Coating compositions preserved by inclusion of multifunctional mixtures

Abstract

Water-based architectural coating compositions including a multifunctional additive including a hydroxamic acid and one or more diols, wherein the weight ratio of the hydroxamic acid to diols is from 1:9 to 1:19. The coating compositions are adequately preserved with reduced or no amounts of traditional biocides such as isothoaizolinones. Also disclosed are methods of preserving water-based coating compositions using the multifunctional additive and coated articles of the disclosed coating compositions coated on a substrate.

Description

COATING COMPOSITIONS PRESERVED BY INCLUSION OF MULTIFUNCTIONALMIXTURESFIELD OF THE DISCLOSURE

[0001] This disclosure relates to the wet-state preservation of water-based paints and coatings against wet-state microbial contamination and spoilage using reduced amounts of or no intentionally-added conventional, isothiazolinone preservatives.BACKGROUND

[0002] Paints or coatings containing a polymeric binder are susceptible to wet-state microbial growth, or contamination, without adequate preservation. Water-based paints or coatings, which typically include a latex polymeric binder, arc particularly susceptible compared to their solvent-based counterparts. Spoilage of a coating composition by microbial contamination or undesirable amount of in-container microbial growth can result in putrefaction, lowered pH, gas fonnation, and changes in viscosity that may make the coating composition unusable or have undesirable properties. As a result, paint and coating compositions must be adequately preserved to remain useful through manufacturing, distribution, and storage.

[0003] To combat microbial grow th and resulting spoilage of tire product, biocides— additives having microbistatic or microbicidal properties— are commonly added to prevent in-can or wet-state microbial spoilage of water-based paints and coatings, and thus ensure paint or coating composition stability.

[0004] Common antimicrobial wet-state additives used in paints and coatings include organic acids, phenols, alcohols, and quaternary ammonium compounds. Quaternary ammonium compounds, such as those disclosed in U.S. Patent No. 9,131,683 B2, act as biocides by damaging cell membranes and killing bacteria. Among the most commonly used w et-state antimicrobial additives are isothiazolinones such as benzisothiazolinone (‘“BIT”), methylisothiazolinone (“MIT”), and 2-methyl-4-isothiazolin-3-one (“CMIT”). Although effective biocides to preserve coatings, isothiazolinones are increasingly at risk due to potentially limited supply, potential emerging regulations, and consumer deselection. Although other antimicrobial additives, for example, those containing metal ions, such as silver-, zinc- (including zinc pyrithiones), and copper-based biocides, or additives include phosphates, metal ion, metal, and biocidecontaining zeolites or hydroxyapatites are known, these antimicrobial additives cannot alw ays provide complete protection against product spoilage, and may present similar supply chain or regulatory risks. Thus there is a need to find ways to adequately preserve paints and coatings using less or none of the conventional biocides.

[0005] Paints and coatings, which typically include a carrier, a film-forming polymeric binder, one or more optional pigments, extenders, or filler, are complex formulations, however. The identity and amounts of these components must be carefully balanced so important properties of the paint or coating,such as viscosity across different shear rates, application quality, in-can stability against separation or settling, and stability against pigment agglomeration, among other properties, are maintained. Organic chemical additives, in particular, must be carefully selected to have a correct hydrophobic / lipophilic balance to ensure proper interaction with other coating components, not change the color, or affect laydown, leveling, or application characteristics. In addition, paints and coatings are typically formulated to have a basic pH in the wet-state, which changes to a neutral pH after application. Coating additives therefore must be compatible to be formulated into coating compositions with varying pH, and not negatively impact coating characteristics.

[0006] Tirus, what is needed are additives that are compatible in water-based coating compositions such as paints, stains, caulks, and sealants, which provide satisfactory resistance against microbial growth, with reduced or no amounts of traditional, isothiazolinone-based biocides.SUMMARY

[0007] Disclosed are water-based coating compositions that are adequately preserved in the wet-state by inclusion of a hydroxamic acid and one or more diols. Thus, the present disclosure provides water-based architectural coating compositions that include an aqueous carrier, a latex polymeric binder, a pigment, and a multi-functional additive including a hydroxamic acid and one or more diols. The coating compositions optionally include an isothiazolinone, and have adequate wet-state preservation according to the Microbial Resistance Test described herein. The coating compositions optionally may also include one or more additives selected from an extender, a rheology modifier, a colorant, a mildewcide, a surfactant, a dispersant, a defoamer, a coalescent, a plasticizer, an anti-settling agent, a pH modifier, a UV absorbent, a crosslinker, a thickener, a coalescing aid, an anti-foaming agent, a freeze-thaw additive, a matting agent or combinations thereof. Coating compositions of the present disclosure are adequately preserved despite including lower amounts of or no intentionally-added conventional isothiazolinone preservatives.

[0008] In some aspects, the hydroxamic acid is present in the coating composition in an amount of at least 0.03 wt.% based on the total weight of components of the paint or stain, and wherein tire weight ratio of the hydroxamic acid to the one or more diols is from 1 :9 to 1 : 19. In some aspects, the hydroxamic acid is an alkyl / alkyloxy hydroxamic acid.

[0009] In some aspects, the water-based coating composition includes about 7 wt.% to 30 wt.% polymer solids of a film-forming polymeric binder, an opacifying pigment, and about 0.5 wt.% to about 3.0 wt.% based on the total weight of components in the coating composition of a multifunctional additive including (a) a hydroxamic acid or salt thereof and (b) one or more diols, wherein the weight ratio of the hydroxamic acid to the one or more diols is from about 1 :9 to 1:19, and optionally, an isothiazolinone.

[0010] Also disclosed are methods of preserving a water-based architectural paint or stain comprising: adding a multifunctional additive including (a) a hydroxamic acid or salt thereof and (b) one or more diols, wherein the weight ratio of the hydroxamic acid or salt thereof to the one or more diols in the multifunctional additive is from 1:9 to 1: 19 to a water-based architectural coating composition that includes: an aqueous carrier, a film-forming polymeric binder, optionally, an isothiazolinone, and optionally, one or more additives selected from an extender, a rheology modifier, a colorant, a mildewcide, a surfactant, a dispersant, a defoamer, a coalescent, a plasticizer, an anti-settling agent, a pH modifier, a UV absorbent, a crosslinker, a thickener, a coalescing aid, an anti-foaming agent, a freezethaw additive, a matting agent or combinations thereof.

[0011] In some aspects, the method includes adding the multifunctional additive in an amount of about 0.5 wt.% to about 3.0 wt.% based on the total weight of components in the coating composition.

[0012] In some aspects, the hydroxamic acid is an alkyl / alkyloxy hydroxamic acid.

[0013] In some aspects, wherein the hydroxamic acid has the formula, where R is a linear or branched, saturated or unsaturated, substituted or unsubstituted chain of alkyl and alkyloxy groups having at least two carbon atoms, and Ri is H or a linear or branched, substituted or unsubstituted chain of alkyl and alkyloxy groups having from 1 to 22 carbon atoms. In some aspects, R or Ri, or both, are saturated. In some aspects, Rhas at most 22 carbon atoms. In some aspects, R has at least 5 carbon atoms. In some aspects, has at most 11 carbons. In some aspects, R has 6 or 7 carbons. In some aspects, R is a saturated, linear hydrocarbon chain of 7 carbons.

[0014] In some aspects, the hydroxamic acid includes capryl hydroxamic acid, or preferably is capryl hydroxamic acid. In some aspects, the hydroxamic acid includes octanohydroxamic acid, or preferably is octanohydroxamic acid. In some aspects, R or RI. or both, is independently substituted with one or more hydroxyl groups, cycloaliphatic groups, aromatic groups, or halogens. In some aspects, Ri is H.

[0015] In some aspects, the hydroxamic acid is present in the coating composition an amount of at least 0.0375 wt.% based on the total weight of components of the coating composition; in some aspects, the hydroxamic acid is present in the coating composition in an amount of at most 0.15 twt.% based on the total weight of components of the paint composition.

[0016] In some aspects, the one or more diols include 1,3-propanediol. In some aspects, the one or more diols includes a vicinal diol, which may be, in aspects, 1,2-octanediol, caprylyl glycol, 1,2-hexanediol, or ethylhexylglycerin.

[0017] In some aspects, the multifunctional additive is present in the coating composition in an amount of at least 0.5 wt.%, at least 1.0 wt.%, at least 1.5 wt.%, or at least 2.0 wt.%, based on the total weight of components of the coating composition.

[0018] In some aspects, the coating composition is substantially free, essentially free, or completely free of isothiazolinones; or includes no intentionally added isothiazolinones. In some aspects, the isothiazolinones are the group consisting of: 1,2-benzisothiazolinone, the reaction product of 2-Methyl- l,2-thiazol-3-one and 5-Chloro-2-methyl-4-isothiazolin-3-one, n-butyl-benzisothiazolinone, n-octyl-4- isothiazolin-3-one, Dichloro-2-octyl-l,2-thiazol-3(2H)-one, and N-methyl benzisothiazolin-3-one.

[0019] In some aspects, the coating composition is substantially free, essentially free, or completely free of a sodium or zinc salt of pyrithione or includes no intentionally added sodium or zinc salts of a pyrithione.

[0020] In some aspects, the coating composition has no more than 200 g / L VOC. or 150 g / L VOC. or 100 g / L VOC, or 50 g / L VOC, or 25 g / L VOC, or no VOC. In some aspects, the coating composition is an architectural paint, an architectural stain, a caulk, or a sealant.

[0021] In some aspects, the polymeric binder of the coating compositions comprises a vinyl acrylic latex, a styrene acrylic latex, an acrylic latex, a waterborne polyurethane dispersion (PUD), a waterborne alkyd resin, a waterborne alkyd-PUD hybrid resin, or blends thereof; in some aspects the polymeric binder is a latex emulsion. In some aspects, the polymeric binder has a MFFT of less than about 30°C, preferably less than about 20°C. In some aspects, the latex emulsion is a single-stage latex emulsion polymer, and in other aspects, the latex emulsion is a multi-stage latex emulsion polymer.

[0022] In some aspects, the polymeric binder is completely free or essentially free of functional monomer units that cross-link the polymeric binder during fdm formation. In other aspects, the polymeric binder includes reactive ketone moieties to cross-link the polymeric binder during film formation. In some aspects, the the reactive ketone moieties are derived from monomers comprising diacetone acrylamide (DAAM); in other aspects, the reactive ketone moieties are derived from monomers comprising acetoacetoxy ethylmethacrylate (AAEM).

[0023] Also disclosed is a coated article comprising the coating composition as described herein, coated on a substrate and cured, wherein the substrate comprises wood, drywall, vinyl, metal, cementitious fibre broad, or a coating on the substrate.

[0024] The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The description that follows more particularly exemplifies illustrative embodiments. In several places throughout the disclosure, guidance is provided through lists of examples, which examples may be used in various combinations. In each instance, the recited list serves only as a representative group and should not be interpreted as anexclusive or exhaustive list. Thus, the scope of the present disclosure should not be limited to the specific illustrative structures described herein, but rather extends at least to the structures described by the language of the claims, and the equivalents of those structures. Any of the elements that are positively recited in this specification as alternatives may be explicitly included in the claims or excluded from the claims, in any combination as desired. Although various theories and possible mechanisms may have been discussed herein, in no event should such discussions serve to limit the claimable subject matter.DEFINITIONS

[0025] Unless otherw ise indicated, concentrations provided in % are weight percent of all ingredients in the referenced composition.

[0026] Tire term “pigment” as used herein includes both colored, dispersible solid particulate materials and colored dispersible or soluble dye materials, w herein the material imparts visually noticeable color or hide to a paint or coating when 5 wt. % (in the case of a colored, dispersible solid particulate) or 0.05 wt. % (in the case of a colored, dispersible or soluble dye) of the material is added to (e.g., dispensed into) the paint or coating. The presence or absence of visually noticeable color may be assessed by preparing drawdown samples of the paint or coating with and without the pigment, casting such samples as 25 micrometer (pm) dry thickness coated films over the w hite part of a BYK-Gardncr No. PA-2811 opacity draw down chart (from BYK-Gardner USA) or comparable chart, and examining the coated films under normal overhead interior illumination. Pigments may also impart opacity to a coating without significant effect on color.

[0027] A reference to a “(meth)acrylate” compound, where “meth” is enclosed in parenthesis, is meant to include both acrylate and methacrylate compounds. For instance, the term “(meth)acrylate polymer” includes independently, each of acrylate homopolymers, methacry late homopolymers, and copolymers that include interpolymerized acrylate and methacrylate monomers.

[0028] The term “multistage.” as used herein with respect to a latex means the latex polymer was made using discrete, sequential charges of two or more monomers or monomer mixtures, or w as made using a continuously-varied charge of two or more monomers. A multistage polymer is distinct from a single stage polymer made using one type of monomer blended with distinct polymer seed particles.

[0029] Tire terms “waterborne” or “water-based” refer to compositions that include a carrier that is more than 50% by w eight water as a percentage of the total carrier weight.

[0030] The term “on”, when used in the context of a coating applied on a surface or substrate, includes both coatings applied directly to the surface or substrate or indirectly such that an intermediate layer is present between the coating and the surface or substrate. Thus, for example, a coating applied to a primer layer overlying a substrate constitutes a coating applied on the substrate.

[0031] Unless otherwise indicated, the term “polymer” includes both homopolymers and copolymers (i.e., polymers of two or more different monomers).

[0032] Tire term “architectural coating composition” encompasses paints and also aerosol coatings, caulks, stains, and sealants. Architectural coating compositions are suitable for use on one or more of the interior or exterior of building or construction surfaces, e.g.. walls, trim, floor, decks, wood or metal railings, ceilings, roofs (including metal roofing, shingles and tiles), roadways, sidewalks, etc.

[0033] The term “paint” means a coating composition including pigment and binder which when applied to form a thin (e.g., 100 pm) wet thickness coating film on a freshly-sanded smooth wood surface, will when dried hide both the w ood grain and its texture and will present a new surface with its own appearance. Although defined with reference to wood, paints may be applied to any solid architectural surface including wood, drywall, metal, roofing materials, concrete, or rock.

[0034] A “stain” refers to a coating composition including optional pigment and film-forming binder that, when applied to form a thin (e.g., approximately 100 pm) wet thickness coating film on a freshly- sanded smooth wood surface will, when dried, does not hide the wood grain of the wood surface.

