Alkaline paint formulations

Abstract

The present disclosure is generally directed to an isothiazolinone-free alkaline paint formulation. The isothiazolinone-free alkaline paint formulation may include about 0.01 wt.% to about 2.0 wt.% of a linear polyetheramine. The formulation may have a pH between about 9.0 and about 11.5.

Description

ALKALINE PAINT FORMULATIONSRELATED APPLICATIONS

[0001] The present application is based on and claims priority to U.S. Provisional Patent application Serial No. 63 / 660,621, filed on June 17, 2024, which is incorporated herein by reference.BACKGROUND

[0002] Due to the regulatory and hazard labeling implications of preservative incorporation, many coatings producers in the European Union, now regulated by the Biocidal Products Authority7(BPR), are producing biocide-free paints. These biocide-free paints are produced by bringing the pH to ~11.. However, while the paints can be shown to be preserved against common spoilage-driving organisms like Pseudomonas. Alcaligenes, Enterobacter , and Bacillus through high alkalinity7, spoilage issues can be driven by extremophiles capable of growth at high pH, like Bacillus and Nesterenkonia species. Additionally, high pH can be irritating, limits the use of many commonly used paint additives, and requires use of alkaline-stable resins, all of which make formulation space for such paints more limited compared to paints produced in the standard pH range of 8.5- 10 that generally require preservation with biocides and other active substances restricted for use in these highly regulated markets.

[0003] Further, biocide use is not the only restriction. Ecolabeling bodies, including Blue Angel, Nordic Swan, and EU Ecolabel, additionally impose restnctions on ingredients based on environmental toxicity, volatile organic compounds (VOC) content, or human health effects. Finding ingredients that meet all these criteria for efficacy, compatibility7, and performance is difficult.

[0004] For these reasons, there exists a strong need to provide a multifunctional ingredient to the industry that creates a more biostable environment in biocide-free paint formulations. It is also particularly desirable to provide ingredients that, while enabling formulation at lower pH, enhance of pH stability, improve scrub resistance, and / or improve viscosity stability. Further, by the ingredient being multifunctional, there can be simultaneous savings and SKU-reduction on functions supplied by numerous other additives (e.g., dispersants, defoamers, rheology7modifiers, surfactants, pH adjusters), enabling a more cost-competitive formulation.SUMMARY

[0005] The present disclosure is generally directed to an isothiazolinone-free alkaline paint formulation. The isothiazolinone-free alkaline paint formulation may include about 0.01 wt.% to about 2.0 wt.% of a linear polyetheramine. The linear polyetheramine may have the following formula, Formula I:, wherein R1 may independently be H or CH? and x may be from about 3.0 to about 50. Also, the formulation may have a pH between about 9.0 and about 11.5.

[0006] Additionally, example aspects of the present disclosure are directed to a multifunctional booster composition including a linear polyetheramine of Formula I. a humectant, and optionally at least one additive. The linear poly etheramine of Formula I and humectant may be present in the multifunctional booster composition at a weight ratio of from about 1 : 10 to about 10: 1. The weight ratio of the poly etheramine to the at least one additive in the multifunctional booster composition may be from about 1:5 to about 100: 1 when the at least one optional additive is present in the multifunctional booster composition.

[0007] Other features and aspects of the present disclosure are discussed in greater detail below.DETAILED DESCRIPTION

[0008] It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present disclosure.

[0009] The present disclosure is generally directed to a multifunctional booster composition. The multifunctional booster composition may include a linear poly etheramine having the structure of Formula I:; a humectant; and optionally at least one additive.

[0010] Advantageously, the linear polyetheramine alone or in combination with additional components act as a multifunctional booster to simultaneously boost activity of in-can preservatives and to provide other benefits to coating properties (e.g., rheology, pH stabilization, scrub resistance, open-time, or a combination thereof).

[0011] The linear polyetheramine may have a molecular weight greater than about 230 Daltons (Da). For instance, the linear poly etheramine may have a molecular weight greater than about 250 Da. such as greater than about 300 Da, such as greater than about 400 Da, such as greater than about 500 Da, such as greater than about 600 Da, such as greater than about 800, such as greater than about 900 Da, such as greater than 1500 Da, such as greater than about 2000 Da, or such as greater than about 2500 Da. In one example embodiment, the linear poly etheramine may have a molecular weight greater than about 300 Da and less than about 500 Da.

[0012] In one example embodiment, the linear polyetheramine of Formula I may include, but are not limited to, JEFF AMINE® ED900, JEFF AMINE® D2000,JEFF AMINE® ED600, JEFFAMINE® D400, and JEFF AMINE® D230, JEFF AMINE® M2005, or JEFFAMINE® M600.

[0013] In one example embodiment, the linear polyetheramine of Formula I may have the following structure:, wherein x may be greater than about 2.5 and less than about 50. In one example embodiment, x may be from about 3 to about 50, such as from about 3.5 to about 40, such as from about 5 to 35, such as from about 6 to 30, or any range therebetween. In one example embodiment, x may be greater than 2.5. In another example embodiment, x may be less than about 50. In yet another example embodiment, x may be from about 3 to about 50. In another example embodiment, x may be from about 3.5 to about 40. In another example embodiment, x may be from about 4 to about 7. In another example embodiment, x may be from about 7 to about 50.

[0014] In another example embodiment, the linear poly etheramine of Formula I may have the following structure:wherein the sum of x and z may be no less than 3 and y may be about 5 to about 20.

[0015] In yet another example embodiment, the linear poly etheramine of Formula I may have the following structure:, wherein the x may be from about 1 to about 40, and y may be about 5 to about 20.

[0016] In one example embodiment, the linear polyetheramine may be present in the multifunctional booster composition at a concentration of from about 30% by weight to about 99% by weight of the composition, such as from about 35% by weight to about 95% by weight, such as from about 40% by weight to about 90% by weight, such as from about 45% by weight to about 85% by weight, such as from about 50% by weight to about 80% by weight, or any range therebetween, based on the weight of the composition. For instance, in one example embodiment, the linear poly etheramine may be present in the multifunctional booster composition at a concentration of from about 30% by weight to about 99% by weight. In another example embodiment, the linear polyetheramine may be present in the multifunctional booster composition at a concentration of from about 35% by weight to about 95% by weight. In another example embodiment, the linear polyetheramine may be present in the multifunctional booster composition at a concentration of from about 40% by weight to about 90% by weight. In another example embodiment, the linear polyetheramine may be present in the multifunctional booster composition at a concentration of from about 45% by weight to about 85% by weight. In another example embodiment, the linear polyetheramine may be present in the multifunctional booster composition at a concentration of from about 50% by weight to about 80% by weight.

[0017] Further, the multifunctional booster composition disclosed herein may include a humectant in combination with the linear poly etheramine of Formula I. For instance, the humectant may be selected from a group consisting of adipic acid, fumaric acid and itssalts, benzoic acid and its salts, glycerine, glycerine triacetate, sodium or magnesium laury l sulfate, magnesium stearate, polyethylene glycol, polyvinylpyrrolidone, boric acid, monolaurate or mono-palmitate, myristyl alcohol, cetyl alcohol, cetylstearyl alcohol, talcum, calcium or magnesium salts of higher fatty' acids, mono-, di- or triglycerides of higher fatty acids, and polytetrafluorethylene. In one example embodiment, the humectant may include glycerine or polyethylene glycol. For instance, in one example embodiment, the humectant may be glycerine. In another example embodiment, the humectant may be polyethylene glycol.

[0018] In one example embodiment, the humectant may be polyethylene glycol. For instance, the polyethylene glycol may have an average molecular weight of about 400 g / mol or greater. In one example embodiment, the polyethylene glycol may have an average molecular weight of from about 400 g / mol to about 2000 g / mol, such as from about 400 g / mol to about 1500 g / mol, such as from about 400 g / mol to about 1000 g / mol, or any range therebetween. In one example embodiment, the polyethylene glycol may have an average molecular weight of from about 400 g / mol to about 2000 g / mol. In another example embodiment, the polyethylene glycol may have an average molecular weight of from about 400 g / mol to about 1500 g / mol. In another example embodiment, the polyethylene glycol may have an average molecular weight of from about 400 g / mol to about 1000 g / mol.

