Aqueous detergent formulation

Abstract

There is provided a laundry detergent formulation comprising an aqueous carrier; a cleaning surfactant; a thickening polymer comprising: from 20% to 80% by weight, based on the dry weight of the thickening polymer, of structural units of a monoethylenically unsaturated vinyl alkanoate having from 4 to 12 carbon atoms; from 20% to 80% by weight, based on the dry weight of the thickening polymer, of structural units of a monoethylenically unsaturated carboxylic acid functionalized vinyl ester having from 4 to 12 carbon atoms; from 0% to 5% by weight, based on the dry weight of the thickening polymer, of structural units of a polyethylenically unsaturated crosslinker; 0% to 20% by weight, based on the dry weight of the thickening polymer, of structural units of other monoethylenically unsaturated monomers; and wherein the thickening polymer contains lt based on the dry weight of the thickening polymer; 10% by weight of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, alkali metal salts thereof, ammonium salts thereof, and mixtures thereof.

Description

[0001] The present invention relates to an aqueous detergent formulation. Specifically, the present invention relates to an aqueous detergent formulation, which comprises: an aqueous carrier, a cleaning surfactant and a thickening polymer, wherein the thickening polymer comprises, based on the dry weight of the thickening polymer, 20% to 80% by weight of structural units of monoethylenically unsaturated alkanoic acid vinyl esters having 4 to 12 carbon atoms; based on the dry weight of the thickening polymer, 20% to 80% by weight of structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; based on the dry weight of the thickening polymer, 0% to 5% by weight of polyethylenically unsaturated crosslinking agents; % to 20% by weight, based on the dry weight of the thickening polymer, of structural units of other monoethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated alkanoic acid vinyl esters having 4 to 12 carbon atoms and the monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; and wherein the thickening polymer contains less than 10% by weight, based on the dry weight of the thickening polymer, of structural units of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, their alkali metal salts, their ammonium salts, and mixtures thereof.

[0002] Aqueous detergent formulations are well known. Nevertheless, conventional aqueous detergent formulations typically contain a variety of non-biodegradable ingredients, including thickeners. There is a desire in the market to increase the biodegradable content of aqueous detergent formulations, particularly aqueous laundry detergent formulations. Many conventional thickeners used in aqueous detergent formulations include alkali-soluble / swellable latexes, which, while non-toxic and not a serious hazard to the environment, are typically non-biodegradable.

[0003] Therefore, there remains a need to discover new biodegradable ingredients suitable for use as thickeners in aqueous detergent formulations.

[0004] The present invention provides an aqueous detergent formulation, which comprises: an aqueous carrier, a cleaning surfactant and a thickening polymer, wherein the thickening polymer comprises, based on the dry weight of the thickening polymer: 20 wt % to 80 wt % of structural units of monoethylenically unsaturated alkanoic acid vinyl esters having 4 to 12 carbon atoms; 20 wt % to 80 wt % of structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms, based on the dry weight of the thickening polymer; 0 wt % to 5 wt % of a polyethylenically unsaturated crosslinking agent, based on the dry weight of the thickening polymer. % by weight; based on the dry weight of the thickening polymer, 0 to 20 % by weight of structural units of other monoethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated alkanoic acid vinyl esters having 4 to 12 carbon atoms and the monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; and wherein the thickening polymer contains less than 10 % by weight, based on the dry weight of the thickening polymer, of structural units of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, their alkali metal salts, their ammonium salts, and mixtures thereof. DETAILED DESCRIPTION

[0005] Applicants have surprisingly discovered that aqueous detergent formulations comprising an aqueous carrier and a cleansing surfactant can be effectively thickened using a thickening polymer comprising, based on the dry weight of the thickening polymer, from 20 to 80 weight percent structural units of a monoethylenically unsaturated alkanoic acid vinyl ester having 4 to 12 carbon atoms; from 20 to 80 weight percent structural units of a monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4 to 12 carbon atoms, based on the dry weight of the thickening polymer; from 0 to 5 weight percent structural units of a polyethylenically unsaturated crosslinking agent, based on the dry weight of the thickening polymer; and from 0 to 5 weight percent structural units of a polyethylenically unsaturated crosslinking agent, based on the dry weight of the thickening polymer. The thickening polymer comprises from 0 to 20% by weight of structural units of other monoethylenically unsaturated monomers, based on the dry weight of the thickening polymer, wherein the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated alkanoic acid vinyl esters having 4 to 12 carbon atoms and the monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; and wherein the thickening polymer contains less than 10% by weight of structural units of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, their alkali metal salts, their ammonium salts and mixtures thereof, based on the dry weight of the thickening polymer; wherein the thickening polymer exhibits biodegradability according to the procedure of OECD 302B.

[0006] Unless otherwise indicated, ratios, percentages, parts, etc. are by weight. Weight percentages (or wt%) in a composition are percentages by dry weight, i.e., excluding any water that may be present in the composition. Percentages of monomer units in a polymer are percentages by solid weight (i.e., excluding any water present in the polymer emulsion).

[0007] As used herein, unless otherwise indicated, the terms "weight average molecular weight" and "Mw" are used interchangeably and refer to the weight average molecular weight measured in a conventional manner using gel permeation chromatography (GPC) and conventional standards such as polystyrene standards. GPC technology is discussed in detail in "Modem Size Exclusion Chromatography", WW Yau, JJ Kirkland, DD Bly; Wiley-lnterscience, 1979, and in "A Guide to Materials Characterization and Chemical Analysis", JP Sibilia; VCH, 1988, pp. 81-84. Weight average molecular weight is reported herein in Daltons.

[0008] Preferably, the aqueous detergent formulation of the present invention is selected from the group consisting of an aqueous laundry detergent formulation, an aqueous dishwashing detergent formulation and an aqueous hand soap formulation. More preferably, the aqueous detergent formulation of the present invention is an aqueous laundry detergent formulation.