[0035] Tire term “pigment volume concentration” (PVC) when used in respect to a paint, stain or colorant means the total percentage of dried coating volume occupied by all inorganic species in the coating. Tire PVC of a coating composition is the ratio of the volume of pigments (including fillers and functional fillers) to the volume of total non-volatile material (i.e. binder solids) present in the coating.

[0036] The temrs “preferred” and “preferably” refer to embodiments that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention or claims.

[0037] The term “post-addition component” or “post-add” refers to a component of a coating composition or aqueous polymeric binder composition that can be added at any stage during the blending of a coating composition or polymeric binder composition prior to application or curing of the composition, but after polymerization of tire polymeric binder from monomers.

[0038] The term “substantially free,” when applied to components of a composition and not to VOC content, means that the composition contains no more than about 1 wt. % of a particular component, based on total weight of solids in the composition. For example, a composition that is substantially free of conventional biocide contains no more than about 1 wt. % conventional biocide as a percentage of the solids weight of the composition. A composition that is “essentially free” when applied to components of a composition and not to VOC levels, means the composition contains no more than about 0.04 wt. % of the material. A composition that is “completely free” when applied to components of a composition andnot to VOC levels, means the composition contains no more than trace amounts of the material on a percentage solids of the composition basis because none of the material is intentionally added to the composition.

[0039] Tire term “VOC” is defined by regulation of the United States Environmental Protection Agency to mean any compound of carbon, excluding carbon monoxide, carbon dioxide, carbonic acid, metallic carbides or carbonates, and ammonium carbonate, which participates in atmospheric photochemical reactions, other than exempt compounds identified in Title 40 Code of Federal Regulations, Sec.51.100. The amount of VOC present in a composition is be measured by gas chromatography via ASTM D6886-18, titled “Standard Test Method for Determination of the Weight Percent of Individual Volatile Organic Compounds in Waterborne Air-Dry Coatings by Gas Chromatography” using methyl palmitate as a market. VOC amounts are reported in grams / Liter less exempt compounds (g / L).

[0040] The phrase “low VOC” when used with respect to a liquid coating composition means that the liquid coating composition contains less than about 250 grams volatile organic compounds per liter composition, excluding water and exempt compounds. The term “very low VOC” means a liquid coating composition that contains less than 150 grams volatile organic compounds per liter of composition, excluding water and exempt compounds. The term “extremely low VOC” means a liquid coating composition that contains less than 50 grams volatile organic compounds per liter of composition, excluding water and exempt compounds. The term “no VOC” means a liquid coating composition that contains less than 5 grams VOCs per liter of composition.

[0041] The term “substantially all” means that at least a majority of the identified composition includes the

[0042] The term “comprises” and variations thereof do not have a limiting meaning where these terms appear in the description and claims.

[0043] As used herein, “a,” “an,” “the,” “at least one.” and “one or more” are used interchangeably. Thus, for example, a coating composition that comprises “an” additive can be interpreted to mean that the coating composition includes “one or more” additives.

[0044] Also herein, the recitations of numerical ranges by endpoints include all numbers subsumed within that range (e.g., 1 to 5 includes 1. 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). Furthermore, disclosure of a range includes disclosure of all subranges included within the broader range (e.g., 1 to 5 discloses 1 to 4, 1.5 to 4.5. 1 to 2, etc.).

[0045] Reference throughout this specification to “aspects,” “an aspect,” “some aspects,” “approaches,” “an approach,” some approaches,” “one embodiment,” “an embodiment,” “certain embodiments,” or “some embodiments,” etc., means that a particular feature, configuration, composition, or characteristic described in connection with the embodiment is included in at least one embodiment of the disclosure.Thus, the appearance of these phrases in various places throughout this specification are not necessarily referring to the same embodiment of the disclosure, even though in both instances the same term (e.g., “aspect” or “approach”) is present. Furthermore, the particular features, configurations, compositions, or characteristics may be combined in any suitable manner in one or more embodiments.DETAILED DESCRIPTION

[0046] Coating compositions of the present disclosure include a multifunctional additive present in the composition, an aqueous carrier, a film-forming polymeric binder, a pigment, and a multifunctional additive that includes a hydroxamic acid and one or more diols. Optionally, the coating composition may include an isothiazolinone. The coating compositions have adequate wet-state preservation despite the inclusion of reduced or no amounts of traditional preservatives such as isothiazolinones.

[0047] In some aspects, the coating composition has no more than 200 g / L VOC. or 150 g / L VOC, or 100 g / L VOC. or 50 g / L VOC, or 25 g / L VOC, or substantially no VOC.

[0048] In some aspects, the coating composition is a paint, a stain, a caulk, or a sealant.Multifunctional Additive

[0049] Tire multifunctional additive of the present disclosure includes a hydroxamic acid and one or more diols. The hydroxamic acid has Formula (1):FORMULA (1) where R is a linear or branched, saturated or unsaturated, substituted or unsubstituted chain of alkyl and alkyloxy groups having at least two carbon atoms, and R1 is H or a linear or branched, saturated or unsaturated, substituted or unsubstituted chain of alkyl and alkyloxy groups having from 1 to 22 carbon atoms. Accordingly, R and R1 may, independently, include a combination of branched or linear alkyl, alkoxy, alkenoxy, or alkynoxy groups. Substitutions present on R and R1 may include one or more hydroxyl groups, cycloaliphatic groups, aromatic groups, halogens, or any other suitable substituent.

[0050] In some embodiments, R has at most 22 carbons. In some aspects, R may have at least 5 carbons, or at most 11 carbons. In some aspects, R has 6 or 7 carbons. Suitable hydroxamic acids include hexanohydroxamic acid, a hydroxamic acid where Ri is H and R is a saturated, linear 5 -carbon alkyl chain; heptoanohydroxamic acid, a hydroxamic acid where Ri is H and R is a saturated, linear 6-carbon alkyl chain; octano hydroxamic acid (capryl hydroxamic acid), a hydroxamic acid where Ri is H and R isa saturated, linear 7-carbon alkyl chain: nonanohydroxamic acid, a hydroxamic acid where Ri is H and R is a saturated, 8 carbon alkyl chain; caprohydroxamic acid, a hydroxamic acid where Ri is H and R is a saturated, linear 9-carbon alkyl chain; or; or laurohydroxamic acid, a hydroxamic acid where Ri is H and R is a saturated, linear 11 -carbon alkyl chain. Tire hydroxamic acid may be in a salt form, having been partially neutralized by, for instance, a sodium, potassium, or ammonium ion.

[0051] The multifunctional additive also includes one or more diols. The diols preferably include a vicinal diol, in which two hydroxyl groups are bonded to adjacent carbon atoms. Preferred diols include 1,3-propanediol, and preferred vicinal diols 1,2-propanediol, 1,2, -hexanediol, ethylhexylglycerin, propylene glycol, hexylene glycol, and caprylyl glycol (1,2-octanediol). Diols of the present disclosure are liquid at room temperature so they may be added to the liquid coating composition via conventional mixing processes.

[0052] In some embodiments, when added to the coating composition, the hydroxamic acid is present in the coating composition in an amount of at least 0.03 wt.% based on the total weight of components in the coating composition, and theweight ratio of hydroxamic acid to diols is from 1:9 to 1: 19. In some aspects, the hydroxamic acid is present in the coating composition in an amount of at least 0.0375 wt.% based on the total components of the coating composition. In some aspects, the hydroxamic acid is present in the coating composition in an amount of at most 0.15 wt.% based on the total components of the coating composition.

[0053] In some embodiments, the multifunctional additive is added to the coating composition as a premixture of hydroxamic acid and diol, wherein the weight ratio of hydroxamic acid to diols is from 1:9 to 1 : 19. In some embodiments, the multifunctional additive is present in the coating composition in an amount of at least 0.5 wt.%, at least 1.0 wt.%, at least 1.5 wt.%, or at least 2.0 wt.% of the total components of the coating composition.

[0054] The multifunctional additive may be added to the coating composition as a post-add and mixed in the coating composition with low shear mixing. Or, the components of the multifunctional additive may each separately be added to the coating composition as a post-add. Or, the multifunctional additive of each component thereof may be added to the polymeric binder and mixed, which is then added to the coating composition and mixed.

[0055] Without being bound by theory, it has been discovered that a multifunctional additive including a hydroxamic acid in combination with a diol can provide adequate wet-state preservation to a coating composition. Surprisingly, the hydroxamic acid component of the multifunctional additive provides these benefits across the pH range of a coating composition, despite its acidic pH, which contrasts to the typically basic pH (8-10) of a coating composition in manufacturing and long-term storage. Further, tire hydroxamic acid component is able to provide these benefits and maintain its solubility in the coatingcomposition through the pH change that accompanies curing, in which the pH of the coating becomes at least neutral to slightly acidic.

[0056] Further, surprisingly, the multifunctional additive can be incorporated into a wet-state coating composition without adversely impacting the properties of the coating composition and the cured coating. Diols are known humectants, and as such, inclusion of a diol tends to slow dry ing and curing of an applied coating. Nonetheless, including diols in compositions of the present disclosure does not detrimentally affect the coating quality, which would be expected with the inclusion of significant amounts of humectant.

[0057] It has surprisingly been discovered that despite having chemistries that nominally can cause adverse impacts on coating composition and coating characteristics, a multifunctional additive including a hydroxamic acid and one or more diols can provide adequate preservation while maintaining coating composition characteristics within acceptable ranges, with lower amounts or no isothiazolinone antimicrobials.

[0058] Thus, in some embodiments, the coating composition is substantially free, essentially free, or completely free of optional isothiazolinones as disclosed herein.Optional Isothiazolinone

[0059] Coating compositions of the present disclosure may optionally include one or more isothiazolinones. As known antimicrobial additives, isothiazolinones can provide for wet-state preservation of coating compositions. However, inclusion of the multi-functional additive disclosed herein provides for adequate wet-state preservation of coating compositions with lower or no amounts of isothiazolinone antimicrobials.

[0060] In some aspects, isothiazolinones are the group consisting of 1,2-benzisothiazolinone (BIT), the reaction product of 2-Methyl-1.2-thiazol-3-one (MIT) and 5-Chloro-2-methyl-4-isothiazolin-3-one (CMIT). n-butyl-benzisothiazolinone (BB1T). n-octyl-4-isothiazolin-3-one (OIT). Dichloro-2-octyl-1.2- thiazol-3(2H)-one (DCOIT), and N-methyl benzisothiazolin-3-one (MBIT).

[0061] Exemplary isothiazolinones include a component of Proxel® AQ (9.25% BIT), Proxel® BC (5.0% BIT, 0.85% CMIT, 0.3% MIT), Proxel® BD (19.3% BIT), Proxel® BD 20 (19.3% BIT), Proxel® BN (13.5% BIT. 6.5% 2-bromo-2-nitro-l,3-propanediol), Proxel® BZ (8% zinc 2 -pyridinethiol- 1 -oxide, 12% BIT), Proxel® CMC (1.11% CMIT, 0.39% MIT), Proxel® DL (9% BIT), Proxel® GXL (19.3% BIT), Proxel® LS (2.0% BIT, 8.0% Sodium 2-pyritdinethiol-l -oxide). Isocil IG from Lonza Inc. (1.18% CMIT. 0.4% MIT), Proxel® Ultra technical (84% BIT), Proxel® Spectra™ (2.0% BIT, 4.0% sodium 2- pyridinethiol-1 -oxide), Proxel® UL (7% BIT), and Proxel® XL2 (9% BIT), all available from Arxada Corporation. Isothiazolinones also include Bioban ™ BT20AS (20% BIT), Bioban™ BT Technical (83.6% BIT), Bioban™ BTCM (0.38% CMIT, 0.14% MIT, 10% BIT), Bioban™ BZ from Lanxess Corp(12% BIT, 8% zinc 2-pyridinethiol-l -oxide), Bioban™ 200 (20% DCOIT), Bioban™ 586 (0.78% CMIT, 0.28% MIT, 7.5% 2-bromo-2-nitro-l,3-propanediol), Bioban™ 607 (12% BIT, 10% 2-bromo-2-nitro-l,3- diol), Bioban™ 63 (2.7% OIT, 20% 3 -(3, 4-dichlorphenyl)-l -dimethylurea, 7.5% carbamic acid, 1H- benzimidazol-2-yl, methyl ester), Bioban™ MT 10 (9.7% MIT), Bioban™ MT 20 (20% MIT), Bioban™ MT50 (50% MIT), Bioban™ M8LE (45% OIT), Kathon™ CF-400 (2.95% CMIT, 1.05% MIT), Kathon™ EDC (1.11% CMIT, 0.39% MIT), Kathon™ 28WT (21.1% CMIT, 6.9% MIT), Kathon™ 287 PXE (26.0% COIT), Kathon™ 287T (98.5% DCOIT), Kathon™ WT 1.5% (1.11% CMIT, 0.39% MIT), Kathon™ 886 MW (10.4% CMIT, 3.7% MIT) from Lanxess Corporation.

[0062] Further, in some embodiments, the coating composition is substantially free, essentially free, or completely free of pyrithiones, as well as sodium and zinc salts thereof, for example, as Sodium Omadine® and Zinc Omadine®, respectively, from Arxada Corporation.Aqueous Carrier

[0063] Coating compositions of the present disclosure also include an aqueous carrier and are waterbased. The carrier is a liquid component of the coating composition which serves to carry all of the other composition components. The carrier of the presently disclosed coating compositions is part of the wet coating composition and usually evaporates as the coating forms a film and dries on a surface. In latex paints, the carrier liquid is usually aqueous. Carriers of the present disclosure are at least 50% by weight water. In some aspects, the carrier is water. In some approaches, the carrier liquid or liquids are selected so as to provide an water-borne coating composition that is low free of VOC, very low VOC, extremely low VOC, or zero VOC.

[0064] Compositions of the present disclosure may include one or more carrier liquids. In some embodiments, carrier liquids may constitute 5-60% by volume of a coating composition. In some embodiments, carrier liquids may constitute 40-60 % of an aqueous polymeric binder composition.Film Forming Polymeric Binder

[0065] Water-based coating compositions in accordance with the present disclosure also comprise a filmforming polymeric binder.

