Aqueous wood preservative and manufacturing method therefor

Abstract

An aqueous wood preservative, according to the present invention, includes an aqueous wood preservative comprising a nano-sol solution containing: an inorganic biocide containing an insoluble copper compound having an average particle size of 1 to 1,000 nm; and a dispersant containing aliphatic amine.

Description

Aqueous wood preservative and method for producing the same

[0001] The present invention relates to an aqueous wood preservative and a method for producing the same, and more particularly, to an aqueous wood preservative comprising an inorganic nano-sol and a method for producing the same.

[0002] Wood preservatives protect wood and other wood-based materials, such as paper, particle board, and oriented strand board (OSB), from fungi, mold, microorganisms, and wood-damaging pests.

[0003] There are three main types of wood preservatives: creosote oil, oil-based and water-based, and wood preservatives.

[0004] Creosote oil was used to preserve wood until the mid-1960s, but it is made by distilling coal tar, which is obtained by dry-distilling coal at high temperatures. It is composed of polycyclic aromatic hydrocarbons (PAHs), which are high in harmful volatile components. In addition, high-boiling oils remain in the wood for a long time, causing a foul odor and poor paintability. Therefore, its use is limited for residential purposes and is only used in special cases.

[0005] Oil-based preservatives are typically made by dissolving in a specific type of light petroleum, such as AWPA P9 Type A, and their active ingredients include pentachlorophenol, copper naphthenate, and copper-8-quinolinolate. These preservatives often leave a paint-resistant surface, sometimes leaving an unnatural, light black stain on wood surfaces, and because the oils are irritating to human skin, they are only suitable for industrial applications, such as on utility poles and railroad ties.

[0006] Water-based preservatives can be divided into three types according to the time of appearance.

[0007] Known first-generation preservatives include chromated copper arsenate (CCA), ammoniacal copper arsenate (ACA), and ammoniacal copper zinc arsenate (ACZA).

[0008] The most commonly used first-generation preservative is CCA. It has been used for a long time due to its low leaching potential. Among these components, chromium is related to wood anchorage, and arsenic is known to be effective against wood-resistant fungi. These components are water-soluble when applied to wood, but after incorporation into wood, they are converted into water-insoluble substances by the cellulose, hemicellulose, and lignin within the wood. This makes them less leaching potential than other wood preservatives and offers economic advantages.

[0009] However, CCA was voluntarily discontinued as a wood preservative for residential use in both foreign and domestic countries around 2000 due to problems with chromium and arsenic, and is now used only in limited, special purposes.

[0010] Second-generation preservatives are characterized by their use of ionic copper compounds in a composition that excludes chromium and arsenic, which cause environmental problems.

[0011] Known compounds of second-generation preservatives include copper alkanolamine complexes, copper polyaspartic acid complexes, copper boron azole, copper bis(dimethyldithiocarbamate), ammoniacal copper citrate, ammoniacal copper quat (ACQ), and copper azole (CA).

[0012] Unlike CCA, these second-generation wood preservatives lack arsenic compounds and, as a result, utilize cationic surfactants such as Didecyl Dimethyl Ammonium Chloride (DDAC) or triazole compounds to combat copper-resistant bacteria. When combined with DDAC, they are collectively known as Alkaline Copper Quaternary (ACQ), and when combined with triazole compounds, they are collectively known as Copper Azole (CA).

[0013] However, second-generation water-based wood preservatives use ionic copper compounds, which can cause corrosion of wood fasteners, promote the growth of wood surface contaminants (sapstains), require the use of expensive amines, and cause the wood to turn green or gray-green due to a chemical reaction between the ionic copper components and the sun's ultraviolet rays.

[0014] To overcome the shortcomings of these second-generation wood preservatives, third-generation wood preservatives whose main component is so-called micronized copper particles, which are made by crushing micro-sized, water-soluble copper compound particles into nano-sized particles by applying physical force through a grinding medium such as a bead mill, have emerged since the early 2000s.

[0015] However, third-generation water-based wood preservatives are limited to use in easily treatable woods such as Southern Yellow Pine (SYP) and refractory woods such as spruce.

[0016] Therefore, there is a need for the development of a water-based wood preservative that is easy to inject into difficult-to-inject wood.

[0017] The present invention aims to provide an aqueous wood preservative that does not contain harmful substances and is easy to inject into wood, and a method for producing the same.

[0018] This application claims priority to Republic of Korea Patent Application No. 10-2024-0046613, filed April 5, 2024, the entire contents of which are incorporated herein by reference.

[0019] The present invention provides an aqueous wood preservative comprising a nano-sol solution containing an inorganic biocide containing a sparingly soluble copper compound having an average particle size of 1 to 1000 nm; and a dispersant containing an aliphatic amine.

