Aqueous and coating compositions, coating, method of preserving an aqueous composition, and coated article.

Description

57 Aqueous and coating compositions, coating, method of preserving an aqueous composition, and coated article. Field of Invention

[001] This application relates to the preservation of coatings and coating compositions by means of additives that exhibit multifunctional effects, including reduced susceptibility to microbial deterioration and improved or maintained paint or coating performance. Background

[002] Coating compositions, such as paints, typically contain four essential ingredients: carrier liquid, binder, pigment, and additives. Each of these ingredients may comprise a single component or several different items mixed into the paint.

[003] The carrier liquid is a fluid component of the coating composition that serves to transport all the other components of the composition. The carrier liquid is part of the wet coating composition and generally evaporates as the coating forms a film and dries on a surface. In latex paints, the carrier liquid is usually water. In oil-based or solvent-based paints, the carrier liquid is usually an organic solvent. The amount and type of carrier liquid are generally determined by the properties of the other paint components.

[004] The binder component of a coating composition enables the coating to form a film and adhere to a substrate, and provides durability to the cured coating, among other benefits. In a water-based coating composition, the binder comprises a polymeric binder, generally selected from (meth)acrylics, vinyl acrylics, styrene acrylics, water-based polyurethane dispersions (PUDs), binders Petition 870250091017, dated 06 / 10 / 2025, p. 15 / 82 / 57 water-based alkyds, water-based alkyd-PUD hybrids or combinations thereof. In the polymeric binder of a water-based coating composition, the polymeric binder is generally provided as an aqueous latex, with latex particles in an emulsion or dispersion in water as the carrier liquid. In a solvent-based paint or coating, the binder or film-forming agent comprises an acrylic-amino, alkyd, polyurethane or epoxy resin.

[005] Pigments give the coating both decorative and protective features, among other benefits. Pigments are dispersed solid particles used to impart various qualities to the paint, including, but not limited to, color, opacity, and durability. The coating may also include other organic or inorganic extenders, which can provide additional performance characteristics, including modifying the surface appearance (e.g., gloss / flatness and luster) of the coating.

[006] Other additives may be included in paints and coating compositions. Additives are typically used in relatively low concentrations in the paint or coating composition compared to the binder, but contribute to various properties of paints and coatings, including rheology, stability, paint performance, and application quality. Paints and coating compositions are complex formulations, and different additives can interact to have unpredictable, favorable, or unfavorable impacts on the various properties of the paint or coating.In the formulation of a paint or coating, the addition or modification of a paint or coating formula with different additives or other components must be carefully balanced so that important properties of the paint or coating, such as washability, abrasion resistance, heat and aging stability, and microbial preservation, to name just a few, are preserved. Petition 870250091017, dated 06 / 10 / 2025, page 16 / 82 / 57, that they be maintained, improved, or subjected only to minimal and tolerable decreases in quality.

[007] Biocides, which are also called antimicrobial agents, are additives that have microbiostatic or microbicidal properties. In coating composition formulations, biocides can have a preservative effect to prevent microbial deterioration in the can or wet state and ensure the stability of the paint or coating composition, and can also provide dry film preservation, whereby a biocide in a dry paint or coating film prevents or mitigates the growth of microbes, usually in the form of mold or fungi, on the coating surface. Deterioration of a coating composition due to microbial contamination or undesirable amounts of microbial growth in the container can cause putrefaction, reduced pH, gas formation, and changes in viscosity that can render the coating composition unusable or give it undesirable properties.As a result, paint and coating compositions must be properly preserved so that they remain usable throughout manufacturing, distribution, and storage.

[008] Several 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 US Patent 9,131,683 B2, act as biocides by damaging cell membranes and killing bacteria. Organic antimicrobial additives additionally include conventional isothiazolinone additives including, but not limited to, benzisothiazolinone (BIT), methylisothiazolinone (MIT), and 2-methyl-4-isothiazolin-3-one (CMIT). While effective biocides for preserving paints, isothiazolinones such as BIT, MIT, and Petition 870250091017, dated 06 / 10 / 2025, page 17 / 82 / 57 CMITs are increasingly exposed to supply chain / manufacturing risks, including limited production sources, as well as potential emerging regulations. There are also inorganic antimicrobial additives, for example, those containing metal ions, such as silver-based, zinc-based (including zinc pyrithiones), and copper-based biocides. Other inorganic antimicrobial additives include phosphates, metal ions, metals, and zeolites or hydroxyapatites containing biocide. These conventional antimicrobial additives may present similar supply chain or regulatory risks, and thus there is a need to find ways to adequately preserve paints and coatings using fewer, or no, conventional biocides.

[009] Summary of the Invention

[0010] Aqueous compositions are disclosed including a carrier liquid, a film-forming polymeric binder, and a nitrogenous organic additive including at least one compound comprising four nitrogen centers, each nitrogen center being linked to at least one other nitrogen center by at least one saturated divalent hydrocarbon linking group. In some embodiments, the aqueous composition is a latex emulsion or polymeric dispersion, paint, coating composition, caulking compound, or sealant. Optionally, the nitrogenous organic additive is a post-addition component of the emulsion, dispersion, paint, coating composition, caulking compound, or sealant.

[0011] In some approaches, the coating compositions of the present disclosure provide maintained or enhanced coating performance characteristics, such as maintained or reduced susceptibility to microbial deterioration, maintained or enhanced washability, maintained or enhanced abrasion resistance, and maintained or enhanced aging or thermal aging stability compared to coating compositions that do not include the nitrogenous organic additive. In some Petition 870250091017, dated 06 / 10 / 2025, page 18 / 82 / 57 approaches, the aqueous compositions of the present disclosure maintain acceptable resistance to microbial growth, despite including reduced amounts of certain known antimicrobial additives.

[0012] The summary of this disclosure is not intended to describe every embodiment disclosed or every implementation of this disclosure. The following description exemplifies illustrative embodiments more particularly. Throughout this disclosure, guidance is provided by means of lists of examples, which may be used in various combinations. In each case, any lists mentioned serve only as a representative group and should not be construed as an exclusive or exhaustive list. Thus, the scope of this disclosure should not be limited to the specific illustrative structures described herein, but extends at least to the structures described by the language of the claims, and to equivalents of those structures. Any of the elements that are positively cited in this descriptive report as alternatives may be explicitly included in the claims or excluded from the claims, in any combination, as desired.Although various theories and possible mechanisms may have been discussed here, in no case should such discussions serve to limit the matter claimed. Definitions

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

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

[0015] As used herein, the term 2K or two-component, when used with reference to a coating composition, means Petition 870250091017, dated 06 / 10 / 2025, p. 19 / 82 / 57, states that the coating composition comprises two parts that are kept separate until the time of application. Typically, 2K coating compositions are reactive, with one of said two parts serving to activate the other of said two parts when the parts are combined to initiate the curing or hardening of the 2K coating composition.

[0016] As used herein, the terms adequate preservation or adequately preserved, when used with reference to a composition, mean that the composition passes the microbial challenge test described below.

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

[0018] The term component refers to any compound that includes a specific feature or a specific structure in a composition. Examples of components include compounds, monomers, oligomers, polymers, and organic groups contained therein. One skilled in the art will recognize that this definition of component is distinct from the term used in the context of a one-component or two-component coating composition, as defined above.

[0019] The term double bond is not 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 that include a carbon-carbon double bond (i.e., -C=C-).

[0020] The term film formation means that a composition includes a sufficient quantity of binder so that, when applied to a surface and cured, the composition forms a continuous coating film.

[0021] The term volatile organic compound (VOC - volatile organic Petition 870250091017, dated 10 / 06 / 2025, page 20 / 82 / 57, compound), as defined by the Environmental Protection Agency (EPA) in 40 CFR 51.100(s), refers to any carbon compound, excluding carbon monoxide, carbon dioxide, carbonic acid, metal carbides or carbonates, and ammonium carbonate, that participates in atmospheric photochemical reactions, except for certain exempt compounds identified by the EPA. As used herein, volatile organic compound content (VOC content) in an aqueous composition, such as a coating composition, aqueous polymer binder composition, or other composition, means the weight of VOC per volume of the coating solids. VOC may be recorded, for example, as grams of VOC per liter (g / L). With respect to a latex polymer described herein, VOC may also be recorded as grams of VOC per 100 grams of latex polymer (with reference to grams of solids in the latex).VOC content is measured using the ASTM D6886-18 method with methyl palmitate as a marker.

[0022] As used herein, the term glass transition temperature or Tg refers to the midpoint of the temperature range at which an amorphous solid material undergoes a reversible transition from a glass-like state to a rubber-like state. 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 polymers is well known in the art. Tg can be measured using differential scanning calorimetry. Composition samples for differential scanning calorimetry (DSC) testing are weighed in standard sample trays and analyzed using the standard DSC heat-cold-heat method. A sample is heated at 10 °C per minute from 50 °C to 150 °C, then cooled to Petition 870250091017, dated 06 / 10 / 2025, p. 21 / 82 / 57 -75 °C at 20 °C / min, then stabilized at -75 °C before reheating to 150 °C at 10 °C / min. Glass transition temperatures are calculated from the thermogram of the last heat cycle. The glass transition is measured at the inflection point of the transition.

[0023] Luster may sometimes be called gloss. In a coating, a glossy finish indicates that the surface that has a coating applied to it (i.e., is finished) is shiny or glass-like. The gloss of a surface is described as the reflection of light from the surface that is independent of color. The ASTM D523 method can be used to measure gloss or shine. The prescribed angle at which light is reflected off the surface may vary, but for the purposes of this disclosure, Luster 85 is measured at 85° relative to the light-reflecting surface. The ASTM D523 method can also be used to describe Gloss 60, which is measured at 60° relative to the light-reflecting surface. Gloss may also refer to the intensity of gloss measured at 20, 60, or 85 degrees and is determined according to ASTM D523. One skilled in the art is able to determine relative levels of gloss (low versus high) in the context of each coating.

[0024] The term substantially VOC-free means that the composition contains less than about 50 g / L of VOCs. Unless otherwise indicated, the terms low in VOC and substantially VOC-free are used interchangeably in the present invention. The term essentially VOC-free means that the composition contains less than 5 g / L of VOCs. The terms zero VOC and essentially VOC-free are used interchangeably in the present invention.

[0025] The term substantially free, when applied to components of a composition and not to the VOC content, means that the composition contains no more than about 1%, by weight, of a specific component, based on the total weight of solids in the composition. For example, Petition 870250091017, dated 06 / 10 / 2025, page 22 / 82 / 57: A composition that is substantially free of conventional biocide contains no more than about 1% by weight of conventional biocide as a percentage of the composition's solids weight. A composition that is essentially free when applied to components of a composition and not to VOC content means that the composition contains no more than about 0.04% by weight of the material. A composition that is completely free when applied to components of a composition and not to VOC content means that the composition contains no more than trace amounts of the material as a percentage of the composition's solids base.

[0026] As used herein, the term container means any vessel (with or without a lid or other type of closure system) used to store, mix, tint or color a paint formulation and includes the 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 abrasion resistance, as used herein, refers to the ability of the surface of a coating film or paint film to resist wear or to maintain its original appearance when rubbed with or against an abrasive surface, typically during cleaning. Abrasion resistance is measured according to ASTM D2486-96 (Standard Test Method for Abrasion Resistance of Wall Paints). As reported according to the standard test method, a higher number of exfoliants indicates greater abrasion resistance.

