Polyetheramine-based multifunctional enhancer composition

Abstract

The present disclosure relates generally to a multifunctional enhancer composition comprising a polyetheramine and at least one additive comprising an inorganic metal compound, a silicate, a pyrithione salt or an organic amine wherein R1 is H or a C1-C9 alkyl group, each of R2, R3 and R4 is independently H or CH3, and each of x, y and z is independently from 1 to 10. According to the present disclosure, the weight ratio of polyetheramine to additive is from about 1: 5 to 100: 1.

Description

[0001] Related Applications

[0002] This application is based upon and claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 351,025 filed on June 10, 2022 and U.S. Provisional Patent Application Serial No. 63 / 405,544 filed on September 12, 2022, and is incorporated herein by reference. Background Art

[0003] The preservation of water-based materials remains complicated by regulations that prohibit or restrict the use of certain active ingredients. For those active ingredients that continue to be widely used, some carry label indications at effective use levels. For this reason, there is a great need for industry to improve the activity of in-can preservatives at "off-label" levels.

[0004] Partly due to regulatory and labeling issues with preservative addition, many paint manufacturers in the EU (currently regulated by the Biocide Products Administration (BPR)) are producing biocide-free paints. These biocide-free paints are produced by adjusting the pH to ~11, which is generally considered to limit the growth of microorganisms. However, although paints do not contain biocides, they are not without problems. For example, high pH can cause irritation, limiting the use of many commonly used paint additives, and large levels of low alkaliphilic bacteria have been detected to actively grow in paints.

[0005] Typical use levels of BIT in coatings are 200–500 ppm. Due to BIT’s weaknesses (e.g., efficacy against Pseudomonas), the active is often combined with an additional biocide ingredient. However, regulatory agencies continue to restrict the use levels of additional biocide ingredients as well as BIT, forcing “residual” ingredients (such as BIT) to become the workhorse of preservation at low levels. At low use levels, the combination of single active preserves can lead to resistance to the biocide in a plant environment and cause severe spoilage problems that are difficult to remediate in an industrial setting.

[0006] In addition to the limits set by regulatory agencies, even in regions where acceptable levels of active substance use are more widespread and unaffected by labelling indications, it is difficult for manufacturers to achieve good preservation at a reasonable cost of use.

[0007] For these reasons, the industry is in urgent need of providing a multifunctional enhancer that simultaneously improves the activity of the active ingredient to improve the overall preservation quality or enable preservation levels to meet the "no labeling" requirements in certain regions. In addition, due to the multifunctionality of the ingredient, the functions provided by many other additives (e.g., dispersants, defoamers, rheology modifiers, surfactants, pH adjusters) can be simultaneously saved and SKU reduced. SUMMARY OF THE INVENTION

[0009] The present disclosure generally relates to a multifunctional enhancer composition comprising a polyetheramine and at least one additive, wherein the additive comprises an inorganic metal compound, a silicate, a pyrithione salt and an organic amine, wherein R1 is H or a C1-C9 alkyl group, each of R2, R3 and R4 is independently H or CH3, and each of x, y and z is independently 1 to 10. According to the present disclosure, the weight ratio of the polyetheramine to the additive is about 1:5 to 100:1.

[0010] Other features and aspects of the disclosure are discussed in greater detail below.

[0011] BRIEF DESCRIPTION OF THE DRAWINGS

[0012] The full and enabling disclosure of the present disclosure is more particularly set forth in the remainder of the specification, including with reference to the accompanying drawings, in which:

[0013] Figure 1 Depicted is the killing curve of the combination of BIT and a dispersion enhancer (1737-35) against Pseudomonas aeruginosa (ATCC #10145) over 24 hours.

[0014] Figure 2 Depicted is the killing curve of the combination of BIT and a lysis enhancer (1737-67) against Pseudomonas aeruginosa (ATCC #10145) over 24 hours.

[0015] Figure 3 Depicted is the killing curve of the combination of BIT and a lysis enhancer (1737-72) against Pseudomonas aeruginosa (ATCC #10145) over 24 hours.

[0016] Figure 4 Shown are the L*, ΔE and Yellowness Index results for an architectural semi-gloss paint over 8 weeks with and without Jeffamine T-403 or "1737-72".

[0017] Figure 5 Describes laboratory testing with and without the Jeffamine T-403 or "1737-72" test pH readings from laboratory testing of architectural semi-gloss paint over an 8 week period.

[0018] Figure 6 Describes grind fineness, air content, and opacity of an architectural semi-gloss paint with and without Jeffamine T-403 or "1737-72".

[0019] Figure 7 Depicting the KU viscosity curve of a standard architectural semi-gloss paint with and without Jeffamine T-403 or "1737-72".

[0020] Fig. 8ADescribes coal black color analysis of architectural paints with and without Jeffamine T-403 or "1737-72".

[0021] Figure 8B Describes the phthalocyanine blue colorimetric readings of architectural paints with and without Jeffamine T-403 or "1737-72".

[0022] Figure 8C Describes the iron oxide red colorimetric readings of architectural paints with and without Jeffamine T-403 or "1737-72".

[0023] Fig. 9 Describes the rub cycle failure results for an architectural semi-gloss paint with and without Jeffamine T-403 or "1737-72".

[0024] Fig.10 Described are actual washability test results for films prepared from semi-gloss architectural paints with and without Jeffamine T-403 or "1737-72".

[0025] Fig.11 Actual washability test results for films prepared from semi-gloss architectural paints with and without Jeffamine T-403 or "1737-72" are shown.

[0026] Fig.12 Described are stain resistance testing and L* and ΔE values ​​for films prepared from architectural paints with and without Jeffamine T-403 or "1737-72".

[0027] Fig.13 Described are the accelerated weathering (accelerated weathering) exposure results (cyclic UV: 8 hours at 60°C. Condensation: 4 hours at 50°C) of films prepared from architectural paints with and without Jeffamine T-403 or "1737-72".

[0028] Fig.14 Describe the in-can appearance and degree of separation or settling of test samples of architectural paints with and without Jeffamine T-403 or "1737-72".

[0029] Repeat use of reference characters in the present specification and drawings is intended to represent the same or analogous features or elements of the invention. DETAILED DESCRIPTION OF THE INVENTION

[0031] Those skilled in the art will appreciate that the current discussion is merely a description of exemplary embodiments and is not intended to limit the broader aspects of the present disclosure.

[0032] The present disclosure generally relates to a multifunctional enhancer composition comprising a polyetheramine having the structure of Formula I below:

[0033]

[0034] At least one additive, including an inorganic metal compound, a silicate, a pyrithione salt and an organic amine, wherein R1 is H or C 1 -C 9 alkyl, each of R2, R3 and R4 is independently H or CH 3 , each of x, y and z is independently 1 to 10. According to the present disclosure, the weight ratio of the polyetheramine to the additive is about 1:5 to 100:1.

[0035] Surprisingly, the polyetheramines, alone or in combination with additional components, function as multifunctional enhancers, simultaneously enhancing the activity of the in-can preservatives and providing other benefits to coating properties (eg, rheology, pH stability, color acceptance, or combinations thereof).

[0036] The degree of polymerization (x, y and z) of Formula I is independently 1-10. In some cases, the degrees of polymerization x, y and z may be the same or different. For example, x may be 1, y may be 2, and z may be 3. In another case, x, y and z may each be 2. In one embodiment, the sum of the polymerizations (e.g., the sum of the values ​​of x, y and z) is not less than 5, such as 6, 7, 8, 9 or 10. In one embodiment, the sum of the values ​​of x, y and z is not greater than 10.

[0037] The polyetheramine is a primary aliphatic polyamine. For example, the polyetheramine can be polyoxypropylene triamine or polyoxypropylene triamine. In one embodiment, the polyetheramine of formula I is T403 polyetheramine (Huntsman Corp., Houston, Texas). The multifunctional reinforcing agent of the present disclosure may include one or more polyetheramines. The polyetheramine may be present in the composition at about 20-80 wt %, such as about 25-75 wt %, such as about 35-60 wt %, such as about 40-55 wt %, or any range therebetween, based on the weight of the composition.

[0038] In addition, the polyetheramine of formula I in the multifunctional enhancer composition disclosed herein is combined with at least one additive or enhancer, the additive or enhancer comprising an inorganic metal compound, a silicate, a pyrithione salt, an organic amine or a combination thereof. In one embodiment, the weight ratio of the polyetheramine to the additive is about 1:500-50:1, such as about 1:400-40:1, such as about 1:250-25:1, such as about 1:100-20:1, such as about 1:50-15:1, such as about 1:20-10:1, or any range therebetween.