[0020] In addition, the present invention provides a method for producing an aqueous wood preservative, comprising the steps of forming a dispersion by mixing a copper salt aqueous solution and a dispersant containing an aliphatic amine, and adding a base dropwise to the dispersion to obtain an aqueous wood preservative comprising a nano-sol solution in which an inorganic biocide containing a sparingly soluble copper compound having an average particle size of 1 to 1000 nm is dispersed.

[0021] The water-based wood preservative according to the present invention has the advantages of being easily injected into injectable wood, containing substantially no harmful substances, being biologically active, and being inexpensive.

[0022] In addition, the method for manufacturing a water-based wood preservative according to the present invention has the advantage of being able to manufacture a water-based wood preservative that can be easily injected into difficult-to-inject wood.

[0023] Figures 1 to 9 show the results of measuring the particle distribution of nano-sols in which an inorganic biocide containing a sparingly soluble metal compound, which is included in a water-based wood preservative manufactured according to some embodiments of the present invention, is dispersed.

[0024] Figure 10 is an image showing the appearance of wood treated with a water-based wood preservative and ACQ manufactured according to an embodiment.

[0025] FIG. 11 is an SEM and SEM-Energy Dispersed X-ray Analysis (EDXA) image measuring the dispersion of copper and chlorine distributed in wood treated with a water-based wood preservative manufactured according to an embodiment of the present invention.

[0026] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention. The present invention is defined solely by the scope of the claims set forth below.

[0027]

[0028] When a part of the present invention is said to "include" a certain component, this does not mean that other components are excluded, but rather that other components may be included, unless otherwise specifically stated.

[0029]

[0030] <Water-based wood preservative>

[0031] One aspect of the present invention relates to an aqueous wood preservative comprising a nano-sol solution comprising an inorganic biocide containing a sparingly soluble copper compound having an average particle size of 1 to 1000 nm; and a dispersant containing an aliphatic amine.

[0032] The water-based wood preservative according to the present invention has the advantage of excellent wood injectability by containing substantially no ㎛-sized metal compounds and containing metal compounds having an average particle size of 1 to 1000 nm, specifically 1 to 300 nm. In addition, it has the advantage of minimizing leaching of inorganic and organic biocides after injecting into wood, containing substantially no harmful substances, and exhibiting excellent biological activity.

[0033]

[0034] In the present invention, “substantially free of harmful substances” means substantially free of harmful substances such as arsenic, chromium, etc. Substantially free of harmful substances such as arsenic, chromium, etc. means that these components are present in an amount of less than 5 parts by weight, preferably less than 1 part by weight, more preferably less than 0.1 part by weight, and most preferably less than 0.01 part by weight, based on 100 parts by weight of the dry weight of the water-based wood preservative.

[0035]

[0036] In the present invention, “biological activity” means that the preservative treatment has a sufficient biocidal effect against at least one unwanted organism among the wood-damaging microorganisms that are the target of the water-based wood preservative.

[0037]

[0038] In the present invention, "wood" means wood; wood-based materials; wood fiber materials; forest products, wood products, engineered wood, woodworking; furniture manufacturing, wood laminates; laminated veneer, plywood (LVL); laminated strand lumber (LSL) and lumber.

[0039]

[0040] In the present invention, "wood products" may include, for example, oriented strand board (OSB); fiber composites; medium-density fiberboard (MDF); particle board (PB); rigid board; oriented strand board (OSB); wood fiber resin composites; plywood; hardboard, etc.

[0041]

[0042] In the present invention, "material" may refer to an engineered wood composite selected from the group consisting of plywood, laminated veneer, glued laminated wood ("glulam"), cross-laminated wood, and oriented strand board.

[0043]

[0044] In the present invention, "preservative" refers to a composition that, when applied to wood or wood products, increases the resistance or tolerance of cellulosic materials to microbial attack such as insects, fungi or imperfect mold.

[0045]

[0046] In the present invention, “wood-damaging microorganisms” refer to fungi and wood pests. Among these, the fungi include brown rots, such as Postia placenta, Gloeophyllum trabeum, and Coniophora puteana; white rots, such as Irpex lacteus and Trametes versicolor; dry rots, such as Serpula lacrymans; and soft rots, such as Cephalosporium, Acremonium, and Chaetomium.

[0047] The above-mentioned wood pests include, for example, termites, beetles, ants, and bees. The above-mentioned wood-damaging organisms damage wood, causing undesirable characteristics such as decay, loss of strength, and discoloration.

[0048]

[0049] In the present invention, “injectable” means that the nano-sized fine particles of the aqueous wood preservative, that is, the inorganic biocide containing a sparingly soluble copper compound having an average particle size of 1 to 1000 nm and other fine particles can be pressurized and injected into wood, wood products, etc. to a depth generally required in the industry, and that the effective dispersion of the biocide particles throughout the injected volume can be provided using appropriate equipment and pressure.

[0050] Additionally, the particulates should have substantially no tendency to form a powdery green residue on or near the wood surface, which may accumulate and form unsightly staining. This may be related to the particle size, particle shape, particle concentration, and particle size distribution, as well as to the wood itself.

