Zinc and boron-containing reinforced wood preservative

Abstract

A wood preservative composition comprising a copper-containing biocide, a zinc-containing biocide, a boron-containing biocide and an azole, and a method for producing the wood preservative composition comprising a copper-containing biocide, a zinc-containing biocide, a boron-containing biocide and an azole are provided. The wood preservative composition exhibits improved biocidal efficacy against copper-resistant fungi.

Description

Technical Field

[0001] Related Applications

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

Background Art

[0002]

[0002] Wood-based products are subject to attack from various types of organisms, including mold, fungi, and insects such as termites. Attack by these organisms can cause the wood in the wood-based products to decay, reducing the quality and structural integrity of the products. To counter microbial attack, 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 or brushing, or by vacuum pressure impregnation. When applying preservatives industrially, the wood is typically impregnated with the treatment solution to achieve either shell or full-cell type penetration into the substrate. Depending on the wood species being treated and the end use, the depth of penetration of the preservative solution into the wood can significantly affect the useful service life of the treated wood.

[0003]

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

[0004]

[0004] Non-metallic substitutes, 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. [Overview of the project] [Problems that the invention aims to solve]

[0005]

[0005] Therefore, there is a need for a wood preservative composition that exhibits enhanced bactericidal efficacy. It is even more beneficial to provide a wood preservative composition that shows improved efficacy against copper-resistant fungi. Furthermore, it is beneficial to provide a biocidal composition that shows long-term efficacy against fungi, including copper-resistant fungi. [Means for solving the problem]

[0006]

[0006] This disclosure primarily concerns wood preservative compositions. The wood preservative compositions exhibit improved bactericidal efficacy against copper-resistant fungi.

[0007]

[0007] In a first exemplary embodiment, the wood preservative composition comprises a copper-containing biocide, a zinc-containing biocide, a boron-containing biocide, and azoles. The boron-containing biocide comprises boric acid, disodium tetraborate pentahydrate, disodium octaborate tetrahydrate, or a combination thereof. 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 about 15:1 to about 1:5. Additionally, the copper-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the ratio of copper ions to boric acid equivalents is about 15:1 to about 1:5.

[0008]

[0008] In the first exemplary embodiment, the copper-containing biocide may include basic copper carbonate, copper oxide, or a combination thereof.

[0009]

[0009] In a second exemplary embodiment, the zinc-containing biocide may include zinc oxide or a combination of zinc oxide and zinc borate.

[0010]

[0010] In a third exemplary embodiment, the boron-containing biocide may be boric acid.

[0011]

[0011] In a fourth exemplary embodiment, the azoles may include tebuconazole, penflufen, or a mixture thereof.

[0012]

[0012] In a fifth exemplary embodiment, the azoles may include tebuconazole, propiconazole, or a mixture thereof.

[0013]

[0013] In a sixth exemplary embodiment, azoles can form complexes with copper-containing biocides.

[0014]

[0014] In a seventh exemplary embodiment, the azoles may include finely powdered azole particles. More than 50% of the finely powdered azole particles may have a particle size of less than about 1 micron.

[0015]

[0015] In the eighth exemplary 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 azoles may include tebuconazole.

[0016]

[0016] In a ninth exemplary embodiment, a copper-containing biocide may constitute about 0.1% to about 75% by weight of the composition, a zinc-containing biocide may constitute about 0.1% to about 50% by weight of the composition, a boron-containing biocide may constitute about 0.1% to about 75% by weight of the composition, and azoles may constitute about 0.1% to about 20% by weight of the composition.

[0017]

[0017] In a tenth exemplary embodiment, the composition may have a pH of about 3 to about 10.

[0018]

[0018] In an eleventh exemplary embodiment, the composition may further comprise alkanolamines.

[0019]

[0019] In a twelfth exemplary embodiment, copper-containing biocides and zinc-containing biocides may be present in the wood preservative composition such that the ratio of copper ions to zinc ions is about 10:1 to about 2:1.

[0020]

[0020] In a 13th exemplary embodiment, copper-containing biocides and boron-containing biocides may be present in the wood preservative composition such that the ratio of copper ions to boric acid equivalents is about 10:1 to about 2:1.

[0021]

[0021] In a 14th exemplary embodiment, a zinc-containing biocide and a boron-containing biocide may be present in the wood preservative composition such that the ratio of zinc ions to boric acid equivalents is about 5:1 to about 1:5.

[0022]

[0022] In a 15th exemplary embodiment, a zinc-containing biocide and a boron-containing biocide may be present in the wood preservative composition such that the ratio of zinc ions to boric acid equivalents is about 3:1 to about 1:1.5.

[0023]

[0023] In a sixteenth exemplary embodiment, a wood product can be treated with any of the wood preservative compositions described.

[0024]

[0024] In a 17th exemplary embodiment, a wood-based product can be treated with any of the wood preservative compositions described. The wood-based product contains copper ions at a concentration of about 200 grams (g / m³) per cubic meter of the product. 3 ) ~ approx. 7.5kg / m 3 Zinc ions may be present in amounts of approximately 40 g / m³ of the product. 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 Azoles may be present in amounts of approximately 20 g / m² of the product. 3 ~about 260g / m 3 It can exist in that quantity.

[0025]

[0025] In a second exemplary 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 ions to zinc ions is about 15:1 to about 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 boric acid equivalents is about 15:1 to about 1:5. 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. The azoles comprises tebuconazole.

[0026]

[0026] In an 18th exemplary embodiment, a method for treating wood with any of the wood preservative compositions disclosed is described. In this method, copper-containing biocides, zinc-containing biocides, boron-containing biocides and azoles can be injected into the wood in a single step.

[0027]

[0027] In a third exemplary embodiment, 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 azole to produce pulverized azoles; and combining a boron-containing biocide containing boric acid with the copper-containing biocide, the zinc-containing biocide and the pulverized azoles. 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 about 15:1 to about 1:5. Additionally, the copper-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the ratio of copper ions to boric acid equivalents is about 15:1 to about 1:5.

[0028]

[0028] In a 19th exemplary embodiment, the copper-containing biocide and the zinc-containing biocide can be pulverized together with at least one dispersant.