[0039] In one embodiment, the multifunctional enhancer composition disclosed herein comprises an inorganic metal compound. For example, the inorganic metal compound may include, but is not limited to, an inorganic zinc compound, an inorganic magnesium compound, an inorganic copper compound, an inorganic lithium compound, or a combination thereof. In one embodiment, the inorganic metal compound is an inorganic zinc compound, such as one or more of zinc oxide (sometimes referred to herein as "ZnO", zinc nitrate, zinc chloride and zinc acetate. Preferably, the zinc oxide includes zinc oxide having a particle size of less than 50 microns. The inorganic zinc compound is present in the multifunctional enhancer composition at a concentration of about 0.2-5 wt%, 0.5-3.5 wt%, 1-2.5 wt%, 1.5-2 wt%, or any range therebetween, based on the weight of the composition. For example, the weight ratio of the polyetheramine to the zinc acetate may be in the range of 50:1-1:5 (including endpoints). In some embodiments, the weight ratio of the polyetheramine to the zinc acetate in the preservative composition disclosed herein is 20:1-1:20, 15:1-1:15, 10:1-1:10, 5:1-1:5 or 4:1-1:4. In another embodiment, the weight ratio of the polyetheramine to the zinc acetate is 2:1.

[0040] The polyetheramines of Formula I in combination with an inorganic zinc compound can act as a multifunctional enhancer to simultaneously enhance the activity of the in-can preservative and provide other benefits to coating performance (e.g., rheology, pH stability, color acceptance, or a combination thereof) at a concentration of about 0.075-1 wt %, such as about 0.1-0.75 wt %, such as about 0.15-0.45 wt %, or any range therebetween.

[0041] In one embodiment, the inorganic metal compound is an inorganic magnesium compound, such as magnesium oxide. For example, the magnesium compound can be present in the composition at a concentration of about 5-20 wt%, such as about 7.5-15 wt%, such as about 10-13.5 wt%, or any range therebetween.

[0042] In one embodiment, the inorganic metal compound is an inorganic copper compound, such as a copper salt. For example, the copper salt may include copper sulfate, copper nitrate, copper carbonate, copper carbonate hydroxide, copper oxide, copper oxychloride, copper hydroxide, copper acetylacetonate, copper pyrrolidone carboxylate (PCA), PCA methylsiliconol copper, acetyltrosine copper methylsiliconol, acetylmethanesulfonate copper, aminoacetamidoimidazole propionate copper, picolinate copper, tripeptide-1 copper, bis (tripeptide-1) acetate copper, ascorbyl phosphate copper succinyl tripeptide-34, pyridinethione copper, calcium copper sodium phosphate, pyridoxal-5-phosphate copper, sodium copper chlorophyllin, copper chlorophyllin, EDTA copper disodium, or a combination thereof. In one embodiment, the copper salt may include one or more of copper sulfate, copper nitrate, copper carbonate, copper oxide, and copper acetylacetonate.

[0043] In one embodiment, the inorganic metal compound is an inorganic lithium compound, such as a lithium salt. For example, the lithium salt may include lithium carbonate, lithium acetate, lithium fluoride, lithium sulfate, lithium nitrate, lithium tetraborate, lithium metaborate, lithium pyrophosphate, lithium tripolyphosphate, lithium orthosilicate, lithium metasilicate, or a combination thereof.

[0044] In another embodiment, the multifunctional enhancer composition disclosed herein may include a silicate. Silicates may include, but are not limited to, silicon dioxide, such as modified silicon dioxide and fumed silica. In one embodiment, the silicate may be one or both of potassium methyl silicate and sodium metasilicate (e.g., sodium metasilicate pentahydrate). Commercial examples include Silres 168 (Wacker), Tyson WR50 (Tyson, Singapore), and Xiameter OFS0777 (Corning). The silicate is present in the multifunctional enhancer composition in an amount of about 0.5-15 wt %, such as about 1-10 wt %, such as about 2.5-7.5 wt %, or any range therebetween, based on the weight of the composition.

[0045] In one embodiment, the multifunctional enhancer composition disclosed herein may include one or more pyrithione salts. For example, such pyrithione salts may include zinc pyrithione, sodium pyrithione, potassium pyrithione, lithium pyrithione, ammonium pyrithione, calcium pyrithione, magnesium pyrithione, organic amine pyrithione, barium pyrithione, strontium pyrithione, copper pyrithione, cadmium pyrithione or a combination thereof. In one embodiment, the multifunctional enhancer composition disclosed herein does not include a pyrithione salt. In another embodiment, the multifunctional enhancer composition may include one or both of zinc pyrithione and sodium pyrithione. The pyrithione salt is present in the multifunctional enhancer composition at about 0.005-1%, such as about 0.015-0.5%, such as about 0.025-0.25%, or any range therebetween, based on the weight of the composition. For example, the pyrithione salt is present in the multi-functional enhancer composition at about 5-500 ppm, such as about 50-300 ppm, such as about 100-250 ppm, or any range therebetween.

[0046] In one embodiment, the multifunctional enhancer composition disclosed herein may include an organic amine, such as a pH regulator. The organic amine may include, but is not limited to, 2-amino-2-methyl-1-propanol (AMP95), ethanolamine, 1-amino-2-propanol, 3-amino-1-propanol, 2-(methylamino)ethanol, 2-(ethylamino)ethanol, 2(propylamino)ethanol, 2(isopropylamino)ethanol, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, 2-amino-2-ethyl-1,3-propanediol (also known as AEPD), 2(2-aminoethoxy)ethanol (also known as diglycolamine), N-methyldiethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylaminoethanol, N,N-dimethylamino-2-propanol, etc. The organic amine may be used alone or in any combination. In one embodiment, the organic amine may include 2-amino-2-methyl-1-propanol (AMP95). For example, AMP95 is present in the composition at a concentration of about 25-75 wt%, such as about 40-65 wt%, such as about 50-60 wt%, or any range therebetween.

[0047] Advantageously, the water-based industrial material comprising the multifunctional enhancer composition disclosed herein does not contain or is "substantially free" of biocides. In one embodiment, the multifunctional enhancer composition disclosed herein does not contain biocides, such as isothiazolin-3-one. For example, the water-based industrial material is "substantially free" of 1,2-benzisothiazolin-3-one (BIT), N-(n-butyl)-1,2-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, water-based industrial materials according to example aspects of the present disclosure may include additional non-isothiazolinone biocides. For example, water-based industrial materials may contain one or more non-isothiazolinone biocides, such as methyl benzimidazol-2-yl carbamate (BCM), IPBC, 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron) and / or 2-bromo-2-nitropropane-1,3-diol (bronopol). Supplementary algaecides that can be used include, but are not limited to, 2-tert-butylamino-4-ethylamino-6-methylthio-1,3,5-triazine (terbutryn) and 3-(4-isopropylphenyl)-1,1-dimethylurea (isoproturon).

[0048] Other examples of non-isothiazolinone biocides are tetraalkylphosphonium halides, guanidine derivatives, imidazole-containing compounds such as 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [medetomidine] and derivatives, macrolides (including avermectins and their derivatives such as ivermectin), or spinosa polysaccharides and their derivatives such as spinosad, or enzymes such as oxidases, or proteolytic, hemicellulolytic, cellulose-hydrolyzing, lipolytic or amylolytic active enzymes.

[0049] Any biocide present in the multifunctional enhancer composition disclosed herein will advantageously be in the form of relatively fine particles, for example, particles with a particle size of 5-75 microns. The desired particle size can be obtained using conventional techniques such as grinding, milling, screening, etc. The biocide is present in the multifunctional enhancer composition at about 0.001-1%, such as about 0.015-0.85%, such as about 0.25-0.5%, or any range therebetween, based on the weight of the composition. For example, the biocide is present in the multifunctional enhancer composition at about 50-1500ppm, such as about 100-1000ppm, such as about 250-750ppm, such as about 350-500ppm, or any range therebetween.

[0050] Optionally, the multifunctional enhancer composition of the present disclosure may use one or more surfactants. Surfactants act as emulsifiers and help keep the water-insoluble ingredients in the formulation in the form of a stable dispersion (emulsion) of small particles suspended in an aqueous phase.

[0051] Suitable types of nonionic surfactants include, but are not limited to, polyoxyalkylene 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 glycol alkylphenol ethers, polyoxypropylene glycol alkylphenol ethers, polyoxyethylene glycol / 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.

[0052] Specific nonionic surfactants include alkoxylated aliphatic monoalcohols and alkoxylated aromatic monoalcohols. 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 monoalcohols (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 monoalcohol may vary as desired, but is typically about 2-50 on average. If more than one type of alkylene oxide is used, the alkylene oxides may be reacted as a mixture (to provide polyoxyalkylene segments having a random copolymer structure) or sequentially (to provide polyoxyalkylene segments having a block copolymer structure).

[0053] Another type of nonionic surfactant useful in the present disclosure is alkoxylated aliphatic monohydric alcohols, which are ethoxylated C 10 -C 18 Aliphatic alcohols (especially straight chain primary C 12 -C 16 An aliphatic alcohol (or mixture of such alcohols) which has been reacted with about 6 to 15 moles of ethylene oxide per mole of aliphatic alcohol to provide an alkoxylated alcohol having an average of about 6 to 15 ethylene oxide repeating units per molecule. For example, the alkoxylated aliphatic monohydric alcohol can be an ethoxylated C 6-12-hydroxyethyl alcohol having an average of about 8 to 12 ethylene oxide units per molecule. 12 -C 16 Straight chain aliphatic alcohols. In particular, ethoxylated tridecanols containing an average of about 10 ethylene oxide units are suitable for use in the present disclosure.

