Vinyl ester latex

Abstract

A vinyl ester latex is provided, which has structural units of 20 to 80% by weight of monoethylenically unsaturated vinyl alkanoates, 20 to 80% by weight of monoethylenically unsaturated carboxylic acid-functionalized vinyl ester structural units, 0 to 5% by weight of multiethylenically unsaturated crosslinking agent structural units, and 0 to 20% by weight of other monoethylenically unsaturated monomer structural units, where the other monoethylenically unsaturated monomer contains structural units of other monoethylenically unsaturated monomers different from monoethylenically unsaturated vinyl alkanoates and monoethylenically unsaturated carboxylic acid-functionalized vinyl esters. The vinyl ester latex contains structural units of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, their alkali metal salts, their ammonium salts, and mixtures thereof in an amount of less than 10% by weight, contains structural units of dicarboxylic acid anhydrides in an amount of less than 5 mol%, contains structural units of 2-acrylamido-2-methyl-propanesulfonic acid in an amount of less than 1.2% by weight, and contains structural units of monoethylenically unsaturated alkyl acrylate monomers containing 2 to 10 carbon atoms in an amount of less than 10% by weight.

Description

Technical Field

[0001] The present invention relates to vinyl ester latex. Specifically, the present invention relates to a structural unit of a monoethylenically unsaturated vinyl alkanate having 4 to 12 carbon atoms in an amount of 20 to 80% by weight based on the dry weight of the vinyl ester latex, a structural unit of a monoethylenically unsaturated carboxylic acid-functionalized vinyl ester having 4 to 12 carbon atoms in an amount of 20 to 80% by weight based on the dry weight of the vinyl ester latex, a structural unit of a multiethylenically unsaturated crosslinking agent in an amount of 0 to 5% by weight based on the dry weight of the vinyl ester latex, and a structural unit of other monoethylenically unsaturated monomers in an amount of 0 to 20% by weight based on the dry weight of the vinyl ester latex, wherein the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated vinyl alkanate having 4 to 12 carbon atoms and the monoethylenically unsaturated carboxylic acid-functionalized vinyl ester having 4 to 12 carbon atoms. The vinyl ester latex contains a structural unit of 2-acrylamido-2-methyl-propanesulfonic acid in an amount of less than 1.2% by weight based on the dry weight of the vinyl ester latex, the vinyl ester latex contains a structural unit of a monoethylenically unsaturated dicarboxylic acid having 4 to 6 carbon atoms, its alkali metal salt, its ammonium salt, and a mixture thereof in an amount of less than 10% by weight based on the dry weight of the vinyl ester latex, the vinyl ester latex contains a structural unit of an anhydride of a dicarboxylic acid in an amount of 5 mol%, and the vinyl ester latex contains a structural unit of a monoethylenically unsaturated alkyl acrylate monomer containing 2 to 10 carbon atoms in an amount of less than 10% by weight based on the dry weight of the vinyl ester latex. The present invention relates to a vinyl ester latex.

[0002] Aqueous complexes are well known. Nevertheless, conventional aqueous complexes often contain various non-biodegradable components, including thickeners. There is a need in the market to increase the biodegradable content of formulations for consumers (e.g., for household and personal care applications). Many conventional thickeners include alkali-soluble / swellable latexes, which are non-toxic and do not pose a serious environmental hazard but are typically not biodegradable.

[0003] Therefore, there remains a need to find new biodegradable components suitable for use as thickeners in aqueous formulations. SUMMARY OF THE INVENTION

[0004] The present invention provides a vinyl ester latex comprising, based on the dry weight of the vinyl ester latex, 20 to 80% by weight of structural units of a monoethylenically unsaturated vinyl alkanate having 4 to 12 carbon atoms, 20 to 80% by weight of structural units of a monoethylenically unsaturated carboxylic acid-functionalized vinyl ester having 4 to 12 carbon atoms, 0 to 5% by weight of structural units of a multiethylenically unsaturated crosslinking agent, 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 vinyl alkanate having 4 to 12 carbon atoms and the monoethylenically unsaturated carboxylic acid-functionalized vinyl ester having 4 to 12 carbon atoms, the vinyl ester latex containing less than 1.2% by weight of structural units of 2-acrylamido-2-methyl-propanesulfonic acid based on the dry weight of the vinyl ester latex, the vinyl ester latex containing less than 10% by weight 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 based on the dry weight of the vinyl ester latex, the vinyl ester latex containing 5 mol% of structural units of the anhydride of the dicarboxylic acid, and the vinyl ester latex containing less than 10% by weight of structural units of a monoethylenically unsaturated alkyl acrylate monomer containing 2 to 10 carbon atoms based on the dry weight of the vinyl ester latex.