[0019] In one example embodiment, the humectant may be present in the multifunctional booster composition at a concentration of from about 1% by weight of the composition to about 70% by weight of the composition, such as from about 5% by weight to about 65% by weight, such as from about 10% by weight to about 60% by weight, such as from about 15% by weight to about 55% by weight, or any range therebetween. For instance, in one example embodiment, the humectant may be present in the multifunctional booster composition at a concentration of from about 1% by weight of the composition to about 70% by weight of the composition. In another example embodiment, the humectant may be present in the multifunctional booster composition at a concentration of from about 5% by weight to about 65% by weight. In another example embodiment, the humectant may be present in the multifunctional booster composition at a concentration of from about 10% by weight to about 60% by weight. In another example embodiment, the humectant may be present in the multifunctional booster composition at a concentration of from about 15% by weight to about 55% by weight.

[0020] In one example embodiment, the linear poly etheramine of Formula I and humectant may be present in the composition at a weight ratio of from about 1 : 10 to about 10: 1, such as from about 1:2 to about 8: 1, such as from about 1:3 to about 6: 1, such as from about 1 :4 to about 5: 1 , or any range therebetween. For instance, in one example embodiment, the linear polyetheramine of Formula I and humectant may be present in the composition at a weight ratio of from about 1 : 10 to about 10: 1. In another example embodiment, the linear poly etheramine of Formula I and humectant may be present in the composition at a weight ratio of from about 1:2 to about 8: 1. In another example embodiment, the linear polyetheramine of Formula I and humectant may be present in the composition at a weight ratio of from about 1:3 to about 6: 1. In another example embodiment, the linear poly etheramine of Formula I and humectant may be present in the composition at a weight ratio of from about 1:4 to about 5: 1.

[0021] Optionally, if desired, the multifunctional booster composition disclosed herein may further include at least one additive including, but is not limited to, a silicate, an additional organic amine not described by Formula I, or a combination thereof. In one example embodiment, the polyetheramine of Formula I to additive may be present in the multifunctional booster composition at a weight ratio of from about 1:5 to about 100:1, such as from about 1: 10 to about 95:1, such as from about 1 :20 to about 80: 1, such as from about 1:25 to about 50:1, such as from about 1 :30 to about 30: 1, or any range therebetween, when the at least one optional additive is present in the multifunctional booster composition. For instance, in one example embodiment, the polyetheramine of Formula I to additive may be present in the multifunctional booster composition at a weight ratio of from about 1 :5 to about 100: 1. In another example embodiment, the poly etheramine of Formula I to additive may be present in the multifunctional booster composition at a weight ratio of from about 1 :3 to about 60: 1. In another example embodiment, the poly etheramine of Formula I to additive may be present in the multifunctional booster composition at a weight ratio of from about 1 :5 to about 75: 1. In another example embodiment, the poly etheramine of Formula I to additive may be present in the multifunctional booster composition at a weight ratio of from about 1 : 10 to about 95: 1. In another example embodiment, the poly etheramine of Formula I to additive may be present in the multifunctional booster composition at a weight ratio of from about 1:20 to about 80:1. In another example embodiment, the polyetheramine of Formula I to additive may be present in the multifunctional booster composition at a weight ratio of from about 1:25 to about 50: 1. In another example embodiment, the polyetheramine of Formula I toadditive may be present in the multifunctional booster composition at a weight ratio of from about 1 : 30 to about 30: 1.

[0022] In another example embodiment, the multifunctional booster composition disclosed herein may include a silicate. Silicates may include, but are not limited to, silicas such as modified silicas and fumed silicas. In one embodiment, the silicate may be one or both of potassium methylsilicionate and sodium metasilicate (e.g., sodium metasilicate pentahydrate). Commercial examples include Silres 168 (Wacker), Tyson WR50 (Tyson, Singapore), and Xiameter OFS0777 (Coming). The silicate may be present in the multifunctional booster composition disclosed herein in an amount of from about 0.5% by weight to about 15% by weight, such as from about 1% by weight to about 10% by weight, such as from about 2.5% by weight to about 7.5% by weight, or any range therebetween, based on the weight of the composition.

[0023] In one example embodiment, the multifunctional booster composition disclosed herein may include an organic amine not described in Formula I, such as a pH adjusting agent. The pH adjusting agent may include, but are not limited to, amines including 2- amino-2-methy 1-1 -propanol (‘LAMP95?’), ethanolamine. 1 -amino-2-propanol. 3-amino-l- propanol, 2-(methylamino)ethanol, 2-(ethylamino)ethanol, 2(propylamino)ethanol, 2(isopropylamino)ethanol, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, , 2-amino-2-ethyl-l,3-propanediol (also called AEPD), 2(2- aminoethoxyjethanol (also called diglycol amine), N-methyldiethanolamine, N,N- dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylaminoethanol, N,N dimethylamino-2-propanol, etc. The pH adjusting agent may also be salts of hydroxides and carbonates, such as sodium carbonate, sodium hydroxide, ammonium hydroxide, or other pH adjusting agents known to the art to be useful for neutralizing acidic functionality in latex formulations.

[0024] Optionally, the multifunctional booster compositions of the present disclosure may utilize one or more surfactants, which may be a component of the at least one additive. The surfactants function as emulsifiers and help to keep the water-insoluble components of the formulation in the form of a stable dispersion (emulsion) of small particles suspended in an aqueous phase.

[0025] Suitable types of nonionic surfactants include, but are not limited to, poly oxy alkylene glycol alkyl ethers (e.g., polyoxyethylene glycol alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene / propylene alkyl ethers), glucoside alkyl ethers, polyoxyalkylene glycol alkylphenol ethers (e.g.. polyoxyethylene glycolalkylphenol ethers, polyoxypropylene glycol alkylphenol ethers, polyoxyethylene / propylene glycol alkylphenol ethers), glycerol alkyl esters, polyoxyalkylene glycol sorbitan alkyl esters (e.g.. polyoxyethylene glycol sorbitan alkyl esters), sorbitan alkyl esters, cocamide MEA, cocamide DEA, block copolymers of polyethylene glycol and polypropylene glycol (poloxamers), polyalkoxylated tallow amines, alkoxylated fatty acids and the like and combinations thereof.

[0026] Particular nonionic surfactants include alkoxylated aliphatic mono-alcohols and alkoxylated aromatic mono-alcohols. Such surfactants are typically prepared by reacting one or more alkylene oxides (e.g., ethylene oxide, propylene oxide, mixtures of ethylene oxide and propylene oxide) with one or more mono-alcohols (e.g., aliphatic alcohols, which may be for example linear or branched, primary’ or secondary’, or aromatic alcohols, such as phenols, including alkyl- and aralkyl-substituted phenols). The number of moles of alkylene oxide reacted per mole of the mono-alcohol may' be varied as may' be desired, but ty pically is from about 2 to about 50 on average. If more than one type of alkylene oxide is used, the alky lene oxides may be reacted as a mixture (to provide a polyoxyalkylene segment having a random copolymer structure) or sequentially (to provide a polyoxyalkylene segment having a block copolymer structure).

[0027] Another type of nonionic surfactant for use in the present disclosure may be an alkoxylated aliphatic mono-alcohol which is an ethoxylated Cio-Cis aliphatic alcohol (in particular, a linear primary C12-C16 aliphatic alcohol (or mixture of such alcohols) which has been reacted with about 6 to about 15 moles of ethylene oxide per mole of aliphatic alcohol to provide an alkoxylated alcohol containing an average of about 6 to about 15 oxy ethylene repeating units per molecule). For example, the alkoxylated aliphatic monoalcohol may be an ethoxylated C12-C16 linear aliphatic alcohol containing an average of about 8 to about 12 ethylene oxide units per molecule. In particular, ethoxylated tridecanol containing an average of about 10 ethylene oxide units is suitable for use in the present disclosure.

[0028] Another ty pe of nonionic surfactant for use in the present disclosure may be an alkoxylated C2-C8 aliphatic alcohol containing both ethylene oxide and propylene oxide units. The C2-C8 aliphatic alcohol may be n-butanol, for example. The ethylene oxide and propylene units may be arranged in a block manner (e.g., the surfactant may contain a polyoxyethylene block and a polyoxypropylene block). Also suitable for use as nonionic surfactants are alkoxylated phenols, in particular ethoxylated phenols wherein the phenolmay be substituted with one or more alkyl groups (in particular, long chain alkyd groups such as nonyl or dodecyl groups or aralkyl groups, such as in tristyrylphenol).