[0054] Another type of nonionic surfactant used in the present disclosure is an alkoxylated C 2 -C 8 Aliphatic alcohols. For example, C 2 -C 8 The aliphatic alcohol may be n-butanol. The ethylene oxide and propylene oxide units may be arranged in blocks (e.g. the surfactant may contain polyoxyethylene blocks and polyoxypropylene blocks). Alkoxylated phenols are also suitable for use as nonionic surfactants, in particular ethoxylated phenols in which the phenol may be substituted with one or more alkyl groups, in particular long-chain alkyl groups, such as nonyl or dodecyl groups, or aralkyl groups, such as tristyrylphenol.

[0055] Suitable anionic surfactants include, but are not limited to, surfactants containing anionic functional groups such as sulfate groups, sulfonate groups, phosphate groups, and carboxylate groups in the surfactant head. The cationic counterions of the anionic functional groups can be, for example, alkali metals (e.g., Na, K) or amine (ammonium) cations, such as quaternary ammonium. Available types of anionic surfactants in the present disclosure include, but are not limited to, alkyl sulfates, alkyl ether sulfates, sulfated alkanolamides, glyceride sulfates, alkyl aryl sulfonates (including linear alkylbenzene sulfonates, branched alkylbenzene sulfonates, alkylnaphthalene sulfonates), α-olefin sulfonates, lignin sulfonates, sulfocarboxylic acid compounds (e.g., sodium lauryl sulfoacetate, sulfosuccinates (including dialkyl sulfosuccinates), sulfosuccinamates, organophosphorus surfactants, sheath glycosides, hydroxyalkane sulfonates, alkyl sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium, N-alkyl sulfosuccinate monoamide disodium, petroleum sulfonates, sulfated castor oil Oil, sulfated tallow oil, aliphatic alkyl ester sulfate salts, alkyl sulfate ester salts, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate, aliphatic monoglyceride sulfate salts, monosulfated monoglyceride sodium salt of hydrogenated coconut oil fatty acid, polyoxyethylene alkylphenyl ether sulfate salts, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts, polyoxyethylene alkylphenyl ether phosphate ester salts, partially saponified compounds of styrene-maleic anhydride copolymers, partially saponified compounds of olefin-maleic anhydride copolymers, naphthalenesulfonate-formaldehyde condensates, sulfoacetic acid higher alkyl esters and 1,2-dihydroxypropanesulfonic acid higher fatty acid esters and combinations thereof. Among these anionic surfactants, sulfonate surfactants are particularly useful, particularly alkyl aryl sulfonates, especially C 8 -C 18 Alkylbenzene sulfonates, such as dodecylbenzene sulfonate, and combinations thereof.

[0056] The total amount of surfactant used should be effective in combination with any thickener and / or suspending agent that may be present in the composition to provide a physically stable dispersion. The amount of surfactant required to achieve a physically stable dispersion will depend on many factors, including, for example, the type and amount of polyetheramine and thickener / suspending agent present and the type of surfactant used. However, typically, the amount of surfactant used is sufficient to provide a weight ratio of polyetheramine:surfactant in the range of about 5:1-50:1 or about 6:1-20:1.

[0057] In addition, certain surfactants and surfactant combinations also have a well-known film-damaging activity that is common to several cationic surfactants and also shared by certain nonionic and ionic surfactants.

[0058] If necessary, the multifunctional enhancer composition of the present disclosure may include one or more substances that can act as thickeners or suspending agents to physically stabilize the composition. In particular, the type and amount of thickeners and / or suspending agents are selected so that the resulting multifunctional enhancer composition has a viscosity of at least 300 cps at 25°C. In other embodiments, the viscosity of the multifunctional enhancer composition at 25°C is at least 400 cps or at least 500 cps. Generally, it is desired that the viscosity of the multifunctional enhancer composition not increase to the extent that it is difficult to transfer or handle the multifunctional enhancer composition by pumping. The viscosity is measured using a Brookfield viscometer (spindle #5, 100 rpm).

[0059] Suitable thickening / suspending agents include, but are not limited to, clays (including natural clays and organically modified clays), silicates (e.g., silicon dioxide, such as modified silicon dioxide and fumed silica), polysaccharides (e.g., gums, such as xanthan gum, cellulose polymers), polyacrylates, and the like, and combinations thereof.

[0060] In addition to the above ingredients, one or more other ingredients may be present in the multifunctional enhancer composition of the present disclosure. However, in some embodiments, the multifunctional enhancer composition consists essentially of or consists only of the above ingredients, but in such embodiments, one or more defoaming agents may be optionally present.

[0061] Additional optional components include, but are not limited to, dispersants, defoamers (antifoams, such as silicone-based defoamers, mineral oil-based defoamers, hydrophobic silica-based defoamers), sequestrants / chelating agents, fillers, colorants, antifreeze agents, corrosion inhibitors (anticorrosion additives), UV stabilizers, antioxidants, solvents, co-solvents, scale inhibitors, etc.

[0062] The multifunctional enhancer composition according to the present disclosure can be prepared by using any technology known in the art, which uses surfactants (emulsifiers), thickeners, suspending agents and combinations of these ingredients to form a dispersion of water-insoluble substances in water. For example, water can be loaded into a mixing container of suitable size and then the surfactant required in the multifunctional enhancer composition is added. While stirring the surfactant / water mixture, polyetheramine and a portion of thickener / suspending agent are added. Mixing can continue at high speed and / or high shear until a uniform emulsion with a desired particle size (usually 5-75 microns) is obtained. In this step, the mixture can be heated to a temperature slightly above room temperature. The remaining thickener / suspending agent can then be added and the mixture can be stirred again until uniform. The mixture can be cooled to room temperature before the thickener / suspending agent is finally added. The multifunctional enhancer composition can then be transferred to one or more suitable storage containers such as tanks, buckets or tote bags by pumping or other means.

[0063] The multifunctional enhancer compositions of the present disclosure can be used to impart resistance to microbial growth (including bacterial, fungal and algal growth) in various working compositions (especially water-based products). Since the multifunctional enhancer compositions are usually prepared to contain relatively high concentrations of active ingredients (i.e., biocides), they are usually used in the form of concentrates, and the concentrates are combined with one or more other ingredients in relatively small amounts to formulate a final product suitable for its intended use.

[0064] The working compositions of the disclosure comprise a polyetheramine and an additional additive or enhancer disclosed herein. In one embodiment, the multifunctional enhancer composition comprises a polyetheramine and an inorganic zinc compound.

[0065] The multifunctional enhancer compositions disclosed herein can effectively enhance the performance of in-container preservatives. "Performance of in-container preservatives" refers to enhancing various properties, including rheology, pH stability, color acceptance, and preservative enhancement of industrial materials. For example, adding the multifunctional enhancer or composition disclosed herein to a non-volatile organic compound (VOC) acrylic semi-gloss architectural coating formulation at a concentration of about 0.2-0.4 wt% can enhance the stability of viscosity over time.

[0066] In various aspects, the working composition is a paint or coating composition, wherein other ingredients may include one or more pigments, a polymer resin binder or filler (e.g., a latex resin), and a carrier (e.g., water). Specific polymer resins may include acrylate, butadiene, PVA, EVA, styrene, or vinyl acetate polymers. In one embodiment of the present disclosure, the multifunctional enhancer composition is added to a coating composition, particularly a water-based coating composition (e.g., a latex paint), in an amount of about 0.02-4 wt % of the coating composition.

[0067] In another exemplary aspect, the water-based industrial material of the present disclosure can be a joint sealing compound. Joint sealing compounds (also known as wallboard joint compounds, drywall joint compounds, or wallboard mud) can be used to apply tape to wallboard (also known as drywall, gypsum board, or plasterboard) to cover the tape and hide imperfections on the wallboard surface. Typical wallboard joint compounds can contain a large amount or proportion of gypsum or limestone and water and a relatively small proportion of stone, clay, and polymers.

[0068] Another exemplary aspect of the present disclosure includes a method of inhibiting or preventing the growth of microorganisms in industrial materials that may be contaminated or susceptible to contamination by bacteria, fungi, yeast, algae, and slime. For example, the method may include incorporating a multifunctional enhancer according to an exemplary aspect of the present disclosure into or onto the industrial material in an amount effective to adversely affect the growth of microorganisms.

[0069] The multifunctional enhancer disclosed herein can be added to an architectural paint. In an exemplary embodiment, the architectural paint includes a solvent (e.g., water), a latex binder (e.g., a polymer including one or more acrylates, vinyl acetate, vinyl chloride, and / or styrene butadiene monomers), and a multifunctional enhancer. Optionally, the architectural paint may also include a dispersant and / or a surfactant to improve the distribution of the latex binder throughout the architectural paint. In this way, the dispersant and / or the surfactant can be used to produce a more uniform mixture, which can provide a more uniform architectural paint coating. Optionally, the architectural paint may include a thickener to adjust the viscosity of the architectural paint, thereby improving the adhesion of the wet paint to an applicator (e.g., a brush or roller). Optionally, the architectural paint may include one or more pigments (e.g., TiO 2 ), used to provide color to architectural paints. Optionally, architectural paints may include co-solvents (e.g., ethylene glycol) that can improve the solubility of the components of the architectural paint. An exemplary aspect of an embodiment according to the present disclosure may include a non-volatile or low volatile organic compound (VOC) content. High VOCs are considered an environmental hazard and a personal hazard to painters working in confined and / or unventilated spaces. In these spaces, VOCs can accumulate in the air, which can cause respiratory problems and possible health problems for painters. Many known paint additives for changing the open time of paints are known to have high VOCs, which poses a challenge. Poor open time performance may require increased working time to correct errors, such as streaks inherent to the paint composition. Therefore, improving open time while reducing VOC content can bring huge advantages to the cost and efficiency of paint projects and the health of painters.

