Vinyl ester latex

Abstract

Provided is a vinyl ester latex comprising: 20% to 80% by weight of structural units of a monoethylenically unsaturated alkanoic acid vinyl ester; from 20% to 80% by weight of structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl esters; 0 wt% to 5 wt% of structural units of a polyethylenically unsaturated crosslinker; from 0% to 20% by weight of structural units of a further monoethylenically unsaturated monomer, wherein the further monoethylenically unsaturated monomer is different from a monoethylenically unsaturated alkanoic acid vinyl ester and a monoethylenically unsaturated carboxylic acid functionalized vinyl ester; wherein the vinyl ester latex contains 1t; 10% by weight of structural units of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, alkali metal salts thereof, ammonium salts thereof, and mixtures thereof; wherein the vinyl ester latex contains 1t; a structural unit of 5 mol% dicarboxylic acid anhydride; wherein the vinyl ester latex contains 1t; 1.2 wt% of a structural unit of 2-acrylamido-2-methyl-propanesulfonic acid; and wherein the vinyl ester latex contains lt; 10% by weight of structural units of a monoethylenically unsaturated alkyl acrylate monomer containing 2 to 10 carbon atoms.

Description

[0001] The present invention relates to a vinyl ester latex. In particular, the present invention relates to a vinyl ester latex, which comprises: based on the dry weight of the vinyl ester latex, 20 wt% to 80 wt% of structural units of monoethylenically unsaturated chain acid vinyl esters having 4 to 12 carbon atoms; based on the dry weight of the vinyl ester latex, 20 wt% to 80 wt% of structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; based on the dry weight of the vinyl ester latex, 0 wt% to 5 wt% of structural units of polyethylenically unsaturated crosslinking agents; based on the dry weight of the vinyl ester latex, 0 wt% to 20 wt% of structural units of other monoethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated chain acid vinyl esters having 4 to 12 carbon atoms. ethylenic ester and a monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4 to 12 carbon atoms; wherein the vinyl ester latex contains less than 1.2 weight percent of structural units of 2-acrylamido-2-methyl-propanesulfonic acid, based on the dry weight of the vinyl ester latex; and wherein the vinyl ester latex contains less than 10 weight percent of structural units of monoethylenically unsaturated dicarboxylic acids, alkali metal salts thereof, ammonium salts thereof, and mixtures thereof, based on the dry weight of the vinyl ester latex; wherein the vinyl ester latex contains less than 5 mol percent of structural units of dicarboxylic acid anhydrides; and wherein the vinyl ester latex contains less than 10 weight percent of structural units of monoethylenically unsaturated alkyl acrylate monomers having 2 to 10 carbon atoms, based on the dry weight of the vinyl ester latex.

[0002] Aqueous formulations are well known. Nevertheless, conventional aqueous formulations typically contain a variety of non-biodegradable ingredients, including thickeners. What is needed in the market is to increase the biodegradable content of formulations for consumer use (e.g., for home and personal care applications). Many conventional thickeners include alkali-soluble / swellable latexes, which, while non-toxic and not a serious hazard to the environment, are typically non-biodegradable.

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

[0004] The present invention provides a vinyl ester latex, which comprises: based on the dry weight of the vinyl ester latex, 20 wt % to 80 wt % of structural units of monoethylenically unsaturated chain acid vinyl esters having 4 to 12 carbon atoms; based on the dry weight of the vinyl ester latex, 20 wt % to 80 wt % of structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; based on the dry weight of the vinyl ester latex, 0 wt % to 5 wt % of structural units of polyethylenically unsaturated crosslinking agents; based on the dry weight of the vinyl ester latex, 0 wt % to 20 wt % of structural units of other monoethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated chain acid vinyl esters having 4 to 12 carbon atoms. ethylenic ester and a monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4 to 12 carbon atoms; wherein the vinyl ester latex contains less than 1.2 weight percent, based on the dry weight of the vinyl ester latex, of structural units of 2-acrylamido-2-methyl-propanesulfonic acid; wherein the vinyl ester latex contains less than 10 weight percent, based on the dry weight of the vinyl ester latex, of structural units of monoethylenically unsaturated dicarboxylic acids, their alkali metal salts, their ammonium salts, and mixtures thereof, having 4 to 6 carbon atoms; wherein the vinyl ester latex contains less than 5 mol percent of structural units of dicarboxylic acid anhydrides; and wherein the vinyl ester latex contains less than 10 weight percent, based on the dry weight of the vinyl ester latex, of structural units of monoethylenically unsaturated alkyl acrylate monomers having 2 to 10 carbon atoms. DETAILED DESCRIPTION

