Zinc and boron-containing reinforced wood preservative

Abstract

Provided are wood preservative compositions comprising a copper-containing biocide, a zinc-containing biocide, a boron-containing biocide and an organic biocide, and methods for making the wood preservative compositions comprising a copper-containing biocide, a zinc-containing biocide, a boron-containing biocide and an organic biocide, which exhibit improved biocidal efficacy against copper-resistant fungi.

Description

[Technical Field]

[0001] Related applications This application is based on U.S. Provisional Patent Application No. 63 / 163,219, filed on 19 March 2021, and U.S. Provisional Patent Application No. 63 / 166,733, filed on 26 March 2021, both of which are incorporated herein by reference, and claims priority to these applications. [Background technology]

[0002] Wood products and other cellulosic products are susceptible to attacks from various types of organisms, including mold, fungi, and insects, such as termites. Attacks by these organisms can cause wood decay in wood and other cellulosic products, reducing the mass and structural integrity of the products. To combat microbial attacks, various types of wood preservatives have been developed and are currently available on the market. These wood preservatives can be applied directly to the surface by deposition, spraying, brushing, or vacuum immersion. When applying preservatives industrially, wood and wood-based and cellulosic products are typically impregnated with the treatment solution to achieve either shell or full-cell penetration into the substrate. Depending on the type of wood being treated and the end-use, the penetration depth of the preservative solution into the wood and other cellulosic products can significantly affect the useful service life of the treated wood and other cellulosic products.

[0003] Copper-based organic wood preservatives have been successfully used worldwide as ground contact preservatives. However, resistance to such compositions has been found, and fungi exist that cause contamination and deterioration of wood containing copper-based preservatives. Other types of biocides, such as zinc, can also be used to treat wood. Although its use is perhaps not as widespread as that of copper, several wood preservatives containing zinc alone or in combination with copper as a biocide metal ion are commercially available. However, these existing compositions, in addition to other problems, have the issue that when used together in the same effective amount as copper alone, zinc either (1) fails to adequately control copper-resistant fungi or (2) lacks sufficient efficacy against non-copper-resistant fungi as well.

[0004] Non-metallic alternatives, such as azoles and boron-based biocides, have been used in combination with metallic preservatives to combat metal-resistant bacteria. However, azoles and boron-based biocides have been found to exhibit drawbacks, including leaching, either alone or in combination.

[0005] Azoles have been found to have limited efficacy against certain aggressive brown rot fungi, except at extremely high concentrations rarely seen in commercial use. It is known that azoles and other organic biocides have a steep penetration gradient across the cross-section of the treated timber. The interior of the timber may exhibit significantly lower azole concentrations compared to the exterior, making the wood more susceptible to fungal attack. [Overview of the project] [Problems that the invention aims to solve]

[0006] Borates are highly effective preservatives against a wide range of wood-decaying fungi. However, boric acid preservatives are generally soluble compounds that tend to leach more readily than metal-based preservatives.

[0007] Therefore, there is a need for a wood preservative composition that exhibits enhanced bactericidal efficacy. It is further beneficial to provide a wood preservative composition that shows improved efficacy against copper-resistant bacteria. Additionally, it is beneficial to provide a biocidal composition that shows long-term efficacy against fungi including copper-resistant bacteria, as well as improved protection of the interior of wood, wood products, and other cellulosic products and penetration into these interiors.

Means for Solving the Problems

[0008] The present disclosure is generally directed to wood preservative compositions. The wood preservative compositions exhibit improved bactericidal efficacy against copper-resistant bacteria. The resulting wood preservative compositions are suitable for the preservation of wood and other cellulosic materials.

[0009] In one embodiment, the wood preservative composition includes a copper-containing biocide, a zinc-containing biocide, a boron-containing biocide, and an organic biocide. The copper-containing biocide and the zinc-containing biocide are present in the wood preservative composition such that the ratio of copper to zinc is from about 15:1 to about 1:5 by weight. Additionally, the copper-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the ratio of copper to boric acid equivalent is from about 15:1 to about 1:5 by weight.

[0010] The copper-containing biocide can include basic copper carbonate, copper oxide, or a combination thereof.

[0011] The copper-containing biocides used in the present invention can form complexes with amino compounds when used in a dispersed, micronized form or in a micronized form having a particle size of 0.01 to 25.0 microns. The particle size of the micronized copper biocides used in the compositions disclosed herein may be 0.01 to 10.0 microns, 0.05 to 10 microns, 0.1 to 10.0 microns, 0.01 to 1.0 microns, 0.05 to 1.0 microns, 0.1 to 1.0 microns, or 0.2 to 1.0 microns. If more uniform penetration is desired, the particle size of the micronized copper biocide compound used in the compositions disclosed herein may be 0.05 to 1.0 microns.

[0012] Zinc-containing biocides may include zinc oxide, zinc acetate, zinc borate, or a combination of zinc oxide and zinc borate.

[0013] The zinc-containing biocides used in the present invention may be used in a micronized form having a particle size of 0.01 to 25.0 microns, or they may form complexes with amino compounds. The particle size of the micronized zinc biocides used in the compositions disclosed herein may be 0.01 to 10 microns, 0.05 to 10 microns, 0.01 to 1.0 microns, 0.05 to 1.0 microns, 0.1 to 1.0 microns, or 0.2 to 1.0 microns. If more uniform penetration is desired, the particle size of the micronized zinc biocide compound used in the compositions disclosed herein may be 0.05 to 1.0 microns.

[0014] Boron-containing biocides may include boric acid, disodium tetraborate pentahydrate, disodium octaborate tetrahydrate, or combinations thereof.

[0015] Boron-containing biocides may also be boric acid.

[0016] Organic biocides are selected from fungicides.

[0017] Organic biocides can be independently selected from the group consisting of azoles, quaternary ammonium compounds, isothiazolones, pyrazolecarboxamides, phenylpyrazoles, haloalkynyl compounds, or combinations thereof.

[0018] The organic biocides used in the present invention may be in a micronized form having a particle size of 0.01 microns to 25.0 microns. The particle size of the micronized organic biocides used in the compositions disclosed herein may be 0.01 to 10 microns, 0.05 to 10 microns, 0.1 to 10.0 microns, 0.01 to 1.0 microns, 0.05 to 1.0 microns, 0.1 to 1.0 microns, or 0.2 to 1.0 microns.

[0019] Organic biocides may also be azoles.

[0020] Azoles can be independently selected from the group consisting of imidazoles, benzimidazoles, triazoles, or combinations thereof.

[0021] The organic biocides may also be 1,2,4-triazoles.

[0022] 1,2,4-Triazoles can be independently selected from the group consisting of cyproconazole, fenbuconazole, propiconazole, tebuconazole, triadimefon, triticonazole, or combinations thereof.

[0023] 1,2,4-triazoles can be independently selected from the group consisting of tebuconazole, propiconazole, or combinations thereof.

[0024] 1,2,4-triazoles can be selected from tebuconazole.

[0025] 1,2,4-triazoles can be selected from propiconazole.

[0026] Azoles can form complexes with copper-containing biocides.

[0027] The azoles used in the present invention may be in a micronized form having a particle size of 0.01 microns to 25.0 microns. The particle size of the micronized azoles used in the compositions disclosed herein may be 0.01 to 10 microns, 0.05 to 10 microns, 0.1 to 10.0 microns, 0.01 to 1.0 microns, 0.05 to 1.0 microns, 0.1 to 1.0 microns, or 0.2 to 1.0 microns. If more uniform penetration is desired, the particle size of the micronized azole compound used in the compositions disclosed herein may be 0.05 to 1.0 microns.

[0028] The organic biocide may also be a quaternary ammonium compound.

[0029] The quaternary ammonium compound can be independently selected from the group consisting of didecyldimethylammonium chloride, didecyldimethylammonium carbonate, didecyldimethylammonium bicarbonate, and combinations thereof.

[0030] Organic biocides may include isothiazolones.

[0031] The isothiazolone compounds can be independently selected from the group consisting of 2-methyl-4-isothiazolin-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 4,5-dichloro-2n-octylisothiazolin-3-one (DCOIT), 5-chloro-2n-octyl-4-isothiazolin-3-one (COIT), 2-octyl-2H-isothiazolin-3-one (OIT), 1,2-benzothiazolin-3-one (BIT), N-methyl-1,2-benzisothiazolin-3-one (MBIT), or 2-butyl-1,2-benzisothiazolin-3(2H)-one (BBIT), or combinations thereof.

[0032] The isothiazolone compound may also be 4,5-dichloro-2n-octylisothiazolin-3-one (DCOIT).

[0033] The organic biocides may also be pyrazole carboxamides.

[0034] Pyrazole carboxamides may also be penflufen.

[0035] The organic biocides may also be phenylpyrazoles.

[0036] The organic biocide may be a haloalkynyl compound.

[0037] The haloalkynyl compound may also be 3-iodo-2-propynylbutylcarbamate (IPBC).

[0038] Organic biocides can form complexes with copper-containing biocides.

[0039] Copper-containing biocides may contain basic copper carbonate; zinc-containing biocides may contain zinc oxide or a combination of zinc oxide and zinc borate; boron-containing biocides may contain boric acid; and organic biocides may be selected from the group consisting of azoles, quaternary ammonium compounds, isothiazolones, pyrazolecarboxamides, phenylpyrazoles, haloalkynyl compounds, or combinations thereof.

[0040] Based on the total weight of the composition, copper-containing biocides can constitute approximately 0.1% to 75% by weight of the composition, zinc-containing biocides can constitute approximately 0.1% to 50% by weight of the composition, boron-containing biocides can constitute approximately 0.1% to 75% by weight of the composition, and organic biocides can constitute approximately 0.1% to 20% by weight of the composition.

[0041] Copper-containing biocides may contain basic copper carbonate; zinc-containing biocides may contain zinc oxide or a combination of zinc oxide and zinc borate; boron-containing biocides may contain boric acid; and organic biocides may contain azoles.

[0042] Copper-containing biocides may contain basic copper carbonate, zinc-containing biocides may contain zinc oxide or a combination of zinc oxide and zinc borate, boron-containing biocides may contain boric acid, and azoles may be independently selected from the group consisting of tebuconazole, propiconazole, or combinations thereof.

[0043] Copper-containing biocides may contain basic copper carbonate, zinc-containing biocides may contain zinc oxide or a combination of zinc oxide and zinc borate, boron-containing biocides may contain boric acid, and azoles may contain tebuconazole.

[0044] Based on the total weight of the composition, copper-containing biocides can constitute approximately 0.1% to 75% by weight of the composition, zinc-containing biocides can constitute approximately 0.1% to 50% by weight of the composition, boron-containing biocides can constitute approximately 0.1% to 75% by weight of the composition, and azoles can constitute approximately 0.1% to 20% by weight of the composition.

[0045] Copper-containing biocides may contain basic copper carbonate, zinc-containing biocides may contain zinc oxide or a combination of zinc oxide and zinc borate, boron-containing biocides may contain boric acid, and organic biocides may contain pyrazole carboxamides.

[0046] Copper-containing biocides may contain basic copper carbonate, zinc-containing biocides may contain zinc oxide or a combination of zinc oxide and zinc borate, boron-containing biocides may contain boric acid, and pyrazole carboxamides may be independently selected from penflufen.

[0047] Copper-containing biocides may contain basic copper carbonate, zinc-containing biocides may contain zinc oxide or a combination of zinc oxide and zinc borate, boron-containing biocides may contain boric acid, and pyrazole carboxamides may contain penflufen.