[0070] Another aspect of the exemplary embodiment may include a class of latex binders. The latex binder may include various polymers suitable for architectural paints, such as acrylates (e.g., polymethyl methacrylate), which may be formed as homopolymers or copolymers. For example, the copolymer may include the introduction of another monomer (e.g., butadiene styrene). In some embodiments, the acrylate may be modified to include one or more nitrile groups. Therefore, the latex binder may include various acrylates, acrylate butadiene styrene copolymers, and acrylonitrile butadiene styrene copolymers. In addition, these latex binders are provided for exemplary purposes and may be used alone or in combination with the embodiments of the disclosure using additional latex binders.

[0071] As an illustrative example, embodiments of the present disclosure may include an architectural paint including a latex binder having an acrylate. The acrylate may include a polymer or copolymer comprising one or more acrylate monomers. Exemplary aspects of an acrylate polymer or copolymer may include a certain mass fraction of acrylate monomers. For example, the acrylate may include a copolymer including a copolymer of an acrylate monomer (e.g., methyl methacrylate) and a second monomer (e.g., butadiene styrene). The mass fraction of the acrylate monomer relative to the total weight of the copolymer may define the mass fraction. In some acrylates, the mass fraction of the acrylate monomer relative to the total weight of the copolymer can be not less than about 20 wt % and not more than about 100 wt %, such as not less than about 30 wt % and not more than about 80 wt %, not less than about 40 wt % and not more than about 70 wt %, or not less than about 45 wt % and not more than about 60 wt % (e.g., 100 wt %, 95 wt %, 90 wt %, 85 wt %, 80 wt %, 75 wt %, 70 wt %, 65 wt %, 60 wt %, 55 wt % or 50 wt %. In particular, certain embodiments may include acrylates having a mass fraction of the acrylate monomer relative to the total weight of the acrylate greater than 50 wt %.

[0072] Exemplary embodiments formulated according to the present disclosure can provide additional benefits for formulating low VOC architectural paints. In particular, exemplary embodiments can include solvents that can be considered low or no VOC. For example, water is not an organic compound, so it is preferably added to the architectural paint of the present disclosure. In addition to water, co-solvents can also be added to improve the solubility of architectural paint ingredients (e.g., multifunctional enhancers, surfactants, pigments, etc.). Exemplary co-solvents can be free of VOCs (e.g., acetone, AMP-95, dimethyl carbonate, methyl acetate, parachlorotrifluorotoluene, tert-butyl acetate, and propylene carbonate) or included in lower concentrations (e.g., lower wt%) to limit the VOC concentration of the architectural paint.

[0073] For example, certain embodiments of the present disclosure may include architectural paints having a VOC content of <0.001%, based on the total weight of the architectural paint. The VOC content can be determined using various methods, and preferred exemplary embodiments may include a specific VOC content determined according to EPA Method 24 for Surface Coatings.

[0074] In some exemplary embodiments, alternative methods of determining VOC content may also be used to determine VOC content. For example, ASTM D6886-14 does not specifically define the composition of VOC components based on chemical properties, but rather states that any component that produces a peak in a gas chromatogram is considered a VOC (exempt or non-exempt). In addition, IOS11890-2 can be used to determine VOC content based on predefined boiling point limits. For example, if the term "VOC" is used for compounds with a boiling point below the boiling point limit, a marker compound with a known purity and a boiling point (BP) within ±3°C of the defined maximum value is used. Therefore, if the EU definition of VOC is adopted (i.e., any compound with a boiling point below 250°C is classified as a VOC), tetradecane (BP of 252.6°C) or a non-polar compound of similar boiling point can be used as a marker compound for non-polar systems, while diethyl adipate (BP of 251°C) can be used for polar systems,

[0075] Exemplary embodiments according to the present disclosure may include a VOC content of not less than 0.00001% and not more than 0.001%, such as a VOC content of not less than 0.00005% and not more than 0.0008%, or not less than 0.0001% and not more than 0.0005%, as determined using one of the methods disclosed herein (e.g., EPA Method 24). In some embodiments, the VOC content may be substantially zero, such as including an amount of VOC that is substantially undetectable based on an analytical tool (e.g., a gas chromatograph) used to determine the VOC content.

[0076] For exemplary embodiments, the multifunctional enhancer can be present in an effective amount in the architectural paint to reduce streaks even in a low humidity environment. For example, the multifunctional enhancer can be present in a concentration of not less than about 0.1% and not more than about 5%, such as not less than about 0.5% and not more than about 4.5%, not less than about 1.0% and not more than about 4.0%, not less than about 1.2% and not more than about 3.5%, and not less than about 2% and not more than about 3%, based on the weight of the multifunctional enhancer relative to the total weight of the architectural paint.

[0077] Another aspect according to some embodiments of the present disclosure may include a solids content of not less than 5% and not more than 70%, such as not less than 8% and not more than 50% or not less than 10% and not more than 30%, such as 12%, 14%, 15%, 16% or 18%, based on the total weight of the latex binder.

[0078] According to aspects of some embodiments of the present disclosure, the water-based industrial material may include a multifunctional reinforcing agent and a latex binder in a certain weight ratio. Advantageously, the weight ratio of the multifunctional reinforcing agent to the latex binder is not greater than 1:999 and not less than 1:9, such as not greater than 1:900 and not less than 1:9, not greater than 1:800 and not less than 1:9, not greater than 1:800 and not less than 1:90, or not greater than 1:800 and not less than 1:200 (e.g., 1:900, 1:800:1:700, 1:600, 1:500, 1:400, 1:300, 1:200, or 1:100).

[0079] The weight ratio of the multifunctional enhancer to the latex binder used herein should be understood based on the multifunctional enhancer. Thus, no greater than 1:999 should be understood as no greater than 999 weight units of latex binder for every 1 weight unit of the multifunctional enhancer. As another example for illustration, no less than 1:9 should be understood as no less than 9 weight units of latex binder for every 1 weight unit of the multifunctional enhancer.

[0080] An exemplary aspect of certain embodiments may include an increase in open time due to the addition of a multifunctional enhancer to an architectural paint. In order to determine the increase in open time, a base paint having a composition that does not include the multifunctional enhancer may be modified by adding an effective amount of the multifunctional enhancer to the base paint to produce an architectural paint. For some embodiments, adding an effective amount of the multifunctional enhancer to the base paint may result in an increase in the open time determined for the architectural paint relative to the base paint alone or a reference paint by not less than 10%, such as not less than 20%, such as not less than 30%, such as not less than 40%, such as not less than 50%, such as not less than 60%, such as not less than 75%. The open time can be determined using a variety of methods, preferably, according to embodiments of the present disclosure, the open time can be determined according to the OTA test ASTM D7488-11 "Standard Test Method for Open Time of Latex Paints".

[0081] Alternatively or additionally, another exemplary aspect of some embodiments may include an increase in the resistance to rubbing due to the addition of the multifunctional reinforcing agent to the paint composition. In order to determine the increase in resistance to rubbing, a test method such as ASTM D2486 can be used to compare the number of scrubs to which the substrate is exposed after failure and / or multiple scrubbing. For example, a first coating can be applied to a substrate using a base paint, and a second coating can be applied to the substrate using an architectural paint, wherein the architectural paint is formulated by adding an effective amount of a multifunctional reinforcing agent to the base paint. After applying an abrasive force (e.g., rubbing) to the coating, the resistance to rubbing can be determined at least in part based on the removal of the coating and / or the exposure of the substrate. In some embodiments, the resistance to rubbing (relative to the base paint) produced by adding an effective amount of a multifunctional reinforcing agent is increased by not less than 300% and not more than 1000%, such as not less than 500% and not more than 800%, such as about 750%.

[0082] Alternatively or additionally, another exemplary aspect of some embodiments may include an increase in stain resistance due to the addition of a multifunctional reinforcing agent to the paint composition. In order to determine the increase in stain resistance, a test method such as ASTM D4828 can be used to compare the number of stains exposed to the substrate after failure and / or multiple contaminations. For example, a first coating can be applied to the substrate using a base paint, and a second coating can be applied to the substrate using an architectural paint, wherein the architectural paint is formulated by adding an effective amount of a multifunctional reinforcing agent to the base paint. After applying abrasive forces (e.g., contamination) to the coating, stain resistance can be determined at least in part based on the removal of the coating and / or exposure of the substrate. It should be understood that the polyetheramines disclosed herein are not used as chemical reactants as the primary mechanism for forming a coating.

[0083] Embodiments of the present disclosure may also include methods of adjusting the open time of a base paint (eg, a waterborne latex paint). The methods may include forming a waterborne latex paint (eg, a water-based acrylate) using a multifunctional enhancer having a structure of Formula I as described herein.