[0066] Film- fomiing polymeric binders useful in coating compositions include waterborne polymeric binders such as acrylic latexes, vinyl acrylic latexes, styrene acrylic latexes, waterborne polyurethane dispersions (PUD), waterborne alkyd resins, waterborne alkyd-PUD hybrid resins, and mixtures or blends thereof. The polymeric binder is present in the aqueous composition in sufficient amount to form a continuous film when the aqueous composition is applied to a substrate and allowed to cure. In some embodiments, the water-based coating composition may comprise for example, at least about 17% by weight, to about 60% by weight of polymeric solids based on the total weight of components of the aqueous composition.

[0067] In certain preferred embodiments, the polymeric binder is a latex emulsion. Monomers interpolymerized into the latex emulsion preferably include one or more ethylenically unsaturated monomers.

[0068] In some approaches, the monomers preferably includes the one or more polymerization product(s) of (i) ethylenically unsaturated monomers, such as, for example, alkyl and alkoxy (meth)acrylates, vinyl esters of saturated carboxylic acids, monoolefins, conjugated dienes, optionally with (ii) one or more monomers, such as, for example, styrene, methyl methacrylate, butyl acrylate, 2- ethylhexyl acrylate, vinyl acetate, acrylonitrile, vinyl chloride, and the like. In an embodiment, the monomers of the latex polymers optionally include one or more polyfunctional (meth)acrylate monomers. In an embodiment, the monomers also include one or more ethylenically unsaturated carboxy-functional amide monomers, e.g., ureido-functional monomers, such as monomers formed as the product of the reaction between aminoalkyl alkylene urea (e.g., amino ethylene urea, for example) with an ethylenically unsaturated carboxylic acid or anhydride (e.g., maleic anhydride, for example).

[0069] Suitable ethylenically unsaturated monomers of the single stage latex or the stages of the multistage latex include, for example, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, or a dialkyl itaconate such as dimethyl itaconate, diethyl itaconate, dipropyl itaconate, or dibutyl itaconate, 2-(acetoacetoxy)ethyl methacrylate (AAEM), diacetone acrylamide (DAAM), acrylamide, methacrylamide, methylol (meth)acrylamide, styrene, a-methyl styrene, vinyl toluene, vinyl acetate, vinyl propionate, allyl methacrylate, and mixtures thereof. Preferred monomers include styrene, methyl acrylate, methyl methacrylate, ethyl acrylate, methacrylic acid, DAAM, AAEM, n-butyl acrylate, tert-butyl acrylate, tert-butyl methacrylate, n-butyl methacrylate, esters of itaconic acid, vinyl acetate, 2-ethyl hexyl acrylate, bio-renewable monomers, and the like.

[0070] In some embodiments, the polymeric binder includes functional monomer units comprising reactive ketone moieties that cross-link the polymeric binder during film formation. In some embodiments, such reactive ketone moieties include diacetone acrylamide (“DAAM”) and acetoacetoxyethylmethacrylate (AAEM). However in other embodiments, the polymeric binder is completely free or essentially free of any such reactive ketone moieties.

[0071] The (meth)acrylate monomers that may polymerized in the polymeric binder include multifunctional acrylates, for example, di-, tri- and tetra-functional acrylates such as dipropylene glycol diacrylatc (DPGDA), propoxylatcd glyceryl triacrylatc (GPTA), pcntacrythritol tctraacrylatc,dipentaerythritol tetraacrylate, mixtures thereof, and the like. Preferred polyfunctional acrylate monomers include pentaerythritol tetraacrylate, dipentaerytrithol tetraacrylate, and the like.

[0072] In some approaches, the latex polymer is formed of at least 80 wt % of two or more monomers selected from methyl methacrylate, ethyl acrylate, vinyl acetate, tert-butyl methacrylate, n-butyl methacrylate, styrene, tert-butyl acrylate, n-butyl acrylate, 2-ethyl hexyl acrylate, methyl acrylate, and esters of itaconic acid, based on the total weight of monomers used to form the latex copolymers (and not factoring any optional seed used).

[0073] In some approaches, the latex polymer is formed of at least 90 wt % of three or more monomers selected from methyl methacrylate, ethyl acrylate, vinyl acetate, tert-butyl methacrylate, n-butyl methacrylate, styrene, tert-butyl acrylate, n-butyl acrylate, 2-ethyl hexyl acrylate, methyl acrylate, and esters of itaconic acid, based on the total weight of monomers used to form the latex polymers (and not factoring any optional seed used).

[0074] Suitable ureido-functional monomers include, for example, monomers with the -NR — (C=O) — NH — functionality, where R may be H, substituted or unsubstituted Cl -CIO alkyl, substituted or unsubstituted C3-C6 cycloalkyl or heteroalkyl, and the like. Without being bound by theory, ureido- functional monomers are believed to promote the wet adhesion of the coating compositions and coating and colorant systems described herein to a substrate.

[0075] Latex emulsions of the present invention may comprise a single stage or multistage latex emulsion polymer, each having its own monomer composition. In some embodiments, aqueous compositions of the present disclosure include a latex polymer that is a multistage latex polymer having at least a first stage and a second stage or a single stage latex polymer.

[0076] A multistage latex does not necessarily exhibit two glass transition temperatures as measured by differential scanning calorimetry (DSC). For example, a DSC curve for a multistage latex made using discrete charges of two or more monomers may exhibit two or more Tgs but may exhibit only one Tg. In cases where a DSC curve shows only a single Tg inflection point, or even no Tg inflection points, it may be difficult to determine whether the latex is single stage or multistage, as the observation of a Tg inflection point depends on various factors, including the relative concentration of monomers in a particular stage. Thus, the presence or absence of Tg inflection points on a DSC curve is not dispositive as to whether a particular latex polymer is single stage or multisgage, but the Tgs of a multistage latex may be described in terms of the theoretical Tg values for each monomer stage, as determined by the Fox equation.

[0077] Various methods can be used to prepare the multistage latex described herein, including for example, sequential monomer feed and continuously varying monomer feed techniques. In a sequential monomer feed process, a first monomer or monomer mixture is fed and polymerization initiated, and asecond monomer (i.e. a different monomer, or a mixture of monomers present in different ratios than in the first monomer mixture) is fed during later stages of polymerization. In a varying monomer feed process, a first monomer composition is fed, followed by the addition of a second monomer at certain points in the polymerization process, and at different speeds. By controlling the type of monomers selected for the feed process, a multistage latex suitable for low VOC coating compositions or paints may be formed, and the latex preferably provides excellent performance characteristics, such as, for example, block resistance, scrub resistance, and the like, for such coating or paint formulations.

[0078] Preferred multistage latexes include at least two stages (e.g., two, three, or four or more stages) with different Tg values (not considering any Tg that may be associated with an optional “seed”). In some embodiments, each of the at least two stages constitute at least 15 weight percent (“wt %”), at least 20 wt %, at least 25 wt %, at least 30 wt %, at least 35 wt %, or at least 40 wt % of the multi-stage latex, based on the total weight of monomers used to make the latex (not including the weight of any optional seed used).

[0079] In some approaches, the multistage latex described herein is made by a sequential monomer feed process, in which polymerization begins with a higher Tg monomer feed followed by a lower Tg monomer feed, and vice-versa.

[0080] In some approaches, the multistage latex described herein is made using varying monomer feeds. The resulting polymer will typically have a DSC curve that exhibits no Tg inflection points, and could be said to have an essentially infinite number of Tg stages. The resultant multistage latex will have a gradient Tg from high to low, or vice-versa, depending on the order that monomers of high Tg are fed into the reaction.

[0081] In a preferred approach, the multistage latex described herein is made by a sequential monomer feed process using at least two distinct feeds of monomers. In an aspect, a “high” Tg stage (i.e., a hard stage) is fed first into a reactor vessel, and a “low” Tg stage (i.e. a soft stage) is added at a later stage in the process. A multistage latex may be formed, and after coalescence, the composition will typically display two distinct Tg values, or at least one Tg corresponding to the monomer stage present at higher concentration. In some instances, no distinct Tg may be observed or detected by DSC for a monomer or monomer mixture in a particular stage that is present in very small quantities relative to the other monomer or monomer mixture.

[0082] The multistage latex optionally may be formed from and include a “seed” phase, i.e., a relatively small monomer or polymer particle. A seed phase, however, is not required, nor essential for preparation or optimal performance of the multistage latex when used in a coating composition or paint formulation.

[0083] In an approach, the relative positions of the first and second phases may be internal and external respectively, or vice-versa. The shape morphology of the first and second phases can vary depending on the monomer feed process used, and the type and amounts of monomer in each phase.

[0084] In an approach, by controlling the monomers used for each stage of the sequential monomer feed process, a multistage latex with a desired minimum film forming temperature (MFFT) is obtained. The MFFT is the minimum temperature at which the composition comprising a multistage latex will form a continuous film, i.e. the temperature below which coalescence does not occur. The MFFT of the composition comprising a multistage latex as described herein is preferably less than about 30°C, more preferably less than about 20°C.

[0085] In some approaches, the latex polymer is a single stage latex, derived by polymerization in a single stage process of an emulsion including one or more ethylenically unsaturated monomers. By controlling the type of monomers used in the emulsion polymerization, a single stage latex suitable for low VOC coating compositions or paints may be formed. By controlling the monomers used in the single stage latex synthesis, a single stage latex composition with desired MFFT is obtained. The MFFT of the single stage film-forming binder as described herein is preferably less than about 30°C, more preferably less than about 20°C.

[0086] In certain approaches, latex copolymers (whether single stage, multistage, or gradient Tg) are made using seed particles as a nucleating agent for polymerization. Such seed particles may be in the form of inorganic particulate seed (e.g., clay or glass particles), preformed particulate polymer seed (latex or non-latex polymer seed), or particulate seed polymer formed in situ. Polymer seed can be an emulsion polymerized polymer seed, but does not encompass polymeric surfactant. In certain embodiments, seed particles are used in an amount of no more than 10 wt %, or no more than 5 wt %, based on latex polymer solids in the final latex.

[0087] Herein, whether inorganic particulate seed, preformed particulate polymer seed, or particulate seed polymer formed in situ, such seed particles will not be deemed to provide a stage of a multistage polymer or to provide a basis for designating a single stage polymer or gradient Tg polymer made using such seed polymer as a multistage polymer.

[0088] In certain approaches, the latex copolymers of the present invention may further include crosslinking monomers having ketone moieties that further react with a polymer chain at some time after initial formation of the latex copolymer (e.g., during coating cure). The crosslinking reaction can occur through the application of energy, e.g., through heat or radiation. Or, dying can activate the crosslinking polymer through changes in pH, oxygen content, evaporation of solvent or carrier, or other changes that causes a reaction to occur. A variety of chemistries arc known in the art to produce crosslinking in latexes. When used, such one or more crosslinking monomers are typically are included in the latexcopolymer in an amount of at least about 0.1 wt %, at least about 1.0 wt %, at least about 2 wt %, at least about 2.5 wt %, at least about 3 wt %, at least about 4 wt %, or at least about 5 wt %, based on the weight of the one or more crosslinking monomers relative to the total weight of monomers used to form the latex copolymer. While the amount of such one or more crosslinking monomers may vary widely, typically the one or more crosslinking monomers are present in the latex copolymer in an amount of about 10 wt % or less, about 9 wt % or less, about 8 wt % or less, about 7 wt % or less, about 6 wt % or less, or about 5 wt % or less, based on the weight of the one or more crosslinking monomers relative to the total weight of monomers used to form the latex copolymer.

[0089] Suitable examples of crosslinking carbonyl-containing monomers include acrolein, methacrolein, diacetone acrylamide, diacetone methacrylamide, 2-butanone methacrylate, formyl styrol, diacetone acrylate, diacetone methacrylate, acetonitrile acrylate, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate and vinylacetoacetate. These monomers normally do not affect crosslinking until during final film formation, for example, when the aqueous polymer emulsion simultaneously contains an appropriate added amount of a polyamine compound as crosslinker. Particularly suitable compounds of this type are the dihydrazides and trihydrazides of aliphatic and aromatic dicarboxylic acids of 2 to 20 carbon atoms. Polyamine compounds useful as crosslinkers for the carboxyl functional groups include those having an average of at least two carbonyl-reactive groups of the formula -NH2 and carbonyl reactive groups derived from such groups. Examples of useful amine functional groups include R-NH2, R-O-NH2, R-O-N=C<, R-NH-C(=O)-O-NH2, wherein R is alkylene, alicyclic or aryl and may be substituted. Representative useful polyamines include ethylene diamine, isophorone diamine, diethylenetriamine and dibutylenetriamine. In one embodiment of the invention, it is useful to utilize polyhydrazides as the polyamine compounds. Representative useful polyhydrazides include oxalic dihydrazide, adipic dihydrazide, succinic dihydrazide, malonic dihydrazide, glutaric dihydrazide, phthalic or terephthalic dihydrazide and itaconic dihydrazide. Additionally, water-soluble hydrazines such as ethylene- 1 ,2-dihydrazide, propylene- 1 ,3-dihydrazide and butylene- 1 ,4-dihydrazide, can also be used as one of the crosslinking agents.

[0090] In a preferred embodiment, the invention described herein includes a latex copolymer that is a single stage latex. In an aspect, the single stage latex is formed from monomers that include about 20 to 60, preferably 30 to 55 percent by weight of methyl methacrylate; 0 to 40, preferably 10 to 30 percent by weight of 2 -ethyl hexyl acrylate; 10 to 60, preferably 15 to 55 percent by weight of butyl acrylate; about 0 to 30, preferably 10 to 20 percent by weight of butyl methacrylate; and about 0 to 10, preferably 1 to 5 percent by weight of methacrylic acid.

[0091] The water-borne coating compositions of the present disclosure may be latex-based coating compositions. That is, in these approaches, at least a majority (i.e., more than 50 wt %), more preferablysubstantially all or all, of the resin solids in the coating compositions are latex polymers. Typically, the coating compositions include at least 20 wt %, at least 30 wt %, at least 40 wt %, or at least 50 wt % of latex polymer solids, based on total solids in the coating composition. Certain high gloss deep base paints may include 80 wt % or more of latex polymer solids. While the upper amount of latex copolymer included in the coating composition may vary widely (e.g., depending upon the amount of pigment included), typically the coating compositions will include less than 90 wt % latex polymer solids, based on total solids.

