Wood preservative compositions

Abstract

In general, the present disclosure is directed to a wood preservative composition. The wood preservative composition may be useful in inhibiting proliferation of wood decaying microorganisms. In one example embodiment, the wood preservative composition may include a copper containing biocide. The wood preservative compound may further include benzovindiflupyr. For instance, benzovindiflupyr and a copper containing biocide may be present in the wood preservative composition at a ratio of from about 1:1 to about 1:1000.

Description

WOOD PRESERVATIVE COMPOSITIONSRELATED APPLICATIONS

[0001] The present application is based on and claims priority to U.S. Provisional Patent application Serial No. 63 / 570,971, filed on March 28, 2024, which is incorporated herein by reference.BACKGROUND

[0002] Wood-based products are subject to attack from a wide variety of organisms, including molds, fungi, and insects. As such, these organisms may cause the wood-based product’ s wood to decay and reduce the product’s mass and structural integrity. Wood preservatives have been developed to combat microorganism attacks. Wood-based products may be treated with a wood preservative via applying the preservative directed to the surface, by dip, spray or brush, or by vacuum pressure immersion. During industrial application of preservatives, wood-based products are typically impregnated with the preservative treatment solution to achieve either shell or full cell type penetration into the substrate. A wood preservative treatment may have a significant bearing on the useful service life of the treated wood-based product.

[0003] Propiconazole and tebuconazole are widely used as wood preservatives to protect treated wood from discoloring and decay fungi. However, in Europe, such azoles have been under regulatory scrutiny. For example, propiconazole use on playground equipment and furniture has been restricted. Issues with tebuconazole include potential resistance. From the long-term perspective, azoles are not the right candidate for future wood preservatives. Therefore, alternatives are needed to replace azoles in existing wood preservatives.

[0004] Accordingly, there is a need for safe wood preservative compositions that are effective against various wood decay microorganisms, including fungi, molds, sapstain, and insects.SUMMARY

[0005] In general, the present disclosure is directed to a wood preservative composition. The wood preservative composition may be useful in inhibiting proliferation of wood decaying microorganisms. In one example embodiment, the wood preservative composition may include a copper containing biocide. The wood preservative compound may further include benzovindiflupyr. For instance, benzovindiflupyr and a copper containing biocide may be present in the wood preservative composition at a ratio of from about 1 : 1 to about 1 : 1000.

[0006] Also, the present disclosure is directed to a method for treating a wood product. The method may include applying to the wood product a biocidally effective amount of a wood preservative composition that includes benzovindiflupyr and a copper containing biocide.

[0007] Additionally, the present disclosure is directed to a method for inhibiting Rhodonia placenta in a wood product by applying to the wood product a biocidally effective amount of the wood preservative composition disclosed herein.

[0008] These and other features and aspects, embodiments and advantages of the present invention will become better understood with reference to the following description and appended claims.DETAILED DESCRIPTION

[0009] 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.

[0010] The present disclosure is directed to a wood preservative composition. The wood preservative composition may be useful in inhibiting proliferation of wood decaying microorganisms. In one example embodiment, the wood preservative composition may include a copper containing biocide. The wood preservative compound may further include benzovindiflupyr. For instance, benzovindiflupyr and a copper containing biocide may be present in the wood preservative composition at a ratio of from about 1 : 1 to about 1 : 1000.

[0011] The wood preservative composition disclosed herein may include a copper containing substance. For instance, the copper containing biocide may be an inorganic copper compound, or copper granulate. The copper containing biocide may include inorganic copper salts including, but not limited to, carbonate, bicarbonate, sulphate, nitrate, chloride, hydroxide, borate, fluoride or oxide.

[0012] In one example embodiment, the copper containing biocide may be a copper oxide, such as cuprous oxide and cupric oxide. In another example embodiment, the copper containing biocide may be a copper salt, such as copper salts of fatty and rosin acids, copper ethylenediamine complex, copper triethanolamine complex, copper ethylenediaminetetraacetate, and copper thiocyanate. Yet in another example embodiment, the copper containing biocide may include, but is not limited to, copper octanoate, copper diammonia diacetate complex, copper ethanolamine complex, copper naphthenate, and copper 8-quinolinoate.