[0029]

[0029] In a 20th exemplary embodiment, a copper-containing biocide may constitute about 1% to about 75% by weight of the composition, a zinc-containing biocide may constitute about 0.1% to about 50% by weight of the composition, a boron-containing biocide may constitute about 0.1% to about 75% by weight of the composition, and azoles may constitute about 0.1% to about 20% by weight of the composition.

[0030]

[0030] In a 21st exemplary 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 azoles may include tebuconazole.

[0031]

[0031] Each of the exemplary embodiments listed above may be combined with one or more of the other exemplary embodiments listed above in a particular embodiment. For example, all 17 exemplary embodiments listed above the first exemplary embodiment may be combined with each other in some embodiments. As another example, any combination of two, three, four, five or more of the 17 exemplary embodiments listed above the first exemplary embodiment may be combined with each other in other embodiments. Thus, each exemplary embodiment listed above each exemplary embodiment may be used in combination with each other in some exemplary embodiments. Alternatively, each exemplary embodiment listed above each exemplary embodiment may be implemented individually in other exemplary embodiments. Thus, it is understood that various exemplary embodiments can be realized by utilizing the exemplary embodiments listed above.

[0032]

[0032] These and other features, aspects 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

[0033] Here, the term "D50" or "D50 particle size" refers to the volume-intermediate particle size, where 50% of the sample volume of particles has a size below that range or value.

[0033]

[0034] Here, the term "D10" or "D10 particle size" refers to the median particle size, where 10% of the sample volume of particles are below that range or value.

[0034]

[0035] Here, the term "D50" or "D50 particle size" refers to the volume-intermediate particle size, where 50% of the sample volume of particles has a size below that range or value.

[0035]

[0036] Similarly, here the term “D90” or “D90 particle size” refers to a value in which 90% of the sample volume of particles have a size below that range or value.

[0036]

[0037] Similarly, here the term "D99" or "D99 particle size" refers to a value in which 99% of the sample volume of particles have a size below that range or value.

[0037]

[0038] Here, the terms “about,” “approximately,” or “generally,” when used to modify a value, indicate that the value may rise or fall by 10%, and may remain within or between any range or value within the disclosed aspect, e.g., 7.5%, e.g., 5%, e.g., 4%, e.g., 3%, e.g., 2%, e.g., 1%. Furthermore, the term “substantially absent,” when used to describe the amount of a substance in a material, should not be limited to the absence of any or all of the substance, but may correspond to the absence of any perceptible or detectable amount of the enumerated substance in the material. Thus, for example, if the amount of a substance in the material is less than the accuracy of an industrially acceptable apparatus or test for measuring the amount of a substance in a material, the material is “substantially absent” of the substance. In certain exemplary embodiments, if the amount of substance in the material is less than 10% by weight, less than 9% by weight, less than 8% by weight, less than 7% by weight, less than 6% by weight, less than 5% by weight, less than 4% by weight, less than 3% by weight, less than 2% by weight, less than 1% by weight, less than 0.5% by weight, or less than 0.1% by weight, the material may be "substantially free" of the substance. [Modes for carrying out the invention]

[0038]

[0039] In general, this disclosure relates to unexpected synergistic combinations of biocides (copper), biocides (zinc), at least one azole, and boron-containing biocides that provide highly effective wood preservative formulations. Surprisingly, the formulations prepared by this disclosure exhibit remarkable synergistic effects between the active ingredients and provide improved fungicidal efficacy against copper-resistant fungi at the same or similar total metal biocides concentrations. In addition, this disclosure has found that when the disclosed formulations are used for wood treatment, the resulting wood products exhibit improved properties and improved long-term protection against copper-resistant fungi in both the core and outer layers of the wood product.

[0039]

[0040] In particular, this disclosure has found that by incorporating specific amounts of boron-containing biocides and zinc-containing biocides with respect to a biocide metal (copper), a synergistic effect can be demonstrated, combating fungi including copper-resistant bacteria and resulting in stronger and longer-lasting preservation than previously shown by biocides containing any 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 a preservative composition in amounts such that the ratio of copper ions to zinc ions in the preservative composition is provided in a ratio of about 15:1 to about 1:5, e.g., about 12.5:1 to about 1:1, e.g., about 10:1 to about 3:1, e.g., about 9:1 to about 4:1, e.g., about 8:1 to about 5:1, or any range or value in between.

[0040]

[0041] Similarly, copper-containing biocides and boron-containing biocides may be present in the preservative composition in amounts such as those provided in the preservative composition, with ratios of copper ions to borate expressed as borate equivalents in any range or value between approximately 15:1 to approximately 1:5, approximately 15:1 to approximately 1:1, e.g., approximately 12.5:1 to approximately 1.5:1, e.g., approximately 10:1 to approximately 2:1, e.g., approximately 9:1 to approximately 3:1, e.g., approximately 8:1 to approximately 4:1, or any range or value in between. In particular, as discussed above, the disclosure has found that supplementing copper ions with zinc ions and boron-containing biocide equivalents provides excellent protection against fungi, including copper-resistant fungi. Conversely, the disclosure has found that when there is too little copper present with zinc and / or boron (e.g., a ratio of less than 1:5), preservation against certain copper-resistant fungi is insufficient and no synergistic effect is observed. Similarly, when the amount of zinc and / or boron present with copper was too low (e.g., a ratio greater than 15:1), the composition showed insufficient preservation against certain copper-resistant bacteria and no synergistic effect was observed.

[0041]

[0042] 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 the biocide in a mixture of copper-containing biocides, zinc-containing biocides, boron-containing biocides, and azoles, which may be due to antimicrobial activity, by the minimum inhibitory concentration of the combination of copper-containing biocides and azoles when tested against a target microorganism. 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 known in the art, any value less than 1 indicates a synergistic interaction.