[0048] In one embodiment, based on the total weight of the composition, the copper-containing biocide may constitute about 0.1% to about 75% by weight of the composition, the zinc-containing biocide may constitute about 0.1% to about 50% by weight of the composition, the boron-containing biocide may constitute about 0.1% to about 75% by weight of the composition, and the pyrazole carboxamides may constitute about 0.1% to about 20% by weight of the composition.

[0049] In one embodiment, the copper-containing biocide may contain basic copper carbonate, the zinc-containing biocide may contain zinc oxide or a combination of zinc oxide and zinc borate, the boron-containing biocide may contain boric acid, and the organic biocide may contain a quaternary ammonium compound.

[0050] In one embodiment, the copper-containing biocide may include basic copper carbonate, the zinc-containing biocide may include zinc oxide or a combination of zinc oxide and zinc borate, the boron-containing biocide may include boric acid, and the quaternary ammonium compound may be independently selected from the group consisting of didecyldimethylammonium chloride, didecyldimethylammonium carbonate, didecyldimethylammonium bicarbonate, or a combination thereof.

[0051] In one embodiment, based on the total weight of the composition, the copper-containing biocide may constitute about 0.1% to about 75% by weight of the composition, the zinc-containing biocide may constitute about 0.1% to about 50% by weight of the composition, the boron-containing biocide may constitute about 0.1% to about 75% by weight of the composition, and the quaternary ammonium compound may constitute about 0.1% to about 20% by weight of the composition.

[0052] In one embodiment, the copper-containing biocide may contain basic copper carbonate, the zinc-containing biocide may contain zinc oxide or a combination of zinc oxide and zinc borate, the boron-containing biocide may contain boric acid, and the organic biocide may contain isothiazolones.

[0053] In one embodiment, the copper-containing biocide may contain basic copper carbonate, the zinc-containing biocide may contain zinc oxide or a combination of zinc oxide and zinc borate, the boron-containing biocide may contain boric acid, and the isothiazolones are 2-methyl-4-isothiazolin-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 4,5-dichloro-2n-octylisothiazolin-3-one (DCOIT), 5-chloro-2n- Octyl-4-isothiazolin-3-one (COIT), 4,5-dichloro-2-cyclohexyl-4-isothiazolin-3-one, 2-octyl-2H-isothiazolin-3-one (OIT), 1,2-benzothiazolin-3-one (BIT), N-methyl-1,2-benzisothiazolin-3-one (MBIT), or 2-butyl-1,2-benzisothiazolin-3(2H)-one (BBIT), or combinations thereof, can be independently selected from the group.

[0054] In one embodiment, based on the total weight of the composition, the copper-containing biocide may constitute about 0.1% to about 75% by weight of the composition, the zinc-containing biocide may constitute about 0.1% to about 50% by weight of the composition, the boron-containing biocide may constitute about 0.1% to about 75% by weight of the composition, and the isothiazolones may constitute about 0.1% to about 20% by weight of the composition.

[0055] In one embodiment, the copper-containing biocide may contain basic copper carbonate, the zinc-containing biocide may contain zinc oxide or a combination of zinc oxide and zinc borate, the boron-containing biocide may contain boric acid, and the organic biocide may contain a haloalkynyl compound.

[0056] In one embodiment, the copper-containing biocide may include basic copper carbonate, the zinc-containing biocide may include zinc oxide or a combination of zinc oxide and zinc borate, the boron-containing biocide may include boric acid, and the haloalkynyl compound may include 3-iodo-2-propynylbutylcarbamate (IPBC).

[0057] In one embodiment, based on the total weight of the composition, the copper-containing biocide may constitute about 0.1% to about 75% by weight of the composition, the zinc-containing biocide may constitute about 0.1% to about 50% by weight of the composition, the boron-containing biocide may constitute about 0.1% to about 75% by weight of the composition, and the haloalkynyl compound may constitute about 0.1% to about 20% by weight of the composition.

[0058] In one embodiment, the composition may have a pH of about 3 to about 10.

[0059] In one embodiment, the composition may further contain alkanolamines.

[0060] In one embodiment, copper-containing biocides and zinc-containing biocides may be present in a wood preservative composition such that the ratio of copper to zinc is approximately 15:1 to approximately 1:5, 15:1 to approximately 1:1, 10:1 to approximately 1:5, 10:1 to approximately 1:2, or 10:1 to approximately 1:1 by weight.

[0061] In one embodiment, copper-containing biocides and boron-containing biocides may be present in a wood preservative composition such that the ratio of copper to boric acid equivalents is approximately 15:1 to approximately 1:5, 15:1 to approximately 1:1, 10:1 to approximately 1:5, 10:1 to approximately 1:2, and 10:1 to approximately 1:1, based on weight.

[0062] In one embodiment, a zinc-containing biocide and a boron-containing biocide may be present in the wood preservative composition such that the ratio of zinc to boric acid equivalents is about 5:1 to about 1:5 and about 3:1 to about 1:1.5, respectively, based on weight.

[0063] Wood and other cellulosic products can be treated with any of the wood preservative compositions described. In wood and other cellulosic products, copper is present in approximately 200 g / m of wood products. 3 (grams per cubic meter) ~ approximately 7.5 kg / m 3 It may be present in the amount of (kilograms per cubic meter), and zinc is present in the product at approximately 40 g / m 3 ~Approx. 1.5kg / m 3 It may be present in that amount, and the boric acid equivalent is approximately 40 g / m² of the product. 3 ~about 3kg / m 3 It may be present in amounts of approximately 20 g / m² of the product, and organic biocides may be present in this amount. 3 ~about 260g / m 3 It can exist in that quantity.

[0064] In one embodiment, the wood preservative composition comprises a copper-containing biocide, a zinc-containing biocide, a boron-containing biocide containing boric acid, and azoles. The copper-containing biocide and the zinc-containing biocide are present in the wood preservative composition such that the ratio of copper to zinc is about 15:1 to about 1:5 by weight. The copper-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the ratio of copper to boric acid equivalents is about 15:1 to about 1:5 by weight. The copper-containing biocide contains basic copper carbonate. The zinc-containing biocide contains zinc oxide or a combination of zinc oxide and zinc borate. The boron-containing biocide contains boric acid. The azoles contain tebuconazole.

[0065] The present invention further provides a method for treating wood with any of the disclosed wood preservative compositions. In this method, copper-containing biocides, zinc-containing biocides, boron-containing biocides, and organic biocides can be injected into the wood in a single step.

[0066] A method for producing a wood preservative composition is described. The method includes the steps of: dispersing at least a portion of a copper-containing biocide and a zinc-containing biocide; pulverizing at least one organic biocide to produce a pulverized organic biocide; and combining a boron-containing biocide containing boric acid with the copper-containing biocide, the zinc-containing biocide and the pulverized organic biocide. The copper-containing biocide and the zinc-containing biocide are present in the wood preservative composition such that the ratio of copper to zinc is about 15:1 to about 1:5 by weight. Additionally, the copper-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the ratio of copper to boric acid equivalents is about 15:1 to about 1:5 by weight.

[0067] Copper-containing biocides and zinc-containing biocides can be pulverized together with at least one dispersant.

[0068] Based on the total weight of the composition, copper-containing biocides can constitute approximately 1% to 75% by weight of the composition, zinc-containing biocides can constitute approximately 0.1% to 50% by weight of the composition, boron-containing biocides can constitute approximately 0.1% to 75% by weight of the composition, and organic biocides can constitute approximately 0.1% to 20% by weight of the composition.

[0069] Copper-containing biocides may contain basic copper carbonate, zinc-containing biocides may contain zinc oxide or a combination of zinc oxide and zinc borate, boron-containing biocides may contain boric acid, and azoles may contain tebuconazole.

[0070] Each of the embodiments listed above may be combined with one or more of the other embodiments listed above in a particular embodiment.

[0071] These and other features, embodiments and advantages of the present invention will be better understood by referring to the following description and the appended claims. The appended drawings incorporated herein and constituting part thereof illustrate embodiments of the present invention and serve to illustrate the principles of the present invention together with the description. definition Here, the term "D50" or "D50 particle size" refers to the medium volume particle size, where 50% of the particles in the sample volume are of a size below that range or value.

[0072] Similarly, here, the term "D95" or "D95 particle size" refers to a value in which 99% of the particles in the sample volume have a size below that range or value.

[0073] Herein, the term "particle size" as used herein refers to the medium particle size D50 unless otherwise specified.

[0074] The terms “intermediate particle size,” “average particle size,” and “D50” are used interchangeably in this specification.

[0075] Herein, the term "micronized" as used herein refers to a medium particle size (D50) in the range of 0.01 to 25 microns.

[0076] The terms "micron (μ)" and "micrometer (μm)" are used interchangeably herein.

[0077] Herein, the term “preservative” as used herein means a composition that makes the material to which the composition is applied more resistant to insect, fungal, and microbial attacks than the same material to which the composition is not applied.

[0078] Here, the term "wood" refers to wood and other cellulosic products. The terms "wood," "timber," and "wood products" are used interchangeably.

[0079] Here, the term "cellulose-based wood products" includes wood; wood products, such as composite wood products (oriented strand board, particleboard, plywood, laminated veneer lumber (LVL), and other laminated wood products); paper and paper products; textiles containing cellulose components; ropes and other products containing cellulose fibers.

[0080] Here, the term "boron-containing biocides" is intended to refer, unless otherwise specified, to compounds containing the element boron, such as boron-containing minerals, boric acid compounds, boron ester compounds, and other organic or inorganic boron-containing compounds.

[0081] Here, the weight-based ratio of copper to zinc is calculated based on the copper content in any copper compound and the zinc content in any zinc compound, in order to enable comparison of the obtained results.

[0082] Here, the ratio of copper to borate equivalent (BAE) based on weight is calculated based on the copper content in any copper compound and the BAE content in any boron compound, in order to enable comparison of the obtained results.

[0083] Here, the ratio of zinc to borate equivalent (BAE) based on weight is calculated based on the zinc content in any zinc compound and the BAE content in any boron compound, in order to enable comparison of the obtained results.

[0084] Here, the term "boric acid equivalent" refers to the amount of boron converted to boric acid equivalent (BAE) to enable comparison of the obtained results. Boron-containing biocides can contain various levels of boron. To compare various boron-containing biocides, the amount of boron was converted to boric acid equivalent (BAE). In the following example, the boric acid equivalent (BAE) was calculated using the following conversion coefficients:

[0085] [Table 1]

[0086] For example, when borax is retained in a wood block at a concentration of 1,000 ppm, the boric acid equivalent is 1,000 ppm * is 0.646 = 646 ppm.

[0087] Here, when the terms "about," "approximately," or "generally" are used to modify a value, the value can increase or decrease by 10%, and can stay within any range or value between, for example, 7.5%, for example, 5%, for example, 4%, for example, 3%, for example, 2%, for example, 1% or those in between. Further, when the term "substantially free of" is used to describe the amount of a substance in a material, it should not be limited to being completely or entirely free of, but can correspond to the absence of any perceivable or detectable amount of the listed substance in the material. Thus, for example, if the amount of a substance in a material is less than the accuracy of an industrially acceptable device or test for measuring the amount of the substance in the material, the material is "substantially free of" the substance. In certain exemplary embodiments, when the amount of a substance in a material is less than 10 wt%, less than 9 wt%, less than 8 wt%, less than 7 wt%, less than 6 wt%, less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, less than 0.5 wt% or less than 0.1 wt% of the material, the material "substantially cannot contain" the substance.

Mode for Carrying Out the Invention

[0088] [[ID=I4]] The present disclosure is directed to an unexpected synergistic combination of a copper-containing biocide, a zinc-containing biocide, a boron-containing biocide, and at least one organic biocide that provides a highly effective wood preservative composition. Surprisingly, the wood preservative composition prepared according to the present disclosure exhibits a significant synergy between the active ingredients and provides improved bactericidal efficacy against copper-resistant bacteria even at the same or similar total metal-based biocide concentrations. Additionally, the present disclosure has found that when the disclosed composition is utilized in the treatment of wood or wood-based products, the resulting wood or wood-based products exhibit improved properties and improved long-term protection against copper-resistant bacteria in both the core layer and the outer layer of the wood or wood-based products.