[0013] In one example embodiment, the copper containing biocide may be basic copper (II) carbonate, copper (II) hydroxide, copper 8-quinolinolate, copper (II) pyrithione, copper acetyl acetonate, or copper (II) oxide. In a preferred example embodiment, the copper containing biocide may be a basic copper carbonate, a copper oxide, or a combination thereof. More preferably, the copper containing biocide may be basic copper carbonate.

[0014] In one example embodiment, the copper containing biocide may include, but is not limited to, a basic copper carbonate, a copper oxide, basic copper carbonate (CuC03.Cu(OH)2), copper (II) acetate, copper ammonium carbonate complex, copper (II) hydroxide, copper (II) oxide, copper oxychloride, copper oxychloride sulfate, copper ammonium complex, chelates of copper citrate, chelates of copper gluconate, copper (II) sulphate pentahydrate, or a combination thereof.

[0015] In one example embodiment, the copper containing biocide may be micronized copper containing biocide particle. For instance, the micronized copper containing biocide particles may have a particle size of from about 0.01 microns to about 25 microns, such as from about 0.1 microns to about 20 microns, such as from about 0.5 microns to about 15 microns, such as from about 1 micron to about 10 microns, such as from about 2 microns to about 10 microns, or any range therebetween.

[0016] The copper containing biocide may be present in the wood preservative composition in an amount of from about 0.05% to about 30% by weight, such as from about 0.1% by weight to about 27% by weight, such as from about 0.5% by weight to about 25% by weight, such as from about 1% by weight to about 20% by weight, such as from about 5% by weight to about 15% by weight, or any range therebetween. In one example embodiment, the copper containing biocide may be present in the preservative composition in an amount of from about 0.05% by weight to about 25% by weight. In another example embodiment, the copper containing biocide may be present in the preservative composition in an amount of from about 0.1% by weight to about 10% by weight.

[0017] In one example embodiment, the preservative composition may include a succinate dehydrogenase inhibitor in combination with the copper containing biocide. For instance, the succinate dehydrogenase inhibitor may be selected from a group consisting of flutolanil, isofetamid, flupyram, fluxapyroxad, penthiopyrad, boscalid, fenfuram, caboxin, thifluzamide, benzovindiflupyr, bixafen, furametpyr, isopyrazam, penthiopyrad, sedaxane, or a combinationthereof. Tn one example embodiment, the succinate dehydrogenase inhibitor may be benzovindiflupyr.

[0018] The succinate dehydrogenase inhibitor may be present in the wood preservative composition in an amount of from about 0.001% by weight to about 30% by weight, such as from about 0.001% by weight to about 25% by weight, such as from about 0.1% by weight to about 20% by weight, such as from about 1% by weight to about 15% by weight, or any range therebetween. In one example embodiment, the succinate dehydrogenase inhibitor may be present in the wood preservative composition in an amount from about 0.001% by weight to about 25% by weight. In another example embodiment, the succinate dehydrogenase inhibitor may be present in the wood preservative composition in an amount from about 0.001% by weight to about 10% by weight.

[0019] Benzovindiflupyr and the copper containing biocide, for instance, may be present in the wood preservative composition disclosed herein at a weight ratio of from about 1 : 1 to about 1 : 1000, such as from about 1 : 10 to about 1 :500, such as from about 1 :30 to about 1 :250, such as from about 1 :50 to about 1 :200, or any range therebetween. In one example embodiment, benzovindiflupyr and the copper containing biocide may be present in the wood preservative composition disclosed herein at a weight ratio of from about 1 : 50 to about 1 :200.

[0020] Optionally, the preservative composition disclosed herein may further include an amine donor compound. For instance, the amine donor compound may include, but are not limited to, monoethanolamine (MEA), diethanolamine, triethanolamine, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, ammonia, ammonium bicarbonate, and ammonium carbonate, or a combination thereof. In one example embodiment, the amine donor compound may be monoethanolamine.

[0021] The amine donor compound may be present in the wood preservative composition in an amount of from about 0.1% by weight to about 35% by weight, such as from about 0.3% by weight to about 30% by weight, such as from about 0.75 % by weight to about 25% by weight, such as from about 1% by weight to about 15% by weight, or any range therebetween. In one example embodiment, the amine donor compound may be present in the wood preservative composition in an amount from about 0.3% by weight to about 30% by weight. In another example embodiment, the amine donor compound may be present in the wood preservative composition in an amount from about 0.75% by weight to about 25% by weight.

