Copper in an oil wood preservative system

Abstract

The present disclosure is directed to an oil-based preservative composition that may be utilized in a method for treating a wood product. The oil-based preservative composition may include at least about 8% copper (ii) salt and at least one organic co-biocide, especially penflufen and / or quaternary ammonium salts.

Description

COPPER IN AN OIL WOOD PRESERVATIVE SYSTEMBACKGROUND

[0001] Timber is the world’s oldest construction material, but it is susceptible to decay by wood destroying organisms (decay fungi and insect attack), and therefore wood must be preserved to extend working service life. The most common water-based wood preservatives are manufactured as concentrated copper solutions (around 8-10% elemental copper) combined with organic co-biocides, which are then delivered to wood treatment facilities, diluted to around 0.1 -0.5% copper as treatment solutions, and applied to the timber through various high pressure treatment operations in cylindrical autoclaves.However, water-based preservatives, designed for the treatment of decking or siding (cladding) in residential applications are typically expected to deliver fifteen year service lives, extended to perhaps twenty- five to thirty years service with higher retentions of preservatives.

[0002] Oil-based preservatives have historically been utilized for industrial applications, such as utility poles, railroad ties, agricultural fencing and bridges, where consequence of early failure is more significant and costs to install are typically higher. For over a century, creosote was the preservative of choice, but with increasing regulation alternative oil-based systems, such as pentachlorophenol (PCP) and 4,5-dichloro-2-octyl- 2H-isothiazol-3-one (DCOIT) have been used.

[0003] There are also currently three commercially available copper-in-oil (Cu-Oil) preservatives, globally, for the treatment of timber: (i) copper naphthenate, which contains 8% copper dissolved in naphthenic acid, which can be further diluted in P9 or Diesel oils before treatment; (ii) PoleProtect® , which contains 3% copper, dissolved in tall oil fatty acid (TOFA); and (iii) Tanasote® S40, which contains 3% copper dissolved in a mineral oil. The latter two are typically manufactured, sold, and used without further dilution.

[0004] Copper is not particularly soluble in most oils, some mineral oils have a relatively high acid value, and can dissolve up to perhaps 3% Cu, or even up to 8% Cu in some naphthenic oils, but this limit of solubility is restrictive with respect to formulating concentrated Cu-oil wood preservatives and can lead to costly transport, globally. If a more concentrated product could be manufactured, transport costs could be reduced as diluent oils could be sourced more locally. As such, a need exists for a concentrated oil-based preservative composition and system that allows for more concentrated products and reduces transport volumes from manufacturing site to customer location.SUMMARY

[0005] In general, the present disclosure is directed to an oil-based preservative composition that may be utilized in method for treating a wood product. The oil-based preservative composition may include at least about 8% copper (ii) salt, at least one organic co-biocide, and a carrier oil.

[0006] Also, the present disclosure is directed to methods for treating a wood product. The method includes contacting the wood product within a treatment system with an oilbased preservative composition disclosed herein.

[0007] 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

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

[0009] The present disclosure is generally directed to an oil-based preservative composition. Beneficially, the oil-based preservative composition may be provided as a concentrated product to a preservative system to protect against a decay caused by wood destroying organisms.

[0010] The oil-based preservative composition may include copper (ii) salt and at least one organic co-biocide. In one example embodiment, copper (ii) salt may be present in the oil-based preservative composition in an amount of at least about 8% by weight of the oilbased preservative composition. For instance, copper (ii) salt may be present in the oilbased preservative composition from about 8% by weight to about 25% by weight of the oil-based preservative composition, such as from about 8% by weight to about 22% by weight, such as from about 8% by weight to about 20% by weight, such as from about 8% by weight to about 13.5% by weight, such as from about 8% by weight to about 12% by weight, or any range therebetween. In one example embodiment, copper (ii) salt may be present in the oil-based preservative composition in an amount of about 12% by weight of the oil-based preservative composition. In another example embodiment, copper (ii) salt may be present in the oil-based preservative composition in an amount of about 13.5% by weight of the oil-based preservative composition. The copper (ii) salt may include amicronized copper (ii) salt that is no less than five nanometers (5 run) and no greater than five thousand nanometers (5000 nm). Particle size of the copper (ii) salt may be measured utilizing conventional laser diffraction techniques, such as utilizing a particle size analyzer (e.g., with a Horiba LA-960 particle size distribution analyzer).

