Water-based detergent formulations

Abstract

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

Description

[Technical field]

[0001] The present invention relates to an aqueous detergent formulation comprising an aqueous carrier, a cleaning surfactant, and a thickening polymer having 20-80% by weight, based on the dry weight of the thickening polymer, of structural units of a monoethylenically unsaturated vinyl alkanoate having 4-12 carbon atoms, 20-80% by weight, based on the dry weight of the thickening polymer, of structural units of a monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4-12 carbon atoms, 0-5% by weight, based on the dry weight of the thickening polymer, of structural units of a multiethylenically unsaturated crosslinker, and 0-20% by weight, based on the dry weight of the thickening polymer, of other monoethylenically unsaturated crosslinkers. and a thickening polymer comprising structural units of an ethylenically unsaturated monomer, the other monoethylenically unsaturated monomers being distinct from monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms and monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms, the thickening polymer containing less than 10% by weight, based on the dry weight of the thickening polymer, of structural units of a monoethylenically unsaturated dicarboxylic acid having 4 to 6 carbon atoms, its alkali metal salts, its ammonium salts, and mixtures thereof. [Background technology]

[0002] Aqueous detergent formulations are well known. Nevertheless, conventional aqueous detergent formulations often contain various non-biodegradable ingredients, including thickeners. There is a demand in the market to increase the biodegradable content of aqueous detergent formulations, especially aqueous laundry detergent formulations. Many conventional thickeners used in aqueous detergent formulations include alkali-soluble / swellable latex, which is non-toxic and does not pose serious environmental hazards, but is typically not biodegradable.

[0003] Thus, there remains a need to find new biodegradable ingredients suitable for use as thickeners in aqueous detergent formulations. Summary of the Invention

[0004] The present invention provides an aqueous detergent formulation comprising a liquid carrier, a cleaning surfactant, and a thickening polymer comprising 20-80% by weight, based on the dry weight of the thickening polymer, of structural units of a monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms, 20-80% by weight, based on the dry weight of the thickening polymer, of structural units of a monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4 to 12 carbon atoms, 0-5% by weight, based on the dry weight of the thickening polymer, of structural units of a multiethylenically unsaturated crosslinker, and 0-20% by weight, based on the dry weight of the thickening polymer, of structural units of other monoethylenically unsaturated monomers, the other monoethylenically unsaturated monomers being different from monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms and monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms, and the thickening polymer containing less than 10% by weight, based on the dry weight of the thickening polymer, of structural units of a monoethylenically unsaturated dicarboxylic acid having 4 to 6 carbon atoms, its alkali metal salts, its ammonium salts, and mixtures thereof. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0005] Applicants have surprisingly found that an aqueous detergent formulation comprising an aqueous carrier and a cleaning surfactant contains from 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, from 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, from 0 to 5% by weight, based on the dry weight of the thickening polymer, of structural units of multiethylenically unsaturated crosslinkers, from 0 to 20% by weight, based on the dry weight of the thickening polymer, of other monoethylenically unsaturated crosslinkers, from 0 to 5 ... In one embodiment of the present invention, the thickening polymer comprises structural units of a monoethylenically unsaturated monomer, unlike other monoethylenically unsaturated monomers such as monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms and monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms, and the thickening polymer can be effectively thickened using a thickening polymer containing less than 10% by weight, based on the dry weight of the thickening polymer, of structural units of a monoethylenically unsaturated dicarboxylic acid having 4 to 6 carbon atoms, its alkali metal salts, its ammonium salts, and mixtures thereof, and 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 of dry weight, i.e., excluding any water that may be present in the composition. Percentages of monomer units in a polymer are percentages of solids weight, i.e., excluding any water present in a polymer emulsion.