[0051]

[0052] In the present invention, "non-staining," or more specifically, "non-staining," means that the water-based wood preservative does not impart an undesirable color to the wood. Large particles or large clumps of small particles impart a visible, undesirable color to the treated wood, and copper typically exhibits a bluish or greenish color. However, the water-based wood preservative according to the present invention is a non-staining preservative and can suppress the formation of color.

[0053]

[0054] The water-based wood preservative according to the present invention comprises an inorganic biocide containing a sparingly soluble copper compound having an average particle size of 1 to 1000 nm.

[0055] The above-mentioned insoluble copper compound has superior biological activity compared to metal compounds containing cobalt, nickel, tin, silver, zinc, etc., and has an advantage over other metal compounds in that it has an ability to bind to wood components when treated by an appropriate method.

[0056]

[0057] In one embodiment of the present invention, the insoluble copper compound may include at least one selected from the group consisting of copper hydroxide, copper oxide, basic copper carbonate, copper oxychloride, basic copper sulfate, basic copper nitrate, and basic copper acetate.

[0058] In another embodiment of the present invention, the sparingly soluble copper compound may be copper oxychloride (COC).

[0059] When the above-mentioned insoluble copper compound is copper oxychloride, it has a lower solubility than other basic copper compounds, which is preferable in terms of content release.

[0060] In another embodiment of the present invention, the inorganic biocide may be dispersed in the form of a nanosol solution.

[0061] In short, the above-mentioned insoluble copper compound is dispersed in the form of the above-mentioned nanosol solution.

[0062]

[0063] In another embodiment of the present invention, the sparingly soluble copper compound may have an average particle size of 1 to 300 nm.

[0064] Specifically, the inorganic biocide may contain the sparingly soluble copper compound having an average particle size satisfying the above range.

[0065] In short, the above-mentioned inorganic biocide is a poorly soluble inorganic biocide.

[0066] The above-mentioned inorganic biocide may be included in an amount of 1 to 30 parts by weight, preferably 3 to 20 parts by weight, and more preferably 5 to 15 parts by weight, based on 100 parts by weight of the total nano-sol solution.

[0067] When the above-mentioned inorganic biocide is included within the above range relative to 100 parts by weight of the entire nano-sol solution, it is preferable because it has the advantage of forming a stable nano-sol solution with a uniform and low viscosity without settling particles.

[0068]

[0069] The water-based wood preservative according to the present invention comprises a dispersant containing an aliphatic amine.

[0070] In another embodiment of the present invention, the aliphatic amine may include at least one selected from the group consisting of primary amines, secondary amines, tertiary amines, and ethoxylated aliphatic amines.

[0071]

[0072] The above primary amine can be represented by the following chemical formula 1.

[0073] [Chemical Formula 1]

[0074] R1-NH2

[0075] The above secondary amine can be represented by the following chemical formula 2.

[0076] [Chemical Formula 2]

[0077]

[0078] The above tertiary amine may be represented by any one of the following chemical formulas 3 to 5.

[0079] [Chemical Formula 3]

[0080]

[0081] [Chemical Formula 4]

[0082]

[0083] [Chemical Formula 5]

[0084]

[0085] In the above chemical formulas 1 to 5,

[0086] R1 to R9 may independently be groups derived from a fatty acid containing carbon atoms of C10 to C24, preferably carbon atoms of C10 to C22, more preferably carbon atoms of C10 to C20, and even more preferably carbon atoms of C10 to C18.

[0087] Specifically, R1 can be lauryl, myristyl; palmityl, stearyl or oleyl.

[0088] The above secondary amine may include at least one selected from the group consisting of diethanolamine, triethylene tetraamine, N-methylethanolamine, diethylenetriamine, and diethylene triamine.

[0089] The above tertiary amine may include at least one selected from the group consisting of methyl diethanolamine, N-butylethanolamine, diethylaminoethanol, and triethanolamine.

[0090]

[0091] The above aliphatic amine may be a monoamine, a diamine, a triamine or a tetraamine.

[0092] The above monoamine may be, for example, a C8 to C18 alkyl amine, specifically, but not limited to, octyl amine, dodecyl amine, hexadecyl amine, octadecyl amine or oleyl amine.

[0093]

[0094] The above diamine can be represented by the general formula (R10)NH(R11)NH(R12).

[0095] The above R10 may be an aliphatic group of C8 to C20.

[0096] The above R11 may be a C2 to C5 alkylene group.

[0097] The above R12 may be hydrogen or an aliphatic group of C8 to C20.

[0098]

[0099] In the present invention, the "aliphatic group" may be a saturated aliphatic group or an unsaturated aliphatic group. The aliphatic group may preferably be a hydrocarbon group. The aliphatic group may be chain-shaped, cyclic, or a combination of chain-shaped and cyclic aliphatic groups. The chain-shaped aliphatic group may have branches.