[0084] An exemplary aspect of using the multifunctional enhancer to form a water-based latex paint can include homogenizing the water-based latex paint while adding the multifunctional enhancer. Homogenization can include various forms of mixing to promote the combination of the multifunctional enhancer and the water-based latex paint. For example, homogenization can include mixing the water-based latex paint at a specified revolutions per minute (RPM), ultrasonically treating the water-based latex paint with a specified frequency and / or vortexing the water-based latex paint. In this way, the multifunctional enhancer can be introduced into the entire water-based latex paint to produce architectural paint according to the exemplary embodiments of the present disclosure. Therefore, exemplary embodiments can also include a method for producing architectural paint, such as using the exemplary methods of the present disclosure to produce the exemplary architectural paint of the present disclosure.

[0085] Another aspect of the method of producing an architectural paint may include determining the solid content of a base paint (e.g., a water-based latex paint), and adding a certain amount of Compound I to the base paint based at least in part on the solid content. In particular, the solid content may determine the basis for including an effective amount of a multifunctional enhancer. For example, the amount of latex binder may be determined based on the solid content, and the effective amount of the multifunctional enhancer may be determined based on the ratio of the multifunctional enhancer to the latex binder disclosed in the exemplary embodiments herein.

[0086] Some methods of producing architectural paints according to the present disclosure may further include modifying Formula I by adjusting the degree of polymerization (eg, by selecting x, y, and / or z) to alter the open time of the waterborne latex paint.

[0087] The foregoing description is exemplary in nature and is not intended to limit the scope, applicability, or configuration of the present disclosure in any way. Various changes in the described embodiments may be made in the function and arrangement of the described elements without departing from the scope of the present disclosure.

[0088] 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 relates.

[0089] As used in this application and claims, the singular forms "a", "an", and "the" include the plural forms unless the context clearly dictates otherwise. In addition, the term "comprising" means "including". The methods and compositions of the present disclosure, including components thereof, may include, consist of, or consist essentially of the basic 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 biocide compositions.

[0090] Unless otherwise indicated, all numerical values ​​used in the specification or claims expressing the amount of ingredients, properties such as molecular weight, percentages, etc. should be understood as being modified by the term "about". Therefore, unless otherwise indicated (implicitly or explicitly), the numerical parameters listed are approximate values, which may depend on the desired properties sought and / or the detection limits under standard test conditions / methods. When the embodiment is directly and clearly distinguished from the prior art in question, the embodiment numbers are not approximate values ​​unless the word "about" is cited.

[0091] As used herein, "optional" or "optionally" means that the subsequently described material, event or circumstance may or may not exist or occur, and the description includes instances where the material, event or circumstance exists or occurs as well as instances where it does not. As used herein, "w / w%" and "wt%" refer to the weight relative to another component or to the percentage of the total weight of the composition.

[0092] The term "about" means approximately, within, 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 ​​recited. Unless otherwise indicated, it should be understood that the numerical parameters listed in the following specification and the appended claims are approximate. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0093] When the term "substantially free" is used to describe the amount of a substance in a material, the term is not limited to being completely free and may correspond to the absence of any appreciable or detectable amount of the substance in the material. Thus, for example, 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-recognized instrument or test for measuring the amount of the substance in the material. In some exemplary 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.

[0094] The phrase "effective amount" refers to an amount of a compound that promotes, ameliorates, stimulates or encourages a response to a particular condition or disorder or a particular symptom of that condition or disorder.

[0095] The terms "enhancer" and "adjuvant" as used herein refer to additives which, when used in combination with an active compound, can influence the performance of the active compound but which do not themselves exhibit any biocidal activity and / or do not themselves exhibit significant biocidal activity in the compositions of the invention at relevant use levels.

[0096] As used herein, the term "biocide" refers to any chemical compound intended to inhibit or kill organisms on a coating surface and / or to prevent or kill "in-can" biological growth in a waterborne paint or coating prior to surface application.

[0097] The terms "antifouling paint" and "antifouling coating" are used interchangeably herein.

[0098] As used herein, the terms "first," "second," and "third" may be used interchangeably to distinguish one component from another, and are not intended to indicate the position or importance of each component.

[0099] Here and throughout the specification and claims, range limitations are combinable and interchangeable, and these ranges are identified and include all subranges 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.

[0100] As used herein, the term "D50" or "D50 particle size" refers to the volume median particle size, where 50% of the particles by volume of a sample have a size below that range or value.

[0101] Similarly, the term "D95" or "D95 particle size" as used herein refers to the value below which 95% of the particles by volume of a sample have a size below the range or value.

[0102] As used herein, unless expressly stated otherwise, the term "particle size" used herein refers to the median particle size D50. The particle size can be measured using a laser scattering particle size analyzer, such as a HORIBA LA 910 particle size analyzer.

[0103] The terms "median particle size" and "average particle size" and D50 are used interchangeably herein.

[0104] As used herein, the term "micronized" refers to a median particle size (D50) in the range of 0.01-25 microns.

[0105] This written description uses examples to disclose the present disclosure, including the best mode, and also to enable those skilled in the art to practice the present disclosure, including making and using any devices or systems and performing any included methods. The patentable scope of the present disclosure is defined by the claims, and may include other examples that occur to those skilled in the art. These 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 that do not differ substantially from the literal language of the claims.

[0106] In addition, some aspects of the present disclosure may be better understood in light of the following examples, which are intended to be non-limiting and illustrative in nature. In addition, it should be understood that the compositions described in the examples may be substantially free of any material not explicitly described. Example

[0107] Example 1

[0108] The improved activity of blends containing Jeffamine T403 in combination with other ingredients was determined. Potassium methyl silicate (CAS#31795-24-1) and metal oxides were added and the effect of combining with traditional biocides against Pseudomonas was determined. The resulting dispersed formulations were prepared from 60% Jeffamine T403, 5% potassium methyl silicate and 3% magnesium oxide (1737-34) or 3% zinc oxide (1737-35) and 32% inert materials (including surfactants, emulsifiers and solvents).

[0109] Reference number "1737-34"

[0110]

[0111] Reference number "1737-35"

[0112]

[0113] Commercial product composition

[0114] product Active content Carrier Mergal K10N 10% BIT water Troyshield FSP40 40% Sodium Pyrithione water Mergal CM1.5 1.5%CMIT / MIT water AMP95 95% 2-amino-2-methyl-1-propanol -

[0115] To examine the preservative enhancement potential of these dispersions, minimum inhibitory concentration (MIC) testing was performed. MIC was determined by micro broth dilution using the following specific test parameters:

[0116]

[0117] By OD 600 Calculate necessary organism dilution based on an OD of 1.0 600 Equivalent to 8*10 8 CFU / mL. For each test, biocide dilutions were performed in 2-fold increments.

[0118] The test results show that the magnesium oxide version "1737-34" achieved a 2-fold lower MIC value for BIT and a 4-fold lower MIC value for CMIT / MIT, but was significantly antagonistic to sodium pyrithione. The zinc oxide version "1737-35" achieved strong enhancement for all three tested biocides. Compared to Jeffamine T403 (Table 1), the dispersion enhancer "1737-34" was weaker on a product basis, while the dispersion enhancer "1737-35" was significantly stronger on a w / w% basis, especially when combined with sodium pyrithione or CMIT / MIT (Table 2).

[0119]

[0120] Table 1 - MICs of three biocides alone and in combination with Jeffamine T403 against Pseudomonas aeruginosa (ATCC #10145). MIC values ​​are reported in ppm. Fold reductions compared to controls without added enhancers are reported in parentheses.

[0121]

[0122] Table 2 - MICs of three biocides alone and in combination with two dispersible enhancers against Pseudomonas aeruginosa (ATCC #10145). MIC values ​​are reported in ppm. Fold reductions compared to controls without added enhancers are reported in parentheses.

[0123] Kill curves were generated using Mergal K10N (10% BIT) at 500 and 1000 ppm loading levels (50 and 100 ppm BIT) with and without the addition of 0.15 w / w% enhancer "1735-37". Pseudomonas aeruginosa (ATCC #10145) cultures grown in tryptic soy broth were diluted to OD 0.05 in Mueller Hinton broth containing the indicated levels of test compound. 600 =0.7 to plot the kill curve. Time points were collected by adding 1 mL of sample to 9 mL of Dey-Engley neutralized broth and serially diluting in 1x Butterfield phosphate buffer. Counts were obtained from pour plates in tryptic soy agar after overnight incubation at 35°C. After incubation at 35°C for 1, 2, 4, and 24 hours, the samples were neutralized with biocide in 1x Dey-Engley broth and serially diluted on plates for viability measurements. Test results ( Figure 1 ) showed that after 24 hours, both concentrations of BIT showed growth inhibition or reduction from the initial counts, but the combination of BIT and enhancer achieved complete killing of P. aeruginosa (<10 CFU / mL). The enhancer showed similar efficacy to the control, strongly suggesting that the combination of enhancer and BIT acted synergistically to kill P. aeruginosa.