[0009] Preferably, the aqueous detergent formulation of the present invention comprises: an aqueous carrier (based on the weight of the aqueous detergent formulation, 15 wt % to 97.9 wt % (preferably, 40 wt % to 94.75 wt %; more preferably, 45 wt % to 92 wt %; most preferably, 47 wt % to 89 wt %) of the aqueous carrier); a cleaning surfactant (based on the weight of the aqueous detergent formulation, preferably, 2 wt % to 60 wt % (preferably, 5 wt % to 40 wt %; more preferably, 7.5 wt % to 30 wt %; most preferably, 10 wt % to 25 wt %) of the cleaning surfactant); a thickening polymer (based on the weight of the aqueous detergent formulation; %, preferably, 0.1 wt % to 7.5 wt % (preferably, 0.25 wt % to 6 wt %; more preferably, 0.5 wt % to 5 wt %; most preferably, 1 wt % to 3 wt %) of a thickening polymer), the thickening polymer comprising: based on the dry weight of the thickening polymer, 20 wt % to 80 wt % (preferably, 24.89 wt % to 77.89 wt %; more preferably, 39.48 wt % to 74.48 wt %; most preferably, 43.96 wt % to 71.46 wt %) of structural units of monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms; ... % (preferably, 22% to 75% by weight; more preferably, 25% to 60% by weight; most preferably, 27.5% to 55% by weight) of structural units of monoethylenically unsaturated carboxylic acid-functionalized vinyl esters having 4 to 12 carbon atoms; 0% to 5% by weight (preferably, 0.01% to 2.5% by weight; more preferably, 0.02% to 1% by weight; most preferably, 0.04% to 0.5% by weight) of structural units of polyethylenically unsaturated crosslinking agents, based on the dry weight of the thickening polymer; 0% to 20% by weight (preferably, 0.1% to 5% by weight; more preferably, 0.5% to 10% by weight) of structural units of polyethylenically unsaturated crosslinking agents, based on the dry weight of the thickening polymer. % to 4 wt. %; most preferably, 1 wt. % to 3 wt. %) of structural units of other monoethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated alkanoic acid vinyl esters having 4 to 12 carbon atoms and the monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; and wherein the thickening polymer contains less than 10 wt. % (preferably, <5 wt. %; more preferably <1 wt. %; still more preferably, <0.1 wt. %; most preferably, <detection limit) of structural units of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, their alkali metal salts, their ammonium salts and mixtures thereof, based on the dry weight of the thickening polymer.

[0010] Preferably, the aqueous detergent formulations of the present invention comprise, based on the weight of the aqueous detergent formulation, 15 wt % to 97.9 wt % (preferably, 40 wt % to 94.75 wt %; more preferably, 45 wt % to 92 wt %; most preferably, 47 wt % to 89 wt %) of an aqueous carrier. More preferably, the aqueous detergent formulations of the present invention comprise, based on the weight of the aqueous detergent formulation, 15 wt % to 97.9 wt % (preferably, 40 wt % to 94.75 wt %; more preferably, 45 wt % to 92 wt %; most preferably, 47 wt % to 89 wt %) of an aqueous carrier; wherein the aqueous carrier comprises water. Most preferably, the aqueous detergent formulations of the present invention comprise from 15 wt % to 97.9 wt % (preferably, from 40 wt % to 94.75 wt %; more preferably, from 45 wt % to 92 wt %; most preferably, from 47 wt % to 89 wt %) of an aqueous carrier, based on the weight of the aqueous detergent formulation; wherein the aqueous carrier comprises deionized water.

[0011] Preferably, the aqueous carrier in the aqueous detergent formulations of the present invention may include a water-miscible liquid such as C 1-3 Alkanolamine, C 1-3 Alkanol, C 1-3 More preferably, the aqueous carrier in the aqueous detergent formulation of the present invention comprises, based on the weight of the aqueous carrier, 0 wt % to 8 wt % (preferably, 0.2 wt % to 8 wt %; more preferably, 0.5 wt % to 5 wt %) of a water-miscible liquid; wherein the water-miscible liquid is selected from C 1-3 Alkanolamine, C 1-3 Alkanol, C 1-3 Most preferably, the aqueous carrier in the aqueous detergent formulation of the present invention comprises 0 wt % to 8 wt % (preferably 0.2 wt % to 8 wt %; more preferably 0.5 wt % to 5 wt %) of a water-miscible liquid based on the weight of the aqueous carrier; wherein the water-miscible liquid is selected from the group consisting of ethanol, propylene glycol and mixtures thereof.

[0012] Preferably, the aqueous detergent formulation of the present invention comprises, based on the weight of the aqueous detergent formulation, 2 wt % to 60 wt % (preferably, 5 wt % to 40 wt %; more preferably, 7.5 wt % to 30 wt %; most preferably, 10 wt % to 25 wt %) of a cleansing surfactant. More preferably, the aqueous detergent formulation of the present invention comprises: based on the weight of the aqueous detergent formulation, 2 wt % to 60 wt % (preferably, 5 wt % to 40 wt %; more preferably, 7.5 wt % to 30 wt %; most preferably, 10 wt % to 25 wt %) of a cleansing surfactant; wherein the cleansing surfactant is selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and mixtures thereof. Still more preferably, the aqueous detergent formulation of the present invention comprises: based on the weight of the aqueous detergent formulation, 2 wt% to 60 wt% (preferably, 5 wt% to 40 wt%; more preferably, 7.5 wt% to 30 wt%; most preferably, 10 wt% to 25 wt%) of a cleaning surfactant; wherein the cleaning surfactant comprises an anionic surfactant. Still more preferably, the aqueous detergent formulation of the present invention comprises: based on the weight of the aqueous detergent formulation, 2 wt% to 60 wt% (preferably, 5 wt% to 40 wt%; more preferably, 7.5 wt% to 30 wt%; most preferably, 10 wt% to 25 wt%) of a cleaning surfactant; wherein the cleaning surfactant comprises a mixture of anionic and nonionic surfactants. Most preferably, the aqueous detergent formulation of the present invention comprises: 2 wt% to 60 wt% (preferably, 5 wt% to 40 wt%; more preferably, 7.5 wt% to 30 wt%; most preferably, 10 wt% to 25 wt%) of a detersive surfactant, based on the weight of the aqueous detergent formulation; wherein the detersive surfactant comprises a mixture of linear alkylbenzene sulfonate, sodium lauryl ethoxy sulfate and nonionic alcohol ethoxylate.