Mode for Carrying Out the Invention

[0005] The applicant has surprisingly found that, based on the dry weight of the vinyl ester latex, there are structural units of monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms in an amount of 20 to 80% by weight, structural units of monoethylenically unsaturated carboxylic acid-functionalized vinyl esters having 4 to 12 carbon atoms in an amount of 20 to 80% by weight, structural units of multiethylenically unsaturated crosslinking agents in an amount of 0 to 5% by weight, and structural units of other monoethylenically unsaturated monomers in an amount of 0 to 20% by weight, where the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms and the monoethylenically unsaturated carboxylic acid-functionalized vinyl esters having 4 to 12 carbon atoms. The vinyl ester latex contains structural units of 2-acrylamido-2-methyl-propanesulfonic acid in an amount of less than 1.2% by weight based on the dry weight of the vinyl ester latex, and contains structural units of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, their alkali metal salts, their ammonium salts, and mixtures thereof in an amount of less than 10% by weight based on the dry weight of the vinyl ester latex. The vinyl ester latex contains structural units of the anhydride of the dicarboxylic acid in an amount of 5 mol%, and contains structural units of monoethylenically unsaturated alkyl acrylate monomers containing 2 to 10 carbon atoms in an amount of less than 10% by weight based on the dry weight of the vinyl ester latex. It has been found that the vinyl ester latex can effectively thicken an aqueous solution (especially an aqueous solution containing a surfactant) according to the procedure of OECD 302B and can also exhibit biodegradability.

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

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

[0008] Preferably, the vinyl ester latex of the present invention is an aqueous emulsion polymer.

[0009] Preferably, the vinyl ester latex of the present invention contains, based on the dry weight of the vinyl ester latex, 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, 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, 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 multiethylenically unsaturated crosslinking agents, 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, wherein 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, the vinyl ester latex contains less than 1.2% by weight (preferably 0 to 1.1% by weight, more preferably 0 to 1.0% by weight, even more preferably 0 to 0.5% by weight, still more preferably 0 to 0.1% by weight, most preferably 0 to 0.01% by weight) of structural units of 2-acrylamido-2-methyl-propanesulfonic acid based on the dry weight of the vinyl ester latex, and the vinyl ester latex contains less than 10% by weight (preferably less than 5% by weight, more preferably less than 1% by weight, even more preferably 0.Contains structural units of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms (less than 1% by weight, most preferably less than the detection limit), their alkali metal salts, their ammonium salts, and mixtures thereof. The vinyl ester latex contains less than 5 mol% (preferably less than 1 mol%, more preferably less than 0.1 mol%, most preferably less than the detection limit) of structural units of anhydrides of dicarboxylic acids (e.g., maleic anhydride, itaconic anhydride). The vinyl ester latex contains less than 10% by weight (preferably less than 5% by weight, more preferably less than 1% by weight, still 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 (e.g., methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate) based on the dry weight of the vinyl ester latex.

[0010] Preferably, the vinyl ester latex of the present invention contains structural units of monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms in an amount of 20 to 80% by weight (preferably 24.89 to 77.89% by weight, more preferably 39.48 to 74.48% by weight, and most preferably 43.96 to 71.46% by weight) based on the dry weight of the vinyl ester latex, and 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 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, 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 vinyl ester latex of the present invention contains structural units of monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms in an amount of 20 to 80% by weight (preferably 24.89 to 77.89% by weight, more preferably 39.48 to 74.48% by weight, and most preferably 43.96 to 71.46% by weight) based on the dry weight of the vinyl ester latex. 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 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 vinyl ester latex of the present invention contains structural units of monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms in an amount of 20 to 80% by weight (preferably 24.89 to 77.89% by weight, more preferably 39.48 to 74.48% by weight, and most preferably 43.96 to 71.46% by weight) based on the dry weight of the vinyl ester latex. 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 pentanoate, vinyl 3-methylbutanoate, vinyl pivalate, vinyl hexanoate, vinyl 4-methylpentanoate, vinyl 3,3-dimethylbutanoate, and mixtures thereof.More preferably, the vinyl ester latex of the present invention contains structural units of monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms in an amount of 20 to 80% by weight (preferably 24.89 to 77.89% by weight, more preferably 39.48 to 74.48% by weight, and most preferably 43.96 to 71.46% by weight) based on the dry weight of the vinyl ester latex. 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 vinyl ester latex of the present invention contains structural units of monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms in an amount of 20 to 80% by weight (preferably 24.89 to 77.89% by weight, more preferably 39.48 to 74.48% by weight, and most preferably 43.96 to 71.46% by weight) based on the dry weight of the vinyl ester latex, and the monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms is vinyl acetate.