[0089] The wood preservative composition of the present invention can be used against a broad spectrum of wood-rotting fungi. Typical wood-rotting fungi include brown rot fungi, white rot fungi, and soft rot fungi. Examples of brown rot fungi include Coniophora puteana, Serpra lacrimans, Fibroporia radiculosa, Fibroporia villanti, Phomitopsis palustris, Gloeophilum trabeum, Gloeophilum sepialium, Lentinum lepideus, Oligoporus placenta, Merulliporia incrassate, Daedarea quercina, Postia placenta, Phaeolus schweinitizii, and Phomitopsis pinicola. Examples of white rot fungi include Trametes versicolor, Faneloccete chrysosporium, Pleurotus ostreatus, Schizophyllum commune, and Irpex lacteus. Examples of soft rot fungi include Chetomium globosum, Lecythophora hoffinannii, Monodichthys putredinis, Fumicola alloparonella, Cephalosporium, Acremonium, and Chetomium.

[0090] Furthermore, this disclosure has found that by incorporating specific amounts of boron-containing biocides and zinc-containing biocides into a biocide metal (copper), a synergistic effect can be demonstrated, combating fungi including copper-resistant bacteria and providing stronger and longer-lasting preservation than previously shown with biocides containing one or more of the above components alone or in amounts other than those specified in this disclosure. For example, copper-containing biocides and zinc-containing biocides may be present in the preservative composition in such quantities that the weight ratio of copper to zinc is provided in the preservative composition in a range or value between approximately 15:1 and approximately 1:5, for example, approximately 12.5:1 and approximately 2:1, for example, approximately 10:1 and approximately 3:1, for example, approximately 9:1 and approximately 4:1, for example, approximately 8:1 and approximately 5:1, for example, approximately 15:1 and approximately 1:5, for example, approximately 15:1 and approximately 1:1, for example, approximately 10:1 and approximately 1:5, for example, approximately 10:1 and approximately 1:2, for example, approximately 10:1 and approximately 1:1, or any range or value in between.

[0091] Similarly, copper-containing biocides and boron-containing biocides may be present in the preservative composition in amounts such that the ratio of copper to boron-containing biocides, expressed as the boric acid equivalent of copper, is provided in the preservative composition, in a ratio of approximately 15:1 to approximately 1:5 by weight, for example, approximately 12.5:1 to approximately 1.5:1, for example, approximately 10:1 to approximately 2:1, for example, approximately 9:1 to approximately 3:1, for example, approximately 8:1 to approximately 4:1, 15:1 to approximately 1:5, 15:1 to approximately 1:1, 10:1 to approximately 1:5, 10:1 to approximately 1:2, 10:1 to approximately 1:1, or any range or value in between thereof. In particular, as discussed above, the disclosure has found that supplementing copper-containing biocides with zinc-containing biocides and boron-containing biocides provides excellent protection against fungi, including copper-resistant fungi.

[0092] For example, this disclosure has found that the combined partial inhibitory concentration of a composition containing copper-containing biocides, zinc-containing biocides, boron-containing biocides, and azoles in the above-mentioned ratios may be less than 1 when tested against target microorganisms, particularly brown rot fungi. The partial inhibitory concentration is calculated as the concentration of a biocide that controls growth in a mixture, divided by the amount of biocide required to control growth when used alone. In particular, here the partial inhibitory concentration is calculated relative to the amount of a composition containing copper and azoles alone required to control the growth of the copper-resistant fungus Fibroporia radiclosa. The partial inhibitory concentration of a biocide can be calculated by dividing the concentration of a biocide that may be due to antimicrobial activity in a mixture of copper-containing biocides, zinc-containing biocides, boron-containing biocides, and azoles when tested against a target microorganism by the minimum inhibitory concentration of the combination of copper-containing biocides and azoles. The minimum inhibitory concentration is the minimum concentration of a biocide that inhibits growth when used alone. According to this disclosure, when targeting specific microorganisms, the combined partial inhibitory concentrations of the first and second biocides, when used in combination with zinc and boron, may be less than approximately 0.9, e.g., less than approximately 0.8, e.g., less than approximately 0.7, which will be discussed in more detail in the following examples. As is well known in the art, any value less than 1 (one) exhibits a synergistic interaction.

[0093] Copper-containing biocides may include any biocide copper compound that provides the copper ratios listed above, but copper-containing biocides may be incorporated into the composition in the form of inorganic copper salts, such as carbonates, bicarbonates, sulfates, nitrates, chlorides, hydroxides, borates, fluorides, or oxides.

[0094] The copper-containing biocides used in the compositions of the present invention include, but are not limited to, known examples such as copper hydroxide, copper(I) oxide, copper(II) oxide, copper carbonate, basic copper carbonate, copper sulfate, basic copper sulfate, copper acetate, copper borate, copper citrate, copper chloride, copper hydroxide, copper oxychloride, copper oleate, copper silicate, copper 8-hydroxyquinolinate, copper dimethyldithiocarbamate, copper omazine, copper naphthenate, cufraneb or copper didimethyldithiocarbamate dichloride, copper salts of fatty acids and rosinic acid, copper ethylenediaminetetraacetate, and copper thiocyanate.

[0095] Alternatively, copper-containing biocides may be in the form of copper complexes, such as N-nitroso-N-cyclohexyl-hydroxylamine-copper (copper-HDO) or copper pyrithione (bis(2-pyridylthio)copper 1,1'-dioxide, CAS number 14915-37-8), copper ethylenediamine complexes, copper triethanolamine complexes, copper diammonium diacetate complexes, and copper ethanolamine complexes.

[0096] Copper-containing biocides may also be in the form of copper(II) ions. For example, forms of copper(II) include basic copper chloride, basic copper carbonate (Cu2(OH)2CO3), copper(II) acetate, ammonium copper carbonate complexes, copper(II) hydroxide, copper(II) oxide, copper oxychloride, copper oxychloride sulfate, ammonium copper complexes, copper citrate chelate, copper gluconate chelate, and copper(II) sulfate pentahydrate.

[0097] In one embodiment, copper is independently selected from the group consisting of copper carbonate, basic copper carbonate, copper hydroxide, or combinations thereof.

[0098] In one embodiment, the copper compound is basic copper carbonate.

[0099] In one embodiment, the copper-containing biocide used in the present invention is in the form of a copper compound having a particle size of 0.01 to 25.0 microns. In one embodiment, the particle size of the micronized copper compound used in the compositions disclosed herein may be 0.01 to 10 microns, 0.05 to 10 microns, 0.1 to 10.0 microns, 0.01 to 1.0 microns, 0.05 to 1.0 microns, 0.1 to 1.0 microns, or 0.2 to 1.0 microns. If more uniform penetration is desired, the particle size of the micronized copper compound used in the compositions disclosed herein may be 0.05 to 1.0 microns.

[0100] In one embodiment, regardless of the type or amount of the selected copper-containing biocide, the copper-containing biocide may exist in a micronized form or in combination with a dispersant. For example, the copper particles may have a particle size D50 of about 25 microns or less, e.g., about 10 microns or less, e.g., about 6 microns or less, e.g., about 5 microns or less, e.g., about 4 microns or less, e.g., about 3 microns or less, e.g., about 2 microns or less, e.g., about 1 micron or less.

[0101] Regardless of the form of the copper-containing biocide, the copper-containing biocide may be present in the composition in an amount of about 1% to about 75% by weight, for example, about 2% to about 45% by weight, for example, about 3% to about 40% by weight, for example, about 4% to about 35% by weight, for example, about 5% to about 32.5% by weight, for example, about 6% to about 30% by weight, for example, about 7.5% to about 27.5% by weight, or any range or value in between.

[0102] The zinc-containing biocides used in the compositions of the present invention include, but are not limited to, known examples such as zinc sulfate, basic zinc sulfate, zinc chloride, basic zinc chloride, zinc bromide, zinc iodide, zinc carbonate, basic zinc carbonate, zinc hydroxide, basic zinc phosphate, basic zinc phosphosulfate, basic zinc nitrate, zinc oxide, zinc naphthenate, zinc trichlorophenoxide, zinc formate, zinc acetate, zinc naphthenate, or zinc pyrithione (bis(2-pyridylthio)zinc 1,1'-dioxide - CAS number 13463-41-7).

[0103] In one embodiment, the zinc-containing biocide can be incorporated into the composition in the form of an inorganic zinc salt, such as an acetate, carbonate, bicarbonate, chloride, hydroxide, borate, oxide, or phosphate; or an organozinc compound, such as a simple organic salt, such as a formate or acetate; or a complex, such as N-nitroso-N-cyclohexyl-hydroxylamine zinc (zinc-HDO), zinc naphthenate, or zinc pyrithione (bis(2-pyridylthio)zinc 1,1'-dioxide - CAS number 13463-41-7).

[0104] In one embodiment, the zinc-containing biocide may include zinc salts, such as zinc salts of organic acids, inorganic acids, or combinations thereof.

[0105] In another embodiment, the zinc-containing biocide is independently selected from the group consisting of zinc oxide, zinc acetate, zinc hydroxide, or combinations thereof.

[0106] In one embodiment, the zinc-containing biocide used in the present invention is in the form of a zinc compound having a particle size of 0.01 to 25.0 microns. In one embodiment, the particle size of the micronized zinc compound used in the compositions disclosed herein may be 0.01 to 10 microns, 0.05 to 10 microns, 0.1 to 10.0 microns, 0.01 to 1.0 microns, 0.05 to 1.0 microns, 0.1 to 1.0 microns, or 0.2 to 1.0 microns. If more uniform penetration is desired, the particle size of the micronized copper compound used in the compositions disclosed herein may be 0.05 to 1.0 microns.

[0107] In one embodiment, regardless of the type or amount of the selected zinc-containing biocide, the zinc-containing biocide may exist in a micronized form, alone or in combination with a dispersant. For example, in one embodiment, the zinc particles may have a particle size D50 of about 25 microns or less, e.g., about 10 microns or less, e.g., about 6 microns or less, e.g., about 5 microns or less, e.g., about 4 microns or less, e.g., about 3 microns or less, e.g., about 2 microns or less, e.g., about 1 micron or less.

[0108] As described in U.S. Patents 4,879,083; 5,763,338; and 5,972,266, zinc borate is known to be used to protect wood or cellulosic products, including particleboard, hardboard, and oriented strandboard, from fungal decay. Solid zinc borate is added to wood composites during manufacturing because its inherently low solubility reduces the leaching of preservatives in high-humidity environments. Examples of such zinc borate compounds include zinc metaborate, diboron trizinc hexaoxide ((Zn2(B(OH)3)3), basic zinc borate, and zinc borate tetrahydrate (2ZnO×3B2O3×3.5H2O). Dev et al. (J Timb. Dev. Assoc., 1997) described a two-step method for treating hardwood with zinc borate, in which the wood is treated with a solution of borax and zinc chloride in two separate steps. However, the high cost of re-treating and re-handling the wood makes such multi-step methods unattractive for commercial use, and zinc borate is not particularly effective against mold.

[0109] However, as will be discussed in more detail below, it should be understood that the use of zinc borate as a zinc-containing biocide does not result in the required ratio of zinc or boric acid equivalents by weight to the preservative composition. In particular, zinc borate alone cannot provide enough zinc to form the copper-to-zinc weight ratio of this disclosure while maintaining the weight ratio of copper to boric acid equivalents by weight. Therefore, when zinc borate is used as a zinc-containing biocide, further zinc compounds must be used together with zinc borate to ensure that a synergistic effect is achieved.