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

[0008] Preferably, the aqueous detergent formulation of the present invention is selected from the group consisting of aqueous laundry detergent formulations, aqueous dishwashing detergent formulations, and aqueous hand soap formulations. 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 (preferably 15 to 97.9 wt. % (preferably 40 to 94.75 wt. %, more preferably 45 to 92 wt. %, most preferably 47 to 89 wt. %) of the aqueous carrier based on the weight of the aqueous detergent formulation), a cleaning surfactant (preferably 2 to 60 wt. % (preferably 5 to 40 wt. %, more preferably 7.5 to 30 wt. %, most preferably 10 to 25 wt. %) of the cleaning surfactant based on the weight of the aqueous detergent formulation), and a thickening polymer (preferably 2 to 60 wt. % (preferably 5 to 40 wt. %, more preferably 7.5 to 30 wt. %, most preferably 10 to 25 wt. %) of the cleaning surfactant based on the weight of the aqueous detergent formulation). %, preferably 0.1 to 7.5% by weight (preferably 0.25 to 6% by weight, more preferably 0.5 to 5% by weight, most preferably 1 to 3% by weight) of the thickening polymer, based on the dry weight of the thickening polymer, and 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 monoethylenically unsaturated vinyl alkanoate structural units having 4 to 12 carbon atoms, based on the dry weight of the thickening polymer. % (preferably 22 to 75 wt. %, more preferably 25 to 60 wt. %, most preferably 27.5 to 55 wt. %) of structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4 to 12 carbon atoms, 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 multiethylenically unsaturated crosslinking agent, based on the dry weight of the thickening polymer, 0 to 20 wt. % (preferably 0.1 to 10 wt. %, more preferably 0.1 to 10 wt. %) of structural units of multiethylenically unsaturated crosslinking agent, based on the dry weight of the thickening polymer, %. The thickening polymer comprises structural units of other monoethylenically unsaturated monomers in an amount of from 10% to 5% by weight, more preferably from 0.5 to 4% by weight, and most preferably from 1 to 3% by weight, based on the dry weight of the thickening polymer, the other monoethylenically unsaturated monomers being different from monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms and monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms, and the thickening polymer comprises less than 10% by weight, based on the dry weight of the thickening polymer (preferably less than 5% by weight, more preferably less than 1% by weight, and even more preferably less than 0.5% by weight, and most preferably less than 0.5% by weight, based on the dry weight of the thickening polymer).The thickening polymer contains less than 1% by weight, most preferably below the detection limit, of structural units of a monoethylenically unsaturated dicarboxylic acid having 4 to 6 carbon atoms, its alkali metal salts, its ammonium salts, and mixtures thereof.

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

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

[0012] Preferably, the aqueous detergent formulation of the present invention comprises 2 to 60% by weight (preferably 5 to 40% by weight, more preferably 7.5 to 30% by weight, most preferably 10 to 25% by weight) of a cleaning surfactant based on the weight of the aqueous detergent formulation. More preferably, the aqueous detergent formulation of the present invention comprises 2 to 60% by weight (preferably 5 to 40% by weight, more preferably 7.5 to 30% by weight, most preferably 10 to 25% by weight) of a cleaning surfactant based on the weight of the aqueous detergent formulation, the cleaning surfactant being selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and mixtures thereof. Even more preferably, the aqueous detergent formulation of the present invention comprises 2 to 60% by weight (preferably 5 to 40% by weight, more preferably 7.5 to 30% by weight, most preferably 10 to 25% by weight) of a cleaning surfactant based on the weight of the aqueous detergent formulation, the cleaning surfactant comprising an anionic surfactant. Even more preferably, the aqueous detergent formulation of the present invention comprises 2-60% by weight (preferably 5-40% by weight, more preferably 7.5-30% by weight, most preferably 10-25% by weight) of a cleaning surfactant based on the weight of the aqueous detergent formulation, the cleaning surfactant comprising a mixture of anionic and nonionic surfactants. Most preferably, the aqueous detergent formulation of the present invention comprises 2-60% by weight (preferably 5-40% by weight, more preferably 7.5-30% by weight, most preferably 10-25% by weight) of a cleaning surfactant based on the weight of the aqueous detergent formulation, the cleaning surfactant comprising a mixture of linear alkyl benzene 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, Alpha-sulfocarboxylates, esters of alpha-sulfocarboxylates, alkyl glyceryl ether sulfonic acids, alkyl glyceryl ether sulfonates, fatty acid sulfates, fatty acid sulfonates, fatty acid ester sulfonates, alkylphenols, alkylphenol polyethoxy ether sulfates, Preferred anionic surfactants include 2-acryloxy-alkane-1-sulfonic acids, 2-acryloxy-alkane-1-sulfonates, beta-alkyloxyalkanesulfonic acids, beta-alkyloxyalkanesulfonates, amine oxides, and mixtures thereof. 8~20 Alkylbenzene sulfate, C 8~20 Alkylbenzene sulfonic acid, C 8~20 Alkylbenzene sulfonates, Paraffin sulfonic acids, Paraffin sulfonates, Alpha-olefin sulfonic acids, Alpha-olefin sulfonates, Alkoxylated alcohols, C 8~20 Alkylphenols, amine oxides, Sulfonates of fatty acids, sulfonates of fatty acid esters, C 8~10 Alkyl polyethoxy sulfates, and mixtures thereof. More preferred anionic surfactants include C 12~16 Alkylbenzene sulfonic 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 quaternary surface active compounds having at least one of ammonium, sulfonium, phosphonium, iodonium, and arsonium groups. More preferred cationic surfactants include at least one of dialkyldimethylammonium chloride and alkyldimethylbenzylammonium chloride. Even more preferred cationic surfactants include C 16~18 Dialkyldimethylammonium chloride, C 8~18 The cationic surfactants include at least one of alkyl dimethyl benzyl ammonium chloride and dimethyl ditallow ammonium chloride. The most preferred cationic surfactants include dimethyl ditallow ammonium chloride.