[0124] Example 2

[0125] To test whether the enhancer is effective in the coating, a bacterial challenge test was performed using a panel of industrially important bacterial isolates such as: Alcaligenes faecalis (ATCC #25094), Enterobacter aerogenes (ATCC #13048), Escherichia coli (ATCC #11229), Pseudomonas aeruginosa (ATCC #10145), Staphylococcus aureus (ATCC #6538), Microbacterium paraoxydans (Troy isolate), Burkholderia cepacia (Troy isolate), Citrobacter ukermanii (Troy isolate), and Acinetobacter spp. (Troy isolate). All bacteria were pooled from separate overnight cultures grown in Tryptic Soy Broth (TSB) and measured at equal CFU by OD 600 Measure the mix and then dilute to OD 600 =7(~10 9 CFU / mL) to produce the final bacterial mixed flora. Each mixture was prepared shortly before each inoculation. Inoculation was performed as follows: 0.1 mL was added to 50 g of the designated test sample to produce ~10 7 CFU / g / inoculation. After each attack, a small amount of test sample was applied to tryptic soy agar (TSA) and vigor readings were taken at specified intervals. The plate was then cultured for 3-5 days at 32°C and evaluated with a semi-quantitative scale afterwards. The scale estimates the approximate CFU / g by visually evaluating the colony density along the streaks. The readings are recorded as the average of two repeated semi-quantitative readings from "0" to "4". The samples were mixed before each vigor reading and after each inoculation.

[0126]

[0127] 1 Lunenburg-Duindam, Jenny & Lindner, Wolfgang, In-can preservation of emulsion paints, European Coatings Journal, 66-73 (2000).

[0128] The challenge test results showed that paints containing up to 0.05 w / w% of Troyshield FSP40 or Mergal K10N were highly susceptible to bacterial contamination, while combination with 0.1-0.4 w / w% of "1737-35" improved antimicrobial properties over the baseline of the biocide in a dose-dependent manner (Table 3).

[0129]

[0130]

[0131] Table 3 - Bacterial challenge test results of dispersion enhancer "1737-35" in combination with low levels of BIT and NaPy in Interior Paint #1 (Ref # U21-0108-2). The passing criterion was a rating of "0" 7 days after each bacterial challenge.

[0132] Example 3

[0133] Solution versions of the multifunctional enhancer were produced while maintaining zero VOC content. Solutions "1737-67" and "1737-72" were produced by combining Jeffamine T403, glycerol, and potassium methyl silicate with varying concentrations of zinc acetate and water.

[0134] Reference number "1737-67"

[0135]

[0136] Reference number "1737-72"

[0137]

[0138]

[0139] As in Example 1, the test began by determining the enhancing activity of "1737-67" and "1737-72" with Mergal K10N, MergalCM1.5 and Troyshield FSP40. The test was performed as described for the dispersed version. The test results (Table 4) show that both versions can significantly enhance Mergal CM1.5 (CMIT / MIT) and Mergal K10N (BIT), but only the version with a higher zinc acetate content can enhance Troyshield FSP40 (sodium pyrithione). It is worth noting that "1737-72" is a more effective enhancer than Jeffamine T403 and the dispersed enhancer "1737-35".

[0140]

[0141] Table 4 - MICs of three biocides used alone and in combination with two clear solution enhancers against Pseudomonas aeruginosa (ATCC #10145). "1737-67" contains 60% Jeffamine T403, 3% potassium methyl silicate, and 0.5% zinc acetate, and "1737-72" contains 60% Jeffamine T403, 3% potassium methyl silicate, and 1.5% zinc acetate. MIC values ​​are reported in ppm. The fold reduction compared to the control without added enhancer is reported in parentheses.

[0142] The activity of the clear solution enhancer was further characterized. Figure 1 ) Same procedure, but using "1737-67" to generate the kill curve. The test showed that "1737-67" itself was inactive at 0.15 w / w%, but significantly improved the activity of 50 ppm and 100 ppm BIT ( Figure 2 The enhanced killing curve results were similar to those of the dispersed version "1737-35". The solution version (1737-72) containing 1.5% zinc acetate had similar enhanced activity ( Figure 3 ).

[0143] Bacterial challenge tests were performed as described in Example 2, but using solution versions "1737-67" and "1737-72", also intended to examine the antibacterial improvements of paints preserved with low levels of BIT and NaPy. As with the dispersion enhancer "1737-35", the BIT levels were selected to be 15 and 50 ppm, and the NaPy levels were selected to be 100 and 200 ppm. The challenge results showed that both enhancers were effective in enhancing BIT and NaPy at low levels, but consistent with the MIC experiment (Table 4), "1737-72" was significantly more effective than "1737-67" in enhancing NaPy (Tables 5, 6).

[0144]

[0145] Table 5 - Bacterial challenge test results of solution enhancer "1737-67" in combination with low levels of BIT and NaPy in a test paint formulation (Ref# U21-0108-2). The passing criterion was a rating of "0" 7 days after each bacterial challenge.

[0146]

[0147]

[0148] Table 6 - Bacterial challenge test results of solution enhancer "1737-72" in combination with low levels of BIT and NaPy in a test paint formulation (Ref# U21-0108-2). The passing criterion was a rating of "0" 7 days after each bacterial challenge.

[0149] Example 4

[0150] The enhancer "1737-72" can be combined with other ingredients to enhance its performance as a multifunctional ingredient. AMP95 (2-amino-2-methyl-1-propanol) is a commonly used ingredient used as a pH adjuster and buffer in paint formulations. In order to ensure that the blend of AMP95 and "1737-72" can maintain its efficient function as an enhancer, MIC enhancement experiments and bacterial challenge tests were performed. AMP95 was mixed with "1737-72" at a weight percentage of 1:1 to produce a clear, uniform solution without precipitation. This solution was used for testing.

[0151] MIC experiments showed that the enhancer reduced the MIC of BIT and CMIT / MIT by 2-fold at 0.075 and 0.15 w / w%, and reduced the MIC of sodium pyrithione by 64-fold at 0.15 w / w% (Table 7).

[0152]

[0153] Table 7 - MICs of three biocides used alone and in combination with a 1:1 mixture of "1737-72" and AMP95 against Pseudomonas aeruginosa (ATCC #10145). MIC values ​​are reported in ppm. The fold reduction compared to the control without added enhancer is reported in parentheses.

[0154] Bacterial challenge tests on the combination of "1737-72" and AMP95 showed a strong enhancing effect of low levels of BIT and sodium pyrithione (Table 8).

[0155]

[0156] Table 8 - Bacterial challenge test results of solution enhancer ["1737-72":AMP95] (1:1) in combination with low levels of BIT and NaPy in interior paint #1 (Ref# U21-0108-2). The passing criterion was a rating of "0" 7 days after each bacterial challenge.

[0157] Example 5

[0158] Measuring the multifunctional benefits of Jeffamine T403 and T403 composition "1737-32".

[0159] Based on the Acronal Edge 4750 resin starting formulation, an Acronal Edge 4750 No-VOC Semi-Gloss Architectural Paint formulation was formulated for this project. The sample was prepared as follows:

[0160] • Prepare a total of 1100 grams of paint masterbatch batch samples each time a formulation is made with a different experimental additive loading. Calculations and adjustments are made during the grinding stage.

[0161] ● Grinding stage: Mix the components at 2760 RPM for 20 minutes using a high speed disperser to achieve a particle size of 7-7.5 Hegman as a reference. The amount of "1737-72" and Jeffamine T-403 used in the grinding is 0.20-0.40% of the total formulation, and the water content is adjusted in the paint.

[0162] • Letdown stage: The formulation ingredients were mixed at 1897 RPM for 15 minutes.

[0163] • Coating performance was evaluated 24 hours after allowing the paint to equilibrate overnight and monitored for 8 weeks.

[0164] ●□ Each masterbatch was then dispensed into 4 x 1 / 2 pint epoxy novolac lined jars and evaluated after heat aging for 2, 4, 6 and 8 weeks.

[0165]

[0166]

[0167] Table 9: Acronal Edge 4750 VOC-free semi-gloss paint formulation (control base)

[0168] The samples prepared from the paint are as follows.

[0169]

[0170] Membrane Application

[0171] Films were prepared from aqueous samples using 3 mil Bird film. It was applied on a sealed Leneta Penopac chart type 1B. The chart was fixed with a vacuum plate to ensure uniform film thickness. The film was dried at room temperature for 24 hours.

[0172] The test films were color measured using a DataColor Check 3 spectrophotometer Model LAV / USAA C31567 to obtain CIE L*, a*, b* and YI-E313 data based on the perceived CIELAB color space. YI–E313 (yellowness index) was recorded to determine how much the sample color deviated from ideal white.

[0173] Gloss and film defects

[0174] The paint film was applied on a Leneta Penopac chart type 1B using a 3 mil Bird film applicator and dried for 1 day, and the gloss at 20°, 60° and 85° was measured on the sealed portion of the chart. The gloss of the dried film was measured using an Elcometer 408 gloss and DOI meter. The gloss was measured at 3 reference points and the average was recorded. Film defects were evaluated at 10x magnification using a MEIJI EMZ-TR optical microscope.

[0175] Contrast Ratio or Ro / Rw Ratio: The L* reflectance value of a paint film on the black area of ​​a Leneta Penopac chart Type 1A (Ro) divided by the L* reflectance value on the white sealed area of ​​the same chart and the same sample (Rw) as described in ASTM D2508 Standard Test Method for Hiding of Paints by Reflection.