[0011] In one example embodiment, the oil-based preservative may include a dissolved copper (ii) salt. For instance, the dissolved copper (ii) salt may be present in the oil-based preservative composition in an amount between 0.5% and 10 % w / w micronized copper (ii) salt, wherein the micronized copper (ii) salt has a particle size of five nanometers (5 nm) to five thousand nanometers (5000 nm). In another example embodiment, the particle size of the micronized copper compound varies by less than fifty nanometers (50 nm) after storage from week one to six months at twenty-four degrees Celsius (24° C).[0012| The copper (ii) salt may include, but are not limited to, copper (ii) oxide, copper (ii) chloride, copper (ii) sulfate, copper (ii) hydroxide, copper (ii) nitrate, copper (ii) acetate, copper (ii) fluoride, copper (ii) carbonate, copper (ii) carbonate hydroxide, copper (ii) chlorate, copper (ii) arsenate, copper (ii) phosphate, copper (ii) sulfide, and combinations thereof. In one example embodiment, the copper (ii) salt may be copper (ii) hydroxide.

[0013] The oil-based based preservative composition may include at least one organic co-biocide. According to example aspects of the present disclosure, the ratio of copper (ii) salt (wt.%) to organic co-biocide (wt.%) in the oil-based preservative may be from about 100: 1 to about 1 : 100, such as from about 50: 1 to about 1 : 1, such as from about 20: 1 to about 1 : 1 , or any range therebetween.

[0014] In one example embodiment, the organic co-biocide may include, but are not limited to, an isothiazolinone, a pyrethroid, a neonicotenoid, a halogenated carbamate, a quaternary ammonium salt, a succinate dehydrogenase inhibitor (SDHI), an azole, or a combination thereof.

[0015] In one example embodiment, the organic co-biocide may be an isothiazolinone. For instance, the isothiazolinone may include, but is not limited to, l,2-benzisothiazolin-3- one (“BIT”), N-(n-butyl)-l,2-benzisothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin- 3-one (“DCOIT”), 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-2H-isothiazol-3-one / 2-methyl-2H- isothiazol-3-one (“CMIT / MIT”), or a combination thereof.

[0016] In another example embodiment, the organic co-biocide may be a pyrethroid. For instance, the pyrethroid may include, but are not limited to, example acrinathrin,allethrin, bifenthrin ((2-methyl[l,l'-biphenyl]-3-yl)methyl (lR,3R)-rel-3-[(lZ)-2-chloro- 3,3,3-trifluoro-l-propen-l-yl]-2,2-dimethylcyclopropanecarboxylate), chloroprallethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma- cyhalothrin, cypermethrin (cyano(3-phenoxyphenyl)methyl 3-(2,2-dichloroethenyl)-2,2- dimethylcyclopropanecarboxylate), alpha-cypermethrin, beta-cypermethrin, theta- cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin ((S)-cyano(3- phenoxyphenyl)methyl ( lR,3R)-3-(2,2-dibromoethenyl)-2,2- dimethylcyclopropanecarboxylate), dimefluthrin, esfenvalerate, etofenprox ((l-[[2-(4- ethoxyphenyl)-2-methylpropoxy]methyl]-3-phenoxybenzene), fenpropathrin, fenvalerate, esfenvalerate, flucythrinate, flumethrin, fluvalinate, tau-fluvalinate, halfenprox, imiprothrin, kadethrin, metofluthrin, permethrin ((3-phenoxyphenyl)methyl 3-(2,2- dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate), phenothrin, prallethrin, profluthrin, protrifenbute, pyrethrins I and II, resmethrin, silafluofen, tefluthrin, tetramethrin, tralomethrin, transfluthrin, valerate, enantiomers thereof, or combinations thereof. In one example embodiment, the pyrethroid may be bifenthrin, cypermethrin, deltamethrin, etofenprox, permethrin, or a combination thereof.