[0029] Suitable anionic surfactants include, but are not limited to, surfactants containing anionic functional groups at their head, such as sulfate groups, sulfonate groups, phosphate groups, and carboxylate groups. The cationic counterion to the anionic functional group may be. for example, an alkali metal (e.g., Na, K) or an amine (ammonium) cation such as a quaternary ammonium. Useful types of anionic surfactants in the present disclosure include, but are not limited to, alkyl sulfates, alkyd ether sulfates, sulfated alkanolamides, glyceride sulfates, alkyl aryl sulfonates (including straight-chain alk dbenzenesulfonates, branched alkydbenzenesulfonates, alkylnaphthal ene-sulfonates), alpha olefin sulfonates, lignosulfonates, sulfo-carboxylic compounds (e.g., sodium lauryl sulfoacetate, sulfosuccinates (including dialkylsulfosuccinates), sulfosuccinamates. organo phosphored surfactants, sacrosides, hydroxyalkane-sulfonates, alkanesulfonates, alkydphenoxy polyoxyethylene propyl sulfonates, salts of polyoxyethylene alk dsulfophenyl ethers, sodium N-methyl-N-oleyltaurates, monoamide disodium N- alkylsulfosuccinates. petroleum sulfonates, sulfated castor oil, sulfated tallow oil, salts of sulfuric esters of aliphatic alkydesters, salts of alkylsulfuric esters, salts of alkylsulfuric esters, sulfuric esters of polyoxyethylenealkylethers, salts of sulfuric esters of aliphatic monoglycerides, sodium salt of the monosulfated monoglyceride of hydrogenated coconut oil fatty acids, salts of sulfuric esters of polyoxyethylene alkylphenylethers, salts of alkylphosphoric esters, salts of phosphoric esters of polyoxyethylenealkylethers, salts of phosphoric esters of polyoxyethylenealkylphenylethers, partially saponified compounds of styrene-maleic anhydride copolymers, partially saponified compounds of olefin-maleic anhydride copolymers, naphthalenesulfonate-formalin condensates, higher alkyl sulfoacetates, and higher fatty acid esters of 1.2-dihydroxy propane sulfonate and combinations thereof. Particular among these anionic surfactants are sulfonate surfactants, in particular salts of alkyl aryl sulfonates, especially salts of Cs-Cis alkyd benzene sulfonates such as salts of dodecylbenzene sulfonate, and combinations thereof.

[0030] A total amount of surfactant is used that is effective, in combination with the any thickeners and / or suspending agent that may be present in the composition, to provide a physically stable dispersion. The amount of surfactant needed to achieve a physically stable dispersion will depend on a number of factors, including, for instance, the types and amounts of linear poly etheramines and thickeners / suspending agents present and well as the types of surfactants utilized. Typically, however, an amount of surfactant is used whichis sufficient to provide a weight ratio of linear poly etheramine to surfactant within the range of from about 5: 1 to about 50: 1 or from about 6: 1 to about 20: 1.

[0031] Further, certain surfactants and combinations of surfactants also have well- known activities disrupting membranes. This activity is general to several cationic surfactants, but is also true of certain non-ionic and ionic surfactants.

[0032] If desired, the multifunctional booster compositions of the present disclosure may include one or more substances capable of functioning as thickener or suspending agents to render the compositions physically stable, e.g., as a component of the at least one additive. In particular, the types and amounts of thickeners and / or suspending agents are selected such that at 25 °C the resulting multifunctional booster composition has a viscosity of at least 300 cps. In other embodiments, the viscosity of the multifunctional booster composition at 25 °C is at least 400 cps or at least 500 cps. Generally, it will be desirable for the viscosity of the multifunctional booster composition to not be increased to the point where it becomes difficult to transfer or handle the multifunctional booster composition by means of pumping. Viscosity is measured using a Brookfield viscometer (spindle #5, 100 rpm).

[0033] Suitable thickeners / suspending agents include, without limitation, clays (including natural clays and organo-modified clays), silicates (e.g., silicas such as modified silicas and fumed silicas), polysaccharides (e.g., gums such as xanthan gum, cellulosic polymers), polyacrylates, and the like and combinations thereof.

[0034] One or more other components, in addition to those mentioned above, may additionally be present in the multifunctional booster compositions of the present disclosure. In certain embodiments, however, the multifunctional booster composition consists essentially of or consists of only the aforementioned components, except that one or more defoamers may optionally be present in such example embodiments.

[0035] Additional optional components include, but are not limited to, dispersants, defoamers (antifoams, e.g., silicone-based defoamers, mineral oil-based defoamers, hydrophobic silica-based defoamers), sequestering / chelating agents, fillers, coloring agents, antifreezing agents, corrosion inhibitors (anti-corrosion additives), ultraviolet light stabilizers, antioxidants, solvents, co-solvents, scale inhibitors, and the like.

[0036] Multifunctional booster compositions in accordance with the present disclosure may be prepared by adaptation of any of the techniques known in the art for creating dispersions of water-insoluble substances in water using surfactants (emulsifiers), thickeners, suspending agents, and combinations of these ingredients. For example, asuitably sized mixing vessel may be charged with water, followed by the surfactants desired to be included in the multifunctional booster composition. While agitating the surfactant / water mixture, the linear poly etheramine and a portion of the thickeners / suspending agents are added. Mixing at high speed and / or high shear may be continued until a homogeneous emulsion having the desired particle size (typically 5 to 75 microns) is obtained. The mixture may be heated to a temperature somewhat above room temperature during this step. The remaining thickeners / suspending agents may then be added and the mixture agitated until homogeneous once again. The mixture may be cooled to room temperature prior to the final addition of thickeners / suspending agents. The multifunctional booster composition may then be transferred by pumping or other means to one or more suitable storage containers such as tanks, drums or totes.

[0037] The multifunctional booster compositions disclosed herein are work with the alkalinity of biocide-free alkaline paint formulations to enhance their biostability against bacterial and fungal organisms. Exemplary microorganisms can include one or more species from one or both of the following groups.

[0038] Bacteria: Alcaligenes such as Alcaligenes faecalis , Acinetobacter such as Acinetobacter calcoaceticus , Bacillus such as Bacillus subtilis, Citrobacter such as Citrobacter freundii, Corynebacterium such as Corynebacterium ammoniagenes , Enterobacter such as Enterobacter aerogenes or Enterobacter cloacae, Enterococcus such as Enterococcus hirae, Escherichia such as Escherichia coll, Proteus such as Proteus hauseri. Pseudomonas such as Pseudomonas aeruginosa. Pseudomonas fluorescens, or Pseudomonas stutzeri, Salmonella such as Salmonella enterica, Staphylococcus such as Staphylococcus aureus,' Nesterenkonia such as Nesterenkonia soli. Bacillus such as Bacillus polygoni.

[0039] Fungi: Acremonium such as Acremonium strictum, Altemaria such as Altemaria tenuis ox Altemaria alternata, Aspergillus such as Aspergillus niger or Aspergillus brasiliensis, Candida such as Candida albicans, Chaetomium such as Chaetomium globosum, Fusarium such as Fusarium solani, Geotrichum such as Geotrichum candidum. Lentinus such as Lentinus tigrinus, Penicillium such as Penicillium glaucum, Penicillium funiculosum, ox Penicillium pinophilum, Rhodotorula such as Rhodotorula rubra ox Rhodotorula mucilaginosa, Stachybotrys such as Stachybotrys chartarum, Trichoderma such as Trichoderma virens.

[0040] The multifunctional booster composition of the present disclosure may be utilized in various formulations to enhance their biostability or other properties. Themultifunctional booster composition may be effective in many aqueous or water-based industrial formulations, including but not limited to solutions including soluble liquids, sols, gels, partially hydrated and / or dispersed biopolymers; suspensions including suspension concentrates, mineral slurries, suspensions of various biological materials including microorganisms in viable and non-viable form; microcapsules of many forms including conventional capsule suspensions; emulsions including oil in water emulsions, water in oil emulsions and microemulsions, and mixtures of the above types of formulations.

[0041] In one example aspect, the multifunctional booster composition of example aspects of the present disclosure may be in an aqueous industrial formulation. In another example aspect, the multifunctional booster composition of example aspects of the present disclosure may be in an aqueous or oil-based formulation which may be a solution, a suspension, a microcapsule, an emulsion, or a mixture thereof, as described herein. In one embodiment, the multifunctional booster composition may be oil soluble.