[0005] The applicant surprisingly discovered such a vinyl ester latex, which comprises: based on the dry weight of the vinyl ester latex, 20 wt% to 80 wt% of structural units of monoethylenically unsaturated chain acid vinyl esters having 4 to 12 carbon atoms; based on the dry weight of the vinyl ester latex, 20 wt% to 80 wt% of structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; based on the dry weight of the vinyl ester latex, 0 wt% to 5 wt% of structural units of polyethylenically unsaturated crosslinking agents; based on the dry weight of the vinyl ester latex, 0 wt% to 20 wt% of structural units of other monoethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated chain acid vinyl esters having 4 to 12 carbon atoms. and a monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4 to 12 carbon atoms; wherein the vinyl ester latex contains less than 1.2 wt% of structural units of 2-acrylamido-2-methyl-propanesulfonic acid, based on the dry weight of the vinyl ester latex; wherein the vinyl ester latex contains less than 10 wt% of structural units of monoethylenically unsaturated dicarboxylic acids, their alkali metal salts, their ammonium salts and mixtures thereof, based on the dry weight of the vinyl ester latex; wherein the vinyl ester latex contains less than 5 mol% of structural units of dicarboxylic acid anhydrides; and wherein the vinyl ester latex contains less than 10 wt% of structural units of monoethylenically unsaturated alkyl acrylate monomers having 2 to 10 carbon atoms, based on the dry weight of the vinyl ester latex; according to the procedure of OECD 302B, the vinyl latex can effectively thicken aqueous solutions (especially aqueous solutions containing surfactants) and also exhibits biodegradability.

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

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

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

[0009] Preferably, the vinyl ester latex of the present invention comprises: based on the dry weight of the vinyl ester latex, 20 wt% to 80 wt% (preferably, 24.89 wt% to 77.89 wt%; more preferably, 39.48 wt% to 74.48 wt%; most preferably, 43.96 wt% to 71.46 wt%) of structural units of monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms; based on the dry weight of the vinyl ester latex, 20 wt% to 80 wt% (preferably, 22 wt% to 75 wt%; more preferably, 25 wt% to 60 wt%; most preferably, 27.5 wt% to 55 wt%) of structural units of monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms; The present invention comprises structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 20 carbon atoms; structural units of polyethylenically unsaturated crosslinking agents of 0 wt % to 5 wt % (preferably, 0.01 wt % to 2.5 wt %; more preferably, 0.02 wt % to 1 wt %; most preferably, 0.04 wt % to 0.5 wt %) based on the dry weight of the vinyl ester latex; structural units of other monoethylenically unsaturated monomers of 0 wt % to 20 wt % (preferably, 0.1 wt % to 5 wt %; more preferably, 0.5 wt % to 4 wt %; most preferably, 1 wt % to 3 wt %) based on the dry weight of the vinyl ester latex, wherein the other monoethylenically unsaturated monomers The present invention relates to a vinyl ester of a monoethylenically unsaturated alkanoic acid having 4 to 12 carbon atoms and a monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4 to 12 carbon atoms; wherein the vinyl ester latex contains less than 1.2 wt. % (preferably 0 wt. % to 1.1 wt. %; more preferably 0 wt. % to 1.0 wt. %; still more preferably 0 wt. % to 0.5 wt. %; still more preferably 0 wt. % to 0.1 wt. %; most preferably 0 wt. % to 0.01 wt. %) of a 2-acrylamido-2-methyl-propanesulfonic acid structural unit based on the dry weight of the vinyl ester latex; wherein the vinyl ester latex contains less than 10 wt. % (preferably 0 wt. % to 1.1 wt. %; more preferably 0 wt. % to 1.0 wt. %; still more preferably 0 wt. % to 0.5 wt. %; still more preferably 0 wt. % to 0.1 wt. %; most preferably 0 wt. % to 0.01 wt. %) of a 2-acrylamido-2-methyl-propanesulfonic acid structural unit based on the dry weight of the vinyl ester latex %; more preferably, <0.1 wt %; most preferably, < detection limit) of structural units of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, their alkali metal salts, their ammonium salts and mixtures thereof; wherein the vinyl ester latex contains less than 5 mol % (preferably <1 mol %; more preferably, <0.1 mol %; most preferably, < detection limit) of structural units of dicarboxylic acid anhydrides (e.g., maleic anhydride, itaconic anhydride); and wherein the vinyl ester latex contains less than 10 wt % (preferably <5 wt %; more preferably <1 wt %; still more preferably, <0.1% by weight; more preferably, < 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).

