Aqueous compositions with multifunctional nitrogen-containing organic additives

Abstract

Aqueous compositions, such as polymeric binder compositions and coating compositions, comprise a carrier liquid, a film-forming polymeric binder, and a nitrogen-containing organic additive comprising at least one compound having four nitrogen centers, each nitrogen center being linked to at least one other nitrogen center by at least one hydrocarbon linking group. These coating compositions may exhibit improved washability, scrub resistance, and dispersion stability as well as less sensitivity to bacterial spoilage compared to conventional coating compositions that do not contain the nitrogen-containing organic additive.

Description

TECHNICAL FIELD

[0001] This application relates to the preservation of coatings and coating compositions by additives that exhibit multifunctional effects, including reducing susceptibility to microbial spoilage and improving or maintaining paint or coating performance. BACKGROUND

[0002] Coating compositions, such as paints, generally contain four basic ingredients: a carrier liquid, a binder, pigments, and additives. Each of these ingredients can include a single component or several different substances mixed into the paint.

[0003] The carrier liquid is the fluid component of the coating composition that carries all of the other composition components. The carrier liquid is part of the wet coating composition and is typically evaporated as the coating forms a film and dries on the surface. In latex paints, the carrier liquid is typically water. In oil-based or solvent-borne paints, the carrier liquid is typically an organic solvent. The amount and type of carrier liquid is generally determined by the characteristics of the other paint components.

[0004] The binder component of the coating composition allows the coating to form a film on and adhere to the substrate, and provides durability of the cured coating layer, among other benefits. In waterborne coating compositions, the binder includes a polymeric binder, typically selected from (meth)acrylic, vinyl acrylic, styrene acrylic, waterborne polyurethane dispersion (PUD), waterborne alkyd binder, waterborne alkyd-PUD hybrid, or combinations thereof. In the polymeric binder of waterborne coating compositions, the polymeric binder is typically provided as a waterborne latex, and the latex particles are in an emulsion or dispersion in water as the carrier liquid. In solvent-borne paints or coatings, the binder or film former includes an acrylic-amino resin, an alkyd resin, a polyurethane resin, or an epoxy resin.

[0005] Pigments provide both decorative and protective features to the coating, among other benefits. Pigments are solid particles used to provide various qualities to the paint, including but not limited to color, opacity, and durability. Coatings can also contain other organic or inorganic extenders, which can provide additional performance characteristics, including by altering the surface appearance of the coating layer (e.g., gloss / flatness and glossiness).

[0006] Other additives can be included in paint and coating compositions. Additives are generally used in paint or coating compositions in relatively low amounts compared to binders, but contribute to various properties of paints and coatings, including rheological properties, stability, paint performance, and application quality. Paint and coating compositions are complex formulations, and different additives can interact with each other to have unpredictable, beneficial, or detrimental effects on various properties of the paint or coating. In formulating paints or coatings, care must be taken to balance the addition of different additives or other components to, or changes in, the paint or coating formulation, such that important properties of the paint or coating (such as, for example, wash-off resistance, scrub resistance, heat and aging stability, and microbiological preservation) are maintained, improved, or only suffer a minimal, tolerable, decrease in quality.

[0007] Biocides, also known as antimicrobials, are additives that have microbistatic or microbicidal properties. In coating composition formulations, biocides can have a preservative effect to prevent in-can or wet-film microbial spoilage and ensure paint or coating composition stability, and can also provide dry-film or dry-state preservation whereby the biocide in the dried paint or coating film prevents or mitigates the growth of microorganisms, often in the form of mold or fungus, on the coating surface. Spoilage of coating compositions caused by microbial contamination or undesirable amounts of in-can microbial growth can result in putrefaction, pH reduction, gas formation, and viscosity changes, which can render the coating composition unusable or have undesirable properties. Thus, paint and coating compositions must be adequately preserved to remain useful during manufacture, distribution, and storage.

[0008] A variety of antimicrobial additives are well known and used for various purposes. Antimicrobial additives include organic biocides such as 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 disrupting cell membranes and killing bacteria. Organic antimicrobial additives also include conventional isothiazolinone additives, including but not limited to benzisothiazolinone (“BIT”), methylisothiazolinone (“MIT”), and 2-methyl-4-isothiazolin-3-one (“CMIT”). Although isothiazolinones such as BIT, MIT, and CMIT are effective at preserving paints, these biocides face increasing supply chain / manufacturing risks, including limited production sources and potential new regulations. There are also inorganic antimicrobial additives, for example those containing metal ions such as silver-based, zinc-based (including zinc pyrithione), and copper-based biocides. Other inorganic antimicrobial additives include phosphate, metal ion, metal, and zeolite or hydroxyapatite-containing biocides. These conventional antimicrobial additives can present similar supply chain or regulatory risks, so there is a need to find ways to adequately preserve paints and coatings using less or no conventional biocides. SUMMARY

[0009] Disclosed are aqueous compositions comprising a carrier liquid, a film-forming polymeric binder, and a nitrogen-containing organic additive comprising at least one compound comprising four nitrogen centers, each nitrogen center being connected to at least one other nitrogen center by at least one saturated divalent hydrocarbon linking group. In some approaches, the aqueous composition is a latex emulsion or polymer dispersion, a paint, a coating composition, a caulk, or a sealant. Optionally, the nitrogen-containing organic additive is a post-addition component of the emulsion, dispersion, paint, coating composition, caulk, or sealant.

[0010] In some approaches, the coating compositions of the present disclosure provide maintained or improved coating performance properties, such as maintained or reduced susceptibility to microbial spoilage, maintained or improved wash-off resistance, maintained or improved scrub resistance, and maintained or improved aging or heat-aging stability, relative to coating compositions that do not comprise the nitrogen-containing organic additive. In some approaches, the aqueous compositions of the present disclosure maintain acceptable resistance to microbial growth despite comprising reduced amounts of certain known antimicrobial additives.

[0011] The summary of the disclosure is not intended to describe each disclosed embodiment or implementation of the present disclosure. The following description more particularly exemplifies illustrative embodiments. Throughout this disclosure, guidance is provided by way of example in a number of lists of examples. Any cited list of examples can be used in various combinations. In each instance, any referenced list of examples is only representative of a general class of components and should not be construed as limiting or exhaustive. Thus, the scope of the present disclosure should not be limited to the specific illustrative structures as described herein, but rather extends to structures described by the language of the claims and the equivalents of those structures. Any recitation of an element in alternative language is expressly incorporated hereinto by reference in any combination. Although various theories and possible mechanisms have been discussed herein, none of these discussions should be used to limit the claimed subject matter in any way.

[0012] Definitions

[0013] Unless otherwise indicated, the following terms as used herein have the following meanings.

[0014] As used herein, the term "1K" or "one-component" when used in reference to a coating composition means that the coating composition is applied to a substrate in only one part and can be cured under ambient or baking conditions without the addition of a second part.

[0015] As used herein, the term "2K" or "two-component" when used in reference to a coating composition means that the coating composition is composed of two parts, which are kept separate prior to application. Typically, 2K coating compositions are reactive, with one of the two parts used to activate the other of the two parts when the parts are combined to initiate curing or hardening of the 2K coating composition.

[0016] As used herein, the term "adequately preserved" or "adequately preserving" when used in reference to a composition means that the composition passes the Microbial Challenge Test described below.

[0017] As used herein, the term "binder resin" refers to a polymeric resin that coagulates, cures, or otherwise assists in the formation of a film from a liquid or solid coating composition.

[0018] The term "component" refers to any chemical compound included in a composition that contains a particular feature or structure. Examples of components include compounds, monomers, oligomers, polymers, and organic groups contained therein. One of ordinary skill in the art will recognize that this definition of "component" is different from the term used in the context of "one-component" or "two-component" coating compositions as defined above.

[0019] The term "double bond" is non-limiting and refers to any type of double bond between any suitable atoms (e.g., C, O, N, etc.). The term "ethylenically unsaturated" refers to compounds containing carbon-carbon double bonds (i.e., -C=C-).

[0020] The term "film-forming" means that the composition contains a sufficient amount of binder such that, when applied to a surface and cured, the composition forms a continuous coating film.

[0021] The term "volatile organic compound" ("VOC") as defined by the United States Environmental Protection Agency (EPA) in 40 C.F.R. 51.100(s) refers to any compound of carbon, except carbon monoxide, carbon dioxide, carbonic acid, metal carbides, or carbonates, and ammonium carbonate, involved in atmospheric photochemical reactions, except certain exempt compounds identified by the EPA. As used herein, the "volatile organic compound content" ("VOC content") in an aqueous composition such as a coating composition, an aqueous polymeric binder composition, or other composition means the weight of VOCs per volume of coating solids. VOCs can be reported, for example, in grams of VOC per liter (g / L). With respect to the latex polymers described herein, VOCs can also be reported in grams of VOC per 100 grams of latex polymer (relative to the grams of solids in the latex). VOC content is measured by ASTM Method D6886-18 with methyl palmitate as the marker.

[0022] As used herein, the term "glass transition temperature" or "Tg" refers to the midpoint of the temperature range over which a reversible transition from a glassy state to a rubbery state of an amorphous solid material occurs. The "glass transition temperature" or Tg can be predicted using the Fox equation or measured by differential scanning calorimetry. Unless otherwise indicated, the Tg values described herein are theoretical values predicted using the Fox equation. The application of the Fox equation to estimate the Tg of a polymer is well known in the art. The Tg can be measured using differential scanning calorimetry. Samples of the composition for differential scanning calorimetry ("DSC") testing are weighed into standard sample pans and analyzed using the standard DSC heat-cool-heat method. The sample is heated from 50 °C to 150 °C at 10 °C / minute, then cooled to -75 °C at 20 °C / minute, then stabilized at -75 °C, then re-heated to 150 °C at 10 °C / minute. The glass transition temperature is calculated from the thermogram of the last heat cycle. The glass transition is measured at the inflection point of the transition.

[0023] Gloss can also sometimes be referred to as "glossiness." In a coating, a glossy finish indicates that the surface to which a coating has been applied (i.e., is "finished") is shiny or glassy. The gloss of a surface is described as the reflection of light from the surface independent of color. ASTM D523 can be used to measure gloss or luster. The specified angle at which light is reflected from the surface can vary, but for the purposes of the present disclosure, 85 Sheen is measured at 85° relative to the surface from which light is reflected. ASTM D523 can also be used to evaluate 60 Gloss, which is measured at 60° relative to the surface from which light is reflected. Gloss can also refer to the intensity of gloss measured at 20 degrees, 60 degrees, or 85 degrees, and determined according to ASTM D523. One skilled in the art is able to determine the relative gloss level (low versus high) of each coating.

[0024] The term "substantially VOC free" means that the composition contains less than about 50 g / L of VOC. The terms "low VOC" and "substantially VOC free" are used interchangeably herein unless otherwise indicated. The term "essentially VOC free" means that the composition contains less than 5 g / L of VOC. The terms "zero VOC" and "essentially VOC free" are used interchangeably herein.