[0042] Surprisingly, the linear polyetheramine disclosed herein may enhance performance characteristics of an aqueous industrial materials with or without additional biocidal agents being present. These performance enhancing characteristics may include, but are not limited to, material property enhancements to pH, defoaming efficacy, viscosity stability, scrub resistance, open-time, or other desired features of the end-use material. In one example embodiment, the aqueous industrial material may include a linear polyetheramine disclosed herein. For instance, the linear poly etheramine of Formula I may be present in the aqueous industrial material in an amount from about 0.01% w / w to about 5% w / w, such as from about 0.1% w / w to about 3% w / w, such as from about 0.5% w / w to about 2.5% w / w, such as from about 0.75% w / w to about 2% w / w, or any range therebetween.

[0043] Advantageously, the aqueous industrial material comprising a multifunctional booster composition disclosed herein does not contain or is “essentially free” of a biocidal agent. In one embodiment, the multifunctional booster composition disclosed herein does not contain a biocidal agent, such as isothiazolin-3-one. For instance, the aqueous industrial material may be “essentially free” of l,2-benzisothiazohn-3-one (“BIT”), N-(n- butyl)-l,2-benzisothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (“DCOIT”), 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4- isothiazolin-3-one, 5-chloro-2-methyl-2H-isothiazol-3-one / 2-methyl-2H-isothiazol-3-one (“CMIT / MIT”), or a combination thereof. However, if desired, the aqueous industrialmaterial according to example aspects of the present disclosure may include additional non-isothiazolinone biocidal agent. For example, the aqueous industrial material may contain include one or more non-isothiazolinone biocidal agents, such as methylbenzimidazole-2-yl carbamate (“BCM’’), TPBC, 3-(3,4-dichlorphenyl)-l ,l - dimethylurea (“Diuron”), and / or 2-bromo-2-nitropropane-l,3-diol (“Bronopol”). Supplemental algaecides that can be used include, but are not limited to, 2-tert- Butylamino-4-ethylamino-6-methylthio-1.3.5-triazin (“Terbutryn”) and 3-(4- isopropylphenyl)-l,l-dimethylurea (“Isoproturon”).

[0044] Other examples of non-isothiazolinone biocidal agents are tetraalkylphosphonium halogenides, guanidine derivatives, imidazole containing compounds such as 4-[l - (2,3-dimethylphenyl)ethyl]-l H-imidazole [medetomidine] and derivatives, macrocyclic lactones including avermectins and derivatives thereof such as ivermectin, or spinosyns and derivatives thereof such as spinosad, or enzymes such as oxidase, or proteolytically, hemicellulolytically, cellulolytically, lipolytically or amylolytically active enzymes.

[0045] In one example embodiment, the aqueous industrial material may include a linear polyetheramine and at least one additive. For instance, the linear poly etheramine of Formula I and the at least one additive may be present in the aqueous industrial material at a weight ratio of from about 50: 1 to about 2:3. such as from about 30: 1 to about 1 :3, or any range therebetween. In one example embodiment, the compound of Formula I and the at least one additive may be present in the aqueous industrial material at a weight ratio of about 1 : 1.

[0046] In one example embodiment, the aqueous industrial material disclosed herein may include at least one additive present at a total concentration of from about 100 parts per million (ppm) to about 10000 ppm, such as from about 20 ppm to about 400 ppm, such as from about 30 ppm to about 200 ppm, or any range therebetween.

[0047] The multifunctional booster compositions disclosed herein may be added to an aqueous industrial formulation as a concentrate. In one example implementation, the concentration of Formula I in the aqueous industrial formulation may be from about 0.01 wt.% to about 5 wt.%, such as from about 0. 1 wt.% to about 4 wt.%, such as from about 0.5% wt.% to about 3 wt.%, such as from about 1 wt.% to about 2.5 wt.%, or any range therebetween.

[0048] The multifunctional booster composition disclosed herein may be employed for various applications. For instance, the applications (or end-use formulations) include, butare not limited to, metalworking fluids, polymer latex, paints, polymer emulsion, coatings, adhesives, admixtures, spackling and joint compounds, sealants, caulks, mineral and pigment slurries, printing inks, household products, personal care products, leather and hide treatment products, etc. In one embodiment, the metalworking fluid may be a coolant.

[0049] The multifunctional booster composition of the present disclosure may be utilized in a metalworking fluid. These fluids are used to reduce heat and friction and to remove metal particles during metalworking processes. For instance, the composition may be utilized to cool and / or lubricant metalworking processes such as turning, grinding, boring, drawing, tapping, gear shaping, reaming, rolling, hobbing, and band- and hacksawing. The composition may improve the quality of the workpiece by continuously removing the fines, chips, and swarfs from the tool being used and the surface of the workpiece.

[0050] The multifunctional booster composition of the present disclosure may be provided in a concentrated form or in a ready to use form which has been diluted. In view of handling ability, the multifunctional booster composition of the present disclosure may be water based and may be prepared as a stock solution having a high concentration so that the user dilutes the fluid as necessary with water to use the diluted fluid as desired.

[0051] In various aspects, the working composition may be a paint or coating composition, wherein other ingredients may include one or more pigments, polymeric resin binders or fillers (e.g., latex resins), and a carrier vehicle such as water. Particular polymeric resins may include acrylate, butadiene, PVA, EVA, styrene, or vinyl acetate polymers. In one embodiment of the disclosure, the multifunctional booster composition is dosed into a coating composition, in particular a water-based coating composition such as a latex paint, in an amount from about 0.01% by weight to about 4% by weight of the coating composition.

[0052] In another example aspect, the aqueous industrial material of the disclosure may be ajoint sealing compound. Joint sealing compound (also known as wallboard j oint compound, dry wall joint compound, or wallboard mud) may be used to attach tape to wallboard (also known as drywall, plasterboard or sheetrock) in order to cover the tape and conceal imperfections in the surface of the wallboard. A typical wallboard joint compound may contain substantial or larger proportions of gypsum or limestone and water and relatively smaller proportions of stone, clay, and a polymer.

[0053] The multifunctional booster disclosed herein may be incorporated into a paint. In one example implementation, the paint includes a solvent (e.g., water), a latex binder(e.g., a polymer including one or more acrylate, vinyl acetate, vinyl chloride, and / or styrene butadiene monomers), and the multifunctional booster. Optionally, the paint can further include a dispersant and / or surfactant to improve distribution of the latex binder throughout the paint. Tn this manner, the dispersant and / or surfactant can be used to produce a more homogenous mixture that can provide a more even coating of the paint. Optionally, the paint can include a thickening agent to adjust the viscosity' of the paint to improve adhesion of the wet paint to an applicator (e.g.. a brush or roller). Optionally, the paint can include one or more pigments (e.g., TiO2) for providing a color to the paint. Optionally, the paint can include a cosolvent (e.g., ethylene glycol) that can improve solubility of components of the paint. An example aspect of implementations according to the present disclosure can include a no or low volatile organic compounds (VOCs) content. High VOCs are recognized as environmental hazards as well as demonstrating personal hazards to painters who work in confined and / or unventilated spaces. In these spaces, VOCs can collect in the air which may cause breathing issues for painters and possible health concerns.

[0054] Another aspect of example implementations can include a type of latex binder. The latex binder can include various polymers suitable for paints such as an acrylate (e.g., polymethylmethacrylate), that can be formed as a homopolymer or co-polymer. For example, a co-polymer can include incorporation of another monomer (e.g., butadiene styrene). In some implementations, the acrylate can be modified to include one or more nitrile groups. Thus, latex binders can include various acrylates, acrylate butadiene styrene copolymers, and acry lonitrile butadiene styrene copolymers. Additionally, these latex binders are provided for example purposes, and additional latex binders may be used alone or in combination with implementations of the disclosure.

[0055] As an example for illustration, an implementation of the present disclosure can include a paint including a latex binder with an acrylate. The acrylate can include a polymer or copolymer that includes one or more acrylate monomers. Example aspects of the acry late polymer or copolymer can include a mass fraction of an acrylate monomer. For instance, the acrylate can include a copolymer that includes an acrylate monomer (e.g.. methyl methacrylate) and a second monomer (e.g., butadiene styrene). The mass fraction of the acrylate monomer to the total weight of the copolymer can define the mass fraction. In some acry lates the mass fraction of acry late monomer to the total weight of the copolymer can be no less than about twenty (20) wt% and no greater than about one hundred (100) wt% such as no less than about thirty (30) wt% and no greater than about eighty (80) wt%.no less than about fort}7(40) wt% and no greater than about seventy (70) wt%, or no less than about forty' five (45) wt% and no greater than about sixty (60) wt% (e.g., one hundred (100) wt%. ninety five (95) wt%, ninety (90) wt%, eighty five (85) wt%, eighty’ (80) wt%, seventy’ five (75) wt%, seventy’ (70) wt%, sixty five (65) wt%, sixty’ (60) wt%, fifty’ five (55) wt%, or fifty' (50) wt%). In particular, certain implementations can include an acrylate having a mass fraction of acrylate monomer to the total weight of acry late greater than fifty' (50) wt%.