[0042]

[0043] Nevertheless, in one embodiment, a copper-containing biocide may include any biocide copper compound that provides the copper ion ratios listed above, but the copper-containing biocide may be incorporated into the formulation in the form of inorganic copper salts, e.g., carbonates, bicarbonates, sulfates, nitrates, chlorides, hydroxides, borates, fluorides, or oxides. Alternatively, copper may be in the form of simple organic salts, e.g., formate or acetate, or complexes, e.g., N-nitroso-N-cyclohexyl-hydroxylamine-copper (copper-HDO) or copper pyrithione (bis(2-pyridylthio)copper 1,1'-dioxide, CAS number 14915-37-8). Other examples of copper-containing biocides include copper sulfate, e.g., basic copper sulfate and copper sulfate pentahydrate, copper oxide, e.g., cuprous oxide and cupric oxide, and copper salts, e.g., copper salts of fatty acids and rosinic acid, copper ethylenediamine complexes, copper triethanolamine complexes, copper ethylenediaminetetraacetate, and copper thiocyanate. Further examples of copper-containing biocides include copper octanoate, diammonium copper diacetate complexes and copper ethanolamine complexes, copper naphthenate and copper 8-quinolinate.

[0043]

[0044] In one embodiment, the biocide copper ion is the copper(II) ion. For example, forms of copper(II) include basic copper chloride, basic copper carbonate (Cu2CO3.Cu(OH)2), copper(II) acetate, ammonium copper carbonate complex, copper(II) hydroxide, copper(II) oxide, copper oxychloride, copper oxychloride sulfate, ammonium copper complex, copper citrate chelate, copper gluconate chelate, and copper(II) sulfate pentahydrate. In one embodiment, the copper-containing biocide is basic copper carbonate or copper oxide. However, in one embodiment, the copper compound used is copper oxide and copper carbonate, for example, basic copper carbonate.

[0044]

[0045] In exemplary embodiments, the copper-containing biocide may include one or more soluble copper biocides. For example, the copper-containing biocide may include, or exist as, copper ethanolamine, copper ammonium complexes, or mixtures thereof.

[0045]

[0046] Regardless of the form of the copper-containing biocide, copper ions may be present in the composition such that they form about 1% to about 75% by weight of the composition, for example, about 1% to about 50% by weight, for example, about 2% to about 50% 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.

[0046]

[0047] Furthermore, regardless of the type or amount of the selected copper-containing biocide, the copper-containing biocide may exist in a micronized form, alone or in combination with a dispersant. For example, in one embodiment, the copper particles have a size of about 10 microns or less, e.g., about 8 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. Additionally or alternatively, at least about 10% or more of the copper particles, e.g., about 25% or more, e.g., about 50% or more, e.g., about 60% or more, e.g., about 70% or more, e.g., about 80% or more, e.g., about 90% or more, e.g., about 95% or more, have a size of about 1 micron or less. Furthermore, the copper-containing biocide may have a D10, D50, D90 or D99 particle size below any one or more of the above ranges. Furthermore, in a further embodiment, as will be discussed in more detail below, azoles, zinc, boron or combinations thereof may also be micronized to have particle sizes according to one or more of the above.

[0047]

[0048] Furthermore, the zinc-containing biocide may be any zinc-containing biocide commonly used in the art. For example, the zinc-containing biocide may be a zinc alloy, a zinc salt, zinc oxide, zinc hydroxide, a zinc ammonium complex, or a combination thereof. In one embodiment, the zinc salt may be a zinc salt of an organic acid and / or a zinc salt of an inorganic acid. In this regard, the zinc-containing biocide may be a zinc alloy, a zinc salt of an organic acid, a zinc salt of an inorganic acid, zinc oxide, zinc hydroxide, or a combination thereof.

[0048]

[0049] In one embodiment, the zinc-containing biocide may include zinc salts, such as zinc salts of organic acids or inorganic acids, or combinations thereof. In another embodiment, the zinc-containing biocide may include zinc oxide, zinc hydroxide, or combinations thereof.

[0049]

[0050] Overall, zinc salts include, but are not limited to, zinc acetate, zinc borate, zinc carbonate, basic zinc carbonate, zinc chloride, zinc sulfate, zinc citrate, zinc fluoride, zinc iodide, zinc lactate, zinc oleate, zinc oxalate, zinc phosphate, zinc propionate, zinc salicylate, zinc selenate, zinc silicate, zinc stearate, zinc sulfide, zinc sulfate, zinc tannate, zinc tartrate, zinc valerate, or any combination thereof.

[0050]

[0051] In one embodiment, the zinc-containing biocide may be a binary zinc-containing biocide. For example, the binary zinc-containing biocide may be zinc oxide, zinc sulfide, zinc halides (e.g., zinc fluoride, zinc iodide, zinc chloride, zinc bromide), zinc peroxide, zinc hydride, zinc carbide, zinc nitride, or any combination thereof. In one particular embodiment, the binary zinc-containing biocide may be a zinc halide, such as zinc chloride. Nevertheless, in one embodiment, the zinc-containing biocide may be zinc oxide, zinc borate, or a combination thereof. It should also be understood that the aforementioned zinc-containing biocides can be used individually or in any combination.

[0051]

[0052] In one embodiment, a zinc-containing biocide may contain zinc pyrithione.

[0052]

[0053] However, as will be discussed in more detail below, it should be understood that zinc borate does not provide the necessary ratio of zinc or boric acid equivalents to the preservative composition. In particular, zinc borate alone cannot provide enough zinc to form the copper ion to zinc ion ratio of this disclosure while maintaining the ratio of copper ions to boric acid equivalents. Therefore, in one embodiment, a further or second zinc compound is used in combination with zinc borate.

[0053]

[0054] Furthermore, regardless of the selected zinc-containing biocide, zinc ions may be present in the composition such that they form approximately 0.01% to approximately 50% by weight of the composition, for example, approximately 0.1% to approximately 45% by weight, for example, approximately 0.25% to approximately 40% by weight, for example, approximately 0.5% to approximately 35% by weight, for example, approximately 0.75% to approximately 32.5% by weight, for example, approximately 1% to approximately 30% by weight, for example, approximately 1.5% to approximately 27.5% by weight, or any range or value in between.