[0028] The term pigment includes both dispersible and colored solid particulate materials and dispersible or soluble colored coloring materials, the material imparting a visibly perceptible color to a paint or coating when 5% by weight (in the case of a dispersible and colored solid particulate material) or 0.05% by weight (in the case of a Petition 870250091017, dated 06 / 10 / 2025, page 23 / 82 / 57 dispersible or soluble colored dye) of the material is added to (e.g., dispensed in) the paint or coating. The presence or absence of visually perceptible color can be evaluated by preparing paint or coating pull samples with and without the pigment, molding such samples as coated films of 25 micrometers (µm) dry thickness onto the white portion of a BYKGardner paint pull opacity chart No. PA-2811 (available from BYK-Gardner USA) or comparable chart, and examining the coated films under normal interior ceiling light illumination. Pigments can also impart opacity to a coating without significant effect on color.

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

[0030] The term post-addition component or post-additive refers to a component of a coating composition or aqueous polymer binder composition that may be added at any stage during the mixing of a coating composition or polymer binder composition before application or curing of the composition, but after polymerization of the polymer binder from monomers.

[0031] Unless otherwise indicated, a reference to a (meth)acrylate compound (where meth is in parentheses) is intended to include both acrylate and methacrylate compounds. For example, the term (meth)acrylate polymer independently includes each of the acrylate homopolymers, methacrylate homopolymers, and copolymers that include interpolymerized acrylate and methacrylate monomers. Petition 870250091017, dated 06 / 10 / 2025, page 24 / 82 / 57

[0032] The term multi-stage, as used here in relation to a latex, means that the latex polymer was made using isolated and sequential loads of two or more monomers or mixtures of monomers, or was made using a continuously varying load of two or more monomers. A multi-stage polymer is distinct from a single-stage polymer made using one type of monomer mixed with distinct polymeric starting particles.

[0033] The terms water-based or water-based refer to compositions that include a vehicle that has more than 50% water by weight as a percentage of the total weight of the vehicle.

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

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

[0036] The term coating composition encompasses paints and also aerosol coatings, caulking compounds, colorants and sealants. Coating compositions may be suitable for use on internal or external surfaces of buildings or constructions, for example, walls, finishes, floors, platforms, wooden or metal handrails, ceilings, roofs (including metal shingles, asphalt shingles and ceramic shingles), roads, sidewalks, etc.

[0037] The term paint means a coating composition including pigment and binder which, when applied so as to form a Petition 870250091017, dated 06 / 10 / 2025, page 25 / 82 / 57 A thin wet coating film (e.g., 100 pm) on a freshly sanded smooth wood surface will, upon drying, conceal both the grain and texture of the wood and present a new surface with its own appearance.

[0038] The term includes and its variations do not have a limiting meaning when these terms appear in the description and claims.

[0039] The terms preferred and preferred refer to embodiments that may produce certain benefits under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, mention of one or more preferred embodiments does not imply that other embodiments are not useful and is intended to exclude other embodiments from the scope of the invention or claims.

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

[0041] Here too, references to numerical ranges by test endpoints include all numbers contained within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). Furthermore, the revelation of a range includes the revelation of all sub-ranges included within the wider range (e.g., 1 to 5 reveals 1 to 4, 1.5 to 4.5, 1 to 2, etc.).

[0042] Reference throughout this descriptive report to aspects, an aspect, some aspects, approaches, an approach, some approaches, a (1) modality, a specific modality, certain modalities or some modalities etc., means that a specific resource, configuration, composition or specific property is described Petition 870250091017, dated 06 / 10 / 2025, p. 26 / 82 / 57, in connection with the modality, is included in at least one modality of disclosure. Therefore, the appearance of these phrases in various parts throughout this descriptive report does not necessarily refer to the same modality of disclosure, although in both cases the same term (e.g., aspect or approach) is present. Furthermore, particular features, configurations, compositions, or characteristics may be combined in any suitable manner in one or more modalities. Detailed description

[0043] The present disclosure provides aqueous compositions that include a nitrogenous organic additive, as further defined herein, as well as a method of preserving aqueous compositions by adding one or more nitrogenous organic additives. Such compositions have been found to exhibit reduced susceptibility to microbial deterioration in the liquid state. In some embodiments, the compositions may provide enhanced or maintained coating performance characteristics, including, but not limited to, enhanced or maintained physical durability, as indicated by abrasion testing, enhanced or maintained washability, and enhanced or maintained dispersion stability, as shown by heat aging stability or aging stability, compared to a coating that does not contain the nitrogenous organic additive.These characteristics are surprisingly found without the need, or with a reduced need, for the use of conventional biocides such as isothiazolinones, pyrithiones, inorganic biocides or other biocides. As further detailed herein, such aqueous compositions may be a coating composition, such as a paint, caulking compound or sealant, or an aqueous latex or an aqueous dispersion or emulsion of a polymeric binder.

[0044] The present disclosure comprises, in some embodiments, a coating composition comprising water, a binder Petition 870250091017, dated 06 / 10 / 2025, page 27 / 82 / 57 polymeric film-forming compound, pigment and additives, wherein such additives include, but are not limited to, nitrogenous organic additives. In some embodiments, the coating composition includes minimal or no pigment and is considered a clear coat type coating. In some embodiments, the coating compositions are substantially, essentially or completely free of conventional biocides.

[0045] In some embodiments, the present disclosure comprises an aqueous polymer binder composition comprising water, polymer binder and the nitrogenous organic additive. In some embodiments, the aqueous polymer binder composition is substantially, essentially or completely free of conventional biocides.

[0046] In other embodiments, the present disclosure provides a coated article wherein the article is coated with the coating compositions containing nitrogenous organic additive disclosed herein, the coating composition being cured on a substrate. In certain embodiments, said coating compositions are formulated to coat the external or internal surfaces of an architectural structure. In other embodiments, the coating compositions are formulated to coat the interior of a beverage can, to coat a steel coil, to coat a plastic, to coat an industrial tank (e.g., water tanks, tanks for bulk chemicals, etc.), or for protective and marine applications. In some embodiments, the coating compositions of the present disclosure can be used to coat wood, plastic, drywall, concrete, metal, rubber, or other natural or synthetic polymers.In some approaches, the compositions of the present disclosure may be employed as a base coat or a topcoat. Other coating applications are considered within the scope of the present invention and disclosure, even if not expressly stated. Petition 870250091017, dated 06 / 10 / 2025, p. 28 / 82 / 57 revealed here. Aqueous compositions

[0047] The aqueous compositions of the present disclosure include, but are not limited to, paints, adhesives, sealants, dyes, caulking compounds and aqueous pastes of minerals and pigments, as well as water-based emulsions and water-based dispersions of polymeric binders and resins. Nitrogenous organic additives

[0048] The nitrogenous organic additives in the compositions of the present disclosure enable the formulation of coating compositions and aqueous polymer binder compositions that are adequately preserved or have reduced susceptibility to microbial deterioration. Such compositions provide other enhanced or maintained coating performance characteristics including, but not limited to, abrasion durability, washability, and heat aging stability or aging stability. In some embodiments, the coating compositions and aqueous polymer binder compositions of the present disclosure can be provided without the need, or with a reduced need, for the use of conventional biocides such as isothiazolinones, pyrithiones, inorganic biocides, or others.

[0049] The organic nitrogen additives useful in the present disclosure include compounds or mixtures of compounds that each include four nitrogen centers, with each nitrogen center linked to at least one other nitrogen center by at least one hydrocarbon linkage group. In exemplary embodiments, the hydrocarbon linkage groups are each saturated and divalent. In exemplary embodiments, the hydrocarbon linkage groups are each independently a linear or branched C1, C2, C3, or C4 chain.

[0050] In additional exemplary embodiments, nitrogenous organic additives are selected from the group consisting of compounds Petition 870250091017, dated 06 / 10 / 2025, p. 29 / 82 16 / 57 that have formulas I, II, III and IV, and mixtures thereof: Formula 1 NH2— Rx— NH — R2— NH — R3—NH2 Formula II NH2—R4—NN—R7— NH2 Formula III NN—R10—NH—Ru—NH2 Formula IV nh2IR13 I . N ^R12 nh2nh2

[0051] In some approaches, each of RI to R4, R7, and RIO to RI4 is a saturated divalent hydrocarbon chain with 1 to 3 carbons, each of R5, R6, R8, and R9 is a saturated divalent hydrocarbon chain with 2 to 3 carbons, and each of RI to R14 is the same or different. In some embodiments, each of RI to R4, R7, and RIO to R14 is a saturated hydrocarbon chain with 1 to 2 carbons, each of R5, R6, R8, and R9 is a saturated hydrocarbon chain with 2 to 3 carbons, and each of RI to R14 is the same or different.

[0052] In some embodiments, suitable nitrogenous organic additives include compounds selected from the group consisting of amino acid hydrazides, carbazidocarboxylic acid hydrazides, bis Petition 870250091017, dated 06 / 10 / 2025, page. 30 / 82 / 57 hydrazides and bis-carbazides, diethylene triamine, N,N'-bis(2-aminoethyl)-1,2ethanediamine, tetraethylene pentamine, pentaethylene hexamine, tris-(2aminoethyl)amine, N-(2-piperazinoethyl)-ethylene diamine, N,N'-bis-(2aminoethyl)-piperazine, N,N,N'-tris-(2-aminoethyl)ethylene diamine, N-(2aminoethyl)-N'-(2-piperazinoethyl-1)-ethylene diamine, N,N-bis-(2-aminoethyl)-N(2-piperazinoethyl)amine, N,N-bis-(2-piperazinoethyl)-amine, polyethylene imine oligomers comprising at least four functional monomeric units, N-(2-aminoethyl)-1,3-propane diamine, oligomers of polyoxypropylene amine comprising at least four functional monomeric units, tetrapropylene pentamine, tripropylene tetramine and N,N-bis-(3-aminopropyl)ethylene diamine and mixtures thereof.

[0053] In some approaches, nitrogenous organic additives do not include any aryl functional groups in their chemical structure.

[0054] In some preferred approaches, suitable organic nitrogen additives include compounds 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) or a mixture thereof.

[0055] In some other preferred approaches, the suitable organic nitrogen additive is a mixture called triethylene tetramine or TETA™ (available from Dow Chemical Company, Midland, MI, USA). TETA™ is a mixture of four organic nitrogen compounds, each having four nitrogen centers, with each nitrogen center linked to at least one other nitrogen center by at least one saturated divalent hydrocarbon linkage group. The four organic nitrogen compounds in TETA™ consist of N,N'-bis(2-aminoethyl)-1,2-ethanediamine, N,N'-bis-(2-aminoethyl)piperazine, N[(2-aminoethyl)2-aminoethyl]piperazine, and tris-(2-aminoethyl)amine. In some approaches, TETA™ may additionally include from about 5% by weight to about 50%, Petition 870250091017, dated 06 / 10 / 2025, page 31 / 82 / 57 by weight, of a vehicle as a percentage of the weight of the nitrogenous organic additive, in additional embodiments, about 50% by weight, to about 30% by weight of vehicle and in further embodiments, about 20% by weight. In some preferred approaches, the vehicle is water, but it may be acetone or methanol or other suitable vehicles.