[0010] Preferably, the vinyl ester latex of the present invention comprises: based on the dry weight of the vinyl ester latex, 20 wt% to 80 wt% (preferably, 24.89 wt% to 77.89 wt%; more preferably, 39.48 wt% to 74.48 wt%; most preferably, 43.96 wt% to 71.46 wt%) of structural units of monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms is selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl 3-methylbutyrate, vinyl pivalate, vinyl hexanoate, vinyl 4-hydroxyethyl ester ... -methyl valerate, vinyl 3,3-dimethyl butyrate, vinyl heptanoate, vinyl 5-methyl hexanoate, vinyl 4,4-dimethyl valerate, vinyl octanoate, vinyl 6-methyl heptanoate, vinyl 5,5-dimethyl hexanoate, vinyl nonanoate, vinyl 7-methyl octanoate, vinyl decanoate, vinyl 8-methyl nonanoate, vinyl 6,6-dimethyl heptanoate, 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 valerate, vinyl 2-ethyl hexanoate and mixtures thereof. More preferably, the vinyl ester latex of the present invention comprises: based on the dry weight of the vinyl ester latex, 20 wt% to 80 wt% (preferably, 24.89 wt% to 77.89 wt%; more preferably, 39.48 wt% to 74.48 wt%; most preferably, 43.96 wt% to 71.46 wt%) of structural units of monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms The vinyl alkanoate is selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl 3-methylbutyrate, vinyl pivalate, vinyl hexanoate, vinyl 4-methylvalerate, vinyl 3,3-dimethylbutyrate, vinyl heptanoate, vinyl 5-methylhexanoate, vinyl 4,4-dimethylvalerate, vinyl octanoate, vinyl 6-methylheptanoate, vinyl 5,5-dimethylhexanoate and mixtures thereof.Still more preferably, the vinyl ester latex of the present invention comprises: based on the dry weight of the vinyl ester latex, 20 wt% to 80 wt% (preferably, 24.89 wt% to 77.89 wt%; more preferably, 39.48 wt% to 74.48 wt%; most preferably, 43.96 wt% to 71.46 wt%) of structural units of monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms is selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl 3-methylbutyrate, vinyl pivalate, vinyl hexanoate, vinyl 4-methylvalerate, vinyl 3,3-dimethylbutyrate and mixtures thereof. Even more preferably, the vinyl ester latex of the present invention comprises: based on the dry weight of the vinyl ester latex, 20 wt% to 80 wt% (preferably, 24.89 wt% to 77.89 wt%; more preferably, 39.48 wt% to 74.48 wt%; most preferably, 43.96 wt% to 71.46 wt%) of structural units of monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms is 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 comprises: based on the dry weight of the vinyl ester latex, 20 wt% to 80 wt% (preferably, 24.89 wt% to 77.89 wt%; more preferably, 39.48 wt% to 74.48 wt%; most preferably, 43.96 wt% to 71.46 wt%) of structural units of monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms is vinyl acetate.

[0011] Preferably, the vinyl ester latex of the present invention comprises: based on the dry weight of the vinyl ester latex, 20 wt% to 80 wt% (preferably, 22 wt% to 75 wt%; more preferably, 25 wt% to 60 wt%; most preferably, 27.5 wt% to 55 wt%) of structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms are selected from the group consisting of: 2-oxo-2- -(vinyloxy)acetic acid, 3-oxo-3-(vinyloxy)propionic acid, 4-oxo-4-(vinyloxy)butanoic acid (also known as vinyl succinic acid), 5-oxo-5-(vinyloxy)pentanoic acid, 6-oxo-6-(vinyloxy)hexanoic acid (also known as vinyl adipic acid), 7-oxo-7-(vinyloxy)heptanoic acid, 8-oxo-8-(vinyloxy)octanoic acid, 9-oxo-9-(vinyloxy)nonanoic acid, 10-oxo-10-(vinyloxy)decanoic acid and mixtures thereof. More preferably, the vinyl ester latex of the present invention comprises: based on the dry weight of the vinyl ester latex, 20 wt% to 80 wt% (preferably, 22 wt% to 75 wt%; more preferably, 25 wt% to 60 wt%; most preferably, 27.5 wt% to 55 wt%) of structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms are selected from the group consisting of: 4-oxo-4-(vinyloxy)butanoic acid, 5-oxo-5-(vinyloxy)pentanoic acid, 6-oxo-6-(vinyloxy)hexanoic acid, 7-oxo-7-(vinyloxy)heptanoic acid, 8-oxo-8-(vinyloxy)octanoic acid and mixtures thereof. Still more preferably, the vinyl ester latex of the present invention comprises: based on the dry weight of the vinyl ester latex, 20 wt% to 80 wt% (preferably, 22 wt% to 75 wt%; more preferably, 25 wt% to 60 wt%; most preferably, 27.5 wt% to 55 wt%) of structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms are selected from the group consisting of: 5-oxo-5-(vinyloxy)pentanoic acid, 6-oxo-6-(vinyloxy)hexanoic acid, 7-oxo-7-(vinyloxy)heptanoic acid, 8-oxo-8-(vinyloxy)octanoic acid and mixtures thereof.Even more preferably, the vinyl ester latex of the present invention comprises: based on the dry weight of the vinyl ester latex, 20 wt% to 80 wt% (preferably, 22 wt% to 75 wt%; more preferably, 25 wt% to 60 wt%; most preferably, 27.5 wt% to 55 wt%) of structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms are selected from the group consisting of: 6-oxo-6-(vinyloxy)hexanoic acid, 7-oxo-7-(vinyloxy)heptanoic acid, 8-oxo-8-(vinyloxy)octanoic acid and mixtures thereof. Most preferably, the vinyl ester latex of the present invention comprises: based on the dry weight of the vinyl ester latex, 20 wt% to 80 wt% (preferably, 22 wt% to 75 wt%; more preferably, 25 wt% to 60 wt%; most preferably, 27.5 wt% to 55 wt%) of structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4 to 12 carbon atoms; wherein the monoethylenically unsaturated carboxylic acid functionalized vinyl ester having 4 to 12 carbon atoms is 6-oxo-6-(vinyloxy)hexanoic acid.