[0025] The term "substantially free of" when applied to a component of a composition, rather than VOC content, means that the composition contains no more than about 1 wt% of the particular component, based on the total weight of solids in the composition. For example, a composition that is substantially free of conventional biocides contains no more than about 1 wt% of conventional biocides, as a percentage of the weight of solids of the composition. A composition that is "essentially free of" when applied to a component of a composition, rather than VOC level, means that the composition contains no more than about 0.04 wt% of the material. A composition that is "completely free of" when applied to a component of a composition, rather than VOC level, means that the composition contains no more than trace amounts of the material, as a percentage of the composition of solids.

[0026] The term "container" as used herein means any container (with or without a lid or other type of closure) used to store, mix, tint, or color a paint formulation, and includes containers in which paints and coatings are typically marketed and sold. Suitable containers include paint cans, paint bottles, containers made of metal, containers made of plastic and / or other polymeric materials, and the like.

[0027] The term "scrub resistance" as used herein refers to the ability of a coating film or paint film to resist abrasion or retain its original appearance when rubbed with or against an abrasive surface, typically during a cleaning process. Scrub resistance is measured according to ASTM D2486-96 (Standard Test Method for Scrub Resistance of Wall Paints). The greater the number of rubs as reported according to the standard test method indicates greater scrub resistance.

[0028] The term "pigment" includes both pigmented, dispersed solid particulate materials as well as pigmented, dispersed or soluble dye materials, where the material imparts a visually perceptible color to a paint or coating when 5 wt% (in the case of pigmented, dispersed solids) or 0.05 wt% (in the case of pigmented, dispersed or soluble dyes) of the material is added to (e.g., dispersed into) the paint or coating. The presence or absence of a visually perceptible color can be assessed by preparing a drawdown sample of paint or coating with and without the pigment, casting such samples as 25 micrometer (pm) dry thickness coating films on the white portion of a BYK-Gardner No. PA-2811 Opacity Drawdown Table (available from BYK-Gardner USA) or a comparable table, and inspecting the coating films under normal overhead interior lighting. Pigments can also impart opacity to a coating without a significant effect on color.

[0029] The term "pigment volume concentration (PVC)" when used in relation to a paint, stain, or colorant means the total percentage of the volume of the dry coating taken up by all inorganic materials in the coating. The PVC of a coating composition is the ratio of the volume of pigments (including fillers and functional fillers) present in the coating to the volume of total non-volatile materials (i.e., binder solids).

[0030] The term "post-addition component" or "post-add" refers to a component of a coating composition or aqueous polymer binder composition that can be added at any stage after the monomers have polymerized into the polymer binder but prior to the application or curing of the composition during the blending of the coating composition or polymer binder composition.

[0031] Unless otherwise indicated, reference to "(meth)acrylate" compounds, with "meth" in parentheses, is intended to include both acrylate and methacrylate compounds. For example, the term "(meth)acrylate polymer" independently includes each of acrylate homopolymers, methacrylate homopolymers, and copolymers comprising interpolymerized acrylate and methacrylate monomers.

[0032] The term "multi-stage" as used herein in relation to a latex means that the latex polymer is made using discrete, sequential charges of two or more monomers or monomer mixtures, or is made using a continuously varying charge of two or more monomers. A multi-stage polymer is distinct from a single-stage polymer made using one type of monomer blended with different polymer seed particles.

[0033] The term "aqueous" or "water-based" means a composition that includes a carrier, i.e., greater than 50 weight percent water, in percent of total carrier weight.

[0034] The term "on" when used in the context of a coating applied on a surface or substrate includes both coatings that are applied directly to the surface or substrate or indirectly to the surface or substrate such that an intervening layer exists between the coating and the surface or substrate. Thus, for example, a coating applied to a primer layer covering a substrate constitutes a coating applied on the substrate.

[0035] Unless otherwise indicated, the term "polymer" includes both homopolymers and copolymers (i.e., polymers of two or more different monomers).

[0036] The term "coating composition" encompasses paints as well as aerosol coatings, caulk, stains, and sealants. The coating composition can be suitable for interior or exterior or construction surfaces, such as walls, moldings, floors, decks, wooden or metal railings, ceilings, roofs (including metal roofs, shingles, and tiles), roads, sidewalks, and the like.

[0037] The term "paint" means a coating composition comprising a pigment and a binder which, when applied to form a thin (e.g., 100 pm) wet film thickness on a freshly sanded smooth wood surface, will, upon drying, hide the wood grain and its texture and will present a new surface with its own appearance.

[0038] The term "comprising" and variations thereof as used in the specification and claims, do not exclude other features, steps or integers.

[0039] The terms "preferred" and "preferably" refer to embodiments of the invention that can provide certain benefits under certain circumstances. However, other embodiments can also be preferred or 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 those other embodiments from the scope of the invention or claims.

[0040] As used herein, "a," "an," "the," "at least one," and "one or more" are used interchangeably. Thus, for example, a coating composition including "a" additive can be interpreted to mean that the coating composition includes "one or more" additives.

[0041] Additionally, ranges of values are used herein to describe the scope of numerical parameters. Such ranges are inclusive of the recited values and are meant to be broken down into every possible value within that range. For example, a range of 1 to 5 includes the values 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc. Further, the disclosure of a range includes disclosure of all sub-ranges included within that range (e.g., 1 to 5 discloses 1 to 4, 1.5 to 4.5, 1 to 2, etc.).

[0042] References throughout this specification to "an aspect," "one aspect," "some aspects," "method," "a method," "some methods," "one embodiment," "an embodiment," "certain embodiments," or "some embodiments," etc., mean 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, appearances of such phrases in various places throughout this specification are not necessarily intended to refer to the same embodiment or embodiments. Furthermore, a particular feature, configuration, composition, or characteristic can be combined in any suitable manner in one or more embodiments. DETAILED DESCRIPTION

[0043] The present disclosure provides aqueous compositions comprising nitrogen-containing organic additives as further defined herein, and methods of preserving aqueous compositions by the addition of one or more nitrogen-containing organic additives. Such compositions have been found to exhibit reduced susceptibility to microbial spoilage in the liquid state. In some embodiments, these compositions can provide improved or maintained paint performance properties compared to paints not containing nitrogen-containing organic additives, including but not limited to improved or maintained physical durability (as indicated by scrub tests), improved or maintained washability, and improved or maintained dispersion stability (as shown by heat aging stability or aging stability). Surprisingly, these properties have been found without the use of, or with reduced need for, conventional biocides such as isothiazolinones, pyridinethiones, inorganic biocides, or other biocides. As further detailed herein, such aqueous compositions can be aqueous latexes or aqueous dispersions or emulsions of paint compositions such as paints, caulk or sealants, or polymer binders.

[0044] In some methods, the present disclosure includes a paint composition comprising water, a film-forming polymeric binder, a pigment, and an additive, where such additive includes but is not limited to a nitrogen-containing organic additive. In some embodiments, the paint composition contains minimal or no pigment and is considered a "clear coat" paint. In some embodiments, the paint composition is substantially, essentially, or completely free of conventional biocides.

[0045] In some methods, the present disclosure includes an aqueous polymeric binder composition comprising water, a polymeric binder, and a nitrogen-containing organic additive. In some embodiments, the aqueous polymeric binder composition is substantially, essentially, or completely free of conventional biocides.

[0046] In another method, the present disclosure provides a coated article, where the article is coated with a paint composition disclosed herein comprising a nitrogen-containing organic additive, which is cured on a substrate. In certain methods, the paint composition is formulated for coating an exterior or interior surface of a building structure. In other embodiments, the paint composition is formulated for coating the interior of a beverage can, for covering steel coils, for coating plastic, for industrial storage tanks (e.g., water tanks, bulk chemical tanks, etc.) liners, or for marine applications. In some methods, the paint compositions of the present disclosure can be used to coat wood, plastic, drywall, concrete, metal, rubber, or other natural or synthetic polymers. In some methods, the compositions of the present disclosure can be used with a primer or topcoat. Other paint applications are considered within the scope of the invention and disclosure even if not explicitly disclosed herein.

[0047] Aqueous composition

[0048] The aqueous compositions of the present disclosure include, but are not limited to, paints, adhesives, sealants, stains, caulks, mineral and pigment suspensions, and aqueous emulsions and aqueous dispersions of polymeric binders and resins.

[0049] Nitrogen-containing organic additive

[0050] The nitrogen-containing organic additives in the compositions of the present disclosure allow for the formulation of coating compositions and aqueous polymeric binder compositions that are shelf-stable or have reduced susceptibility to microbial spoilage. Such compositions provide other improved or maintained coating performance properties including, but not limited to, scrub durability, wash-off resistance, and heat or weathering stability. In some embodiments, the coating compositions and aqueous polymeric binder compositions of the present disclosure can be provided without the need for, or with reduced need for, the use of conventional biocides such as isothiazolinones, pyridinethiones, inorganic biocides, or other biocides.

[0051] The nitrogen-containing organic additives useful in the present disclosure include compounds or mixtures of compounds each comprising four nitrogen centers, wherein each nitrogen center is connected to at least one other nitrogen center by at least one hydrocarbon linking group. In exemplary embodiments, the hydrocarbon linking groups are each saturated and divalent. In exemplary embodiments, the hydrocarbon linking groups are each independently a straight or branched C1, C2, C3, or C4chain.

[0052] In further exemplary embodiments, the nitrogen-containing organic additive is selected from the group consisting of compounds having formula I, II, III, and IV, and mixtures thereof: Formula I

[0053] Formula II

[0054] Formula III

[0055] Formula IV

[0056] In some methods, each of R1-R4, R7, and R10-R14is a saturated divalent hydrocarbon chain having 1 to 3 carbons, each of R5, R6, R8, and R9is a saturated, divalent hydrocarbon chain having 2 to 3 carbons, and each of R1-R14is the same or different. In some embodiments, each of R1-R4, R7, and R10-R14is a saturated hydrocarbon chain having 1 to 2 carbons, each of R5, R6, R8, and R9is a saturated hydrocarbon chain having 2 to 3 carbons, and each of R1-R14is the same or different.

[0057] In some embodiments, suitable nitrogen-containing organic additives include compounds selected from the group consisting of amino acid hydrazides, hydrazides of carbazide-carboxylic acids, bis-hydrazides and bis-carbazides, diethylenetriamine, N,N'-bis(2-aminoethyl)-l,2-ethanediamine, tetraethylenepentamine, pentaethylenehexamine, tri-(2-aminoethyl)amine, N-(2-piperazinoethyl)-ethylenediamine, N,N'-bis-(2-aminoethyl)-piperazine, N,N,N'-tris-(2-aminoethyl)ethylenediamine, N-(2-aminoethyl)-N'-(2-piperazinoethyl-l)-ethylenediamine, N,N-bis-(2-aminoethyl)-N-(2-piperazinoethyl)amine, N,N-bis-(2-piperazinoethyl)-amine, polyethyleneimine oligomers comprising at least four functional monomer units, N-(2-aminoethyl)-l,3-propanediamine, polyoxypropylenamine oligomers comprising at least four functional monomer units monomers, tetrapropylenepentamine, tripropylenetetramine, and N,N'-bis-(3-aminopropyl)ethylenediamine, and mixtures thereof.