[0016] Examples of amphoteric surfactants include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amine oxides, acylated amino acids, derivatives of aliphatic quaternary ammonium compounds, and mixtures thereof. Examples of preferred amphoteric surfactants include derivatives of aliphatic quaternary ammonium compounds. Examples of more preferred amphoteric surfactants include derivatives of aliphatic quaternary ammonium compounds having a long chain group with 8 to 18 carbon atoms. Examples of even more preferred amphoteric surfactants include C 12~14 Alkyl dimethyl amine oxide, 3-(N,N-dimethyl-N-hexadecyl-ammonio)propane-1-sulfonate, 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate. The most preferred amphoteric surfactants include at least one of C 12~14 At least one of alkyl dimethyl amine oxides may be mentioned.

[0017] Preferably, the aqueous detergent formulation of the present invention comprises 0.1 to 7.5 wt. % (preferably 0.25 to 6 wt. %, more preferably 0.5 to 5 wt. %, most preferably 1 to 3 wt. %) of a thickening polymer based on the weight of the aqueous detergent formulation and 20 to 80 wt. % (preferably 24.89 to 77.89 wt. %, more preferably 39.48 to 74.48 wt. %, most preferably 43.96 to 71.46 wt. %) of a 4 to 12 carbon atom thickening polymer 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, based on the dry weight of the thickening polymer; 0 to 5% by weight (preferably 0.01 to 2.5% by weight, more preferably 0.02 to 1 %, most preferably 0.04-0.5% by weight, of structural units of a multiethylenically unsaturated crosslinker, and 0-20% by weight (preferably 0.1-5% by weight, more preferably 0.5-4% by weight, most preferably 1-3% by weight) of structural units of other monoethylenically unsaturated monomers, based on the dry weight of the thickening polymer, the other monoethylenically unsaturated monomers being distinct from monoethylenically unsaturated vinyl alkanoates having 4-12 carbon atoms and monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4-12 carbon atoms, and the thickening polymer contains less than 10% by weight (preferably less than 5% by weight, more preferably less than 1% by weight, even more preferably less than 0.1% by weight, most preferably below the detection limit) of structural units of a monoethylenically unsaturated dicarboxylic acid having 4-6 carbon atoms, alkali metal salts thereof, ammonium salts thereof, 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 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 monoethylenically unsaturated vinyl alkanoate structural units having 4 to 12 carbon atoms, based on the dry weight of the thickening polymer, and the monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms is selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pentanoate, vinyl 3-methylbutanoate, vinyl pivalate, vinyl hexanoate, vinyl 4-methylpentanoate, vinyl 3,3-dimethylbutanoate, vinyl hex ... In some embodiments, the vinyl ester may be selected from the group consisting of vinyl 2-methyl-2-propyl hexanoate, vinyl 2-ethyl-2-methyl heptanoate, vinyl 2,2-dimethyl octanoate, vinyl 2,2-dimethyl heptanoate, vinyl 2-ethyl-2-methyl hexanoate, vinyl 2-methyl-2-propyl pentanoate, vinyl 2-ethyl hexanoate, vinyl 2-ethyl hexanoate, vinyl 2-methyl-2-propyl pentanoate, vinyl 2-ethyl hexanoate, and mixtures thereof.More preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises 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 alkanoate having 4 to 12 carbon atoms, based on the dry weight of the thickening polymer, the monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms being selected from the group consisting of vinyl acetate, vinyl propionate, vinyl methacrylate ... In some embodiments, the vinyl ester may be selected from the group consisting of vinyl ester, vinyl butyrate, vinyl isobutyrate, vinyl pentanoate, vinyl 3-methylbutanoate, vinyl pivalate, vinyl hexanoate, 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, and mixtures thereof. Even more preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises 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 a monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms, based on the dry weight of the thickening polymer, wherein the monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms is selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pentanoate, vinyl 3-methylbutanoate, vinyl pivalate, vinyl hexanoate, vinyl 4-methylpentanoate, vinyl 3,3-dimethylbutanoate, and mixtures thereof.Even more preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises 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 a monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms, based on the dry weight of the thickening polymer, wherein the monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms is 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 20 to 80% (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 a monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms, based on the dry weight of the thickening polymer, 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 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 a monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4 to 12 carbon atoms, based on the dry weight of the thickening polymer, the monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4 to 12 carbon atoms being selected from the group consisting of 2-oxo-2-(vinyloxy)acetic acid, 3-oxo-3-(vinyloxy)propanoic acid, 4-oxo-4-(vinyloxy)butanoic acid (also known as vinylsuccinic acid), 5-oxo-5-(vinyloxy)pentanoic acid, 6-oxo-6-(vinyloxy)hexanoic acid (also known as vinyladipic acid), 7-oxo-7-(vinyloxy)heptanoic acid, 8-oxo-8-(vinyloxy)octanoic acid, 9-oxo-9-(vinyloxy)nonanoic acid, More preferably, the biodegradable thickening polymer in the aqueous detergent formulation of the present invention comprises 20-80% by weight (preferably 22-75%, more preferably 25-60%, most preferably 27.5-55% by weight) of structural units of a monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4-12 carbon atoms, based on the dry weight of the thickening polymer, the monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4-12 carbon atoms being 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, Even more preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises 20-80 wt. % (preferably 22-75 wt. %, more preferably 25-60 wt. %, most preferably 27.5-55 wt. %) of structural units of a monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4-12 carbon atoms, based on the dry weight of the thickening polymer, the monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4-12 carbon atoms being selected from the group consisting of 5-oxo-5-(vinyloxy)pentanoic acid, 6-oxo-6-(vinyloxy)hexanoic acid, Even more preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises 20-80 wt. % (preferably 22-75 wt. %, more preferably 25-60 wt. %, most preferably 27.5-55 wt. %) of structural units of a monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4-12 carbon atoms, based on the dry weight of the thickening polymer, the monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4-12 carbon atoms being 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. 8-oxo-8-(vinyloxy)octanoic acid, and mixtures thereof. Most preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises 20-80 wt. % (preferably 22-75 wt. %, more preferably 25-60 wt. %, most preferably 27.5-55 wt. %) of structural units of a monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4-12 carbon atoms, based on the dry weight of the thickening polymer, wherein the monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4-12 carbon atoms is 6-oxo-6-(vinyloxy)hexanoic acid.

[0020] Preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises 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 a multiethylenically unsaturated crosslinker structural unit, based on the dry weight of the thickening polymer, the multiethylenically unsaturated crosslinker being selected from the group consisting of multiethylenically unsaturated crosslinkers having an average of 2 or 3 vinyl groups per molecule. More preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises 0 to 5 wt. % (preferably 0.01 to 2.5 wt. %, more preferably 0.02 to 1 wt. %, and most preferably 0.04 to 0.5 wt. %) of structural units of a multiethylenically unsaturated crosslinker, based on the dry weight of the thickening polymer, wherein the multiethylenically unsaturated crosslinker 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-butylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, diallyl phthalate, trimethylolpropane tri(meth)acrylate, divinylbenzene, divinyltoluene, trivinylbenzene, divinylnaphthalene, and mixtures thereof. Most preferably, the thickening polymer in the aqueous detergent formulation of the present invention comprises 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 multiethylenically unsaturated crosslinker, based on the dry weight of the thickening polymer, and the multiethylenically unsaturated crosslinker is diallyl phthalate.