[0100] Specifically, the above R10 may be a C10 to C18 aliphatic group derived from a fatty acid, R11 may be a propylene group, and R12 may be hydrogen.

[0101] The diamine may be, for example, N-coco-1,3-propylene diamine, N-oleyl-1,3-propylene diamine or N, N-tallow-1,3-propylene diamine.

[0102] The above diamine is available from Nouryon under the trade name Duomeen. TM It is commercially available as, preferably N-coco-1,3-propylene diamine (Duomeen TM C) may be.

[0103] The triamine may be, for example, N-tallow-dipropylene triamine, N-coco-dipropylene triamine or N-oleyl-dipropylene triamine. The triamine is available under the trade name Triameen. TM It is commercially available from Nouryon.

[0104] The tetraamine may be, for example, N-tallow-tripropylene tetramine, N-coco-tripropylene tetramine or N-oleyl-tripropylene tetramine.

[0105] The above tetraamine is a brand name Tetrameen TM It is commercially available from Nouryon.

[0106]

[0107] The above ethoxylated fatty amine may include an ethoxylated propoxy fatty amine.

[0108] The above ethoxylated aliphatic amine can be represented by the following chemical formula 6.

[0109] [Chemical Formula 6]

[0110]

[0111] In the above chemical formula 6,

[0112] R13 is a hydrocarbon group of R1 to R30,

[0113] c and d independently represent 1 to 50 moles of ethylene oxide (EO),

[0114] x and y independently represent 0 to 20 moles of propylene oxide (PO),

[0115] The sum of c, d, x and y is at least 1, and preferably may be from 2 to 22.

[0116] In the above chemical formula 6, the appropriate group can be independently placed on each amine and substituent chain. For example, it can be EO-PO-EO, EO-EO-PO, EO-EO-EO, PO-PO-PO, EO-PO-PO, PO-EO-PO.

[0117] The hydrocarbon group may be a linear, branched or cyclic aliphatic group. The hydrocarbon group may contain an ethylenically unsaturated group.

[0118] Preferred aliphatic groups may be selected from alkyl groups and their substituted alkyl groups such as long chain alkyl groups preferably having from 6 to 30 carbon atoms such as stearyl, lauryl, oleyl, cetyl, tridecyl, tetradecyl, hexadecyl, dodecyl.

[0119] Additionally, octadecyl, nonadecyl, tallow, coco, soy, palmityl, myristyl and other natural fatty radicals of animal, fish, vegetable and oilseed sources (coconut oil; palm kernel oil; rapeseed oil; sunflower seed oil, etc.) or substituted groups thereof may be derived from natural or synthetic sources.

[0120] In another embodiment of the present invention, the aliphatic amine is N-coco-1,3-propylene diamine, N-oleyl-1,3-propylene diamine, N-tallow-1,3-propylene diamine, N-tallow-dipropylene triamine, N-coco-dipropylene triamine, N-oleyl-dipropylene triamine, N-tallow-dipropylene triamine, N-coco-dipropylene triamine, N-oleyl-dipropylene triamine, cocamine It may be at least one selected from the group consisting of ethoxylate, cocamine ethoxylate propoxylate, laurylamine ethoxylate, laurylamine ethoxylate propoxylate, tallowamine ethoxylate, tallowamine ethoxylate propoxylate, oleylamine ethoxylate, oleylamine ethoxylate propoxylate, stearylamine ethoxylate, stearylamine ethoxylate propoxylate, myristylamine ethoxylate, myristylamine ethoxylate propoxylate, cetylamine ethoxylate, and cetylamine ethoxylate propoxylate.

[0121]

[0122] In another embodiment of the present invention, the dispersant may be included in an amount of 1 to 30 parts by weight, preferably 2 to 20 parts by weight, and more preferably 3 to 10 parts by weight, based on 100 parts by weight of the total nano-sol solution.

[0123] When the above dispersant is included within the above range, the dispersing effect is excellent, and the viscosity of the nano sol solution is appropriate, so the stability of the nano sol solution is excellent, which is preferable.

[0124]

[0125] In another embodiment of the present invention, the water-based wood preservative may further include an organic biocide comprising at least one selected from the group consisting of long-chain quaternary ammonium compounds, aromatic quaternary ammonium compounds, and triazole compounds.

[0126] The above organic biocide may include at least one selected from the group consisting of fungicides, moldicides, termiticides, insecticides, algaecides and bactericides.

[0127]

[0128] The above organic biocide can be effective not only against white rot fungi but also against brown rot fungi.

[0129] The above copper compounds are highly effective against white rot fungi, but may be somewhat less effective against brown rot fungi consisting of copper-resistant fungi. Therefore, if an organic biocide consisting of a long-chain quaternary ammonium compound, an aromatic quaternary ammonium compound, and a triazole compound is included, the effect against brown rot fungi can be increased.

[0130] Specifically, the organic biocide may include a surfactant or a triazole compound including a long-chain quaternary ammonium compound or an aromatic quaternary ammonium compound.