[0013] Anionic surfactants include alkyl sulfates, alkylbenzene sulfates, alkylbenzene sulfonic acids, alkylbenzene sulfonates, alkyl polyethoxy sulfates, alkoxylated alcohols, paraffin sulfonic acids, paraffin sulfonates, olefin sulfonic acids, olefin sulfonates, α-sulfocarboxylates, esters of α-sulfocarboxylates, alkyl glyceryl ether sulfonic acids, alkyl glyceryl ether sulfonates, fatty acid sulfates, fatty acid sulfonates, sulfonates of fatty acid esters, alkylphenols, alkylphenol polyethoxy ether sulfates, 2-acryloyloxy-alkane-1-sulfonic acids, 2-acryloyloxy-alkane-1-sulfonates, β-alkoxy alkane sulfonic acids, β-alkoxy alkane sulfonates, amine oxides, and mixtures thereof. Preferred anionic surfactants include C 8-20 Alkylbenzene sulfate, C 8-20 Alkylbenzenesulfonic acid, C 8-20Alkylbenzene sulfonate, paraffin sulfonic acid, paraffin sulfonate, α-olefin sulfonic acid, α-olefin sulfonate, alkoxylated alcohol, C 8-20 Alkylphenols, amine oxides, fatty acid sulfonates, fatty acid ester sulfonates, C 8-10 Alkyl polyethoxy sulfates and mixtures thereof. More preferred anionic surfactants include C 12-16 Alkylbenzenesulfonic acid, C 12-16 Alkylbenzene sulfonate, C 12-18 Paraffin-sulfonic acid, C 12-18 Paraffin-sulfonate, C 12-16 Alkyl polyethoxy sulfates and mixtures thereof.

[0014] Nonionic surfactants include alkoxylates (e.g., polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers, hydroxy 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. Most preferred nonionic surfactants include secondary alcohol ethoxylates.

[0015] Cationic surfactants include quaternary surface-active compounds. Preferred cationic surfactants include those having ammonium groups, sulfonium groups, Iodine Motowa A quaternary surfactant comprising at least one of the following: a) a quaternary surfactant comprising at least one of the following: b) a quaternary surfactant comprising at least one of the following: c) a quaternary surfactant comprising at least one of the following: 16-18 Dialkyldimethylammonium chloride, C 8-18 Alkyl dimethyl benzyl ammonium chloride and dimethyl ditallow ammonium chloride. The most preferred cationic surfactants include dimethyl ditallow ammonium chloride.

[0016] Amphoteric surfactants include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amine oxides, acylated amino acids, derivatives of fatty quaternary ammonium compounds, and mixtures thereof. Preferred amphoteric surfactants include derivatives of fatty quaternary ammonium compounds. More preferred amphoteric surfactants include derivatives of fatty quaternary ammonium compounds having long chain groups (having 8 to 18 carbon atoms). Still more preferred amphoteric surfactants include at least one of the following: C 12-14Alkyl dimethyl amine oxide, 3-(N,N-dimethyl-N-hexadecyl-ammonio) propane-1-sulfonate, 3-(N,N-dimethyl-N-hexadecyl ammonio)-2-hydroxypropane-1-sulfonate. The most preferred amphoteric surfactants include C 12-14 At least one of alkyl dimethyl amine oxides.

[0017] Preferably, the aqueous detergent formulation of the present invention comprises, based on the weight of the aqueous detergent formulation, 0.1 wt % to 7.5 wt % (preferably, 0.25 wt % to 6 wt %; more preferably, 0.5 wt % to 5 wt %; most preferably, 1 wt % to 3 wt %) of a thickening polymer, wherein the thickening polymer comprises: based on the dry weight of the thickening polymer, 20 wt % to 80 wt % (preferably, 24.89 wt % to 77.89 wt %; more preferably, 39.48 wt % to 74.48 wt %) of a thickening polymer. %; most preferably, 43.96 wt % to 71.46 wt %) of structural units of monoethylenically unsaturated alkanoic acid vinyl esters having 4 to 12 carbon atoms; based on the dry weight of the thickening polymer, 20 wt % to 80 wt % (preferably, 22 wt % to 75 wt %; more preferably, 25 wt % to 60 wt %; most preferably, 27.5 wt % to 55 wt %) of structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; based on the dry weight of the thickening polymer, 0 wt % to 55 wt % ... % to 5% by weight (preferably, 0.01% to 2.5% by weight; more preferably, 0.02% to 1% by weight; most preferably, 0.04% to 0.5% by weight) of structural units of a polyethylenically unsaturated crosslinking agent; and 0% to 20% by weight (preferably, 0.1% to 5% by weight; more preferably, 0.5% to 4% by weight; most preferably, 1% to 3% by weight) of structural units of other monoethylenically unsaturated monomers, based on the dry weight of the thickening polymer, wherein the other monoethylenically unsaturated and monomers other than the monoethylenically unsaturated alkanoic acid vinyl esters having 4 to 12 carbon atoms and the monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; and wherein the thickening polymer contains less than 10 wt. % (preferably, <5 wt. %; more preferably <1 wt. %; still more preferably, <0.1 wt. %; most preferably, <detection limit) of structural units of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, their alkali metal salts, their ammonium salts and mixtures thereof, based on the dry weight of the thickening polymer.