[0011] Preferably, the vinyl ester latex of the present invention contains structural units of monoethylenically unsaturated carboxylic acid-functionalized vinyl esters having 4 to 12 carbon atoms in an amount of 20 to 80% by weight (preferably 22 to 75% by weight, more preferably 25 to 60% by weight, and most preferably 27.5 to 55% by weight) based on the dry weight of the vinyl ester latex. The monoethylenically unsaturated carboxylic acid-functionalized vinyl ester having 4 to 12 carbon atoms is 2-oxo-2-(vinyloxy)acetic acid. 3-oxo-3-(vinyloxy)propanoic 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 adipic acid), 7-oxo-7-(vinyloxy)heptanoic acid, 8-oxo-8-(vinyloxy)octanoic acid. It is selected from the group consisting of 9-oxo-9-(vinyloxy)nonanoic acid, 10-oxo-10-(vinyloxy)decanoic acid, and mixtures thereof. More preferably, the vinyl ester latex of the present invention contains, based on the dry weight of the vinyl ester latex, 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, and the monoethylenically unsaturated carboxylic acid-functionalized vinyl ester having 4 to 12 carbon atoms is 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. Even more preferably, the vinyl ester latex of the present invention contains, based on the dry weight of the vinyl ester latex, 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, and the monoethylenically unsaturated carboxylic acid-functionalized vinyl ester having 4 to 12 carbon atoms is 5-oxo-5-(vinyloxy)pentanoic acid, 6-oxo-6-(vinyloxy)hexanoic acid, 7-oxo-7-(vinyloxy)heptanoic acid, It is selected from the group consisting of 8-oxo-8-(vinyloxy)octanoic acid and mixtures thereof. Even more preferably, the vinyl ester latex of the present invention contains structural units of monoethylenically unsaturated carboxylic acid-functionalized vinyl esters having 4 to 12 carbon atoms in an amount of 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) based on the dry weight of the vinyl ester latex, and the monoethylenically unsaturated carboxylic acid-functionalized vinyl ester having 4 to 12 carbon atoms is 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 vinyl ester latex of the present invention contains structural units of monoethylenically unsaturated carboxylic acid-functionalized vinyl esters having 4 to 12 carbon atoms in an amount of 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) based on the dry weight of the vinyl ester latex, and the monoethylenically unsaturated carboxylic acid-functionalized vinyl ester having 4 to 12 carbon atoms is 6-oxo-6-(vinyloxy)hexanoic acid.

[0012] Preferably, the vinyl ester latex of the present invention contains 0 to 5% by weight (preferably 0.01 to 2.5% by weight, more preferably 0.02 to 1% by weight, and most preferably 0.04 to 0.5% by weight) of structural units of a multi-ethylenically unsaturated crosslinking agent, based on the dry weight of the vinyl ester latex. The multi-ethylenically unsaturated crosslinking agent is selected from the group consisting of multi-ethylenically unsaturated crosslinking agents having an average of two or three vinyl groups per molecule. More preferably, the vinyl ester latex of the present invention contains 0 to 5% by weight (preferably 0.01 to 2.5% by weight, more preferably 0.02 to 1% by weight, and most preferably 0.04 to 0.5% by weight) of structural units of a multi-ethylenically unsaturated crosslinking agent, based on the dry weight of the vinyl ester latex. The multi-ethylenically 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-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 vinyl ester latex of the present invention contains 0 to 5% by weight (preferably 0.01 to 2.5% by weight, more preferably 0.02 to 1% by weight, and most preferably 0.04 to 0.5% by weight) of structural units of a multi-ethylenically unsaturated crosslinking agent, based on the dry weight of the vinyl ester latex. The multi-ethylenically unsaturated crosslinking agent is diallyl phthalate.