[0092] In certain approaches, the polymeric binders of the present invention may further include one or more bio-based monomers. “Bio-based,” as used with respect to monomers herein, refers to monomers that are preferably obtained from bio-renewable olefmically unsaturated monomers. Such bio-renewable olefinically unsaturated monomers have a carbon- 14 (C-14) that is significantly higher than olefmically unsaturated monomers derived from fossil fuels. This is because C-14 has a relatively short half-life on the scale of the age of fossil-fuel-based materials. Thus, “bio-renewable” monomers as used herein mean monomers for which the level of C-14 isotope is comparable to the mean level of C-14 in atmospheric CO2, as measured by ASTM D6866 or such monomers having at least about 1.5 dpm / gC (disintegrations per minute per gram carbon), at least 2.5 dpm / gC, or at least 3.0 dpm / gC of C-14, as measured through liquid scintillation counting.

[0093] Exemplary bio-based monomers include esters of itaconic acid, bio-derived (meth)acrylic acid, and alkyl (meth)acrylic acid. In embodiments, bio-based monomers make up at least 20 wt %, at least 30 wt %, or at least 40 wt % of the polymeric binder by weight of all monomers interpolymerized to form the polymeric binder.

[0094] The polymeric film-forming binder may also include a water-borne alkyd resin. Any suitable waterborne alkyd resin may be employed, including for instance long-oil alkyds, medium-oil alkyds, short-oil alkyds, or modified alkyds (e.g., a urethane alkyd). Exemplary processes for making an alkyd resin include condensation of alcohols and any one or more of acids and anhydrides. Exemplary alcohols include polyhydric alcohols such as ethylene glycol, diethylene glycol, dipentaerythritol, dipropylene glycol, glycerol, neopentyl glycol, pentaerythritol, polyethylene glycol, polypropylene glycol, sorbitol, triethylene glycol, trimethylol ethane, trimethyol propane, 1 ,2-butanediol, 1 ,2-propanediol, 1,3- butanediol, 1,3 -propanediol, 1 ,4-butanediol, 1 ,6-hexanediol, 2-butyl-2-ethyl-l,3-propanediol, 3-methyl- 1,5 -pentanediol, etc. Exemplary acids include polycarboxylic acids and fatty acids. Suitable polycarboxylic acids include adipic acid, azelaic acid, citric acid, cyclohexane dicarboxylic acid, dodecane dioic acid, fumaric acid, glutaric acid, isophthalic acid, itaconic acid, maleic acid, nadic acid, phthalic acid, pyromcllitic acid, scbacic acid, succinic acid, terephthalic acid, tctrahydrophthalic acid, trimellitic acid, etc. Useful fatty acids include non-drying, semi-drying, and drying fatty acids. Fatty acidsmay be derived from natural or synthetic materials, and may be saturated or unsaturated. Exemplary fatty acids include those derived from oils such as calendula oil, castor oil, coconut oil, corn oil, cottonseed oil, herring oil, linseed oil, mustard seed oil, olive oil, palm oil, peanut oil, rapeseed oil, safflower oil, sesame oil, soybean oil, sunflower oil, tall oil, tallow oil, tung oil, veronia oil, etc.

[0095] Suitable anhydrides include adipic anhydride, azelaic anhydride, phthalic anhydride, isophthalic anhydride, maleic anhydride, terephthalic anhydride, itaconic anhydride, nadic anhydride, pyromellitic dianhydride, succinic anhydride, sebacic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, etc. An exemplary alkyd resin comprises a residue of pentaerythritol and phthalic anhydride monomers.

[0096] The alkyd resin may also include urethane groups. An exemplary water-borne alkyd including urethane groups comprises a residue of isophorone diisocyanate. A commercially available waterborne urethane alkyd comprising a residue of isophorone diisocyanate is NeoPAC PU580 (sold by DSM). This resin is believed to be an alkyd / aliphatic polyurethane copolymer in water.

[0097] Processes for producing alkyds from conventional oils have been disclosed, for example, in U.S. Pat. Nos. 4,133,786 , 4,517,322 , and 6,946,509.

[0098] Water-borne polyurethane dispersions (PUDs) may be produced by the reaction of a polyol component with a isocyanate or polyisocyanate component. Exemplary alcohols include the alcohols disclosed herein as useful in polymerizing an alkyd resin. Exemplary isocyanate components can be aliphatic, cycloaliphatic or aromatic, and may be used singly or in combination with other isocyanate functional materials. The isocyanate functional material may have at least two or more reactive isocyanate groups. Exemplary diisocyanates include the aliphatic, cycloaliphatic and aromatic diisocyanates either alone or in admixture. Generally, such diisocyanates have the formula OCN — R — CO where R is arylene (e.g. phenylene and diphenylene), alkylarylene (e.g. dimethylbiphenylene, methylenebisphenyl and dimethylmethylenebisphenylene), alkylene (e.g. methylene, ethylene, tetramethylene, hexamethylene, a 36 methylene species, and trimethylhexylene), and / or cyclic (e.g. isophorone and methylcyclohexylene). Or, R can be a hydrocarbon group containing ester or ether linkages. Specific examples of such diisocyanates include 1 ,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (trade name: Desmodur-H®), 2,2,4-trimethyl-l,6-diisocyanato hexane, 1,10-decamethylene diisocyanate, 1,4- cyclohexylene diisocyanate, 4,4'-methylene bis(isocyanato cyclohexane), p-phenylene diisocyanate, 2,6- toluene diisocyanate, 2,4-toluene diisocyanate, xylene diisocyanate, isophorone diisocyanate, bis para- isocyanato cyclohexylmethane, 4,4-biphenylene diisocyanate, 4,4-methylene diphenyl isocyanate, 1,5- naphthalene diisocyanate, benzene 1,3-bis (1-isocyanato-l -methylethyl) and 1,5-tetrahydronaphthalene diisocyanatc. If producing a branched composition, suitable triisocyanatcs include aromatic triisocyanatc adduct of trimethylol propane and tolylene diisocyanate sold under the brand name Mondur CB-75, andaliphatic triisocyanate product of the hydrolytic trimerization of 1 ,6-hexamethylene diisocyanate, sold under the brand name Desmodur N®, or dicyclohexylmethane-4,4'-diisocyanate sold under the brand name Desmodur-W®, isophorone diisocyanate, diphenylmethane-4,4'-diisocyanate sold under the brand name Mondur XP744® and isocyanurate trimer of hexamethylene diisocyanate sold under the brand name Desmodur N-33OO®.