[0017] In yet another example embodiment, the organic co-biocide may be a neonicotenoid. For instance, the neonicotinoid may include, but are not limited to, acetamiprid ((lE)-N-[(6-chloro-3-pyridinyl)methyl]-N'-cyano-N-methylethanimidamide), clothianidin ((E)-l-[(2-chlorothiazol-5-yl)methyl]-3-methyl-2-nitroguanidine), dinotefuran (N-methyl-N'-nitro-N"-[(tetrahydro-3-furanyl)methyl]guanidine), imidacloprid ((2E)- 1 - [(6-chloro-3-pyridinyl)methyl]-N-nitro-2-imidazolidinimin), imidaclothiz, nitenpyram, nithiazine, paichongding, thiacloprid ((Z)-[3-[(6-chloro-3-pyridinyl)methyl]-2- thiazolidinylidene]cyanamide and thiamethoxam (3-[(2-chloro-5- thiazolyl)methyl]tetrahydro-5-methyl-N-nitro-4H-l,3,5-oxadiazin-4-imine). In one example embodiment, the neonicotinoid may be acetamiprid, clothianidin, dinotefuran, imidacloprid, thiacloprid and thiamethoxam, or a combination thereof.

[0018] In one example embodiment, the organic co-biocide may be a halogenated carbamate. For instance, the halogenated carbamate may include, but are not limited to, 3- iodo-2-propynyl butyl carbamate (IPBC), 3-iodo-2- propynyl hexyl carbamate (IPHC), 3- iodo -2-propynyl cyclohexyl carbamate (IPCC), 3-iodo-2-propynyl phenyl carbamate (IPPhC), 3-iodo-2-propynyl benzyl carbamate (IP Benzyl C), 3-iodo-2-propynyl propyl carbamate (IPPC), 4-iodo-3- butynyl propyl carbamate (IBPC), 3-iodo-2-propynyl-4- chloro phenyl carbamate (1PC1 PhC), 3-iodo-2-propynyl-4-chloro butyl carbamate (1PC1BC) and mixtures thereof. In one example embodiment, the halogenated carbamate may be 3-iodo-2-propynyl butyl carbamate (IPBC).

[0019] In one example embodiment, the organic co-biocide may be an SHDI. For instance, the SDHT may include, but is not limited to, flutolanil, isofetamid, flupyram, fluxapyroxad, penthiopyrad, boscalid, fenfuram, caboxin, thifluzamide, benzovindiflupyr, bixafen, furametpyr, isopyrazam, penflufen, penthiopyrad, sedaxane, or combinations thereof.

[0020] In one example embodiment, the organic co-biocide may be a quaternary ammonium salt (quat). For instance, the quat might include, but are not limited to, quatemaiy ammonium salts, such as didecyldimethylammonium chloride, didecyldimethylammonium carbonate, dimethylbenzyl ammonium chloride, didecylmethylpoly(oxyethyl)ammonium proprionate, or combinations thereof.

[0021] In one example embodiment, the organic co-biocide may be an azole. For instance, the azole may include, but are not limited to, clotrimazole, imazalil, oxpoconazole, prochloraz, pefurazoate, triflumizole, triforine, buthiobate, pyrifenox, fenarimol, nuarimol, triarimol, azaconazole, bitertanol, bromuconazole, cyproconazole (a- (4-chloropheny l)-a-( 1 -cyclopropylethyl)- 1 H- 1 ,2 ,4-triazole- 1 -ethanol), diclobutrazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole (rel-l-[[(2R,3S)-3-(2- chlorophenyl)-2-(4-fhiorophenyl)-2-oxiranyl]methyl]-lH-l,2,4-triazole), etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, (a-butyl-a-(2,4-dichlorophenyl)-lH-1.2.4-triazole-l -ethanol), imibenconazole, ipconazole, ipfentrifluconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole (l-[2-(2,4- dichlorophenyl)pentyl]-lH-l,2,4-triazole), propiconazole (l-[[2-(2,4-dichlorophenyl)-4- propyl-I,3-dioxolan-2-yl]methyl]-IH-I,2,4-triazole), prothioconazole, quinconazole, simeconazole, tebuconazole (a-[2-(4-chlorophenyl)ethyl]-a-( 1 , 1 -dimethylethyl)- 1 H- 1 ,2,4- triazole-1 -ethanol), tetraconazole, triadimefon (l -(4-chlorophenoxy)-3,3-dimethyl-l -(l H-1.2.4-triazol-l-yl)-2-butanone), triadimenol (|3-(4-chlorophenoxy)-a-(l,l-dimethylethyl)- 1H- 1,2, 4-triazole-l -ethanol), triticonazole, uniconazole, or combinations thereof. In one example embodiment, the azole may be cyproconazole, epoxiconazole, penconazole, propiconazole, tebuconazole, triadimefon, triadimenol, or combinations thereof.