[0131] The above quaternary ammonium compound and the above aromatic quaternary ammonium compound have surfactant properties and biocidal performance, and have the effect of destroying cell membranes, so they can exhibit bacteriostatic or bactericidal properties depending on the concentration.

[0132] The above long-chain quaternary ammonium compound and the above aromatic quaternary ammonium compound can be represented by the following chemical formula 7.

[0133] [Chemical Formula 7]

[0134]

[0135] In the above chemical formula 7,

[0136] R14 to R17 are independently C1 to C20 alkyl or C6 to C20 aryl groups,

[0137] X - may be chloride, bromide, iodide, carbonate, bicarbonate, borate, carboxylate, hydroxide, sulfate, acetate, laurate, or any other anionic group.

[0138] In the present invention, “alkyl” may be straight chain or branched chain, and for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc. However, it is not limited to these.

[0139] In the present invention, “aryl” may be a monocyclic aryl group or a polycyclic aryl group. The monocyclic aryl group may include, but is not limited to, a phenyl group, a biphenyl group, a terphenyl group, a stilbenyl group, and the like. The polycyclic aryl group may include, but is not limited to, a naphthyl group, anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like.

[0140] Specifically, the quaternary ammonium compounds are didecyldimethylammonium chloride (or bromide, carbonate / bicarbonate), alkyldimethylbenzylammonium chloride (or bromide, carbonate / bicarbonate), didodecyldimethylammonium chloride (or bromide, carbonate / bicarbonate), tetradecyltrimethyl ammonium chloride (or bromide, carbonate / bicarbonate), myristyltrimethyl ammonium chloride (or bromide), carbonate / bicarbonate, benzethonium chloride (or bromide, carbonate / bicarbonate), benzethonium chloride (or bromide, carbonate / bicarbonate), stearalkonium chloride (or bromide, carbonate / bicarbonate), docetriyltrimethyl-ammonium chloride (or bromide, carbonate / bicarbonate), lauryl trimethyl ammonium chloride (or Examples include, but are not limited to, bromides, carbonates / bicarbonates), didodecyldimethylammonium propionate, N,N-didecyl-N-methyl-poly(oxyethyl)ammonium propionate, etc.

[0141] More specifically, the quaternary ammonium compound may be didecyldimethylammonium chloride, didecyldimethylammonium carbonate / bicarbonate, alkyldimethylbenzylammonium chloride, or didodecyldimethylammonium chloride.

[0142] Antrodia spp., such as Antrodia vaillantii, Antrodia sinuosa, and Antrodia radiculosa, are known as decay fungi that secrete excessive oxalic acid and thus can withstand preservatives containing chromate. However, when a quaternary ammonium compound is included, it is effective against Antrodia spp. Specifically, when the inorganic biocide according to the present invention, more specifically, the inorganic biocide including a copper compound, and the quaternary ammonium compound as the organic biocide are used together, it is advantageous in that it is effective against Antrodia spp.

[0143] The above triazole compound may refer to any compound having biocidal activity containing a triazole group.

[0144] The above triazole compound can be represented by the following chemical formula 8 or 9.

[0145] [Chemical Formula 8]

[0146]

[0147] [Chemical Formula 9]

[0148]

[0149]

[0150] In the above chemical formulas 8 and 9,

[0151] R18 is a branched or straight-chain C1 to C5 alkyl group,

[0152] R19 and R20 are phenyl groups optionally substituted with one or more substituents selected from halogen, C1 to C3 alkyl, C1 to C3 alkoxy, phenyl and nitro,

[0153] R21 is a phenyl group substituted with a hydrogen atom or a C1 to C5 straight or branched chain alkyl group.

[0154] The above alkyl group can be applied as described above.

[0155] The above halogen element may be chlorine, fluorine or bromine.

[0156] The triazole compound may include, for example, at least one selected from the group consisting of azaconazole, hexaconazole, imibenconazole, tetraconazole, fenaconazole, methaconazole, bitteranol, difenoconazole, diniconazole, epoxiconazole, fluquinazole, fluciazole, flutriafol, imazalil, ipconazole, pyrifenox, prochloraz, triadimefon, triadleneol, tripumizole, tebuconazole, propiconazole, siproconazole, and triticonazole.

[0157] Preferably, the triazole compound may include at least one selected from the group consisting of tebuconazole, propiconazole, and ciproconazole.

[0158] The inclusion of the above triazole compound is preferred because it enhances fungicidal activity. Specifically, the use of the inorganic biocide according to the present invention, more specifically, the inorganic biocide comprising a copper compound, together with the above triazole compound as the organic biocide is preferred because it enables the imparting of excellent fungicidal activity.

[0159]

[0160] The organic biocide may be provided in an aqueous emulsion or solubilized form by emulsifying the organic biocide compound with the help of one or more emulsifiers or solubilizers. The emulsifiers or solubilizers may include one or more selected from the group consisting of cationic and nonionic surfactants.