[0056] In some approaches, the aqueous composition includes at least 50 ppm of the nitrogenous organic additive (based on the weight of the total components of the compositions). In some approaches, the aqueous composition includes at least 60 ppm of the nitrogenous organic additive, in additional embodiments at least 75 ppm of the nitrogenous organic additive, in additional embodiments at least 125 ppm of the nitrogenous organic additive, in additional embodiments at least 250 ppm of the nitrogenous organic additive, in additional embodiments at least 400 ppm of the nitrogenous organic additive, in additional embodiments at least 1500 ppm of the nitrogenous organic additive, and in still additional embodiments at least 5000 ppm of the nitrogenous organic additive.

[0057] In some useful embodiments, the aqueous composition includes a maximum of 200,000 ppm of the nitrogenous organic additive (based on the weight of the total components of the composition). In further embodiments, the aqueous composition includes a maximum of 100,000 ppm of the nitrogenous organic additive, in further embodiments a maximum of 75,000 ppm of the nitrogenous organic additive, in further embodiments a maximum of 50,000 ppm of the nitrogenous organic additive, in further embodiments a maximum of 30,000 ppm of the nitrogenous organic additive, in further embodiments a maximum of 20,000 ppm of the nitrogenous organic additive, and in still further embodiments, a maximum of 10,000 ppm of the nitrogenous organic additive.

[0058] The organic nitrogen additives useful in the present disclosure enable the formulation of aqueous compositions that are adequately preserved or have reduced susceptibility to microbial deterioration and Petition 870250091017, dated 06 / 10 / 2025, page 32 / 82 / 57 other enhanced or maintained coating performance characteristics, including, but not limited to, abrasion durability, washability, and heat aging stability or aging stability. In embodiments, said coating compositions may be provided without the need or with a reduced need for the use of conventional biocides such as isothiazolinones, pyrithiones, or inorganic or other materials. Carrier fluid

[0059] The compositions of the present disclosure comprise a carrier liquid prior to application to a substrate. The carrier liquid may be water, include water, or be water-based (>50% water in the carrier liquid system). The carrier liquid may further include a solvent selected from aliphatic, cycloaliphatic, and aromatic hydrocarbons such as colorless petroleum distillate (white spirit), cyclohexane, toluene, xylene, and naphtha-based solvents, esters such as methoxypropyl acetate, n-butyl acetate, and 2-ethoxyethyl acetate; octamethyltrisiloxane or other solvents used in solvent-based systems and mixtures thereof. Carrier liquids may also be other liquids used in paints, adhesives, sealants, dyes, caulking compounds, and aqueous pastes of minerals and pigments. The compositions of the present disclosure may include one or more carrier liquids.In some approaches, the carrier liquid or liquids are selected to provide an aqueous composition that is substantially VOC-free, essentially VOC-free, VOC-free, or zero VOC.

[0060] In a preferred embodiment of this disclosure, the carrier liquid of a coating composition is water or is water-based or water-based (>50% by weight of water in the carrier liquid system).

[0061] In some embodiments, carrier liquids may constitute 5 to 60% by volume of a coating composition. In Petition 870250091017, dated 06 / 10 / 2025, page 33 / 82 / 57 In some forms, the carrier liquids may constitute 40 to 60% of an aqueous polymeric binder composition. Polymeric binders

[0062] The aqueous compositions according to the present disclosure also comprise a film-forming polymeric binder.

[0063] Film-forming polymeric binders useful in coating compositions are known in the art and include water-based polymeric binders such as acrylics, vinyl acrylics, styrene acrylics, water-based polyurethane dispersions (PUDs), water-based alkyd binder resins, water-based alkyd-PUD hybrid resins, and mixtures thereof. The polymeric binder is present in the aqueous composition in sufficient quantity to form a continuous film when the aqueous composition is applied to a substrate and allowed to cure. In some embodiments, the aqueous composition may comprise, for example, at least about 17% by weight to about 60% by weight of polymeric solids based on the total weight of the components of the aqueous composition.

[0064] In some embodiments, the polymeric binder is completely free or essentially free of any functional monomeric units comprising reactive ketone moieties that crosslink the polymeric binder during film formation. In some embodiments, such reactive ketone moieties include diacetone acrylamide (DAAM) and acetoacetoxyethyl methacrylate (AAEM).

[0065] In certain preferred embodiments, the polymeric binder is a latex polymer. The latex polymers of the present invention may comprise a single-stage or multi-stage latex polymer. In some embodiments, the aqueous compositions of the present disclosure include 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. Petition 870250091017, dated 06 / 10 / 2025, p. 34 / 82 / 57

[0066] A multi-stage latex does not necessarily exhibit two glass transition temperatures measured by differential scanning calorimetry (DSC). For example, a DSC curve for a multi-stage latex made using isolated loads of two or more monomers may exhibit two or more Tgs, but it may exhibit only one Tg. In cases where a DSC curve shows only a single Tg inflection point, or even no Tg inflection point, it can be difficult to determine whether the latex is single-stage or multi-stage, as the observation of a Tg inflection point depends on several factors, including the relative concentration of monomers in a specific stage.Thus, the presence or absence of Tg inflection points on a DSC curve is not decisive as to whether a specific latex polymer is single-stage or multi-stage, but the Tgs of a multi-stage latex can be described in terms of the theoretical Tg values ​​for each monomer stage, as determined by the Fox equation.

[0067] Several methods can be used to prepare the multistage latex described herein, including, for example, sequential monomer feed flow and continuously variable monomer feed techniques. In a sequential monomer feed process, a first monomer or mixture of monomers is fed and polymerization is initiated, and a second monomer (i.e., a different monomer, or a mixture of monomers present in ratios different from those in the first monomer mixture) is fed during later stages of polymerization. In a variable monomer feed process, a first monomer composition is fed, followed by the addition of a second monomer at certain points in the polymerization process and at different rates. By controlling the type of monomers selected for the feed process, a multistage latex suitable for coating compositions or inks can be obtained. Petition 870250091017, dated 06 / 10 / 2025, page 35 / 82 / 57 low VOC can be formed and the latex preferably provides excellent performance characteristics, such as blocking resistance, abrasion resistance and the like, for such coating or paint formulations.

[0068] Preferred multistage latexes include at least two stages (e.g., two, three, or four or more stages) with different Tg values ​​(not considering any Tg that may be associated with an optional starter particle). In some embodiments, each of the at least two stages constitutes at least 15 percent by weight (% by weight), at least 20 percent by weight, at least 25 percent by weight, at least 30 percent by weight, at least 35 percent by weight, or at least 40 percent by weight of the multistage latex, based on the total weight of monomers used to produce the latex (not including the weight of any optional starter particle used).

[0069] In some approaches, the multistage latex described herein is produced by a sequential monomer feed process. In one aspect, polymerization begins with a higher Tg monomer feed stream followed by a lower Tg monomer feed stream and vice versa. In a preferred aspect, polymerization begins with a higher Tg monomer feed stream followed by a lower Tg monomer feed stream.

[0070] In some approaches, the multistage latex described here is produced using different monomer feed streams. The resulting polymer will typically have a DSC curve that does not exhibit Tg inflection points and can be said to have an essentially infinite number of Tg stages. The resulting multistage latex will have a high-to-low Tg gradient, or vice versa, depending on the order in which the high-Tg monomers are fed into the reaction.

[0071] In a preferred approach, multi-stage latex Petition 870250091017, dated 06 / 10 / 2025, page 36 / 82 / 57 described herein is produced by a sequential monomer feed process using at least two distinct monomer feed streams. In one aspect, a high Tg stage (i.e., a hard stage) is fed first into a reactor vessel and a low Tg stage (i.e., a soft stage) is added at a later stage of the process. A multi-stage latex can be formed and, after coalescence, the composition will typically exhibit two distinct Tg values, or at least one Tg corresponding to the monomer stage present in the higher concentration. In some cases, no distinct Tg can be observed or detected by DSC for a monomer or monomer mixture at a specific stage that is present in very small quantities relative to the other monomer or monomer mixture.

[0072] In one approach, multistage latex optionally includes an initial particle phase, i.e., a relatively small monomer or polymer particle, but the initial particle is neither required nor essential for the preparation or for the optimal performance of the multistage latex when used in a coating composition or paint formulation.

[0073] In one approach, the relative positions of the first and second phases can be internal and external, respectively, or vice versa. In another aspect, the first and second phases can be neighbors or adjacent. Without adhering to theory, it is believed that the relative position of the stages of multi-stage latex is influenced by the method used to produce the latex.

[0074] In one approach, by controlling the monomers used for each stage of the sequential monomer feeding process, a multi-stage latex with a desired minimum film forming temperature (MFFT) is obtained. The MFFT is the minimum temperature at which the composition comprising a latex Petition 870250091017, dated 06 / 10 / 2025, page 37 / 82 / 57 of multi-stage will form a continuous film, that is, the temperature below which coalescence does not occur. The MFFT of the composition comprising a multi-stage latex, as described herein, is preferably less than about 30 °C, more preferably less than about 20 °C.

[0075] In some approaches, the latex polymer is a single-stage latex, derived by polymerization in a single-stage process of an emulsion including one or more ethylenically unsaturated monomers. By controlling the type of monomers used in the emulsion polymerization, a single-stage latex suitable for low-VOC coating compositions or paints can be formed.

[0076] In some approaches, by controlling the monomers used in the synthesis of single-stage latex, a single-stage latex composition with the desired MFFT is obtained. The MFFT of the single-stage film-forming binder, as described herein, is preferably less than about 30 °C, more preferably less than about 20 °C.

[0077] The monomers interpolymerized in single-stage latex or multi-stage latex stages separately and preferably include one or more ethylenically unsaturated monomers.

[0078] In some embodiments, the single-stage latex monomers or the first and second stages of multi-stage latex separately and preferably include one or more polymerization products of (i) ethylenically unsaturated monomers, such as, for example, alkyl and alkoxy (meth)acrylates, vinyl esters of saturated carboxylic acids, monoolefins, conjugated dienes, optionally with (ii) one or more monomers, such as, for example, styrene, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, vinyl acetate, acrylonitrile, vinyl chloride and the like. In one embodiment, the latex polymer monomers optionally include one or more polyfunctional (meth)acrylate monomers. In one embodiment, the monomers include Petition 870250091017, dated 06 / 10 / 2025, page 38 / 82 / 57 also one or more ethylenically unsaturated carboxy-functional amide monomers, for example, ureido-functional monomers, such as monomers formed as the product of the reaction between aminoalkyl alkylene urea (for example, aminoethylene urea, for example) with an ethylenically unsaturated carboxylic acid or anhydride (for example, maleic anhydride, for example).

[0079] Suitable ethylenically unsaturated monomers of single-stage latex or 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 a dialkyl itaconate, such as dimethyl itaconate, diethyl itaconate, dipropyl itaconate, or dibutyl itaconate, methacrylate of 2-(acetoacetoxy)ethyl (AAEM), diacetone acrylamide (DAAM), acrylamide, methacrylamide, methylol (meth)acrylamide, styrene, α-methyl styrene, vinyl toluene, vinyl acetate, propionate, allyl methacrylate and mixtures thereof.Preferred monomers include styrene, methyl acrylate, methyl methacrylate, ethyl acrylate, methacrylic acid, DAAM, AAEM, n-butyl acrylate, tert-butyl acrylate, tert-butyl methacrylate, n-butyl methacrylate, itaconic acid esters, vinyl acetate, 2-ethylhexyl acrylate, biorenewable monomers and the like.