[0018] Preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises, based on the dry weight of the thickening polymer, 20% to 80% by weight (preferably, 24.89% to 77.89% by weight; more preferably, 39.48% to 74.48% by weight; most preferably, 43.96% to 71.46% by weight) of structural units of monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms are selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl 3-methylbutyrate, vinyl pivalate, vinyl hexanoate, esters, vinyl 4-methylpentanoate, vinyl 3,3-dimethylbutanoate, vinyl heptanoate, vinyl 5-methylhexanoate, vinyl 4,4-dimethylpentanoate, vinyl octanoate, vinyl 6-methylheptanoate, vinyl 5,5-dimethylhexanoate, vinyl nonanoate, vinyl 7-methyloctanoate, vinyl decanoate, vinyl 8-methylnonanoate, vinyl 6,6-dimethylheptanoate, vinyl 2-methyl-2-propylhexanoate, vinyl 2-ethyl-2-methylheptanoate, vinyl 2,2-dimethyloctanoate, vinyl 2,2-dimethylheptanoate, vinyl 2-ethyl-2-methylhexanoate, vinyl 2-methyl-2-propylpentanoate, vinyl 2-ethylhexanoate, and mixtures thereof. More preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises, based on the dry weight of the thickening polymer, 20 wt % to 80 wt % (preferably, 24.89 wt % to 77.89 wt %; more preferably, 39.48 wt % to 74.48 wt %; most preferably, 43.96 wt % to 71.46 wt %) of structural units of monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms are preferably monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms. The unsaturated alkanoic acid vinyl ester is selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl 3-methylbutyrate, vinyl pivalate, vinyl hexanoate, vinyl 4-methylvalerate, vinyl 3,3-dimethylbutyrate, vinyl heptanoate, vinyl 5-methylhexanoate, vinyl 4,4-dimethylvalerate, vinyl octanoate, vinyl 6-methylheptanoate, vinyl 5,5-dimethylhexanoate and mixtures thereof.Still more preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises, based on the dry weight of the thickening polymer, 20 wt.% to 80 wt.% (preferably, 24.89 wt.% to 77.89 wt.%; more preferably, 39.48 wt.% to 74.48 wt.%; most preferably, 43.96 wt.% to 71.46 wt.%) of structural units of monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms are selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl 3-methylbutyrate, vinyl pivalate, vinyl hexanoate, vinyl 4-methylvalerate, vinyl 3,3-dimethylbutyrate and mixtures thereof. Still more preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises, based on the dry weight of the thickening polymer, 20 wt.% to 80 wt.% (preferably, 24.89 wt.% to 77.89 wt.%; more preferably, 39.48 wt.% to 74.48 wt.%; most preferably, 43.96 wt.% to 71.46 wt.%) of structural units of monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms are selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate and mixtures thereof. Most preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises, based on the dry weight of the thickening polymer, 20 wt.% to 80 wt.% (preferably, 24.89 wt.% to 77.89 wt.%; more preferably, 39.48 wt.% to 74.48 wt.%; most preferably, 43.96 wt.% to 71.46 wt.%) of structural units of monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms is vinyl acetate.

[0019] Preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises, based on the dry weight of the thickening polymer, 20% to 80% by weight (preferably, 22% to 75% by weight; more preferably, 25% to 60% by weight; most preferably, 27.5% to 55% by weight) of structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms are selected from the group consisting of: 2- Oxo-2-(vinyloxy)acetic acid, 3-oxo-3-(vinyloxy)propionic acid, 4-oxo-4-(vinyloxy)butanoic acid (also known as vinyl succinic acid), 5-oxo-5-(vinyloxy)pentanoic acid, 6-oxo-6-(vinyloxy)hexanoic acid (also known as vinyl adipate), 7-oxo-7-(vinyloxy)heptanoic acid, 8-oxo-8-(vinyloxy)octanoic acid, 9-oxo-9-(vinyloxy)nonanoic acid, 10-oxo-10-(vinyloxy)decanoic acid and mixtures thereof. More preferably, the biodegradable thickening polymer in the aqueous detergent formulation of the present invention comprises, based on the dry weight of the thickening polymer, 20% to 80% by weight (preferably, 22% to 75% by weight; more preferably, 25% to 60% by weight; most preferably, 27.5% to 55% by weight) of structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms are selected from the group consisting of: 4-oxo-4-(vinyloxy)butanoic acid, 5-oxo-5-(vinyloxy)pentanoic acid, 6-oxo-6-(vinyloxy)hexanoic acid, 7-oxo-7-(vinyloxy)heptanoic acid, 8-oxo-8-(vinyloxy)octanoic acid and mixtures thereof. Still more preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises: based on the dry weight of the thickening polymer, 20 wt.% to 80 wt.% (preferably, 22 wt.% to 75 wt.%; more preferably, 25 wt.% to 60 wt.%; most preferably, 27.5 wt.% to 55 wt.%) of structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms are selected from the group consisting of: 5-oxo-5-(vinyloxy)pentanoic acid, 6-oxo-6-(vinyloxy)hexanoic acid, 7-oxo-7-(vinyloxy)heptanoic acid, 8-oxo-8-(vinyloxy)octanoic acid and mixtures thereof.Still more preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises, based on the dry weight of the thickening polymer, 20 wt.% to 80 wt.% (preferably, 22 wt.% to 75 wt.%; more preferably, 25 wt.% to 60 wt.%; most preferably, 27.5 wt.% to 55 wt.%) of structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms are selected from the group consisting of: 6-oxo-6-(vinyloxy)hexanoic acid, 7-oxo-7-(vinyloxy)heptanoic acid, 8-oxo-8-(vinyloxy)octanoic acid and mixtures thereof. Most preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises, based on the dry weight of the thickening polymer, 20 wt.% to 80 wt.% (preferably, 22 wt.% to 75 wt.%; more preferably, 25 wt.% to 60 wt.%; most preferably, 27.5 wt.% to 55 wt.%) of structural units of a monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4 to 12 carbon atoms is 6-oxo-6-(vinyloxy)hexanoic acid.