[0054]

[0055] In one embodiment, boron-containing biocides may include a variety of borates, including soluble and insoluble borates, boron-containing acids, oxides, salts, or combinations thereof. For example, in one embodiment, metallic borates, borate minerals, borate esters, and other inorganic or organic borates. In one embodiment, boron-containing biocides may include boron oxide, boric acid, salts of boric acid, or combinations thereof. In particular, in one embodiment, boron-containing biocides may include boron oxide, boric acid, sodium borate, calcium borate, magnesium borate, zinc borate, disodium octaborate tetrahydrate, copper borate, borate silicates, or combinations thereof. Furthermore, in one embodiment, boron-containing biocides are boric acid, disodium octaborate tetrahydrate, disodium tetraborate pentahydrate, or combinations thereof. However, in one embodiment, boron-containing biocides may also be pulverized and have any one or more of the particle sizes considered herein.

[0055]

[0056] Nevertheless, the boron-containing biocide may be present in the composition such that boron ions form from about 0.01 wt% to about 75 wt% of the composition, such as from about 0.1 wt% to about 70 wt% of the composition, such as from about 0.25 wt% to about 65 wt%, such as from about 0.5 wt% to about 60 wt%, such as from about 0.75 wt% to about 57.5 wt%, such as from about 1 wt% to about 55 wt%, such as from about 1.5 wt% to about 52.5 wt%, or any range or value therebetween.

[0056]

[0057] As discussed above, the preservative composition further comprises at least one azole, i.e., a compound containing an azole group. The azoles may be imidazoles or 1,2,4-triazoles, or in an embodiment pyrazoles, such as penflufen. Nevertheless, in an embodiment, the azoles are of general formula (III)

[0057]

Chemical formula

[0058] (wherein, X represents CR 4 or N, and R 1 represents hydrogen or a straight-chain, branched, cyclic, aromatic or any combination thereof, saturated or unsaturated, substituted or unsubstituted C1-C 40 group, and any of the carbon atoms other than those bonded to the nitrogen atom represented by formula (IV) may optionally be replaced by a heteroatom which is substituted, R 2 represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C6-C 10 aromatic, C5-C 10 heteroaromatic or C1-C4 alkyl carbamate, and R 3 and R 4 represent hydrogen, or R 3 and R 4 may together provide a benzimidazole group (i.e., R3 and R 4 These may combine to form -(CH)4-. It can be expressed as follows.

[0059]

[0058] The preservative compositions of the present disclosure may contain one or more azole compounds, for example, 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. However, in one embodiment, the preservative compositions of the present disclosure utilize one or more 1,2,4-triazoles alone or in combination with imidazoles.

[0060]

[0059] The imidazole compound incorporates a five-membered diunsaturated ring consisting of three carbon atoms and two nitrogen atoms at non-adjacent positions. The imidazole compound may also be a benzimidazole. In one embodiment, the azoles may include thiabendazole, imazalil, carbendazim, and prochloraz.

[0061]

[0060] The 1,2,4-triazole compound incorporates a five-membered diunsaturated ring consisting of three nitrogen atoms and two carbon atoms at non-adjacent positions.

[0062]

[0061] In one embodiment, the triazole compound is of formula (IV)

[0063] [ka]

[0064] (In the formula, R 5 R represents a branched or linear C1-C5 alkyl group (e.g., t-butyl), 6(This represents a phenyl group optionally substituted with a halogen (e.g., chlorine, fluorine, or bromine) atom or one or more substituents selected from C1-C3 alkyl (e.g., methyl), C1-C3 alkoxy (e.g., methoxy), phenyl, or nitro groups.) It contains a triazole compound selected from the compounds.

[0065]

[0062] Alternatively, the triazole compound is of formula (V)

[0066] [ka]

[0067] (In the formula, R 7 R 6 As defined, R 8 (This represents a hydrogen atom or a branched or linear C1-C5 alkyl group (e.g., n-propyl)) The compounds can be selected from the following.

[0068]

[0063] In particular, in one embodiment, the azoles include, but are not limited to, one or more triazoles including triadimefon, triadimenol, triazbutyl, propiconazole, cyproconazole, difenoconazole, fluquinconazole, tebuconazole, flusilazole, uniconazole, diniconazole, vitertanol, hexaconazole, azaconazole, flutriafoll, epoxyconazole, tetraconazole, penconazole, ipconazole, prothioconazole, and mixtures thereof.

[0069]

[0064] In a further embodiment, triazoles include propiconazole, azaconazole, hexaconazole, tebuconazole, cyproconazole, triadimefon, ipconazole, prothioconazole, and mixtures thereof, for example, in one embodiment, propiconazole, tebuconazole, cyproconazole, and mixtures thereof. Furthermore, in a further embodiment, azoles include propiconazole, tebuconazole, or mixtures thereof.

[0070]

[0065] Furthermore, in one embodiment, when a mixture of propiconazole and tebuconazole is used, propiconazole and tebuconazole are used in the mixture in a ratio of propiconazole to tebuconazole by weight 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.

[0071]

[0066] Regardless of the selected azoles, the 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.

[0072]

[0067] Furthermore, 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 size of about 10 microns or less, e.g., about 8 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. Additionally or alternatively, at least about 10% or more of the azole particles, e.g., about 25% or more, e.g., about 50% or more, e.g., about 60% or more, e.g., about 70% or more, e.g., about 80% or more, e.g., about 90% or more, e.g., about 95% or more, have a size of about 1 micron or less.

[0073]

[0068] Furthermore, in one embodiment, the preservative composition may also include a dispersant and / or solvent. In one embodiment, the dispersant and / or solvent is an alkanolamine, such as monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, and tripolanolamine. In one embodiment, the dispersant and / or solvent is an ethanolamine, such as monoethanolamine. However, it should be understood that other dispersants and / or solvents known in the art may be used. As a particular example, the dispersants and / or solvents listed above may be solvents for boric acid in certain exemplary embodiments.

[0074]

[0069] Additionally or alternatively, the dispersant may complex with some or all of one or more components of the preservative formulation. For example, in one embodiment, the dispersant may complex with azoles, at least some of the copper-containing biocides, or both the azoles and the copper-containing biocides. 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.

[0075]

[0070] In one embodiment, the above combination of azoles, copper-containing biocides, zinc-containing biocides, and boron-containing biocides can be used alone as a preservative composition. However, in one embodiment, the preservative composition may include one or more additional organic fungicidal wood decay preservatives other than those mentioned above. For example, organic fungicidal wood decay preservatives suitable 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.