[0058] In some methods, the nitrogen-containing organic additive does not include any aryl functional groups in its chemical structure.

[0059] In some preferred methods, suitable nitrogen-containing organic additives include compounds selected from the group consisting of N,N'-bis(2-aminoethyl)-l,2-ethanediamine, N,N'-bis-(2-aminoethyl)piperazine, N[(2-aminoethyl)2-aminoethyl]piperazine, tri-(2-aminoethyl)amine, or mixtures thereof.

[0060] In some further preferred methods, the suitable nitrogen-containing organic additive is a mixture of four nitrogen-containing organic compounds known as triethylenetetramine or TETA ™ , which is commercially available from Dow Chemical Company, Midland, MI. TETA ™ is a mixture of four nitrogen-containing organic compounds each having four nitrogen centers, wherein each nitrogen center is connected to at least one other nitrogen center by at least one saturated divalent hydrocarbon linking group. The four nitrogen-containing organic compounds in TETA ™ consist of N,N'-bis(2-aminoethyl)-l,2-ethanediamine, N,N'-bis-(2-aminoethyl)piperazine, N[(2-aminoethyl)2-aminoethyl]piperazine, and tri-(2-aminoethyl)amine. In some methods, TETA ™A carrier can also be included in an amount of about 5 wt% to about 50 wt% of the nitrogen-containing organic additive, in further embodiments about 50 wt% to about 30 wt% of the nitrogen-containing organic additive, and in other further embodiments about 20 wt% of the nitrogen-containing organic additive, based on the weight percent of the nitrogen-containing organic additive. In some preferred methods, the carrier is water, but can be acetone or methanol or other suitable carrier.

[0061] In some methods, the aqueous composition includes at least 50 ppm of the nitrogen-containing organic additive (based on the weight of the total components of the composition). In some methods, the aqueous composition includes at least 60 ppm of the nitrogen-containing organic additive, in further embodiments at least 75 ppm of the nitrogen-containing organic additive, in further embodiments at least 125 ppm of the nitrogen-containing organic additive, in further embodiments at least 250 ppm of the nitrogen-containing organic additive, in further embodiments at least 400 ppm of the nitrogen-containing organic additive, in further embodiments at least 1500 ppm of the nitrogen-containing organic additive, and in other further embodiments at least 5000 ppm of the nitrogen-containing organic additive.

[0062] In some useful methods, the aqueous composition includes at most 200,000 ppm of the nitrogen-containing organic additive (based on the weight of the total components of the composition). In further embodiments, the aqueous composition includes at most 100,000 ppm of the nitrogen-containing organic additive, in further embodiments at most 75,000 ppm of the nitrogen-containing organic additive, in further embodiments at most 50,000 ppm of the nitrogen-containing organic additive, in further embodiments at most 30,000 ppm of the nitrogen-containing organic additive, in further embodiments at most 20,000 ppm of the nitrogen-containing organic additive, and in other further embodiments at most 10,000 ppm of the nitrogen-containing organic additive.

[0063] The nitrogen-containing organic additives useful in the present disclosure allow for the formulation of aqueous compositions that are sufficiently preserved or have reduced susceptibility to microbial spoilage and other improved or maintained coating performance properties including, but not limited to, scrub resistance, wash resistance, and heat or weathering stability. In embodiments, the coating compositions can be provided without the need for or with reduced need for the use of conventional biocides such as isothiazolinones, pyridinethiones, or inorganic or other materials.

[0064] Carrier liquid

[0065] The compositions of the present disclosure include a carrier liquid prior to application to a substrate. The carrier liquid can be water, include water, or be water-based (water > 50 wt% in the carrier liquid system). The carrier liquid can also include solvents selected from aliphatic, cycloaliphatic, and aromatic hydrocarbons such as petroleum solvents, cyclohexane, toluene, xylene, and naphtha solvents; esters such as methoxypropyl acetate, n-butyl acetate, and 2-ethoxyethyl acetate; octamethyltrisiloxane; or other solvents used in solvent-borne systems; and mixtures thereof. The carrier liquid can also be other liquids used in paints, adhesives, sealants, stains, caulks, and mineral and pigment suspensions. The compositions of the present disclosure can include one or more carrier liquids. In some methods, one or more carrier liquids are selected so as to provide a waterborne composition that is substantially free of VOCs, essentially free of VOCs, free of VOCs, or zero VOCs.

[0066] In a preferred embodiment of the present disclosure, the carrier liquid of the coating composition is water or is water-based or aqueous (water > 50 wt% in the carrier liquid system).

[0067] In some embodiments, the carrier liquid can comprise 5% to 60% by volume of the coating composition. In some embodiments, the carrier liquid can comprise 40% to 60% of the aqueous polymeric binder composition.

[0068] Polymeric binder

[0069] The aqueous compositions according to the present disclosure further include a film-forming polymeric binder.

[0070] Film-forming polymeric binders useful in the coating compositions are known in the art and include aqueous polymeric binders such as acrylic, vinyl acrylic, styrene acrylic, aqueous polyurethane dispersions (PUDs), aqueous alkyd binder resins, aqueous alkyd-PUD hybrid resins, and mixtures thereof. The polymeric binder is present in the aqueous composition in sufficient amount to form a continuous film upon application of the aqueous composition to a substrate and allowing it to cure. In some embodiments, the aqueous composition can include, for example, at least about 17 wt% to about 60 wt% of polymeric solids, based on the total weight of the components of the aqueous composition.

[0071] In some embodiments, the polymeric binder is entirely free or essentially free of any functional monomer units that include a reactive ketone moiety that crosslinks the polymeric binder during film formation. In some embodiments, such reactive ketone moieties include diacetone acrylamide (“DAAM”) and acryloyloxyethyl acetoacetate (AAEM).

[0072] In certain preferred embodiments, the polymeric binder is a latex polymer. The latex polymers of the present application can include single-stage or multi-stage latex polymers. In some embodiments, the aqueous compositions of the present disclosure comprise a latex polymer that is a multi-stage latex polymer having at least a first stage and a second stage or a single-stage latex polymer.

[0073] Multi-stage latexes do not necessarily exhibit two glass transition temperatures, as measured by differential scanning calorimetry (DSC). For example, a DSC curve of a multi-stage latex made using discrete charges of two or more monomers can exhibit two or more Tgs, but can also exhibit only one Tg. In cases where the DSC curve shows only a single Tg inflection or even no Tg inflection, it can be difficult to determine whether the latex is single-stage or multi-stage, as the observation of a Tg inflection depends on various factors, including the relative concentrations of monomers in a particular stage. Thus, the presence or absence of a Tg inflection on a DSC curve is not determinative of whether a particular latex polymer is single-stage or multi-stage, but the Tg of a multi-stage latex can be described in terms of the theoretical Tg value of each monomer stage, as determined by the Fox equation.

[0074] Various methods can be used to prepare the multi-stage latexes described herein, including, for example, sequential monomer feed and continuous varying monomer feed techniques. In a sequential monomer feed method, a first monomer or monomer mixture is fed and polymerization is initiated, and a second monomer (i.e., a different monomer, or a mixture of monomers present in a different ratio than in the first monomer mixture) is fed at a later stage of polymerization. In a varying monomer feed method, a first monomer composition is fed, and then a second monomer is added at a different rate at some point during the polymerization process. By controlling the type of monomers selected for the feed method, a multi-stage latex can be formed that is suitable for use in a low VOC coating composition or paint, and that preferably provides superior performance properties to such coating or paint formulations, such as block resistance, scrub resistance, and the like.

[0075] Preferred multi-stage latexes include at least two stages (e.g., two, three, or four or more stages) having different Tg values (not considering any Tg that can be associated with an optional “seed”). In some embodiments, each of the at least two stages comprises 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).

[0076] In some methods, the multi-stage latexes described herein are prepared by a sequential monomer feed method. In one aspect, the polymerization is initiated with a higher Tg monomer feed followed by a lower Tg monomer feed, or vice versa, the polymerization is initiated with a lower Tg monomer feed followed by a higher Tg monomer feed. In one preferred aspect, the polymerization is initiated with a higher Tg monomer feed followed by a lower Tg monomer feed.

[0077] In some methods, the multi-stage latexes described herein are prepared using different monomer feeds. The resulting polymer typically has a DSC curve that does not show a Tg inflection point, and can be said to have a substantially infinite number of Tg stages. The resulting multi-stage latex will have a gradient Tg from high to low, or vice versa, depending on the order in which the high Tg monomer is fed to the reaction.

[0078] In one preferred method, the multi-stage latexes described herein are prepared by a sequential monomer feed method using at least two different monomer feeds. In one aspect, a "high" Tg stage (i.e., hard stage) is first fed to the reaction vessel, and a "low" Tg stage (i.e., soft stage) is added at a later stage of the process. A multi-stage latex can be formed, and after coagulation, the composition will typically show two different Tg values, or at least one Tg corresponding to the monomer stage present in higher concentration. In some cases, no appreciable Tg can be observed or detected by DSC for a monomer or monomer mixture present in very small amounts relative to other monomers or monomer mixtures in a particular stage.

[0079] In one method, the multi-stage latex optionally includes a "seed" phase, i.e., a relatively small monomer or polymer particle, but the seed is not required or necessary for the preparation or optimal performance of the multi-stage latex when used in a coating composition or paint formulation.

[0080] In one method, the relative position of the first and second phases can be internal and external, respectively, or vice versa, the relative position of the first and second phases can be external and internal, respectively. In another aspect, the first and second phases can be adjacent or proximate. Without being bound by theory, it is believed that the relative position of the stages of the multi-stage latex is influenced by the method used to prepare the latex.

[0081] In one method, a multi-stage latex having a desired minimum film formation temperature (MFFT) is obtained by controlling the monomers for each stage of the sequential monomer feed method. The MFFT is the lowest temperature at which a composition comprising the multi-stage latex will form a continuous film, i.e., the temperature below which coagulation does not occur. The MFFT of a composition comprising a multi-stage latex as described herein is preferably less than about 30°C, more preferably less than about 20°C.

[0082] In some methods, the latex polymer is a one-stage latex obtained by polymerization of an emulsion comprising one or more ethylenically unsaturated monomers in a one-stage process. By controlling the type of monomers used in the emulsion polymerization, one-stage latexes suitable for low VOC coating compositions or paints can be formed.

[0083] In some methods, by controlling the monomers used in the one-stage latex synthesis, one-stage latex compositions having a desired MFFT are obtained. The MFFT of the one-stage film-forming binder as described herein is preferably less than about 30°C, more preferably less than about 20°C.

[0084] The monomers are respectively interpolymerized into the one-stage latex or into the respective stages of the multi-stage latex, and preferably include one or more ethylenically unsaturated monomers.

[0085] In some methods, the one-stage latex monomers or the first and second stages of the multi-stage latex respectively and preferably include one or more polymerized products of (i) ethylenically unsaturated monomers such as alkyl (meth)acrylates and alkoxy (meth)acrylates, vinyl esters of saturated carboxylic acids, mono-olefins, conjugated dienes, optionally with (ii) one or more monomers such as styrene, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, vinyl acetate, acrylonitrile, vinyl chloride, and the like. In one embodiment, the monomers of the latex polymer optionally include one or more multifunctional (meth)acrylate monomers. In one embodiment, the monomers further include one or more ethylenically unsaturated carboxyl-functional amide monomers, for example ureido-functional monomers such as those formed as reaction products between an aminoalkylalkyleneurea (e.g., aminoethyl urea) and an ethylenically unsaturated carboxylic acid or anhydride (e.g., maleic anhydride).