[0022] The oil-based preservative may include one or more organic co-biocides. In one example embodiment, the oil-based preservative may include at least one organic co- biocide, such as one organic co-biocide. In another example embodiment, the oil-based preservative may include at least two organic co-biocides, such as two organic co-biocides.In yet another example embodiment, the oil-based preservative may include at least three organic co-biocides, such as three organic co-biocides.

[0023] In one example embodiment, the at least one organic co-biocide is present at no less than about 0.01 % by weight of the oil-based preservative and no greater than about 15% by weight of the oil-based preservative, such as from about 0.05% by weight to about 7.5% by weight, such as from about 0.5% by weight to about 5% by weight, such as about 1% by weight to about 2.5% by weight, or any range therebetween.

[0024] Optionally, the oil-based based preservative composition may include a carrier oil. For instance, the carrier oil may include, but are not limited to, light mineral oils, heavy mineral oils, paraffinic oils, synthetic oils, vegetable oils, bio-oils, naphthenic acids, or any combination thereof.[0025| In one example embodiment, the carrier oil used for the oil-based preservative may be a base mineral oil (such as, but not limited to, API petroleum derived and synthetically modified oils which fall within API Groups 1-5, including PAOs, alkylated naphthalenes, naphethenic oils and esters, kerosene, diesel, p9 oils, etc.). In other example embodiments, the carrier oil used for the oil-based preservative may be a tail-oil derivative (such as, but not limited to, sylphat), a vegetable oil derivative (such as, but not limited to, linseed oil) derivative. In certain example embodiments, the carrier oil for the oil-based preservative may be a combination of two or more of mineral oil, tall oil, vegetable oil, and synthetic oils.

[0026] According to example aspects of the present disclosure, an acid may be used to dissolve the copper (ii) salt in oils in the oil-based preservative composition. For instance, at least one organic acid may be used to dissolve copper (ii) salt. In one example embodiment, the at least one organic acid may be an organic acid with chain lengths of C6- CI2 or any combination thereof. In another example embodiment, the at least one organic acid may include, but are not limited to, C6-C8, C8-C10, C10-C12, C12-C14, C14-C16, or combinations thereof.

[0027] In one example embodiment, the oil-based preservative composition may include at least two organic acids. For instance, the at least two organic acids may include, but are not limited to, C6-C8 and C8-C10, C6-C8 and CI0-C12, C6-C8 and C12-C14, C6- C8 and C14-C16, or any mixtures thereof.

[0028] The acids used to dissolve the copper (ii) salt in carrier oils in the wood preservative formulation could be chosen from, but is not limited to, at least one organic acid with from plant or animal derived sources.

[0029] According to example aspects of the present disclosure, the oil-based preservative composition may be utilized in a method for treating a wood product. Methods disclosed herein may include contacting the wood product within a system with an oil-based preservative composition disclosed herein. For example, interior volume of a pressure tank may be pressurized with the wood product and the treatment fluid, e.g., with the oil-based preservative, in order to impregnate the wood product with the treatment fluid. Immersing the wood product in the pressurized interior volume of pressure tank containing the treatment fluid, e.g., with the oil-based preservative, results in the treatment fluid being homogenously impregnated into the surface of the wood product rather than merely applied onto the surface or penetrating only partially or inhomogenously into the wood product. The pressure applied to the interior volume of the pressure tank in order to penetrate the wood product with the treatment fluid may be from about one (1) bar to about ten (10) bar, such as about two (2) bar, about three (3) bar, about four (4) bar, about five (5) bar, about six (6) bar, about seven (7) bar, about eight (8) bar, or about nine (9) bar. It is understood that the exact pressure value may depend on the wood product size and can be readily adapted by a skilled artisan.