[0161] For example, the emulsifier or solubilizer may be, but is not limited to, an alkyl phenol, an amine, an amide, an aryl phenol, a fatty ester, a fatty acid and derivatives, an ethoxylated alcohol and derivatives, a sulfonated amine, a carboxylated alcohol, an alkyl phenol ethoxylate, a glycol ether or a glycol ester.

[0162]

[0163] In another embodiment of the present invention, the organic biocide may be included in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, and more preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of the total nano sol solution.

[0164]

[0165] In another embodiment of the present invention, the composition may further include at least one auxiliary dispersant selected from the group consisting of cationic and nonionic surfactants, at least one selected from the group consisting of water, a co-biocide, a neutralizing agent, a rust inhibitor, and a functional additive.

[0166]

[0167] The auxiliary dispersant comprising at least one selected from the group consisting of the cationic and nonionic surfactants may be included to enhance the particle size of the metal compound, the dispersion state, the metal compound, specifically the metal compound's response to resistant bacteria, and the penetration into wood.

[0168]

[0169] The above nonionic surfactant may include an amine oxide. When the amine oxide is included as the auxiliary dispersant, penetration of the aqueous wood preservative is promoted, which is preferable.

[0170] The above amine oxide may be a trialiphatic substituted amine oxide. The above trialiphatic substituted amine oxide may refer to a compound formed as a reaction product in the reaction of an amine and hydrogen peroxide.

[0171] The above trialiphatic substituted amine oxide can be represented by the following chemical formula 10.

[0172] [Chemical Formula 10]

[0173] R22R23R24N→O

[0174] In the above chemical formula 10,

[0175] Arrows indicate semipolar bonds,

[0176] R22 may be a linear or cyclic group having C6 to C40 saturated or unsaturated groups, such as coco, hydrogenated resin, soybean, decyl, hexadecyl, oleyl, or any combination thereof.

[0177] R23 and R24 are independently a saturated or unsaturated group having C1 to C40, which is linear, branched, cyclic or any combination thereof.

[0178] The above amine oxide type auxiliary dispersant is, for example, coconut, tallow alkyldi-(alkyl)amine oxide, dodecyldimethylamine oxide, tridecyldimethylamine oxide, tetradecyldimethylamine oxide, pentadecyldimethylamine oxide, hexadecyldimethylamine oxide, heptadecyldimethylamine oxide, octadecyldimethylamine oxide, dodecyldipropylamine oxide, tetradecyldipropylamine oxide, hexadecyldipropylamine oxide, tetradecyldibutylamine oxide, octadecyldibutylamine oxide, bis(2-hydroxyethyl)dodecyl amine oxide, bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamine oxide or 3-Dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide. Some of the above amine oxides are commercially available as Barlox™, FMBAO-8™ (trade name of Lonza), and Aromox™ (trade name of Nouryon).

[0179]

[0180] The above nonionic surfactants are generally characterized by the presence of organic hydrophobic groups and organic hydrophilic groups, and are typically produced by the condensation of an organic aliphatic, alkyl aromatic or polyoxyalkylene hydrophobic compound with a hydrophilic alkaline oxide moiety.

[0181] The length of the hydrophilic polyoxyalkylene moiety condensed with any particular hydrophobic compound can be readily adjusted to produce a water-dispersible or water-soluble compound having a desired balance between hydrophilic and hydrophobic properties.

[0182] The above nonionic surfactant may include:

[0183] (1) A compound in which an alkylene oxide (hereinafter abbreviated as AO: C2 to C4, for example, ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO) and / or a combination of two or more thereof) is added to a higher alcohol (C8 to C18), a higher fatty acid (C12 to C24), an alkyl phenol or a higher alkyl amine (C8 to C24), etc. [number average molecular weight (hereinafter abbreviated as Mn) 174 to 200,000: Mn is a value measured by GPC], and some specific examples may include an alkyl chain of C6 to C18.

[0184] Typical examples of these are EO, PO, BO adducts such as coconut oil, lauric acid, stearic acid, oleic acid, tall oil, etc., ABA type block type and mixtures thereof. A specific example of ABA type block type is Pluronic, a brand name manufactured by BASF Corp. TM and Tetronic TM is commercially available.

[0185] The above Pluronic TM The compound is a difunctional (two reactive hydrogen) compound formed by condensing EO with a hydrophobic base formed by adding PO to the two hydroxyl groups of propylene glycol. The molecular weight of this hydrophobic portion of the molecule ranges from about 1,000 to about 4,000.

[0186] Tetronic above TM The compound is a tetrafunctional block copolymer derived by sequentially adding propylene oxide and ethylene oxide to ethylenediamine. The molecular weight of the propylene oxide hydrotype ranges from about 500 to about 7,000.

[0187] (2) Examples include those obtained by reacting polyalkylene glycols (Mn=110∼6,000) obtained by adding AO to glycols with higher fatty acids.