[0086] Suitable ethylenically unsaturated monomers for each stage of a single-stage latex or a multi-stage 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 dialkyl itaconate esters (such as dimethyl itaconate, diethyl itaconate, dipropyl itaconate, or dibutyl itaconate), 2-(acetoacetoxy)ethyl methacrylate (AAEM), diacetone acrylamide (DAAM), acrylamide, methacrylamide, hydroxymethyl(meth)acrylamide, styrene, a-methylstyrene, 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, t-butyl acrylate, t-butyl methacrylate, n-butyl methacrylate, esters of itaconic acid, vinyl acetate, 2-ethylhexyl acrylate, bio-renewable monomers, and the like.

[0087] In some methods, the latex polymer is completely free or substantially free of any functional monomer units comprising a reactive ketone moiety that crosslinks the latex polymer during film formation. In some embodiments, such reactive ketone moieties include diacetone acrylamide (DAAM) or 2-(acetoacetoxy)ethyl methacrylate (AAEM).

[0088] Suitable multifunctional (meth)acrylate monomers such as di-functional acrylates, tri-functional acrylates, and tetra-functional acrylates, such as dipropylene glycol diacrylate (DPGDA), propoxylated glyceryl triacrylate (GPTA), pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, mixtures thereof, and the like. Preferred multifunctional acrylate monomers include pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, and the like.

[0089] In some methods, the latex polymer is formed from at least 80 weight percent, based on the total weight of monomers used to form the latex copolymer (and not accounting for any optional seeds used), of two or more monomers selected from the group consisting of methyl methacrylate, ethyl acrylate, vinyl acetate, t-butyl methacrylate, n-butyl methacrylate, styrene, t-butyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl acrylate, and esters of itaconic acid.

[0090] In some methods, the latex polymer is formed from at least 90 weight percent of three or more monomers selected from the group consisting of methyl methacrylate, ethyl acrylate, vinyl acetate, t-butyl methacrylate, n-butyl methacrylate, styrene, t-butyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl acrylate, and esters of itaconic acid, based on the total weight of monomers used to form the latex polymer (and not considering any optional seeds used).

[0091] Suitable ureido-functional monomers include, for example, monomers having a -NR-(C=0)-NH- functional group, where R can be H, a substituted or unsubstituted Ci-Cio alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, or a heteroalkyl group, and the like. Without being bound by theory, it is believed that ureido-functional monomers promote the wet adhesion of the coating compositions described herein, as well as coating and colorant systems, to substrates.

[0092] In certain methods, the latex copolymer (whether single stage, multi-stage, or gradient Tg) is typically prepared using a seed particle as a nucleating agent for polymerization. Such seed particles can be in the form of inorganic particulate seeds (such as clay or glass particles), preformed particulate polymer seeds (latex or non-latex polymer seeds), or in situ formed particulate seed polymers. The polymer seeds can be emulsion polymerized polymer seeds, but do not encompass polymeric surfactants. In certain embodiments, the amount of seed particles is no more than 10 weight percent, or no more than 5 weight percent, based on the latex polymer solids in the final latex.

[0093] In this document, whether inorganic particulate seeds, preformed particulate polymer seeds, or in situ formed particulate seed polymers, such seed particles are not considered to provide a stage of a multi-stage polymer or to provide a basis for a single-stage polymer or a gradient Tg polymer made using such seed polymers as specified.

[0094] In certain methods, the latex copolymer of the present application can also include crosslinking monomers, which have the ability to further react with the polymer chains at some time after the latex copolymer is initially formed, for example, during curing of the coating. The crosslinking reaction can occur by the application of energy, for example, by heating or radiation. Alternatively, the dyeing can be activated by changes in pH, oxygen content, evaporation of solvent or carrier, or other changes that cause the reaction to occur. A variety of chemical methods are known in the art to produce crosslinking in latexes. When used, the one or more crosslinking monomers are typically included in the latex copolymer 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 the one or more crosslinking monomers can 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.

[0095] Suitable examples of crosslinking carbonyl-containing monomers include propenal, methylpropenal, diacetone acrylamide, diacetone methacrylamide, 2-butanone methacrylate, formylstyrene, diacetone acrylate, diacetone methacrylate, acetonitrile acrylate, acetylacetoxyethyl methacrylate, acetylacetoxyethyl acrylate, and acetylvinyl acetate. These monomers generally do not affect crosslinking until during final film formation, for example, when the aqueous polymer emulsion also contains an appropriate added amount of a polyamine compound as a crosslinking agent. Particularly suitable compounds of this type are di- and trihydrazides of aliphatic and aromatic di- and tricarboxylic acids of 2 to 20 carbon atoms. Polyamine compounds useful as crosslinking agents for carboxyl functionality 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, where R is an alkylene, alicyclic, or aromatic group and can be substituted. Representative useful polyamines include ethylenediamine, isophorone diamine, diethylenetriamine, and dibutylenetriamine. In one embodiment of the present invention, it is useful to employ a polyhydrazide as the polyamine compound. Representative useful polyhydrazides include oxalic dihydrazide, adipic dihydrazide, succinic dihydrazide, malonic dihydrazide, glutaric dihydrazide, phthalic dihydrazide or terephthalic dihydrazide, and itaconic dihydrazide. In addition, 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.

[0096] Examples of suitable commercially available latex polymer dispersions for the film-forming binder include EPS 2720 and EPS 2799 available from Engineered Polymer Solutions (Marengo, IL).

[0097] In a preferred embodiment, the invention described herein includes a latex copolymer that is a single stage latex. In one aspect, the single stage latex is formed from monomers including about 20 to 60 weight percent, preferably 30 to 55 weight percent, of methyl methacrylate; 0 to 40 weight percent, preferably 10 to 30 weight percent, of 2-ethylhexyl acrylate; 10 to 60 weight percent, preferably 15 to 55 weight percent, of butyl acrylate; about 0 to 30 weight percent, preferably 10 to 20 weight percent, of butyl methacrylate; and about 0 to 10 weight percent, preferably 1 to 5 weight percent, of methacrylic acid.

[0098] The aqueous compositions of the present disclosure can be latex-based coating compositions. Thus, in some methods, at least a majority (i.e., greater than 50 wt. %), more preferably substantially all or all of the resin solids in the coating composition are latex polymers. Typically, the coating composition includes at least 20 wt. %, at least 30 wt. %, at least 40 wt. %, or at least 50 wt. % of latex polymer solids, based on the total solids in the coating composition. Certain high gloss dark base paints can include 80 wt. % or more of latex polymer solids. While the upper limit amount of latex copolymer included in the coating composition can vary widely (e.g., depending on the amount of pigment included), typically the coating composition will include less than 90 wt. % of latex polymer solids, based on total solids.

[0099] In certain methods, the polymeric binders of the present invention can also include one or more biobased monomers. "Biobased" as used herein in reference to monomers means monomers that are preferably obtained from biorenewable ethylenically unsaturated monomers. Such biorenewable ethylenically unsaturated monomers have significantly higher carbon-14 (C-14) than ethylenically unsaturated monomers derived from fossil fuels. This is because C-14 has a relatively short half-life on the time scale of fossil fuel-based materials. Thus, as used herein, "biorenewable" monomers means monomers having a level of C-14 isotopes comparable to the average level of C-14 in atmospheric CO2, as measured by ASTM D6866; or such monomers have a C-14 of at least about 1.5 dpm / g C (disintegrations per minute per gram of carbon), at least 2.5 dpm / g C, or at least 3.0 dpm / g C, as measured by liquid scintillation counting.

[0100] Exemplary biobased monomers include itaconic acid, bio-derived (meth)acrylic acid, and esters of alkyl (meth)acrylic acid. In embodiments, the biobased monomers comprise at least 20 wt. %, at least 30 wt. %, or at least 40 wt. % of the polymeric binders, based on the weight of all monomers interpolymerized to form the polymeric binders.

[0101] Other additives, pigments and fillers

[0102] Additional components can be added to the compositions disclosed herein. These components can be added to the polymer binder composition before, during, or after polymerization is complete, or can be added as a post-addition to another aqueous composition. Additional components or additives can be added to the reaction mixture of monomers used to make the polymer binder, to the aqueous polymer binder composition, or to a coating or paint composition that includes or will include the polymer binder. Suitable additives are known to those skilled in the art and include, but are not limited to, for example, surfactants, open time agents, pH adjusters, initiator and chaser solutions, crosslinkers, preservatives, defoamers, anti-erosion agents, thixotropic agents, rheology modifiers, colorants, and flatting agents, among others. The additives can include one or more ingredients added to a paint or coating to alter properties or enhance coating performance during storage, handling, application, and other or subsequent stages. Desired performance properties of the paint or coating include, for example, chemical resistance, hardness, gloss, reflectivity, appearance, and / or combinations of these properties and similar other properties. Preferred performance enhancing additives include lacquers, waxes, leveling agents, additives to prevent wear, abrasion, and the like.

[0103] Pigments and fillers can also be added to the coating composition (by pigment grinding) to provide a desired opacity, hiding properties, or PVC. Without being bound by theory, it is generally understood that lower PVC coatings exhibit higher gloss and greater scrub durability because such coatings contain a larger volumetric proportion of polymer binder, which is generally recognized to provide gloss and durability to the cured coating.

[0104] Pigments can be supplemented with extenders or fillers such as talc, china clay, barite, carbonates, silicates, and mixtures thereof, for example, magnesium silicate, 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 vesicular polymeric particles (e.g., those discussed in U.S. Patent 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. Patent No. 5,510,422). Other exemplary extenders or fillers include EXPANCEL ™ 551 DE20 acrylonitrile / vinyl chloride expanding particles (from Expancel Inc.), SIL-CEL ™ 43 glass microsphere fillers (from Silbrico Corporation), FILLITE ™100 Ceramic spherical particles (from Trelleborg Fillite Inc.), SPHERICEL ™ Hollow glass spheres (from Potter Industries Inc.), including G-200, G-400, G-600, G-800, W-210, W-410, and W-610 grades 3M Ceramic Microspheres (from 3M), 3M Hollow Microspheres including 3M Performance Additive iM30K (also from 3M), INHANCE ™ UH 1900 polyethylene particles (from Fluoro-Seal Inc.) and BIPHOR aluminum phosphate (from Bunge Fertilizantes S.A., Brazil).

