Formulation of liquid detergent for laundry, and method for washing a fabric item.

Abstract

This is a liquid detergent formulation for washing clothes, and a method for washing a fabric article. It is a liquid detergent formulation for washing clothes 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) and, optionally, structural units of an ethylenically unsaturated monomer of formula (ii).

Description

Formulation of liquid detergent for laundry, and method for washing a fabric item.

[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; structural units of an ethylenically unsaturated monomer of formula (I) (I) structural and, optionally, ethylenically unsaturated units of formula (II) R3 of a monomer R2(II).

[002] Liquid laundry detergents and gel forms that provide excellent overall cleaning are desirable for consumers. Such laundry detergents typically include surfactants, among other components, to provide the consumer with... Petition 870210103827, dated 10 / 11 / 2021, page 13 / 41 / 25 desired cleaning benefits. 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) 50 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 50% by weight, based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (I) Petition 870210103827, dated 10 / 11 / 2021, page 14 / 41 / 25 (I) wherein α is an average of 1 to 3; wherein b is an average of 1 to 3; wherein c is an average of 0 to 5; wherein d is 4 to 100; wherein A is an anion; and wherein M is an NH4+ charge that balances the anion; and (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 (II) R3 R2(II) wherein each R2 is independently selected from a -C1-4 alkyl group; and wherein each R3 is independently selected from the group consisting of a hydrogen and a methyl group.

[006] The present invention provides a method for washing a fabric article of the present invention comprising: providing a soiled fabric article; 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 in order to provide a clean fabric article. Petition 870210103827, dated 10 / 11 / 2021, page 15 / 41 / 25 DETAILED DESCRIPTION

[007] 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.

[008] 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.

[009] 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.

[0010] 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 870210103827, dated 10 / 11 / 2021, page 16 / 41 / 25, in which the dotted lines represent the attachment points to the polymer's main chain and where R is a hydrogen for acrylic acid structural units and a -CH3 group for methacrylic acid structural units.

[0011] 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 greater 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 870210103827, dated 10 / 11 / 2021, page 17 / 41 / 25 where α is an average of 1 to 3 (preferably 1 to 2; more preferably 2); where b is an average of 1 to 3 (preferably 1 to 2; more preferably 1); where c is an average of 0 to 5 (preferably 0 to 2; more preferably 0); where d is 4 to 100 (preferably 5 to 50; more preferably 7.5 to 20; most preferably 10 to 20); where A is an anion (preferably an SO3- or a PO32-; more preferably SO3-); and where M is an NH4+ charge that balances the anion; and, optionally, structural units (c) of an ethylenically unsaturated monomer of formula (II) -----λ R3 The < O----R2(II) wherein each R2 is independently selected from a -C1-4 alkyl group; and wherein each R3 is independently selected from the group consisting of a hydrogen and a methyl group.

[0012] Preferably, the liquid laundry detergent formulation of the present invention comprises a liquid carrier. More preferably, the liquid laundry detergent formulation Petition 870210103827, dated 10 / 11 / 2021, page 18 / 41 / 25 clothes of the present invention comprise 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.

[0013] Preferably, the liquid carrier may include water-miscible liquids such as C1-3 alkanolamines and C1-3 alkanols. More 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.

[0014] 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 Petition 870210103827, dated 10 / 11 / 2021, page 19 / 41 / 25 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. Even 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; where 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 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 includes a mixture of a linear alkylbenzene sulfonate, a sodium lauryl ethoxysulfate and a nonionic ethoxylate alcohol. Petition 870210103827, dated 10 / 11 / 2021, page 20 / 41 / 25

[0015] Anionic surfactants include alkyl sulfates, alkylbenzene sulfates, alkylbenzene sulfonates, alkyl polyethoxy sulfates, alkoxylated alcohols, paraffin sulfonates, olefin sulfonates, alpha-sulfocarboxylates, alpha-sulfocarboxylate esters, alkyl glyceryl ether sulfonates, fatty acid sulfates, fatty acid sulfonates, fatty acid ester sulfonates, alkyl phenols, alkyl phenol polyethoxy ether sulfates, 2-acryloxyalkane-1-sulfonic acid, 2-acryloxyalkane-1-sulfonate, beta-alkyloxyalkanesulfonic acid, beta-alkyloxyalkanesulfonate, amine oxides 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 alkyl phenols, 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.