[0110] In one embodiment, regardless of the selected zinc-containing biocide, the zinc-containing biocide may be present in the composition in an amount of about 0.01% to about 50% by weight, for example, about 0.1% to about 45% by weight, for example, about 0.25% to about 40% by weight, for example, about 0.5% to about 35% by weight, for example, about 0.75% to about 32.5% by weight, for example, about 1% to about 30% by weight, for example, about 1.5% to about 27.5% by weight, or any range or value in between, based on the total weight of the composition.

[0111] Copper-containing biocides and zinc-containing biocides may be included in the compositions of the present invention as solubilized metal ions. Suitable methods for solubilizing metal ions, such as copper and zinc, are known in the art, for example, from WO93 / 02557. Suitable complexing agents for copper or zinc ions include, for example, polyphosphates, such as tripolyphosphate; ammonia; water-soluble amines and alkanolamines that can form complexes with copper or zinc cations; and aminocarboxylic acids, such as glycine, glutamic acid, ethylenediaminetetraacetic acid (EDTA), hydroxyethyldiaminetriacetic acid, nitrilotriacetic acid, and N-dihydroxyethylglycine. If the complexing agent is essentially acidic, it can be used either as a free acid or as an alkali metal or ammonium salt thereof. These complexing agents can be used alone or in combination with each other.

[0112] In one embodiment, copper-containing biocides and zinc-containing biocides can form complexes with ammonia, water-soluble amines or alkanolamines, and aminocarboxylic acids selected from the group consisting of amino compounds. Suitable amino compounds for forming complexes with copper-containing biocides and zinc-containing biocides are ammonia, monoethanolamine, and primary, secondary, or tertiary amines, C8-C 14 Alkyl chain, preferably C 12 Alkyl chains are incorporated, such as laurylamine or dimethyllaurylamine.

[0113] In one embodiment, the complexing agent can be independently selected from the group consisting of alkanolamines, such as monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, and tripolamine, or combinations thereof.

[0114] In another embodiment, the complexing agent can be independently selected from the group consisting of ethanolamine, monoethanolamine, or combinations thereof.

[0115] In another embodiment, the complexing agent may be monoethanolamine.

[0116] In another embodiment, the copper-containing biocide may exist as a copper-ammonium complex.

[0117] In another embodiment, the zinc-containing biocide may exist as a zinc-ammonium complex.

[0118] The boron-containing biocides used in the compositions of the present invention include, but are not limited to, well-known soluble and insoluble borates, boric acid, diboron tetrahydroxylate, borates, boron oxides, boranes, perborates, metaborates, tetraborates, octaborates, and borate esters. Preferred boron compounds include, but are not limited to, boranes and borate esters that produce boron oxides in aqueous media. Further examples of boron-containing biocides are metal borates (sodium borate, calcium borate, magnesium borate, zinc borate, potassium borate, copper borate), such as disodium tetraborate decahydrate, disodium octaborate tetrahydrate, sodium metaborate, sodium perborate monohydrate, disodium octaborate, sodium tetraborate pentahydrate, sodium tetraborate, copper metaborate, zinc borate, and barium metaborate. A more suitable boron-containing biocide is bis(2-aminoethyl) borate.

[0119] In one embodiment, the boron-containing biocide is independently selected from the group consisting of boron oxide, boric acid, salts of boric acid, boric acid esters, sodium borate, calcium borate, magnesium borate, zinc borate, disodium octaborate tetrahydrate, copper borate, borosilicate, or combinations thereof.

[0120] In one embodiment, the boron-containing biocide is independently selected from the group consisting of boric acid, boric acid esters, boron oxide, disodium octaborate tetrahydrate, or combinations thereof.

[0121] In one embodiment, the boron-containing biocide is disodium octaborate tetrahydrate.

[0122] In one embodiment, the boron-containing biocide is boric acid.

[0123] In one embodiment, the boron-containing biocide is a boric acid ester selected from trihexylene glycol diborate and general formula (I) B-(OR)3(I) Or general formula (II)

[0124] [ka]

[0125] (In the formula, R is C1~C 18 (Independently selected from the group consisting of alkyl, aryl, or combinations thereof) Compounds having the characteristic can be independently selected from the group consisting of these compounds.

[0126] In one embodiment, the boric acid ester may be trihexylene glycol diborate.

[0127] In one embodiment, boron-containing biocides can also be pulverized and may have one or more of the particle sizes considered herein.

[0128] In one embodiment, the boron-containing biocide may be present in the composition in an amount of about 0.01% to about 75% by weight of the composition, for example, about 0.1% to about 70% by weight of the composition, for example, about 0.25% to about 65% by weight, for example, about 0.5% to about 60% by weight, for example, about 0.75% to about 57.5% by weight, for example, about 1% to about 55% by weight, for example, about 1.5% to about 52.5% by weight, or any range or value in between thereof.

[0129] The preservative composition of the present invention further comprises at least one organic biocide. In one embodiment, the organic biocide is a fungicide.

[0130] The fungicides used in the compositions of the present invention include, but are not limited to, known azoles (including, but not limited to, benzimidazoles, imidazoles, and triazoles), morpholine derivatives, quaternary ammonium compounds, isothiazolones, pyrazolecarboxamides, phenylpyrazoles, haloalkynyl compounds, strobilurins, and phenylsulfamides.

[0131] In one embodiment, the organic biocide can be independently selected from the group consisting of azoles, quaternary ammonium compounds, isothiazolones, pyrazolecarboxamides, phenylpyrazoles, haloalkynyl compounds, or combinations thereof.

[0132] In one embodiment, the organic biocide may contain azoles.

[0133] In one embodiment, the azole fungicide can be independently selected from the group consisting of imidazoles, benzimidazoles, triazoles, or combinations thereof.

[0134] In one embodiment, the organic biocide may contain triazoles.

[0135] In one embodiment, the organic biocide may contain a quaternary ammonium compound.

[0136] In one embodiment, the organic biocide may contain isothiazolones.

[0137] In one embodiment, the organic biocide may include pyrazole carboxamides.

[0138] In one embodiment, the organic biocide may contain phenylpyrazoles.

[0139] In one embodiment, the organic biocide may contain a haloalkynyl compound.

[0140] The azole compound, that is, the compound containing an azole group, may be an imidazole or a 1,2,4-triazole, preferably of general formula (III)

[0141] [ka]

[0142] (In the formula, X is selected independently of CR4 or N. R1 is hydrogen or a linear, branched, cyclic, aromatic, saturated or unsaturated, substituted or unsubstituted C1-C 40 Independently selected from groups consisting of bases or combinations thereof, Therefore, any of the carbon atoms other than those bonded to the nitrogen atom shown in formula (A) may be replaced by the heteroatom which is substituted in some cases. R2 is hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C5-C 10 Aryl, C5~C 10 Independently selected from the group consisting of heteroaryls or C1-C4 alkylcarbamates, R3 and R4 are hydrogen, or R3 and R4 together may provide a benzimidazole group. It is represented as follows.

[0143] In one embodiment, the azole compound may be an imidazole.

[0144] Imidazole compounds incorporate a five-membered diunsaturated ring consisting of three carbon atoms and two nitrogen atoms at non-adjacent positions.

[0145] In one embodiment, the imidazole compound can be independently selected from the group consisting of 1-[2-(2,4-dichlorophenyl)-2-(2-propene-1-yloxy)ethyl]-1H-imidazole (imazalil), N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]-1H-imidazole-1-carboxamide (prochloraz), or combinations thereof.

[0146] In one embodiment, the imidazole compound may be a benzimidazole.

[0147] In one embodiment, benzimidazoles can be independently selected from the group consisting of 2-(4-thiazolyl)-1H-benzimidazole (thiabendazole), methyl N-1H-benzimidazole-2-ylcarbamate (carbendazim), 2-(2-furanyl)-1H-benzimidazole (fuberidazole), or combinations thereof.

[0148] In one embodiment, the azole compound may be a 1,2,4-triazole compound.

[0149] 1,2,4-triazole compounds incorporate a five-membered diunsaturated ring consisting of three nitrogen atoms and two carbon atoms at non-adjacent positions.

[0150] In one embodiment, the 1,2,4-triazole compound is of formula (IV)

[0151] [ka]

[0152] (In the formula, R5 is independently selected from the group consisting of branched or linear C1-C5 alkyl groups (e.g., t-butyl). R is independently selected from the group consisting of a halogen (e.g., chlorine, fluorine, or bromine) atom or a phenyl group optionally substituted with one or more substituents selected from C1-C3 alkyl (e.g., methyl), C1-C3 alkoxy (e.g., methoxy), phenyl, or nitro groups. These compounds can be independently selected.

[0153] In another embodiment, the 1,2,4-triazole compound is of formula (V)

[0154] [ka]

[0155] (In the formula, R7 is independently selected from the group consisting of a halogen (e.g., chlorine, fluorine, or bromine) atom or a phenyl group optionally substituted with one or more substituents selected from C1-C3 alkyl (e.g., methyl), C1-C3 alkoxy (e.g., methoxy), phenyl, or nitro groups. R8 is independently selected from the group consisting of a hydrogen atom or a branched or linear C1-C8 alkyl group (e.g., methyl, ethyl, propyl, etc.). These compounds can be independently selected.

[0156] The 1,2,4-triazole compounds used in the compositions of the present invention include, for example, 1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole (azaconazole), 1-[[4-bromo-2-(2,4-dichlorophenyl)tetrahydro-2-furanyl]methyl]-1H-1,2,4-triazole (bromoconazole), α-(4-chlorophenyl)-α-(1-cyclopropylethyl)-1H-1,2,4-triazole-1-ethanol (cyproconazole), (2RS,3RS)-1-( 2,4-Dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazole-1-yl)pentan-3-ol (diclobutrazol), 1-[[2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole (difenoconazole), (E)-(RS)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazole-1-yl)penta-1-en-3-ol (diniconazole), (E)-(R)-1- (2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazole-1-yl)penta-1-en-3-ol (diconazole-M), (2RS,3SR)-1-[3-(2-chlorophenyl)-2,3-epoxy-2-(4-fluorophenyl)propyl]-1H-1,2,4-triazole (epoxyconazole), 1-[[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole (etaconazole), α-[2-(4-chlorophenyl)ethyl ]-α-phenyl-1H-1,2,4-triazole-1-propanenitrile (fenbuconazole), 3-(2,4-dichlorophenyl)-6-fluoro-2-(1H-1,2,4-triazole-1-yl)quinazoline-4(3H)-one (fluquinconazole), 1-[[bis(4-fluorophenyl)methylsilyl]methyl]-1H-1,2,4-triazole (flusilazole), α-(2-fluorophenyl)-α-(4-fluorophenyl)-1H-1,2,4-triazole-1-ethanol (flutriafole), 1-[[2-(2,4-Dichlorophenyl)tetrahydro-5-(2,2,2-trifluoroethoxy)-2-furanyl]methyl]-1H-1,2,4-triazole (fluconazole), (2RS,5RS)-5-(2,4-dichlorophenyl)tetrahydro-5-(1H-1,2,4-triazole-1-ylmethyl)-2-furyl 2,2,2-trifluoroethyl ether (fluconazole-cis), α-butyl-α-(2,4-dichlorophenyl)-1H-1,2,4-triazole-1-ethanol (hexaconazole), (4-chlorophenyl)methyl N-(2,4-dichlorophenyl)-1H-1,2,4-triazole-1-ethaneimidothioate (imibenconazole), 2-[(4-chlorophenyl)methyl]-5-(1-methylethyl)-1-(1H-1,2,4-triazole-1-ylmethyl)cyclopentanol (ipconazole), 5-[(4-chlorophenyl)methyl]-2,2-dimethyl-1-(1H-1,2,4-triazole-1-ylmethyl)cyclopentanol (methconazole), α-butyl-α-(4-chlorophenyl)-1H-1,2,4-triazole -1-Propanenitrile (microbutanil), 1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole (penconazole), 1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole (propiconazole), 2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-3H-1,2,4-triazole-3-thion (prothioconazole), 3-(2,4-dichloro (Lofenyl)-2-(1H-1,2,4-triazol-1-yl)-4(3H)-quinazolinone (quinconazole), α-(4-fluorophenyl)-α-[(trimethylsilyl)methyl]-1H-1,2,4-triazol-1-ethanol (simeconazole), α-[2-(4-chlorophenyl)ethyl]-α-(1,1-dimethylethyl)-1H-1,2,4-triazol-1-ethanol (tebuconazole), 1-[2-(2,4-dichlorophenyl)-3-(1,1,2,2-tetrafluoroethoxy)propyl]-1H-1,2,4-Triazole (Tetraconazole), 1-(4-Chlorophenoxy)-3,3-Dimethyl-1-(1H-1,2,4-Triazole-1-yl)-2-Butanone (Triadimefon), β-(4-Chlorophenoxy)-α-(1,1-Dimethylethyl)-1H-1,2,4-Triazole-1-ethanol (Triadimenol), (5E)-5-[(4-Chlorophenyl)methylene]-2,2-Dimethyl-1-(1H-1,2,4-Triazole-1- Ilmethyl)cyclopentanol (triconazole), (βE)-β-[(4-chlorophenyl)methylene]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol (uniconazole), and (αS,βE)-β-[(4-chlorophenyl)methylene]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol (uniconazole-P) are known and include, but are not limited to, these.