[0013] Preferably, the vinyl ester latex of the present invention contains structural units of 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 other monoethylenically unsaturated monomers based on the dry weight of the vinyl ester latex. 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, and the other monoethylenically unsaturated monomers are selected from the group consisting of alkyl (meth)acrylates, alkyl (meth)acrylamides, vinyl ethers, vinyl sulfonic acids, styrene sulfonic acids, acrylamidopropylmethanesulfonic acids, (meth)acrylic acids, maleic acids, salts thereof, and mixtures thereof. More preferably, the vinyl ester latex of the present invention contains structural units of 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 other monoethylenically unsaturated monomers based on the dry weight of the vinyl ester latex. 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, and the other monoethylenically unsaturated monomers are C 1~4 alkyl (meth)acrylate, C 1~4It is selected from the group consisting of alkyl (meth) acrylamide, vinyl ether, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropylmethanesulfonic acid, (meth) acrylic acid, maleic acid, its salts, and mixtures thereof. More preferably, the vinyl ester latex of the present invention contains 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 vinyl ester latex. 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, 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, its salts, and mixtures thereof. Most preferably, the vinyl ester latex of the present invention contains 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 vinyl ester latex. 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, and the other monoethylenically unsaturated monomers are selected from the group consisting of vinyl sulfonic acid, salts of vinyl sulfonic acid, and mixtures thereof.

[0014] Preferably, the vinyl ester latex of the present invention contains 0 to 1.1% by weight (preferably 0 to 1.0% by weight, more preferably 0 to 0.5% by weight, still more preferably 0 to 0.1% by weight, most preferably 0 to 0.01% by weight) of structural units of 2-acrylamido-2-methyl-propane sulfonic acid based on the dry weight of the vinyl ester latex.

[0015] Preferably, the vinyl ester latex of the present invention contains, based on the dry weight of the vinyl ester latex, less than 5% by weight (preferably less than 1% by weight, more preferably less than 0.1% by weight, and most preferably less than 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.

[0016] Preferably, the vinyl ester latex of the present invention contains less than 5 mol% (preferably less than 1 mol%, more preferably less than 0.1 mol%, and most preferably less than the detection limit) of structural units of dicarboxylic acid anhydrides. More preferably, the vinyl ester latex of the present invention contains less than 5 mol% (preferably less than 1 mol%, more preferably less than 0.1 mol%, and most preferably less than the detection limit) of structural units of dicarboxylic acid anhydrides selected from the group consisting of maleic anhydride, itaconic anhydride, and mixtures thereof.

[0017] Preferably, the vinyl ester latex of the present invention contains, based on the dry weight of the vinyl ester latex, less than 10% by weight (preferably less than 5% by weight, more preferably less than 1% by weight, still more preferably less than 0.1% by weight, and most preferably less than the detection limit) of structural units of monoethylenically unsaturated alkyl acrylate monomers containing 2 to 10 carbon atoms. More preferably, the vinyl ester latex of the present invention contains, based on the dry weight of the vinyl ester latex, less than 10% by weight (preferably less than 5% by weight, more preferably less than 1% by weight, still more preferably less than 0.1% by weight, and most preferably less than the detection limit) of structural units of monoethylenically unsaturated alkyl acrylate monomers containing 2 to 10 carbon atoms 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.

[0018] 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 for 70 to 100% by weight (more preferably 75 to 100% by weight, still more preferably 80 to 100% by weight, even more preferably 85 to 99.9% by weight, still even more preferably 90 to 99.5% by weight, and most preferably 95 to 99% by weight) in total of the vinyl ester latex, based on the dry weight of the vinyl ester latex.

[0019] Preferably, the vinyl ester latex of the present invention contains structural units of a monoethylenically unsaturated amide-containing monomer in an amount of less than 0.1 mol% (preferably less than 0.01 mol%, more preferably less than 0.001 mol%, and most preferably less than the detection limit). More preferably, the vinyl ester latex of the present invention contains structural units of a monoethylenically unsaturated amide-containing monomer 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, in an amount of less than 0.1 mol% (preferably less than 0.01 mol%, more preferably less than 0.001 mol%, and most preferably less than the detection limit).

[0020] Preferably, the vinyl ester latex of the present invention is an aqueous emulsion polymer. More preferably, the vinyl ester latex of the present invention is an aqueous emulsion polymer, and the aqueous emulsion polymer contains less than 2% by weight (preferably less than 1% by weight), more preferably less than 0.01% by weight, still more preferably less than 0.001% by weight, and most preferably less than the detection limit) of drying oil based on the dry weight of the vinyl ester latex. Most preferably, the vinyl ester latex of the present invention is an aqueous emulsion polymer, and the aqueous emulsion polymer contains less than 2% by weight (preferably less than 1% by weight, more preferably less than 0.01% by weight, still more preferably less than 0.001% by weight, most preferably less than 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, kiri oil, very long oil alkyd, long oil alkyd, and mixtures thereof based on the dry weight of the vinyl ester latex.