[0099] The polyurethane polymer may contain a suitable amount of salt-containing and / or salt-forming groups to facilitate preparation of a polyurethane dispersion in an aqueous carrier. Examples of suitable salt-forming groups include neutralizable groups (e.g., acidic or basic groups). At least a portion of the salt-forming groups may be neutralized to form salt groups useful for dispersing the polyurethane polymer into an aqueous carrier. Acidic or basic salt-forming groups may be introduced into the polyurethane polymer by any suitable method. One or more compounds containing an active hydrogen group and active acid or base group may be included as reactants for forming the polyurethane polymer. Examples of suitable compounds having active hydrogen and acid groups include hydroxy and mercapto carboxylic acids, aminocarboxylic acids, aminohydroxy carboxylic acids, sulfonic acids, hydroxy sulfonic acids, aminosulfonic acids, and combinations thereof. Examples of suitable compounds having active hydrogen and basic groups include aliphatic, cycloaliphatic and heterocyclic amino alcohols, diols and triols, amines, diamines, triamines, tetramines, amides, and combinations thereof.[000100] The polymers can be made water-dispersible by incorporating amine or acid functionality into the polyurethane polymers. For example, water-based anionically stabilized polyurethane polymers can be prepared by reacting polyols and dihydroxy carboxylic acid compounds (e.g., dimethylol propionic acid and / or dimethylol butanoic acid) with an excess of diisocyanate to provide a carboxylic acid functional polymer having NCO terminal groups. The acid groups can be neutralized with tertiary amines to provide salt groups. The resulting neutralized polymer can be readily dispersed in water. Alternatively, the anionic stabilizing group of the water-dispersible polyurethane polymers can be replaced with cationic stabilizing groups or non-ionic stabilizing groups, to facilitate water dispersibility.[000101] Any acid or base may be used to neutralize the acidic or basic salt-forming groups and form salt groups. Examples of suitable neutralizing bases include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, triethylamine, dimethyl ethanol amine, and combinations thereof. Examples of suitable neutralizing acids include organic acids such as formic acid and acetic acid, inorganic acids such as hydrochloric acid and sulfuric acid, and combinations thereof.[000102] In some aspects, inclusion of a salt-containing group may enable the polyurethane prepolymer to be suitably dispersed in an aqueous carrier without requiring a neutralization step. Examples of suitable salt-containing groups include sulfonate groups present in the form of alkali metalsalts (e.g., lithium, sodium, potassium, etc.); sulfonate groups present in the form of ammonium, tertiary amine, copper, or iron salts; and combinations thereof. Examples of preferred monomers having sulfonate groups that may be incorporated into the PU polymer include, 5-(sodiosulfo)isophthalic acid (SSIPA), 5- (lithiosulfo)isophthalic acid (LSIPA) and the like. Non-sulfonate salt-containing groups may also be employed in addition to, or in place of, sulfonate groups.[000103] The PUD may be formed using techniques and equipment that will be familiar to persons skilled in the art. For example, in the embodiments in which the polyurethane polymers are formed with polyurethane prepolymers, the polyurethane prepolymers may be dispersed into an aqueous carrier and chain extended (or otherwise modified) to obtain higher molecular weight polyurethane polymers.Extension of the polyurethane prepolymers may be achieved by reaction of the neutralized water- dispersed polyurethane prepolymers with one or more chain extenders. This may occur, for example, by reacting one or more chain extenders with terminal or pendant isocyanate(s) present on the polyurethane prepolymer. Examples of suitable chain extenders include alkyl amino alcohols, cycloalkyl amino alcohols, heterocyclic amino alcohols, polyamines (e.g., ethylene diamine, diethylene triamine, triethylene tetra amine, melamine, etc.), hydrazine, substituted hydrazine, hydrazide, amides, amides, water, other suitable compounds having active hydrogen groups, and combinations thereof.Opacifying Pigments, Extenders and Fillers[000104] The water-based coating compositions of the present disclosure may also optionally include one or more opacifying pigments or extenders. Pigments may added to a coating composition (via a pigment grind) to provide a desired opacity, hiding characteristics, or PVC. Formulators may adjust the amount of polymeric binder to pigments to a desired PVC, as higher PVC coatings generally show higher gloss and greater scrub durability.[000105] Architectural paints, architectural stains, caulks, however, generally include at least one opacifying pigment. Sealants, for example, may be a clear coating and may not include a pigment in the water-based coating compositions.[000106] The pigment or pigments may be incorporated separately as a particle, in a slurry, or as a particle-polymer complex. A preferred pigment is titanium dioxide, which may comprise anatase titanium dioxide, rutile titanium dioxide, Brookite titanium dioxide, or mixtures thereof with or without other pigments. In some approaches, the rutile titanium dioxide is surface treated with an inorganic oxide, such as silica (SiO2), alumina, zirconia, or combinations thereof. In some approaches, iron oxide may be used as a pigment.[000107] Generally, the opacifying pigments, such as titanium dioxide, have a particle size less than a micron, such as about 0.2 to about 0.3 microns in diameter and provided in powder form, or in an aqueous slurry. Exemplary commercially available titanium dioxide particles and those provided in slurryor dry forms, e.g., KRONOS™ 1071, 2020, 2044, 2090, 2101, 2102, 2131, 2160, 2210, 2310, 4102, 4310 and 4311 from Kronos, Inc., TIONA™ 595 and.596i from Millennium Specialty Chemicals Inc. TIPURE™ TS-6200, R-706, R-741, R-746, R-900, R-902+, R 931 and R-960 from E. I. duPont de Nemours and Company, TRONOX™ CR-813, CR 15 813S, CR-826, CR-826S, CR-828, CR-834 and CR-880 from Tronox Corporation, and products from other suppliers including Bluestar New Chemical Materials Co.. Ltd., Hebei Chuanghui Chemicals Co., Ltd., Henan Billions Chemicals Co., Ltd.. Ishihara Sangyo Kaisha, Ltd., Nanjing Hengsiman Chemical Co., Ltd., Pangang Titanium Industry' Co., Ltd., Qingdao Gracecorp Co., Ltd., Sakai Chemical Industry Co., Ltd., Shanghai Yuejiang 20 Titanium Chemical Manufacturer Co., Ltd., Shijiazhuang Kelichuangxin Chemicals Co., Ltd. and Xuzhou Zhonglian Chemical Technology Co., Ltd. and mixtures thereof.[000108] Pigments may be supplemented with extenders and fillers. Extenders and fillers may include solids which provide additional functional characteristics to the coating. Intumescent ingredients, such as ammonium polyphosphates, melamines, pentaerythritol and similar compounds are examples of functional fillers. Other extenders and fillers include talc, china clay, barytes, carbonates, silicates and mixtures thereof, for example magnesium silicates, calcium carbonate, aluminosilicates, silica and various clays; organic materials including plastic beads (e.g., polystyrene or polyvinyl chloride beads), microspherical materials containing one or more voids, and vesiculated polymer particles (e.g., those discussed in U.S. Pat. Nos. 4,427,835. 4,920,160, 4.594.363, 4,469,825. 4,468,498, 4.880.842, 4,985,064. 5,5157, 084, 5,041,464, 5,036,109, 5,409,776, and U.S. Pat. No. 5,510,422). Other exemplary extenders or fillers include EXPANCEL™ 551DE20 acrylonitrile / vinyl chloride expanded particles (from Expancel Inc.), SIL-CEL™ 43 glass micro cellular fillers (from Silbrico Corporation), FILLITE™ 100 ceramic spherical particles (from Trelleborg Fillite Inc.), SPHERICEL™ hollow glass spheres (from Potter Industries Inc.), 3M ceramic microspheres including grades G-200, G-400, G-600, G-800. W-210, W- 410. and W-610 (from 3M). 3M hollow microspheres including 3M Performance Additives iM30K (also from 3M), INHANCE™ UH 1900 polyethylene particles (from Fluoro-Seal Inc ), and BIPHOR aluminum phosphate (from Bunge Fertilizantes S.A., Brazil). Extenders and fillers can be selected to provide desired characteristics to the coating, like increased abrasion resistance, scrub resistance, or matting.[000109] In some approaches, aqueous coating compositions of the present disclosure may comprise at least about 5% and up to about 50% by weight pigments, extenders, and fillers based on the total solids present in the composition. In some approaches, the water-based compositions disclosed herein may include about 10 to about 30 weight percent of pigments, extenders and fillers, about 15 to about 20 weight percent pigments, extenders, and fillers, or about 18 to about 25 weight percent of pigments, extenders, and fillers based on the total amount of components in the coating composition.[000110] The coating compositions may comprise, for example, about zero percent (for an ultradeep paint), at least about 11% by weight, further for example, at least about 12% by weight, further for example, at least about 13% by weight, further for example, at least about 14% by weight, further for example at least about 15% by weight, further for example, at least about 16%, further for example at least about 17%. further for example, at least about 18%, further for example at least about 19%, and even further for example at least about 20% by weight titanium dioxide based on the total solids of the coating composition. In some aspects, the coating compositions may include up to about 30% by weight titanium dioxide. In some approaches, the coating compositions comprise more than 10% titanium dioxide based on the total solids present in the composition.[000111] Other colored pigments or dyes may also be added to tire coating, alone or in combination, to produce a wide range of colored coating. Suitable additional pigments may include calcium carbonate, talc, clay, silicates, aluminum silicates, calcium metasilicates, aluminum potassium silicates, magnesium silicates, barium sulfates, nepheline syenite, feldspar, zinc oxides or sulfides, or others known to those skilled in the art. Such additional colored pigments may be included in amounts up to about 30% by weight, for example, about 10% to about 20%, based on the total solids present in the composition.[000112] In other approaches, the waterborne coating compositions herein may include a pigment present in an amount of about 3 to about 60 PVC, preferably about 10 to about 50 PVC. and more preferably, about 20 to about 45 PVC. The amount of pigment may vary depending on the application. For instance, the PVC of architectural exterior coatings may be about 10 to about 50, the PVC of masonry coatings may be about 10 to about 40, the PVC of a water-based metal coating may be about 10 to about 40, the PVC of stains may be about 10 to about 40, and extra while formulations may contains more PVC, such as about 20 to about 45.Additives[0001 13] The water-borne coating compositions of the present disclosure may also include other optional additives as needed for typical applications. For instance, the water-borne coating composition of the present disclosure is produced using techniques known to those skilled in the art of manufacturing paint or coatings. In addition to the film-forming binder and the composite particles, the water-borne coating compositions herein may contain conventional additives including, but not limited to rheology modifiers, colorants, mildewcides. surfactants, dispersants, defoamers, coalescents, plasticizers, antisettling agents, pH modifiers, UV absorbents, crosslinkers, thickeners, coalescing aids, anti-foaming agents, freeze-thaw additives, matting agents, and the like. These and other optional additives for use in the disclosed coating compositions herein arc described in Kolcskc ct al., Paint and Coatings Industry, April, 2003, pages 12-86.Method of Preserving Water-based Coating Composition[000114] The present disclosure includes a method of adequately preserving a water-based coating composition comprising adding to a coating composition a multi-functional additive comprising a hydroxamic acids or salts thereof as described herein and one of more diols as described herein, the ratio of the hydroxamic acid or salt thereof to the one or more diols in the multifunctional additive is from 1:9 to 1: 19. The multi-functional additive is added in an amount of at least 0.5 wt.%, at least 1.0 wt.%, at least 1.5 wt.%, or at least 2.0 wt.% based on the total weight of components of the coating composition.[000115] Tire multifunctional additive may be added during the grind stage, mixing, let-down, or as a post -add of the coating composition.Coated Article[000116] Also disclosed is a coated article comprising the water-based coating composition as described herein, coated on a substrate such as wood, drywall, vinyl, metal, cementitious fibrebroad, The coating composition may be coated directly on the substrate, or indirectly on the substrate such that the coating composition is coated on another cured coating itself coated on the substrate.LIST OF PREFERRED EMBODIMENTS[000117] A list of non-limiting embodiments of the invention are as follows:[000118] Embodiment 1: A water-based architectural coating composition comprising: anqueous, carrier, a film-forming polymeric binder, optionally, a pigment, extender, or filler, and a multifunctional additive including (a) a hydroxamic acid or salt thereof and (b) one or more diols, optionally, an isothiazolinone, and optionally, one or more additives selected from an extender, a rheology modifier, a colorant, a mildewcide, a surfactant, a dispersant, a defoamer, a coalescent, a plasticizer, an anti-settling agent, a pH modifier, a UV absorbent, a crosslinker, a thickener, a coalescing aid, an anti -foaming agent, a freeze-thaw additive, a matting agent or combinations thereof, wherein the coating composition has adequate wet-state preservation as evaluated according to the Microbial Challenge Test.[0001 19] Embodiment 2: The coating composition of Embodiment 1 , wherein the hydroxamic acid or salt thereof is present in an amount of at least 0.03 wt.% based on the total weight of components of the coating composition stain and wherein the weight ratio of the hydroxamic acid or salt thereof to the one or more diols in the multifunctional additive is from 1:9 to 1: 19.[000120] Embodiment 3: A water-based coating composition comprising: an aqueous carrier, about 7 wt.% to 30 wt.% polymer solids of a film-forming polymeric binder, an opacifying pigment, and about 0.5 wt.% to about 3.0 wt.% based on the total weight of components in the coating composition of a multifunctional additive including (a) a hydroxamic acid or salt thereof and (b) one or more diols, wherein the weight ratio of the hydroxamic acid to the one or more diols is from about 1:9 to 1: 19, and optionally, an isothiazolinone.[000121] Embodiment 4: A method of preserving an architectural paint or stain comprising: adding a multifunctional additive including (a) a hydroxamic acid or salt thereof and (b) one or more diols, wherein the weight ratio of the hydroxamic acid or salt thereof to the one or more diols in the multifunctional additive is from 1:9 to 1: 19 to a water-based architectural coating composition that includes: an aqueous carrier, a film-forming polymeric binder, optionally, an isothiazolinone, and optionally, one or more additives selected from an extender, a rheology modifier, a colorant, a mildewcide, a surfactant, a dispersant, a defoamer, a coalescent, a plasticizer, an anti-settling agent, a pH modifier, a UV absorbent, a crosslinker, a thickener, a coalescing aid, an anti-foaming agent, a freezethaw additive, a matting agent or combinations thereof.[000122] Embodiment 5: The method of Embodiment 4, wherein the multifunctional additive is added in an amount of about 0.5 v .% to about 3.0 wt.% based on the total weight of components in the coating composition.[000123] Embodiment 6: The coating composition or method of any one of the preceding Embodiments, wherein the hydroxamic acid is an alkyl / alkyloxy hydroxamic acid.[000124] Embodiment 7: The coating composition or method of any one of the preceding --.Embodiments, wherein the hydroxamic acid has the formula , where R is a linear or branched, saturated or unsaturated, substituted or unsubstituted chain of alkyl and alkyloxy groups having at least two carbon atoms, and Ri is H or a linear or branched, substituted or unsubstituted chain of alkyl and alkyloxy groups having from 1 to 22 carbon atoms.[000125] Embodiment 8: The coating composition or method of Embodiment 7, wherein R or Ri, or both, are saturated.[000126] Embodiment 9: The coating composition or method of Embodiment 7, wherein Rhas at most 22 carbon atoms.[000127] Embodiment 10: The coating composition or method of any one of Embodiments 7 to 9, wherein R has at least 5 carbon atoms.[000128] Embodiment 11: The coating composition or method of any one of Embodiments 7 to 10, wherein R has at most 11 carbons.[000129] Embodiment 12: Tire coating composition or method of any one of Embodiments 7 to 11, wherein R has 6 or 7 carbons.[000130] Embodiment 13: The coating composition or method of any one of Embodiments 7 to 12. wherein R is a saturated, linear hydrocarbon chain of 7 carbons.[000131] Embodiment 14: The coating composition or method of Embodiment 13, wherein the hydroxamic acid includes capryl hydroxamic acid, or preferably is capryl hydroxamic acid.[000132] Embodiment 15: The coating composition or method of any one of Embodiments 12 or 13, wherein the hydroxamic acid includes octanohydroxamic acid, or preferably is octanohydroxamic acid.[000133] Embodiment 16: The coating composition or method of any one of Embodiments 7 to 13. wherein R or Rl, or both, is independently substituted with one or more hydroxyl groups, cycloaliphatic groups, aromatic groups, or halogens.[000134] Embodiment 17: The coating composition or method of any one of Embodiments 7 to 13 or 16, wherein Ri is H.[000135] Embodiment 18: The coating composition or method of any one of the preceding Embodiments, wherein the hydroxamic acid is present in the coating composition an amount of at least 0.0375 wt.% based on the total weight of components of the coating composition.[000136] Embodiment 19: The coating composition or method of any one of the preceding Embodiments, wherein the hydroxamic acid is present in the coating composition in an amount of at most 0.15 wt.% based on the total weight of components of the paint composition.[000137] Embodiment 20: The coating composition or method of any one of the preceding Embodiments, wherein the one or more diols include 1,3 -propanediol.[000138] Embodiment 21 : The coating composition or method of any one of the preceding Embodiments, wherein the one or more diols includes a vicinal diol.[000139] Embodiment 22: The coating composition or method of Embodiment 21, wherein the vicinal diol is 1,2-octanediol.[000140] Embodiment 23: The coating composition or method of Embodiment 21, wherein the one or more diols include caprylyl glycol.[000141] Embodiment 24: The coating composition or method of Embodiment 21, wherein the one or more diols include 1,2-hexanedioL[000142] Embodiment 25 : Tire coating composition or method of Embodiment 21 , wherein the one or more diols include ethylhexylglycerin.[000143] Embodiment 26: The coating composition or method of any one of the preceding Embodiments, wherein the multifunctional additive is present in the coating composition in an amount of at least 0.5 wt.%, at least 1 .0 wt.%, at least 1 .5 wt.%, or at least 2.0 wt.%, based on the total weight of components of the coating composition.[000144] Embodiment 27: The coating composition or method of any one of the preceding Embodiments, wherein the coating composition is substantially free, essentially free, or completely free of isothiazolinones.[000145] Embodiment 28: Hie coating composition or method of any one of the preceding Embodiments, wherein the coating composition includes no intentionally added isothiazolinones. [000146] Embodiment 29: The coating composition or method of Embodiment 28, wherein the isothiazolinones are the group consisting of: 1,2-benzisothiazolinone, the reaction product of 2-Methyl- l,2-thiazol-3-one and 5-Chloro-2-methyl-4-isothiazolin-3-one, n-butyl-benzisothiazolinone, n-octyl-4- isothiazolin-3-one, Dichloro-2 -octyl- l,2-thiazol-3(2H)-one, and N-methyl benzisothiazolin-3-one.[000147] Embodiment 30: Hie coating composition or method of any one of the preceding Embodiments, wherein the coating composition is substantially free, essentially free, or completely free of a sodium or zinc salt of pyrithione.[000148] Embodiment 31 : The coating composition or method of any one of the precedingEmbodiments, wherein the coating composition includes no intentionally added sodium or zinc salts of a pyrithione.[000149] Embodiment 32: The coating composition or method of any one of tire preceding Embodiments, wherein the coating composition has no more than 200 g / L VOC, or 150 g / L VOC, or 100 g / L VOC. or 50 g / L VOC. or 25 g / L VOC, or no VOC.[000150] Embodiment 33: The coating composition or method of any one of the preceding Embodiments, wherein the coating composition is an architectural paint, an architectural stain, a caulk, or a sealant.[000151] Embodiment 34: The coating composition or method of any one of the preceding Embodiments, wherein the polymeric binder comprises a vinyl acrylic latex, a styrene acrylic latex, an acrylic latex, a waterborne polyurethane dispersion (PUD), a waterborne alkyd resin, a waterborne alkyd- PUD hybrid resin, or blends thereof.[000152] Embodiment 35: The coating composition or method of any one of the preceding Embodiments, wherein the polymeric binder is a latex emulsion.[000153] Embodiment 36: The coating composition or method of any one of the preceding Embodiments, wherein the polymeric binder has a MFFT of less than about 30°C. preferably less than about 20°C.[000154] Embodiment 37: The coating composition or method of any one of Embodiments 35 or 36, wherein the latex emulsion is a single-stage latex emulsion polymer.[000155] Embodiment 38: The coating composition or method of any one of Embodiments 35 or 36, wherein the latex emulsion is a multi-stage latex emulsion polymer.[000156] Embodiment 39: The coating composition or method of any one of the preceding Embodiments, where in the polymeric binder is completely free or essentially free of functional monomer units that cross-link the polymeric binder during film formation.[000157] Embodiment 40: Tire coating composition or method of any one of Embodiments 1 to 38, wherein the polymeric binder includes reactive ketone moieties to cross-link the polymeric binder during film formation.[000158] Embodiment 41 : The coating composition or method of Embodiment 40, wherein the reactive ketone moieties are derived from monomers comprising diacetone acrylamide (DAAM).[000159] Embodiment 42: The coating composition or method of Embodiment 40, wherein the reactive ketone moieties are derived from monomers comprising acetoacetoxy ethylmethacrylate (AAEM).[000160] Embodiment 43: A coated article comprising the coating composition of any one of the preceding Embodiments, coated on a substrate and cured, wherein the substrate comprises wood, drywall, vinyl, metal, cementitious fibrebroad, or a coating on the substrate.TEST METHODS[000161] The following test methods w ere used in the evaluation of the control and example paints. Where standard test methods arc used to evaluate a property, the standard test methods arc provided. Where a property is tested according to a modified version of a standard test method, deviations from the standard test method are described.[000162] Microbial Challenge Test. Preservative efficacy is tested via microbial challenge test. As conducted herein, microbial challenge test is conducted by subjecting each composition to microbial challenge test in in a manner materially similar to the testing protocol detailed in ASTM D2574 - 16 Standard Test Method for Resistance of Emulsion Paints in the Container to Attack by Microorganisms (2016). The preservative testing used herein is described below. Discrepancies with ASTM D2574 are included in this description.[000163] Duplicate, 50 mb samples of each of the sample compositions (each sample composition including a different variation of nitrogenous, organic additive and conventional biocide concentration) were taken and each of the duplicate samples inoculated with: (Challenge 1) 5.0 mL of pooled culture of 11 organisms including Pseudomonas aeruginosa and organisms isolated from spoiled paint of a similar type as that tested, at concentration of approximately 109CFU / mL on day 0 resulting in a final concentration of approximately 10sCFU / mL within the sample: (Challenge 2) 2.5 mL of the pooled culture at approximately 109CFU / mL on day 7 resulting in a final concentration of approximately 108CFU / mL within the sample; and (Challenge 3) 1.25 mL of the pooled culture at approximately 109CFU / mL on day 14 resulting in a final concentration of approximately 108CFU / mL within the sample. Immediately following inoculation, each sample w as then incubated at 30°C ± 2°C. For each sample,duplicate spread plates were made at 72 hours incubation and 7 days incubation by spreading 0.1 mL of the sample evenly on a tryptic soy agar plate using aseptic techniques. Each spread plate, so prepared, is then incubated for an additional 72 hours at 30°C ± 2°C and microbial growth observed at that time. Challenge testing was also perfonned with respect to negative controls, which are agar plates with bacterial challenge, but no paint applied (not to be confused with Negative Control Paint). Negative control spread plate test results are conducted as process verification to check for possible experimental error and are not reported in the below results. Bacterial survival is quantified according to the rating scale shown below in TABLE 1 . A total score for the Microbial Challenge Test is determined by averaging the 7-day sample ratings for the third challenge for a given composition. Compositions having a Microbial Challenge Test total score of 4 or less (i.e., developing on average less than IxlO3CFU / mL — showing “Moderate” contamination) on all plates are deemed to pass the Microbial Challenge Test and thus be adequately preserved. A failing grade for a 72-hour sample is excused if the same material shows a passing grade at 7-days incubation. Thus, a passing grade indicates the sample has less than 25 CFU / mL for all plates.