[0157] In one embodiment, the 1,2,4-triazole fungicide can be independently selected from the group consisting of cyproconazole, fenbuconazole, propiconazole, tebuconazole, triadimefon, triticonazole, or combinations thereof.

[0158] In one embodiment, the azole fungicide can be independently selected from the group consisting of tebuconazole, propiconazole, or a combination thereof.

[0159] In one embodiment, the azole fungicide can be selected from tebuconazole.

[0160] In one embodiment, the azole fungicide can be selected from propiconazole.

[0161] In one embodiment, the preservative composition of the present disclosure may contain one or more azole compounds, such as a mixture of imidazoles and 1,2,4-triazoles, or a mixture of two or more 1,2,4-triazoles. The use of a mixture of azoles may enable a broader range of activity against fungi in some embodiments.

[0162] In another embodiment, the preservative compositions of the present disclosure utilize one or more 1,2,4-triazoles alone or in combination with imidazoles.

[0163] In one embodiment, when a mixture of propiconazole and tebuconazole is used, propiconazole and tebuconazole are used in the mixture in a weight ratio of propiconazole to tebuconazole of about 1:10 to about 10:1, for example, about 1:5 to about 5:1, for example, about 1:1 to 5:1, for example, about 3:1, or any range or value in between thereof.

[0164] Regardless of the selected azoles, azoles may be present in the preservative composition in amounts of about 0.01% to about 20% by weight, for example, about 0.1% to about 18% by weight, for example, about 0.25% to about 16% by weight, for example, about 0.5% to about 15% by weight, for example, about 0.75% to about 14% by weight, for example, about 0.9% to about 12.5% ​​by weight, or any range or value in between.

[0165] In one embodiment, regardless of the type or amount of selected azoles, the azoles may exist in a finely powdered form, either alone or in combination with a dispersant. For example, in this embodiment, the azole particles have a particle size D50 of about 25 microns or less, e.g., about 10 microns or less, e.g., about 6 microns or less, e.g., about 5 microns or less, e.g., about 4 microns or less, e.g., about 3 microns or less, e.g., about 2 microns or less, e.g., about 1 micron or less.

[0166] The pyrazole carboxamides used in the compositions of the present invention include, for example, N-(3',4'-dichloro-5-fluoro[1,1'-biphenyl]-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (benzovindiflupyr), N-(3',4'-dichloro-5-fluoro[1,1'-biphenyl]-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (bixafen), and N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3- (Difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (fluveneteram), 3-(difluoromethyl)-N-(7-fluoro-2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-1-methyl-1H-pyrazole-4-carboxamide (fluindapyr), 5-chloro-N-(1,3-dihydro-1,1,3-trimethyl-4-isobenzofuranyl)-1,3-dimethyl-1H-pyrazole-4-carboxamide (flamethopyr), 3-(difluoromethyl)-1-methyl-N-(3',4',5 '-Trifluoro[1,1'-biphenyl]-2-yl)-1H-pyrazole-4-carboxamide (fluxapyroxade), N-[[5-chloro-2-(1-methylethyl)phenyl]methyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (isoflucipram), 3-(difluoromethyl)-1-methyl-N-[1,2,3,4-tetrahydro-9-(1-methylethyl)-1,4-methanonaphthalene-5-yl]-1H-pyrazole-4-carboxamide (isopi Razam), N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide (penflufen), N-[2-(1,3-dimethylbutyl)-3-thienyl]-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide (penthiopyrad), 3-(difluoromethyl)-N-methoxy-1-methyl-N-[1-methyl-2-(2,4,6-trichlorophenyl)ethyl]-1H-pyrazole-4-carboxamide (pidiflumetofen), N-[2-[1,1'-Bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (sedaxane) is known and is included, but is not limited to.

[0167] In one embodiment, pyrazole carboxamides may be penflufen.

[0168] The isothiazolones used in the compositions of the present invention include, for example, 2-methyl-4-isothiazolin-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 4,5-dichloro-2n-octylisothiazolin-3-one (DCOIT), 5-chloro-2n-octyl-4-isothiazolin-3-one (COIT), and 4,5-dichloro-2-cyclohexyl-4-isothiazolin -3-one, 2-octyl-2H-isothiazolin-3-one (OIT), 1,2-benzothiazolin-3-one (BIT), N-methyl-1,2-benzisothiazolin-3-one (MBIT), 2-butyl-1,2-benzisothiazolin-3(2H)-one (BBIT), and 2-methyl-4,5-trimethylene-4-isothiazolin-3-one are known and include, but are not limited to, these.

[0169] In one embodiment, isothiazolones can be independently selected from the group consisting of 2-methyl-4-isothiazolin-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 4,5-dichloro-2n-octylisothiazolin-3-one (DCOIT), 5-chloro-2n-octyl-4-isothiazolin-3-one (COIT), 4,5-dichloro-2-cyclohexyl-4-isothiazolin-3-one, 2-octyl-2H-isothiazolin-3-one (OIT), 1,2-benzothiazolin-3-one (BIT), N-methyl-1,2-benzisothiazolin-3-one (MBIT), or 2-butyl-1,2-benzisothiazolin-3(2H)-one (BBIT), or combinations thereof.

[0170] In one embodiment, isothiazolones can be independently selected from the group consisting of 2-methyl-4-isothiazolin-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 4,5-dichloro-2n-octylisothiazolin-3-one (DCOIT), 2-octyl-2H-isothiazolin-3-one (OIT), or combinations thereof.

[0171] In one embodiment, the isothiazolone is 4,5-dichloro-2n-octylisothiazolin-3-one (DCOIT).

[0172] The quaternary ammonium compounds used in the compositions of the present invention include, but are not limited to, known tetraalkylammonium salts, trialkylarylammonium salts, trialkylammonium oxide salts, or combinations thereof.

[0173] The quaternary ammonium compound used in the composition of the present invention is, for example, general formula (VI) NR1R2R3R4-X(VI) (In the formula, R1, R2, R3, and R4 are linear, branched, saturated, or unsaturated C1-C12 18 Alkyl, C1-C 18 Alkenyl, C1~C 18 Alkynyl, C1-C4 hydroxyalkyl, C2-C5 hydroxyalkenyl, C2-C5 hydroxyalkynyl, C5-C 12 Aryl, C5~C 12 Independently selected from the group consisting of aralkyl and C3-C5 hydroxyaryl compounds, X is independently selected from halogens, carbonates, bicarbonates, hydroxides, and boric acid. Quaternary ammonium compounds having or combinations thereof are known, including but not limited to these.

[0174] In one embodiment, the quaternary ammonium compound is R1, R2, R3, and R4 are independently selected from the group consisting of methyl, ethyl, octyl, decyl, and didecyl. X is independently selected from halogens, carbonates, bicarbonates, hydroxides, and boric acid. A compound is independently selected from the group consisting of compounds of formula (VI) or combinations thereof.

[0175] The quaternary ammonium compounds used in the compositions of the present invention include, for example, trimethylalkyl quaternary ammonium compounds, such as cocotrimethylammonium chloride; dialkyldimethyl quaternary ammonium compounds, such as didecyldimethylammonium chloride, didecyldimethylammonium carbonate, didecyldimethylammonium bicarbonate, dioctyldimethylammonium chloride, and octyldecyldimethylammonium chloride, or mixtures thereof; alkyldimethyl or diethylbenzylammonium salts, such as benzalkonium chloride and benzalkonium hydroxide; and polyethoxylated quaternary ammonium compounds, such as N,N-didecyl-N-methyl-poly(oxyethyl)ammonium propionate (Bardap 26) or N,N-didecyl-N-methyl-poly(oxyethyl)ammonium lactate; monoalkylmethylbisalkoxylated quaternary ammonium compounds, e.g., ethoxylated forms of cocoalkylmethylbis(hydroxyethyl)ammonium chloride; dialkylbisalkoxylated quaternary ammonium compounds, e.g., ethoxylated forms of didecylbis(hydroxyethyl)ammonium hydroxide; additive compounds such as didecylbis(hydroxyethyl)ammonium borate, also called betaine polymers, e.g., boron-containing compounds, e.g., quaternary ammonium compounds that form complexes with boric acid, are known and include, but are not limited to, these.

[0176] In one embodiment, the quaternary ammonium compound can be independently selected from the group consisting of benzalkonium chloride, didecylbis(hydroxyethyl)ammonium borate, didecyldimethylammonium chloride, didecyldimethylammonium carbonate, didecyldimethylammonium bicarbonate, or a combination thereof.

[0177] In one embodiment, the quaternary ammonium compound can be independently selected from the group consisting of benzalkonium chloride, didecyldimethylammonium chloride, didecyldimethylammonium carbonate, didecyldimethylammonium bicarbonate, or combinations thereof.

[0178] In one embodiment, the quaternary ammonium compound can be independently selected from the group consisting of didecyldimethylammonium chloride, didecyldimethylammonium carbonate, didecyldimethylammonium bicarbonate, or combinations thereof.

[0179] In another embodiment, the quaternary ammonium compound can be independently selected from the group consisting of didecyldimethylammonium carbonate, didecyldimethylammonium bicarbonate, or combinations thereof.

[0180] The haloalkynyl compound used in the composition of the present invention is of the following formula (VII)

[0181] [ka]

[0182] (In the formula, R is hydrogen, substituted and unsubstituted C1-C 20 Alkyl alkyl groups, substituted and unsubstituted C6-C 20 Aryl, C6~C 20 Alkylaryl and C6-C 20 Aralkil, C3~C 10 Cycloalkyl or C3-C 10 Independently selected from the group consisting of cycloalkenyls, (m and n are independent integers between 1 and 3.) These are known as iodopropynylcarbamates or carbamic acid esters or combinations thereof, and are generally referred to as such.