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

[0022] Preferably, the thickening polymer of the present invention contains less than 10% by weight (preferably less than 5% by weight, more preferably less than 1% by weight, even more preferably less than 0.1% by weight, and most preferably below the 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.

[0023] Preferably, 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 account in total for 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, even more preferably, 80 to 100% by weight, even more preferably, 85 to 99.9% by weight, even more preferably, 90 to 99.5% by weight, and most preferably, 95 to 99% by weight).

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

[0025] Preferably, the thickening polymer of the present invention contains less than 5 mol % (preferably less than 1 mol %, more preferably less than 0.1 mol %, most preferably below the detection limit) of structural units of an anhydride of a dicarboxylic acid. More preferably, the thickening polymer of the present invention contains less than 5 mol % (preferably less than 1 mol %, more preferably less than 0.1 mol %, most preferably below the detection limit) of structural units of an anhydride of a dicarboxylic acid 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 less than 5% by weight, more preferably less than 1% by weight, even more preferably less than 0.1% by weight, most preferably less than the 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. Preferably, the thickening polymer of the present invention contains less than 10% by weight (preferably less than 5% by weight, more preferably less than 1% by weight, even more preferably less than 0.1% by weight, most preferably less than the 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, 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 less than 0.01 mol %, more preferably less than 0.001 mol %, most preferably below the detection limit) of structural units of monoethylenically unsaturated amide-containing monomers. More preferably, the thickening polymer of the present invention contains less than 0.1 mol % (preferably less than 0.01 mol %, more preferably less than 0.001 mol %, most preferably below the detection limit) of structural units of monoethylenically unsaturated amide-containing monomers selected from the group consisting of N-vinylformamide, (meth)acrylamide, 2-acrylamido-2-methyl-propanesulfonic acid (AMPS), 3-(methacrylamide)propyl trimethylammonium 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 can be made using conventional or otherwise known polymerization techniques.

[0030] Preferably, the aqueous detergent formulation of the present invention further comprises optionally providing an additive selected from the group consisting of builders (e.g., sodium bicarbonate, sodium carbonate, zeolites, sodium citrate, sodium tripolyphosphate, and aminocarboxylates (such as methylglycine diacetate sodium salt or glutamic acid diacetate, sodium salt)); fillers; enzymes (e.g., proteases, cellulases, lipases, amylases, mannanases); pigments; dyes; structuring agents; colorants; bleaching agents (e.g., sodium percarbonate, sodium perborate, sodium hypochlorite); bleach activators (tetra acetyl ethylene diamine, 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 0-10 wt. % (preferably 0.1-10 wt. %, more preferably 0.2-8 wt. %, most preferably 0.5-7.5 wt. %) of a hydrotrope based on the weight of the aqueous detergent formulation. More preferably, the aqueous detergent formulation of the present invention further comprises 0-10 wt. % (preferably 0.1-10 wt. %, more preferably 0.2-8 wt. %, most preferably 0.5-7.5 wt. %) of a hydrotrope based on the weight of the aqueous detergent formulation, the hydrotrope being 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 cumene sulfonic acid; salts thereof, and mixtures thereof. Even more preferably, the aqueous detergent formulation of the present invention further comprises 0-10 wt. % (preferably 0.1-10 wt. %, more preferably 0.2-8 wt. %, most preferably 0.5-7.5 wt. %) of a hydrotrope based on the weight of the aqueous detergent formulation, the hydrotrope being 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 cleaning formulation of the present invention further comprises 0-10 wt. % (preferably 0.1-10 wt. %, more preferably 0.2-8 wt. %, most preferably 0.5-7.5 wt. %) of a hydrotrope based on the weight of the aqueous detergent formulation, the hydrotrope being sodium xylene sulfonate.