[0080] In some approaches, the latex polymer is completely free or essentially free of any functional monomeric units comprising reactive ketone moieties that crosslink the latex polymer during film formation. In some embodiments, such reactive ketone moieties include diacetone acrylamide (DAAM) or 2-(acetoacetoxy)ethyl methacrylate (AAEM). Petition 870250091017, dated 06 / 10 / 2025, page 39 / 82 / 57

[0081] Suitable polyfunctional (meth)acrylate monomers, such as, for example, di-, tri- and tetra-functional acrylates, such as dipropylene glycol diacrylate (DPGDA), glyceryl propoxylate triacrylate (GPTA), pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, mixtures thereof and the like. Preferred polyfunctional acrylate monomers include pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate and the like.

[0082] In some approaches, the latex polymer is formed from at least 80%, by weight, of two or more monomers selected from methyl methacrylate, ethyl acrylate, vinyl acetate, tert-butyl methacrylate, n-butyl methacrylate, styrene, tert-butyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl acrylate and itaconic acid esters, based on the total weight of monomers used to form the latex copolymers (and not considering any optional starting particles used).

[0083] In some approaches, the latex polymer is formed from at least 90%, by weight, of three or more monomers selected from methyl methacrylate, ethyl acrylate, vinyl acetate, tert-butyl methacrylate, n-butyl methacrylate, styrene, tert-butyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl acrylate and itaconic acid esters, based on the total weight of monomers used to form the latex polymers (and not considering any optional starting particles used).

[0084] Suitable ureido-functional monomers include, for example, monomers with the functionality -NR—(C=O)—NH—, where R can be H, substituted or unsubstituted C1-C10 alkyl, cycloalkyl or substituted or unsubstituted C3-C6 heteroalkyl and the like. Without adhering to theory, it is believed that ureido-functional monomers promote the wet adhesion of the coating compositions and coating and dye systems described herein to a substrate.

[0085] In certain approaches, latex copolymers (either Tg of Petition 870250091017, dated 06 / 10 / 2025, page 40 / 82 / 57. Single-stage, multi-stage, or gradient polymerization (STP) is typically produced using starter particles as a nucleating agent for polymerization. Such starter particles may be in the form of particulate inorganic starter particles (e.g., clay or glass particles), pre-formed particulate polymer starter particles (latex or non-latex polymer starter particles), or locally formed particulate polymer starter particles. The polymer starter particle may be an emulsion polymerized starter particle, but does not encompass polymeric surfactant. In certain embodiments, the starter particles are used in an amount not greater than 10% by weight, or not greater than 5% by weight based on latex polymer solids in the final latex.

[0086] In the present invention, whether the inorganic particulate starter particle, the pre-formed particulate polymer starter particle, or the locally formed particulate starter polymer, such starter particles shall not be considered as providing a stage of a multi-stage polymer or as providing a basis for designating a single-stage polymer or gradient Tg polymer made using such starter particle polymer as a multi-stage polymer.

[0087] In certain approaches, the latex copolymers of the present invention may additionally include crosslinking monomers with the ability to further react with a polymer chain at some point after the initial formation of the latex copolymer (e.g., during coating curing). The crosslinking reaction may occur through the application of energy, for example, through heat or radiation. Or, dyeing may activate the crosslinking polymer through changes in pH, oxygen content, solvent or vehicle evaporation, or other changes that cause a reaction to occur. Several chemicals are known in the art to produce crosslinking in latex. When used, one or more such crosslinking monomers are typically included in the copolymer. Petition 870250091017, dated 06 / 10 / 2025, page 41 / 82 / 57 latex in an amount of at least about 0.1% by weight, at least about 1.0% by weight, at least about 2% by weight, at least about 2.5% by weight, at least about 3% by weight, at least about 4% by weight, or at least about 5% by weight, based on the weight of one or more crosslinking monomers relative to the total weight of monomers used to form the latex copolymer. Although the amount of one or more such crosslinking monomers may vary widely, typically one or more crosslinking monomers are present in the latex copolymer in an amount of about 10% by weight or less, about 9% by weight or less, about 8% by weight or less, about 7% by weight or less, about 6% by weight or less, or about 5% by weight or less, based on the weight of one or more crosslinking monomers relative to the total weight of monomers used to form the latex copolymer.

[0088] Suitable examples of crosslinking carbonyl-containing monomers include acrolein, metacrolein, diacetone acrylamide, diacetone methacrylamide, 2-butanone methacrylate, formyl styrol, diacetone acrylate, diacetone methacrylate, acetonitrile acrylate, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, and vinylacetoacetate. These monomers do not normally affect crosslinking until during final film formation, for example, when the aqueous polymer emulsion simultaneously contains a suitable added amount of a polyamine compound as a crosslinker. Particularly suitable compounds of this type are the dihydrazides and trihydrazides of aliphatic and aromatic dicarboxylic acids with 2 to 20 carbon atoms. Polyamine compounds useful as crosslinkers for carboxyl functional groups include those that have 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, RO-NH2, RON=C<, R-NHC(=O)-O-NH2, where R is alkylene, alicyclic or aryl and can be. Petition 870250091017, dated 06 / 10 / 2025, page 42 / 82 / 57 replaced. Representative useful polyamines include ethylenediamine, isophorone diamine, diethylenetriamine, and dibutylenetriamine. In one embodiment of the invention, it is useful to use polyhydrazides as the polyamine compounds. Representative useful polyhydrazides include oxalic dihydrazide, adipic dihydrazide, succinic dihydrazide, malonic dihydrazide, glutaric dihydrazide, phthalic or terephthalic dihydrazide, and itaconic dihydrazide. 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.

[0089] Examples of suitable commercially available latex polymer dispersions of a film-forming binder include EPS 2720 and EPS 2799 available from Engineered Polymer Solutions of Marengo, IL, USA.

[0090] 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 that include about 20 to 60, preferably 30 to 55 percent by weight of methyl methacrylate; 0 to 40, preferably 10 to 30 percent by weight of 2-ethylhexyl acrylate; 10 to 60, preferably 15 to 55 percent by weight of butyl acrylate; about 0 to 30, preferably 10 to 20 percent by weight of butyl methacrylate; and about 0 to 10, preferably 1 to 5 percent by weight of methacrylic acid.

[0091] The aqueous compositions of the present disclosure may be latex-based coating compositions. Thus, in some embodiments, at least a majority (i.e., more than 50% by weight), more preferably substantially all or all of the resin solids in the coating compositions are latex polymers. Typically, the coating compositions include at least 20% by weight, at least 30% by weight, at least 40% by weight, or at least 50% by weight of solids. Petition 870250091017, dated 06 / 10 / 2025, page 43 / 82 / 57 latex polymers, based on the total solids of the coating composition. Certain high-gloss deep base coats may include 80% by weight or more of latex polymer solids. Although the upper amount of latex copolymer included in the coating composition may vary widely (e.g., depending on the amount of pigment included), typically coating compositions will include less than 90% by weight of latex polymer solids, based on total solids.

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

[0093] Exemplary biobased monomers include itaconic acid esters, bioderivative (meth)acrylic acid, and alkyl (meth)acrylic acid. In embodiments, the biobased monomers constitute at least 20% by weight, at least 30% by weight, or at least 40% by weight of the polymeric binder, by weight, of all interpolymerized monomers. Petition 870250091017, dated 06 / 10 / 2025, page 44 / 82 / 57 to form the polymeric binder. Other additives, pigments and fillers

[0094] Additional components may be added to the compositions disclosed herein. The components may be added to a polymer binder composition before, during, or after the completion of polymerization, or they may be added to another aqueous composition as a post-addition. The additional components or additives may be added to the reaction mixture of monomers used to produce a polymer binder, to an 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 complement solutions, crosslinking agents, preservatives, defoaming agents, anti-corrosion agents, thixotropes, rheology modifiers, colorants, and matting agents and the like.Additives may include one or more ingredients added to a paint or coating to modify its properties or improve its performance during storage, handling, application, and other subsequent stages. Desirable performance characteristics of a paint or coating include, for example, chemical resistance, hardness, gloss, reflectivity, appearance, and / or a combination of such properties and other similar properties. Preferred performance-enhancing additives include lacquers, waxes, matting agents, anti-scratch additives, abrasion additives, and the like.

[0095] Pigments and fillers can also be added to a coating composition (through pigment grinding) to provide a desired opacity, concealment, or PVC characteristics. Without delving into theory, it is generally understood that lower PVC coatings exhibit higher gloss and greater abrasion durability because such Petition 870250091017, dated 06 / 10 / 2025, p. 45 / 82 / 57 coatings contain a higher proportion by volume of polymeric binder, which is generally believed to provide gloss and durability to cured coatings.

[0096] Pigments may be supplemented with extenders or fillers, such as talc, Chinese clay, barites, carbonates, silicates and mixtures thereof, for example, magnesium silicates, calcium carbonate, aluminosilicates, silica and various clays; Organic materials including plastic spheres (e.g., polystyrene or polyvinyl chloride spheres), microspherical materials containing one or more voids, and vesicular polymeric particles (e.g., those discussed in U.S. Patents Nos. 4,427,835, 4,920,160, 4,594,363, 4,469,825, 4,468,498, 4,880,842, 4,985,064, 5,515,7084, 5,041,464, 5,036,109, 5,409,776 and U.S. Patent No. 5,510,422). Other exemplary extenders or fillers include expanded acrylonitrile / vinyl chloride particles EXPANCEL™ 551DE20 (available from Expancel Inc.)), SIL-CEL™ 43 glass microcellular fillers (available from Silbrico Corporation), FILLITE™ 100 ceramic spherical particles (available from Trelleborg Fillite Inc.), SPHERICEL™ hollow glass spheres (available from Potter Industries Inc.), 3M ceramic microspheres including grades G-200, G-400, G-600, G-800, W-210, W-410, and W-610 (available from 3M), hollow microspheres including 3M Performance Additives iM30K (also available from 3M), INHANCE™ UH 1900 polyethylene particles (available from Fluoro-Seal Inc.) and BIPHOR aluminum phosphate (available from Bunge Fertilizantes SA, Brazil).

[0097] In some embodiments, the aqueous coating compositions of the present disclosure may comprise at least about 5% and up to about 50%, by weight, of pigments based on the total solids present in the composition. In preferred embodiments, the pigments may comprise inorganic pigments, such as titanium dioxide. Petition 870250091017, dated 06 / 10 / 2025, p. 46 / 82 / 57 coating compositions may comprise, for example, about zero percent (for an ultradeep paint), at least about 11%, in weight, additionally for example, at least about 12%, by weight, additionally for example, at least about 13%, by weight, additionally for example, at least about 14%, by weight, additionally for example, at least about 15%, by weight, Additionally, for example, at least about 16%, additionally for example, at least about 17%, additionally for example, at least about 18%, additionally for example, at least about 19%, and further additionally for example, at least about 20% up to about 30%, by weight, of titanium dioxide. In some approaches, the coating compositions comprise more than 10% titanium dioxide based on the total solids present in the composition. Other colored pigments or dyes may also be added to the coating, alone or in combination, to produce a wide range of colored coatings. Suitable additional pigments may include calcium carbonate, talc, clay, silicates, aluminum silicates, calcium metasilicates, aluminum and potassium silicates, magnesium silicates, barium sulfates, nepheline syenite, feldspar, zinc oxides or sulfides, or others known to those skilled in the art.These additional colored pigments may be included in amounts of up to about 30% by weight, for example, from about 10% to about 20%, based on the total solids present in the compositions. In some cases, pigments may also refer to functional fillers that are water-insoluble solids. Such functional fillers may include solids that provide additional functional characteristics to the coating, for example, intumescent ingredients such as ammonium polyphosphates, melamines, pentaerythritol, and similar compounds. In a useful embodiment, the coating composition of the present invention is substantially free or entirely free of intumescent ingredients. Petition 870250091017, dated 06 / 10 / 2025, p. 47 / 82 / 57 as ammonium polyphosphates, melamines, pentaerythritol and similar compounds.