[0030] In certain example embodiments, the interior volume of the pressure tank may be pressurized for no less than about thirty (30) minutes to impregnate the wood product with the treatment fluid, such as no less than about sixth (60) minutes, such as no less than about one hundred and twenty (120) minutes, such as no less than about one hundred and eighty (180) minutes, such as no less than about two hundred and forty (240) minutes. In certain example embodiments, the interior volume of the pressure tank may be pressurized for no greater than three hundred (300) minutes to impregnate the wood product with the treatment fluid, such as no greater than about two hundred (200) minutes, such as no greater than about one hundred and fifty (150) minutes, such as no greater than about one hundred (100) minutes, such as no greater than about sixty (60) minutes.

[0031] In certain example embodiments, the temperature of the oil-based preservative may be no greater than ninety degrees Celsius (90 °C) when the wood product is impregnated with the treatment fluid, such as no greater than eighty-five degrees Celsius (85 °C), such as no greater than eighty degrees Celsius (80 °C), such as no greater than seventy- five degrees Celsius (75 °C), such as no greater than seventy degrees Celsius (70 °C), such as no greater than sixty-five degrees Celsius (65 °C), such as no greater than sixty degrees Celsius (60 °C), such as no greater than fifty-five degrees Celsius (55 °C), such as no greater than fifty degrees Celsius (50 °C), such as no greater than forty-fivedegrees Celsius (45 °C). In certain example embodiments, at 410, the temperature of the treatment fluid may be greater than forty degrees Celsius (40 °C) when the wood product is impregnated with the treatment fluid, such as greater than fifty degrees Celsius (50 °C), such as greater than sixty degrees Celsius (60 °C), such as greater than seventy degrees Celsius (70 °C), such as greater than eighty degrees Celsius (80 °C).

[0032] If desired, the oil-based preservative concentrate may be diluted from about 1% to about 30% in a carrier oil prior to application to the wood product.

[0033] In one example embodiment, the wood product may be a solid wood component including, but not limited to, utility poles or railroad ties. In another example embodiment, the wood product may be a wood-based material including, but not limited to, wood chips of fibers for the production of wood-based panels such as, but not limited to, orientated strand board (OSB), or thin veneer for production of plywood sheets. In yet another example embodiment, the wood product may be an engineered wood product including, but not limited to, glulam or cross-lam and other mass timber products.

[0034] The preceding description is exemplary in nature and is not intended to limit the scope, applicability or configuration of the disclosure in any way. Various changes to the described embodiments may be made in the function and arrangement of the elements described herein without departing from the scope of the disclosure.

[0035] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention is related.

[0036] As used in this application and in the claims, the singular forms “a”, “an”, and “the” include the plural forms unless the context clearly dictates otherwise. Additionally, the term “includes” means “comprises”. The methods and compositions of the present disclosure, including components thereof, can comprise, consist of, or consist essentially of the essential elements and limitations of the embodiments described herein, as well as any additional or optional ingredients, components or limitations described herein or otherwise useful in biocidal compositions.

[0037] 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 distinguishingembodiments from discussed prior art, the embodiment numbers are not approximates unless the word “about” is recited.

[0038] As used herein, “optional” or “optionally” means that the subsequently described material, event or circumstance may or may not be present or occur, and that the description includes instances where the material, event or circumstance is present or occurs and instances in which it does not. As used herein, “w / w%” and “wt%” mean by weight as relative to another component or a percentage of the total weight in the composition.

[0039] The term “about” is intended to mean approximately, in the region of, roughly, or around. When the term “about” is used in conjunction with a numerical range, it modifies that range by extending the boundaries above and below the numerical values set forth. Unless otherwise indicated, it should be understood that the numerical parameters set forth in the following specification and attached claims are approximations. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, numerical parameters should be read in light of the number of reported significant digits and the application of ordinary rounding techniques.