[0012] Preferably, the vinyl ester latex of the present invention comprises: based on the dry weight of the vinyl ester latex, 0 wt% to 5 wt% (preferably, 0.01 wt% to 2.5 wt%; more preferably, 0.02 wt% to 1 wt%; most preferably, 0.04 wt% to 0.5 wt%) of structural units of a polyethylenically unsaturated crosslinking agent; wherein the polyethylenically unsaturated crosslinking agent is selected from the group consisting of polyethylenically unsaturated crosslinking agents having an average of two or three vinyl groups per molecule. More preferably, the vinyl ester latex of the present invention comprises: based on the dry weight of the vinyl ester latex, 0 wt% to 5 wt% (preferably, 0.01 wt% to 2.5 wt%; more preferably, 0.02 wt% to 1 wt%; most preferably, 0.04 wt% to 0.5 wt%) of structural units of a polyethylenically unsaturated crosslinking agent; wherein the polyethylenically unsaturated crosslinking agent is selected from the group consisting of allyl (meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, diallyl phthalate, trimethylolpropane tri(meth)acrylate, divinylbenzene, divinyltoluene, tridivinyltoluene, trivinylbenzene, divinylnaphthalene and mixtures thereof. Most preferably, the vinyl ester latex of the present invention comprises: 0 wt% to 5 wt% (preferably, 0.01 wt% to 2.5 wt%; more preferably, 0.02 wt% to 1 wt%; most preferably, 0.04 wt% to 0.5 wt%) structural units of a polyethylenically unsaturated crosslinking agent, based on the dry weight of the vinyl ester latex; wherein the polyethylenically unsaturated crosslinking agent is diallyl phthalate.

[0013] Preferably, the vinyl ester latex of the present invention comprises: based on the dry weight of the vinyl ester latex, 0 wt% to 20 wt% (preferably, 0.1 wt% to 5 wt%; more preferably, 0.5 wt% to 4 wt%; most preferably, 1 wt% to 3 wt%) of structural units of other monoethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from monoethylenically unsaturated chain acid vinyl esters having 4 to 12 carbon atoms and monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms, and wherein the other monoethylenically unsaturated monomers are selected from the group consisting of: (meth) acrylates, (meth) acrylamide alkyl esters, vinyl ethers, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropylmethanesulfonic acid, (meth) acrylic acid, maleic acid, their salts and their mixtures. More preferably, the vinyl ester latex of the present invention comprises: based on the dry weight of the vinyl ester latex, 0 wt% to 20 wt% (preferably, 0.1 wt% to 5 wt%; more preferably, 0.5 wt% to 4 wt%; most preferably, 1 wt% to 3 wt%) of structural units of other monoethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from monoethylenically unsaturated alkanoic acid vinyl esters having 4 to 12 carbon atoms and monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms, and wherein the other monoethylenically unsaturated monomers are selected from the group consisting of: (meth)acrylic acid C 1-4 Alkyl ester, (meth)acrylamide C 1-4Alkyl esters, vinyl ethers, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropyl methane sulfonic acid, (meth) acrylic acid, maleic acid, their salts and mixtures thereof. Still more preferably, the vinyl ester latex of the present invention comprises: based on the dry weight of the vinyl ester latex, 0 wt% to 20 wt% (preferably, 0.1 wt% to 5 wt%; more preferably, 0.5 wt% to 4 wt%; most preferably, 1 wt% to 3 wt%) of structural units of other monoethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from monoethylenically unsaturated alkanoic acid vinyl esters having 4 to 12 carbon atoms and monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms, and wherein the other monoethylenically unsaturated monomers are selected from the group consisting of: methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylamide, ethyl (meth) acrylamido, vinyl ethers, vinyl sulfonic acid, styrene sulfonic acid, (meth) acrylic acid, maleic acid, their salts and mixtures thereof. Most preferably, the vinyl ester latex of the present invention comprises: based on the dry weight of the vinyl ester latex, 0 wt% to 20 wt% (preferably, 0.1 wt% to 5 wt%; more preferably, 0.5 wt% to 4 wt%; most preferably, 1 wt% to 3 wt%) of structural units of other monoethylenically unsaturated monomers, wherein the other monoethylenically unsaturated monomers are different from monoethylenically unsaturated chain acid vinyl esters having 4 to 12 carbon atoms and monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms, and wherein the other monoethylenically unsaturated monomers are selected from the group consisting of vinyl sulfonic acid, vinyl sulfonates and mixtures thereof.