[0056] The multifunctional booster composition disclosed herein may be incorporated into an isothiazolinone-free alkaline paint. As used herein, the term “alkaline paint” refers to a paint formulation having a pH greater than 7.0. The term “isothiazolinone-free alkaline paint” refers to a paint formulation having a pH greater than 7.0 that does not include an isothiazolinone. For instance, the isothiazolinone-free alkaline paint formulation may include the linear poly etheramine of Formula I disclosed herein. In one example embodiment, the isothiazolinone-free alkaline paint formulation may have a pH between about 9.0 and 11.5.

[0057] In one example embodiment, the linear polyetheramine of Formula I disclosed herein may be present in the isothiazolinone-free alkaline paint formulation at a concentration of from about 0.01 wt.% to about 2.0 wt.%, such as from about 0.02 wt.% to about 1.5 wt.%, such as from about 0.05 wt.% to about 1.0 wt.%, or any range therebetween. For instance, in one example embodiment, the linear poly etheramine of Formula I disclosed herein may be present in the isothiazolinone-free alkaline paint formulation at a concentration of from about 0.01 wt.% to about 2.0 wt.%. In another example embodiment, the linear polyetheramine of Formula I disclosed herein may be present in the isothiazolinone-free alkaline paint formulation at a concentration of from about 0.02 wt.% to about 1.5 wt.%. In another example embodiment, the linear polyetheramine of Formula I disclosed herein may be present in the isothiazolinone-free alkaline paint formulation at a concentration of from about 0.05 wt.% to about 1.0 wt.%.

[0058] Optionally, if desired, the isothiazolinone-free alkaline paint formulation may include a humectant in combination with the linear polyetheramine of Formula I disclosed herein. For instance, in one example embodiment, the linear polyetheramine of Formula I and humectant may be present in the isothiazolinone-free alkaline paint formulation at a weight ratio of from about 1 :10 to about 10: 1, such as from about 1:2 to about 8: 1, such as from about 1:3 to about 6: 1, such as from about 1:4 to about 5: 1, or any range therebetween. For instance, in one example embodiment, the linear polyetheramine ofFormula I and humectant may be present in the isothiazolinone-free alkaline paint formulation at a weight ratio of from about 1 : 10 to about 10: 1. In another example embodiment, the linear polyetheramine of Formula I and humectant may be present in the isothiazolinone-free alkaline paint formulation at a weight ratio of from about 1 :2 to about 8: 1. In another example embodiment, the linear poly etheramine of Formula I and humectant may be present in the isothiazolinone-free alkaline paint formulation at a weight ratio of from about 1:3 to about 6: 1. In another example embodiment, the linear poly etheramine of Formula I and humectant may be present in the isothiazolinone-free alkaline paint formulation at a weight ratio of from about 1 :4 to about 5: 1.

[0059] Example implementations formulated according to the present disclosure may provide additional benefits for formulating low VOC paints. In particular, example implementations may include a solvent that can be considered low or no VOC. For instance, water is not an organic compound and so is preferably incorporated in paints of the present disclosure. In addition to water, a co-solvent can be included to improve solubility of components of the paint (e.g., the multifunctional booster, surfactants, pigments, etc.). Example co-solvents may be VOC exempt (e.g., acetone. AMP-95, dimethyl carbonate, methyl acetate, parachlorobenzotrifluoride, tert-butyl acetate, and propylene carbonate) or be included in lower concentrations (e.g., lower weight percentages) to limit the VOC concentration of the paint.

[0060] For instance, certain implementations of the present disclosure can include paints having a VOC content of less than one thousandth of a percent (<0.001 %) based on the total weight of the paint. VOC content can be determined using various methods, preferably example implementations can include specific VOC content determined according to EPA Method 24 for surface coatings.

[0061] Alternative methods for determining VOC content may also be used to determine VOC content in some example implementations. For instance, ASTM D6886-14 does not specifically define what constitutes a VOC ingredient based on chemical properties, but rather, implies that any components that produce a peak in a gas chromatogram are considered VOC (exempt or non-exempt). Additionally, ISO 11890-2 can be used to determine VOC content based on a pre-defined boiling point limit. As an example, if the term “VOC” is being used for compounds whose boiling points are below the boiling point limit, a marker compound of known purity and with a boiling point (BP) within ±3 °C of the defined maximum is used. So, if the EU definition for VOC is being employed (i.e.. any compound with a boiling point below 250 °C is classified as VOC),tetradecane (with a BP of 252.6 °C) or a similar boiling point non-polar compound can be used as a marker compound for non-polar systems, while diethyl adipate (with a BP of 251 °C) can be used for polar systems.

[0062] Example implementations in accordance with the present disclosure may include a VOC content, as determined using one of the methods disclosed herein (e.g., EPA Method 24. ASTM D6686, ISO 11890, or chamber methods like ASTM D5116), of less than 5 grams per liter by ASTM D6886, or lower, less than 1000 ppm total VOC and SVOC by ISO 11890. In a preferable embodiment, the VOC content is less than 500 ppm SVOC and less than 600 ppm VOC. In some implementations, the VOC content can be substantially zero, for example including a substantially undetectable amount of VOC based on the analytical tool used to determine VOC content (e.g., a gas chromatograph).

[0063] One example aspect of certain implementations can include an increase in open time resulting from the addition of the multifunctional booster to the paint. To determine the increase in open time, a base paint having a composition that does not include the multifunctional booster can be modified to produce the paint, by adding an effective amount of the multifunctional booster to the base paint. For some implementations, the addition of the effective amount of the multifunctional booster to the base paint can produce an increase in the open time determined for the paint, relative to the base or reference paint alone, of no less than ten percent (10%), such as no less than twenty percent (20%), such as no less than thirty percent (30%), such as no less than forty percent (40%), such as no less than fifty percent (50%), such as no less than sixty percent (60%), such as no less than seventy-five percent (75%). Open time can be determined using a variety of methods, preferably implementations according to the present disclosure can determine open time according to OTA test ASTM D7488-11 ‘‘Standard Test Method for Open Time of Latex Paints.”

[0064] In one example embodiment, the baseline aqueous industrial material does not include the multifunctional booster composition and has a relative composition for other components included in the aqueous industrial material that is approximately the same, and wherein the open time is determined according to OTA test ASTM D7488 “Standard Test Method for Open Time of Latex Paints.”

[0065] Alternatively or additionally, another example aspect of certain implementations can include an increase in scrub resistance resulting from the addition of the multifunctional booster to the paint composition. To determine the increase in scrub resistance, a testing method such as ASTM D2486 can be used to compare number ofscrubs to failure and / or exposure of a substrate material after a number of scrubs. For instance, a first coating can be applied to the substrate material using a base paint and a second coating applied to the substrate material using a paint, the paint having been formulated by adding an effective amount of the multifunctional booster to the base paint. After applying an abrasive force (e.g., a scrub) to the coatings, the scrub resistance can be determined based at least in part on removal of the coating and / or exposure of the substrate material. In some implementations, addition of an effective amount of the multifunctional booster can produce an increase in scrub resistance (relative to the base paint) of no less than 110 hundred percent (110%) and no greater than one thousand percent (1000%).

[0066] Alternatively or additionally, another example aspect of certain implementations can include an increase in stain resistance resulting from the addition of the multifunctional booster to the paint composition. To determine the increase in scrub resistance, a testing method such as ASTM D4828 can be used to compare number of stains to failure and / or exposure of a substrate material after a number of stain. For instance, a first coating can be applied to the substrate material using a base paint and a second coating applied to the substrate material using a paint, the paint having been formulated by adding an effective amount of the multifunctional booster to the base paint. After applying an abrasive force (e.g., a stain) to the coatings, the stain resistance can be determined based at least in part on removal of the coating and / or exposure of the substrate material. It is understood that the polyetheramine disclosed herein is not used as a chemical reactant as a primary mechanism of forming the coating.