[0076]

[0071] In one embodiment, the organic fungicidal wood decay preservative is selected from quaternary ammonium compounds, isothiazolones, and fungicidal heterocyclic compounds, such as fenpropimorphs.

[0077]

[0072] The quaternary ammonium compounds may include trimethylalkyl quaternary ammonium compounds, e.g., cocotrimethylammonium chloride; dialkyldimethyl quaternary ammonium compounds, e.g., didecyldimethylammonium chloride, didecyldimethylammonium carbonate, didecyldimethylammonium bicarbonate, dioctyldimethylammonium chloride, and octyldecyldimethylammonium chloride or mixtures thereof; alkyldimethyl or diethylbenzylammonium salts, e.g., benzalkonium chloride and benzalkonium hydroxide; polyethoxylated quaternary ammonium compounds, e.g., N,N-didecyl-N-methyl-poly(oxyethyl)ammonium propionate (Bardap 26) or N,N-didecyl-N-methyl-poly(oxyethyl)ammonium lactate; and N-substituted pyridinium compounds, e.g., cetylpyridinium chloride. In one embodiment, the quaternary ammonium compounds may include benzalkonium chloride, didecyldimethylammonium chloride, and didecyldimethylammonium carbonate.

[0078]

[0073] In one aspect of the present disclosure, preferred isothiazolinones are those of general formula (I)

[0079] [ka]

[0080] (In the formula, R 1 C1-C is a hydrogen atom, and in some cases, a substituted C1-C 18 Alkyl, C2-C8 alkenyl or alkynyl, C2-C8 haloalkynyl, and in some cases substituted C3-C 12 This refers to cycloalkyl, aralkyl or aryl substituted with up to 10 carbon atoms, respectively. R 2 and R 3 These independently represent hydrogen, halogen, or C1-C4 alkyl, or R 2 and R 3Together, the 1,2-benzisothiazoline-3-one group (i.e., R 2 and R 3 (These may combine to form -(CH)4-) It is represented as follows.

[0081]

[0074] In one direction, R 2 and R 3 This independently represents chloro or hydrogen, or R 2 and R 3 These may together provide a 1,2-benzisothiazoline-3-one group.

[0082]

[0075] Therefore, in this embodiment, R 1 The substituents are selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, cyclohexyl, 4-methoxyphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, benzyl, 4-methoxybenzyl, 4-chlorobenzyl, 3,4-dichlorobenzyl, phenethyl, 2-(4-methoxyphenyl)ethyl, 2-(4-chlorophenyl)ethyl, 2-(3,4-dichlorophenyl)ethyl, hydroxymethyl, chloromethyl, and chloropropyl.

[0083]

[0076] In one such embodiment, R in the compound of formula (I) 1 The substituents are hydrogen, and in some cases, substituted C1-C 18 This represents alkyl, aralkyl, or aryl substituted with up to 10 carbon atoms. In a further embodiment, R 1 C1-C is a hydrogen atom or, if applicable, a substituted C1-C 18 Indicates alkyl. Additionally or alternatively, R 1 R is hydrogen or a C1-C8 alkyl group, and hydrogen, methyl, butyl, and octyl are the most preferred R. 1 It is a substituent.

[0084]

[0077] Accordingly, in one embodiment, the isothiazolinones used in the biocide compositions according to the present disclosure are R 1 However, it represents hydrogen or C1-C8 alkyl, R 2 and R 3 Either independently represents chloro or hydrogen, or R 2 and R 3 The above general formula (I) may also provide a 1,2-benzisothiazoline-3-one group.

[0085]

[0078] In one embodiment, the isothiazolinones used in the preservative compositions according to the present disclosure are R 1 However, R represents hydrogen, methyl, butyl, or octyl. 2 and R 3 However, they independently represent chloro or hydrogen, or R 2 and R 3 The above general formula (I) may also provide a 1,2-benzisothiazoline-3-one group.

[0086]

[0079] Furthermore, as discussed above, in one embodiment, the isothiazolinones of formula (I) are of formula (II)

[0087] [ka]

[0088] (In the formula, R is a hydroxyl, halogen (especially chlorine), C1-C4 alkyl, or C1-C4 alkoxy, R 1 (This is as previously defined herein, where n is between 0 and 4.) These are benzisothiazolinone compounds.

[0089] In this embodiment, R is located at one or both of the 5th and 6th positions of the phenyl ring of the benzisothiazolinone. However, in a further embodiment, n is zero.

[0090]

[0080] In one embodiment, the benzisothiazolinones of formula (II) are R 1 is H or C1-C5 alkyl, or R 1 The compound is H or C3-C5 alkyl. Examples of compounds of formula (II) include, for example, 1,2-benzisothiazolinone-3-one, Nn-butyl-, N-methyl-, N-ethyl-, Nn-propyl-, N-isopropyl-, Nn-pentyl-, N-cyclopropyl-, N-isobutyl-, and N-tert-1,2-benzisothiazolinone-3-one. Therefore, in one embodiment, the benzisothiazolinone of formula (I) is 1,2-benzisothiazolinone-3-one.

[0091]

[0081] For example, in one embodiment, isothiazolones include, but are not limited to, methylisothiazol-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT), octylisothiazol-3-one (OIT), 1,2-benzisothiazol-3(2H)-one (BIT), N-methyl-1,2-benzisothiazol-3-one (MBIT), and N-(n-butyl)-1,2-benzisothiazol-3-one (BBIT). Particularly preferred isothiazolones include, but are not limited to, methylisothiazol-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), octylisothiazol-3-one (OIT), 1,2-benzisothiazol-3(2H)-one (BIT), N-methyl-1,2-benzisothiazol-3-one (MBIT), and N-(n-butyl)-1,2-benzisothiazol-3-one (BBIT). Even more preferred isothiazole-3-ones are 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), octylisothiazolon (OIT), 1,2-benzisothiazolon-3(2H)-one (BIT), and N-(n-butyl)-1,2-benzisothiazolon-3-one (BBIT), more preferably octylisothiazolon (OIT), 1,2-benzisothiazolon-3(2H)-one (BIT), and N-(n-butyl)-1,2-benzisothiazolon-3-one (BBIT), or a combination thereof.