[0016] Nonionic surfactants include alkoxylates (e.g., polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers, hydroxy ethers, fatty acid polyglycol esters, and mixtures thereof). Preferred nonionic surfactants include fatty alcohol polyglycol ethers. More preferred nonionic surfactants include secondary alcohol ethoxylates, 2-ethylhexanol ethoxylate, ethoxylated seed oils, butanol-capped 2-ethylhexanol ethoxylate, and mixtures thereof. More preferred nonionic surfactants Petition 870210103827, dated 10 / 11 / 2021, page 21 / 41 / 25 includes secondary alcohol ethoxylates.

[0017] 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 alkyl dimethyl benzyl ammonium chloride. Even more preferred cationic surfactants include at least one of C16-18 dialkyldimethylammonium chloride, C8-18 alkyl dimethyl benzyl ammonium chloride, and dimethyl disebo ammonium chloride. The most preferred cationic surfactant includes dimethyl disebo ammonium chloride.

[0018] 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. Furthermore, more preferred amphoteric surfactants include at least one C12-14 alkyldimethylamine oxide, 3-(N,N-dimethyl-N-hexadecylammonium)propane-1-sulfonate, 3-(N,N-dimethyl-N-hexadecylammonium)-2-hydroxypropane-1-sulfonate. Amphoteric surfactants of greatest preference include at least one of C12-14 alkyldimethylamine oxides.

[0019] Preferably, the liquid laundry detergent formulation of the present invention comprises: a cleaning-enhancing polymer. More preferably, the liquid laundry detergent formulation of the present invention comprises: Petition 870210103827, dated 10 / 11 / 2021, page 22 / 41 / 25 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. 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) 50 to 95% by weight (preferably 60 to 92% by weight; more preferably 70 to 90% by weight; even more preferably 75 to 85% by weight);(a) 5 to 50% by weight (preferably 8 to 40% by weight; more preferably 10 to 30% by weight; most preferably 15 to 25% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated carboxylic acid monomer of formula (I); where α is an average of 1 to 3 (preferably 1 to 2; more Petition 870210103827, dated 10 / 11 / 2021, p. 23 / 41 / 25 preferably 2); where b is an average of 1 to 3 (preferably 1 to 2; more preferably 1); where c is an average of 0 to 5 (preferably 0 to 2; more preferably 0); where d is 4 to 100 (preferably 5 to 50; more preferably 7.5 to 20; more preferably 10 to 20); where A is an anion (preferably an SO3- or a PO32-; more preferably SO3-); and where M is an NH4+ cation that balances the anion; and (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 (II) wherein each R2 is independently selected from a -C1-4 alkyl group; and wherein each R3 is independently selected from the group consisting of a hydrogen and a methyl group.

[0020] 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 100,000 Daltons (preferably 1,000 to 50,000 Daltons; more preferably 2,000 to 20,000 Daltons; most preferably 2,500 to 7,500 Daltons).

[0021] Preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 50 to 95% by weight (preferably 60 to 92% by weight; more preferably 70 to 90% by weight; most preferably 75 to 85% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of a carboxylic acid monomer.Petition 870210103827, dated 10 / 11 / 2021, page 24 / 41 / 25 monoethylenically unsaturated. More preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 50 to 95% by weight (preferably 60 to 92% by weight; more preferably 70 to 90% by weight; most preferably 75 to 85% 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 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: 50 to 95% by weight (preferably 60 to 92% by weight; more preferably 70 to 90% by weight; most preferably 75 to 85% 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.Even more preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 50 to 95% by weight (preferably 60 to 92% by weight; more preferably 70 to 90% by weight; most preferably 75 to 85% 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. Petition 870210103827, dated 10 / 11 / 2021, page 25 / 41 / 25 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: 50 to 95% by weight (preferably 60 to 92% by weight; more preferably 70 to 90% by weight; most preferably 75 to 85% 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: 50 to 95% by weight (preferably 60 to 92% by weight; more preferably 70 to 90% by weight; most preferably 75 to 85% 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.