[0176] The test films were color measured using a DataColor Check 3 spectrophotometer Model LAV / USAA C31567 to obtain CIE L*, a*, b* and YI-E313 data based on the perceived CIELAB color space. YI–E313 (yellowness index) was recorded to determine how much the sample color deviated from ideal white. Figure 4 Shows the color analysis recorded over an 8-week period of the laboratory trials tested in this study. The T-403 coating showed a slight increase in L* value compared to the control, with a negligible effect on color and no significant co-dispersant performance as the increase was less than 0.6 units. All samples showed similar yellowing in the initial evaluation. As the samples aged, the YI-313 values ​​increased, but not by more than 2.2%. Therefore, no significant effect on dry film yellowing was found as the control (U210533-01) yellowed at a similar rate. 0.20% "1737-72" (U210533-02) showed the lowest DE value, which is considered to be the smallest change from the control. Overall, compared to the control, "1737-72" and The addition of T-403 will not impair the dry film properties.

[0177] Example 6

[0178] Using Thermos Scientific Orion pH measurements were evaluated using an A111 pH meter and reconfirmed using a HannaInstruments HI2550 pH / ORP and TDS pH meter. All evaluations were repeated to ensure the accuracy of the pH values. Figure 5 Point out that "1737-72" and The effectiveness of T-403 as a pH enhancer and pH stabilizer. 0.2% "1737-72" (U210533-02) and 0.4% "1737-72" (U210533-03) provided a maximum pH boost of 0.3 and 0.4 units, respectively, and a maximum boost of 0.5 units over the 6-week and 8-week heat aging intervals. While not seemingly much, this slight boost is enough for the formulator to take notice and understand that the addition of this product may result in a slight reduction in the conventional pH adjuster loading to bring the coating pH within specification. 0.20% Jeffamine T-403 (U210533-04) and 0.40% Jeffamine T-403 (U210533-05) also showed positive results, but at much lower rates. The control sample (U210533-01) contained AMP-95 at an optimized use level. TM As a traditional pH adjuster. All samples showed pH stability over time. Alkaline stability is critical when formulating because issues such as carrier stability, packaging corrosion, viscosity profile and pigment dispersion stability can be severely affected.

[0179] Example 7

[0180] Fineness of grind is measured according to ASTM D1210, Standard Test Method for Fineness of Dispersion of Pigment-Carrier Systems Using a Hegman-Type Meter. A Precision Gage and Tool Company grind meter is used and the results are reported in Hegman units and microns.

[0181] Figure 6 The fineness of grind, air content, and opacity of the coatings are shown. These properties are developed during the grinding stage of coating production. All masterbatches exhibited similar particle size distributions at an initial reading of 7.2 Hegman (10μ microns). There was no significant enhancement or negative effect on the particle size of the coatings over time. The contrast ratio values ​​describing opacity paralleled the results for all samples and negligible changes were observed upon heat aging. There were no significant benefits or detrimental effects on the air release or air entrainment characteristics. However, samples 0.20% Jeffamine T-403 (U210533-04) and 0.40% Jeffamine T-403 (U210533-05) did show slightly higher air entrainment. No film defects due to entrained air were observed.

[0182] Example 8

[0183] Krebs Unit (KU) viscosity measurements were made using a Stormer Viscometer according to ASTM D562 Standard Test Method for Paint Consistency. ICI viscosity measurements were made using an ICI Cone / Plate Viscometer Model 106-110v-60HZ according to ASTM D4287 Standard Test Method for High Shear Viscosity at a temperature of 25°C.

[0184] The coating samples were heat aged at 50° C. for 2, 4, 6, and 8 weeks in a Thermo Scientific Heratherm OMS180 Model #41298000 convection oven. The coating samples were removed from the oven and allowed to equilibrate to room temperature before viscosity measurements were made.

[0185] Figure 7 The graph depicts the viscosity curves for all samples tested over an 8 week period. Preliminary evaluations showed similar viscosity curves. The viscosity curves for the aged coatings containing 0.20% "1737-72" (U210533-02) and 0.40% "1737-72" (U210533-03) were 13 and 25 units higher than the control, respectively. 0.20% Jeffamine T-403 (U210533-04) and 0.40% Jeffamine T-403 (U210533-05) had a much greater effect on viscosity stability, with both loadings increasing viscosity by 30 units during heat exposure.

[0186] Example 9

[0187] With BASF Pure Color acceptance was performed by tinting the test paints at 2.5 wt% in coal black, phthalocyanine blue, and iron oxide red with low VOC universal colorants representing a variety of pigment chemistries, color spectra, and dispersant / surfactant packages. Fig. 8A Coal black results are shown. 0.20% "1737-72" (U210533-02) and 0.40% "1737-72"

[0188] (U210533-03) had improved color acceptance performance, showing little change in DL* values ​​when rubbed. Delta-E values ​​followed a similar trend. Low DL* and DE values ​​in the rub test strongly indicate improved color acceptance. Jeffamine T-403 (U210533-4) at 0.20% and Jeffamine T-403 (U210533-05) at 0.40% also showed good color acceptance compared to the control, but were not as effective as "1737-72". A reduction in gloss was observed for the tinted base paint compared to the untinted base paint, which is normal and within parameters. The gloss readings for the tinted samples containing Jeffamine T-403 were lower (up to 10 units) than those containing "1737-72" when compared to the control, which may be a sign of some type of incompatibility. Figure 8B Phthalocyanine blue and Figure 8C A similar trend was observed in the pigment dispersions.

[0189] Example 10

[0190] Use 7 mil Bird film The test paint was applied to a 165×432 mm vinyl chloride / vinyl acetate copolymer plate and 3 different plates. After curing for 7 days, the 2 best plates were selected and each plate was placed on a linear washable machine Gardco Model # D10-WA-2151 with a brass shim (12.7×0.25 mm) below the plate. A nylon brush with bristles was placed on a brush holder, where the bristles extended 19 mm from the brush plate in a 5 / 4 pattern, and the number of cycles at which the coating broke was recorded. The test measurements were carried out according to the standard test method for wiping resistance of wall paints of ASTM D2486.

[0191] Fig. 9 Scrub resistance, or the resistance of a wall paint to erosion caused by wiping, as determined by the traditional cycle-to-failure concept, is shown. 0.20% "1737-72" (U210533-02) and 0.40% "1737-72" (U210533-03) showed no significant change in scrub resistance compared to the control. While 0.4% "1737-72" showed only a very slight decrease, higher doses may have compromised erosion resistance, as shown in the pure Jeffamine T-403 data. 0.20% Jeffamine T-403 (U210533-04) and 0.40% Jeffamine T-403 (U210533-05) showed lower erosion resistance, with a difference of 538 cycles and 760 cycles, respectively, compared to the control. Although the test has an acceptable level of repeatability of up to 30%, the raw data was consistent between tests with little variation.

[0192] Embodiment 11

[0193] Use 7 mil Bird film The test paint was applied to a 165×432 mm vinyl chloride / vinyl acetate copolymer panel and 3 different panels. After curing for 7 days, the best 2 panels were selected and common household stains were applied to each panel in the following order: (1) Leneta Stain Medium ST-1, (2) Grape Juice, (3) Mustard, (4) Coffee, (5) Red Marker, (6) Red Wine, (7) Purple Marker, (8) Lipstick, (9) Black Tea, and (10) Ketchup. The stains were allowed to dry at room temperature for 1 hour. Subsequently, the panels were placed on a linear washable machine Gardco Model #D10-WA-2151, where the sponge was placed on the brush holder; a liquid cleaner was applied to the film and washed for up to 100 cycles. Test measurements were made in accordance with ASTM D4828 Standard Test Method for Practical Washability of Organic Coatings.

[0194] Fig.10 and 11 The panels were evaluated in a mechanical cleaning tester for up to 100 cycles to examine the relative ease of removal of common household stains. Visual evaluation of the test films for color or erosion was performed. Results showed that the panels containing "1737-72" and "U210533-01" were significantly better than the control (U210533-01). The stains on the T-403 film showed roughly parallel effects on stain resistance. Leneta Stain Medium ST1, Coffee, and Red Wine stains were slightly more difficult to remove from the dosed paint, requiring additional cycles for complete removal.

[0195] Fig.12 Will Fig.10 and 11 The visual observations in were correlated with the color analysis of each stain. The results showed that, in general, there was no significant change in stain resistance. Some stains had a slightly higher or lower L*, DL*, and DE change compared to the performance of the control, but no significant advantage or disadvantage was observed. Some slight enhancements noted with "1737-72" were purple marker and tea stains. Slight enhancements noted with T-403 were grape juice, red marker, and red wine.

[0196] Example 12

[0197] The five coatings were tested for a total of 500 hours using ASTM D4587-11(2019) Standard Practice for Fluorescent UV-Condensation Exposure of Paints and Related Coatings, with color measurements taken at initial and final intervals. The QUV cabinet was programmed as follows:

[0198]

[0199] Use 3 mil Bird film All films were applied on sealed Leneta Penopac charts Model WB. The chart was secured with a vacuum plate to ensure uniform film thickness. The films were dried at room temperature for 24 hours and then tested.