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

[0015] Preferably, the vinyl ester latex of the present invention contains <5 wt% (preferably, <1 wt%; more preferably <0.1 wt%; most preferably, <detection limit) structural units of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, their alkali metal salts, their ammonium salts and mixtures thereof, based on the dry weight of the vinyl ester latex.

[0016] Preferably, the vinyl ester latex of the present invention contains <5 mol% (preferably, <1 mol%; more preferably, <0.1 mol%; most preferably, <detection limit) of structural units of dicarboxylic acid anhydrides. More preferably, the vinyl ester latex of the present invention contains <5 mol% (preferably, <1 mol%; more preferably, <0.1 mol%; most preferably, <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 <10 wt% (preferably, <5 wt%; more preferably <1 wt%; still more preferably, <0.1 wt%; most preferably, <detection limit) of structural units of monoethylenically unsaturated alkyl acrylate monomers containing 2 to 10 carbon atoms, based on the dry weight of the vinyl ester latex. More preferably, the vinyl ester latex of the present invention contains <10 wt% (preferably, <5 wt%; more preferably <1 wt%; still more preferably, <0.1 wt%; more preferably, <detection limit) of structural units of monoethylenically unsaturated alkyl acrylate monomers containing 2 to 10 carbon atoms, based on the dry weight of the vinyl ester latex, and the monoethylenically unsaturated alkyl acrylate monomer is 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, based on the dry weight of the vinyl ester latex, the structural units of monoethylenically unsaturated alkanoic acid vinyl esters having 4 to 12 carbon atoms and the structural units of monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms account for 70 wt % to 100 wt % of the vinyl ester latex (more preferably, 75 wt % to 100 wt %; still more preferably, 80 wt % to 100 wt %; yet more preferably, 85 wt % to 99.9 wt %; still more preferably, 90 wt % to 99.5 wt %; most preferably, 95 wt % to 99 wt %).

[0019] Preferably, the vinyl ester latex of the present invention contains <0.1 mol% (preferably, <0.01 mol%; more preferably, <0.001 mol%; most preferably, <detection limit) of structural units of monomers containing monoethylenically unsaturated amides. More preferably, the vinyl ester latex of the present invention contains <0.1 mol% (preferably, <0.01 mol%; more preferably, <0.001 mol%; most preferably, <detection limit) of structural units of monomers containing monoethylenically unsaturated amides selected from the group consisting of: N-vinylformamide; (meth)acrylamide; 2-acrylamido-2-methyl-propanesulfonic acid (AMPS); 3-(methacrylamido)propyltrimethylammonium chloride (MAPTAC) and mixtures thereof.

[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, wherein the aqueous emulsion polymer contains less than 2 wt% (preferably, <1 wt%; more preferably <0.01 wt%; still more preferably, <0.001 wt%; most preferably, <detection limit) of a 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, wherein the aqueous emulsion polymer contains less than 2 wt% (preferably, <1 wt%; more preferably <0.01 wt%; still more preferably, <0.001 wt%; most preferably, <detection limit) of a drying oil selected from the group consisting of safflower oil, linseed oil, castor oil, oat oil, sunflower oil, soybean oil, perilla oil, tall oil, dehydrated castor oil, tung oil, very long oil alkyd resin, long oil alkyd resin, 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 as determined according to the procedure of OECD 302B. More preferably, the vinyl ester latex of the present invention has inherent ultimate biodegradability as determined according to the procedure of OECD 302B.

[0022] The vinyl ester latexes of the present invention may 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. In particular, the vinyl ester latex of the present invention is suitable for use as a thickening polymer in aqueous formulations containing surfactants, such as personal care formulations (e.g., shampoos, body washes, hand soaps, conditioners) and home care formulations (e.g., hard surface cleaners).

[0024] Some embodiments of the present invention will now be described in detail in the following examples.