[0001] TABLE 1 - Preservative Testing Rating ScaleWherein “TNTC” = “Too Numerous to Count” and “CFU / mL” = “Colony Forming Unit / milliliter”[000164] Syneresis and Settling. Syneresis and settling are evaluations of the ability of a coating composition to maintain a homogenous mixture. Syneresis is a separation of a liquid layer from an otherwise homogenous coating composition. When syneresis occurs, a liquid layer is visibly present on top of a coating composition. Syneresis is assessed by measuring the depth of a liquid layer on top of a coating composition using a calibrated ruler to fractions of an inch or cm. Any spot or trace amount oflayer separation on top of a layer is noted, together with the quality of the separation (e.g., spot amount, foamy, etc). Settling occurs when inorganic pigments or extenders settle out from an otherwise homogenous coating composition. Settling is assessed after allowing a coating composition to rest undisturbed for an identified number of weeks at room temperature or in a 140°F oven. Settling is evaluated according to the following scale.[000165] Skinning. Skinning is a phenomenon occurring when small amounts of a coating composition dry or coalesce over time in a container during storage and / or distribution, and is often associated w ith repeated heating and cooling cycles of the coating composition. Skinning generally occurs at the uppermost layer of a coating composition, though from movement during distribution, the resulting skin and portions thereof can be deposited on the interior of the container or in the coating composition. Herein, skinning is assessed by visual examination of a coating composition and container following a heat cycle as described for a particular test. The presence of any dried coating on the surface of the coating composition, on the container lid or sides, is noted.[000166] Gloss and sheen are measures of the reflectiveness of a coating. In a coating, a glossy finish indicates that the surface which has a coating applied to it (i.e., is finished) it is shiny or glass- likc. The gloss of a surface is described as the reflection of light from the surface that is independent of color. ASTM D523 may be used to measure sheen. The prescribed angle at which light is reflected off the surface may vary, but for the purposes of this disclosure to measure 85 Sheen, is measured at 85° relative to the surface reflecting the light. ASTM D523 may also be used to measure 60 Gloss, which is measured at 60° relative to the surface reflecting the light. Gloss and Sheen measurements are made of coating composition drawdowns made using 4 mil (0.10 mm) Bird bar, which are allowed to cure for 30 minutes at room temperature or 10 minutes at 50°C followed by a 10 minute cool.[000167] The amount of VOC present in a composition is be measured by gas chromatography via ASTM D6886-18, titled “Standard Test Method for Determination of the Weight Percent of Individual Volatile Organic Compounds in Waterborne Air-Dry Coatings by Gas Chromatography” using methyl palmitate as a market. VOC amounts are reported in grams / Liter less exempt compounds (g / L).[000168] Washability is a measure of the ease of removal of stains from a paint or coating. Washability can be evaluated according to ASTM D4828-94 (Reapproved 2020), titled “Standard Test Method for Practical Washability of Organic Coatings.” Washability is assessed after 50 washing cycles according to a scale modified from ASTM D4282-94 as follows:[000169] Scrubs or scrub resistance refers to the ability of the surface of a coating film or paint film to resist being worn away or to maintain its original appearance when rubbed with or against an abrasive surface, typically during cleaning. Scrub resistance can be evaluated through ASTM D2486-96 (Standard Test Method for Scrub Resistance of Wall Paints).[000170] Burnish refers to the ability of a coating to retain its gloss value after being subjected to rubbing or polishing, such as abrasion. Both dry burnish and wet burnish may be measured. Dry burnish refers to abrasion by rubbing with a dry cheesecloth as measured according to ASTM D6736-08. Results are reported as the % loss of 85 Sheen. Wet burnish refers to abrasion according to ASTM D6736-08 with abrasion by a wet melamine sponge for 50 cycles in place of cheesecloth, with results reported as the % loss of 85 Sheen.[000171] Accelerated Weathering refers to a test intended to simulate the results of exposure to ultraviolet light from sunlight. Two coats of the test coating are applied to an alumirnim Q-Panel, from Q-Lab, Westlake, Ohio, by brash, allowing each coating to cure overnight. The coated panels are then subjected to accelerated weathering using the QUV-A method, where panels are exposed to 340-nm peak irradiance uv radiation in a Q UV tester, available from Q-Lab, Florida. Test panels are exposed to alternating cycles of UV light and moisture as follows:Irradiance: 0.83 W / m2 / nmUV cycle: 4 hours @ 60+ / 0 3°CCondensation cycle: 4 hours @ 50 + / - 3°CFollowing the indicated duration of accelerated weathering, each panel is assessed for 85° Gloss according to the test method described herein. La*b* values are obtained via spectrophotometer and AE is calculated.[000172] Block resistance refers to the ability of the surface of a coating, when applied against the same coating applied to a substrate, to resist sticking to itself following prolonged contact under pressure. Block resistance is particularly useful in assessing the possibility of doors or windows to stick closed after painting. The Block Resistance Test, as defined and used herein, is ASTM D4946-89, with the following changes: an applicator blade having 3 mil clearance is used for coating on a Leneta chart. Tire coated substrates are allowed to cure for 1 day, 2 days, 3 days, or 7 days at 77°F (25°C) and 50% relative humidity, the cure time noted in experimental results. Following the noted cure time, 1 inch squares of the coated substrate are placed in a blocking apparatus compressed under 1 kg weight, coated face against coated face, for 1, 6, or 24 hours as noted in results. The time of compression is usually identified as “1- hour,” “6-hour” or “24-hour” block resistance. Block resistance is evaluated following drawdown according to the following scale:Block Resistance is considered to be adequate when 24-hour block resistance is measured as greater than 3 at each of 1-day, 3-day, and 7-day cure at 77°F (25°C) and 50% relative humidity.GLOSSARY OF ABBREVIATIONS[000173] Tire following abbreviations apply to this specification:EXAMPLES[000174] Example 1: Antimicrobial Effectiveness of Mixture of Capryl Hydroxamic Acid, Caprylyl Glycol, and 1,3-Propanediol with and without BIT.[000175] A ladder study was conducted to study the effectiveness of a combination of an alkylhydroxamic acid and a diol to preserve samples of ProMarp l200 Zero VOC-Interior Latex Paint, SemiGloss, Extra White, product # B31W02651, available from The Sherwin-Williams Company, Cleveland, Ohio. A negative control paint (“Negative Control Paint”) was prepared by conventional paint making methods according to the same fonnula but omitting post-add preservatives from the fonnula.. The Negative Control Paint was compared to several paints including varying amounts of a first multifunctional additive (MF #1) containing 7.5% capryl hydroxamic acid (N-hydroxyoctanamide). 35% caprylyl glycol (1,2 -octanediol) and 57.5% 1,3 -propanediol. The effectiveness of the preceding mixture to preserve against microbial growth was assessed according to the Microbial Challenge Test described herein, with and without varying amounts of Proxel® BD-20, a 19.3% solution of BIT in water, available from Arxada Corp.). The results are below'.[000176] In Example 1 , the weight ratio of the capryl hydroxamic acid to diols was 1 : 12.3. All experimental samples showed adequate preservation with the presence of the mixture of capryl hydroxamic acid and diols. The use of BIT alone as a preservative was insufficient to provide adequate preservation at the concentrations tested without the mixture of capryl hydroxamic acid and diols.[000177] Example 2: Antimicrobial Effectiveness of Lower Concentration Mixture of Capryl Hydroxamic Acid, Caprylyl Glycol, and 1,3-Propanediol with and without BIT,[000178] The same ladder study as Example 1 was performed, at lower concentration levels of the first multifunctional additive (MF #1), which contained 7.5% capryl hydroxamic acid (N- hydroxyoctanamide), 35% caprylyl glycol (1,2-octanediol) and 57.5% 1,3-propanediol, and lower levels of optional BIT.[000179] The data shows effective preservation in compositions including at least 375 ppm (0.0375 wt.%) of capryl hydroxamic acid. The ratio of capryl hydroxamic acid to diols in Example 2 was 1: 12.3.[000180] Example 3: Antimicrobial Effectiveness of Mixture of Capryl Hydroxamic Acid, Caprylyl Glycol, 1,3-Propanediol, and EHG, with and without BIT.[000181] A similar ladder study to Examples 1 and 2 was performed utilizing a multifunctional additive that included capryl hydroxamic acid, capry lyl glycol, 1,3 -propanediol, and EHG. More specifically, the effectiveness of a combination of an alkyl-hydroxamic acid, a diol, and ethylhexyl glycerin to preserve samples of ProMar™ 200 Zero VOC-Interior Latex Paint, Semi-Gloss, Extra White, product # B31W02651, available from The Sherwin-Williams Company, Cleveland, Ohio, was assessed. A negative control paint (‘'Negative Control Paint ") was prepared by conventional paint making methods according to the same formula but omitting post-add preservatives from the formula.. Tire Negative Control Paint was compared to several paints including vary ing amounts of a multifunctional additive (MF#2) containing 7.5% capryl hydroxamic acid (N-hydroxyoctanamide), 25% caprylyl glycol (1,2- octanediol), 57.5% 1,3 -propanediol, and 10% EHG. The effectiveness of the preceding mixture to preserve against microbial growth was assessed according to the Microbial Challenge Test described herein, with and without varying amounts of Proxel® BD-20, a 19.3% solution of BIT in water, available from Arxada Corp.). The results are below.[000182] In Example 3, the weight ratio of the capryl hydroxamic acid to diols was 1 : 12.3. All experimental samples showed adequate preservation with the presence of the mixture of capryl hydroxamic acid and diols. The use of BIT alone as a preservative was insufficient to provide adequate preservation at the concentrations tested without the mixture of capryl hydroxamic acid and diols.[000183] Example 4: Antimicrobial Effectiveness of Lower Concentration Mixture of Capryl Hydroxamic Acid, Caprylyl Glycol, 1,3-Propanediol, and Ethylhexyl Glycerin, with and without BIT.[000184] Tire same ladder study as Example 3 was performed, at lower concentration levels of the second multifunctional additive (MF #2), which contained 7.5% capryl hydroxamic acid (N- hydroxyoctanamide), 25% caprylyl glycol (1,2-octanediol), 57.5% 1,3-propanediol, and 10% EHG, and lower levels of optional BIT.[000185][000186] The data shows effective preservation in compositions including at least 375 ppm (0.0375 wt.%) of capryl hydroxamic acid. Tire weight ratio of capryl hydroxamic acid to diols in Example 4 was 1: 12.3.[000187] Example 5: Antimicrobial Effectiveness of Mixture of Capryl Hydroxamic Acid, 1,2- hexanediol, and Propanediol, with and without BIT.[000188] A similar ladder study to Examples 1 and 2 was performed utilizing a multifunctional additive that included capryl hydroxamic acid, 1.2-hexanediol, and propanediol. More specifically, the effectiveness of a combination of an alkyl -hydroxamic acid, and diols to preserve samples of ProMar™ 200 Zero VOC-Interior Latex Paint. Semi-Gloss, Extra White, product # B31W02651, available from The Sherwin-Williams Company, Cleveland, Ohio, was assessed. A negative control paint (‘'Negative Control Paint”) was prepared by conventional paint making methods according to the same formula but omitting post-add preservatives from the formula.. Tire Negative Control Paint was compared to several paints including varying amounts of multifunctional additive (MF#3) containing 5% capryl hydroxamic acid (N- hydroxyoctanamide), 30% 1,2-hexanediol, and 65% propanediol. The effectiveness of the preceding mixture to preserve against microbial growth was assessed according to the Microbial Challenge Test described herein, with and without varying amounts of Proxel® BD-20, a 19.3% solution of BIT in water. available from Arxada Corp. The results are below. [000189][000190] The data shows effective preservation in compositions including at least 500 ppm (0.05 wt.%) of capryl hydroxamic acid. Tire ratio of capryl hydroxamic acid to diols in Example 2 was 1: 19.[000191] Example 6: Antimicrobial Effectiveness of Lower Concentrations of Mixture of Capryl Hydroxamic Acid, 1,2-hexanediol, and Propanediol, with and without BIT.[000192] A similar ladder study to Example 5 was perfonned utilizing lower concentrations of the same multifunctional additive of Example 5. The assessment was made to assess the preservation capabilities of lower concentrations in the same water-based architectural coating, Pro Mar1'1200 Zero VOC-Interior Latex Paint, Semi-Gloss, Extra White, product # B31 W02651 , available from The Sherwin-Williams Company, Cleveland, Ohio. A negative control paint ('‘Negative Control Paint”) was prepared by conventional paint making methods according to the same formula but omitting post-add preservatives from the fonnula. Hie Negative Control Paint was compared to several paints including varying amounts of MF#3 from Example 5. The effectiveness of the preceding mixture to preserve against microbial growth was assessed according to the Microbial Challenge Test described herein, with and without varying amounts of Proxel ® BD-20, a 19.3% solution of BIT in water, available from Arxada Corp. The results are below.[000193][000194] The data shows effective preservation in compositions including at least 375 ppm (0.0375 wt.%) of capryl hydroxamic acid. The ratio of capryl hydroxamic acid to diols in Example 2 was 1: 19.[000195] Example 7: Heat-Age Stability Testing for Combination of Hydroxamic Acid and Diols in Exemplar Vinyl Acrylic Architectural Paint.[000196] Tire effect of including combinations of hydroxamic acid and diols at concentrations that provided effective preservation was evaluated for certain end-use characteristics. Three architectural paints were evaluated as part of the study.[000197] Positive Control Paint A, a vinyl acrylic base paint ProMar™ 200 Zero VOC-lnterior Latex Gloss Sheen, Extra White, B20W12651, available from The Sherwin-Williams Company, Cleveland, Ohio, was prepared. Positive Control Paint A contained post-add wet-state preservatives consisting of 0.30 wt.% of Acticide MBS (available from Thor Specialties, Inc., Shelton, CT.), a mixture of 2.5 wt.% BIT and 2.5 wt. % MIT, and 0.25 wt.% of Acticide MV (available from Thor Specialties,Inc., Shelton, CT), a mixture of 1.11% CMIT and 0.37 wt.% MIT. Experimental Paint A was a paint mixed according to the same formula, but without the post-add wet-state preservatives.[000198] Positive Control Paint B was a vinyl acrylic paint, Painters Edge® Interior Latex paint, extra white, flat sheen, DU160200, available from The Sherwin-Williams Company, Cleveland, Ohio. Positive Control Paint B contained post-add preservatives consisting of 0.30 wt.% of Acticide MBS (available from Thor Specialties, Inc.. Shelton, CT.), a mixture of 2.5 wt.% BIT and 2.5 wt. % MIT, and 0.25 wt.% of Acticide MV (available from Thor Specialties, Inc., Shelton, CT), a mixture of 1. 11% CMIT and 0.37 wt.% MIT. Experimental Paint B was a paint mixed according to the same formula, but without the post-add preservatives.[000199] Positive Control Paint C w as a styrene -acrylic architectural primer, Multi-purpose Interior / Exterior Latex Primer / Sealer, B51W00450, available from The Sherwin-Williams Company, Cleveland, Ohio. Positive Control Paint C contained post-add preservatives consisting of preservatives consisting of 0.30 wt.% of Acticide MBS (available from Thor Specialties, Inc., Shelton, CT.), a mixture of 2.5 wt.% BIT and 2.5 wt. % MIT.[000200] Each of Experimental Paint A, Experimental Paint B, and Experimental Paint C w ere mixed according to the same fonnula as Positive Control Paint A, Positive Control Paint B, and Positive Control Paint C. respectively, but omitted the post-add preservatives. Instead, Experimental Paint A, Experimental Paint B. and Experimental Paint C each included a post-add multifunctional mixture consisting of 7.5% capryl hydroxamic acid (N-hydroxyoctanamide), 35% caprylyl glycol (1,2-octanediol) and 57.5% 1,3-propanediol, which was added in an amount of 2.0 wt.% of the total coating composition weight. Tire multifunctional mixture w as mixed into the paint as a post-addition component under low' shear.[000201] The following tests were performed on each paint initially after mixing, and after 1. 2, 4, or 8 weeks of exposure to a controlled room at room temperature (RT) or an oven held at 140°F (Oven): Synerasis, settling, skinning, pH, 60° gloss, 85° sheen, and color (by Delta L and Delta E measurements).[000202] Table 7A: Paint A Room Temperature Heat-Age Stability Data[000203] Table 7B: Paint A Oven Temperature Heat- Age Stability Data[000204] The tests of Paint A show that the multifunctional hydroxamic acid / diol mixture could be incorporated into Control Paint A at a 2% loading level without significantly impacting the coating composition characteristics. The multifunctional mixture made the paint slightly more glossy but otherwise did not appear to negatively impact the coating composition characteristics.[000205] Table 8A: Paint B Room Temperature Heat-Age Stability Data[000206] Table 8B: Paint B Oven Temperature Heat- Age Stability Data[000207] The tests of Paint B show that the multifunctional hydroxamic acid / diol mixture could be incorporated into Control Paint B at a 2% loading level without significantly impacting the coating composition characteristics. The multifunctional mixture made the paint slightly more glossy with a slight change in lightness / chroma but otherwise did not appear to negatively impact the coating composition characteristics.