[0022] Optionally, the preservative composition disclosed herein may further include an emulsifier. Suitable emulsifiers may include an ethoxylate that helps to keep water-insoluble components of the formulation in the form of a stable emulsion of small particles suspended in an aqueous phase.

[0023] A suitable type of ethoxylate 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 mono-alcohol 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.

[0024] Another suitable type of ethoxylate for use in the present disclosure is 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 emulsifier may contain a polyoxyethylene block and a polyoxypropylene block). Also suitable for use as an emulsifier are alkoxylated phenols, in particular ethoxylated phenols wherein 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 in tristyrylphenol).

[0025] The emulsifier may be present in the wood preservative composition in an amount of from about 0.001% by weight to about 7% by weight, such as from about 0.05% by weight to about 5% by weight, such as from about 0.1% by weight to about 3% by weight, such as from about 0.5% by weight to about 1.5% by weight, or any range therebetween. In one example embodiment, the emulsifier may be present in the wood preservative composition in an amount from about 0.05% by weight to about 5% by weight. In another example embodiment, the emulsifier may be present in the wood preservative composition in an amount from about 0.1% by weight to about 3% by weight.

[0026] Optionally, the preservative composition disclosed herein may further include a dispersant or a dispersing agent. For instance, the dispersant may include, but is not limited to, an acrylate, a surfactant, or a combination thereof.

[0027] In one example embodiment, the dispersant may be an acrylate that may be formed as a homopolymer or a 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, the preservative composition may include various acrylates, acrylate butadiene styrene copolymers, and acrylonitrile butadiene styrene copolymers. In one example embodiment, the acrylate may be a styrene acrylic co-polymer. Additionally, said dispersants are provided for example purposes, and additional dispersants may be used alone or in combination with embodiments of the present disclosure.

[0028] The acrylate polymer or copolymer may include a mass fraction of an acrylate monomer. For instance, the acrylate may 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 acrylates, the mass fraction of acrylate 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 forty (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 embodiments may include an acrylate having a mass fraction of acrylate monomer to the total weight of acrylate greater than fifty (50) wt%.

[0029] In one example embodiment, the dispersant may be a surfactant, such as a nonionic surfactant. The nonionic surfactant may have a hydrophilic-lipophilic balance (HLB) in the range of from about 8-20, such as from about 10-18, such as from about 12-15, or any range therebetween. For instance, in one example embodiment, the HLB of the nonionic surfactant may be in the range of from about 8-20. In another example embodiment, the HLB of the nonionic surfactant may be in the range of from about 12-15. In yet another exampleembodiment, the HLB of the nonionic surfactant may be in the range of from about 10-18. Tn one example embodiment, the HLB of the nonionic surfactant may be greater than about 10.

[0030] 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 / 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.

[0031] 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 typically is from about 2 to about 50 on average. If more than one type of alkylene oxide is used, the alkylene 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).

[0032] 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, alkyl ether sulfates, sulfated alkanolamides, glyceride sulfates, alkyl aryl sulfonates (including straight-chain alkylbenzenesulfonates, branched alkylbenzenesulfonates, alkylnaphthalene-sulfonates), alpha olefin sulfonates, lignosulfonates, sulfo-carboxylic compounds (e.g., sodium lauryl sulfoacetate, sulfosuccinates (includingdialkylsulfosuccinates), sulfosuccinamates, organo phosphored surfactants, sacrosides, hydroxyalkane-sulfonates, alkanesulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, salts of polyoxyethylene alkyl sulfophenyl ethers, sodium N-methyl-N-oleyltaurates, monoamide disodium N-alkylsulfosuccinates, petroleum sulfonates, sulfated castor oil, sulfated tallow oil, salts of sulfuric esters of aliphatic alkylesters, 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-C is alkyl benzene sulfonates such as salts of dodecylbenzene sulfonate, and combinations thereof.