[0188] (3) Examples include those in which AO is added to an ester compound obtained by reacting a higher fatty acid with a polyhydric alcohol (e.g., dihydric to octahydric or higher polyhydric alcohol such as ethylene glycol; propylene glycol; glycerin; pentaerythritol; sorbitan, etc.).

[0189] (4) An exemplary product obtained by adding AO to a higher fatty acid amide (Mn = 243 to 30,000) is a condensation product of 10 to 30 mol of ethylene oxide and coconut oil amine and amide. It is possible to form a block copolymer by condensing the same fatty acid amine or amide with a different alkylene oxide.

[0190] (5) It is a polyvalent (2-8 or more) alkyl alcohol (3-60 carbon atoms) nonionic surfactant.

[0191] (6) It is an AO adduct of an alkylglycoside having a relatively low degree of polymerization. Such oxyalkylated glycosides include fatty ether derivatives such as monosaccharides, disaccharides, and trisaccharides having an AO moiety. Preferred examples include those containing 1 to 30 units of AO, typically 1 to 3 units of AO, a pentose or hexasaccharide, and an alkyl group of a fatty group having 6 to 20 carbon atoms. The oxyalkylated glycoside can be represented by the following chemical formula 11.

[0192] [Chemical Formula 11]

[0193] H-(AO) m -G y -OR

[0194] In the above chemical formula 11,

[0195] AO is an alkylene oxide moiety,

[0196] m is the alkyl oxide substitution degree of 1 to about 30 on average,

[0197] G is a reducing sugar containing 5 or 6 carbon atoms, i.e., a moiety derived from a pentose or hexose. Exemplary reducing sugars include glucose, fructose, mannose, galactose, talose, gulose, allose, altrose, idose, arabinose, xylose, lyxose, and ribose. Because glucose is readily available, it is a common specific example for making polyglycosides.

[0198] R is a saturated or unsaturated fatty alkyl group containing 6 to 20 carbon atoms, and y, the degree of polymerization (DP) of the polyglycoside (Alkylpolyglycosides), represents the number of monosaccharide repeating units in the polyglycoside, and is an integer based on individual molecules, but may not be an integer if taken as an average when used as a polyglycoside.

[0199] Some specific examples include Spans TM and Tweens TM Sorbitan fatty acid esters, such as polyoxyethylene derivatives of sorbitan and fatty acid esters known as sorbitan, may be included. These may be polyoxyethylene sorbitan and fatty acid esters prepared from fatty esters by adding sorbitan and ethylene oxide. Some specific examples of these may be polysorbate 20, polyoxyethylene 20 sorbitan monolaurate, polysorbate 40, polyoxyethylene 20 sorbitan monopalmatate, polysorbate 60, polyoxyethylene 20 sorbitan monostearate, polysorbate 85, polyoxyethylene 20 sorbitan trioleate.

[0200] (7) A nonionic surfactant ethoxylated and / or ethoxylate propoxylated on a linear secondary alcohol having alkyl group carbons C12-14 can be represented by the following chemical formula 12.

[0201] [Chemical Formula 12]

[0202]

[0203] In the above chemical formula 12,

[0204] m+n has between 9 and 15 carbon atoms,

[0205] x is 1 to 50 moles of ethylene oxide (EO),

[0206] y represents 0 to 20 moles of propylene oxide (PO),

[0207] The sum of x and y is at least 2, and preferably from about 2 to about 22, where a, b, x and y represent average values ​​and the chemical formula is an average expression.

[0208] These surfactants are commercially available as SOFTANOL™ P and SOFTANOL™ EP from Nippon Shokubai and as TERGITOL™ 15-Sx from Dow.

[0209] The cationic surfactant may include at least one selected from the group consisting of long-chain quaternary ammonium compounds and aromatic quaternary ammonium compounds. The above-described content may be applied to the quaternary ammonium compounds and aromatic quaternary ammonium compounds.

[0210] The cationic surfactant may include, but is not limited to, didecyldimethyl ammonium chloride.

[0211]

[0212] The above auxiliary dispersant may be included in an amount of 0.1 to 40 parts by weight, preferably 0.5 to 10 parts by weight, and more preferably 1 to 5 parts by weight, based on 100 parts by weight of the total nano sol solution.

[0213] It is preferable that the above auxiliary dispersant be included within the above range, as this produces a stable nano sol.

[0214]

[0215] The above-mentioned joint biocide may be used without limitation as long as it does not hinder the purpose of the present invention. For example, (thiocyanomethylthio)benzothiazole (TCMTB), chlorothalonil, dichlorfluanid, isothiazolone, 4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT), 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one (MIT), benzisothiazolin-3-one (BIT), 2-octyl-3-isothiazolone (OIT), imidacloprid, iodopropynyl butylcarbamate (IPBC), bifenthrin, cypermethrin, permethrin, chitin, chitosan, chlorpyrifos, 4-alpha-cumylphenol, fipronil, carbendazim, cyfluthrin, etc., allethrin, bifenthrin, cypermethrin, cyphenothrin, deltamethrin, Examples thereof include permethrin, pralethrin, resmethrin, sumitrin, tetramethrin, tralomethrin, transfluthrin, and imiprothrin, and preferably synthetic pyrethroids such as allethrin, bifenthrin, cypermethrin, cyphenothrin, deltamethrin, permethrin, pralethrin, resmethrin, sumitrin, tetramethrin, tralomethrin, transfluthrin, and imiprothrin.