[0067] One example aspect forming the aqueous latex paint with the multifunctional booster can include homogenizing the aqueous latex paint while adding the multifunctional booster. Homogenizing can include various forms of mixing to facilitate incorporation of the multifunctional booster with the aqueous latex paint. For instance, homogenizing can include mixing at a specified rotation per minute (RPM) the aqueous latex paint, sonicating the aqueous latex paint at a specified frequency, and / or vortexing the aqueous latex paint. In this manner, the multifunctional booster can be incorporated throughout the aqueous latex paint to produce a paint according to example implementations of the present disclosure. Thus, example implementations can further include methods for producing paints, such as example paints of the disclosure using example methods of the disclosure.

[0068] Another aspect of methods for producing a paint can include determining a solids content for the base paint (e g., the aqueous latex paint), and, based at least in part on the solids content, adding an amount of Formula 1 to the base paint. In particular, the solidscontent can determine a basis for including an effective amount of the multifunctional booster. For instance, the amount of latex binder can be determined based on the solids content and an effective amount of the multifunctional booster can be determined according to the ratio of the multifunctional booster to the latex binder disclosed in example implementations herein.

[0069] The preceding description is exemplary' in nature and is not intended to limit the scope, applicability or configuration of the disclosure in any way. Various changes to the described embodiments may be made in the function and arrangement of the elements described herein without departing from the scope of the disclosure.

[0070] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention is related.

[0071] As used in this application and in the claims, the singular forms “a”, “an”, and “the” include the plural forms unless the context clearly dictates otherwise. Additionally, the term “includes” means “comprises”. The methods and compositions of the present disclosure, including components thereof, can comprise, consist of. or consist essentially of the essential elements and limitations of the embodiments described herein, as well as any additional or optional ingredients, components or limitations described herein or otherwise useful in biocidal compositions.

[0072] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, percentages, and so forth, as used in the specification or claims are to be understood as being modified by the term “about”. Accordingly, unless otherwise indicated, implicitly or explicitly, the numerical parameters set forth are approximations that may depend on the desired properties sought and / or limits of detection under standard test conditions / methods. When directly and explicitly distinguishing embodiments from discussed prior art, the embodiment numbers are not approximates unless the word “about” is recited.

[0073] As used herein, “optional” or “optionally” means that the subsequently described material, event or circumstance may or may not be present or occur, and that the description includes instances where the material, event or circumstance is present or occurs and instances in which it does not. As used herein, “w / w%” and “wt%” mean by weight as relative to another component or a percentage of the total yveight in the composition.

[0074] The term “about’' is intended to mean approximately, in the region of, roughly, or around. When the term “about” is used in conjunction with a numerical range, it modifies that range by extending the boundaries above and below the numerical values set forth. Unless otherwise indicated, it should be understood that the numerical parameters set forth in the following specification and attached claims are approximations. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, numerical parameters should be read in light of the number of reported significant digits and the application of ordinary rounding techniques.

[0075] The term “substantially free of’ when used to describe the amount of substance in a material is not to be limited to entirely or completely free of and may correspond to a lack of any appreciable or detectable amount of the recited substance in the material. Thus, e.g., a material is “substantially free of’ a substance when the amount of the substance in the material is less than the precision of an industry-accepted instrument or test for measuring the amount of the substance in the material. In certain example embodiments, a material may be “substantially free of’ a substance when the amount of the substance in the material is less than 10%, less than 9%, less than 8%, less than 7%, less than 6%. less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, less than 0.5%, or less than 0.1% by weight of the material.

[0076] The phrase “effective amount” means an amount of a compound that promotes, improves, stimulates, or encourages a response to the particular condition or disorder or the particular symptom of the condition or disorder.

[0077] The terms “potentiator” and “adjuvant” as used herein refers to an additive that can affect the performance of an active compound when used in combination with the active compound but does not exhibit any biocidal activity itself and / or does not exhibit significant biocidal activity’ itself in the compositions of the invention at relevant use levels.

[0078] The term “biocidal agent” as used herein refers to any chemical compound that is intended to inhibit or kill organisms on a coating surface and / or that prevents or kills the growth of organisms “in-can” in an aqueous paint or coating prior to surface application.

[0079] The terms “antifouhng paint” and “antifouling coating” are used interchangeably herein.

[0080] As used herein, the terms “first”, “second”, and “third” may be used interchangeably to distinguish one component from another and are not intended to signify location or importance of the individual components.

[0081] Here and throughout the specification and claims, range limitations are combined and interchanged, such ranges are identified and include all the sub-ranges contained therein unless context or language indicates otherwise. For example, all ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other.

[0082] As used herein, the term “D50” or “D50 particle size” refers to the volume median particle size, where 50% of the particles of the sample volume have a size below that range or value.

[0083] Analogously, as used herein, the term “D95” or “D95 particle size” refers to a value where 95% of the particles of the sample volume have a size below that range or value.

[0084] As used herein, the term “particle size” as used herein, unless specifically stated otherwise, refers to the median particle size D50. Particle size can be measured using a laser scattering particle size analyzer, such as a HORIBA LA 910 particle size analyzer.

[0085] The terms “median particle size” and “average particle size” and D50 are used herein interchangeably.

[0086] As used herein, the term “micronized” as used herein means a median particle size (D50) in the range of 0.01 to 25 microns.

[0087] This written description uses examples to disclose the present disclosure, including the best mode, and also to enable any person skilled in the art to practice the disclosure, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the disclosure is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they include structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

[0088] Furthermore, certain aspects of the present disclosure may be better understood according to the following examples, which are intended to be non-limiting and exemplary in nature. Moreover, it will be understood that the compositions described in the examples may be substantially free of any substance not expressly described.EXAMPLESExample 1Wet-State Preservation of Polyether amine-dosed Preservative-free Emulsion Paints against Nesterenkonia soli and Standard 4 Bacteria

[0089] The biostability of alkaline paint which includes poly etheramines were evaluated in a preservative-free alkaline paint (including polymer emulsion, titanium dioxide, calcium carbonate, silicates, polymer filler material, water and additive; VOC: max. 1 g / L; pH = 10.5-11.4) using a modified ASTM D2574, Standard Test Method of Resistance of Emulsion Paints in the Container to Attack by Microorganisms. To do so, poly etheramines (PEA) were dosed into the alkaline paint to achieve concentrations of 100, 200, 500. 1000, and 5000 ppm. The dosed paints were speed mixed at 2000 rpm for 2 min and then equilibrated for at least overnight prior to all tests.

[0090] The following two groups of bacterial strains were utilized for the inoculations: Group 1 bacteria: Nesterenkonia soli ATCC TSD-321 and Group 2 bacteria: Acinetobacter calcoacelicus ATCC 14987, Enterobacter cloacae ATCC 7256, Escherichia coll ATCC 11229, and Pseudomonas aeruginosa ATCC 10145.

[0091] Bacterial cultures were obtained from American Type Culture Collection (ATCC) culture collection and stored at -80 °C. Test bacteria were adapted to grow at pH level of 9. Nesterenkonia soli was used because it was isolated from high alkaline paint. Lawns of the test bacteria were harvested from tryptic soy agar (TSA) using sterile PBS and adjusted to ~108CFU / mL with a spectrophotometer. For multi-organism inoculations, the ~108CFU / mL organism suspensions are mixed at equal volume before inoculation.

[0092] A standard inoculation regimen was followed. For each of the sample ladder(s) the initial inoculum volume was equivalent to 10% of the initial sample size. A 5% inoculation was used for the second challenge and a 2.5% inoculation was used for the third.