[000208] Table 9A: Paint C Room Temperature Heat-Age Stability Data[000209] Table 9B: Paint C Oven Temperature Heat- Age Stability Data[000210] The tests of Paint B show that the multifunctional hydroxamic acid / diol mixture could be incorporated into Control Paint B at a 2% loading level without significantly impacting the coating composition characteristics. The multifunctional mixture made the paint slightly more glossy, with a small change in lightness or chroma (based on Delta E) but otherwise did not appear to negatively impact the coating composition characteristics.[000211] Example 8: Washability and Scrub Resistance of Interior Latex Paints.[000212] The washability and scrub resistance of Control Paint A and Control Paint B were compared to Experimental Paint A and Experimental Paint B, respectively. Table 10 shows washability results according to the Washability Test described herein.[000213] Table 10: Washability of Interior Latex Paints.[000214] The data shows that the addition of the multifunctional mixture has little impact on washability, scrubs, and dry burnish.[000215] Example 9: Block Resistance of Interior and Exterior Latex Paints.[000216] Tire block resistance of Experimental Paints A, B, and C as compared to Control Paints A, B, and C, respectively, were evaluated according to the Block Resistance Test described herein.Measurements were performed in triplicate, with the average reported.[000217] Table 11: Block Resistance.[000218] The data shows that Experimental Paint A had notably lower early block ( 1 Day) resistance as compared to the positive control. Experimental Paints B and C showed equivalent block resistance performance compared to Control Paints B and C, respectively.[000219] Example 10: Accelerated Weathering of Exterior Paints.1Average of all stains: crayon, pencil, ballpoint pen lipstick.2Full break, normalized value.3Reported as 85 Sheen measurement initially, following 5 cycles, and following 25 cycles of burnish.[000220] The change in 60 Gloss and 85 Sheen after Accelerated Weathering was evaluated based on Experiment Paint C, an exterior paint / primer, as compared to Control Paint C. Duplicate samples were tested; averages are reported.Table 12: Accelerated Weathering[000221] Tire data shows nominal change in gloss and sheen, and acceptable levels of color change following accelerated weathering.LIST OF EXEMPLARY EMBODIMENTS[000222] The following is a list of exemplary embodiments of the present disclosure. This list is not intended to encompass all potential embodiments of the present disclosure and should not be interpreted as limiting the scope of the disclosure otherwise presented herein.[000223] Embodiment 1: A water-based architectural coating composition comprising: an aqueous carrier, a film-forming polymeric binder, optionally, a pigment, extender, or filler and a multifunctional additive including (a) a hydroxamic acid or salt thereof and (b) one or more diols, optionally, an isothiazolinone, and optionally, one or more additives selected from an extender, a rheology modifier, a colorant, a mildeweide, a surfactant, a dispersant, a defoamer, a coalescent, a plasticizer, an anti-settling agent, a pH modifier, a UV absorbent, a crosslinker, a thickener, a coalescing aid, an anti-foaming agent, a freezethaw additive, a matting agent or combinations thereof, wherein the coating composition has adequate w et-state preservation as evaluated according to the Microbial Challenge Test.[000224] Embodiment 2: The coating composition of Embodiment 1, wherein the hydroxamic acid or salt thereof is present in an amount of at least 0.03 wt.% based on the total w eight of components of the coating composition stain and wherein the weight ratio of the hydroxamic acid or salt thereof to the one or more diols in the multifunctional additive is from 1:9 to 1: 19.[000225] Embodiment 3: A water-based coating composition comprising:an aqueous carrier, about 7 wt.% to 30 wt.% polymer solids of a film-forming polymeric binder, an opacifying pigment, and about 0.5 wt.% to about 3.0 wt.% based on the total weight of components in the coating composition of a multifunctional additive including (a) a hydroxamic acid or salt thereof and (b) one or more diols, wherein the weight ratio of the hydroxamic acid to the one or more diols is from about 1:9 to 1: 19, and optionally, an isothiazolinone.[000226] Embodiment 4: A method of preserving an architectural paint or stain comprising: adding a multifunctional additive including (a) a hydroxamic acid or salt thereof and (b) one or more diols, wherein tire weight ratio of the hydroxamic acid or salt thereof to the one or more diols in the multifunctional additive is from 1:9 to 1: 19 to a water-based architectural coating composition that includes: an aqueous carrier, a film-forming polymeric binder, optionally, an isothiazolinone, and optionally, one or more additives selected from an extender, a rheology modifier, a colorant, a mildewcide. a surfactant, a dispersant, a defoamer, a coalescent, a plasticizer, an anti-settling agent, a pH modifier, a UV absorbent, a crosslinker, a thickener, a coalescing aid. an antifoaming agent, a freeze-thaw additive, a matting agent or combinations thereof.[000227] Embodiment 5 : The method of Embodiment 4, wherein the multifunctional additive is added in an amount of about 0.5 wt.% to about 3.0 wt.% based on the total weight of components in the coating composition.[000228] Embodiment 6: Hie coating composition or method of any one of the preceding Embodiments. wherein the hydroxamic acid is an alkyl / alkyloxy hydroxamic acid.[000229] Embodiment 7 : The coating composition or method of any one of the preceding Embodiments, wherein the hydroxamic acid has the fonnulawhere R is a linear or branched, saturated or unsaturated, substituted or unsubstituted chain of alkyl and alkyloxy groups having at least two carbon atoms, and Ri is H or a linear or branched, substituted or unsubstituted chain of alkyl and alkyloxy groups having from 1 to 22 carbon atoms.[000230] Embodiment 8: The coating composition or method of Embodiment 7, wherein R or Ri, or both, are saturated.[000231] Embodiment 9: Tire coating composition or method of any one of Embodiments 7 or 8. wherein R has at most 22 carbon atoms.[000232] Embodiment 10: The coating composition or method of any one of Embodiments 7 to 9, wherein R has at least 5 carbon atoms.[000233] Embodiment 11: Tire coating composition or method of any one of Embodiments 7 to 10, wherein R has at most 11 carbons.[000234] Embodiment 12: The coating composition or method of any one of Embodiments 7 to 11. wherein R has 6 or 7 carbons.[000235] Embodiment 13: The coating composition or method of any one of Embodiments 7 to 12, wherein R is a saturated, linear hydrocarbon chain of 7 carbons.[000236] Embodiment 14: The coating composition or method of Embodiments 13, wherein the hydroxamic acid includes capryl hydroxamic acid, or preferably is capryl hydroxamic acid. [000237] Embodiment 15: The coating composition or method of any one of Embodiments 12 or 13, wherein the hydroxamic acid includes an octanohydroxamic acid, or preferably is octanohydroxamic acid. [000238] Embodiment 16: The coating composition or method of any one of Embodiments 7 to 13, wherein R or RI, or both, is independently substituted with one or more hydroxyl groups, cycloaliphatic groups, aromatic groups, or halogens.[000239] Embodiment 17: The coating composition or method of any one of Embodiments 7 to 13 or 16, wherein Ri is H.[000240] Embodiment 18: The coating composition or method of any one of the preceding Embodiments, wherein the hydroxamic acid is present in the coating composition an amount of at least 0.0375 wt.% based on the total weight of components of the coating composition.[000241] Embodiment 19: The coating composition or method of any one of the preceding Embodiments, wherein the hydroxamic acid is present in the coating composition in an amount of at most 0.15 wt.% based on the total weight of components of the paint composition.[000242] Embodiment 20: The coating composition or method of any one of the preceding Embodiments, wherein the one or more diols include 1,3 -propanediol.[000243] Embodiment 21 : Hie coating composition or method of any one of the preceding Embodiments. wherein the one or more diols includes a vicinal diol.[000244] Embodiment 22: The coating composition or method of Embodiment 21, wherein the vicinal diol is 1,2-octanedioL[000245] Embodiment 23: The coating composition or method of Embodiment 21, wherein the one or more diols include caprylyl glycol.[000246] Embodiment 24: The coating composition or method of Embodiment 21, wherein the one or more diols include 1.2-hexanediol.[000247] Embodiment 25: The coating composition or method of Embodiment 21, wherein the one or more diols include ethylhexylglycerin.[000248] Embodiment 26: The coating composition or method of any one of the preceding Embodiments, wherein the multifunctional additive is present in the coating composition in an amount of at least 0.5 wt.%, at least 1.0 wt.%, at least 1.5 wt.%, or at least 2.0 wt.%. based on the total weight of components of the coating composition.[000249] Embodiment 27: The coating composition or method of any one of the preceding Embodiments, wherein the coating composition is substantially free, essentially free, or completely free of isothiazolinones.[000250] Embodiment 28: The coating composition or method of any one of the preceding Embodiments, wherein the coating composition includes no intentionally added isothiazolinones.[000251] Embodiment 29: The coating composition or method of claim 28, wherein the isothiazolinones are the group consisting of: 1,2-benzisothiazolinone, the reaction product of 2-Methyl- l,2-thiazol-3-one and 5-Chloro-2-methyl-4-isothiazolin-3-one, n-butyl-benzisothiazolinone. n-octyl-4- isothiazolin-3-one, Dichloro-2 -octyl- l,2-thiazol-3(2H)-one. and N-methyl benzisothiazolin-3-one.[000252] Embodiment 30: The coating composition or method of any one of the preceding Embodiments, wherein the coating composition is substantially free, essentially free, or completely free of a sodium or zinc salt of pyrithione.[000253] Embodiment 31 : The coating composition or method of any one of the preceding Embodiments, wherein the coating composition includes no intentionally added sodium or zinc salts of a pyrithione.[000254] Embodiment 32: Tire coating composition or method of any one of the preceding Embodiments. wherein the coating composition has no more than 200 g / L VOC, or 150 g / L VOC, or 100 g / L VOC, or 50 g / L VOC, or 25 g / L VOC, or no VOC.[000255] Embodiment 33: The coating composition or method of any one of the preceding Embodiments, wherein the coating composition is an architectural paint, an architectural stain, a caulk, or a sealant. [000256] Embodiment 34: The coating composition or method of any one of the preceding Embodiments. wherein the polymeric binder comprises a vinyl acrylic latex, a styrene acrylic latex, an acrylic latex, a waterborne polyurethane dispersion (PUD), a waterborne alkyd resin, a waterborne alkyd-PUD hybrid resin, or blends thereof.[000257] Embodiment 35: The coating composition or method of any one of tire preceding Embodiments, wherein the polymeric binder is a latex emulsion.[000258] Embodiment 36: The coating composition or method of any one of the preceding Embodiments, wherein the polymeric binder has a MFFT of less than about 30°C, preferably less than about 20°C.[000259] Embodiment 37: The coating composition or method of any one of Embodiments 35 or 36, wherein the latex emulsion is a single-stage latex emulsion polymer.[000260] Embodiment 38: The coating composition or method of any one of Embodiments 35 or 36, wherein the latex emulsion is a multi-stage latex emulsion polymer.[000261] Embodiment 39: The coating composition or method of any one of the preceding Embodiments, where in the polymeric binder is completely free or essentially free of functional monomer units that cross-link the polymeric binder during film formation.[000262] Embodiment 40: The coating composition or method of any one of Embodiments 1 to 38. wherein the polymeric binder includes reactive ketone moieties to cross-link the polymeric binder during film formation.[000263] Embodiment 41 : The coating composition or method of Embodiment 40, wherein the reactive ketone moieties are derived from monomers comprising diacetone acrylamide (DAAM).[000264] Embodiment 42: The coating composition or method of Embodiment 40,wherein the reactive ketone moieties are derived from monomers comprising acetoacetoxy ethyl me th aery I ate (AAEM).[000265] Embodiment 43: A coated article comprising the coating composition of any one of the preceding Embodiments, coated on a substrate and cured, wherein the substrate comprises wood, drywall, vinyl, metal, cementitious fibrebroad, or a coating on the substrate.[000266] The aforementioned coatings, methods, and articles and the like have been described with respect to interaction between several components and / or elements. It should be appreciated that such materials and elements can include those elements or sub-elements specified therein, some of the specified elements or sub-elements, and / or additional elements. Further yet, one or more elements and / or sub-elements may be combined into a single component to provide aggregate functionality. The elements may also interact with one or more other elements not specifically described herein.[000267] While the embodiments discussed herein have been related to the coatings, methods, and articles discussed above, these embodiments are intended to be exemplary and are not intended to limit the applicability of these embodiments to only those discussions set forth herein.[000268] The above examples are merely illustrative of several possible embodiments of various aspects of the present application, wherein equivalent alterations and / or modifications will occur to others skilled in the art upon reading and understanding this specification and the annexed drawings. In particular regard to the various functions performed by the above described components (binders, discrete particles, extenders, pigments, and the like), the terms used to describe such components are intended to correspond, unless otherwise indicated, to any component that performs the specified function of the described component (e.g., that is functionally equivalent), even though not structurally equivalent to the disclosed structure which performs the function in the illustrated implementations of the invention. In addition although a particular feature of the application may have been disclosed with respect to only one of several implementations, such feature may be combined with one or more other features of the other implementations as may be desired and advantageous for any given or particular application. Also, to the extent that the terms “including”, “includes”, “having”, “has”, “with”, or variants thereof are used in the detailed description and / or in the claims, such terms are intended to be inclusive in a manner similar to the tenn “comprising.”[000269] This written description uses examples to disclose the application, including the best mode, and also to enable one of ordinary skill in the art to practice the application, including making and using any particles, coatings, and performing any incorporated methods. The protectable scope of the application is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements thatare not different from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.[000270] In the specification and claims, reference will be made to a number of terms that have the following meanings. Tire singular forms “a”, “an" and “the" include plural referents unless the context clearly dictates otherwise. Approximating language, as used herein throughout the specification and claims, may be applied to modify a quantitative representation that could permissibly van- without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term such as “about” is not to be limited to the precise value specified and means an amount of a measurement accounting for error associated with the measurement technique and manufacturing variability. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. Moreover, unless specifically stated otherwise, a use of the terms “first," “second," etc., do not denote an order or importance, but rather the tenns “first," “second," etc., are used to distinguish one element from another.[000271] As used herein, the terms “may" and “may be” indicate a possibility of an occurrence within a set of circumstances; a possession of a specified property, characteristic or function; and / or qualify another verb by expressing one or more of an ability, capability, or possibility associated with the qualified verb. Accordingly, usage of “may” and “may be” indicates that a modified tenn is apparently appropriate, capable, or suitable for an indicated capacity, function, or usage, while taking into account that in some circumstances the modified term may sometimes not be appropriate, capable, or suitable. For example, in some circumstances an event or capacity can be expected, while in other circumstances the event or capacity cannot occur - this distinction is captured by the tenns “may” and “may be. [000272] The best mode for carrying out the application has been described for purposes of illustrating the best mode known to the applicant at the time and enable one of ordinary skill in the art to practice the application, including making and using devices or systems and performing incorporated methods. The examples are illustrative only and not meant to limit the application, as measured by the scope and merit of the claims. The application has been described with reference to preferred and alternate embodiments. Obviously, modifications and alterations will occur to others upon the reading and understanding of the specification. It is intended to include all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof. The patentable scope of the application is defined by the claims, and may include other examples that occur to one of ordinary skill in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differentiate from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.

