloyl group, a methacryloyl group, a 2-hydroxy-3-(allyloxy)propyl group and a functional group of formula (II) R4-Y-R3- (II) wherein R3 is a C1-5 alkylene group; wherein Y is selected from the group consisting of an O- and an -NR5-, wherein R5 is selected from the group consisting of a hydrogen and a C1-8 alkyl group; and wherein R4 is selected from the group consisting of Petition 870260039332, dated 28 / 04 / 2026, p. 14 / 22 2 / 4 a 2-hydroxy-3-(allyloxy)propyl, a vinyl group, a methacryloyl group, an acryloyl group and a methacryloyloxyacetic group; (c) 0 to 20% by weight, based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (III) ο H 6 b (III) wherein A is selected from the group consisting of an O- and an -NR5-;wherein each R6 is independently selected from the group consisting of a -CH2CH2O- group, a -CH2CH(CH3)O- group and a -CH2CH(CH2CH3)O- group; and wherein b is 2 to 20; (d) 0 to 5% by weight, based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (IV) R8 O O---R7 (IV) wherein each R7 is independently selected from a -C1-4 alkyl group; and wherein each R8 is independently selected from the group consisting of a hydrogen and a methyl group.; 2. Liquid laundry detergent formulation as defined in claim 1, wherein the liquid laundry detergent formulation is characterized in that it comprises Petition 870260039332, dated 04 / 28 / 2026, page 15 / 22 3 / 4 25 to 97.9% by weight, based on the weight of the liquid laundry detergent formulation, of the liquid carrier; 2 to 60% by weight, based on the weight of the liquid laundry detergent formulation, of the cleaning surfactant; and 0.1 to 15% by weight, based on the weight of the liquid laundry detergent formulation, of the cleaning enhancer polymer.

3. Liquid laundry detergent formulation as defined in claim 1, characterized in that the liquid carrier comprises water.

4. Liquid laundry detergent formulation as defined in claim 3, characterized in that the cleaning enhancer polymer has a weight-average molecular weight, MW, of 500 to 100000 Daltons.

5. Liquid laundry detergent formulation as defined in claim 4, characterized in that the structural units of the monoethylenically unsaturated carboxylic acid monomer are structural units of formula (V) OH (V) wherein each R9 is independently selected from a hydrogen and a -CH3 group.

6. Liquid laundry detergent formulation as defined in claim 5, characterized in that each R9 is a hydrogen with 50 to 100 mol% of the structural units of formula (V) in the cleaning enhancer polymer.

7. Liquid laundry detergent formulation as defined in claim 6, characterized in that the ethylenically unsaturated monomer of formula (I) is of formula (Ia) wherein Y is selected from the group consisting of an O- and an -NR5-, wherein R5 is selected from the group consisting of a hydrogen and a C1-8 alkyl group; wherein R1 is selected from the group consisting of a -CH2CH2CH2- group, a -CH(CH3)CH2- group and a -CH2CH2- group; wherein R3 is a C1.5 alkylene group; and wherein X is selected from the group consisting of an oxygen atom and a sulfur atom.

8. Liquid laundry detergent formulation as defined in claim 7, characterized in that Y is an -O-; wherein R1 is a -CH2CH2- group; wherein R3 is a C2-4 alkylene group and wherein X is an oxygen.

9. Liquid laundry detergent formulation as defined in claim 8, characterized in that R3 is a -CH2CH2- group.