[0021] Preferably, the vinyl ester latex of the present invention is biodegradable when determined according to the OECD 302B procedure. More preferably, the vinyl ester latex of the present invention has inherent ultimate biodegradability when determined according to the OECD 302B procedure.

[0022] The vinyl ester latex of the present invention can be prepared using conventional or otherwise known polymerization techniques.

[0023] The vinyl ester latex of the present invention is suitable for use as a thickening polymer in various aqueous formulations. Specifically, the vinyl ester latex of the present invention is suitable for use as a thickening polymer in surfactant-containing aqueous formulations, such as personal care formulations (e.g., shampoos, body washes, hand soaps, conditioners) and home care formulations (e.g., hard surface cleaners).

[0024] Here, some embodiments of the present invention will be described in detail in the following examples.

[0025] Comparative Examples C1 - C2 and Examples 1 - 18: Vinyl Ester Latex Into a glass reactor, 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 charged. Subsequently, the contents of the reactor were heated to 30°C with stirring. Separately, in a vessel, a monomer emulsion (ME), which is identified and described in Table 1, of deionized water (3.4 g), secondary C 13An aqueous solution of an alkyl ethoxylate (0.23 g, 70 wt%, available from Dow Chemical Company under the trade name Tergitol™ 15-S-40), an aqueous solution of a lauryl ethoxylated sulfate surfactant (0.45 g, 31 wt%), and a combination of vinyl alkanate monomers, A, and an aqueous solution C of other monomers in the amounts described in Table 1 (if present) were prepared by vortex mixing. Then, while stirring continued, the vortexed ME was added to the reactor. Next, the ME container was rinsed into the reactor with deionized water (6 g). After holding for 5 minutes, the carboxylic acid-functionalized vinyl ester monomer, B, identified and in the amounts described in Table 1, was added to the reactor. If present, the crosslinking agent, D, identified and in the amounts described in Table 1, was added to the reactor. After holding for 2 minutes, an aqueous solution of ferrous sulfate heptahydrate (1.2 g, 0.015 wt%) was then added to the reactor. After holding for 1 minute, a solution of ammonium persulfate (0.16 g) in deionized water (1.7 g) was added to the reactor. After holding for 1 minute, a sulfur-based formaldehyde-free reducing agent (0.212 g, Bruggolite FF6 M available from Brueggemann) 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 holding for 1 minute, another solution of a sulfur-based formaldehyde-free reducing agent (0.212 g, Bruggolite FF6 M available from Brueggemann) in water (3.0 g) was added to the reactor. After 15 minutes, the reactor product was collected for analysis.

[0026]

Table 1

[0027] Comparative Example C3: Vinyl Ester Latex A 250 mL round-bottom flask was equipped with a glass rod propeller having a Teflon stirring blade, a condenser, and a thermocouple. The propeller was driven by an overhead mechanical stirrer, and the thermocouple was connected to a J-KEM temperature controller connected to an air pot lifter to achieve the desired temperature. The flask was filled with deionized water (47.7 g), lauryl ethoxylated sulfate surfactant (2.66 g, 31 wt%, available from BASF under the trade name Disponil FES-32), and an aqueous solution of ferrous sulfate heptahydrate (0.26 g, 0.15 wt%). The temperature controller was set to 70 °C, and the flask was placed under nitrogen.

[0028] The first glass jar was filled with vinyl 2-methyl-2-propylhexanoate (3.56 g), vinyl acetate (21.28 g), vinyl succinic acid (10.25 g), and diallyl phthalate (0.071 g) and mixed under gentle heating to form a homogeneous mixture, which served as the monomer feed.

[0029] The second glass jar was filled with deionized water (33.80 g), 2-acrylamido-2-methyl-propanesulfonic acid (0.11 g), an aqueous solution of secondary C 13 alkyl ethoxylate (0.25 g, 70 wt%, available from Dow Chemical Company under the trade name Tergitol™ 15-S-40), and lauryl ethoxylated sulfate surfactant (1 g, 31 wt%, available from BASF under the trade name Disponil FES-32) to serve as the aqueous co-feed.

[0030] The third glass jar was filled with a solution of ammonium persulfate (0.22 g) in deionized water (12.0 g) and an aqueous solution of tert-butyl hydroperoxide (0.10 g, 70% active) to serve as the co-feed catalyst.

[0031] The fourth glass jar was filled with a solution of a sulfur-based formaldehyde-free reducing agent (0.43 g, Bruggolite FF6 M available from Brueggemann) in deionized water (12.0 g) to serve as the co-feed activator.