[0092]

[0082] In one embodiment, the formulation may include pyrithione compounds. For example, the pyrithione compounds may include sodium pyrithione, zinc pyrithione, copper pyrithione, 1-hydroxy-2-pyridinone, and pyrithione disulfide, as well as mixtures thereof.

[0093]

[0083] Nevertheless, if any further organic fungicidal preservatives are present, they 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. However, as discussed above, it should be understood that the preservative composition does not have to contain any one or a combination of the further organic fungicidal preservatives as a whole due to the unexpected synergies of the preservative compositions of this disclosure.

[0094]

[0084] Furthermore, in one embodiment, the preservative composition may include a solvent, a surfactant, a diluent, an emulsifier, or a combination thereof.

[0095]

[0085] For example, in one embodiment, the amounts and ratios referenced above correspond to a preservative composition that can be considered as a concentrate. Whether or not the preservative composition exists as a concentrate, it may contain a solvent, a surfactant, or a combination 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 form.

[0096]

[0086] 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 made 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.

[0097]

[0087] In one embodiment, the preservative composition is 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.

[0098]

[0088] 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 described above, in one embodiment the preservative composition in the form of a concentrate does not have to contain the solvent entirely and may therefore be in the form of a solid or a paste.

[0099]

[0089] For example, in one embodiment, the preservative composition comprises about 1% to about 50% 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 azoles, the remainder being a solvent, a surfactant, an emulsifier, an optional component (including further organic fungicidal preservatives) or a combination thereof.

[0100]

[0090] Furthermore, in some embodiments, the preservative composition comprises about 5% to about 32.5% 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, the remainder being a solvent, a surfactant, an emulsifier, an optional component (including further organic fungicidal preservatives) or a combination thereof.

[0101]

[0091] Additionally or alternatively, in one embodiment, the preservative composition comprises 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, the remainder being a solvent, a surfactant, an emulsifier, an optional component (including further organic fungicidal preservatives) or a combination thereof.

[0102]

[0092] Nevertheless, in one embodiment, 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 the diluent to the preservative composition of about 200:1 to about 1:1, 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, in one embodiment, the preservative composition is 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, or any range or value in between thereof.

[0103]

[0093] In other words, the diluent may be present in an amount such that copper ions are present in a ready-to-use formulation (e.g., a diluted preservative formulation) in an amount of about 1% by weight or less, for example, about 0.5% or less, for example, about 0.1% or less, for example, about 750 ppm or less, for example, about 500 ppm or less, for example, about 400 ppm or less, or any range or value in between thereof. Similarly, zinc ions may be present in a ready-to-use formulation in an amount such that copper ions are present in an amount of about 1% by weight or less, for example, about 0.5% or less, for example, about 0.1% or less, for example, about 750 ppm or less, for example, about 500 ppm or less, for example, about 400 ppm or less, for example, about 200 ppm or less, for example, about 100 ppm or less, or any value or range in between thereof. Boron ions 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. Additionally or alternatively, azoles 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.

[0104]

[0094] In one embodiment, the preservative composition or ready-to-use formulation 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, in one embodiment, the above pH values ​​refer to the pH of the preservative composition. Furthermore, in one embodiment, the ready-to-use formulation 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 known in the art, pH builders, pH buffers and other pH adjusters can be used to obtain and stabilize the above pH values.

[0105]

[0095] In one embodiment, the preservative formulation is used to treat cellulose or wood-based substrates. In one embodiment, cellulose materials that can be treated with the preservative compositions of the Disclosure include 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, the 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 composition is applied to sawn timber, logs or laminated veneers, OSB, or MDF, though not exclusively. In one embodiment, the substrate is wood or wood composite material intended to be wet throughout its lifespan, e.g., window frame wood, timber used on the ground in exposed environments, e.g., decking, and timber used in grounded or freshwater environments.

[0106]

[0096] In one embodiment, the cellulose or wood-based substrate to be treated is made up of approximately 150 grams (g / m³) of cellulose or wood-based substrate per cubic meter. 3 ) ~ approx. 7.5kg / m 3 For example, copper, about 200g / m 3 ~about 6kg / m 3 Copper, approximately 40g / m 3 ~about 2kg / m 3 For example, zinc, about 200 g / m² 3 ~Approx. 1.5kg / m 3 Zinc, approximately 20g / m² 3 ~about 3.5kg / m 3 The equivalent amount of boric acid, for example, about 40 g / m². 3 ~About 3kg / m 3 The equivalent amount of boric acid is approximately 10 g / m². 3 ~about 300g / m 3 Azoles, for example, about 20 g / m² 3 ~about 260g / m 3The materials can be treated with a preservative formulation (or a ready-to-use formulation) in an amount containing azoles or combinations thereof. For example, as shown in the examples, the disclosure has found that the preservative formulation can penetrate into the core of cellulose or wood-based products and distribute the preservative evenly.

[0107]

[0097] However, in some embodiments, the wood or cellulosic substrate may be treated with the ready-to-use preservative composition of the Disclosure. In such embodiments, the wood or cellulosic substrate may contain, in the amounts considered above, a copper-containing biocide, a zinc-containing biocide, boric acid, and tebuconazole relative to the ready-to-use composition.

[0108]

[0098] Nevertheless, in one embodiment, the disclosure further relates to a method for forming a preservative composition and a method for treating a wood-based substrate with the 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. Furthermore, in one embodiment, azoles, copper-containing biocides, zinc-containing biocides and boron-containing biocides may be pre-mixed as discussed above, but it should be understood that in some embodiments, the preservative composition may exist in a multi-part form and be mixed immediately before treating the wood or cellulosic substrate. However, in one embodiment, the preservative composition is in a partial form, e.g., a pack or a mix, containing azoles, copper-containing biocides, zinc-containing biocides and boron-containing biocides in the amounts discussed above.

[0109]

[0099] Regardless of the form of the preservative composition, it is used to treat wood or cellulosic substrates, diluted as discussed above in one embodiment. For example, in one embodiment, 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, or by impregnation of the wood or other material body, for example, by high-pressure or double-vacuum impregnation. In one embodiment, the method is impregnation under reduced pressure.