[0105] In some methods, the aqueous coating compositions of the present disclosure can comprise at least about 5 wt% and up to about 50 wt% of pigment, based on the total solids present in the composition. In preferred embodiments, the pigment can include inorganic pigments, such as titanium dioxide. The coating compositions can comprise, for example, from about zero percent (for super dark paints), at least about 11 wt%, further comprising, for example, at least about 12 wt%, further comprising, for example, at least about 13 wt%, further comprising, for example, at least about 14 wt%, further comprising, for example, at least about 15 wt%, further comprising, for example, at least about 16 wt%, further comprising, for example, at least about 17 wt%, further comprising, for example, at least about 18 wt%, further comprising, for example, at least about 19 wt%, and even further comprising, for example, at least about 20 wt% up to about 30 wt% of titanium dioxide. In some methods, the coating compositions comprise more than 10% of titanium dioxide, based on the total solids present in the composition. Other colored pigments or dyes can also be added to the coating, either alone or in combination, to produce a wide range of colored coatings. Suitable additional pigments can include calcium carbonate, talc, clay, silicates, aluminum silicates, calcium metasilicate, potassium aluminum silicate, magnesium silicate, barium sulfate, nepheline syenite, feldspar, zinc oxide or sulfide, or other pigments known to those skilled in the art. Such additional colored pigments can be present in an amount of up to about 30 wt%, for example, from about 10 wt% to about 20 wt%, based on the total solids present in the composition. In some cases, “pigment” can also refer to functional fillers that are non-water soluble solids. Such functional fillers can include solids that provide additional functional properties to the coating, such as intumescent ingredients, such as ammonium polyphosphate, melamine, pentaerythritol, and similar compounds. In one useful embodiment, the coating compositions of the present invention are substantially free or completely free of intumescent ingredients, such as ammonium polyphosphate, melamine, and pentaerythritol, and similar compounds.

[0106] The coating compositions of the present disclosure preferably have a PVC of from about 5 to about 60.

[0107] In one aspect, the compositions described herein can include a coalescing agent that aids in film formation, which is added to the reaction mixture of monomers used to make the polymeric binder, to the aqueous polymeric binder composition, or to the coating composition including the polymeric binder. Suitable coalescing agents or coalescing compounds can be dispersed in the polymeric binder, coating, or paint composition including the polymeric binder and promote film formation at temperatures below about 25 °C, even at temperatures of 5 °C to 10 °C. Preferred coalescing agents are low VOC coalescing agents and have a VOC content of less than about 50%, preferably less than about 30%, more preferably less than about 20%, most preferably less than about 15%. Exemplary suitable coalescing agents include low VOC compounds of the type described in detail in at least U.S. Patent Nos. 6,762,230 and 7,812,079. Other suitable low VOC coalescing agents include Optifilm (Eastman Chemical, Kingsport TN), Loxanol (Cognis, Kankakee IL, now BASF), Archer RC (ADM, Decator IL), and the like. Conventional coalescing agents such as Texanol (Eastman Chemical), and the like, can also be used, either alone or in combination with other solvents such as 2-butoxyethanol (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), and the like, provided that low VOC levels are maintained in the coating composition or paint.

[0108] In one aspect, the compositions described herein can include a UV-VIS absorber. Suitable compounds for use as UV-VIS absorbers in the present disclosure include ultraviolet absorbers, visible light absorbers, or combinations thereof. These can also be referred to as photoinitiators.

[0109] Suitable UV-VIS absorbers are water-insoluble. This means that the compound will not dissolve to a measurable extent in water (i.e., will not dissolve in amounts greater than 5 wt%) at temperatures typically used to make coating compositions as described herein.

[0110] In certain embodiments, suitable UV-VIS absorbers are those compounds capable of absorbing ultraviolet and / or visible radiation in the range of 240 nm to 465 nm. For certain embodiments, they are capable of absorbing radiation in the range of 280 nm to 450 nm. In certain embodiments, suitable visible light absorbers are those compounds capable of absorbing visible radiation in the range of 420 nm to 450 nm. In certain embodiments, suitable ultraviolet absorbers are those compounds capable of absorbing ultraviolet radiation in the range of 240 nm to 400 nm. For certain embodiments, they are capable of absorbing ultraviolet radiation in the range of 280 nm to 400 nm, and for certain embodiments, they are capable of absorbing ultraviolet radiation in the range of 315 nm to 375 nm.

[0111] Examples of suitable UV absorbers include the following: benzophenone (commercially available from Lamberti, Gallaratte, Italy); phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (commercially available as IRGACURE 819DW from BASF, Florham Park, N.J.); ethyl 2,4,6-trimethylbenzoylphenylphosphinate (commercially available as LUCIRIN TPO-L (previously LUCIRIN LR 8893) from BASF, Florham Park, N.J.); 2,4,6-trimethylbenzophenone and 4-methylbenzophenone (commercially available as a mixture as ESACURE TZT from Lamberti, Gallaratte, Italy); 2,2-dimethoxy-1,2-diphenyl ethanone (i.e., benzoin dimethyl ketal) (commercially available as ESACURE KB 1 from Lamberti); 1 -hydroxycyclohexyl phenyl ketone (i.e., a-hydroxy cyclohexyl phenyl ketone) (commercially available as ESACURE KS 300 from Lamberti); 2-hydroxy-2-methyl-1 -phenyl-1 -propanone (commercially available as ESACURE KL 200 from Lamberti); polymeric benzophenone (commercially available as EBECRYL P39 from Cytec, Woodland Park, N.J.); isopropyl thioxanthone (commercially available as GENOCURE ITX from Rahn USA, Aurora, IL); methyl o-benzoylbenzoate (commercially available as GENOCURE MBB from Rahn); methyl benzoylformate (commercially available as GENOCURE MBF from Rahn); benzoin ethyl ether (commercially available from Aldrich. St. Louis, MO); 4'-ethoxyacetophenone (from Aldrich. St. Louis, MO); and combinations thereof. Other suitable UV-VIS absorbers are commercially available from BASF under the trade names IRGACURE and LUCERIN. Methyl o-benzoylbenzoate is a preferred UV-VIS absorber for, e.g., improving gloss retention and / or stain resistance.

[0112] The compositions of the present application can also include various other additives in amounts up to about 10 wt.%, for example, about 1 wt.% to about 2 wt.%, including but not limited to thickeners, such as polyurethane thickeners and acrylic thickeners. Synthetic organic materials can also be incorporated; these materials include plastic beads, hollow spheres, or other similar materials. Other optional components include glycols, such as ethylene glycol and / or propylene glycol, in amounts up to about 7%, and other solvents such as diethylene glycol dibenzoate and dipropylene glycol dibenzoate in amounts up to about 3%. These compositions can also contain pigment dispersants, which can be solvents or surfactants; additional liquid paint preservatives; additional dry film preservatives; foam control agents, such as oils, fatty acids, and silicones; slip and abrasion additives; tackifiers, and / or other known paint additives. The compositions of the present application can also include additional biocides or preservatives, including but not limited to metal ion containing compounds, polymeric biocides, quaternary ammonium compounds, heterocyclic compounds, phenols, organometallic compounds, aldehydes, proteins, peroxides, alcohols, enzymes, polypeptides, and halogen releasing compounds.

[0113] Aqueous coating composition

[0114] In certain embodiments of the present application, the nitrogen-containing organic additive can be added to the coating composition, such as a paint, either individually or mixed into other components of the coating composition at different stages of formation of the coating composition.

[0115] In some embodiments, the aqueous composition is an aqueous coating composition. In some embodiments, the aqueous composition is a paint.

[0116] In some embodiments, the aqueous composition is a 1K coating composition.

[0117] In some embodiments, the aqueous composition is a 2K coating composition.

[0118] In some embodiments, the aqueous composition comprises up to 300 ppm of BIT, based on the total components present in the aqueous composition. In further embodiments, the aqueous composition comprises up to 150 ppm of BIT, and in further embodiments, up to 50 PPM of BIT. In some embodiments, the coating composition is substantially free of BIT, essentially free of BIT, or completely free of BIT.

[0119] In some embodiments, the aqueous composition comprises at most 150 ppm of MIT, based on the total components present in the composition. In further embodiments, the aqueous composition comprises at most 50 ppm of MIT, in further embodiments, at most 20 PPM of MIT. In some embodiments, the aqueous composition is substantially free of MIT, essentially free of MIT, or completely free of MIT.

[0120] In some embodiments, the aqueous composition comprises at most 40 ppm of the reaction product of MIT and CMIT, based on the total components present in the composition. In further embodiments, the aqueous composition comprises at most 25 ppm of the reaction product of MIT and CMIT, in further embodiments, at most 10 PPM of the reaction product of MIT and CMIT. In some embodiments, the aqueous composition is substantially free of the reaction product of MIT and CMIT, essentially free of the reaction product of MIT and CMIT, or completely free of the reaction product of MIT and CMIT.

[0121] In some embodiments, the aqueous composition comprises at most 5000 ppm of zinc pyrithione or sodium pyrithione, based on the total components present in the composition. In further embodiments, the paint or coating composition comprises at most 3000 ppm of zinc pyrithione or sodium pyrithione, in further embodiments, at most 1000 ppm of zinc pyrithione or sodium pyrithione, in still further embodiments, at most 50 ppm of zinc pyrithione or sodium pyrithione. In some embodiments, the coating composition is substantially free of zinc pyrithione and sodium pyrithione, essentially free of zinc pyrithione and sodium pyrithione, or completely free of zinc pyrithione and sodium pyrithione.

[0122] Aqueous polymeric binder composition

[0123] In certain embodiments of the present application, the nitrogen-containing organic additive can be added to the aqueous polymeric binder composition separately, or mixed into other components of the composition at various stages of the composition formation. In some useful embodiments, the aqueous polymeric binder is a latex.

[0124] In some embodiments, the aqueous polymer binder composition comprises at least 50 ppm of a nitrogen-containing organic additive (based on the total weight of polymer solids). In further embodiments, the aqueous polymer binder composition comprises at least 110 ppm of a nitrogen-containing organic additive, in further embodiments at least 140 ppm of a nitrogen-containing organic additive, in further embodiments at least 230 ppm of a nitrogen-containing organic additive, in further embodiments at least 730 ppm of a nitrogen-containing organic additive, in further embodiments at least 2,800 ppm of a nitrogen-containing organic additive, and in other further embodiments at least 9,000 ppm of a nitrogen-containing organic additive.

[0125] In some useful embodiments, the aqueous polymer binder composition comprises at most 300,000 ppm of a nitrogen-containing organic additive (based on the total weight of polymer solids). In further embodiments, the aqueous polymer binder composition comprises at most 230,000 ppm of a nitrogen-containing organic additive, in further embodiments at most 150,000 ppm of a nitrogen-containing organic additive, in further embodiments at most 80,000 ppm of a nitrogen-containing organic additive, in further embodiments at most 50,000 ppm of a nitrogen-containing organic additive, and in other further embodiments at most 20,000 ppm of a nitrogen-containing organic additive.

[0126] The nitrogen-containing organic additives useful in the present application allow for the formulation of aqueous polymer binder compositions that are shelf-stable or have reduced susceptibility to microbial spoilage and provide other improved or maintained coating performance properties when added as a component of a coating composition, including but not limited to scrub resistance, wash resistance, and heat or weathering stability. In embodiments, the aqueous polymer binder compositions can be provided without the need for or with reduced need for the use of conventional biocides such as isothiazolinones, pyridinethiones, inorganic biocides, or other biocides.