[0098] The coating compositions of the present disclosure preferably have a PVC of about 5 to about 60.

[0099] In one aspect, the compositions described herein may include a coalescing agent that aids in film formation, added to the monomer reaction mixture used to produce the polymer binder, to the aqueous polymer binder composition, or to a coating composition that includes the polymer binder. Suitable coalescing agents or coalescing compounds are dispersible in a polymer binder, coating, or paint composition that includes the polymer binder and facilitate film formation at temperatures lower than about 25°C and even at temperatures of 5 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%, and most preferably less than about 15%.Suitable coalescing agents include low-VOC compounds of the type described in detail at least in US Patents Nos. 6,762,230 and 7,812,079. Other suitable low-VOC coalescing agents include Optifilm (Eastman Chemical, Kingsport TN, USA), Loxanol (Cognis, Kankakee IL, USA, now BASF), Archer RC (ADM, Decator IL, USA) and similar products. Conventional coalescing agents such as Texanol (Eastman Chemical) and similar products may also be used, alone or in combination with other solvents such as, for example, 2-butoxyethanol (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol) and similar products, provided that low VOC levels are maintained in the coating composition or paint.

[00100] In one aspect, the compositions described herein may include a UV-VIS absorber. The compounds that are suitable for use in Petition 870250091017, dated 06 / 10 / 2025, pp. 48 / 82 / 57 present disclosure that UV-VIS absorbers include ultraviolet absorbers, visible light absorbers, or combinations thereof. These may also be called photoinitiators.

[00101] Suitable UV-VIS absorbers are insoluble in water. This means that the compounds will not dissolve to an appreciable extent (i.e., will not dissolve in an amount greater than 5% by weight) in water at the temperatures typically used to prepare coating compositions as described herein.

[00102] In certain embodiments, suitable UV-VIS absorbers are those compounds capable of absorbing ultraviolet and / or visible radiation within a range of 240 to 465 nm. For certain embodiments, they are capable of absorbing radiation in the range of 280 to 450 nm. In certain embodiments, suitable visible light absorbers are those compounds capable of absorbing visible radiation within a range of 420 to 450 nm. In certain embodiments, suitable ultraviolet absorbers are those compounds capable of absorbing UV radiation within a range of 240 to 400 nm. For certain embodiments, they are capable of absorbing UV radiation in the range of 280 to 400 nm and for certain embodiments in the range of 315 to 375 nm.

[00103] Examples of suitable ultraviolet absorbers include the following: benzophenone (available from Lamberti, Gallaratte, Italy); phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (available under the trade name IRGACURE 819DW from BASF, Florham Park, NJ, USA); ethyl-2,4,6-trimethylbenzoylphenylphosphinate (available under the trade name LUCIRIN TPO-L (formerly: LUCIRIN LR 8893) from BASF, Florham Park, NJ, USA); 2,4,6-trimethylbenzophenone and 4-methylbenzophenone (available as a mixture under the trade name ESACURE TZT from Lamberti, Gallaratte, Italy); 2,2-dimethoxy-1,2-diphenylethanone (i.e., Benzyldimethyl ketal) (available under the trade name ESACURE KB 1 from Lamberti); 1-hydroxycyclo. Petition 870250091017, dated 06 / 10 / 2025, p. 49 / 82 / 57 hexyl phenyl ketone (i.e., α-hydroxycyclohexylphenyl ketone) (available under the trade name ESACURE KS 300 available at Lamberti); 2-hydroxy-2-methyl-1-phenyl-1-propanone (available under the trade name ESACURE KL 200 available next to Lamberti); polymeric benzophenone (available under the trade name EBECRYL P39 available near Cytec, Woodland Park, NJ, USA); isopropyl thioxanthone (available under the trade name GENOCURE ITX available at Rahn USA, Aurora, IL, USA); methyl-obenzoyl-benzoate (available under the trade name GENOCURE MBB available with Rahn); Methylbenzoyl formate (available under the trade name GENOCURE MBF available from Rahn); benzoyl ethyl ether (available from Aldrich, St. Louis, MO, USA); 4'-ethoxyacetophenone (available from Aldrich, St. Louis, MO, USA); and combinations thereof.Other suitable UV-VIS absorbers are commercially available from BASF under the trade names IRGACURE and LUCERIN. Methyl-o-benzoyl-benzoate is a preferred UV-VIS absorber for, for example, improving gloss retention and / or resistance to dirt pickup.

[00104] The compositions of the invention may also include various other additives, including, but not limited to, thickeners, such as urethane-based thickeners, and acrylic thickeners in amounts of up to about 10% by weight, for example, about 1% to about 2%. Synthetic organic materials may also be incorporated; these include plastic granules, hollow spheres or other similar materials. Other optional components include glycols such as ethylene and / or propylene glycol in amounts of up to about 7% and other solvents such as diethylene glycol dibenzoate and dipropylene glycol dibenzoate in amounts of up to about 3%. The compositions may also contain pigment dispersing agents, which may be solvents or surfactants; additional liquid coating preservatives; additional dry film preservatives; Petition 870250091017, dated 06 / 10 / 2025, page 50 / 82 / 57 foam control agents, such as oils, fatty acids and silicones; slip and anti-scratch additives; adhesion promoters and / or other known coating additives. The compositions of the present invention may also comprise other biocides or preservatives, including, but not limited to, compounds containing metal ions, polymeric biocides, quaternary ammonium compounds, heterocyclic compounds, phenols, organometallics, aldehydes, proteins, peroxides, alcohols, enzymes, polypeptides and halogen-releasing compounds. Aqueous coating composition

[00105] In certain embodiments of the present invention, the nitrogenous organic additive can be added to a coating composition, such as an individual paint or mixed into other components of the coating composition at varying stages of the coating composition formation.

[00106] In some embodiments, the aqueous composition is a water-based coating composition. In some embodiments, the aqueous composition is a paint.

[00107] In some embodiments, the aqueous composition is a 1K coating composition.

[00108] In some embodiments, the aqueous composition is a 2K coating composition.

[00109] In some embodiments, the aqueous composition includes a maximum of 300 ppm of BIT based on the total components present in the aqueous composition. In additional embodiments, the aqueous composition includes a maximum of 150 ppm of BIT, in further embodiments, a maximum of 50 ppm of BIT. In some embodiments, the coating compositions are substantially BIT-free, essentially BIT-free, or completely BIT-free.

[00110] In some embodiments, the aqueous composition includes Petition 870250091017, dated 06 / 10 / 2025, p. 51 / 82 / 57 maximum 150 ppm of MIT based on the total components present in the composition. In additional embodiments, the aqueous composition includes a maximum of 50 ppm of MIT, in further embodiments, a maximum of 20 ppm of MIT. In some embodiments, the aqueous compositions are substantially free of MIT, essentially free of MIT, or completely free of MIT.

[00111] In some embodiments, the aqueous composition includes a maximum of 40 ppm of the MIT and CMIT reaction product based on the total components present in the composition. In further embodiments, the aqueous composition includes a maximum of 25 ppm of the MIT and CMIT reaction product, and in further embodiments, a maximum of 10 ppm of the MIT and CMIT reaction product. In some embodiments, the aqueous compositions are substantially free of the MIT and CMIT reaction product, essentially free of the MIT and CMIT reaction product, or completely free of the MIT and CMIT reaction product.

[00112] In some embodiments, the aqueous compositions include a maximum of 5,000 ppm of zinc pyrithione or sodium pyrithione based on the total components present in the composition. In further embodiments, the paint or coating composition includes a maximum of 3,000 ppm of zinc pyrithione or sodium pyrithione, in further embodiments, a maximum of 1,000 ppm of zinc pyrithione or sodium pyrithione, and in still further embodiments, a maximum of 50 ppm of zinc pyrithione or sodium pyrithione. In some embodiments, the coating compositions are 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. Aqueous polymeric binder compositions

[00113] In certain embodiments of the present invention, the nitrogenous organic additive can be added to an aqueous polymer binder composition individually or mixed into other components. Petition 870250091017, dated 06 / 10 / 2025, page 52 / 82 / 57 of the composition in varying stages of composition formation. In some useful embodiments, the aqueous polymeric binder is a latex.

[00114] In some embodiments, the aqueous composition of the polymeric binder includes at least 50 ppm of the nitrogenous organic additive (based on the total weight of polymeric solids). In additional embodiments, the aqueous composition of the polymeric binder includes at least 110 ppm of the nitrogenous organic additive, in additional embodiments at least 140 ppm of the nitrogenous organic additive, in additional embodiments at least 230 ppm of the nitrogenous organic additive, in additional embodiments at least 730 ppm of the nitrogenous organic additive, in additional embodiments at least 2,800 ppm of the nitrogenous organic additive, and in still additional embodiments at least 9,000 ppm of the nitrogenous organic additive.

[00115] In some useful embodiments, the aqueous polymer binder composition includes a maximum of 300,000 ppm of the nitrogenous organic additive (based on the total weight of polymeric solids). In further embodiments, the aqueous polymer binder composition includes a maximum of 230,000 ppm of the nitrogenous organic additive, in further embodiments a maximum of 150,000 ppm of the nitrogenous organic additive, in further embodiments a maximum of 80,000 ppm of the nitrogenous organic additive, in further embodiments a maximum of 50,000 ppm of the nitrogenous organic additive, and in still further embodiments, a maximum of 20,000 ppm of the nitrogenous organic additive.

[00116] The organic nitrogen additives useful in the present invention enable the formulation of aqueous polymer binder compositions that are adequately preserved or have reduced susceptibility to microbial deterioration and, when added as a component of a coating composition, provide other enhanced or maintained coating performance characteristics, including, but not limited to, abrasion durability, washability, and stability to Petition 870250091017, dated 06 / 10 / 2025, page 53 / 82 / 57 heat aging or aging stability. In embodiments, said aqueous polymeric binder compositions can be supplied without the need, or with a reduced need, for the use of conventional biocides such as isothiazolinones, pyrithiones, inorganic biocides or others.

[00117] In some useful embodiments, the aqueous polymer binder compositions include a maximum of 600 ppm of BIT (based on the total weight of polymer solids). In further embodiments, the aqueous polymer binder composition includes a maximum of 300 ppm of BIT, and in further embodiments, a maximum of 100 ppm of BIT. In some embodiments, the aqueous polymer binder compositions are substantially BIT-free, essentially BIT-free, or completely BIT-free.

[00118] In some useful embodiments, the aqueous polymer binder compositions include a maximum of 300 ppm of MIT (based on the total weight of polymer solids). In further embodiments, the aqueous polymer binder composition includes a maximum of 100 ppm of MIT, in further embodiments, a maximum of 40 ppm of MIT. In some embodiments, the aqueous polymer binder compositions are substantially MIT-free, essentially MIT-free, or completely MIT-free.