[0093] The biostability' of the paints were monitored at 24 hours, 72 hours, and 7 days after each inoculation by streaking the samples on plates of TSA (pH=9.6 adjusted by the addition of NazCOs / NaHCCL) for bacterial challenge samples. TSA plates were evaluated following incubation at 33 °C for 48 hours. "Streak" plates were ranked from 0 to 5 according to the degree of contamination as interpreted in Table 1.Table 1. Rating Scale of Microbial GrowthVery severely contaminated| Fail |

[0094] The biostability of polyetheramine-dosed biocide-free alkaline paints are summarized in Table 2 and Table 3 against Nesterenkonia soli and standard 4 bacteria (Acinetobacter calcoaceticus, Enterobacter cloacae, Escherichia coli, Pseudomonas aeruginosa), respectively. 100 ppm PEA D230, 500 ppm PEA D400, and 200 ppm PEA T403 resisted the growth of Nesterenkonia soli (Group 1 bacteria) while 100 ppm PEA D230, 100 ppm PEA D400, 5000 ppm PEA D2000 and 200 ppm PEA T403 resisted the growth against Group 2 bacteria. Thus, the addition of poly etheramine into alkaline paint surprisingly creates a more biostable environment. Alkaline paint is known to be selfpreserving (as described in EP1297079B1, EP3252109A1), but addition of PEA improves the self-preserving activity of the paint, possibly by maintaining or increasing the pH.Table 2. Biostability of biocide-free alkaline paints using Group 1 bacteriaTable 3. Biostability of biocide-free alkaline paints using Group 2 bacteriaExample 2Open Times of Polyetheramine-dosed Emulsion Paints

[0095] The open times of polyetheramine-dosed alkaline paints were determined using ASTM D7488, Standard Test Method for Open Time of Latex Paints. Polyetheramines were dosed into alkaline paint to achieve 0.2%, 0.5%, 1.0% and 2.0% level. The dosed paints were speed mixed at 2000 rpm for 2 min for homogenous paints and then were equilibrated for at least overnight prior to tests. The open time test was performed at 23 ± 2 °C and 50 ± 5% relative humidity (RH). 3 mil wet thickness of paint was drawn down onto a sealed Leneta chart and then a series of “X"’ marks were made in the center of the wet film. After a fixed period (1 or 2 minutes), a minimal amount of paint was brushed over each X area in a perpendicular direction to the initial draw-down using 10 cycles of back and forth across the film. The time at which the X " begins to show through the layer of the brushed paint is the open time. Each chart w as dried overnight and observed to determine the open time.

[0096] The open times of polyetheramine-dosed alkaline paints are summarized in Table 4. 0.2% PEA D230 and 0.2% PEA D2000 give >20% increase in open time while 2.0% PEA D400 gives >10% increase in open time, resulting in an improved workability after applying the paint.Example 3Scrub Resistances of Polyetheramine-dosed Emulsion Paints

[0097] The scrub resistance properties of polyetheramine-dosed alkaline paints were evaluated following an ASTM D2486 Standard Test Methods for Scrub Resistance of Wall Paints. Polyetheramines were dosed into alkaline paint to achieve 0.2%, 0.5%, 1.0%. and 2.0% level. The dosed paints were speed mixed at 2000 rpm for 2 min for homogenous paints and then equilibrated overnight at ambient condition. 6 mil wet thickness fdms of the dosed and blank paints were simultaneously drawn down side-by-side perpendicular to the length of a plastic Byko chart. The films of the testing and blank paints were duplicated by reversing their positions on the panel. The coatings were dried at ambient conditions for 7 days. A nylon bristle brush was conditioned in water for 24 hours prior to use. The brush was then removed and shaken vigorously to remove any excessive water. 10 g of the abrasive scrub medium from the Leneta Company was added on top of the brush evenly and 5 mL water was placed on the surface of the coatings along the path of the brush. The coating films were scrubbed at the rate of 37 cycle / minute. The test was stopped after each 400 cycles before failure. The brush was removed for re-applying 10 g of the scrub medium, and 5 mL water was placed on the coating surface along the path of the brush. The testing was resumed until the failure of the coatings (one continuous thin line of 12.7 mm width of the shim). The numbers of cycles to failure were recorded for both reference and test coatings, and the percentage of scrub resistance retained for treated paint was calculated as follows:# of Cycles to Failure of Testing Paint% Scrub Resistance = x 100%# of Cycles to Failure of Blank Paint

[0098] The scrub resistances of polyetheramine-dosed alkaline paints are summarized in Table 5. Surprisingly, all three polyetheramines give a dose-dependent increase in scrub resistance up to >200% increase for 2.0% PEA D230 and D400, resulting in an improved resistance of dry paint fdm to erosion caused by scrubbing.Table 5. Scrub Resistance of Polyetheramine-dosed alkaline PaintsExample 4 pHs of Polyetheramine-dosed Alkaline Paints

[0099] The pHs of polyetheramine-dosed alkaline paints were measured using a pH meter before and after thermal aging. Poly etheramines were dosed into alkaline paint to achieve 0.2%, 0.5%, 1.0%. and 2.0% level. The dosed paints were speed mixed at 2000 rpm for 2 min for homogenous paints and then equilibrated overnight at ambient condition prior to initial pH measurements. These paints were then aged at 54 °C for 2 and 4 weeks and the pHs were measured again after the thermal aging to assess the stability of alkaline pH.

[0100] The pHs of polyetheramine-dosed alkaline paints are summarized in Table 6. Poly etheramines generally improve the initial pH, which results in a better maintained alkaline pHs after thermal aging and may translate into longer shelf-life.Table 6. pHs of Polyetheramine-dosed alkaline PaintsExample 5Viscosities of Polyetheramine-dosed Emulsion Paints

[0101] The viscosities of polyetheramine-dosed alkaline paints were measured by aBroofield DV2T viscometer (Spindle: RV06, Spin speed: 60 rpm) before and after thermalaging. Polyetheramines were dosed into alkaline paint to achieve 0.2%, 0.5%, 1.0%, and 2.0% level. The dosed paints were speed mixed at 2000 rpm for 2 min for homogenous paints and then equilibrated overnight at ambient condition prior to initial viscosity measurements. These paints were then aged at 54 °C for 2 and 4 weeks and the viscosities were measured again after the thermal aging.

[0102] The viscosities of polyetheramine-dosed alkaline paints are summarized in Table 7. The additions of PEA D230, D400 and D2000 give insignificant impact on initial paint viscosities (< 10% change relative to blank paint). Upon aging at 54 °C for 2 and 4 weeks, PEA D230 and D2000 still give insignificant impact on paint viscosities (mostly < 20% change relative to blank paint) up to 2.0% level; meanwhile PEA D400 gives insignificant impact on paint viscosities up to 0.5% but > 30% change at > 1.0% level. Overall, this suggests minimal impact of polyetheramines on the application of paint such as flow and spread, coverage, texture, and sagging resistance etc.Table 7. Viscosities of Polvetheramine-dosed alkaline PaintsExample 6VOC Content of Poly ether amine containing Alkaline Paints

[0103] Alkaline paints are generally sold to consumers for interior do-it-yourself (DIY) who desire to meet stringent VOC requirements. One important VOC requirement is set and certified by the German environmental ecolabel association (RAL GmbH), which provides companies with the opportunity to meet Blue Angel standards. For interior low- emission wall paints (DE-UZ 102), Blue Angel requires paints to be low emission.essentially free of biocide, free of lead-containing pigments and PF AS, free of harmful plasticizers, and free of ingredients known to be carcinogenic, mutagenic, or otherwise toxic to human health. The low emissions (VOC) requirement set by Blue Angel sets VOC limits using test method ISO 1 1890-2 to a max 700 ppm for compounds with boiling point < 252.6 °C. The term VOC covers all organic substances (e.g. residual monomers, solvents, film-forming aids, preservatives and other production-related accompanying substances) that following total evaporation and subsequent gas chromatographic analysis are eluted at retention times lower than that of tetradecane (boiling point: 252.6 °C) on a non-polar separation column. SVOC limits are set at max 500 ppm (ISO 11890-2). According to ISO 11890-2, SVOCs include all species that elute between diethyladipate (DEA, with a boiling point of 251 °C) and n-docosane (with a boiling point of 368 °C) on the chromatogram.

[0104] To investigate the ability of polyetheramine-containing alkaline paint to meet these strict VOC / SVOC requirements, a Blue Angel certified alkaline paint formulation was dosed with 0.24 %wt. Jeffamine D230 or Jeffamine D400 and tested according to the ISO 11890-2 procedure. The results are summarized in Table 8.Table 8. VOC / SVOC Content according to DIN EN ISO 11890-2

[0105] The results show that with the addition of 0.24% D230, the VOC levels exceed the Blue Angel criteria, while the addition of 0.24% D400 allows the paint to remain within the required limits.Example 7Formulations of Polyether amine and other Additives

[0106] Formulations of linear poly etheramines and silicates, salts, amine, or humectant were prepared through simple mixture. The prepared solutions were clear shortly after mixing. Example formulations are summarized in Table 9.Table 9. Formulations of Poly etheramine and other AdditivesExample 8Biostability of Polyetheramine-dosed Preservative-free Emulsion Paints against Nesterenkonia soli and Standard 4 Bacteria in Paints with Lower pH values

[0107] The biostability of alkaline paint adjusted to pH 9, 10, and 1 1 in a preservative- free alkaline paint (including polymer emulsion, titanium dioxide, calcium carbonate, silicates, polymer filler material, water and additive; VOC: max. 1 g / L; pH = 10.5-11.4) was assessed using a modified ASTM D2574. Standard Test Method of Resistance of Emulsion Paints in the Container to Attack by Microorganisms. Paints were dosed with multifunctional booster Formulation 7.5 at 0, 0.1, 0.2, 0.5, and 1.0 %wt (600 to 6000 ppm Jeffamine D400) adjusted to pH 9, 10, and 11 with citric acid, and then subjected to the testing protocol. All dosed paints were speed mixed at 2000 rpm for 2 min and then equilibrated for at least overnight prior to all tests.