[0033] The dispersant may be present in the wood preservative composition in an amount of from about 0.01% by weight to about 20% by weight, such as from about 0.05% by weight to about 15% by weight, such as from about 0.1% by weight to about 10% by weight, such as from about 0.5% by weight to about 5% by weight, or any range therebetween. In one example embodiment, the dispersant may be present in the wood preservative composition in an amount from about 0.05% by weight to about 15% by weight. In another example embodiment, the dispersant may be present in the wood preservative composition in an amount from about 0.1% by weight to about 10% by weight.

[0034] In one example embodiment, the wood preservative composition disclosed herein may be used to treat a cellulosic or wood-based product. In one aspect, cellulosic materials which may be treated with a wood preservative composition of the present disclosure includes lignocellulosic substrates, engineered wood products, wood plastic composites, cardboard and cardboard faced building products such as plasterboard, and cellulosic material, such as cotton. Also, leather, textile materials and even synthetic fibers, hessian, rope, and cordage as well as composite wood materials. For convenience, the present disclosure is described with reference tothe treatment of wood but it will be appreciated that other cellulosic materials may be treated analogously. However, in one example aspect, though not exclusively, the wood preservative composition may be applied to sawn timber, logs or laminated veneer lumber, oriented strand board (OSB), or medium density fiberboard (MDF). In one example aspect, the product is wood or a wood composite material which is intended to become wet during its life, for example, wood for window frames, timber used above ground in exposed environments, such as decking and timber used in ground contact or fresh water environments.

[0035] In one example aspect, a treated cellulosic or wood based product may be treated with an amount of the preservative formulation (or ready to use formulation) such that the treated cellulosic or wood based product includes from about 5 grams per meter cubed (g / m3) to about 1000 g / m3benzovindiflupyr, such as from about 10 g / m3to about 500 g / m3benzovindiflupyr, such as from about 50 g / m3to about 400 g / m3benzovindiflupyr, such as from about 75 g / m3to about 250 g / m3benzovindiflupyr, or a combination thereof. For instance, as shown in the examples, the present disclosure has found that the preservative formulation is able to penetrate even to the core of the cellulosic or wood-based product, and evenly distribute the preservative.

[0036] In one example embodiment, a treated cellulosic or wood based product may retain copper in an amount of from about 0.5 kg / m3to about 5.0 kg / m3, such as from about 0.75 kg / m3to about 4.0 kg / m3, such as from about 1.0 kg / m3to about 3.0 kg / m3, or any range therebetween. For instance, in one example embodiment, the treated cellulosic or wood based product may retain copper in an amount of from about 0.5 kg / m3to about 5.0 kg / m3. In another example embodiment, the treated cellulosic or wood based product may retain copper in an amount of from about 0.75 kg / m3to about 4.0 kg / m3. In another example embodiment, the treated cellulosic or wood based product may retain copper in an amount of from about 1.0 kg / m3to about 3.0 kg / m3.

[0037] In one example embodiment, the wood-based product may be selected from the group comprising sawn timber, lumber, logs, posts, glued solid timber, glued laminated timber, laminated veneer lumber, plywood, strand board, oriented strand board, flake board, particle board, medium density fiberboard, high density fiberboard, hardboard, or a combination product.

[0038] In an example aspect, a wood or cellulosic based product may be treated with a ready to use wood preservative composition of the present disclosure. In such an example aspect, the wood or cellulosic based product may include a copper containing biocide, a succinatedehydrogenase inhibitor, or a combination thereof in the amounts discussed above in regards to the ready to use composition. For instance, the wood-based product may be treated by applying to the wood product a biocidally effective amount of the wood preservative composition including benzovindiflupyr and a copper containing biocide.