[0200] Fig.13 Shown is color analysis of samples exposed to 500 hours in a QUV accelerated weathering chamber, cycling UV: 8 hours at 60°C, condensing: 4 hours at 50°C. The control (U210533-01) showed no changes that affected dry film properties after weathering exposure. 0.20% "1737-72" (U210533-02) and 0.40% "1737-72" (U210533-03) showed minimal changes in L* values ​​and low DE values ​​of 0.51-0.92 units between the two tests. Additionally, the Yellowness Index results showed no significant effect on dry film yellowing as the control (U210533-01) yellowed at a similar rate. However, the 0.20% Jeffamine T-403 (U210533-04) and 0.40% Jeffamine T-403 (U210533-05) showed a greater decrease in L* values ​​( Figure 4 ), as weathering exposure resulted in color degradation. By adopting higher use levels of Jeffamine T-403, the coating performance deteriorated and the L* value decreased. It is worth noting that the Yellowness Index showed slightly higher values. Overall, 0.20% "1737-72" (U210533-02) and 0.40% "1737-72" (U210533-03) are more weather resistant than the samples containing Jeffamine T-403.

[0201] Embodiment 13

[0202] Fig.14 Shown is the in-can stability rating of the test coatings during 8 weeks of heat aging. The samples were evaluated for separation and settling according to ASTM D869, Standard Test Method for Evaluating Settling of Paints. The settling of the samples was rated on a scale of 0 to 10, where 0 is complete separation / hard settling and 10 is no separation or settling.

[0203] Rating Description of Sample Conditions

[0204]

[0205] The test paints were stored at 50°C under accelerated weathering conditions for a total of 8 weeks. Laboratory testing observed signs of syneresis after each storage interval. Test specimens were rated for syneresis classification according to ASTM D1849 and Spektrochem ratings.

[0206] Classification of syneresis

[0207] Rating describe 5 There is no syneresis in the tank. 4 The water layer is not visible when the tank is standing. After tilting, the smallest film of water is concentrated at the edge of the tank. 3 The water layer is barely visible when the can is standing upright. When tilted, a clearly visible film of water forms at the edge of the can. 2 The water layer was clearly visible without tilting the tank; however, its thickness was not very significant. 1 Very thick layer of water on the tank.

[0208] No settling was observed in any of the samples; however, in the samples containing "1737-72" and Jeffamine T-403, there was evidence of syneresis at both use levels. Syneresis refers to the release of small amounts of liquid from the container onto the coating surface and was evaluated according to both test methods to provide precise evidence of the behavior. In addition, the exact time at which syneresis occurs in the coating was determined. Signs of syneresis were observed at the 2-week mark during accelerated aging. Even though syneresis was present on the surface, no pigment settling was observed and uniformity was easily achieved once the coating was mixed with a spatula. Syneresis did not adversely affect film properties and no film defects were observed.

[0209] Overall, the 1737-72 T-403 was added to a non-VOC acrylic semi-gloss architectural paint formulation at 0.2% and 0.4% by weight during the production grind stage. The effect on coating performance and stability was evaluated at all stages of the preparation process as well as on dry film and stability properties. The data generally showed that while 0.2-0.4 w / w% T-403 can have both positive and negative effects on paint performance, but the blended multifunctional enhancer product "1737-72" significantly and surprisingly T-403 minimizes most of the observed negative effects on paint properties, even at equivalent active polyetheramine levels, while also improving its ability to act as an in-tank enhancer.

[0210] Without departing from the spirit and scope of the present invention, those of ordinary skill in the art may practice these and other modifications and changes to the present invention, which are more specifically set forth in the appended claims. In addition, it should be understood that the aspects of the various embodiments may be interchanged in whole or in part. In addition, those of ordinary skill in the art will appreciate that the foregoing description is exemplary only and is not intended to limit the invention further described in such appended claims.

Claims

1. A multifunctional enhancer composition comprising: At least one compound of the following formula I, wherein R1 is H or C1-C9 alkyl, each of R2, R3 and R4 is independently H or CH3, and each of x, y and z is independently 1-10; and at least one additive comprising an inorganic metal compound, a silicate, a pyrithione salt, or an organic amine; The weight ratio of the compound of formula I to the additive is 1:5-100:

1.

2. The composition according to claim 1, wherein the sum of x, y and z is not less than 5.

3. The composition according to claim 1 or 2, wherein the sum of x, y and z is no greater than 10.

4. The composition of claim 1, wherein the compound of formula I is present in the composition at a concentration of about 20-80 wt%.

5. The composition according to claim 1, wherein the inorganic metal compound comprises one or two of an inorganic zinc compound, an inorganic magnesium compound, an inorganic copper compound or an inorganic lithium compound.

6. The composition according to any one of claims 1 to 5, wherein the inorganic zinc compound comprises one or more of zinc oxide, zinc nitrate, zinc chloride and zinc acetate.

7. The composition of any one of claims 1-5, wherein the inorganic magnesium compound comprises magnesium oxide.

8. The composition according to any one of claims 1 to 5, wherein the inorganic copper compound comprises one or more of copper sulfate, copper nitrate, copper carbonate, copper oxide and copper acetylacetonate.

9. The composition of any one of claims 1-5, wherein the inorganic lithium compound comprises one or more of lithium carbonate, lithium acetate, lithium fluoride, lithium sulfate, lithium nitrate, lithium tetraborate, lithium metaborate, lithium pyrophosphate, lithium tripolyphosphate, lithium orthosilicate and lithium metasilicate.

10. The composition according to claim 1, wherein the silicate comprises one or both of potassium methyl silicate and sodium metasilicate.

11. The composition of claim 1, wherein the pyrithione salt comprises one or both of zinc pyrithione and sodium pyrithione.

12. The composition of claim 1, wherein the organic amine comprises a pH adjuster.

13. The composition of claim 12, wherein the pH adjuster comprises 2-amino-2-methyl-1-propanol.

14. A water-based industrial material comprising: A multifunctional enhancer of at least one compound of the following formula I: in, R1 is H or C1-C9 alkyl, each of R2, R3 and R4 is independently H or CH3, and each of x, y and z is independently 1-10; and at least one additive comprising an inorganic metal compound, a silicate, a pyrithione salt, or an organic amine; wherein the weight ratio of the compound of formula I to the additive is 1:5-100:1, and The water-based industrial material is a non-reactive water-based industrial material.

15. The water-based industrial material according to claim 14, wherein the industrial material is selected from paint, coating, plaster of Paris, adhesive, sealant, caulking agent, slurry, pigment dispersion, pigment slurry, concrete, polymer emulsion, polymer dispersion, ink, sizing agent, agricultural pesticide formulation, household cleaning product, personal care product, varnish, sealing composition, leather auxiliary agent, paper finishing agent, cosmetics, shampoo, shower gel, conditioner and preservative for the industrial material.

16. The water-based industrial material according to claim 14, wherein the at least one compound of Formula I is present in the composition at a concentration of about 20-80% by weight of the composition.

17. The water-based industrial material according to any one of claims 14 to 16, wherein the inorganic metal compound is present in the composition at a concentration of about 0.2 to 20% by weight of the composition.

18. The water-based industrial material according to any one of claims 14 to 17, wherein the inorganic metal compound comprises one or two of an inorganic zinc compound, an inorganic magnesium compound, an inorganic copper compound or an inorganic lithium compound.

19. The water-based industrial material according to claim 18, wherein the inorganic zinc compound comprises one or more of zinc oxide, zinc nitrate, zinc chloride and zinc acetate.

20. The water-based industrial material according to claim 18, wherein the inorganic magnesium compound comprises magnesium oxide.

21. The water-based industrial material according to claim 18, wherein the inorganic copper compound comprises one or more of copper sulfate, copper nitrate, copper carbonate, copper oxide, and copper acetylacetonate.

22. The water-based industrial material according to claim 18, wherein the inorganic lithium compound comprises one or more of lithium carbonate, lithium acetate, lithium fluoride, lithium sulfate, lithium nitrate, lithium tetraborate, lithium metaborate, lithium pyrophosphate, lithium tripolyphosphate, lithium orthosilicate and lithium metasilicate.

23. The water-based industrial material according to claim 14, wherein the silicate is present in the composition at a concentration of about 0.5-15% by weight of the composition.

24. The water-based industrial material according to claim 14, wherein the silicate comprises one or both of potassium methyl silicate and sodium metasilicate.

25. The water-based industrial material according to claim 14, wherein the pyrithione salt is present in a concentration of about 5-500 ppm.

26. The water-based industrial material according to claim 14, wherein the pyrithione salt comprises one or both of pyrithione zinc and pyrithione sodium.

27. The water-based industrial material according to claim 14, wherein the organic amine comprises a pH adjuster.

28. The water-based industrial material according to claim 27, wherein the pH adjuster comprises 2-amino-2-methyl-1-propanol.

29. A method for enhancing the storage performance of a water-based industrial material in a container, comprising adding an effective amount of the multifunctional enhancer of claim 1 to the water-based industrial material.

30. The method of claim 29, comprising inhibiting or preventing the growth of microorganisms in the industrial material.

31. The method of claim 30, wherein the microorganism is selected from the group consisting of bacteria, fungi, yeast, algae, mucus, and combinations thereof.

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