[00119] In some useful embodiments, the aqueous polymer binder compositions include a maximum of 80 ppm of the MIT and CMIT reaction product (based on the total weight of polymer solids). In further embodiments, the aqueous polymer binder composition includes a maximum of 50 ppm of the MIT and CMIT reaction product, and in further embodiments, a maximum of 20 ppm of the MIT and CMIT reaction product. In some embodiments, the aqueous polymer binder compositions are substantially free of the MIT and CMIT reaction product. Petition 870250091017, dated 06 / 10 / 2025, p. 54 / 82 / 57 essentially free of the reaction product of MIT and CMIT, or completely free of the reaction product of MIT and CMIT.

[00120] In some useful embodiments, the aqueous polymer binder compositions include a maximum of 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 includes a maximum of 6,000 ppm of zinc pyrithione or sodium pyrithione, in further embodiments, a maximum of 2,000 ppm of zinc pyrithione or sodium pyrithione, and in still further embodiments, a maximum of 100 ppm of zinc pyrithione or sodium pyrithione. In some embodiments, the aqueous polymer binder compositions are 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. Manufacturing method of a composition and manufacturing methods of a coated article.

[00121] In certain embodiments of the present invention, a method for manufacturing an aqueous composition is provided. In embodiments, a nitrogenous organic additive is added to a composition at any stage of formation or after the formation of the composition in order to form an aqueous coating composition, such as a paint, or an aqueous polymeric binder composition according to any of the embodiments disclosed herein. The nitrogenous organic additive may be added as a separate component, mixed with other components in the aqueous composition, or added as a mixture with a polymeric binder.

[00122] In further embodiments, a method of manufacturing a coated article is disclosed, the method comprising the steps of providing an ink or coating composition according to any of the embodiments disclosed herein and coating a substrate with a Petition 870250091017, dated 06 / 10 / 2025, p. 55 / 82 / 57 aqueous coating composition of the present disclosure to form a coated article. Suitable substrates include, but are not limited to, wood, plastic, plasterboard, concrete, metal, rubber, or a natural or synthetic polymer. The substrate may be single or multi-layered. The aqueous coating composition of the present disclosure may be applied directly to the substrate or may be applied indirectly to the substrate, such as when the substrate is pre-coated with a primer or an undercoat. The aqueous coating composition may be applied by any suitable method, including brush application, roller application, paint pulling, spraying, or fusion. After application, the coating is cured. Curing may occur by drying, including at ambient or elevated temperature, exposure to actinic or ultraviolet radiation, or crosslinking, among other means. Illustrative examples

[00123] Modality 1. An aqueous coating composition comprising: (a) a carrier liquid; (b) a film-forming polymeric binder; and (c) at least one nitrogenous organic additive including a compound comprising four nitrogen centers, each nitrogen center linked to at least one other nitrogen center by at least one saturated divalent hydrocarbon linking group, wherein the nitrogenous organic additive is a post-addition component of the aqueous composition.

[00124] Modality 2. The aqueous composition of embodiment 1, wherein the linking groups are each independently a linear or branched C1, C2, C3 or C4 chain.

[00125] Modality 3. The aqueous coating composition of any previous embodiment, wherein the carrier liquid comprises Petition 870250091017, dated 06 / 10 / 2025, pp. 56 / 82 43 / 57 water.

[00126] Modality 4. The aqueous composition of any previous embodiment, where the aqueous composition is a latex, a paint, a coating, a caulking compound or a sealant.

[00127] Embodiment 5. The aqueous composition of any previous embodiment, the polymeric binder comprising a multi-stage latex.

[00128] Embodiment 6. The aqueous composition of any previous embodiment, the polymeric binder comprising a vinyl acrylic latex, a styrene acrylic latex, an all-acrylic latex, a polyurethane dispersion (PUD), a water-based alkyd resin, a water-based alkyd-PUD hybrid resin or mixtures thereof.

[00129] Modality 7. The aqueous composition of any previous embodiment, wherein the nitrogenous organic additive is selected from the group consisting of compounds of formulas I, II, III and IV, and mixtures thereof, wherein Formula I is: NHZ— Rl—NH — R2— NH— R3—NH2where Formula II is: NH2—R4—NN—R7—NH2where Formula III is: NN—R1D—NH—Rn—NH2 where Formula IV is: Petition 870250091017, dated 06 / 10 / 2025, p. 57 / 82 44 / 57 nh2I I , N ^,^12 NH2nh2 where each of RI to R4, R7, and RIO to RI4 is a saturated hydrocarbon chain that has 1 to 3 carbons, each of R5, R6, R8 and R9 is a saturated hydrocarbon chain that has 2 to 3 carbons, and each of RI to R14 is the same or different.

[00130] Modality 8. The aqueous composition of the immediately preceding embodiment, wherein each of RI to R4, R7 and R10 to 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 RI to R14 is the same or different.

[00131] Modality 9. The aqueous composition of any previous embodiment, wherein the nitrogenous organic additive is selected from the group consisting of the compounds: 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.

[00132] Modality 10. The aqueous composition of any of the modalities 1 to 6, wherein the nitrogenous organic additive is selected from the group consisting of the following compounds: amino acid hydrazides, carbazidocarboxylic acid hydrazides, bis-hydrazides and bis-carbazides, diethylene triamine, N,N'-bis(2-aminoethyl)-1,2-ethanediamine, tetraethylene pentamine, pentaethylene hexamine, tris-(2-aminoethyl)amine, N-(2-piperazinoethyl)-ethylene diamine, N,N'-bis-(2-aminoethyl)-piperazine, N,N,N'-tris-(2-aminoethyl)ethylene diamine, N-(2-aminoethyl)-N'-(2-piperazinoethyl-1)-ethylene diamine, N,N-bis-(2-aminoethyl)-N-(2-piperazinoethyl)amine, N,N-bis-(2-piperazinoethyl)-amine, polyethylene imine oligomers comprising at least four functional monomeric units, N-(2-aminoethyl)-1,3-propanediamine, oligomers Petition 870250091017, dated 06 / 10 / 2025, page 58 / 82 / 57 of polyoxypropylene amine comprising at least four functional monomeric units, tetrapropylene pentamine, tripropylene tetramine and N,N'-bis-(3-aminopropyl)ethylene diamine and mixtures thereof.

[00133] Embodiment 11. The aqueous composition of any previous embodiment, wherein the polymeric film-forming binder is substantially free of any functional monomeric units comprising reactive ketone moieties that crosslink the film-forming binder during film formation.

[00134] Embodiment 12. The aqueous composition of the immediately preceding embodiment, wherein the reactive ketone moieties that crosslink the film-forming binder during film formation comprise diacetone acrylamide (DAAM).

[00135] Modality 13. The aqueous composition of any previous embodiment, provided that the compounds of the nitrogenous organic additive are substantially free of any aryl functional groups.

[00136] Modality 14. The aqueous composition of any previous embodiment, wherein the aqueous composition comprises at least about 50 ppm, by weight, of the nitrogenous organic additive based on the total weight of the components of the composition.

[00137] Modality 15. The aqueous composition of any previous embodiment, wherein the aqueous composition comprises a maximum of about 100,000 ppm by weight of the nitrogenous organic additive based on the total weight of the components of the composition.

[00138] Modality 16. The aqueous composition of any previous embodiment, wherein the aqueous composition comprises a maximum of about 75,000 ppm by weight of the nitrogenous organic additive based on the total weight of the components of the composition.

[00139] Modality 17. The aqueous composition of any previous embodiment, wherein the aqueous composition comprises at most about Petition 870250091017, dated 06 / 10 / 2025, pp. 59 / 82 / 57 50,000 ppm, by weight, of the nitrogenous organic additive based on the total weight of the components of the composition.

[00140] Modality 18. The aqueous composition of any previous embodiment, wherein the aqueous composition comprises at least about 75 ppm, by weight, of the nitrogenous organic additive based on the total weight of the components of the composition.

[00141] Modality 19. The aqueous composition of any previous embodiment, wherein the aqueous composition comprises a maximum of about 25,000 ppm by weight of the nitrogenous organic additive based on the total weight of the components of the composition.

[00142] Modality 20. The aqueous composition of any previous embodiment, wherein the aqueous composition additionally comprises not more than about 300 ppm of BIT, by weight, based on the total weight of the components of the composition.

[00143] Modality 21. The aqueous composition of any of the preceding embodiments, wherein the aqueous composition additionally comprises not more than about 150 ppm of BIT, by weight, based on the total weight of the components of the composition.

[00144] Modality 22. The aqueous composition of any previous embodiment, wherein the aqueous composition comprises not more than about 50 ppm of BIT, by weight, based on the total weight of the components of the composition.

[00145] Modality 23. The aqueous composition of any previous embodiment, wherein the aqueous composition additionally comprises not more than about 150 ppm of MIT, by weight, based on the total weight of the components of the composition.

[00146] Embodiment 24. The aqueous composition of any previous embodiment, with the aqueous composition additionally comprising not more than about 50 ppm of MIT based on the total weight of the components. Petition 870250091017, dated 06 / 10 / 2025, p. 60 / 82 / 57 of the composition.

[00147] Modality 25. The aqueous composition of any previous embodiment, wherein the aqueous composition additionally comprises not more than about 20 ppm of MIT based on the total weight of the components of the composition.

[00148] Modality 26. The aqueous composition of any previous embodiment, wherein the aqueous composition is substantially free of MIT based on the total weight of the components of the composition.

[00149] Embodiment 27. The aqueous composition of any previous embodiment, the aqueous composition additionally comprising not more than about 40 ppm of the reaction product of CMIT and MIT based on the total weight of the components of the composition.

[00150] Embodiment 28. The aqueous composition of any previous embodiment, wherein the aqueous composition additionally comprises not more than about 25 ppm of the reaction product of CMIT and MIT based on the total weight of the components of the composition.

[00151] Embodiment 29. The aqueous composition of any previous embodiment, wherein the aqueous composition additionally comprises not more than about 10 ppm of the reaction product of CMIT and MIT based on the total weight of the components of the composition.

[00152] Embodiment 30. The aqueous composition of any previous embodiment, wherein the aqueous composition is substantially free of the reaction product of CMIT and MIT based on the total weight of the components of the composition.

[00153] Embodiment 31. The aqueous composition of any previous embodiment, the aqueous composition additionally comprising not more than about 5,000 ppm of zinc pyrithione or sodium pyrithione based on the total weight of the components of the composition.

[00154] Modality 32. The aqueous composition of any modality Petition 870250091017, dated 06 / 10 / 2025, p. 61 / 82 / 57 above, and the aqueous composition further comprises no more than about 3,000 ppm of zinc pyrithione or sodium pyrithione based on the total weight of the components of the composition.

[00155] Embodiment 33. The aqueous composition of any previous embodiment, wherein the aqueous composition additionally comprises not more than about 1,000 ppm of zinc pyrithione or sodium pyrithione based on the total weight of the components of the composition.

[00156] Embodiment 34. The aqueous composition of any previous embodiment, the aqueous composition additionally comprising not more than about 50 ppm of zinc pyrithione or sodium pyrithione based on the total weight of the components of the composition.

[00157] Modality 35. The aqueous composition of any previous embodiment, provided that the aqueous composition is substantially free of zinc pyrithione and sodium pyrithione.

[00158] Embodiment 36. The aqueous composition of any preceding embodiment, wherein when the aqueous composition is a coating or is included in a coating and the coating is applied to a substrate and cured, the coating exhibits equivalent or better abrasion durability as measured in accordance with ASTM Method D2486-96 (Standard Test Method for Abrasion Resistance of Wall Paints) and compared with a second coating having the same composition, except that the second coating contains isothiazolinone in an equivalent amount and instead of the nitrogenous organic additive.