[0020] Preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises, based on the dry weight of the thickening polymer, 0 to 5 wt. % (preferably 0.01 to 2.5 wt. %; more preferably 0.02 to 1 wt. %; most preferably 0.04 to 0.5 wt. %) of structural units of a polyethylenically unsaturated crosslinking agent; wherein the polyethylenically unsaturated crosslinking agent is selected from the group consisting of polyethylenically unsaturated crosslinking agents having an average of two or three vinyl groups per molecule. More preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises, based on the dry weight of the thickening polymer, 0 to 5 wt. % (preferably, 0.01 to 2.5 wt. %; more preferably, 0.02 to 1 wt. %; most preferably, 0.04 to 0.5 wt. %) of structural units of a polyethylenically unsaturated crosslinking agent; wherein the polyethylenically unsaturated crosslinking agent is selected from the group consisting of allyl (meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, diallyl phthalate, trimethylolpropane tri(meth)acrylate, divinylbenzene, divinyltoluene, tridivinyltoluene, trivinylbenzene, divinylnaphthalene and mixtures thereof. Most preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises from 0 wt. % to 5 wt. % (preferably, from 0.01 wt. % to 2.5 wt. %; more preferably, from 0.02 wt. % to 1 wt. %; most preferably, from 0.04 wt. % to 0.5 wt. %) structural units of a polyethylenically unsaturated crosslinking agent, based on the dry weight of the thickening polymer; wherein the polyethylenically unsaturated crosslinking agent is diallyl phthalate.

[0021] Preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises, based on the dry weight of the thickening polymer, 0 wt. % to 20 wt. % (preferably, 0.1 wt. % to 5 wt. %; more preferably, 0.5 wt. % to 4 wt. %; most preferably, 1 wt. % to 3 wt. %) of structural units of other monoethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from monoethylenically unsaturated alkanoic acid vinyl esters having 4 to 12 carbon atoms and monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms, and wherein the other monoethylenically unsaturated monomers are selected from the group consisting of: (meth) acrylates, (meth) acrylamide alkyl esters, vinyl ethers, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropylmethanesulfonic acid, (meth) acrylic acid, maleic acid, their salts and mixtures thereof. More preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises, based on the dry weight of the thickening polymer, 0 to 20 wt. % (preferably 0.1 to 5 wt. %; more preferably 0.5 to 4 wt. %; most preferably 1 to 3 wt. %) of structural units of other monoethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from monoethylenically unsaturated alkanoic acid vinyl esters having 4 to 12 carbon atoms and monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms, and wherein the other monoethylenically unsaturated monomers are selected from the group consisting of: (meth)acrylic acid C 1-4 Alkyl ester, (meth)acrylamide C 1-4Alkyl esters, vinyl ethers, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropyl methane sulfonic acid, (meth) acrylic acid, maleic acid, their salts and mixtures thereof. Still more preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises, based on the dry weight of the thickening polymer, 0 wt % to 20 wt % (preferably, 0.1 wt % to 5 wt %; more preferably, 0.5 wt % to 4 wt %; most preferably, 1 wt % to 3 wt %) of structural units of other monoethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from monoethylenically unsaturated alkanoic acid vinyl esters having 4 to 12 carbon atoms and monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms, and wherein the other monoethylenically unsaturated monomers are selected from the group consisting of: methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylamide, ethyl (meth) acrylamido, vinyl ethers, vinyl sulfonic acid, styrene sulfonic acid, (meth) acrylic acid, maleic acid, their salts and mixtures thereof. Most preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises, based on the dry weight of the thickening polymer, 0 wt % to 20 wt % (preferably, 0.1 wt % to 5 wt %; more preferably, 0.5 wt % to 4 wt %; most preferably, 1 wt % to 3 wt %) of structural units of other monoethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from monoethylenically unsaturated alkanoic acid vinyl esters having 4 to 12 carbon atoms and monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms, and wherein the other monoethylenically unsaturated monomers are selected from the group consisting of vinyl sulfonic acid, vinyl sulfonates and mixtures thereof.

[0022] Preferably, the thickening polymer according to the invention contains less than 10 wt.-% (preferably <5 wt.-%; more preferably <1 wt.-%, still more preferably <0.1 wt.-%; most preferably <detection limit) structural units of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, their alkali metal salts, their ammonium salts and mixtures thereof, based on the dry weight of the thickening polymer.

[0023] Preferably, the structural units of monoethylenically unsaturated alkanoic acid vinyl esters having 4 to 12 carbon atoms and the structural units of monoethylenically unsaturated carboxylic acid-functionalized vinyl esters having 4 to 12 carbon atoms account for a total of 70% to 100% by weight of the thickening polymer, based on the dry weight of the thickening polymer (more preferably, 75% to 100% by weight; still more preferably, 80% to 100% by weight; yet more preferably, 85% to 99.9% by weight; still more preferably, 90% to 99.5% by weight; most preferably, 95% to 99% by weight).

[0024] Preferably, the thickening polymer of the present invention contains less than 1.2 wt% (preferably, 0 wt% to 1.1 wt%; more preferably, 0 wt% to 1.0 wt%; still more preferably, 0 wt% to 0.5 wt%; yet more preferably, 0 wt% to 0.1 wt%; most preferably, 0 wt% to 0.01 wt%) of structural units of 2-acrylamido-2-methylpropanesulfonic acid, based on the dry weight of the thickening polymer.