[0127] In some useful embodiments, the aqueous polymer binder composition comprises at most 600 ppm of BIT (based on the total weight of polymer solids). In further embodiments, the aqueous polymer binder composition comprises at most 300 ppm of BIT, in further embodiments at most 100 PPM of BIT. In some embodiments, the aqueous polymer binder composition is substantially free of BIT, essentially free of BIT, or completely free of BIT.

[0128] In some useful embodiments, the aqueous polymer binder composition comprises up to 300 ppm of MIT (based on the total weight of polymer solids). In further embodiments, the aqueous polymer binder composition comprises up to 100 ppm of MIT, in further embodiments, up to 40 PPM of MIT. In some embodiments, the aqueous polymer binder composition is substantially free of MIT, essentially free of MIT, or completely free of MIT.

[0129] In some useful embodiments, the aqueous polymer binder composition comprises up to 80 ppm of the reaction product of MIT and CMIT (based on the total weight of polymer solids). In further embodiments, the aqueous polymer binder composition comprises up to 50 ppm of the reaction product of MIT and CMIT, in further embodiments, up to 20 PPM of the reaction product of MIT and CMIT. In some embodiments, the aqueous polymer binder composition is substantially free of the reaction product of MIT and CMIT, essentially free of the reaction product of MIT and CMIT, or completely free of the reaction product of MIT and CMIT.

[0130] In some useful embodiments, the aqueous polymer binder composition comprises up to 10,000 ppm of zinc pyrithione or sodium pyrithione (based on the total weight of polymer solids). In further embodiments, the aqueous polymer binder composition comprises up to 6,000 ppm of zinc pyrithione or sodium pyrithione, in further embodiments, up to 2,000 ppm of zinc pyrithione or sodium pyrithione, in other further embodiments, up to 100 ppm of zinc pyrithione or sodium pyrithione. In some embodiments, the aqueous polymer binder composition is substantially free of zinc pyrithione and sodium pyrithione, essentially free of zinc pyrithione and sodium pyrithione, or completely free of zinc pyrithione and sodium pyrithione.

[0131] Method of making a composition and method of making a coated article

[0132] In certain embodiments of the present application, methods of making an aqueous composition are provided. In embodiments, a nitrogen-containing organic additive is added to the composition at any stage of composition formation or after composition formation so as to form an aqueous coating composition (such as a paint) or an aqueous polymer binder composition according to any of the embodiments disclosed herein. The nitrogen-containing organic additive can be added as a separate component, mixed with other components in the aqueous composition, or as a mixture with a polymer binder.

[0133] In further embodiments, a method of making a coated article is disclosed, the method comprising the steps of providing a paint or coating composition according to any of the embodiments disclosed herein, and coating a substrate with the waterborne coating composition of the present disclosure to form a coated article. Suitable substrates include, but are not limited to, wood, plastic, drywall, concrete, metal, rubber, or natural or synthetic polymers. The substrate can be single or multi-layered. The waterborne coating composition of the present disclosure can be applied directly to the substrate, or indirectly such as when the substrate is pre-coated with a primer or base coat. The waterborne coating composition can be applied by any suitable method, including brushing, rolling, spreading, spraying, or melt application. After application, the coating is cured. Curing can be by drying, including at ambient or elevated temperatures, exposure to actinic or ultraviolet radiation, or crosslinking, among others.

[0134] Exemplary embodiments

[0135] Embodiment 1. A waterborne composition comprising: (a) a carrier liquid; (b) a film-forming polymeric binder; and (c) at least one nitrogen-containing organic additive comprising a compound comprising four nitrogen centers, each nitrogen center being connected to at least one other nitrogen center by at least one saturated divalent hydrocarbon linking group, wherein the nitrogen-containing organic additive is a post-addition component of the waterborne composition.

[0136] Embodiment 2. The waterborne composition of Embodiment 1, wherein the linking groups are each independently linear or branched C1, C2, C3, or C4 chains.

[0137] Embodiment 3. The waterborne composition of any preceding embodiment, wherein the carrier liquid comprises water.

[0138] Embodiment 4. The waterborne composition of any preceding embodiment, wherein the waterborne composition is a latex, paint, coating, caulk, or sealant.

[0139] Embodiment 5. The waterborne composition of any preceding embodiment, wherein the polymeric binder comprises a multi-stage latex.

[0140] Embodiment 6. The waterborne composition of any preceding embodiment, wherein the polymeric binder comprises a vinyl acrylic latex, a styrene acrylic latex, an all-acrylic latex, a polyurethane dispersion (PUD), a waterborne alkyd resin, a waterborne alkyd resin-PUD hybrid resin, or a blend thereof.

[0141] Embodiment 7. The aqueous composition of any preceding embodiment, wherein the nitrogen-containing organic additive is selected from the group consisting of compounds of Formula I, II, III, and IV, and mixtures thereof, wherein Formula I is:

[0142] wherein Formula II is:

[0143] wherein Formula III is:

[0144] wherein Formula IV is:

[0145] wherein each of R1-R4, R7, and R10-R14 is a saturated hydrocarbon chain having 1 to 3 carbons, each of R5, R6, R8, and R9 is a saturated hydrocarbon chain having 2 to 3 carbons, and each of R1-R14 is the same or different.

[0146] Embodiment 8. The aqueous composition of the immediately preceding embodiment, wherein each of R1-R4, R7, and R10-R14 is a saturated hydrocarbon chain having 1 to 2 carbons, each of R5, R6, R8, and R9 is a saturated hydrocarbon chain having 2 to 3 carbons, and each of R1-R14 is the same or different.

[0147] Embodiment 9. The aqueous composition of any preceding embodiment, wherein the nitrogen-containing organic additive is selected from the group consisting of N,N'-bis(2-aminoethyl)- 1,2-ethanediamine, N,N'-bis-(2-aminoethyl)piperazine, N[(2-aminoethyl)2-aminoethyl]piperazine, tris-(2-aminoethyl)amine), and mixtures thereof.

[0148] Embodiment 10. The aqueous composition of any one of embodiments 1 to 6, wherein the nitrogen-containing organic additive is selected from the group consisting of: an amino acid hydrazide, a hydrazide of carbazide-carboxylic acid, a bis-hydrazide and bis-carbazide, diethylenetriamine, N,N'-bis(2-aminoethyl)-l,2-ethanediamine, tetraethylenepentamine, pentaethylenehexamine, tri-(2-aminoethyl)amine, N-(2-piperazinoethyl)-ethylenediamine, N,N'-bis-(2-aminoethyl)-piperazine, N,N,N'-tris-(2-aminoethyl)ethylenediamine, N-(2-aminoethyl)-N'-(2-piperazinoethyl-l)-ethylenediamine, N,N-bis-(2-aminoethyl)-N-(2-piperazinoethyl)amine, N,N-bis-(2-piperazinoethyl)-amine, a polyethyleneimine oligomer comprising at least four functional monomer units, N-(2-aminoethyl)-l,3-propanediamine, a polyoxypropylenamine oligomer comprising at least four functional monomer units monomers, tetrapropylenepentamine, tripropylenetetramine, and N,N'-bis-(3-aminopropyl)ethylenediamine, and mixtures thereof.

[0149] Embodiment 11. The aqueous composition of any preceding embodiment, wherein the film- forming polymeric binder is substantially free of any functional monomer units comprising a reactive ketone moiety that crosslinks the film-forming binder during film formation.

[0150] Embodiment 12. The aqueous composition of the immediately preceding embodiment, wherein the reactive ketone moiety that crosslinks the film-forming binder during film formation comprises a diketone acrylamide ("DAAM").

[0151] Embodiment 13. The aqueous composition of any preceding embodiment, wherein the compound of the nitrogen-containing organic additive is substantially free of any aryl functional groups.

[0152] Embodiment 14. The aqueous composition of any preceding embodiment, wherein the aqueous composition comprises at least about 50 ppm by weight of the nitrogen-containing organic additive, based on the total weight of the components of the composition.

[0153] Embodiment 15. The aqueous composition of any preceding embodiment, wherein the aqueous composition comprises at most about 100,000 ppm by weight of the nitrogen-containing organic additive, based on the total weight of the components of the composition.

[0154] Embodiment 16. The aqueous composition of any preceding embodiment, wherein the aqueous composition comprises at most about 75,000 ppm by weight of the nitrogen-containing organic additive, based on the total weight of the components of the composition.

[0155] Embodiment 17. The aqueous composition of any preceding embodiment, wherein the aqueous composition comprises up to about 50,000 ppm by weight of the nitrogen-containing organic additive, based on the total weight of components of the composition.

[0156] Embodiment 18. The aqueous composition of any preceding embodiment, wherein the aqueous composition comprises at least about 75 ppm by weight of the nitrogen-containing organic additive, based on the total weight of components of the composition.

[0157] Embodiment 19. The aqueous composition of any preceding embodiment, wherein the aqueous composition comprises up to about 25,000 ppm by weight of the nitrogen-containing organic additive, based on the total weight of components of the composition.

[0158] Embodiment 20. The aqueous composition of any preceding embodiment, wherein the aqueous composition further comprises no more than about 300 ppm by weight of BIT, based on the total weight of components of the composition.

[0159] Embodiment 21. The aqueous composition of any preceding embodiment, wherein the aqueous composition further comprises no more than about 150 ppm by weight of BIT, based on the total weight of components of the composition.

[0160] Embodiment 22. The aqueous composition of any preceding embodiment, wherein the aqueous composition comprises no more than about 50 ppm by weight of BIT, based on the total weight of components of the composition.

[0161] Embodiment 23. The aqueous composition of any preceding embodiment, wherein the aqueous composition further comprises no more than about 150 ppm by weight of MIT, based on the total weight of components of the composition.

[0162] Embodiment 24. The aqueous composition of any preceding embodiment, wherein the aqueous composition further comprises no more than about 50 ppm of MIT, based on the total weight of components of the composition.

[0163] Embodiment 25. The aqueous composition of any preceding embodiment, wherein the aqueous composition further comprises no more than about 20 ppm of MIT, based on the total weight of components of the composition.

[0164] Embodiment 26. The aqueous composition of any preceding embodiment, wherein the aqueous composition is substantially free of MIT, based on the total weight of components of the composition.

[0165] Embodiment 27. The aqueous composition of any preceding embodiment, wherein the aqueous composition further comprises no more than about 40 ppm of a reaction product of CMIT and MIT, based on the total weight of components of the composition.

[0166] Embodiment 28. The aqueous composition of any preceding embodiment, wherein the aqueous composition further comprises no more than about 25 ppm of the reaction product of CMIT and MIT, based on the total weight of components of the composition.

[0167] Embodiment 29. The aqueous composition of any preceding embodiment, wherein the aqueous composition further comprises no more than about 10 ppm of the reaction product of CMIT and MIT, based on the total weight of components of the composition.

[0168] Embodiment 30. The aqueous composition of any preceding embodiment, wherein the aqueous composition is substantially free of the reaction product of CMIT and MIT, based on the total weight of components of the composition.

[0169] Embodiment 31. The aqueous composition of any preceding embodiment, wherein the aqueous composition further comprises no more than about 5,000 ppm of zinc pyrithione or sodium pyrithione, based on the total weight of components of the composition.