Claims

CLAIMSWhat is claimed is:

1. A water-based architectural coating composition comprising: an aqueous carrier, a film-forming polymeric binder, optionally, a pigment, extender, or filler and a multifunctional additive including (a) a hydroxamic acid or salt thereof and (b) one or more diols, optionally, an isothiazolinone, and optionally, one or more additives selected from an extender, a rheology modifier, a colorant, a mildewcide. a surfactant, a dispersant, a defoamer, a coalescent, a plasticizer, an anti-settling agent, a pH modifier, a UV absorbent, a crosslinker, a thickener, a coalescing aid. an antifoaming agent, a freeze-thaw additive, a matting agent or combinations thereof, wherein the coating composition has adequate wet-state preservation as evaluated according to the Microbial Challenge Test.

2. The coating composition of claim 1. wherein the hydroxamic acid or salt thereof is present in an amount of at least 0.03 wt.% based on the total weight of components of the coating composition stain and wherein the weight ratio of the hydroxamic acid or salt thereof to the one or more diols in the multifunctional additive is from l:9 to 1: 19.

3. A water-based coating composition comprising: an aqueous carrier, about 7 wt.% to 30 wt.% polymer solids of a film-forming polymeric binder, an opacifying pigment, and about 0.5 wt.% to about 3.0 wt.% based on the total weight of components in the coating composition of a multifunctional additive including (a) a hydroxamic acid or salt thereof and (b) one or more diols, wherein the weight ratio of the hydroxamic acid to the one or more diols is from about 1 : 9 to 1: 19, and optionally, an isothiazolinone.

4. A method of preserving an architectural paint or stain comprising: adding a multifunctional additive including (a) a hydroxamic acid or salt thereof and (b) one or more diols, wherein the weight ratio of the hydroxamic acid or salt thereof to the one or more diols in the multifunctional additive is from 1:9 to 1: 19 to a water-based architectural coating composition that includes:an aqueous carrier, a film-forming polymeric binder, optionally, an isothiazolinone, and optionally, one or more additives selected from an extender, a rheology modifier, a colorant, a mildewcide. a surfactant, a dispersant, a defoamer, a coalescent, a plasticizer, an anti-settling agent, a pH modifier, a UV absorbent, a crosslinker, a thickener, a coalescing aid. an antifoaming agent, a freeze-thaw additive, a matting agent or combinations thereof.

5. The method of claim 4, wherein the multifunctional additive is added in an amount of about 0.5 wt.% to about 3.0 wt.% based on the total weight of components in the coating composition.

6. The coating composition or method of any one of the preceding claims, wherein the hydroxamic acid is an alkyl / alkyloxy hydroxamic acid.

7. The coating composition or method of any one of the preceding claims, wherein the hydroxamic acid has the formula-v SA' where R is a linear or branched, saturated or unsaturated, substituted or unsubstituted chain of alkyl and alkyloxy groups having at least two carbon atoms, and Ri is H or a linear or branched, substituted or unsubstituted chain of alkyl and alkyl oxy groups having from 1 to 22 carbon atoms.

8. The coating composition or method of claim 7, wherein R or R or both, are saturated.

9. The coating composition or method of claim 7, wherein R has at most 22 carbon atoms.

10. The coating composition or method of any one of claims 7 to 9. wherein Rhas at least 5 carbon atoms.

11. The coating composition or method of any one of claims 7 to 10, wherein R has at most 11 carbons.

12. The coating composition or method of any one of claims 7 to 11, wherein R has 6 or 7 carbons.

13. The coating composition or method of any one of claims 7 to 12, wherein R is a saturated, linear hydrocarbon chain of 7 carbons.

14. The coating composition or method of claim 13, wherein the hydroxamic acid includes capryl hydroxamic acid, or preferably is capryl hydroxamic acid.

15. Tire coating composition or method of any one of claims 12 or 13, wherein the hydroxamic acid includes octanohydroxamic acid, or preferably is octanohydroxamic acid.

16. The coating composition or method of any one of claims 7 to 13, wherein R or Rl, or both, is independently substituted with one or more hydroxyl groups, cycloaliphatic groups, aromatic groups, or halogens.

17. Tire coating composition or method of any one of claims 7 to 13 or 16, wherein Ri is H.

18. The coating composition or method of any one of the preceding claims, wherein the hydroxamic acid is present in the coating composition an amount of at least 0.0375 wt.% based on the total weight of components of the coating composition.

19. The coating composition or method of any one of the preceding claims, wherein the hydroxamic acid is present in the coating composition in an amount of at most 0.15 wt.% based on the total weight of components of the paint composition.

20. The coating composition or method of any one of the preceding claims, wherein the one or more diols include 1,3-propanediol.

21. The coating composition or method of any one of the preceding claims, wherein the one or more diols includes a vicinal diol.

22. Tire coating composition or method of claim 21, wherein the vicinal diol is 1,2-octanediol.

23. The coating composition or method of claim 21, wherein the one or more diols include caprylyl glycol.

24. The coating composition or method of claim 21, wherein the one or more diols include 1,2-hexanediol.

25. Tire coating composition or method of claim 21, wherein the one or more diols include ethylhexylglycerin.

26. The coating composition or method of any one of the preceding claims, wherein the multifunctional additive is present in the coating composition in an amount of at least 0.5 wt.%, at least 1 .0 wt.%, at least 1 .5 wt.%, or at least 2.0 wt.%, based on the total weight of components of the coating composition.

27. Tire coating composition or method of any one of the preceding claims,wherein the coating composition is substantially free, essentially free, or completely free of isothiazolinones.

28. Tire coating composition or method of any one of the preceding claims, wherein the coating composition includes no intentionally added isothiazolinones.

29. The coating composition or method of claim 28, wherein the isothiazolinones are the group consisting of: 1.2-benzisothiazolinone, the reaction product of 2-Methyl-l,2-thiazol-3-one and 5- Chloro-2-methyl-4-isothiazolin-3-one, n-butyl-benzisothiazolinone, n-octyl-4-isothiazolin-3-one, Dichloro-2-octyl-l,2-thiazol-3(2H)-one, and N-methyl benzisothiazolin-3-one.

30. Tire coating composition or method of any one of the preceding claims, wherein the coating composition is substantially free, essentially free, or completely free of a sodium or zinc salt of pyrithione.

31. The coating composition or method of any one of the preceding claims. wherein the coating composition includes no intentionally added sodium or zinc salts of a pyrithione.

32. Tire coating composition or method of any one of the preceding claims, wherein the coating composition has no more than 200 g / L VOC, or 150 g / L VOC, or 100 g / L VOC, or 50 g / L VOC. or 25 g / L VOC, or no VOC.

33. The coating composition or method of any one of the preceding claims. wherein the coating composition is an architectural paint, an architectural stain, a caulk, or a sealant.

34. Tire coating composition or method of any one of the preceding claims, wherein the polymeric binder comprises a vinyl acrylic latex, a styrene acrylic latex, an acry lic latex, a waterborne polyurethane dispersion (PUD), a waterborne alkyd resin, a waterborne alkyd- PUD hybrid resin, or blends thereof.

35. The coating composition or method of any one of the preceding claims, wherein the polymeric binder is a latex emulsion.

36. Tire coating composition or method of any one of the preceding claims, wherein the polymeric binder has a MFFT of less than about 30°C, preferably less than about 20°C.

37. The coating composition or method of any one of claims 35 or 36, wherein the latex emulsion is a single-stage latex emulsion polymer.

38. The coating composition or method of any one of claims 35 or 36, wherein the latex emulsion is a multi-stage latex emulsion polymer.

39. The coating composition or method of any one of the preceding claims, where in the polymeric binder is completely free or essentially free of functional monomer units that cross-link the polymeric binder during film formation.

40. Tire coating composition or method of any one of claims 1 to 38, wherein the polymeric binder includes reactive ketone moieties to cross-link the polymeric binder during film formation.

41. The coating composition or method of claim 40, wherein the reactive ketone moieties are derived from monomers comprising diacetone acrylamide (DAAM).

42. Tire coating composition or method of claim 40, wherein the reactive ketone moieties are derived from monomers comprising acetoacetoxy ethylmethacrylate (AAEM).

43. A coated article comprising the coating composition of any one of the preceding claims, coated on a substrate and cured, wherein the substrate comprises wood, drywall, vinyl, metal, cementitious fibrebroad, or a coating on the substrate.

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