[0025] Preferably, the thickening polymer of the present invention contains less than 5 mol% (preferably, <1 mol%; more preferably, <0.1 mol%; most preferably, <detection limit) of structural units of dicarboxylic anhydrides. More preferably, the thickening polymer of the present invention contains less than 5 mol% (preferably, <1 mol%; more preferably, <0.1 mol%; most preferably, <detection limit) of structural units of dicarboxylic anhydrides selected from the group consisting of maleic anhydride, itaconic anhydride and mixtures thereof.

[0026] Preferably, the thickening polymer of the present invention contains less than 10% by weight (preferably <5% by weight; more preferably <1% by weight; still more preferably <0.1% by weight; most preferably < detection limit) of structural units of monoethylenically unsaturated alkyl acrylate monomers containing 2 to 10 carbon atoms, based on the dry weight of the thickening polymer. Most preferably, the thickening polymer of the present invention contains less than 10% by weight (preferably <5% by weight; more preferably <1% by weight; still more preferably <0.1% by weight; most preferably < detection limit) of structural units of monoethylenically unsaturated alkyl acrylate monomers containing 2 to 10 carbon atoms, based on the dry weight of the thickening polymer, the monoethylenically unsaturated alkyl acrylate monomers being selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and mixtures thereof.

[0027] Preferably, the thickening polymer of the present invention contains less than 0.1 mol% (preferably, <0.01 mol%; more preferably, <0.001 mol%; most preferably, <detection limit) of structural units of monomers containing monoethylenically unsaturated amides. More preferably, the thickening polymer of the present invention contains less than 0.1 mol% (preferably, <0.01 mol%; more preferably, <0.001 mol%; most preferably, <detection limit) of structural units of monomers containing monoethylenically unsaturated amides selected from the group consisting of: N-vinylformamide; (meth)acrylamide; 2-acrylamido-2-methyl-propanesulfonic acid (AMPS); 3-(methacrylamido)propyltrimethylammonium chloride (MAPTAC) and mixtures thereof.

[0028] Preferably, the thickening polymers of the present invention are biodegradable as determined according to the procedure of OECD 302B. More preferably, the thickening polymers of the present invention have inherent ultimate biodegradability as determined according to the procedure of OECD 302B.

[0029] The thickening polymers of the present invention may be prepared using conventional or otherwise known polymerization techniques.

[0030] Preferably, the aqueous detergent formulations of the present invention optionally further include additives selected from the group consisting of: builders (e.g., sodium bicarbonate, sodium carbonate, zeolite, sodium citrate, sodium tripolyphosphate and aminocarboxylates (such as methylglycine diacetic acid, sodium salt or glutamic acid diacetic acid, sodium salt)); fillers; enzymes (e.g., proteases, cellulases, lipases, amylases, mannanases); pigments; dyes; structurants; colorants; bleaches (e.g., sodium percarbonate, sodium perborate, sodium hypochlorite); bleach activators (tetraacetylethylenediamine (TAED)); stabilizers; foam control agents (e.g., fatty acids, polydimethylsiloxanes); optical brighteners; hydrotropes (e.g., sodium xylene sulfonate); fragrances (e.g., essential oils, such as D-limonene); conditioning polymers; preservatives and mixtures thereof.

[0031] Preferably, the aqueous detergent formulation of the present invention further comprises, based on the weight of the aqueous detergent formulation, 0 wt % to 10 wt % (preferably, 0.1 wt % to 10 wt %; more preferably, 0.2 wt % to 8 wt %; most preferably, 0.5 wt % to 7.5 wt %) of a hydrotrope. More preferably, the aqueous detergent formulation of the present invention further comprises, based on the weight of the aqueous detergent formulation, 0 wt % to 10 wt % (preferably, 0.1 wt % to 10 wt %; more preferably, 0.2 wt % to 8 wt %; most preferably, 0.5 wt % to 7.5 wt %) of a hydrotrope; wherein the hydrotrope is selected from the group consisting of: alkyl hydroxides; glycols; urea; calcium, sodium, potassium, ammonium and alkanolammonium salts of xylene sulfonic acid, toluene sulfonic acid, ethylbenzene sulfonic acid, naphthalene sulfonic acid and isopropylbenzene sulfonic acid; their salts and mixtures thereof. Still more preferably, the aqueous detergent formulation of the present invention further comprises, based on the weight of the aqueous detergent formulation, 0 wt% to 10 wt% (preferably, 0.1 wt% to 10 wt%; more preferably, 0.2 wt% to 8 wt%; most preferably, 0.5 wt% to 7.5 wt%) of a hydrotrope; wherein the hydrotrope is selected from the group consisting of 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. Most preferably, the aqueous detergent formulation of the present invention further comprises, based on the weight of the aqueous detergent formulation, 0 wt% to 10 wt% (preferably, 0.1 wt% to 10 wt%; more preferably, 0.2 wt% to 8 wt%; most preferably, 0.5 wt% to 7.5 wt%) of a hydrotrope; wherein the hydrotrope is sodium xylene sulfonate.

[0032] Preferably, the aqueous detergent formulation of the present invention further comprises 0 to 30 wt % (preferably 1 to 20 wt %; more preferably 2.5 to 10 wt %) of a builder, based on the weight of the aqueous detergent formulation. More preferably, the aqueous detergent formulation of the present invention further comprises, based on the weight of the aqueous detergent formulation, 0 wt % to 30 wt % (preferably 1 wt % to 20 wt %; more preferably 2.5 wt % to 10 wt %) of a builder; wherein the builder is selected from the group consisting of: inorganic builders (e.g., tripolyphosphates, pyrophosphates); alkali metal carbonates; borates; bicarbonates; hydroxides; zeolites; citrates (e.g., sodium citrate); polycarboxylates; monocarboxylates; aminotrimethylenephosphonic acid; salts of aminotrimethylenephosphonic acid; hydroxyethylidene diphosphonic acid; salts of hydroxyethylidene diphosphonic acid; diethylenetriamine penta(methylenephosphonic acid); salts of diethylenetriamine penta(methylenephosphonic acid); ethylenediaminetetraethylenephosphonic acid; salts of ethylenediaminetetraethylenephosphonic acid; oligomeric phosphonates; polymeric phosphonates; mixtures thereof. Most preferably, the aqueous detergent formulation of the present invention further comprises 0 wt % to 30 wt % (preferably 1 wt % to 20 wt %; more preferably 2.5 wt % to 10 wt %) of a builder, based on the weight of the aqueous detergent formulation; wherein the builder comprises sodium citrate.