[0040] The term “substantially free of’ when used to describe the amount of substance in a material is not to be limited to entirely or completely free of and may correspond to a lack of any appreciable or detectable amount of the recited substance in the material. Thus, e.g., a material is “substantially free of’ a substance when the amount of the substance in the material is less than the precision of an industry-accepted instrument or test for measuring the amount of the substance in the material. In certain example embodiments, a material may be “substantially free of’ a substance when the amount of the substance in the material is less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, less than 0.5%, or less than 0. 1 % by weight of the material.

[0041] As used herein, the terms “first”, “second”, and “third” may be used interchangeably to distinguish one component from another and are not intended to signify location or importance of the individual components.

[0042] Here and throughout the specification and claims, range limitations are combined and interchanged, such ranges are identified and include all the sub-ranges contained therein unless context or language indicates otherwise. For example, all ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other.

[0001] As used herein, the term “D50” or “D50 particle size” refers to the volume median particle size, where 50% of the particles of the sample volume have a size below that range or value.

[0002] Analogously, as used herein, the term “D95” or “D95 particle size” refers to a value where 95% of the particles of the sample volume have a size below that range or value.

[0043] As used herein, the term “particle size” as used herein, unless specifically stated otherwise, refers to the median particle size D50. Particle size can be measured using a laser scattering particle size analyzer, such as a HORIBA LA 910 particle size analyzer.

[0003] The terms “median particle size” and “average particle size” and D50 are used herein interchangeably.[0044| This written description uses examples to disclose the present disclosure, including the best mode, and also to enable any person skilled in the art to practice the disclosure, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the disclosure is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they include structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

[0045] Furthermore, certain aspects of the present disclosure may be better understood according to the following examples, which are intended to be non-limiting and exemplary in nature. Moreover, it will be understood that the compositions described in the examples may be substantially free of any substance not expressly described.EXAMPLESExample 1

[0046] Generally, preservative compositions disclosed herein were prepared by dissolving a selected organic co-biocide in the formulation by continuously stirring at 40 °C until the selected organic co-biocide is dissolved. Subsequently, a selected carrier oil and copper (ii) salt are added to the formulation and mixed for about 60 minutes. Next, the temperature of the mixture is increased to 60 °C while stirring and a vacuum is applied for 3 hours at 60 °C to remove the reaction water, resulting in a preservative concentrate.Following vacuum, the preservative concentrate was filtered. The preservative concentrate was analyzed for copper and any organic biocide using appropriate analytical techniques.Preservative Concentrate - 1Preservative Concentrate - 2Preservative Concentrate - 3Preservative Concentrate - 3

[0047] These and other modifications and variations to the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention, which is more particularly set forth in the appended claims. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention so further described in such appended claims.

Claims

What Is Claimed;1. An oil-based preservative composition, the composition comprising: at least about 8% copper (ii) salt by weight of the oil-based preservative composition; and at least one organic co-biocide.

2. The oil-based preservative composition of claim 1, wherein the copper (ii) salt is present in the preservative composition in an amount of from about 8% to about 25% by weight of the oil-based preservative composition.

3. The oil-based preservative composition of claim 2, wherein the copper (ii) salt is present in the preservative composition in an amount of from about 8% to about 20% by weight of the oil-based preservative composition.

4. The oil-based preservative composition of claim 2, wherein the copper (ii) salt is present in the preservative composition in an amount of from about 8% to about 15% by weight of the oil-based preservative composition.

5. The oil-based preservative composition of claim 1, wherein the copper (ii) salt is selected from a group consisting of copper (ii) oxide, copper (ii) chloride, copper (ii) sulfate, copper (ii) hydroxide, copper (ii) nitrate, copper (ii) acetate, copper (ii) fluoride, copper (ii) carbonate, copper (ii) carbonate hydroxide, copper (ii) chlorate, copper (ii) arsenate, copper (ii) phosphate, copper (ii) sulfide, and combinations thereof.

6. The oil-based preservative composition of claim 1, wherein the copper (ii) salt comprises copper (ii) hydroxide.

7. The oil-based preservative composition of claim 1, wherein the at least one organic co-biocide is present at no less than about 0.01% by weight of the oil-based preservative and no greater than about 15% by weight of the oil-based preservative.