[0022] Preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 50 to 95% by weight (preferably 60 to 92% by weight; more preferably 70 to 90% by weight; most preferably 75 to 85% 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 (III) Petition 870210103827, dated 10 / 11 / 2021, page 26 / 41 / 25 oh (III) where each R4 is independently selected from a hydrogen and a -CH3 group (preferably a hydrogen).More preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 50 to 95% by weight (preferably 60 to 92% by weight; more preferably 70 to 90% by weight; most preferably 75 to 85% 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 (III), wherein each R4 is independently selected from a hydrogen and a -CH3 group; wherein R4 is a hydrogen in 50 to 100 mol% (preferably 75 to 100 mol%; more preferably 90 to 100 mol%; even more preferably 98 to 100 mol%; most preferably 100 mol%) of the structural units of formula (III) in the cleaning enhancer polymer.

[0023] Preferably, the cleaning enhancer polymer used in the liquid laundry detergent formulation of the present invention comprises: 5 to 50% by weight (preferably 8 to 40% by weight; more preferably 10 to 30% by weight; most preferably 15 to 25% by weight), based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (I) Petition 870210103827, of 10 / 11 / 2021, p. 27 / 41 / 25 (I) where α is an average of 1 to 3 (preferably 1 to 2; more preferably 2); where b is an average of 1 to 3 (preferably 1 to 2; more preferably 1); where c is an average of 0 to 5 (preferably 0 to 2; more preferably 0); where d is 4 to 100 (preferably 5 to 50; more preferably 7.5 to 20; with maximum preference 10 to 20); where A is an anion (preferably an SO3- or a PO32-; more preferably SO3-); and where M is a charge of NH4+ that balances the anion.

[0024] 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 (II) R3 O----R2(II) wherein each R2 is independently selected from a -C1-4 alkyl group (preferably a methyl group, an ethyl group and Petition 870210103827, dated 10 / 11 / 2021, page 28 / 41 / 25 a butyl group; more preferably, an ethyl group and a butyl group; most preferably, an ethyl group) and wherein each R3 is independently selected from the group consisting of a hydrogen 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 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 (II), wherein R2 is an ethyl group in 75 to 100% by mole (preferably 90 to 100% by mole; more preferably 98 to 100% by mole, most preferably 100% by mole) of the structural units of formula (II) in the cleaning enhancer polymer and wherein R3 is a hydrogen in 75 to 100% by mole (preferably 90 to 100% by mole) in mol; more preferably, 98 to 100% by mol; most preferably, 100% by mol) of the structural units of formula (II) in the cleaning enhancer polymer.

[0025] 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; 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). Mais preferencialmente, o polímero intensificador de limpeza usado na formulação de detergente líquido para lavagem de 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 peso; com ainda mais preferência, Petition 870210103827, dated 10 / 11 / 2021, p. 29 / 41 / 25 <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 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 lavagem de 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 peso; com ainda mais preferência, <0,01% em peso; com máxima preferência, <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.The modified vinyl alcohol polymer includes anion-modified PVA (e.g., PVA modified with a sulfonic acid group and PVA modified with a carboxylic acid group); cation-modified PVA (e.g., PVA modified with a quaternary amine group); amide-modified PVA; PVAs modified with an acetoacetyl group; PVA modified with diacetone acrylamide and PVA modified with ethylene.