[0033] Preferably, the aqueous detergent formulation of the present invention further comprises 0 wt % to 2 wt % (preferably 0.05 wt % to 0.8 wt %; more preferably 0.1 wt % to 0.4 wt %) of a structurant, based on the weight of the aqueous detergent formulation. More preferably, the aqueous detergent formulation of the present invention further comprises 0 wt % to 2 wt % (preferably 0.05 wt % to 0.8 wt %; more preferably 0.1 wt % to 0.4 wt %) of a structurant, based on the weight of the aqueous detergent formulation; wherein the structurant is a non-polymeric crystalline hydroxy-functional material capable of forming a linear structural system throughout the aqueous detergent formulation upon in situ crystallization.

[0034] Preferably, the aqueous detergent formulation of the present invention further comprises 0 wt % to 10 wt % (preferably, 0.001 wt % to 5 wt %; more preferably, 0.005 wt % to 3 wt %; most preferably, 0.01 wt % to 2.5 wt %) of a fragrance, based on the weight of the aqueous detergent formulation.

[0035] Preferably, the aqueous detergent formulation of the present invention further comprises 0% to 10% by weight (preferably 0.5% to 10% by weight) of a conditioning polymer, based on the weight of the aqueous detergent formulation. More preferably, the aqueous detergent formulation of the present invention further comprises 0% to 10% by weight (preferably 0.5% to 10% by weight) of a conditioning polymer, based on the weight of the aqueous detergent formulation; wherein the conditioning polymer is a cationic coacervate polymer (e.g., cationic hydroxyethylcellulose; polyquaternium polymers and combinations thereof).

[0036] Preferably, the pH of the aqueous detergent formulation of the present invention is 6 to 12.5 (preferably 6.5 to 11; more preferably 7.5 to 10). Bases used to adjust the pH include mineral bases such as sodium hydroxide (including soda ash) and potassium hydroxide; sodium bicarbonate; sodium silicate; ammonium hydroxide; and organic bases (e.g., monoethanolamine, diethanolamine or triethanolamine; and 2-dimethylamino-2-methyl-1-propanol (DMAMP)). Acids for adjusting the pH include inorganic acids (e.g., hydrochloric acid, phosphoric acid and sulfuric acid) and organic acids (e.g., acetic acid).

[0037] Preferably, the aqueous detergent formulations of the present invention contain less than 2 wt% (preferably <1 wt%; more preferably <0.01 wt%; still more preferably <0.001 wt%; most preferably <detection limit) of drying oils, based on the dry weight of the thickening polymer. More preferably, the aqueous detergent formulations of the present invention contain less than 2 wt% (preferably <1 wt%; more preferably <0.01 wt%; still more preferably <0.001 wt%; most preferably <detection limit) of drying oils selected from the group consisting of safflower oil, linseed oil, castor seed oil, oatmeal oil, sunflower oil, soybean oil, perilla oil, tall oil, dehydrated castor seed oil, poppy oil, tung oil, very long oil alkyd resin, long oil alkyd resin and mixtures thereof, based on the dry weight of the thickening polymer.

[0038] Some embodiments of the present invention will now be described in detail in the following examples.

[0039] Synthesis S1-S6: Thickening polymer

[0040] A mixture of deionized water (65.5 g) and an aqueous solution of lauryl ethoxylated sulfate surfactant (2.4 g, 31 wt %, available from BASF under the trade name Disponil FES-32) was added to a glass reactor. The reactor contents were then heated to 30° C. with stirring. Separately, in a container, deionized water (3.4 g), an aqueous solution of sodium vinyl sulfonate (SVS) (1.32 g, 0.24 wt %), secondary C 13An aqueous solution of alkyl ethoxylate (0.23 g, 70 wt %, sold under the trade name Tergitol TM A monomer emulsion (ME) was prepared by mixing 15-S-40 (available from Dow Chemical Company), an aqueous solution of lauryl ethoxylated sulfate surfactant (0.45 g, 31 wt%), and an alkanoic acid vinyl ester monomer A in an amount as shown in Table 1. The swirled ME was then added to the reactor with continued stirring. The ME container was then rinsed forward into the reactor with deionized water (6 g). After a 5 minute hold, carboxylic acid functionalized vinyl ester monomer B was added to the reactor in an amount as shown in Table 1. Crosslinker C (if any) was added to the reactor in an amount as shown in Table 1. After a 2 minute hold, an aqueous solution of ferric sulfate (1.2 g, 0.015 wt%) was then added to the reactor. After a 1 minute hold, a solution of ammonium persulfate (0.16 g) in deionized water (1.7 g) was added to the reactor. After a 1 minute hold, a sulfur-based formaldehyde-free reducing agent (0.212 g, Bruggolite FF6 M, available from Bruggemann) in water (3.0 g) was added to the reactor. After 30 minutes, another solution of ammonium sulfate (0.16 g) in deionized water (1.7 g) was added to the reactor. After holding for 1 minute, another solution of sulfur-based formaldehyde-free reducing agent (0.212 g, Bruggolite FF6 M, obtained from Bruggemann) in water (3.0 g) was added to the reactor. After 15 minutes, the reactor product was collected for analysis. The pH and solid weight percent of the reactor product are reported in Table 2.