[0170] Embodiment 32. The aqueous composition of any preceding embodiment, wherein the aqueous composition further comprises no more than about 3,000 ppm of zinc pyrithione or sodium pyrithione, based on the total weight of components of the composition.

[0171] Embodiment 33. The aqueous composition of any preceding embodiment, wherein the aqueous composition further comprises no more than about 1,000 ppm of zinc pyrithione or sodium pyrithione, based on the total weight of components of the composition.

[0172] Embodiment 34. The aqueous composition of any preceding embodiment, wherein the aqueous composition further comprises no more than about 50 ppm of zinc pyrithione or sodium pyrithione, based on the total weight of components of the composition.

[0173] Embodiment 35. The aqueous composition of any preceding embodiment, wherein the aqueous composition is substantially free of zinc pyrithione or sodium pyrithione.

[0174] Embodiment 36. The aqueous composition of any preceding embodiment, wherein when the aqueous composition is or is included in a coating, and the coating is applied to a substrate and cured, the coating exhibits equivalent or better scrub durability compared to a second coating having the same composition, except that the second coating contains an equivalent amount of isothiazolinone to the nitrogen-containing organic additive instead of the nitrogen-containing organic additive, as measured according to ASTM D2486-96 (Standard Test Method for Scrub Resistance of Wall Paints).

[0175] Embodiment 37. The aqueous composition of any preceding embodiment, wherein when the aqueous composition is or is included in a coating, and the coating is applied to a substrate and cured, the coating exhibits equivalent or better KU viscosity reduction at about 140 °F over a period of about 3 weeks compared to a second coating having the same composition, except that the second coating contains an equivalent amount of isothiazolinone to the nitrogen-containing organic additive instead of the nitrogen-containing organic additive, as measured according to ASTM D562-10 (Standard Test Method for Paint Consistency Using a Stormer-Type Viscosity Cup to Measure Krebs Units (KU) Viscosity).

[0176] Embodiment 38. The aqueous composition of any preceding embodiment, wherein when the aqueous composition is or is included in a coating, and the coating is applied to a substrate and cured, the coating exhibits equivalent or better wash resistance compared to a second coating having the same composition, except that the second coating contains an equivalent amount of isothiazolinone to the nitrogen-containing organic additive instead of the nitrogen-containing organic additive, as measured according to ASTM D4828-94 (2003) “Standard Test Method for Washability of Organic Coatings”.

[0177] Embodiment 39. The aqueous composition of any preceding embodiment, wherein the aqueous composition is shelf-stable, as defined herein.

[0178] Embodiment 40. The aqueous composition of any preceding claim, wherein the aqueous composition produces, on average, less than 1 x 10 3 CFU / mL when the aqueous composition is subjected to the microbial challenge test.

[0179] Embodiment 41. The aqueous composition of any preceding claim, wherein the aqueous composition produces, on average, less than 5 x 10 2 CFU / mL when the aqueous composition is subjected to the microbial challenge test.

[0180] Embodiment 42. The aqueous composition of any preceding embodiment, wherein the aqueous composition comprises at least 17 wt% of the polymeric binder solids.

[0181] Embodiment 43. The aqueous composition of any preceding embodiment, wherein the aqueous composition is a coating, and the coating further comprises a pigment.

[0182] Embodiment 44. The coating of embodiment 43, wherein the coating is a 1K waterborne coating.

[0183] Embodiment 45. The coating of either of embodiments 43 or 44, wherein the coating comprises from about 10 wt% to about 30 wt% titanium dioxide, based on the total solids present in the coating.

[0184] Embodiment 46. A coating composition comprising: (a) from about 7 wt% to about 30 wt% of the polymeric solids of a film-forming polymeric binder; (b) from about 50 ppm to about 50,000 ppm by weight of a nitrogen-containing organic additive comprising at least one compound comprising four nitrogen centers, each nitrogen center being connected to at least one other nitrogen center by at least one saturated divalent hydrocarbon linking group, wherein the nitrogen-containing organic additive is a post- addition component of the coating composition and is selected from the group consisting of N,N'-bis(2-aminoethyl)-l,2-ethanediamine, N,N'-bis-(2-aminoethyl)piperazine, N[(2-aminoethyl)2-aminoethyl]piperazine, tris-(2-aminoethyl)amine), and mixtures thereof; (c) from at least 10 wt% to about 30 wt% titanium dioxide; and (d) water.

[0185] Embodiment 47: A method of preserving an aqueous composition, the method comprising: adding a nitrogen-containing organic additive to a composition comprising at least a carrier and a film-forming binder, the nitrogen-containing organic additive comprising at least one compound comprising four nitrogen centers, each nitrogen center being connected to at least one other nitrogen center by at least one saturated divalent hydrocarbon linking group.

[0186] Embodiment 48: A coated article comprising: a coating composition according to any preceding embodiment coated on a substrate, wherein the substrate comprises wood, plastic, drywall, concrete, metal, rubber, or natural or synthetic polymers.

[0187] Examples

[0188] Test methods

[0189] The following test methods were used in the evaluation of the control and example paints. Where a standard test method was used to evaluate a property, the standard test method is provided. Where a property was tested according to a modified version of a standard test method, the deviation from the standard test method is described.

[0190] Microbial challenge test

[0191] The preservative efficacy was tested by microbial challenge testing. As conducted herein, the microbial challenge testing was conducted by subjecting each composition to a microbial challenge test in a manner substantially similar to the test protocol detailed in ASTM D2574-16 Standard Test Method for Resistance of Emulsion Paints in Containers to Microbial Attack (2016). The preservative testing used herein is described below. Differences from ASTM D2574 are included in this specification.

[0192] Each sample composition was sampled 50 mL each in duplicate (each sample composition included a different variation of a nitrogen-containing organic additive and a conventional biocide concentration), and each of the duplicate samples was: (Challenge 1) inoculated on Day 0 with about 10 9 CFU / mL of mixed culture resulting in a final concentration of about 10 8 CFU / mL within the sample; (Challenge 2) inoculated on Day 7 with about 10 9 CFU / mL of mixed culture resulting in a final concentration of about 10 8 CFU / mL within the sample; and (Challenge 3) inoculated on Day 14 with about 10 9 CFU / mL of mixed culture resulting in a final concentration of about 10 8 CFU / mL within the sample; each sample was incubated at 30 °C ± 2 °C immediately after inoculation. For each sample, a spread plate was prepared by using aseptic technique to evenly spread 0.1 mL of sample on a tryptic soy agar plate, in duplicate at 72 hours incubation and at 7 days incubation. Each spread plate so prepared was then incubated for an additional 72 hours at 30 °C ± 2 °C, and observed at that time for microbial growth. The challenge test was also performed on negative controls, which were agar plates with bacterial challenge but no paint applied (not to be confused with negative control paints). The negative control spread plate test results were performed as process verification to check for possible experimental errors, and are not reported in the results below. Bacterial survival was quantified according to the rating scale shown in Table 1 below. The overall score for the microbial challenge test was determined by averaging the 7-day sample rating for the third challenge for a given composition. Compositions with an overall microbial challenge test score of 6 or less (i.e., an average occurrence of less than 1 x 10 3CFU / mL - showing "moderate" contamination) were considered to pass the microbial challenge test and, therefore, were adequately preserved.

[0193] Table 1 - Rating scale for corrosion testing

[0194] where "TNTC" = "too numerous to count" and "CFU / mL" = "colony forming units per milliliter"

[0195] Wash resistance: Wash-off resistance is a measure of the relative ease of removal of common soils and stains from a coated surface by hand or machine washing. Wash-off resistance is evaluated according to ASTM D4828-94, wherein at least crayon, black ink pen, pencil, and red lipstick are used as stains, and 10 mL of Formula 409 is used as a liquid cleaner, with evaluation after 50 cycles.

[0196] Scrub durability: Scrub resistance is a measure of the relative ability of a coating to resist erosion or removal of the coating from the substrate due to scrubbing. Scrub resistance is measured by ASTM D2486-17 Test Method A or B.

[0197] Aging and heat aging stability of dispersions: "Thermal aging stability" or "thermally aging stable" as generally used herein in reference to a composition means that the composition exhibits less than a 10 unit KU viscosity increase after aging at about 140 °F for about 3 weeks. "Aging stability" or "aging stable" as generally used herein in reference to a composition means that the composition exhibits less than a 5 unit KU to 10 unit KU viscosity increase after aging at room temperature (about 68 °F) for about 3 weeks. Viscosity is measured in KU or Krebs units according to ASTM D562-10 (Standard Test Method for Paint Ductility by Stormer-Type Viscometer), and in ICI units according to ASTM D4287-00 (Standard Test Method for High-Shear Viscosity Using a Cone / Plate Viscometer).

[0198] Example 1

[0199] A positive control vinyl acrylic base paint ("positive control paint") was obtained, namely ProMar ™ 200 Zero VOC - Interior Latex Gloss Sheen (Extra White) containing 800 ppm Proxel ®BD-20 (aqueous dispersion containing 19.3 wt% 1,2-benzisothiazolin-3-one; available from Arxada Corp.) and 300 ppm Zinc Omadine ® ZOE (emulsion containing 48 wt% 2-pyridinethiol-1-oxide zinc emulsion; available from Arxada Corp.) consisting of a post-addition preservative. Control paints were prepared by conventional paint preparation methods using the same formulation but omitting the post-addition preservative (800 ppm Proxel ® BD-20 and 300 ppm Zinc Omadine ® emulsion) were prepared. The control paints were compared to ProMar ™ 200 Zero VOC - Interior Latex Gloss Sheen (Extra White) (vinyl acrylic paint) consisting of several example paints. The paints were prepared by mixing the conventional components using techniques known to one of ordinary skill in the art.

[0200] Table 2 - Corrosion inhibitor in ppm for control and example base paints

[0201] The preservative efficacy testing of the positive control paint, negative control paint, and example paints 1-4 is shown in Table 3 below.

[0202] Table 3 - Results of corrosion efficacy testing

[0203] Example paint 4 produced a total microbial challenge test score of (2+1) / 2 = 1.5. Thus, example paint 4 showed an average of less than 5 x 10 1 CFU / mL of bacterial contamination when subjected to the microbial challenge test.

[0204] The wash resistance test results of the positive control paint and example paint 4 are shown in Table 4 below.

[0205] Table 4 - Results of wash resistance testing

[0206] The scrub durability test results (ASTM D2486-17, Test Method B) of the positive control paint and example paint 4 are shown in Table 5 below. The “standard paint” was employed to allow the results to be normalized according to ASTM D2486-17.

[0207] Table 5 - Results of scrub durability testing

[0208] The results of the weathering stability test for the positive control paint and Example Paint 4, and the results of the heat aging stability test for Example Paint 4 are shown in Table 6 below.

[0209] Table 6 - Results of aging and heat aging stability testing

Claims

1. An aqueous composition comprising: (a) a carrier liquid; (b) a film-forming polymeric binder; and (c) a nitrogen-containing organic additive comprising at least one compound comprising four nitrogen centers, each nitrogen center being connected to at least one other nitrogen center by at least one saturated divalent hydrocarbon linking group.