[0032] Preferably, the aqueous detergent formulation of the present invention further comprises 0 to 30% by weight (preferably 1 to 20% by weight, more preferably 2.5 to 10% by weight) of a builder based on the weight of the aqueous detergent formulation. More preferably, the aqueous detergent formulation of the present invention further comprises 0 to 30% by weight (preferably 1 to 20% by weight, more preferably 2.5 to 10% by weight) of a builder based on the weight of the aqueous detergent formulation, and the builder is an inorganic builder (e.g. tripolyphosphate, pyrophosphate), alkali metal carbonate, borate, bicarbonate, hydroxide, zeolite, citrate (e.g. sodium citrate), polycarboxylate, monocarboxylate, amino tris methylene phosphonic acid, salts of amino tris methylene phosphonic acid, hydroxyethane diphosphonic acid, salts of hydroxyethane diphosphonic acid, diethylene triamine penta (methylene phosphonic acid), salts of diethylene triamine penta (methylene phosphonic acid), Preferably, the phosphonic acid is selected from the group consisting of ethylenediaminetetraethylene-phosphonic acid, salts of ethylenediaminetetraethylene-phosphonic acid, oligomeric phosphonates, polymeric phosphonates, and mixtures thereof. Most preferably, the aqueous cleaning formulation of the present invention further comprises 0-30 wt. % (preferably, 1-20 wt. %, more preferably, 2.5-10 wt. %) of a builder, based on the weight of the aqueous detergent formulation, the builder comprising sodium citrate.

[0033] Preferably, the aqueous detergent formulation of the present invention further comprises 0-2 wt. % (preferably 0.05-0.8 wt. %, more preferably 0.1-0.4 wt. %) of a structuring agent based on the weight of the aqueous detergent formulation. More preferably, the aqueous detergent formulation of the present invention further comprises 0-2 wt. % (preferably 0.05-0.8 wt. %, more preferably 0.1-0.4 wt. %) of a structuring agent based on the weight of the aqueous detergent formulation, the structuring agent being a non-polymeric crystalline hydroxy-functional material capable of forming a thread-like structured system throughout the aqueous detergent formulation when crystallized in situ.

[0034] Preferably, the aqueous detergent formulation of the present invention further comprises 0 to 10 wt. % (preferably, 0.001 to 5 wt. %, more preferably, 0.005 to 3 wt. %, and most preferably, 0.01 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 wt % (preferably 0.5 to 10 wt %) 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 wt % (preferably 0.5 to 10 wt %) of a conditioning polymer based on the weight of the aqueous detergent formulation, the conditioning polymer being a cationic coacervated polymer (e.g., cationic hydroxyl ethyl cellulose, polyquaternium polymer, and combinations thereof).

[0036] Preferably, the aqueous detergent formulations of the present invention have a pH of 6 to 12.5 (preferably 6.5 to 11, more preferably 7.5 to 10). Bases for adjusting the pH include inorganic bases such as sodium hydroxide (including soda ash) and potassium hydroxide, sodium bicarbonate, sodium silicate, ammonium hydroxide, and organic bases (e.g., mono-, di-, or tri-ethanolamine, and 2-dimethylamino-2-methyl-1-propanol (DMAMP)). 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 formulation of the present invention contains less than 2% by weight (preferably less than 1% by weight, more preferably less than 0.01% by weight, even more preferably less than 0.001% by weight, most preferably below the detection limit) of drying oil based on the dry weight of the thickening polymer. More preferably, the aqueous detergent formulation of the present invention contains less than 2% by weight (preferably less than 1% by weight, more preferably less than 0.01% by weight, even more preferably less than 0.001% by weight, most preferably below the detection limit) of drying oil selected from the group consisting of safflower oil, linseed oil, castor oil, oiticica oil, sunflower oil, soybean oil, perilla oil, tall oil, dehydrated castor oil, poppy oil, tung oil, very long oil alkyd, long oil alkyd, and mixtures thereof.

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

[0039] Synthetic S1-S6: Thickening polymers A glass reactor was charged with 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). The reactor contents were then heated to 30° C. with stirring. Separately, in a vessel, a monomer emulsion (ME) was prepared by mixing deionized water (3.4 g), an aqueous solution of sodium vinyl sulfonate (SVS) (1.32 g, 0.24 wt %), secondary C 100% dimethylformamide (DMSO) (1.0 g, 0.24 wt %), and the amounts identified and listed in Table 1. 13A combination of an alkyl ethoxylate aqueous solution (0.23 g, 70 wt %, available from Dow Chemical Company under the trade name Tergitol™ 15-S-40), an aqueous solution of lauryl ethoxylated sulfate surfactant (0.45 g, 31 wt %), and a vinyl alkanoate monomer, A, was prepared by vortex mixing. The vortexed ME was then added to the reactor with continued stirring. The ME container was then rinsed into the reactor with deionized water (6 g). After a 5 minute hold, a carboxylic acid functionalized vinyl ester monomer, B, was added to the reactor in the amount identified and set forth in Table 1. If present, a crosslinker, C, was added to the reactor in the amount identified and set forth in Table 1. After a 2 minute hold, an aqueous solution of ferrous 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 persulfate (0.16 g) in deionized water (1.7 g) was added to the reactor. After a 1 minute hold, another solution of 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 15 minutes, the reactor product was collected for analysis. The pH and weight percent solids of the reactor product are reported in Table 2.