[0041] Table 1

[0042]

[0043] Table 2

[0044] synthesis pH Solid (wt%) S1 2.9 15.3 S2 2.9 15.3 S3 2.6 14.7 S4 2.5 15.0 S5 3.9 16.8 S6 3.6 16.8

[0045] Comparative Examples CF1-CF4 and Examples F1-F6: Laundry Detergents

[0046] A laundry detergent formulation was prepared in each of the comparative examples CF1-CF4 and embodiments F1-F6 having the formulations shown in Table 3. The formulation was prepared by combining the ingredients in the order listed in Table 3 while constantly mixing with an overhead mixer to produce a vortex. The anionic surfactant, water, and solvent were fully mixed until all components were incorporated, and then a nonionic surfactant pre-melted at 50°C was added. The pH was then adjusted to 8.5 with a NaOH solution. Then a thickening polymer as shown in Table 3 was added to the formulation in an amount sufficient to provide 1.2% by weight of active thickening polymer in the formulation while mixing with an overhead mixer. If necessary, the pH was adjusted back to 8.5 using a NaOH or HCl solution. Water was then added as needed to bring the formulation to 100% by weight.

[0047] Table 3

[0048]

[0049] Viscosity of laundry detergent formulations

[0050] The viscosity of laundry detergent formulations prepared according to Comparative Examples CF1-CF4 and Examples F1-F6 was measured with a Brookfield viscometer using a LV-2 (62) spindle at 3 rpm. The results are provided in Table 4.

[0051] Table 4

[0052] Laundry detergent preparations Viscosity(cP) Comparative Example CF1 380 Comparative Example CF2 1,560 Comparative Example CF3 1,220 Comparative Example CF4 1,700 Example F1 680 Example F2 1,020 Example F3 540 Example F4 1,040 Example F5 1,530 Example F6 1,460

[0053] Biodegradability

[0054] The biodegradability of the thickening polymer prepared according to Synthesis S1 was evaluated according to the inherent aerobic biodegradation test procedure described in OECD 302 B. The results are provided in Table 5.

[0055] Table 5

[0056]

Claims

1. An aqueous detergent formulation comprising: Aqueous carrier; Cleansing surfactants; A thickening polymer, the thickening polymer comprising: 20% to 80% by weight, based on the dry weight of the thickening polymer, of structural units of monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms; 20% to 80% by weight, based on the dry weight of the thickening polymer, of structural units of monoethylenically unsaturated carboxylic acid-functionalized vinyl esters having 4 to 12 carbon atoms; 0% to 5% by weight, based on the dry weight of the thickening polymer, of structural units of a polyethylenically unsaturated crosslinker; 0 to 20 wt. % of structural units of other monoethylenically unsaturated monomers, based on the dry weight of the thickening polymer, wherein the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated alkanoic acid vinyl esters having 4 to 12 carbon atoms and the monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; and The thickening polymer contains less than 10% by weight, based on the dry weight of the thickening polymer, of structural units of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, alkali metal salts thereof, ammonium salts thereof and mixtures thereof.

2. The aqueous detergent formulation according to claim 1, wherein the structural units of the monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms and the structural units of the monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4 to 12 carbon atoms together account for 70% to 100% by weight of the thickening polymer, based on the dry weight of the thickening polymer.

3. The aqueous detergent formulation according to claim 2, wherein the structural unit of the monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms is selected from the group of structural units consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl 3-methylbutyrate, vinyl pivalate, vinyl hexanoate, vinyl 4-methylvalerate, vinyl 3,3-dimethylbutyrate, vinyl heptanoate, vinyl 5-methylhexanoate, vinyl 4,4-dimethylvalerate, vinyl octanoate, vinyl 6-methylheptanoate, vinyl 5,5-dimethylhexanoate and mixtures thereof.

4. The aqueous detergent formulation according to claim 3, wherein the structural unit of the monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4 to 12 carbon atoms is selected from the group of structural units consisting of: 4-oxo-4-(vinyloxy)butanoic acid, 5-oxo-5-(vinyloxy)pentanoic acid, 6-oxo-6-(vinyloxy)hexanoic acid, 7-oxo-7-(vinyloxy)heptanoic acid, 8-Oxo-8-(vinyloxy)octanoic acid and mixtures thereof.

5. The aqueous detergent formulation according to claim 4, wherein the thickening polymer comprises from 0.01% to 2.5% by weight, based on the dry weight of the thickening polymer, of structural units of the polyethylenically unsaturated crosslinking agent.

6. An aqueous detergent formulation according to claim 5, wherein the polyethylenically unsaturated crosslinker is diallyl phthalate.

7. The aqueous detergent formulation according to claim 6, wherein the thickening polymer further comprises 0.1 wt. % to 5 wt. % of structural units of the other monoethylenically unsaturated monomers, based on the dry weight of the thickening polymer; wherein the other monoethylenically unsaturated monomers are selected from the group consisting of: (meth)acrylates, (meth)acrylamides, vinyl ethers, vinyl sulfonic acid, styrene sulfonic acid, (meth)acrylic acid, maleic acid, salts thereof, and mixtures thereof.

8. The aqueous detergent formulation according to claim 7, wherein the structural unit of the monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms is a structural unit of vinyl acetate.

9. The aqueous detergent formulation according to claim 8, wherein the structural units of the monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4 to 12 carbon atoms are structural units of 6-oxo-6-(vinyloxy)hexanoic acid; and wherein the other monoethylenically unsaturated monomers are selected from the group consisting of vinyl sulfonic acid, vinyl sulfonates and mixtures thereof.

10. The aqueous detergent formulation according to claim 9, further comprising an optional component selected from the group consisting of builders, fillers, enzymes, pigments, dyes, colorants, bleaches, bleach activators, stabilizers, foam control agents, fluorescent whitening agents, hydrotropes, fragrances, preservatives and mixtures thereof.

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