8. The oil-based preservative composition of claim 1, wherein the at least one organic co-biocide is present at no less than about 0.05% by weight of the oil-based preservative and no greater than about 7.5% by weight of the oil-based preservative.

9. The oil-based preservative composition of claim 1, wherein the at least one organic co-biocide is present at no less than about 0.5% by weight of the oil-based preservative and no greater than about 5% by weight of the oil-based preservative.

10. The oil-based preservative composition of claim 1, wherein the at least one organic co-biocide is present at no less than about 1% by weight of the oil-based preservative and no greater than about 2.5% by weight of the oil-based preservative.

11. The oil-based preservative composition of claim 1, wherein the preservative composition comprises at least two organic co-biocides.

12. The oil-based preservative composition of claim 1, wherein the preservative composition comprises at least three organic co-biocides.

13. The oil-based preservative composition of claim 1, wherein the at least one organic co-biocide comprises an isothiazolinone, a pyrethroid, a neonicotenoid, a halogenated carbamate, a quaternary ammonium salt, a succinate dehydrogenase inhibitor (SDHI), an azole, or combinations thereof.

14. The oil-based preservative composition of claim 13, wherein the isothiazolinone is selected from a group consisting of l,2-benzisothiazolin-3-one (“BIT”), N-(n-butyl)-l,2- benzisothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (“DCOIT”), 2-methyl- 4-isothiazolin-3-one. 5-chloro-2-methyl-4-isothiazolin-3-one. 2-methyl-4-isothiazolin-3- one, 5-chloro-2-methyl-2H-isothiazol-3-one / 2-methyl-2H-isothiazol-3-one (“CMIT / MIT”), or combinations thereof.

15. The oil-based preservative composition of claim 13, wherein the pyrethroid is selected from a group consisting of acrinathrin, allethrin, bifenthrin ((2-methyl[l,T- biphenyl]-3-yl)methyl (lR,3R)-rel-3-[(lZ)-2-chloro-3,3,3-trifluoro-l-propen-l-yl]-2,2- dimethylcyclopropanecarboxylate), chloroprallethrin, cycloprothrin, cyfluthrin, beta- cyfluthrin, cyhalothrin. lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin (cyano(3- phenoxyphenyl)methyl 3-(2.2-dichloroethenyl)-2.2-dimethylcyclopropanecarboxylate), alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin.cyphenothrin, deltamethrin ((S)-cyano(3-phenoxyphenyl)methyl (lR,3R)-3-(2,2- dibromoethenyl)-2,2-dimethylcyclopropanecarboxylate), dimefl uthrin, esfenvalerate. etofenprox (( 1 -[[2-(4-ethoxyphenyl)-2-methylpropoxy] methyl] -3 -phen oxybenzene), fenpropathrin, fenvalerate, esfenvalerate, flucythrinate, flumethrin, fluvalinate, tau- fluvalinate, halfenprox, imiprothrin, kadethrin, metofluthrin, permethrin ((3- phenoxyphenyl)methyl 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate), phenothrin. prallethrin. profluthrin, protrifenbute, pyrethrins I and II, resmethrin. silafl uofen, tefluthrin, tetramethrin, tralomethrin, transfluthrin, valerate, enantiomers thereof, or combinations thereof.

16. The oil-based preservative composition of claim 13. wherein the neonicotinoid is selected from a group consisting of acetamiprid ((lE)-N-[(6-chloro-3-pyridinyl)methyl]- N'-cyano-N-methylethanimidamide), clothianidin ((E)-l-[(2-chlorothiazol-5-yl)methyl]-3- methyl-2-nitroguanidine), dinotefuran (N-methyl-N'-nitro-N"-[(tetrahydro-3- furanyl)methyl]guanidine), imidacloprid ((2E)-l-[(6-chloro-3-pyridinyl)methyl]-N-nitro-2- imidazolidinimin), imidaclothiz, nitenpyram, nithiazine, paichongding, thiacloprid ((Z)-[3- [(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]cyanamide and thiamethoxam (3-[(2- chloro-5-thiazolyl)methyl]tetrahydro-5-methyl-N-nitro-4H-l,3,5-oxadiazin-4-imine), or combinations thereof.