[0183] In one embodiment, iodopropynylcarbamates are of formula (VIII)

[0184] [ka]

[0185] (In the formula, R is independently selected from the group consisting of methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, cyclohexyl, phenyl, benzyl, tolyl, cumyl, chlorobutyl, chlorophenyl, ethoxyphenyl, or combinations thereof. These compounds can be independently selected.

[0186] In one embodiment, the iodopropynyl compound can be independently selected from the group consisting of 3-iodo-2-propynylpropylcarbamate, 3-iodo-2-propynylbutylcarbamate, 3-iodo-2-propynylhexylcarbamate, 3-iodo-2-propynylcyclohexylcarbamate, 3-iodo-2-propynylphenylcarbamate, or a combination thereof.

[0187] In another embodiment, the iodopropynyl compound may be 3-iodo-2-propynylbutylcarbamate (IPBC).

[0188] Furthermore, the preservative composition may also include a dispersant and / or solvent. The dispersant and / or solvent may be alkanolamines, such as monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, and tripolanolamine. In one embodiment, the dispersant and / or solvent is ethanolamine, such as monoethanolamine. However, it should be understood that other dispersants and / or solvents known in the art may be used. As a specific example, the dispersants and / or solvents listed above may be solvents for boric acid in certain exemplary embodiments.

[0189] Additionally or alternatively, dispersants may complex with some or all of one or more components of a preservative composition. For example, a dispersant may complex with at least some or any combination thereof of organic biocides, copper-containing biocides, or zinc-containing biocides. However, in one embodiment, it should be understood that at least some of the dispersants may be “free” in solution, in the sense that at least some do not complex with other components.

[0190] Additionally or alternatively, the dispersant may complex with at least some of azoles, copper-containing biocides, zinc-containing biocides, or any combination thereof. However, in one embodiment, it should be understood that at least some of the dispersant may be “free” in solution, in the sense that at least some of it does not complex with other components.

[0191] The above combinations of copper-containing biocides, zinc-containing biocides, boron-containing biocides, and one or more organic biocides can be used individually as preservative compositions.

[0192] However, in one embodiment, the preservative composition may include one or more further second organic co-biocides selected from fungicides (fungicidal wood decay preservatives) or insecticides, the second organic biocides may be other than those described above.

[0193] For example, suitable organic fungicidal wood decay preservatives for use in the preservative compositions of this disclosure include fungicidal amides, e.g., prochloraz, diclofluanide and tolfluanide; fungicidal aromatic compounds, e.g., chlorothalonil, cresol, dichlorane, pentachlorophenol, sodium pentachlorophenol, 2-(thiocyanatomethylthio)-1,3-benzothiazole (TCMBC), dichlorophene, fludioxonil and 8-hydroxyquinoline; fungicidal heterocyclic compounds, e.g., dazomet, fenpropimorph, bethoxazine and dehydroacetic acid; strobilurins, e.g., azoxystrobin; pyraclostrobin; fluazinam; quaternary ammonium compounds; isothiazolone; pyrithione; and mixtures thereof.

[0194] In one embodiment, the preservative composition may include one or more further fungicidal wood decay preservatives independently selected from the group consisting of azoles, quaternary ammonium compounds, isothiazolones, pyrithiones, or combinations thereof.

[0195] In one embodiment, further fungicidal wood decay preservatives are the azoles defined above.

[0196] In one embodiment, a further fungicidal wood decay preservative is a quaternary ammonium compound as defined above.

[0197] In one embodiment, a further fungicidal wood decay preservative is the isothiazolone compound defined above.

[0198] In one embodiment, further fungicidal wood decay preservatives are pyrithiones independently selected from the group consisting of sodium pyrithione, zinc pyrithione, copper pyrithione, 1-hydroxy-2-pyridinone, and pyrithione disulfide or mixtures thereof.

[0199] In one embodiment, the preservative composition may include one or more further organic biocides selected from insecticides.

[0200] Insecticides that can be used in the compositions of the present invention include, but are not limited to, pyrethroids, neonicotinoids, organophosphates, and borates, which are known to exist.

[0201] In one embodiment, the insecticide that can be used in the composition of the present invention is independently selected from pyrethroids, neonicotinoids, organophosphates, borates, or combinations thereof.

[0202] In one embodiment, the insecticide that can be used in the composition of the present invention is pyrethroids.

[0203] Examples of pyrethroid compounds that can be used in the wood preservative composition of the present invention include acrinatrin, arethrin, bioarethrin, barthrin, bifenthrin, bioetanomethrin, ciclethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, dimefluthrin, dimethrin, empenthrin, fenfluthrin, fenpyritrin, fenpropathrin, Fenvalerate, esfenvalerate, flucitrinate, fluvalinate, tau-fluvalinate, frethrin, imiprothrin, metofluthrin, permethrin, biopermethrin, transpermethrin, phenothrin, prallethrin, profluthrin, pyrethmethrin, resmethrin, bioresmethrin, cismethrin, tefluthrin, teralethrin, tetramethrin, tralomethrin, transfluthrin, etofenprox, flufenprox, halfenprox, protrefenbut, and silafluofen are known and include, but are not limited to, these.

[0204] In one embodiment, the pyrethroid compound can be independently selected from the group consisting of bifenthrin, cypermethrin, permethrin, or mixtures thereof.

[0205] In one embodiment, the pyrethroid compound can be independently selected from the group consisting of bifenthrin, permethrin, or mixtures thereof.

[0206] In one embodiment, the insecticide that can be used in the composition of the present invention is neonicotinoids.

[0207] Examples of neonicotinoid compounds that can be used in the wood preservative composition of the present invention include (1E)-N-[(6-chloro-3-pyridinyl)methyl]-N'-cyano-N-methylethaneimidoamide (acetamiprid), (E)-1-[(2-chlorothiazol-5-yl)methyl]-3-methyl-2-nitroguanidine (clothianidin), (2E)-1-[(6-chloro-3-pyridinyl)methyl]-N-nitro-2-imidazolidinimine (imidacloprid), and (1E)-N-[(6-chloro-3-pyridinyl)methyl] -N-ethyl-N'-methyl-2-nitro-1,1-ethendiamine (nitenpyram), tetrahydro-2-(nitromethylene)-2H-1,3-thiazine (nithiazine), (Z)-[3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]cyanamide (thiacloprid), and 3-[(2-chloro-5-thiazolyl)methyl]tetrahydro-5-methyl-N-nitro-4H-1,3,5-oxadiazine-4-imine (thiamethoxam) are known and include, but are not limited to, these.

[0208] In one embodiment, the neonicotinoid compound may be imidacloprid.

[0209] In one embodiment, the insecticide that can be used in the composition of the present invention may include organophosphates.

[0210] In one embodiment, the insecticides that can be used in the composition of the present invention may include borates.

[0211] In another embodiment, the boric acid compound may be disodium octaborate tetrahydrate (DOT).

[0212] Nevertheless, if present, further organic biocides selected from fungicides (fungicidal wood decay preservatives) or insecticides may be present in amounts of about 10% by weight or less of the composition, for example, about 9% by weight or less, for example, about 8% by weight or less, for example, about 7% by weight or less, for example, about 6% by weight or less, for example, about 5% by weight or less, for example, about 4% by weight or less, for example, about 3% by weight or less, for example, about 2% by weight or less, for example, about 1% by weight or less, for example, about 0.5% by weight or less.

[0213] However, as discussed above, it should be understood that, due to the unexpected synergies of the preservative compositions of this disclosure, the preservative compositions may not, in whole, contain any one or a combination of further organic fungicidal preservatives.

[0214] Furthermore, the preservative composition may include a solvent, surfactant, diluent, emulsifier, or a combination thereof.

[0215] For example, the amounts and ratios referenced above correspond to preservative compositions that can be considered as concentrates. Whether or not the preservative composition exists as a concentrate, it may contain solvents, surfactants, or combinations thereof, which are present in the preservative composition in amounts sufficient to stabilize and maintain the “active” components discussed above in their dispersed or solubilized forms.

[0216] In particular, the preservative composition can be considered as a concentrate existing in the form of a liquid composition. However, in one embodiment, it should be understood that there is no solvent and the preservative composition may be a solid embedding or paste. However, in one embodiment, the preservative composition is in the form of an emulsion consisting of solubilized droplets. Preferably, the emulsion is in the form of a microemulsion. Those skilled in the art of producing emulsions will know of methods for producing emulsions according to the present invention by using suitable solvents and emulsifiers.

[0217] The preservative composition may be an aqueous solution, but one or more organic solvents or mixtures of water and organic solvents can also be used. Suitable organic solvents include both aromatic and aliphatic hydrocarbon solvents, such as volatile oils, petroleum distillates, kerosene, diesel oil, and naphtha. In addition, glycol ethers, benzyl alcohol, 2-phenoxyethanol, methyl carbitol, propylene carbonate, benzyl benzoate, ethyl lactate, and 2-ethylhexyl lactate can be used alone or in combination with water.

[0218] If the solvent is present in the preservative composition, it may be present in an amount of about 0.1% to about 85% by weight, for example, about 2% to about 80% by weight, for example, about 3% to about 75% by weight, for example, about 4% to about 70% by weight, for example, about 5% to about 65% by weight, for example, about 6% to about 60% by weight, for example, about 7% to about 55% by weight, for example, about 8% to about 50% by weight, for example, about 9% to about 45% by weight, for example, about 10% to about 40% by weight, or any range or value in between. Of course, as stated above, in one embodiment, the preservative composition in the form of a concentrate may not contain the solvent at all and may therefore be in the form of a solid or a paste.

[0219] In one embodiment, the preservative composition comprises, based on the total weight of the wood preservative composition, about 1% to about 75% by weight of a copper-containing biocide, about 0.1% to about 50% by weight of a zinc-containing biocide, about 0.1% to about 75% by weight of boric acid, about 0.1% to about 20% by weight of an organic fungicide, with the remainder being a solvent, surfactant, emulsifier, an optional component (including further organic fungicidal preservatives), or a combination thereof.

[0220] For example, in another embodiment, the preservative composition comprises, based on the total weight of the wood preservative composition, about 1% to about 50% by weight of a copper-containing biocide, about 0.1% to about 75% by weight of a zinc-containing biocide, about 0.1% to about 75% by weight of boric acid, about 0.1% to about 20% by weight of azoles, with the remainder being a solvent, a surfactant, an emulsifier, an optional component (including further organic fungicidal or insecticidal preservatives or combinations thereof) or a combination thereof.

[0221] In another embodiment, the preservative composition comprises, based on the total weight of the wood preservative composition, about 1% to about 75% by weight of a copper-containing biocide, about 0.1% to about 50% by weight of a zinc-containing biocide, about 0.1% to about 75% by weight of boric acid, about 0.1% to about 20% by weight of a quaternary ammonium compound, with the remainder being a solvent, surfactant, emulsifier, optional components (including further organic fungicidal or insecticidal preservatives or combinations thereof) or combinations thereof.

[0222] In another embodiment, the preservative composition comprises, based on the total weight of the wood preservative composition, about 1% to about 75% by weight of a copper-containing biocide, about 0.1% to about 50% by weight of a zinc-containing biocide, about 0.1% to about 75% by weight of boric acid, about 0.1% to about 20% by weight of isothiazolones, with the remainder being a solvent, surfactant, emulsifier, an optional component (including further organic fungicidal or insecticidal preservatives or combinations thereof) or a combination thereof.

[0223] In another embodiment, the preservative composition comprises, based on the total weight of the wood preservative composition, about 1% to about 75% by weight of a copper-containing biocide, about 0.1% to about 50% by weight of a zinc-containing biocide, about 0.1% to about 75% by weight of boric acid, about 0.1% to about 20% by weight of pyrazole carboxamides, with the remainder being a solvent, surfactant, emulsifier, optional components (including further organic fungicidal or insecticidal preservatives or combinations thereof) or combinations thereof.