[0040] [Table 1]

[0041] [Table 2]

[0042] Comparative Examples CF1 to CF4 and Examples F1 to F6: Laundry Detergent Laundry detergent formulations were prepared in each of Comparative Examples CF1-CF4 and Examples F1-F6 having the recipes set forth in Table 3. The formulations were prepared by combining the ingredients in the order listed in Table 3 while constantly mixing with an overhead mixer to create a vortex. The anionic surfactant, water and solvent were thoroughly mixed until all ingredients were incorporated, and then the nonionic surfactant pre-melted at 50°C was added. The pH was then adjusted to 8.5 with NaOH solution. A thickening polymer as shown in Table 3 was then added to the formulation in an amount sufficient to provide 1.2 wt. % active thickening polymer in the formulation while mixing with an overhead mixer. If necessary, the pH was adjusted back to 8.5 using NaOH or HCl solution. The formulation was then completed to 100 wt. % by adding water, if necessary.

[0043] [Table 3]

[0044] Viscosity of Laundry Detergent Formulations The viscosities of laundry detergent formulations prepared according to Comparative Examples CF1-CF4 and Examples F1-F6 were measured with a Brookfield viscometer using an LV-2(62) spindle at 3 rpm. The results are provided in Table 4.

[0045] [Table 4]

[0046] biodegradable The biodegradability of the thickening polymer prepared according to synthesis S1 was evaluated according to the specific aerobic biodegradation test procedure described in OECD 302B. The results are provided in Table 5.

[0047] [Table 5]

Claims

1. 1. An aqueous detergent formulation comprising: An aqueous carrier; A cleaning surfactant; A thickening polymer comprising: 20 to 80% by weight, based on the dry weight of the thickening polymer, of monoethylenically unsaturated vinyl alkanoate structural units having 4 to 12 carbon atoms; 20 to 80 weight percent of 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; 0 to 5 weight percent of structural units of a multiethylenically unsaturated crosslinker, based on the dry weight of the thickening polymer; 0 to 20 weight percent, based on the dry weight of said thickening polymer, of structural units of other monoethylenically unsaturated monomers other than said monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms and said monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; and a thickening polymer, the thickening polymer containing less than 10% by weight, based on the dry weight of the thickening polymer, of structural units of a monoethylenically unsaturated dicarboxylic acid having 4 to 6 carbon atoms, its alkali metal salts, its ammonium salts, and mixtures thereof.

2. 2. The aqueous detergent formulation of claim 1, wherein the structural units of monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms and the structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4 to 12 carbon atoms comprise a combined total of 70 to 100 weight percent of the thickening polymer, based on the dry weight of the thickening polymer.

3. 3. The aqueous detergent formulation of 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 pentanoate, vinyl 3-methylbutanoate, vinyl pivalate, vinyl hexanoate, 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, and mixtures thereof.

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

5. 5. The aqueous detergent formulation of claim 4, wherein said thickening polymer comprises from 0.01 to 2.5 weight percent of structural units of said multiethylenically unsaturated crosslinker, based on the dry weight of said thickening polymer.

6. 6. The aqueous detergent formulation of claim 5, wherein said multiethylenically unsaturated crosslinking agent is diallyl phthalate.

7. 7. The aqueous detergent formulation of claim 6, wherein said thickening polymer further comprises 0.1 to 5 weight percent, based on the dry weight of said thickening polymer, of structural units of said other monoethylenically unsaturated monomers, said other monoethylenically unsaturated monomers being 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. 8. The aqueous detergent formulation of claim 7, wherein the structural units of the monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms are structural units of vinyl acetate.

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

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

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