17. The oil-based preservative composition of claim 13, wherein the halogenated carbamate is selected from a group consisting of3-iodo-2-propynyl butyl carbamate (IPBC), 3-iodo-2- propynyl hexyl carbamate (IPHC), 3-iodo -2-propynyl cyclohexyl carbamate (IPCC), 3-iodo-2-propynyl phenyl carbamate (IPPhC). 3-iodo-2-propynyl benzy l carbamate (IP Benzyl C), 3-iodo-2-propynyl propyl carbamate (IPPC), 4-iodo-3- butynyl propyl carbamate (IBPC), 3-iodo-2-propynyl-4-chloro phenyl carbamate (IPCI PhC), 3-iodo-2-propynyl-4-chloro buty l carbamate (IPCI BC), or combinations thereof.

18. The oil-based preservative composition of claim 13. wherein the SDHI is selected from a group consisting of flutolanil, isofetamid, flupyram, fluxapyroxad, penthiopyrad, boscalid, fenfuram, caboxin, thifluzamide, benzovindiflupyr, bixafen, furametpyr, isopyrazam, penflufen, penthiopyrad, sedaxane, or combinations thereof.

19. The oil-based preservative composition of claim 13, wherein the quaternary ammonium salt is selected from a group consisting of didecyldimethylammonium chloride, didecyldimethylammonium carbonate, dimethylbenzyl ammonium chloride, didecylmethy lpoly(oxyethyl)ammonium proprionate, or combinations thereof.

20. The oil-based preservative composition of claim 13, wherein the azole is selected from a group consisting of clotrimazole, imazalil, oxpoconazole, prochloraz, pefurazoate, triflumizole, triforine, buthiobate, pyrifenox, fenarimol, nuarimol, triarimol, azaconazole, bitertanol, bromuconazole, cyproconazole (a-(4-chlorophenyl)-a-(l-cyclopropylethyl)-lH-1.2.4-triazole-l -ethanol), diclobutrazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole (rel-l-[[(2R,3S)-3-(2-chlorophenyl)-2-(4-fluorophenyl)-2-oxiranyl]methyl]- lH-l,2,4-triazole), etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, (a- butyl-a-(2,4-dichlorophenyl)-lH-l, 2, 4-triazole-l -ethanol), imibenconazole, ipconazole, ipfentrifluconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole (1 -[2- (2,4-dichlorophenyl)pentyl]-lH-l,2,4-triazole), propiconazole (l-[[2-(2,4-dichlorophenyl)- 4-propyl-l,3-dioxolan-2-yl]methyl]-lH-l,2,4-triazole), prothioconazole, quinconazole, simeconazole, tebuconazole (a-[2-(4-chlorophenyl)ethyl]-a-(l,l-dimethylethyl)-lH-l,2,4- triazole-1 -ethanol), tetraconazole, triadimefon (l-(4-chlorophenoxy)-3,3-dimethyl-l-(lH-1.2.4-triazol-l-yl)-2-butanone), triadimenol (P-(4-chlorophenoxy)-a-(l,l-dimethylethyl)- lH-l,2.4-triazole-l-ethanol). triticonazole, uniconazole, or combinations thereof.

21. The oil-based preservative composition of claim 1, further comprising a carrier oil .

22. The oil-based preservative composition of claim 21, wherein the carrier oil comprises light mineral oils, heavy mineral oils, paraffinic oils, synthetic oils, vegetable oils, bio-oils, naphthenic acids, or combinations thereof.

23. The oil-based preservative composition of claim 1, wherein the ratio of copper (ii) salt (wt%) to organic co-biocide (wt%) in the oil-based preservative composition is from about 100: 1 to about 1:100.

24. The oil-based preservative composition of claim 23, wherein the ratio of copper (ii) salt (wt.%) to organic co-biocide (wt.%) in the oil-based preservative composition is from about 50: 1 to about 1: 1.

25. The oil-based preservative composition of claim 23. wherein the ratio of copper (ii) salt (wt.%) to organic co-biocide (wt.%) in the oil-based preservative composition is from about 20: 1 to about 1: 1.

26. A method for treating a wood product, comprising contacting the wood product with the oil-based preservative composition of claim 1.

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