[0032] When the contents of the flask reached 70 °C, 2-acrylamido-2-methyl-propanesulfonic acid (0.32 g) in deionized water (1.4 g) was transferred to the flask as a shot addition. Subsequently, the addition of the co-fed catalyst and co-fed activator solution to the flask was started at a rate of 0.13 g / min, and the target total feed time was set to 95 minutes. After 5 minutes, the addition of the monomer feed and co-fed aqueous solution to the flask was started at a rate of 0.44 g / min, and the target total feed time was set to 80 minutes. The controller setpoint temperature remained at 70 °C. After all four feeds to the flask were completed, the contents of the flask were held at 70 °C for 15 minutes. Then, cooling was started. When the contents of the flask reached 60 °C, aqueous ammonia solution (0.50 g, 30% active) was added to the flask. Once the contents of the flask were cooled to ambient temperature, they were passed through a nylon filter (mesh size: 150 μm) to obtain a white emulsion having a solids content of 19.5 wt%, a pH of 4.1, a particle size (by dynamic light scattering) of 201 nm (polydispersity, 0.056), and a residual vinyl acetate content (by headspace gas chromatography) of 1756 ppm.

[0033] Example 19: Vinyl Ester Latex A 250 mL round-bottom flask was equipped with a glass rod propeller having a Teflon stirring blade, a condenser, and a thermocouple. The propeller was driven by an overhead mechanical stirrer, and the thermocouple was connected to a J-KEM temperature controller connected to an air pot lifter to achieve the desired temperature. The flask was first filled with deionized water (32.0 g) and an aqueous solution of a lauryl ethoxylated sulfate surfactant (2.66 g, 31 wt%, available from BASF under the trade name Disponil FES-32). The temperature controller was set to 70 °C, and the flask was placed under nitrogen.

[0034] Fill the first glass jar with vinyl 2-methyl-2-propylhexanoate (3.56 g), vinyl acetate (17.44 g), vinyl succinic acid (14.17 g), and diallyl phthalate (0.071 g), and mix under gentle heating to form a homogeneous mixture, which serves as the monomer feed.

[0035] Fill the second glass jar with deionized water (33.80 g), an aqueous solution of sodium vinyl sulfonate (0.712 g, 25% active), an aqueous solution of a secondary C 13 alkyl ethoxylate (0.51 g, 70 wt%, available under the trade name Tergitol™ 15-S-40 from Dow Chemical Company), and a lauryl ethoxylated sulfate surfactant (1.0 g, 31 wt%, available under the trade name Disponil FES-32 from BASF) to obtain an aqueous co-feed.

[0036] Fill the third glass jar with a solution of ammonium persulfate (0.1 g) in deionized water (10.0 g) and an aqueous solution of tert-butyl hydroperoxide (0.042 g, 70% active) to obtain a co-feed catalyst.

[0037] Fill the fourth glass jar with a solution of a sulfur-based formaldehyde-free reducing agent (0.065 g, Bruggolite FF6 M available from Brueggemann) in deionized water (10.0 g) to obtain a co-feed activator.

[0038] When the contents of the flask reached 70 °C, two shot additives were charged into the contents of the flask in the following order: First, an aqueous solution of sodium vinyl sulfonate (0.712 g, 25% active) and deionized water (1.4 g), second, an aqueous solution of ferrous sulfate heptahydrate (0.26 g, 0.15%). Subsequently, the addition of the co-fed catalyst and co-fed activator solution to the flask was started at a rate of 0.11 g / min with a target total feed time of 95 minutes. After 5 minutes, the addition of the monomer feed and co-fed aqueous solution to the flask was started at a rate of 0.44 g / min with a target total feed time of 80 minutes. The controller set point temperature remained at 70 °C. After all four feeds to the flask were complete, the contents of the flask were held at 70 °C for 15 minutes. Then, cooling was started. When the contents of the flask reached 60 °C, an aqueous ammonia solution (0.50 g, 30% active) was added to the contents of the flask. Subsequently, a separate chase catalyst feed was added to the contents of the flask at a rate of 0.17 g / min over 30 minutes, - the first stream, ammonium persulfate (9.3 mg), aqueous tert-butyl hydroperoxide (31 mg, 70% active) and deionized water (5.0 g), the second stream, sodium metabisulfite (47 mg) in deionized water (5 g). After the two chase feeds were complete, the contents of the flask were held at 60 °C for 15 minutes. Then, the contents of the flask were cooled to ambient temperature. Once ambient temperature was reached, the contents of the flask were passed through a nylon filter (mesh size: 150 μm) to obtain a white emulsion having a solids content of 22.89 wt%, a pH of 3.3, a particle size (by dynamic light scattering) of 181 nm (polydispersity, 0.001) and a residual vinyl acetate content (by headspace gas chromatography) of 165 ppm.