[0110]

[0100] Various boron-containing compounds can contain various levels of boron. Therefore, when comparing boron-containing compounds, it may be useful to convert the amount of one boron-containing compound to an equivalent amount based on the boron content of another boron-containing compound. In the following example, the boric acid equivalent was calculated using the following conversion coefficient:

[0111] [Table 1]

[0112]

[0101] For example, if zinc borate is retained in a wood block at a concentration of 1,000 ppm, the boric acid equivalent is 1,000 ppm. * 0.852 = 852 ppm.

[0113]

[0102] Furthermore, certain aspects of the present disclosure can be better understood by the following embodiments, which are intended to be non-limiting and illustrative in nature. [Examples]

[0114]

[0103] It is understood that the preservative compositions described in the examples may substantially not contain any substances not explicitly stated.

[0115] abbreviation

[0116] [Table 2]

[0117] 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.

[0118]

[0104] Particle size: Particle size was analyzed using a Horiba LA-910 particle size distribution analyzer (PSDA).

[0119] Example 1 AWPA E10-16 Soil / Block Test

[0105] Wood type: Southern Yellow Pine (SYP)

[0106] Microorganisms: The following organisms were used in this test: Fibroporia radiclosa and Fomitopsis palustris. Fibroporia radiclosa (basidiomycete) and Fomitopsis palustris (basidiomycete) are brown rot fungi that, due to their copper resistance, have been documented to cause premature damage to wooden piles treated with copper-based wood preservatives in the field.

[0120]

[0107] 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 to 0.5 microns, with D50 being 0.35 and D95 ​​being less than 1 micron.

[0121]

[0108] Soil block tests were conducted according to the procedure described in AWPA E10-16. The tests were performed on wood blocks that had been treated by vacuum impregnation with the wood preservative composition of the present invention before and after leaching by the microorganisms described above.

[0122]

[0109] 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.

[0123] [Table 3]

[0124]

[0110] The loss of large amounts of wood blocks indicates that a particular wood preservative composition fails to protect the wood from fungal attack. The retention level of a particular preservative corresponds to the minimum amount of preservative required to protect a wood block from fungal decay. Retention was calculated according to AWPA E10-16. The obtained weight loss data is summarized in Table 2.

[0125] [Table 4]

[0126]

[0111] 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.

[0127]

[0112] These and other modifications and changes to the present invention are within the scope of the appended claims. This invention can be implemented by those skilled in the art without departing from the spirit and scope of the invention, which will be shown in more detail. Furthermore, it should be understood that the various aspects are interchangeable, both whole and in part. Moreover, those skilled in the art will recognize that the foregoing description is merely illustrative and is not intended to limit the invention to those further described in the attached claims. The following is the description of the claims before amendment. [Claim 1] (a) Copper-containing biocides, (b) Zinc-containing biocides, (c) Boron-containing biocides including boric acid, disodium tetraborate pentahydrate, disodium octaborate tetrahydrate, or combinations thereof, and (d) Azoles A wood preservative composition containing, 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 approximately 15:1 to approximately 1:5. The copper-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the ratio of copper ions to boric acid equivalents is approximately 15:1 to approximately 1:5. Wood preservative composition. [Claim 2] The wood preservative composition according to claim 1, wherein the copper-containing biocide comprises basic copper carbonate, copper oxide, or a combination thereof. [Claim 3] The wood preservative composition according to claim 1 or 2, wherein the zinc-containing biocide comprises zinc oxide or a combination of zinc oxide and zinc borate. [Claim 4] The wood preservative composition according to any one of claims 1 to 3, wherein the boron-containing biocide is boric acid. [Claim 5] The wood preservative composition according to any one of claims 1 to 4, wherein the azoles include tebuconazole, penflufen, or a mixture thereof. [Claim 6] The wood preservative composition according to any one of claims 1 to 5, wherein the azoles include tebuconazole, propiconazole, or a mixture thereof. [Claim 7] The wood preservative composition according to any one of claims 1 to 6, wherein the azoles form a complex with a copper-containing biocide. [Claim 8] The wood preservative composition according to any one of claims 1 to 7, wherein the azoles include finely powdered azole particles, and 50% or more of the finely powdered azole particles have a particle size of less than about 1 micron. [Claim 9] The wood preservative composition according to any one of claims 1 to 8, 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. [Claim 10] The wood preservative composition according to any one of claims 1 to 9, wherein the copper-containing biocide constitutes about 0.1% to about 75% by weight of the composition, the zinc-containing biocide constitutes about 0.1% to about 50% by weight of the composition, the boron-containing biocide constitutes about 0.1% to about 75% by weight of the composition, and the azoles constitute about 0.1% to about 20% by weight of the composition. [Claim 11] A wood preservative composition according to any one of claims 1 to 10, having a pH of approximately 3 to approximately 10. [Claim 12] A wood preservative composition according to any one of claims 1 to 11, further comprising alkanolamines. [Claim 13] The wood preservative composition according to any one of claims 1 to 12, wherein 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 about 10:1 to about 2:1. [Claim 14] The wood preservative composition according to any one of claims 1 to 13, wherein the copper-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the ratio of copper ions to boric acid equivalents is about 10:1 to about 2:1. [Claim 15] The wood preservative composition according to any one of claims 1 to 14, wherein the zinc-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the ratio of zinc ions to boric acid equivalents is about 5:1 to about 1:5. [Claim 16] The wood preservative composition according to any one of claims 1 to 15, wherein the zinc-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the ratio of zinc ions to boric acid equivalents is about 3:1 to about 1:1.5. [Claim 17] A wood-based product treated with the wood preservative composition according to any one of claims 1 to 16. [Claim 18] Copper ions are present in wood-based products at a concentration of approximately 200 grams (g / m³) per cubic meter of the product. 3 ) ~ approx. 7.5kg / m 3 The amount of zinc ions present in the wood-based product is approximately 40 g / m² of the product. 3 ~Approx. 1.5kg / m 3 It is present in an amount of approximately 40 g / m² of the wood-based product, and the boric acid equivalent is approximately 40 g / m² of the product. 3 ~About 3kg / m 3 The amount present is approximately 20 g / m² of the wood-based product, and the azoles are present in the wood-based product. 3 ~about 280g / m 3 The wood-based product according to claim 17, which exists in the quantity of [amount]. [Claim 19] (a) Copper-containing biocides, (b) Zinc-containing biocides, (c) Boron-containing biocides containing boric acid, and (d) Azoles A wood preservative composition containing, 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 approximately 15:1 to approximately 3:1. The copper-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the ratio of copper ions to boric acid equivalents is approximately 15:1 to approximately 1:1. A wood preservative composition comprising: a copper-containing biocide containing basic copper carbonate; a zinc-containing biocide containing zinc oxide or a combination of zinc oxide and zinc borate; a boron-containing biocide containing boric acid; and an azole containing tebuconazole. [Claim 20] A method for treating wood with a wood preservative composition according to any one of claims 1 to 19, wherein a copper-containing biocide, a zinc-containing biocide, a boron-containing biocide, and azoles are injected into the wood in a single step. [Claim 21] A method for producing a wood preservative composition, (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 at least one type of azole, (c) The step of combining a 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 approximately 15:1 to approximately 1:5. A method wherein the copper-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the ratio of copper ions to boric acid equivalents is about 15:1 to about 1:5. [Claim 22] The method according to claim 21, further comprising the step of grinding the copper-containing biocide and the zinc-containing biocide together with at least one dispersant. [Claim 23] Any combination of the methods of claims 21 and 22, wherein the copper-containing biocide constitutes about 1% to about 75% by weight of the composition, the zinc-containing biocide constitutes about 0.1% to about 50% by weight of the composition, the boron-containing biocide constitutes about 0.1% to about 75% by weight of the composition, and the azoles constitute about 0.1% to about 20% by weight of the composition. [Claim 24] The method according to any one of claims 21 to 23, 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.