[0026] 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 a Petition 870210103827, dated 10 / 11 / 2021, page 30 / 41 / 25 crystalline non-polymeric hydroxyfunctional material capable of forming thread-like structuring systems throughout the liquid laundry detergent formulation when crystallized in situ.

[0027] 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 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.More 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 alkyl hydroxides; glycols; urea; monoethanolamine; diethanolamine; triethanolamine; ammonium salts of calcium, sodium, potassium, ammonium and alkanol 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, cumene sulfonate. Petition 870210103827, dated 10 / 11 / 2021, page 31 / 41 / 25 sodium, sodium cumene sulfonate, ammonium cumene sulfonate and mixtures thereof.

[0028] 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.

[0029] 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; most 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); acid. Petition 870210103827, dated 10 / 11 / 2021, page 32 / 41 / 25 ethylenediaminetetraethylenephosphonic acid; salts of ethylenediaminetetraethylenephosphonic acid; oligomeric phosphonates; polymeric phosphonates; mixtures thereof.

[0030] 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 coacervation polymer (e.g., cationic hydroxyethyl cellulose; polyquaternium polymers and combinations thereof).

[0031] 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 tri-ethanolamine; 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., acid Petition 870210103827, dated 10 / 11 / 2021, page 33 / 41 / 25 (acetic acid).

[0032] 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).

[0033] 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 clay and powdered tallow; more preferably, wherein the soiled fabric article is soiled with powdered tallow) (preferably, wherein the soiled fabric article is stained cotton; more preferably, wherein the soiled fabric article is cotton stained with powdered tallow); providing a liquid laundry detergent formulation of the present invention; providing washing water; and applying the washing water and the liquid laundry detergent formulation to the soiled fabric in order 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 clay and tallow powder; more preferably, wherein the soiled fabric article is soiled with tallow powder) (preferably, wherein the soiled fabric article is a stained cotton; more preferably, wherein the soiled fabric article is cotton stained with tallow powder); 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 fabric to provide a clean fabric article; and then applying. Petition 870210103827, dated 10 / 11 / 2021, page 34 / 41 / 25 the rinse water to the clean fabric item to remove the liquid laundry detergent formulation from the clean fabric item.

[0034] Some embodiments of the present invention will now be described in detail in the following Examples. SYNTHESIS S1: POLYMER 1

[0035] 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 loaded with deionized water (300 g). The contents of the flask were then adjusted to be stirred and heated to 74 °C. Once the contents of the flask reached the reaction temperature of 74 °C, 0.15% of an aqueous ferrous sulfate heptahydrate promoter solution (2.5 g) was added, followed by the addition of sodium metabisulfite (SMBS) (1.43 g) dissolved in deionized water (7.0 g) as a pre-charge. Separate feeds were then made into the flask as follows:

[0036] Co-feeding of the primer: feed the flask with sodium persulfate (5.98 g) dissolved in deionized water (25 g) for 110 minutes.

[0037] Chain transfer agent (CTA) co-feeding: feed the flask with sodium metabisulfite (22.43 g) dissolved in deionized water (40 g) for 98 minutes.

[0038] Monomer co-feeding: Feed a monomer solution containing glacial acrylic acid (239.2 g) and an ethylenically unsaturated monomer of formula (I), wherein a is 2, wherein b is 1, wherein c is 0, wherein d is 15, wherein A is -SO3- and wherein M is an NH4+ (available from Ethox Chemicals, LLC under the designation E-Sperse®RS-1596)(59.8 g) into the vial for 95 minutes.