[0039] Example 20: Vinyl Ester Latex A 250 mL round-bottom flask was equipped with a glass rod propeller having a Teflon stirring blade, a condenser, and a thermocouple. The propeller was driven by an overhead mechanical stirrer, and the thermocouple was connected to a J-KEM temperature controller connected to an air pot lifter to achieve the desired temperature. The flask was first filled with deionized water (32 g) and an aqueous solution of a lauryl ethoxylated sulfate surfactant (2.66 g, 31 wt%, available from BASF under the trade name Disponil FES-32). The temperature controller was set to 70 °C and the flask was placed under nitrogen.

[0040] A first glass jar was filled with vinyl 2-methyl-2-propylhexanoate (3.56 g), vinyl acetate (17.44 g), vinyl succinic acid (14.17 g), and diallyl phthalate (0.071 g) and mixed under gentle heating to form a homogeneous mixture, which served as the monomer feed.

[0041] A second glass jar was filled with deionized water (33.80 g), an aqueous solution of sodium vinyl sulfonate (0.712 g, 25% active), an aqueous solution of a secondary C 13 alkyl ethoxylate (0.51 g, 70 wt%, available from Dow Chemical Company under the trade name Tergitol™ 15-S-40), and a lauryl ethoxylated sulfate surfactant (1 g, 31 wt%, available from BASF under the trade name Disponil FES-32) to serve as the aqueous co-feed.

[0042] A third glass jar was filled with a solution of sodium persulfate (0.071 g) in deionized water (10.0 g) and an aqueous solution of tert-butyl hydroperoxide (0.028 g, 70% active) to serve as the co-feed catalyst.

[0043] A fourth glass jar was filled with a solution of isoascorbic acid (0.057) in deionized water (10.0 g) to serve as the co-feed activator.

[0044] When the contents of the flask reached 70 °C, two shot additives were charged into the contents of the flask in the following order: First, an aqueous solution of sodium vinyl sulfonate (0.712 g, 25% active) and deionized water (1.4 g), second, an aqueous solution of ferrous sulfate heptahydrate (0.26 g, 0.15%). Next, the addition of the co-feed catalyst and co-feed activator solution to the flask was started at a rate of 0.11 g / min with a target total feed time of 95 minutes. After 5 minutes, the addition of the monomer feed and co-feed aqueous solution to the flask was started at a rate of 0.44 g / min with a target total feed time of 80 minutes. The controller setpoint temperature remained at 70 °C. After all four feeds to the flask were complete, the contents of the flask were held at 70 °C for 15 minutes. Then, cooling was started. When the contents of the flask reached 60 °C, an aqueous ammonia solution (0.5 g, 30% active) was added as a shot addition to the contents of the flask. Next, a separate chase feed was added to the contents of the flask at a rate of 0.5 g / min over 10 minutes. - The first stream, an aqueous solution of tert-butyl hydroperoxide (85 mg, 70% active) and deionized water (5.0 g), the second stream, sodium metabisulfite (62 mg) in deionized water (5.0 g). After the two chase feeds were complete, the contents of the flask were held at 60 °C for 15 minutes. Then, the contents of the flask were cooled to ambient temperature. Once ambient temperature was reached, the contents of the flask were passed through a nylon filter (mesh size: 150 μm) to obtain a white emulsion having a solids content of 22.21 wt%, a pH of 3.8, a particle size (by dynamic light scattering) of 186 nm (polydispersity, 0.050), and a residual vinyl acetate content (by headspace gas chromatography) of 177 ppm.

[0045] Thickening performance and turbidity The viscosities of the aqueous solutions of vinyl ester latexes prepared according to Comparative Examples C1 - C3 and Examples 1 - 20 were measured at various concentrations as described using a Brookfield viscometer with the spindle used at 3 rpm as described. Sodium hydroxide (0.5 N) was used to adjust the pH of the solution to 7 - 8. The results are provided in Table 3.

[0046] The turbidity of the pH-adjusted aqueous vinyl ester latex solution was measured at 21 °C using a turbidimeter. The instrument was calibrated according to the instructions included with the instrument. The turbidity measured in Nephelometric Turbidity Units (NTU) is provided in Table 3.

[0047] The viscosities of the aqueous solutions of vinyl ester latexes prepared according to Comparative Example C3 and Examples 1-6 and Examples 17-20 were also measured at 1 wt% or 5 wt% using a Brookfield viscometer, using the spindle and rpm indicated, as described in Table 4. The pH of the solution was adjusted to 7-8 using sodium hydroxide (0.5 N). The results are provided in Table 4.