[0108] As in Example 1, two groups of bacterial strains were utilized for the inoculations: Group 1 bacteria: Nesterenkonia soli ATCC TSD-321 and Group 2 bacteria: Acinetobacter calcoaceticus ATCC 14987, Enterobacter cloacae ATCC 7256, Escherichia coli ATCC 11229, and Pseudomonas aeruginosa ATCC 10145.

[0109] Bacterial cultures were obtained from American Type Culture Collection (ATCC) culture collection and stored at -80 °C. Test bacteria were adapted to grow at pH level of 9. Lawns of the test bacteria were harvested from try ptic soy agar (TSA) using sterile PBS and individually adjusted to ~108CFU / mL using a spectrophotometer. For multi-organism inoculations, the ~108CFU / mL organism suspensions are mixed at equal volume before inoculation. A standard inoculation regimen was followed. Each sample was tested with an initial inoculum volume of 10% of the initial sample size. A 5% inoculation was used for the second challenge and a 2.5% inoculation was used for the third.

[0110] The biostability of the paints were monitored at 24 hours, 72 hours, and 7 days after each inoculation by streaking the samples on plates of TSA (pH=9.6 adjusted by the addition of Na2COs / NaHCCh) for bacterial challenge samples. TSA plates were evaluated following incubation at 33 °C for 48 hours. "Streak" plates were ranked from 0 to 4 according to the degree of contamination as interpreted in Table 10.Table 10. Rating Scale of Microbial Growth

[0111] The biostability of polyetheramine-dosed biocide-free alkaline paints are summarized in Tables 11 and 12 against Nesterenkonia soli and standard 4 bacteria (Acinetobacter calcoaceticus, Enterobacter cloacae, Escherichia coli, Pseudomonas aeruginosa), respectively. Alkaline paint is known to be self-preserving (as described in EP1297079BL EP3252109A1) within the pH range of 9 - 11, but the addition of Formulation 7.5 worked with the alkalinity of the paint formulation and achieved biostability at 0. 1 wt.% at pH 11 and 10, but required up to 1.0 wt.% to achieve the same degree of biostability at pH 9. The results in the pH 9 paint were more severe when challenged with Group 2 bacteria, common spoilage drivers in standard paints (formulated to pH -8.5-10), suggesting that the formulations can retain biostability even as the pH is lowered to alter the types of organisms capable of driving spoilage at lower pH.Table 11. Biostability of biocide-free alkaline paints using Group 1 bacteria

[0112] These and other modifications and variations to the present disclosure may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present disclosure, which is more particularly set forth in the appended claims. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary7skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the disclosure so further described in such appended claims.

Claims

What Is Claimed:

1. An isothiazolinone-free alkaline paint formulation, comprising: about 0.01 wt.% to about 2 wt.% of a linear polyetheramine of Formula I:, wherein R1 is H or CH3 and x is from about 3 to about 50; wherein the formulation pH is between about 9.0 and about 11.5.

2. The isothiazohnone-free alkaline paint of claim 1. wherein the linear poly etheramine has a molecular weight greater than 230 Daltons (Da).

3. The isothiazolinone-free alkaline paint of claim 1, wherein the linear polyetheramine comprises the following structure:, wherein x is from about 5 to about 40.

4. The isothiazolinone-free alkaline paint of claim 3. wherein x is from about 6 to about 35.

5. The isothiazolinone-free alkaline paint of claim 3. wherein x is from about 7 to about 35.

6. The isothiazolinone-free alkaline paint of claim 1, wherein the linear polyetheramine comprises the following structure:wherein the sum of x and z is no less than 3 and y is from about 5 to about 20.

7. The isothiazolinone-free alkaline paint of claim 1, further comprising a humectant.

8. The isothiazolinone-free alkaline paint of claim 7, wherein linear poly etheramine of Formula I and humectant is from about 1: 10 to about 10: 1.

9. The isothiazolinone-free alkaline paint of claim 1. wherein the isothiazohnone-free alkaline paint formulation has a pH of from about 8.5 to about 10, the isothiazohnone-free alkaline paint formulation further comprises a vinyl acetate-acrylic binder, and theisothiazolinone-free alkaline paint formulation has a solids content greater than thirty percent and less than sixty percent.

10. The isothiazolinone-free alkaline paint of claim 1. wherein the isothiazolinone-free alkaline paint formulation displays an open time of no less than ten percent compared to a baseline open time displayed for an isothiazolinone-free alkaline paint without the linear polyetheramine and the humectant.

11. The isothiazolinone-free alkaline paint of claim 1, wherein the isothiazolinone-free alkaline paint has an improved scrub resistance of at least 110% compared to an isothiazolinone-free alkaline paint without the linear polyetheramine and the humectant.

12. The isothiazolinone-free alkaline paint of claim 1, wherein the isothiazolinone-free alkaline paint has a total VOC content of less than 1000 ppm.

13. The isothiazolinone-free alkaline paint of claim 1, wherein the isothiazolinone-free alkaline paint has a total VOC content of less than 600 ppm.

14. A multifunctional booster composition, comprising: a linear polyetheramine of Formula I:, wherein R1 is H or CH3 and x is from about 2.5 to about 50; a humectant; and optionally at least one additive comprising a silicate, pH adjusting agent, , additional organic amine not described by Formula I, or a combination thereof. wherein the linear poly etheramine of Formula I and humectant are present in the composition at a weight ratio of from about 1 : 10 to about 10: 1, and wherein the at least one optional additive and the poly etheramine of Formula I are present in the composition at a weight ratio of from about 1 :5 to about 100: 1 when the at least one optional additive is present in the multifunctional booster composition.

15. The composition of claim 14, wherein the at least one additive is present in the multifunctional booster composition at a weight ratio of the compound of Formula I to the at least one additive is from about 75: 1 to about 1:5.

16. The composition of claim 14, wherein the at least one additive is present in the multifunctional booster composition, and the weight ratio of the compound of Formula I to the at least one additive is from about 60: 1 to about 1 :3.

17. The composition of claim 14, wherein the linear polyetheramine has a molecular weight greater than 230 Daltons (Da).

18. The composition of claim 14, wherein the linear polyetheramine comprises the following structure:wherein x is from about 5 to about 40.

19. The composition of claim 18, wherein x is from about 6 to about 7.

20. The composition of claim 18, wherein x is from about 7 to about 50.

21. The composition of claim 14, wherein the linear poly etheramine comprises the following structure:wherein the sum of x and z is no less than 3 and y is from about 5 to about 20.

22. The composition of claim 14, wherein the compound of the Formula 1 is present in the composition at a concentration of from about 30% by weight of the composition to about 99% by weight of the composition.

23. The composition of claim 14, wherein the humectant is present in the composition at a concentration of from about 1% by weight of the composition to about 70% by weight of the composition.

24. The composition of claim 14, wherein the humectant comprises polyethylene glycol or glycerine.

25. The composition of claim 24, wherein the polyethylene glycol has an average molecular weight of about 400 g / mol or greater.

26. The composition of claim 14, wherein the composition is substantially free of an isothiazolinone.

27. The composition of claim 14, wherein the organic amine comprises a pH adjusting agent.

28. The composition of claim 27, wherein the pH adjusting agent comprises 2-amino-2- methyl- 1 -propanol .

29. A multifunctional booster composition, consisting of:30% to about 99% by weight of a linear poly etheramine of Formula I:, wherein R1 is H or CH3 and x is from about 2.5 to about 50;1% to about 70% by weight of a humectant; and optionally less than 10% by weight of at least one additive comprising a pH adjusting agent, an organic amine, or a combination thereof.

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