2. The aqueous composition of claim 1, wherein the linking groups are each independently linear or branched C1, C2, C3, or C4 chains.

3. The aqueous composition of any preceding claim, wherein the carrier liquid comprises water.

4. The aqueous composition of any preceding claim, wherein the aqueous composition is a latex, a paint, a coating composition, a caulk, or a sealant.

5. The aqueous composition of claim 4, wherein the nitrogen-containing organic additive is a post-addition component of the aqueous composition.

6. The aqueous composition of any preceding claim, wherein the polymeric binder comprises a single-stage latex.

7. The aqueous composition of any preceding claim, wherein the polymeric binder comprises a multi-stage latex.

8. The aqueous composition of any preceding claim, wherein the polymeric binder comprises a vinyl acrylic latex, a styrene acrylic latex, an all-acrylic latex, a polyurethane dispersion (PUD), a waterborne alkyd resin, a waterborne alkyd resin-PUD hybrid resin, or a blend thereof.

9. The aqueous composition of any preceding claim, wherein the nitrogen-containing organic additive comprises at least one compound selected from the group consisting of compounds of Formulae I, II, III, and IV, wherein Formula I is: wherein Formula II is: wherein Formula III is: wherein Formula IV is: wherein each of R1-R4, R7, and R10-R14 is a saturated hydrocarbon chain having 1 to 3 carbons, each of R5, R6, R8, and R9 is a saturated hydrocarbon chain having 2 to 3 carbons, and each of R1-R14 is the same or different.

10. The aqueous composition of the immediately preceding claim, wherein each of R1-R4, R7, and R10-R14 is a saturated hydrocarbon chain having 1 to 2 carbons, each of R5, R6, R8, and R9 is a saturated hydrocarbon chain having 2 to 3 carbons, and each of R1-R14 is the same or different.

11. The aqueous composition of any preceding claim, wherein the nitrogen-containing organic additive is selected from the group consisting of the following compounds: N,N'-bis(2-aminoethyl)-l,2-ethanediamine, N,N'-bis-(2-aminoethyl)piperazine, N[(2-aminoethyl)2-aminoethyl]piperazine, tris-(2-aminoethyl)amine), and mixtures thereof.

12. The aqueous composition of any one of claims 1 to 6, wherein the nitrogen-containing organic additive is selected from the group consisting of amino acid hydrazides, hydrazides of carbazide-carboxylic acids, bis-hydrazides and bis-carbazides, diethylenetriamine, N,N'-bis(2-aminoethyl)-l,2-ethanediamine, tetraethylenepentamine, pentaethylenehexamine, tri-(2-aminoethyl)amine, N-(2-piperazinoethyl)-ethylenediamine, N,N'-bis-(2-aminoethyl)-piperazine, N,N,N'-tris-(2-aminoethyl)ethylenediamine, N-(2-aminoethyl)-N'-(2-piperazinoethyl-l)-ethylenediamine, N,N-bis-(2-aminoethyl)-N-(2-piperazinoethyl)amine, N,N-bis-(2-piperazinoethyl)-amine, polyethyleneimine oligomers comprising at least four functional monomer units, N-(2-aminoethyl)-l,3-propanediamine, polyoxypropylenamine oligomers comprising at least four functional monomer units monomers, tetrapropylenepentamine, tripropylenetetramine, and N,N'-bis-(3-aminopropyl)ethylenediamine, and mixtures thereof.

13. The aqueous composition of any preceding claim, wherein the film-forming polymeric binder is substantially free of any functional monomer units comprising a reactive ketone moiety that crosslinks the film-forming polymeric binder during film formation.

14. The aqueous composition of the immediately preceding claim, wherein the reactive ketone moiety that crosslinks the film-forming polymeric binder during film formation comprises diketone acrylamide ("DAAM").

15. The aqueous composition of any preceding claim, wherein the compound of the nitrogen-containing organic additive is substantially free of any aryl functional groups.

16. The aqueous composition of any preceding claim, wherein the aqueous composition comprises at least about 50 ppm by weight of the nitrogen-containing organic additive based on the total weight of the components of the composition.

17. The aqueous composition of any preceding claim, wherein the aqueous composition comprises at most about 100,000 ppm by weight of the nitrogen-containing organic additive based on the total weight of the components of the composition.

18. The aqueous composition of any preceding claim, wherein the aqueous composition comprises at most about 75,000 ppm by weight of the nitrogen-containing organic additive based on the total weight of the components of the composition.

19. The aqueous composition of any preceding claim, wherein the aqueous composition comprises at most about 50,000 ppm by weight of the nitrogen-containing organic additive based on the total weight of the components of the composition.

20. The aqueous composition of any preceding claim, wherein the aqueous composition comprises at least about 75 ppm by weight of the nitrogen-containing organic additive based on the total weight of the components of the composition.

21. The aqueous composition of any preceding claim, wherein the aqueous composition comprises up to about 25,000 ppm by weight of the nitrogen-containing organic additive based on the total weight of components of the composition.

22. The aqueous composition of any preceding claim, wherein the aqueous composition further comprises no more than about 300 ppm by weight of BIT based on the total weight of components of the composition.

23. The aqueous composition of any preceding claim, wherein the aqueous composition further comprises no more than about 150 ppm by weight of BIT based on the total weight of components of the composition.

24. The aqueous composition of any preceding claim, wherein the aqueous composition comprises no more than about 50 ppm by weight of BIT based on the total weight of components of the composition.

25. The aqueous composition of any preceding claim, wherein the aqueous composition further comprises no more than about 150 ppm by weight of MIT based on the total weight of components of the composition.

26. The aqueous composition of any preceding claim, wherein the aqueous composition further comprises no more than about 50 ppm of MIT based on the total weight of components of the composition.

27. The aqueous composition of any preceding claim, wherein the aqueous composition further comprises no more than about 20 ppm of MIT based on the total weight of components of the composition.

28. The aqueous composition of any preceding claim, wherein the aqueous composition is substantially free of MIT based on the total weight of components of the composition.

29. The aqueous composition of any preceding claim, wherein the aqueous composition further comprises no more than about 40 ppm of a reaction product of CMIT and MIT based on the total weight of components of the composition.

30. The aqueous composition of any preceding claim, wherein the aqueous composition further comprises no more than about 25 ppm of the reaction product of CMIT and MIT based on the total weight of components of the composition.

31. The aqueous composition of any preceding claim, wherein the aqueous composition further comprises no more than about 10 ppm of the reaction product of CMIT and MIT based on the total weight of components of the composition.

32. The aqueous composition of any preceding claim, wherein the aqueous composition is substantially free of the reaction product of CMIT and MIT based on the total weight of components of the composition.

33. The aqueous composition of any preceding claim, wherein the aqueous composition further comprises no more than about 5,000 ppm of zinc pyrithione or sodium pyrithione based on the total weight of components of the composition.

34. The aqueous composition of any preceding claim, wherein the aqueous composition further comprises no more than about 3,000 ppm of zinc pyrithione or sodium pyrithione based on the total weight of components of the composition.

35. The aqueous composition of any preceding claim, wherein the aqueous composition further comprises no more than about 1000 ppm of zinc pyrithione or sodium pyrithione, based on the total weight of components of the composition.

36. The aqueous composition of any preceding claim, wherein the aqueous composition further comprises no more than about 50 ppm of zinc pyrithione or sodium pyrithione, based on the total weight of components of the composition.

37. The aqueous composition of any preceding claim, wherein the aqueous composition is substantially free of zinc pyrithione or sodium pyrithione, based on the total weight of components of the composition.

38. The aqueous composition of any preceding claim, wherein when the aqueous composition is or is included in a coating, and the coating is applied to a substrate and cured, the coating exhibits equivalent or better scrub durability as compared to a second coating having the same composition, except that the second coating contains an equivalent amount of isothiazolinone to the nitrogen-containing organic additive instead of the nitrogen-containing organic additive, as measured according to ASTM D2486-96 (Standard Test Method for Scrub Resistance of Wall Paints).

39. The aqueous composition of any preceding claim, wherein when the aqueous composition is or is included in a coating, and the coating is applied to a substrate and cured, the coating exhibits equivalent or better KU viscosity reduction at about 140 °F over a period of about 3 weeks as compared to a second coating having the same composition, except that the second coating contains an equivalent amount of isothiazolinone to the nitrogen-containing organic additive instead of the nitrogen-containing organic additive, as measured according to ASTM D562-10 (Standard Test Method for Paint Consistency Using a Stormer-Type Viscosity Cup to Measure Krebs Units (KU) Viscosity).

40. The aqueous composition of any preceding claim, wherein when the aqueous composition is or is included in a coating, and the coating is applied to a substrate and cured, the coating exhibits equivalent or better wash resistance as compared to a second coating having the same composition, except that the second coating contains an equivalent amount of isothiazolinone to the nitrogen-containing organic additive instead of the nitrogen-containing organic additive, as measured according to ASTM D4828-94 (2003) "Standard Test Method for Washability of Organic Coatings".

41. The aqueous composition of any preceding claim, wherein the aqueous composition is shelf-stable, as defined herein.

42. The aqueous composition of any preceding claim, wherein the aqueous composition yields, on average, less than 1 x 10 3 CFU / mL when the aqueous composition is subjected to a microbial challenge test as defined herein.

43. The aqueous composition of any preceding claim, wherein the aqueous composition yields, on average, less than 5 x 10 2 CFU / mL when the aqueous composition is subjected to a microbial challenge test as defined herein.

44. The aqueous composition of any preceding claim, wherein the aqueous composition comprises at least 17 weight percent of polymeric binder solids.

45. The aqueous composition of any preceding claim, wherein aqueous composition is a coating, and the coating further comprises a pigment.

46. The coating of claim 42, wherein the coating is a 1K waterborne coating.

47. The coating of any of claims 42 or 43, wherein the coating comprises about 10 weight percent to about 30 weight percent titanium dioxide.

48. A coating composition comprising: (a) from about 7 wt% to about 30 wt% of the polymer solids of a film-forming polymeric binder; (b) from about 50 ppm to about 50,000 ppm by weight of a nitrogen-containing organic additive comprising at least one compound comprising four nitrogen centers, each nitrogen center being connected to at least one other nitrogen center by at least one saturated divalent hydrocarbon linking group, wherein the nitrogen-containing organic additive is a post-addition component of the coating composition and is selected from the group consisting of N,N'-bis(2-aminoethyl)-l,2-ethanediamine, N,N'-bis-(2-aminoethyl)piperazine, N[(2-aminoethyl)2-aminoethyl]piperazine, tris-(2-aminoethyl)amine), and mixtures thereof; (c) from at least 10 wt% to about 30 wt% of titanium dioxide; and (d) water.

49. A method of preserving an aqueous composition, the method comprising: adding the nitrogen-containing organic additive of any preceding claim to a composition comprising at least a carrier and a film-forming binder to produce the aqueous composition of any preceding claim.

50. A coated article comprising: the coating composition of any preceding claim coated on a substrate, wherein the substrate comprises wood, plastic, drywall, concrete, metal, rubber, or a natural or synthetic polymer.

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