[00159] Embodiment 37. The aqueous composition of any preceding embodiment, wherein when the aqueous composition is a coating or is included in a coating and the coating is applied to a substrate and cured, the coating exhibits a KU viscosity drop equivalent or better over a period of about 3 weeks at about 140°F and as measured in accordance with ASTM Method D562-10 (Test Method). Petition 870250091017, dated 06 / 10 / 2025, page 62 / 82 / 57 standard for the consistency of paints by measuring viscosity in Krebs Unit (KU - Krebs Unit) using a Stormer type viscometer) and comparing it to a second coating with the same composition, except that the second coating contains isothiazolinone in an equivalent amount and instead of the nitrogenous organic additive.

[00160] Embodiment 38. The aqueous composition of any preceding embodiment, wherein when the aqueous composition is a coating or is included in a coating and the coating is applied to a substrate and cured, the coating exhibits equivalent or better washability as measured in accordance with ASTM D4828-94 (2003) Standard Test Method for Washability of Organic Coatings and compared with a second coating having the same composition, except that the second coating contains isothiazolinone in an equivalent amount and instead of the nitrogenous organic additive.

[00161] Modality 39. The aqueous composition of any previous embodiment, provided that the aqueous composition is suitably preserved as defined herein.

[00162] Modality 40. The aqueous composition of any of the previous modalities, wherein the aqueous composition develops less than 1x103 CFU / mL on average when the aqueous composition is subjected to the microbial challenge test.

[00163] Modality 41. The aqueous composition of any of the above modalities, with the aqueous composition developing less than 5x102 CFU / mL on average when the aqueous composition is subjected to the microbial challenge test.

[00164] Modality 42. The aqueous composition of any previous embodiment, wherein the aqueous composition comprises at least 17% by weight of polymeric binder solids.

[00165] Modality 43. The aqueous composition of any modality Petition 870250091017, dated 06 / 10 / 2025, p. 63 / 82 / 57 above, wherein the aqueous composition is a coating and the coating additionally comprises a pigment.

[00166] Modality 44. The coating of modality 43, where the coating is a 1K water-based coating.

[00167] Modality 45. The coating of any of the embodiments 43 or 44, wherein the coating comprises from about 10% by weight to about 30% by weight of titanium dioxide on the basis of the total solids present in the coating.

[00168] Modality 46. A coating composition comprising: (a) about 7% to about 30%, by weight, of polymeric solids of a film-forming polymeric binder; (b) from about 50 ppm to about 50,000 ppm by weight of a nitrogenous organic additive including at least one compound comprising four nitrogen centers, each nitrogen center linked to at least one other nitrogen center by at least one saturated divalent hydrocarbon linking group, wherein said nitrogenous organic additive is a post-addition component of the coating composition and 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; (c) at least 10% to about 30%, by weight, of titanium dioxide; and (d) water.

[00169] Modality 47: A method for preserving an aqueous composition comprising: adding a nitrogenous organic additive including at least one compound comprising four nitrogen centers, each nitrogen center linked to at least one other nitrogen center by at least one saturated divalent hydrocarbon linkage group to a Petition 870250091017, dated 06 / 10 / 2025, page 64 / 82 / 57 composition including at least one carrier and one film-forming binder.

[00170] Modality 48: A coated article comprising: the coating composition of any previous embodiment coated onto a substrate, wherein the substrate comprises wood, plastic, plasterboard, concrete, metal, rubber or a natural or synthetic polymer. Examples Testing methods

[00171] The following test methods were used in the evaluation of the control and sample paints. When standard test methods are used to evaluate a property, the standard test methods are provided. When a property is tested according to a modified version of a standard test method, deviations from the standard test method are described. Microbial challenge test

[00172] The preservative efficacy is tested through the microbial challenge test. As conducted in this document, the microbial challenge test is carried out by subjecting each composition to the microbial challenge test in a manner materially similar to the test protocol detailed in ASTM D2574 - 16 Standard Test Method for Resistance of Emulsion Paints in the Container to Attack by Microorganisms (2016). The preservative test used in the present invention is described below. Discrepancies with ASTM D2574 are included in this description.

[00173] Duplicate, 50 mL samples of each of the sample compositions (each sample composition including a different variation of nitrogen, organic additive, and conventional biocide concentration) were taken and each of the duplicate samples inoculated with: (Challenge 1) 5.0 mL of pooled culture at approximately 109 CFU / mL on day 0, resulting Petition 870250091017, dated 06 / 10 / 2025, page 65 / 82 / 57 at a final concentration of approximately 10⁸ CFU / mL within the sample; (Challenge 2) 2.5 mL of pooled culture at approximately 10⁹ CFU / mL on day 7, resulting in a final concentration of approximately 10⁸ CFU / mL within the sample; and (Challenge 3) 1.25 mL of pooled culture at approximately 10⁹ CFU / mL on day 14, resulting in a final concentration of approximately 10⁸ CFU / mL within the sample. Immediately after inoculation, each sample was then incubated at 30 °C ± 2 °C. For each sample, duplicate spread plates were made at 72 hours and 7 days of incubation by spreading 0.1 mL of the sample uniformly onto a tryptic soy agar plate using aseptic techniques. Each spread plate, thus prepared, was then incubated for a further 72 hours at 30 °C ± 2 °C and microbial growth observed at that time.The challenge test was also performed against negative controls, which are agar plates with bacterial challenge but no ink applied (not to be confused with negative control ink). The results of the negative control spread plate test are conducted as a process check to assess possible experimental errors and are not reported in the results below. Bacterial survival is quantified according to the rating scale shown below in TABLE 1. A total score for the microbial challenge test is determined by calculating the average of the 7-day sample ratings for the third challenge for a given composition. Compositions with a total microbial challenge test score of 6 or less (i.e., developing on average less than 1x10³ CFU / mL showing Moderate contamination) are considered to have passed the microbial challenge test and are therefore properly stored. Petition 870250091017, dated 06 / 10 / 2025, pages 66 / 82 / 57 Table 1 - Preservative test rating scale Number of colonies CFU / mL (approx.) Descriptive classification Classification No growth <101 Clear 1 1 to 5 1x101 to 5x101 Slight 2 6 to 10 6x101 to 1x102 Moderate 3 11 to 25 1.1x102 to 2.5x102 Moderate 4 26 to 50 2.6x102 to 5x102 Moderate 5 51 to 100 5.1x102 to 1x103 Moderate / Severe 6 101 to 200 1.1x103 to 2x103 Severe 7 201 to 300 2.1x103 to 3x103 Severe 8 TNTC (irregular edges) 3.1x103 to 9x105 Severe 9 TNTC (edges (smooth) 1x106 Grave 10 Where TNTC = Too numerous to count and CFU / mL = Colony forming unit / milliliter Washability:

[00174] Washability is a measure of the relative ease with which common dirt and stains can be removed from a coated surface by hand or mechanical washing. Washability is evaluated according to the ASTM D4828-94 method, with at least crayon, black ink pen, pencil and red lipstick used as stains and 10 mL of Formula 409 as a liquid cleaner, with evaluation after 50 cycles. Abrasion durability:

[00175] Abrasion is a measure of the relative ability of a coating to resist erosion, or removal of coating from the substrate, from rubbing. Abrasion is measured using the ASTM D2486-17 method, test method A or B. Stability against aging and stability against aging heat dispersion:

[00176] Heat aging stability or heat aging stable, as generically used in reference to the compositions in this document, refers to a composition that exhibits a viscosity increase of less than 10 KU units after approximately 3 weeks of aging at approximately 140 °F. Aging stability or aging stable, as generically used in reference to the compositions described herein, refers to a composition that exhibits Petition 870250091017, dated 06 / 10 / 2025, page 67 / 82 / 57: viscosity increase less than 5 to 10 KU units after approximately 3 weeks of aging at room temperature (approximately 68 °F). Viscosity is measured in KU or Krebs units according to ASTM D562-10 (Standard Test Method for Consistency of Paints Measuring Krebs Unit (KU) Viscosity Using a Stormer-Type Viscometer) and ICI units according to ASTM D4287-00 (Standard Test Method for High-Shear Viscosity Using a Cone / Plate Viscometer). Example 1

[00177] A positive control, vinyl acrylic, base paint (Positive Control Paint), ProMar™ 200 Zero VOC-Gloss Latex Interior Gloss, Extra White, available from The Sherwin-Williams Company, Cleveland, Ohio, USA, containing post-added preservatives consisting of 800 ppm of Proxel® BD-20 (an aqueous dispersion containing 19.3% by weight of 1,2-benzisothiazolin-3-one; available from Arxada Corp.) and 300 ppm of Zinc Omadine® ZOE (an emulsion containing 48% by weight of zinc 2-pyridinethiol-1-oxide emulsion; available from Arxada Corp.) was obtained. A negative control ink (Negative Control Ink) was prepared by conventional ink manufacturing methods using the same formula, but omitting post-addition preservatives (800 ppm Proxel® BD-20 and 300 ppm Omadine® Zinc Emulsion).The control paints were compared with several exemplary paints consisting of ProMar™ 200 Zero VOC-Gloss Interior Latex Gloss, Extra White (vinyl acrylic) with alternative post-addition preservatives, as shown in Table 2. Each paint was prepared by mixing conventional components using techniques known to those skilled in the art. Petition 870250091017, dated 06 / 10 / 2025, pages 68 / 82 / 57 Table 2 - Control base ink preservatives and examples in ppm1 Sample Proxel BD-20 Zinc Emulsion Omadine® ZOE TETA2 Positive control ink 800 300 - Negative control ink - - - Sample ink 1 800 300 750 Sample ink 2 800 300 500 Sample ink 3 800 300 250 Sample ink 4 - - 750 1The concentrations are given as ppm of additive based on the weight of the total sample composition. 2TETA™, an organic nitrogen additive available from Dow Chemical Company, Midland, MI, USA.

[00178] Preservative efficacy tests for positive control ink, negative control ink, and exemplary inks 1 to 4 are shown below in TABLE 3. Table 3 - Results of preservative efficacy tests Challenge 1 Challenge 2 Challenge 3 Time from sample application 72 h 72 h 7 days 7 days 72 h 72 h 7 days 7 days 72 h 72 h 7 days 7 days Sample Plate for smear application ABABABABABABA Positive control ink 1 5 7 9 2 1 2 1 1 1 2 1 Negative control ink 2 3 2 3 10 10 10 10 10 10 10 10 Sample ink 1 1 1 1 1 1 1 1 1 1 1 1 1 Sample ink 2 1 1 1 1 1 1 1 1 1 1 1 1 Sample ink 3 1 1 1 1 1 1 1 1 1 1 1 2 Sample ink 4 2 2 2 2 2 2 2 2 8 8 2 1

[00179] Sample ink 4 produces a total test score of Petition 870250091017, dated 06 / 10 / 2025, p. 69 / 82 / 57 microbial challenge of (2+1) / 2 = 1.5. Therefore, sample ink 4 shows bacterial contamination of less than 5x101 CFU / mL on average when subjected to the microbial challenge test.