[0224] In another embodiment, the preservative composition comprises, based on the total weight of the wood preservative composition, about 1% to about 75% by weight of a copper-containing biocide, about 0.1% to about 50% by weight of a zinc-containing biocide, about 0.1% to about 75% by weight of boric acid, about 0.1% to about 20% by weight of an iodopropynyl compound, with the remainder being a solvent, a surfactant, an emulsifier, an optional component (including further organic fungicidal or insecticidal preservatives or combinations thereof) or a combination thereof.

[0225] In another embodiment, the preservative composition comprises, based on the total weight of the wood preservative composition, about 5% to about 45% by weight of a copper-containing biocide, about 0.75% to about 32.5% by weight of a zinc-containing biocide, about 0.75% to about 32.5% by weight of boric acid, about 0.5% to about 15% by weight of an organic biocide, with the remainder being a solvent, surfactant, emulsifier, an optional component (including further organic fungicidal or insecticidal preservatives or combinations thereof) or a combination thereof.

[0226] In another embodiment, the preservative composition comprises, based on the total weight of the wood preservative composition, about 5% to about 45% by weight of a copper-containing biocide, about 0.75% to about 32.5% by weight of a zinc-containing biocide, about 0.75% to about 32.5% by weight of boric acid, about 0.5% to about 15% by weight of azoles, with the remainder being a solvent, surfactant, emulsifier, an optional component (including further organic fungicidal or insecticidal preservatives or combinations thereof) or a combination thereof.

[0227] In another embodiment, the preservative composition comprises, based on the total weight of the wood preservative composition, about 5% to about 45% by weight of a copper-containing biocide, about 0.75% to about 32.5% by weight of a zinc-containing biocide, about 0.75% to about 32.5% by weight of boric acid, about 0.5% to about 15% by weight of a quaternary ammonium compound, with the remainder being a solvent, surfactant, emulsifier, optional components (including further organic fungicidal or insecticidal preservatives or combinations thereof) or combinations thereof.

[0228] In another embodiment, the preservative composition comprises, based on the total weight of the wood preservative composition, about 5% to about 45% by weight of a copper-containing biocide, about 0.75% to about 32.5% by weight of a zinc-containing biocide, about 0.75% to about 32.5% by weight of boric acid, about 0.5% to about 15% by weight of isothiazolones, with the remainder being a solvent, surfactant, emulsifier, optional components (including further organic fungicidal or insecticidal preservatives or combinations thereof) or combinations thereof.

[0229] In another embodiment, the preservative composition comprises, based on the total weight of the wood preservative composition, about 5% to about 45% by weight of a copper-containing biocide, about 0.75% to about 32.5% by weight of a zinc-containing biocide, about 0.75% to about 32.5% by weight of boric acid, about 0.5% to about 15% by weight of pyrazole carboxamides, with the remainder being a solvent, surfactant, emulsifier, optional components (including further organic fungicidal or insecticidal preservatives or combinations thereof) or combinations thereof.

[0230] In another embodiment, the preservative composition comprises, based on the total weight of the wood preservative composition, about 5% to about 45% by weight of a copper-containing biocide, about 0.75% to about 32.5% by weight of a zinc-containing biocide, about 0.75% to about 32.5% by weight of boric acid, about 0.5% to about 15% by weight of an iodopropynyl compound, with the remainder being a solvent, surfactant, emulsifier, an optional component (including further organic fungicidal or insecticidal preservatives or combinations thereof) or a combination thereof.

[0231] In addition or alternatively, in another embodiment, the preservative composition comprises, based on the total weight of the wood preservative composition, about 7.5% to about 27.5% by weight of a copper-containing biocide, about 1.5% to about 27.5% by weight of a zinc-containing biocide, about 1.5% to about 52.5% by weight of boric acid, about 0.9% to about 12.5% ​​by weight of an organic biocide, with the remainder being a solvent, surfactant, emulsifier, an optional component (including further organic fungicidal preservatives) or a combination thereof.

[0232] In addition or alternatively, in another embodiment, the preservative composition comprises, based on the total weight of the wood preservative composition, about 7.5% to about 27.5% by weight of a copper-containing biocide, about 1.5% to about 27.5% by weight of a zinc-containing biocide, about 1.5% to about 52.5% by weight of boric acid, about 0.9% to about 12.5% ​​by weight of azoles, with the remainder being a solvent, surfactant, emulsifier, an optional component (including further organic fungicidal preservatives) or a combination thereof.

[0233] In addition or alternatively, in another embodiment, the preservative composition comprises, based on the total weight of the wood preservative composition, about 7.5% to about 27.5% by weight of a copper-containing biocide, about 1.5% to about 27.5% by weight of a zinc-containing biocide, about 1.5% to about 52.5% by weight of boric acid, about 0.9% to about 12.5% ​​by weight of a quaternary ammonium compound, with the remainder being a solvent, surfactant, emulsifier, an optional component (including further organic fungicidal preservatives) or a combination thereof.

[0234] In addition or alternatively, in another embodiment, the preservative composition comprises, based on the total weight of the wood preservative composition, about 7.5% to about 27.5% by weight of a copper-containing biocide, about 1.5% to about 27.5% by weight of a zinc-containing biocide, about 1.5% to about 52.5% by weight of boric acid, about 0.9% to about 12.5% ​​by weight of isothiazolones, with the remainder being a solvent, surfactant, emulsifier, an optional component (including further organic fungicidal preservatives) or a combination thereof.

[0235] In addition or alternatively, in another embodiment, the preservative composition comprises, based on the total weight of the wood preservative composition, about 7.5% to about 27.5% by weight of a copper-containing biocide, about 1.5% to about 27.5% by weight of a zinc-containing biocide, about 1.5% to about 52.5% by weight of boric acid, about 0.9% to about 12.5% ​​by weight of pyrazole carboxamides, with the remainder being a solvent, surfactant, emulsifier, an optional component (including further organic fungicidal preservatives) or a combination thereof.

[0236] In addition or alternatively, in another embodiment, the preservative composition comprises, based on the total weight of the wood preservative composition, about 7.5% to about 27.5% by weight of a copper-containing biocide, about 1.5% to about 27.5% by weight of a zinc-containing biocide, about 1.5% to about 52.5% by weight of boric acid, about 0.9% to about 12.5% ​​by weight of an iodopropynyl compound, with the remainder being a solvent, surfactant, emulsifier, an optional component (including further organic fungicidal preservatives) or a combination thereof.

[0237] The preservative composition may be diluted with one or more diluents before use. The diluents may be one or more solvents as further discussed, or other diluents known in the art. In any case, the diluents may be added to the preservative composition in a ratio of about 300:1 to about 1:1 by weight, e.g., about 100:1 to about 1:1, e.g., about 75:1 to about 2:1, e.g., about 50:1 to about 3:1, e.g., about 40:1 to about 4:1, e.g., about 20:1 to about 5:1, or any range or value in between. Therefore, the preservative composition may be present in the ready-to-use formulation in an amount of about 20% by weight or less, for example, about 15% by weight or less, for example, about 10% by weight or less, for example, about 7.5% by weight or less, for example, about 5% by weight or less, for example, about 2.5% by weight or less, for example, about 2% by weight or less, for example, about 1.5% by weight or less, for example, about 1% by weight or less, for example, about 0.1% by weight or any range or value in between.

[0238] In other words, the diluent may be present in a ready-to-use formulation (e.g., a diluted preservative formulation) in an amount such that the copper-containing biocide is present in an amount such that it Boron-containing biocides may be present in ready-to-use formulations in amounts of approximately 1% by weight or less, e.g., approximately 0.5% or less, e.g., approximately 0.1% or less, e.g., approximately 750 ppm or less, e.g., approximately 500 ppm or less, e.g., approximately 400 ppm or less, e.g., approximately 200 ppm or less, e.g., approximately 100 ppm or less, or any value or range in between. One or more organic biocides may be present in ready-to-use formulations in amounts of approximately 1% by weight or less, e.g., approximately 0.5% or less, e.g., approximately 0.1% or less, e.g., approximately 750 ppm or less, e.g., approximately 500 ppm or less, e.g., approximately 400 ppm or less, e.g., approximately 200 ppm or less, e.g., approximately 100 ppm or less, e.g., approximately 50 ppm or less, e.g., approximately 5 ppm or less, or any value or range in between.

[0239] Preservative compositions or ready-to-use formulations may have a pH of about 3 to about 10, for example, about 3.5 to about 9.5, for example, about 4 to about 9, for example, about 4.5 to about 8.5, for example, about 5 to about 8, or any range or value in between. However, the above pH values ​​refer to the pH of the preservative composition. Furthermore, ready-to-use formulations may have a pH of about 4 to about 11, for example, about 4.5 to about 10.5, for example, about 5 to about 10, for example, about 5.5 to about 9.5, for example, about 6 to about 9, or any range or value in between. As is well known in the art, pH builders, pH buffers and other pH adjusters can be used to obtain and stabilize the above pH values.

[0240] The preservative compositions are used to treat wood or wood cellulosic substrates. Wood or cellulosic products that can be treated with the preservative compositions of this disclosure include, but are not limited to, lignocellulose substrates, wood-plastic composites, cardboard and cardboard-clad building materials, e.g., gypsum board, and cellulose materials, e.g., cotton. Also included are leather, textile materials, synthetic fibers, Hessian, ropes and tacks, and composite wood. For convenience, this disclosure is described in relation to the treatment of wood, but it is recognized that other cellulose materials can be treated similarly. However, in one embodiment, the preservative compositions are applied, but are not exclusive, to sawn timber, logs or laminated veneers, OSB, plywood, MDF, or any other cellulosic products. In one embodiment, the substrate is wood or wood composite material intended to be wet for the duration of its life, e.g., window frame wood, timber used on the ground in exposed environments, e.g., decking, and timber used in grounded or freshwater environments.

[0241] In one embodiment, the wood or cellulosic substrate to be treated is approximately 150 g / m² 3 (grams per cubic meter) ~ approximately 7.5 kg / m 3 For example, copper, about 200g / m 3 ~about 6kg / m 3 Copper-containing biocide, approximately 40g / m² 3 ~about 2kg / m 3 A zinc-containing biocide, for example, about 200 g / m² 3 ~Approx. 1.5kg / m 3 A zinc-containing biocide, approximately 20g / m² 3 ~About 3.5kg / m 3 Boron-containing biocides, for example, about 40 g / m² 3 ~about 3kg / m 3 Boron-containing biocide, approximately 10g / m² 3 ~about 300g / m 3 Organic biocides, for example, about 20 g / m² 3 ~about 260g / m 3The material may be treated with a preservative composition (or ready-to-use formulation) in an amount containing an organic biocide, the organic biocide being a fungicide, which can be independently selected from the group consisting of azoles, quaternary ammonium compounds, isothiazolones, pyrazolecarboxamides, phenylpyrazoles, haloalkynyl compounds, or combinations thereof. For example, as shown in the examples, the disclosure has found that the preservative composition can penetrate into the core of wood or cellulosic products and distribute the preservative evenly.

[0242] In another embodiment, the wood or cellulosic substrate to be treated is approximately 150 g / m² 3 (grams per cubic meter) ~ approximately 7.5 kg / m 3 For example, copper, about 200g / m 3 ~about 6kg / m 3 Copper-containing biocide, approximately 40g / m² 3 ~about 2kg / m 3 A zinc-containing biocide, for example, about 200 g / m² 3 ~Approx. 1.5kg / m 3 A zinc-containing biocide, approximately 20g / m² 3 ~About 3.5kg / m 3 Boron-containing biocides, for example, about 40 g / m² 3 ~about 3kg / m 3 Boron-containing biocide, approximately 10g / m² 3 ~about 300g / m 3 Azoles, for example, about 20 g / m² 3 ~about 260g / m 3 The material can be treated with an amount of preservative composition (or ready-to-use formulation) containing azoles or combinations thereof. For example, as shown in the examples, the disclosure has found that the preservative composition can penetrate into the core of wood or cellulosic products and distribute the preservative evenly.