[0039] After the completion of the co-feedings, deionized water (10 g) was added as a rinse. The contents of the flask were then retained at Petition 870210103827, dated 10 / 11 / 2021, page 35 / 41 / 25 °C for 10 minutes. At the conclusion 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 (0.42 g) in deionized water (8 g) and were added for 10 minutes. Then, a 35% aqueous hydrogen peroxide sequestering solution (3 g) was added to the vial contents. The vial contents were then cooled to <35 °C. The polymeric product had a solids content of 45.9%, a pH of 1.62, and a Brookfield viscosity of 0.52 Pa^s (520 cps). The residual monomer was measured below 52 ppm. The final weight-average molecular weight, Mw, as measured by gel permeation chromatography was 5.721 Daltons. COMPARATIVE EXAMPLE C1 AND EXAMPLE 1: LIQUID LAUNDRY DETERGENT

[0040] 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 noted in Table 2, and were prepared by standard liquid laundry 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 Ex. Comp. C1 ethoxylated poly(ethyleneimine)1 Ex. 1 Polymer 1 1 available from BASF under the trade name Sokolan™ HP-20 PRIMARY CLEANING PERFORMANCE

[0041] The primary cleaning performance of liquid laundry detergent formulations from Comparative Example C1 and Petition 870210103827, dated 10 / 11 / 2021, page 36 / 41 / 25 of Example 1 was evaluated in a Model TOM-52-A Thermometer available from SR Lab Instruments (6 x 1 l wells) agitated at 90 cycles per minute with the conditions observed in Table 3. TABLE 3 Parameter Context Temperature 15 °C Water hardness 200 ppm, Ca / Mg = 2 / 1 Fabric types (3 in each well) Cotton Stained 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

[0042] The soil removal index (SRI) was calculated using ASTM Method D4265-14. 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 Example ASRI stain: Ground clay, Motor oil, Tallow powder. Ex. Comp. C1 +8 +5 +1 Ex. 1 +7 +3 +4 Petition 870210103827, dated 10 / 11 / 2021, pages 37 / 41

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) 50 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 50% by weight, based on the dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (I) Z (I) wherein α is 1 to 3; wherein b is 1 to 3; wherein c is 0 to 5; wherein d is 4 to 100; wherein A is an anion selected from SO3- and PO32-; and wherein M is an NH3- load that balances the anion; and (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 (II) Petition 870260025210, dated 03 / 18 / 2026, page.12 / 17 2 / 3 R3 O =( O----R2 (II) wherein each R2 is independently selected from a -C1-4 alkyl group; and wherein each R3 is independently selected from the group consisting of a hydrogen and a methyl group.

2. Liquid laundry detergent formulation according to claim 1, wherein the liquid laundry detergent formulation is characterized in that it comprises 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 detergent formulation for washing clothes, according to claim 1 or 2, characterized in that the liquid carrier comprises water.

4. Liquid laundry detergent formulation according to any one of claims 1 to 3, characterized in that the cleaning enhancer polymer has a weight-average molecular weight, MW, of 500 to 100,000 Daltons.

5. Liquid detergent formulation for washing clothes, according to any one of claims 1 to 4, characterized in that the structural units of the monoethylenically unsaturated carboxylic acid monomer are structural units of formula (III) Petition 870260025210, dated 03 / 18 / 2026, page 13 / 17 3 / 3 oh (III) wherein each R4 is independently selected from a hydrogen and a -CH3 group.

6. Liquid laundry detergent formulation according to claim 5, characterized in that R4 is a hydrogen in 50 to 100 mol% of the structural units of formula (III) in the cleaning enhancer polymer.

7. Liquid detergent formulation for washing clothes, according to any one of claims 1 to 6, characterized in that a is 2, where b is 1 and where c is 0.

8. Liquid detergent formulation for washing clothes, according to any one of claims 1 to 7, characterized in that d is from 10 to 20, wherein A is an SO3-; and wherein M is an NH4+.

9. Liquid laundry detergent formulation according to any one of claims 1 to 8, characterized in that it further comprises at least one structuring agent, a hydrotrope, a fragrance, a former, and a fabric softener.

10. Method for washing a fabric article of the present invention, characterized in that it comprises: providing a soiled fabric article; providing a liquid laundry detergent formulation as defined in claim 1; providing wash water; and applying the wash water and the liquid laundry detergent formulation to the soiled fabric in order to provide a clean fabric article.