[0048]

Table 2

[0049]

Table 3

[0050] Comparative Examples CF1-CF4 and Examples F1-F6: Laundry Detergents Laundry detergent formulations were prepared in each of Comparative Examples CF1-CF4 and Examples F1-F6 having the recipes described in Table 5. The formulations were prepared by continuously mixing with an overhead mixer and combining the components in the order listed in Table 5 while generating a vortex. After thoroughly mixing the anionic surfactant, water, and solvent, the nonionic surfactant (pre-melted at 50 °C) was added until all components were incorporated. The pH was then adjusted to 8.5 with an NaOH solution. Next, the vinyl ester latex as shown in Table 5 was added to the formulation in an amount sufficient to provide 1.2 wt% active vinyl ester latex in the formulation while mixing with an overhead mixer. The pH was adjusted back to 8.5 using an NaOH or HCl solution as needed. Then, water was added as needed to complete the formulation to 100 wt%.

[0051]

Table 4

[0052] Viscosity of the laundry detergent complex The viscosities of the laundry detergent complexes 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 6.

[0053]

Table 5

[0054] Biodegradability The biodegradability of the vinyl ester latex prepared according to Example 1 was evaluated according to the specific aerobic biodegradation test procedure described in OECD 302B. The results are provided in Table 7.

[0055]

Table 6

Claims

1. A vinyl ester latex, comprising: Based on the dry weight of the vinyl ester latex, 20 to 80% by weight of structural units of monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms; Based on the dry weight of the vinyl ester latex, 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 vinyl ester latex, 0 to 5% by weight of structural units of multiethylenically unsaturated crosslinking agents; Based on the dry weight of the vinyl ester latex, 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 vinyl alkanoates having 4 to 12 carbon atoms and the monoethylenically unsaturated carboxylic acid-functionalized vinyl esters having 4 to 12 carbon atoms, and include structural units of other monoethylenically unsaturated monomers; The vinyl ester latex contains less than 1.2% by weight of structural units of 2-acrylamido-2-methyl-propanesulfonic acid based on the dry weight of the vinyl ester latex; The vinyl ester latex 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 vinyl ester latex; The vinyl ester latex contains less than 5 mol% of structural units of dicarboxylic acid anhydrides; The vinyl ester latex contains less than 10% by weight of structural units of monoethylenically unsaturated alkyl acrylate monomers containing 2 to 10 carbon atoms based on the dry weight of the vinyl ester latex.

2. The vinyl ester latex according to claim 1, wherein the structural units of the monoethylenically unsaturated vinyl alkanoates having 4 to 12 carbon atoms and the structural units of the monoethylenically unsaturated carboxylic acid-functionalized vinyl esters having 4 to 12 carbon atoms account for 70 to 100% by weight of the total vinyl ester latex based on the dry weight of the vinyl ester latex.

3. The vinyl ester latex according to claim 2, wherein the vinyl ester latex contains structural units of a monoethylenically unsaturated amide-containing monomer in an amount of less than 0.1 mol%.

4. The vinyl ester latex according to claim 3, wherein the structural units of the monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms are 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.

5. 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, 8-oxo-8-(vinyloxy)octanoic acid, and mixtures thereof, and the vinyl ester latex according to claim 4 is selected from the group of structural units consisting of these.

6. The vinyl ester latex according to claim 5, wherein the vinyl ester latex contains 0.01 to 2.5% by weight of the structural units of the multiethylenically unsaturated crosslinking agent based on the dry weight of the vinyl ester latex.

7. The vinyl ester latex according to claim 6, wherein the multiethylenically unsaturated crosslinking agent is diallyl phthalate.

8. Based on the dry weight of the vinyl ester latex, the vinyl ester latex further contains 0.1 to 5% by weight of the structural units of the other monoethylenically unsaturated monomer, and the other monoethylenically unsaturated monomer is selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl ether, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropylmethanesulfonic acid, (meth)acrylic acid, maleic acid, salts thereof, and mixtures thereof. The vinyl ester latex according to claim 7.

9. The vinyl ester latex according to claim 8, wherein the structural unit of the monoethylenically unsaturated vinyl alkanate having 4 to 12 carbon atoms is a structural unit of vinyl acetate.

10. The vinyl ester latex according to claim 9, wherein the structural unit of the monoethylenically unsaturated carboxylic acid-functionalized vinyl ester having 4 to 12 carbon atoms is a structural unit 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.

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