[0243] However, wood or cellulosic substrates may be treated with the ready-to-use preservative compositions of this disclosure. Such wood or cellulosic substrates may contain copper-containing biocides, zinc-containing biocides, boric acid, and organic biocides in the amounts considered above relative to the ready-to-use composition.

[0244] This disclosure further relates to a method for producing a wood preservative composition and a method for treating a wood-based substrate with the wood preservative composition. For example, in one embodiment, copper-containing biocides and azoles may be pulverized together (e.g., reduced from micron size or larger to the size / particle size distribution discussed above), either alone or in combination with one or more dispersants / complexing agents, or they may be pulverized separately and then combined.

[0245] Furthermore, in one embodiment, the copper-containing biocide, zinc-containing biocide, boron-containing biocide, and organic biocide may be pre-mixed as discussed above. However, it should be understood that the preservative composition may also exist in multiple parts and be mixed immediately before treating the wood or cellulosic substrate. However, in another embodiment, the preservative composition may be in a partial form, e.g., a pack or a mix, containing the copper-containing biocide, zinc-containing biocide, boron-containing biocide, and organic biocide in the amounts discussed above.

[0246] Regardless of the form of the wood preservative composition, the composition is diluted as discussed above and used to treat wood or cellulosic substrates. For example, application of the preservative composition of the Disclosure to wood or cellulosic substrates may be by one or more of the following means: deposition, deluging, spraying, brushing, or other surface coating methods, or by impregnation of the wood or other material body, such as by high-pressure or double-vacuum impregnation. In one embodiment, the method is impregnation under reduced pressure.

[0247] Furthermore, certain aspects of this disclosure may be better understood by the following embodiments, which are intended to be non-limiting and illustrative in nature. [Examples]

[0248] It is understood that the preservative compositions described in the examples may substantially omit any substances not explicitly stated.

[0249] abbreviation

[0250] [Table 2]

[0251] method AWPA E10-16: "Experimental method for evaluating the decay resistance of wood-based materials to pure basidiomycete cultures: soil / block test." This method is a screening test for determining the resistance of wood-based materials to decay by selected fungi under controlled laboratory conditions. It can also be used to establish the minimum amount of preservative that is effective in preventing decay of selected wood species by selected fungi under optimal laboratory conditions. This test method is intended to provide information on the standardization of protective treatments. Wood blocks are first conditioned by vacuum impregnation with a preservative solution. Typically, after immersion in the treatment solution, the blocks are subjected to vacuum treatment (100 mmHg for 30 minutes), followed by pressurization treatment (700 kPa for 60 minutes) and exposure to atmospheric pressure for 30 minutes. The test blocks must be cubes crushed as precisely as possible to 14 mm or 19 mm, each 2.7 cm. 3 or 6.9cm 3 The nominal volume is obtained. After conditioning, the wood block is exposed to wood-rotting fungi.

[0252] Particle size: Particle size was analyzed using a Horiba LA-910 particle size distribution analyzer (PSDA).

[0253] Example 1 AWPA E10-16 Soil / Block Test Wood species: Southern Yellow Pine (SYP) Microorganisms: The following organisms were used in this test: Fibroporia radiculosa and Fomitopsis palustris. Fibroporia radiculosa (Basidiomycetes) and Fomitopsis palustris (Basidiomycetes) are brown rot fungi that have been documented to cause early damage to wooden piles treated with copper-based wood preservatives in the field due to their copper tolerance.

[0254] Particle size: The particle sizes of BCC, tebuconazole, and zinc oxide were analyzed using a Horiba LA-910 particle size distribution analyzer (PSDA). The average particle sizes of BCC, tebuconazole, and zinc oxide were 0.15 - 0.5 microns, with a D50 of 0.35 and a D95 of less than 1 micron.

[0255] The soil block test was conducted according to the procedure described in AWPA E10-16. The test was performed on wood blocks treated via vacuum impregnation with the wood preservative composition of the present invention before and after leaching by the above-mentioned microorganisms.

[0256] The properties and ratios of the wood preservative composition are summarized in Table 1. The ratios are expressed in weight % based on the total weight of the wood preservative composition. The leaching protocol was carried out according to the procedure described in AWPA E10-16.

[0257]

Table 3

[0258] The loss of a large number of wood blocks indicates that a specific wood preservative composition cannot protect the wood from fungal attack. The retention level of a specific preservative corresponds to the minimum amount of preservative that protects the wood block from fungal decay. The calculation of retention was in accordance with AWPA E10-16. The obtained weight loss data are summarized in Table 2.

[0259]

Table 4

[0260] In this test, both F. radiclosa and F. palustris were highly active, as indicated by the mean weight loss of 52.5% and 41.5% of the untreated control, respectively. The wood preservative composition of the present invention demonstrates to be highly efficient in protecting impregnated blocks from decay by a given test fungus.

[0261] These and other modifications and changes to the present invention can be implemented by those skilled in the art without departing from the spirit and scope of the invention as further detailed in the appended claims. In addition, it should be understood that the various aspects of the invention are interchangeable, both in whole and in part. Furthermore, those skilled in the art will recognize that the foregoing description is illustrative and not intended to limit the invention further described in the appended claims.

Claims

1. (a) Copper-containing biocides, (b) Zinc-containing biocides, (c) Boron-containing biocides, and (d) Organic biocides Includes, A wood preservative composition wherein the aforementioned organic biocide is an azole.

2. The wood preservative composition according to claim 1, wherein the copper-containing biocide is independently selected from the group consisting of basic copper carbonate, copper oxide, or a combination thereof.

3. The wood preservative composition according to claim 1, wherein the zinc-containing biocide is independently selected from the group consisting of zinc oxide, zinc acetate, zinc borate, or a combination thereof.

4. The wood preservative composition according to claim 1 or 2, wherein the boron-containing biocide is independently selected from the group consisting of boric acid, disodium tetraborate pentahydrate, disodium octaborate tetrahydrate, or combinations thereof.

5. The wood preservative composition according to any one of claims 1 to 3, wherein the boron-containing biocide is boric acid.

6. The wood preservative composition according to any one of claims 1 to 3, wherein the azoles include tebuconazole.

7. The wood preservative composition according to any one of claims 1 to 4, wherein the azoles include tebuconazole, propiconazole, or a mixture thereof.

8. The wood preservative composition according to any one of claims 1 to 5, wherein the azoles form a complex with a copper-containing biocide.

9. The wood preservative composition according to any one of claims 1 to 5, wherein the azoles include finely powdered azole particles, and 50% or more of the finely powdered azole particles have a medium particle size of less than 1 micron.

10. The wood preservative composition according to any one of claims 1 to 5, wherein the copper-containing biocide comprises basic copper carbonate, the zinc-containing biocide comprises zinc oxide, zinc acetate, zinc borate, or a combination of zinc oxide and zinc borate, the boron-containing biocide comprises boric acid, and the azoles comprises tebuconazole.

11. A wood preservative composition according to any one of claims 1 to 5, A wood preservative composition in which, based on the total weight of the wood preservative composition, the copper-containing biocide constitutes 0.1% to 75% by weight of the wood preservative composition, the zinc-containing biocide constitutes 0.1% to 50% by weight of the wood preservative composition, the boron-containing biocide constitutes 0.1% to 75% by weight of the wood preservative composition, and the organic biocide constitutes 0.1% to 20% by weight of the wood preservative composition.

12. A wood preservative composition according to any one of claims 1 to 5, having a pH of 3 to 10.

13. A wood preservative composition according to any one of claims 1 to 5, having a pH of 3 to 8.

5.

14. The wood preservative composition according to claim 13, which is in the form of a liquid, solid, or paste.

15. A wood preservative composition according to any one of claims 1 to 6, further comprising alkanolamines.

16. The wood preservative composition according to any one of claims 1 to 7, wherein the copper-containing biocide and the zinc-containing biocide are present in the wood preservative composition such that the weight ratio of copper to zinc is 15:1 to 1:5 based on weight.

17. The wood preservative composition according to any one of claims 1 to 8, wherein the copper-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the weight ratio of copper to the boron-containing biocide is 15:1 to 1:5 based on weight.

18. The wood preservative composition according to any one of claims 1 to 9, wherein the zinc-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the weight ratio of zinc to the boron-containing biocide is 5:1 to 1:

5.

19. The wood preservative composition according to any one of claims 1 to 10, wherein the zinc-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the weight ratio of zinc to the boron-containing biocide is 3:1 to 1:1.

5.

20. A wood-based product treated with the wood preservative composition according to any one of claims 1 to 11.

21. (a) Copper-containing biocides, (b) Zinc-containing biocides, (c) Boron-containing biocides, and (d) Organic biocides A wood preservative composition comprising, The aforementioned organic biocides are azoles, The copper-containing biocide and the zinc-containing biocide are present in the wood preservative composition such that the ratio of copper to zinc is 15:1 to 1:5 by weight. The copper-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the ratio of copper to the boron-containing biocide is 15:1 to 1:5 by weight. The copper-containing biocide contains basic copper carbonate, the zinc-containing biocide contains zinc oxide or a combination of zinc oxide and zinc borate, the boron-containing biocide contains boric acid, and the azoles contain tebuconazole. Wood preservative composition.

22. The wood preservative composition according to claim 21, having a pH of 3 to 8.

5.

23. The wood preservative composition according to claim 22, which is in the form of a liquid, solid, or paste.

24. A method for treating wood with a wood preservative composition according to any one of claims 1 to 16, wherein a copper-containing biocide, a zinc-containing biocide, a boron-containing biocide, and at least one azole are injected into the wood in a single step.

25. A biocide comprising a copper-containing biocide, a zinc-containing biocide, a boron-containing biocide containing boric acid, and an organic biocide, A method for producing a wood preservative composition in which the organic biocide is an azole, (a) A step of dispersing at least a portion of the copper-containing biocide and the zinc-containing biocide, (b) A step of producing micronized azoles by micronizing the azoles, (c) The step of combining the boron-containing biocide containing boric acid with the copper-containing biocide, the zinc-containing biocide, and the micronized azoles. Includes, The copper-containing biocide and the zinc-containing biocide are present in the wood preservative composition such that the ratio of copper ions to zinc ions is 15:1 to 1:

1. The copper-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the ratio of copper ions to the boron-containing biocide is 15:1 to 1:

5. method.

26. The method according to claim 25, further comprising the step of adjusting the pH of the wood preservative composition to 3 to 8.

5.

27. ​​The method according to claim 26, wherein the wood preservative composition is in the form of a liquid, a solid, or a paste.

28. The method according to any one of claims 25 to 27, further comprising the step of grinding the copper-containing biocide and the zinc-containing biocide together with at least one dispersant.

29. A method according to any combination of claims 25 to 28, wherein, based on the total weight of the composition, the copper-containing biocide constitutes 1% to 75% by weight of the wood preservative composition, the zinc-containing biocide constitutes 0.1% to 50% by weight of the wood preservative composition, the boron-containing biocide constitutes 0.1% to 75% by weight of the wood preservative composition, and the azoles constitute 0.1% to 20% by weight of the wood preservative composition.

30. The method according to any one of claims 25 to 29, wherein the copper-containing biocide comprises basic copper carbonate, the zinc-containing biocide comprises zinc oxide or a combination of zinc oxide and zinc borate, the boron-containing biocide comprises boric acid, and the azoles comprises tebuconazole.

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