[0039] The wood preservative compositions disclosed herein are particularly effective against fungi and / or insects. Exemplary microorganisms may include one or more species from one or both of the following groups:

[0040] Fungi: Acremonium such as Acremonium strictnm, Alternaria such as Alternaria tenuis o Alternaria ahernata, Aspergillus such as Aspergillus niger ox Aspergillus brasiliensis, Candida such as Candida albicans, Chaetomium such as Chaetomium globosum, Coniophora such as Coniophora puteana, Fibroporia such as Fibroporia radiculosa, Fusarium such as Fusarium solani, Geotrichum such as Geotrichum candidum, Gloeophyllum such as Gloeophyllum trabeum, Lentinus such as Lentinus tigrinus, Penicillium such as Penicillium glaucum, Penicillium funiculosum or Penicillium pinophilum, Rhodotorula such as Rhodotorula rubra or Rhodotorula mucilaginosa, Rhodonia such as Rhodonia placenta, Serpula such as Serpula lacrymans, Stachybotrys such as Stachybotrys chartarum, Trametes such as Trametes versicolor, Trichoderma such as Trichoderma virens, Wolfiporia such as Wolfiporia cocos,' and

[0041] Insects: Reticultimermes such as Reticulitermes flavipes, Reticulitermes hesperus, Anobium such as Anobium punctatum, Coptotermes such as Comitermes cumulans, Coptotermes formosanus, Cryptotermes spp., Heterotermes such as Heterotermes ferox, Heterotermes paradoxus, Heterotermes vagus, Hylotrupes such as Hylotrupes bajulus, or Lyctus such as Lyctus brunneus.

[0042] In one example embodiment, the wood preservative compositions disclosed herein are particularly effective against Rhodonia placenta. In another example embodiment, the wood preservative compositions disclosed herein are particularly effective against Wolfiporia cocos. In yet another example embodiment, the wood preservative compositions disclosed herein are particularly effective against Trametes versicolor.

[0043] In one example embodiment, the present disclosure is further directed to a method of forming a wood preservative composition as well as treating a wood-based product with the wood preservative composition. For instance, in one example aspect, the copper containing biocide and the succinate dehydrogenase inhibitor may be homogenized (e.g. decreased in sizefrom larger than micron size to the above discussed sizes / particle size distribution), together, or may instead be homogenized separately and then combined, either alone, or in combination with one or more dispersants / complexing agents. Furthermore, in one example aspect, the copper containing biocide and the succinate dehydrogenase inhibitor may be pre-mixed, however, it should be understood that, in some example aspects, the wood preservative composition may be present in a multi-part form and mixed shortly before treating the wood or cellulose based product. However, in an example aspect, the wood preservative composition is in one-part form, such as a pack or mix, and contains each of the copper containing biocide and the succinate dehydrogenase inhibitor in the amounts discussed above.

[0044] Regardless of the form of the wood preservative composition, in one example aspect is diluted as discussed above, and used to treat a wood or cellulose based product. For instance, in one example aspect, the application of the wood preservative composition of the present disclosure to the wood or cellulose based product may be by one or more of dipping, deluging, spraying, brushing, misting, or other surface coating means or by impregnation methods, e.g., partial vacuum, high pressure or double vacuum impregnation into the body of the wood or other material. In one aspect, the method is impregnation under pressure.

[0045] Within this specification, embodiments have been described in a way that enables a clear and concise specification to be written, but it is intended and will be appreciated that embodiments may be variously combined or separated without departing from the disclosure. For example, it will be appreciated that all preferred features described herein are applicable to all aspects of the disclosure described herein.

[0046] In some example embodiments, the disclosure herein can be construed as excluding any element or process step that does not materially affect the basic and novel characteristics of the composition or process. Additionally, in some embodiments, the disclosure can be construed as excluding any element or process step not specified herein.

[0047] As used herein, the terms “about,” “approximately,” or “generally,” when used to modify a value, indicates that the value can be raised or lowered by 10% and remain within the disclosed aspect, such as 7.5%, such as 5%, such as 4%, such as 3%, such as 2%, such as 1%, or any ranges or values therebetween. Moreover, 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 substancein 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. It will be understood that, in certain example embodiments, the compositions described herein may be substantially free of any substance not specifically recited.

[0048] 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 nutritional compositions.

[0049] 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.

[0050] 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%” means by weight as a percentage of the total weight or relative to another component in the composition.

[0051] 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.