[00180] The washability test results for positive control ink and exemplary ink 4 are shown below in TABLE 4. Table 4 - Washability test results Ink Washability Results Tea Red Wine Ketchup Mustard Grape Coffee Crayon Lipstick Pencil Pen Total Positive Control Ink 3 3 3 3 3 3 10 10 7 7 52 Sample Ink 4 3 3 7 3 3 3 10 7 7 3 52

[00181] The results of the abrasion durability test (ASTM D2486-17 method, Test Method B) for the positive control paint and exemplary paint 4 are shown below in TABLE 5. A standard paint is used to enable the normalization of results according to ASTM D2486-17. Table 5 - Abrasion durability test results First pattern break First ink break Sample A Sample B Average Sample A Sample B Average % Ink / Standard Ink 568 575 571.5 Control ink 891 909 900 157 Positive standard Ink 565 504 534.5 Ink 1011 824 917.5 172 Exemplary standard 4

[00182] The results of the aging stability test for the positive control ink and the exemplary ink 4 and the results of the heat aging stability test for the exemplary ink 4 are shown below in TABLE 6. Petition 870250091017, dated 06 / 10 / 2025, pp. 70 / 82 57 / 57 Table 6 - Results of the heat aging and aging stability test Paint Viscosity Initial Time Week 1 Week 2 Week 4 Temp. Room temperature Room temperature 140 °F Room temperature 140 °F Room temperature 140 °F Positive control paint Average shear in KU 111 111 N / A 112 N / A 117 N / A High shear in ICI 1.334 1.359 N / A 1.395 N / A 1.538 N / A Exemplary paint 1 Average shear in KU 107 109 115 111 118 112 117 High shear in ICI 1.310 1.332 1.574 1.407 1.649 1.420 1.632 Petition 870250091017, dated 06 / 10 / 2025, pp. 71 / 82

Claims

1 / 10 CLAIMS 1. Aqueous composition, characterized in that it comprises: (a) a carrier liquid; (b) a film-forming polymeric binder; and (c) a nitrogenous organic additive including at least one compound comprising four nitrogen centers, each nitrogen center linked to at least one other nitrogen center by at least one saturated divalent hydrocarbon linking group.

2. Aqueous composition according to claim 1, characterized in that the linking groups are each independently a linear or branched C1, C2, C3 or C4 chain.

3. An aqueous composition according to any one of the preceding claims, characterized in that the carrier liquid comprises water.

4. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized by being a latex, paint, coating composition, caulking compound or sealant.

5. Aqueous composition according to claim 4, characterized in that the nitrogenous organic additive is a post-addition component of the aqueous composition.

6. Aqueous composition according to any of the preceding claims, characterized in that the polymeric binder comprises a single-stage latex.

7. Aqueous composition according to any of the preceding claims, characterized in that the polymeric binder comprises a multi-stage latex.

8. Aqueous composition according to any of the preceding claims, characterized in that the polymeric binder comprises a vinyl acrylic latex, a styrene acrylic latex, an all-acrylic latex, a polyurethane dispersion (PUD), a water-based alkyd resin, a water-based alkyd-PUD hybrid resin, or mixtures thereof.

9. Aqueous composition according to any of the preceding claims, characterized in that the nitrogenous organic additive includes at least one compound selected from the group consisting of compounds of Formulas I, II, III and IV, wherein Formula I is: NH2—Rx—NH—R2—NH—R3—NH2 wherein Formula II is: NH2—R4—NN—R2—NH2 wherein Formula III is: NN—R10—NH—Rn—NH2 wherein Formula IV is: nh2 I R13 I . N ^R12 nh2 nh2 where each of RI to R4, R7, and RIO to RI4 is a saturated hydrocarbon chain that has 1 to 3 carbons, each of R5, R6, R8 and R9 is a saturated hydrocarbon chain that has 2 to 3 Petition 870250091017, of 06 / 10 / 2025, page 73 / 82 3 / 10 carbons, and each of R1 to R14 is the same or different.

10. Aqueous composition according to the immediately preceding claim, characterized in that each of R1 to R4, R7 and R10 to 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 to R14 is the same or different.

11. Aqueous composition according to any of the preceding claims, characterized in that the nitrogenous organic additive is selected from the group consisting of the compounds: 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.

12. Aqueous composition according to any one of claims 1 to 6, characterized in that the nitrogenous organic additive is selected from the group consisting of the following compounds: amino acid hydrazides, carbazidocarboxylic acid hydrazides, bis-hydrazides and bis-carbazides, diethylene triamine, N,N'-bis(2-aminoethyl)-1,2-ethanediamine, tetraethylene pentamine, pentaethylene hexamine, tris-(2-aminoethyl)amine, N-(2-piperazinoethyl)-ethylene diamine, N,N'-bis-(2-aminoethyl)-piperazine, N,N,N'tris-(2-aminoethyl)ethylene diamine, N-(2-aminoethyl)-N'-(2-piperazinoethyl-1)ethylene diamine, N,N-bis-(2-aminoethyl)-N-(2-piperazinoethyl)amine, N,N-bis(2-piperazinoethyl)-amine, polyethylene imine oligomers comprising at least four functional monomeric units, N-(2-aminoethyl)-1,3-propanediamine, polyoxypropylene amine oligomers comprising at least four functional monomeric units, tetrapropylene pentamine, tripropylene tetramine and N,N'-bis-(3-aminopropyl)ethylene diamine and mixtures thereof.

13. Aqueous composition according to any of the preceding claims, characterized in that the polymeric film-forming binder is substantially free of any functional monomeric units comprising reactive ketone moieties that crosslink the polymeric film-forming binder during film formation.

14. Aqueous composition according to the immediately preceding claim, characterized in that the reactive ketone moieties that crosslink the film-forming polymeric binder during film formation comprise diacetone acrylamide (DAAM).

15. Aqueous composition according to any of the preceding claims, characterized in that the compounds of the nitrogenous organic additive are substantially free of any aryl functional groups.

16. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it comprises at least about 50 ppm, by weight, of the nitrogenous organic additive based on the total weight of the components of the composition.

17. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it comprises at most about 100,000 ppm, by weight, of the nitrogenous organic additive based on the total weight of the components of the composition.

18. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it comprises at most about 75,000 ppm, by weight, of the nitrogenous organic additive based on the total weight of the components of the composition.

19. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized by the fact that it comprises a maximum of about 50,000 ppm, by weight, of the nitrogenous organic additive based on the total weight of the components of the composition.

20. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it comprises at least about 75 ppm, by weight, of the nitrogenous organic additive based on the total weight of the components of the composition.

21. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it comprises at most about 25,000 ppm, by weight, of the nitrogenous organic additive based on the total weight of the components of the composition.

22. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it further comprises no more than about 300 ppm of BIT, by weight, based on the total weight of the components of the composition.

23. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it further comprises no more than about 150 ppm of BIT, by weight, based on the total weight of the components of the composition.

24. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it comprises no more than about 50 ppm of BIT, by weight, based on the total weight of the components of the composition.

25. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it further comprises no more than about 150 ppm of MIT, by weight, based on the total weight of the components of the composition.

26. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it additionally comprises no more than about 50 ppm of MIT based on the total weight of the components of the composition.

27. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it further comprises no more than about 20 ppm of MIT based on the total weight of the components of the composition.

28. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized by being substantially free of MIT based on the total weight of the components of the composition.

29. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it further comprises no more than about 40 ppm of the reaction product of CMIT and MIT based on the total weight of the components of the composition.

30. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it further comprises no more than about 25 ppm of the reaction product of CMIT and MIT based on the total weight of the components of the composition.

31. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it further comprises no more than about 10 ppm of the reaction product of CMIT and MIT based on the total weight of the components of the composition.

32. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized by being substantially free of the reaction product of CMIT and MIT, based on the total weight of the components of the composition.

33. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it further comprises no more than about 5000 ppm of zinc pyrithione or sodium pyrithione based on the total weight of the components of the composition.

34. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it further comprises no more than about 3000 ppm of zinc pyrithione or sodium pyrithione based on the total weight of the components of the composition.

35. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it further comprises no more than about 1000 ppm of zinc pyrithione or sodium pyrithione based on the total weight of the components of the composition.

36. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it further comprises no more than about 50 ppm of zinc pyrithione or sodium pyrithione based on the total weight of the components of the composition.

37. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized by being substantially free of zinc pyrithione and sodium pyrithione based on the total weight of the components of the composition.

38. Aqueous composition according to any of the preceding claims, characterized in that, when the aqueous composition is a coating or is included in a coating and the coating is applied to a substrate and cured, the coating exhibits equivalent or better abrasion durability, as measured according to ASTM D2486-96 (Standard Test Method for Abrasion Resistance of Wall Paints) and compared with a second coating of the same composition, except that the second coating contains isothiazolinone in an equivalent amount and instead of the nitrogenous organic additive.

39. An aqueous composition according to any of the preceding claims, characterized in that when the aqueous composition is a coating or is included in a coating and the coating is applied to a substrate and cured, the coating exhibits a viscosity drop in equivalent or greater KU units over a period of about 3 weeks at about 140 °F, as measured according to ASTM D562-10 (Standard Test Method for Consistency of Paints – Measurement of Viscosity in Krebs Units (KU) using a Stormer-type viscometer) and compared with a second coating of the same composition, except that the second coating contains isothiazolinone in an equivalent amount and instead of the nitrogenous organic additive.

40. Aqueous composition according to any of the preceding claims, characterized in that when the aqueous composition is a coating or is included in a coating and the coating is applied to a substrate and cured, the coating exhibits equivalent or better washability as measured according to ASTM D4828-94 (2003) Standard Test Method for Washability of Organic Coatings and compared with a second coating with the same composition, except that the second coating contains isothiazolinone in an equivalent amount and instead of the nitrogenous organic additive.

41. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized by being adequately preserved, as defined herein. Petition 870250091017, dated 06 / 10 / 2025, pp. 79 / 82 9 / 10 42. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it develops less than 1x103 CFU / mL on average when the aqueous composition is subjected to the microbial challenge test, as defined herein.

43. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it develops less than 5x102 CFU / mL on average when the aqueous composition is subjected to the microbial challenge test, as defined herein.

44. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it comprises at least 17% by weight of polymeric binding solids.

45. Aqueous composition according to any of the preceding claims, the aqueous composition being characterized in that it is a coating and the coating further comprises a pigment.

46. ​​Coating, as defined in claim 42, the coating being characterized in that it is a 1K water-based coating.

47. Coating, as defined in either of claims 42 or 43, the coating being characterized in that it comprises from about 10% by weight to about 30% by weight of titanium dioxide.

48. Coating composition, characterized in that it comprises: (a) about 7% to about 30%, by weight, of polymeric solids of a film-forming polymeric binder; (b) about 50 ppm to about 50,000 ppm, by weight, of a nitrogenous organic additive including at least one compound Petition 870250091017, dated 06 / 10 / 2025, page. 80 / 82 10 / 10 comprising four nitrogen centers, each nitrogen center linked to at least one other nitrogen center by at least one saturated divalent hydrocarbon linking group, wherein said nitrogenous organic additive is a post-addition component of the coating composition and is selected from the group consisting of the compounds: 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; (c) at least 10% to about 30%, by weight, of titanium dioxide; and (d) water.

49. A method for preserving an aqueous composition, characterized in that it comprises: adding the nitrogenous organic additive, as defined in any of the preceding claims, to a composition including at least one carrier and a film-forming binder to produce the aqueous composition, as defined in any of the preceding claims.

50. Coated article, characterized in that it comprises: the coating composition, as defined in any of the preceding claims, on a substrate, wherein the substrate comprises wood, plastic, plasterboard, concrete, metal, rubber or a natural or synthetic polymer. Petition 870250091017, dated 06 / 10 / 2025, pp. 81 / 82