[0025] Comparative Examples C1-C2 and Examples 1-18: Vinyl Ester Latex

[0026] A mixture of deionized water (65.5 g) and an aqueous solution of lauryl ethoxylated sulfate surfactant (2.4 g, 31 wt %, available from BASF under the trade name Disponil FES-32) was added to a glass reactor. The reactor contents were then heated to 30° C. with stirring. Separately, in a container, deionized water (3.4 g), an aqueous solution of secondary C13 alkyl ethoxylate (0.23 g, 70 wt %, available from Tergitol TM A monomer emulsion (ME) was prepared by combining an aqueous solution of 15-S-40 (available from Dow Chemical Company), an aqueous solution of lauryl ethoxylated sulfate surfactant (0.45 g, 31 wt%), an aqueous solution of an alkanoic acid vinyl ester monomer A in the amount shown in Table 1, and an aqueous solution of other monomers C (if any) in the amount shown in Table 1. The swirled ME was then added to the reactor with continued stirring. The ME container was then rinsed forward into the reactor with deionized water (6 g). After a 5 minute hold, carboxylic acid functionalized vinyl ester monomer B was added to the reactor in the amount shown in Table 1. Crosslinker D (if any) was added to the reactor in the amount shown in Table 1. After a 2 minute hold, an aqueous solution of ferrous sulfate heptahydrate (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 holding for 1 minute, a sulfur-based formaldehyde-free reducing agent (0.212 g, Bruggolite FF6 M, obtained from Brueggemann) in water (3.0 g) was added to the reactor. After 30 minutes, another solution of ammonium sulfate (0.16 g) in deionized water (1.7 g) was added to the reactor. After holding for 1 minute, another solution of sulfur-based formaldehyde-free reducing agent (0.212 g, Bruggolite FF6 M, obtained from Brueggemann) in water (3.0 g) was added to the reactor. After 15 minutes, the reactor product was collected for analysis.

[0027] Table 1

[0028]

[0029]

[0030] Comparative Example C3: Vinyl Ester Latex

[0031] The 250-mL round-bottom flask is equipped with a glass rod propeller, a condenser and a thermocouple with a Teflon stirring blade. The propeller is driven by an overhead mechanical stirrer, and the thermocouple is connected to a J-KEM temperature controller, which is connected to a pneumatic tank lifter to achieve the desired temperature. Deionized water (47.7 g), lauryl ethoxylated sulfate surfactant (2.66 g, 31% by weight, obtained from BASF with trade name Disponil FES-32) and an aqueous solution of ferrous sulfate heptahydrate (0.26 g, 0.15% by weight) are added to the flask. The temperature controller is set to 70 ° C, and the flask is placed under nitrogen.

[0032] To a first glass jar were added 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 with moderate heating to form a homogeneous mixture for use as the monomer feed.

[0033] To a second glass jar were added deionized water (33.80 g), 2-acrylamido-2-methyl-propanesulfonic acid (0.11 g), an aqueous solution of secondary C13 alkyl ethoxylate (0.25 g, 70 wt %, sold under the trade name Tergitol TM 15-S-40 available from Dow Chemical Company) and lauryl ethoxylated sulfate surfactant (1 g, 31 wt %, available under the trade name Disponil FES-32 from BASF) were used as aqueous co-feeds.

[0034] To a third glass jar was added 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) as a co-feed catalyst.

[0035] To a fourth glass jar was added 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 a co-feed activator.

[0036] 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 in one go. Then co-feed catalyst and co-feed activator solutions were added to the flask at a rate of 0.13 g / min, with a target total feed time of 95 minutes. After 5 minutes, monomer feed and co-feed aqueous solution were added to the flask at a rate of 0.44 g / min, with a target total feed time of 80 minutes. The controller set point temperature was maintained at 70°C. After all four feeds were added to the flask, the contents of the flask were kept at 70°C for 15 minutes and then cooling was started. When the contents of the flask reached 60°C, aqueous ammonia solution (0.50 g, 30% active matter) was added to the flask. Once the flask contents had cooled to ambient temperature, they were passed through a nylon filter (mesh size: 150 μm) to produce a white emulsion with a solids content of 19.5 wt %, a pH of 4.1, a particle size of 201 nm (determined by dynamic light scattering) (dispersity, 0.056), and a residual vinyl acetate content of 1,756 ppm (determined by headspace gas chromatography).

[0037] Example 19: Vinyl Ester Latex

[0038] The 250-mL round-bottom flask is equipped with a glass rod propeller, condenser and thermocouple with Teflon stirring blades. The propeller is driven by an overhead mechanical stirrer, and the thermocouple is connected to a J-KEM temperature controller and to a pneumatic tank lifter to achieve the desired temperature. Deionized water (32.0 g) and lauryl ethoxylated sulfate surfactant (2.66 g, 31% by weight, obtained from BASF with trade name Disponil FES-32) are first added to the flask. The temperature controller is set to 70 ° C, and the flask is placed under nitrogen.

[0039] To a first glass jar were added 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 with moderate heating to form a homogeneous mixture for use as the monomer feed.

[0040] To a second glass jar were added deionized water (33.80 g), an aqueous solution of sodium vinyl sulfonate (0.712 g, 25% active), an aqueous solution of secondary C13 alkyl ethoxylate (0.51 g, 70% by weight, available under the trade name Tergitol TM 15-S-40 available from Dow Chemical Company) and lauryl ethoxylated sulfate surfactant (1.0 g, 31 wt % available from BASF under the trade name Disponil FES-32) were used as aqueous co-feeds.