[0052] Although the disclosure is illustrated and described herein with reference to specific embodiments, the disclosure is not intended to be limited to the details shown. Rather, various modifications may be made in the details within the scope and range of equivalents of the claims and without departing from the disclosure.EXAMPLESExample 1Benzovindiflupyr as a Wood Preservative

[0053] The efficacy of benzovindiflupyr was tested for activity against wood destroying fungus, Rhodonia placenta, in accordance with the EN113 standard test (Table 1).Table 1Benzovindiflupyr ret .ent .i •on ( zg / ,m ) Weight loss (%)0 29.4210 13.2450 0.28100 -0.13200 -0.08400 0.07

[0054] As benzovindiflupyr retention (i.e., the amount of benzovindiflupyr taken up by the wood product) increases, weight loss of benzovindiflupyr in the wood product decreased.Example 2

[0055] The synergistic interaction of dissolved copper in combination with benzovindiflupyr was tested against wood decay fungi. To do so, fungal cultures were grown on potato dextrose agar (PDA) plates in the presence of dissolved copper in combination with benzovindiflupyr at varying ratios. The PDA plates were incubated at 25 °C under 80% relative humidity for two weeks.

[0056] A simple 96-well matrix was constructed with varied ratios of the two compounds under investigation. 2x Potato Dextrose Agar (PDA) was melted in a water bath set to 60 °C andthen poured to the appropriate wells. To prepare the test samples, stock solutions for biocide “A” (copper) and biocide “B” (benzovindiflupyr) were prepared separately. 2 mL of the slurry was dispersed into the appropriate wells using a 10 mL serological pipet to minimize the presence of air bubbles on the agar surface.

[0057] A plug of the inoculum of each fungal sample was transferred to an agar well. Tests were repeated in biological duplicate, utilizing culture transferred from different secondary inoculum. After inoculation the plates are placed in a clean tote and incubated at 25±2 °C and 80% relative humidity for two weeks.

[0058] At the end of incubation, the plates are rated for growth in the wells by test fungi and the minimum inhibitory concentrations for each test solution combination determined. If there is no growth of the test organism on the control wells, well H12, the test is not valid and should be repeated. For wells having little or no visible growth, a stereoscope should be used for verification of presence / absence of growth.

[0059] The lowest concentration which inhibits fungal growth is the MIC value and recorded as the result for the respective solution / species. The MIC value for each of the samples individually (biocide “A” and “B”) was determined from the row or column that contains just that sample. Then the MIC values of the combination was determined by the rest of the plate which has various concentration combinations. The MIC values were then used to calculate the fractional inhibitory concentration (FIC) for the combination. The FIC values are then used to determine if the compounds are synergistic, antagonistic, or additive. The formula for determining the FIC is:FIC = MIC of Combination / MIC of Solution “A" + MIC of Combination / MIC of Solution “B"

[0060] Once the FIC is calculated for each combination MIC result, the average is taken. If the average FIC value is:<0.5 There is a synergistic effect between the two biocides;0.51-1.00 There is partial synergy between the two biocides; 1.01-2.00 There is additive effect between the two biocides; and >2.00 There is an antagonistic effect between the two biocides.Table 2

[0061] Benzovindiflupyr in combination with copper were synergistic against Basidiomycete wood decay species, Wolfiporia cocos and Trametes versicolor (Table 2).Example 3

[0062] Treatment containing both dispersed copper and benzovindiflupyr was tested according to EN113 standard for activity against wood destroying fungi, Rhodonia placenta.Table 3

[0063] Surprisingly, benzovindiflupyr and copper were more efficacious combined at Benzovindiflupyr: Copper ratios ranging from 1 : 1 to 1 : 1000 compared to benzovindiflupyr or copper alone.

[0064] 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 inwhole or in part. Furthermore, those of ordinary skill 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. A wood preservative composition comprising: benzovindiflupyr and a copper containing biocide, wherein the weight ratio of benzovindiflupyr to the copper containing biocide is about 1 : 1 to about 1 : 1000.

2. The wood preservative composition of claim 1, wherein the weight ratio of benzovindiflupyr to the copper containing biocide is about 1 : 10 to about 1 :500.

3. The wood preservative composition of claim 1, wherein the weight ratio of benzovindiflupyr to the copper containing biocide is about 1 :30 to about 1 :250.

4. The wood preservative composition of claim 1, wherein the weight ratio of benzovindiflupyr to the copper containing biocide is about 1 : 50 to about 1 :200.