Claims

1. (a) Copper-containing biocides, (b) Zinc-containing biocides, (c) Boron-containing biocides comprising boric acid, disodium tetraborate pentahydrate, disodium octaborate tetrahydrate, or combinations thereof, and (d) Azoles A wood preservative composition containing, 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:

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

5. Wood preservative composition.

2. The wood preservative composition according to claim 1, wherein the copper-containing biocide comprises basic copper carbonate, copper oxide, or a combination thereof.

3. The wood preservative composition according to claim 1 or 2, wherein the zinc-containing biocide comprises zinc oxide or a combination of zinc oxide and zinc borate.

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

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

6. The wood preservative composition according to any one of claims 1 to 5, wherein the azoles include tebuconazole, propiconazole, or a mixture thereof.

7. The wood preservative composition according to any one of claims 1 to 6, wherein the azoles form a complex with a copper-containing biocide.

8. The wood preservative composition according to any one of claims 1 to 7, wherein the azoles include finely powdered azole particles, and 50% or more of the finely powdered azole particles have a particle size of less than 1 micron.

9. The wood preservative composition according to any one of claims 1 to 8, wherein 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.

10. The wood preservative composition according to any one of claims 1 to 9, wherein the copper-containing biocide constitutes 0.1% to 75% by weight of the composition, the zinc-containing biocide constitutes 0.1% to 50% by weight of the composition, the boron-containing biocide constitutes 0.1% to 75% by weight of the composition, and the azoles constitute 0.1% to 20% by weight of the composition.

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

12. A wood preservative composition according to any one of claims 1 to 11, further comprising alkanolamines.

13. The wood preservative composition according to any one of claims 1 to 12, wherein 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 10:1 to 2:

1.

14. The wood preservative composition according to any one of claims 1 to 13, wherein the copper-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the ratio of copper ions to boric acid equivalents is 10:1 to 2:

1.

15. The wood preservative composition according to any one of claims 1 to 14, wherein the zinc-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the ratio of zinc ions to boric acid equivalents is 5:1 to 1:

5.

16. The wood preservative composition according to any one of claims 1 to 15, wherein the zinc-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the ratio of zinc ions to boric acid equivalents is 3:1 to 1:1.

5.

17. A wood-based product treated with a wood preservative composition according to any one of claims 1 to 16.

18. Copper ions are present in wood-based products at a concentration of 200 grams (g / m³) per cubic meter of the product. ３ ) ~7.5 kg / m ３ The amount present in the wood-based product is 40 g / m of the product, and zinc ions are present in the wood-based product. ３ ~1.5 kg / m ３ It is present in an amount of 40 g / m² of the wood-based product, and the boric acid equivalent is present in the wood-based product. ３ ~3 kg / m ３ The azoles are present in the wood-based product at a concentration of 20 g / m² of the product. ３ ~280g / m ３ The wood-based product according to claim 17, which exists in the amount of [amount].

19. (a) Copper-containing biocides, (b) Zinc-containing biocides, (c) Boron-containing biocides containing boric acid, and (d) Azoles A wood preservative composition containing, 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 3:

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 boric acid equivalents is 15:1 to 1:

1. A wood preservative composition comprising: a copper-containing biocide containing basic copper carbonate; a zinc-containing biocide containing zinc oxide or a combination of zinc oxide and zinc borate; a boron-containing biocide containing boric acid; and an azole containing tebuconazole.

20. A method for treating wood with a wood preservative composition according to any one of claims 1 to 19, wherein a copper-containing biocide, a zinc-containing biocide, a boron-containing biocide, and azoles are injected into the wood in a single step.

21. A method for producing a wood preservative composition, (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 at least one type of azole, (c) The step of combining a 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:

5. A method wherein the copper-containing biocide and the boron-containing biocide are present in the wood preservative composition such that the ratio of copper ions to boric acid equivalents is 15:1 to 1:

5.

22. The method according to claim 21, further comprising the step of grinding the copper-containing biocide and the zinc-containing biocide together with at least one dispersant.

23. The method according to either claim 21 or 22, wherein the copper-containing biocide constitutes 1% to 75% by weight of the composition, the zinc-containing biocide constitutes 0.1% to 50% by weight of the composition, the boron-containing biocide constitutes 0.1% to 75% by weight of the composition, and the azoles constitute 0.1% to 20% by weight of the composition.

24. The method according to any one of claims 21 to 23, 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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