[0041] To a third glass jar was added 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) as a co-feed catalyst.

[0042] To a fourth glass jar was added a solution of a sulfur-based formaldehyde-free reducing agent (0.065 g, Bruggolite FF6M, available from Brueggemann) in deionized water (10.0 g) to serve as a co-feed activator.

[0043] When the contents of the flask reached 70°C, two feeds were added to 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%). The co-feed catalyst and co-feed activator solutions were then added to the flask at a rate of 0.11 g / min, with a target total feed time of 95 minutes. After 5 minutes, the monomer feed and aqueous co-feed were added to the flask at a rate of 0.44 g / min, with a target total feed time of 80 minutes. The controller set point temperature was maintained at 70°C. After all four feeds were added to the flask, the contents of the flask were maintained at 70°C for 15 minutes, and then cooling was initiated. 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. Separate chase catalyst feeds were then added to the flask contents at a rate of 0.17 g / min over 30 minutes - a first stream of ammonium persulfate (9.3 mg), aqueous tert-butyl hydroperoxide (31 mg, 70% active), and deionized water (5.0 g); a second stream of sodium metabisulfite (47 mg) in deionized water (5 g). After both chase feeds were complete, the flask contents were held at 60° C. for 15 minutes. The flask contents were then cooled to ambient temperature. Once at ambient temperature, the flask contents were passed through a nylon filter (mesh size: 150 μm) to produce a white emulsion having a solids content of 22.89 wt %, a pH of 3.3, a particle size of 181 nm (determined by dynamic light scattering) (dispersity, 0.001), and a residual vinyl acetate content of 165 ppm (determined by headspace gas chromatography).

[0044] Example 20: Vinyl Ester Latex

[0045] The 250-mL round-bottom flask is equipped with a glass rod propeller, condenser and thermocouple with Teflon stirring blades. The propeller is driven by an overhead mechanical stirrer, and the thermocouple is connected to a J-KEM temperature controller, and is connected to a pneumatic tank lifter, to achieve the required temperature. First, deionized water (32 g) and lauryl ethoxylated sulfate surfactant (2.66 g, 31% by weight, derived from BASF with trade name Disponil FES-32) are added to the flask. The temperature controller is set to 70 ° C, and the flask is placed under nitrogen.

[0046] To a first glass jar were added 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 with moderate heating to form a homogeneous mixture for use as the monomer feed.

[0047] To a second glass jar were added deionized water (33.80 g), aqueous sodium vinyl sulfonate solution (0.712 g, 25% active), secondary C 13 Alkyl ethoxylate aqueous solution (0.51 g, 70 wt %, trade name Tergitol TM 15-S-40 available from Dow Chemical Company) and lauryl ethoxylated sulfate surfactant (1 g, 31 wt %, available under the trade name Disponil FES-32 from BASF) were used as aqueous co-feeds.

[0048] To a third glass jar was added 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) as a co-feed catalyst.

[0049] To a fourth glass jar was added a solution of isoascorbic acid (0.057) in deionized water (10.0 g) to serve as a co-feed activator.

[0050] When the contents of the flask reached 70°C, two feeds were added to 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%). Then, the co-feed catalyst and co-feed activator solutions were added to the flask at a rate of 0.11 g / min, with a target total feed time of 95 minutes. After 5 minutes, the monomer feed and aqueous co-feed were added to the flask at a rate of 0.44 g / min, with a target total feed time of 80 minutes. The controller set point temperature was maintained at 70°C. After all four feeds were added to the flask, the contents of the flask were maintained at 70°C for 15 minutes, and then cooling was started. When the contents of the flask reached 60°C, an aqueous ammonia solution (0.5 g, 30% active) was added to the contents of the flask in one portion. Separate chaser feeds were then added to the flask contents at a rate of 0.5 g / min over 10 minutes - a first stream of aqueous tert-butyl hydroperoxide solution (85 mg, 70% active) and deionized water (5.0 g); a second stream of sodium metabisulfite (62 mg) in deionized water (5.0 g). After both chaser feeds were complete, the flask contents were held at 60° C. for 15 minutes. The flask contents were then cooled to ambient temperature. Once at ambient temperature, the flask contents were passed through a nylon filter (mesh size: 150 μm) to produce a white emulsion having a solids content of 22.21 wt %, a pH of 3.8, a particle size of 186 nm (determined by dynamic light scattering) (dispersity, 0.050), and a residual vinyl acetate content of 177 ppm (determined by headspace gas chromatography).

[0051] Thickening properties and turbidity

[0052] The viscosity of the aqueous vinyl ester latex solutions prepared according to Comparative Examples C1-C3 and Examples 1-20 was measured at various concentrations as described using a Brookfield viscometer using a spindle as described at 3 rpm. The pH of the solution was adjusted to 7-8 using sodium hydroxide (0.5 N). The results are provided in Table 3.