5. The wood preservative composition of claim 1, wherein the copper containing biocide comprises copper granulate, a basic copper carbonate, a copper oxide, basic copper carbonate (CUC03.CU(OH)2), copper (II) acetate, copper ammonium carbonate complex, copper (II) hydroxide, copper (II) oxide, copper oxychloride, copper oxychloride sulfate, copper ammonium complex, chelates of copper citrate, chelates of copper gluconate, copper (II) sulphate pentahydrate, or a combination thereof.

6. The wood preservative composition of claim 1, further comprising an amine donor.

7. The wood preservative composition of claim 6, wherein the amine donor is selected from a group consisting of monoethanolamine (MEA), diethanolamine, triethanolamine, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, ammonia, ammonium bicarbonate, and ammonium carbonate, or a combination thereof.

8. The wood preservative composition of claim 6, wherein the amine donor compound comprises monoethanolamine.

9. The wood preservative composition of claim 1, further comprising an emulsifier.

10. The wood preservative composition of claim 9, wherein the emulsifier comprises an ethoxylate.

11. The wood preservative composition of claim 1, further comprising a dispersant.

12. The wood preservative composition of claim 11, wherein the dispersant comprises an acrylate, a surfactant, or a combination thereof.

13. The wood preservative composition of claim 12, wherein the acrylate comprises a styrene acrylic co-polymer.

14. The wood preservative composition of claim 12, wherein the surfactant comprises a nonionic surfactant.

15. The wood preservative composition of claim 14, wherein the nonionic surfactant comprises a hydrophilic-lipophilic balance (HLB) in the range of from about 10 to 18.

16. A method for treating a wood product, the method comprising: applying to the wood product a biocidally effective amount of a wood preservative composition comprising benzovindiflupyr and a copper containing biocide.

17. The method of claim 16, wherein the wood preservative composition is applied to the wood product by spraying, pressure, partial vacuum, dipping, painting, brushing, coating, misting or a combination thereof.

18. The method of claim 16, wherein the wood preservative composition is applied to the wood product by pressure treatment.

19. The method of claim 16, wherein the weight ratio of benzovindiflupyr to the copper containing biocide is about 1 : 1 to about 1 : 1000.

20. The method of claim 19, wherein the weight ratio of benzovindiflupyr to the copper containing biocide is about 1 : 10 to about 1 :500.

21. The method of claim 19, wherein the weight ratio of benzovindiflupyr to the copper containing biocide is about 1 :30 to about 1 :250.

22. The method of claim 19, wherein the weight ratio of benzovindiflupyr to the copper containing biocide is about 1 :50 to about 1 :200.

23. The method of claim 16, wherein the basic copper carbonate, a copper oxide, or a combination thereof.

24. The method of claim 16, wherein an amount of copper retained in the wood product is from about 0.5 kg / m3to about 5.0 kg / m3.

25. The method of claim 16, wherein the wood product is selected from the group comprising sawn timber, lumber, logs, posts, glued solid timber, glued laminated timber, laminated veneer lumber, plywood, strand board, oriented strand board, flake board, particle board, medium density fiberboard, high density fiberboard, hardboard, and a combination product.

26. A method for inhibiting Rhodonia placenta in a wood product, the method comprising: applying to the wood product a biocidally effective amount of a wood preservative composition comprising benzovindiflupyr and a copper containing biocide.

27. The method of claim 26, wherein the wood preservative composition is applied to the wood product by spraying, pressure, partial vacuum, dipping, painting, brushing, coating, misting or a combination thereof.

28. The method of claim 26, wherein the wood preservative composition is applied to the wood product by pressure treatment.

29. The method of claim 26, wherein the weight ratio of benzovindiflupyr to the copper containing biocide is about 1 : 1 to about 1 : 1000.

30. The method of claim 29, wherein the weight ratio of benzovindiflupyr to the copper containing biocide is about 1 : 10 to about 1 : 500.

31. The method of claim 29, wherein the weight ratio of benzovindiflupyr to the copper containing biocide is about 1 :30 to about 1 :250.

32. The method of claim 29, wherein the weight ratio of benzovindiflupyr to the copper containing biocide is about 1 :50 to about 2:200.

33. The method of claim 26, wherein the basic copper carbonate, a copper oxide, or a combination thereof.

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