[0053] The turbidity of the pH adjusted aqueous vinyl ester latex solution was measured at 21° C. using a turbidimeter. The meter was calibrated according to the instructions provided with the machine. The turbidity measured in nephelometric units (NTU) is provided in Table 3.

[0054] The viscosity of the aqueous vinyl ester latex solutions prepared according to Comparative Example C3 and Examples 1-6 and 17-20 was also measured at 1 wt % or 5 wt % as shown in Table 4 using a Brookfield viscometer using the indicated spindle at the indicated rpm. The pH of the solution was adjusted to 7-8 using sodium hydroxide (0.5 N). The results are provided in Table 4.

[0055] Table 3

[0056]

[0057] Table 4

[0058]

[0059] Comparative Examples CF1-CF4 and Examples F1-F6: Laundry Detergents

[0060] A laundry detergent formulation was prepared in each of Comparative Examples CF1-CF4 and Examples F1-F6 having the formulations shown in Table 5. The formulation was prepared by combining the ingredients in the order listed in Table 5 while constantly mixing with an overhead mixer to produce a vortex. The anionic surfactant, water, and solvent were thoroughly mixed until all components were incorporated, and then a nonionic surfactant (pre-melted at 50° C.) was added. The pH was then adjusted to 8.5 with a NaOH solution. Then vinyl ester latex as shown in Table 5 was added to the formulation in an amount sufficient to provide 1.2% by weight of active vinyl ester latex in the formulation while mixing with an overhead mixer. If necessary, the pH was adjusted back to 8.5 using NaOH or HCl solutions. Water was then added as needed to bring the formulation to 100% by weight.

[0061] Table 5

[0062]

[0063]

[0064] Viscosity of laundry detergent formulations

[0065] The viscosity of laundry detergent formulations prepared according to Comparative Examples CF1-CF4 and Examples F1-F6 was measured with a Brookfield viscometer using a LV-2 (62) spindle at 3 rpm. The results are provided in Table 6.

[0066] Table 6

[0067]

[0068]

[0069] Biodegradability

[0070] The biodegradability of the vinyl ester latex prepared according to Example 1 was evaluated according to the inherent aerobic biodegradation test procedure described in OECD 302B. The results are provided in Table 7.

[0071] Table 7

[0072]

Claims

1. A vinyl ester latex comprising: 20 to 80 wt % structural units of monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms, based on the dry weight of the vinyl ester latex; 20 to 80 wt % 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 wt % structural units of a polyethylenically unsaturated crosslinking agent, based on the dry weight of the vinyl ester latex; 0 to 20 wt % structural units of other monoethylenically unsaturated monomers, based on the dry weight of the vinyl ester latex, wherein the other monoethylenically unsaturated monomers are different from the monoethylenically unsaturated alkanoic acid vinyl esters having 4 to 12 carbon atoms and the monoethylenically unsaturated carboxylic acid functionalized vinyl esters having 4 to 12 carbon atoms; wherein the vinyl ester latex contains less than 1.2 wt % of structural units of 2-acrylamido-2-methyl-propanesulfonic acid based on the dry weight of the vinyl ester latex; wherein the vinyl ester latex contains less than 10 wt % of structural units of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, alkali metal salts thereof, ammonium salts thereof, and mixtures thereof, based on the dry weight of the vinyl ester latex; wherein the vinyl ester latex contains less than 5 mol% of dicarboxylic acid anhydride structural units; and The vinyl ester latex contains less than 10 wt % 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.

2. The vinyl ester latex according to claim 1, wherein the structural units of the monoethylenically unsaturated alkanoic acid vinyl ester 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 wt% to 100 wt% of the vinyl ester latex in total, 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 less than 0.1 mol% of structural units of a monomer containing a monoethylenically unsaturated amide.

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

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

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

7. The vinyl ester latex of claim 6, wherein the polyethylenically unsaturated crosslinking agent is diallyl phthalate.

8. The vinyl ester latex according to claim 7, further comprising: 0.1 wt % to 5 wt % of structural units of the other monoethylenically unsaturated monomers, based on the dry weight of the vinyl ester latex; wherein the other monoethylenically unsaturated monomers are selected from the group consisting of: (meth)acrylates, (meth)acrylamides, vinyl ethers, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropylmethanesulfonic acid, (meth)acrylic acid, maleic acid, their salts and mixtures thereof. 9 . The vinyl ester latex according to claim 8 , wherein the structural unit of the monoethylenically unsaturated vinyl alkanoate having 4 to 12 carbon atoms is a structural unit of vinyl acetate.

10. The vinyl ester latex of 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 wherein the other monoethylenically unsaturated monomer is selected from the group consisting of vinyl sulfonic acid, vinyl sulfonate, and mixtures thereof.

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