[0216] The above-mentioned co-biocide may be included in an amount of 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, and more preferably 0.3 to 1 part by weight, relative to 100 parts by weight of the total nano-sol solution.

[0217] It is preferable that the above-mentioned co-biocide be included within the above range as it has the advantage of controlling brown rot fungi.

[0218]

[0219] Additionally, an additional inorganic biocide may be further mixed within a range that does not impair the stability of the nano-sol solution. For example, one or more selected from the group consisting of sodium fluoride, sodium borate, boric acid, DOT (Disodium Octaborate Tetrahydrate), and amine salts of boric acid may be further included.

[0220] The above additional inorganic biocide may be included in an amount of 0.1 to 5 parts by weight, preferably 0.1 to 3 parts by weight, and more preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of the total nano sol solution.

[0221]

[0222] The above-mentioned corrosion inhibitor can be added to suppress the corrosion of a nano-sol solution containing a sparingly soluble copper compound.

[0223] The above corrosion inhibitors include inorganic nitrite salts such as sodium nitrite, potassium nitrite, and calcium nitrite, azoles and azole derivatives which are compounds containing heteroatoms (N, S, O atoms), aromatic rings, and π electrons, and specific examples thereof include benzotriazole and its derivatives, namely 5-methyl-1H-benzotriazole (MBTAH) and 5-chloro-1H-benzotriazole (CBTAH), and dibasic acid mixtures containing about 70 wt% or more of dibasic acids having 10 to 12 carbon atoms per molecule, such as CORFREE M1. ® You can hear the back.

[0224] The above-mentioned anti-corrosion agent may be included in an amount of 10 parts by weight or less, preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total nano-sol solution.

[0225]

[0226] The functional additives mentioned above may be any additive commonly used in the art without limitation, as long as they do not impede the purpose of the present invention. For example, they may be water repellants, defoaming agents, wood dimensional stabilizers, colorants, emulsifying agents, stabilizers, or UV inhibitors, and non-sterilized products may also be used.

[0227] It is preferable that the above functional additives be further included, as this can improve the appearance and performance of the treated product.

[0228] The water repellent may be, for example, paraffin wax, olefin wax, petroleum wax, carnauba wax, polyethylene wax, silicone wax, polypropylene wax, PTFE wax, and synthetic wax.

[0229] The above-mentioned defoaming agent may be a silicone-containing or non-silicon-containing defoaming agent.

[0230] The dimensional stabilizer may be, for example, waxes such as paraffin wax, olefin wax, petroleum wax, carnauba wax, polyethylene wax, silicone wax, polypropylene wax, PTFE wax and synthetic waxes, and natural resins such as polystyrene, polyethylene, polypropylene, polyvinyl chloride, polyacrylonitrile, polyvinyl acetate, polyester, acrylic polymers, polyamides, polyurethanes, phenolic novolacs, phenolic resoles, urea formaldehyde resins, melamine formaldehyde resins, epoxy resins, rosins and rosin esters, hydrocarbon resins, ketone resins, terpene resins, alkyd resins, silicone resins and silicate resins and other water-insoluble polymers.

[0231] The colorant may include an inorganic pigment or an organic pigment, for example, pigments such as iron oxide, iron hydroxide, calcium carbonate, calcium phosphate, calcium oxide, calcium hydroxide, bismuth oxide, bismuth hydroxide, bismuth carbonate, copper carbonate, copper hydroxide, basic copper carbonate, silicon oxide, zinc carbonate, barium carbonate, barium sulfate, barium oxide, strontium carbonate, zinc oxide, zinc phosphate, zinc chromate, barium chromate, chromium oxide, titanium dioxide, zinc sulfide, antimony oxide, cobalt phthalocyanine, organic azo compounds such as copper phthalocyanine, copper semichloro or monochlorophthalocyanine, copper phthalocyanine, metal-free phthalocyanine, copper polychlorophthalocyanine, organic nitro compounds, phthalocyanine pigments, polycyclic compounds such as quinacridone pigments, perylene and perinone pigments, Examples include diketopyrrolo-pyrrole (DPP) pigments, thioindigo pigments, dioxazine pigments, quinophthalone pigments, and triacrylcarbonium pigments.

[0232] The above-mentioned weathering agent may include, for example, pigments such as zinc oxide, zinc sulfide, iron oxide, carbon black, and titanium dioxide; ultraviolet absorbers such as hydroxyl-substituted benzophenone, hydroxyphenyl benzotriazide, and substituted acrylonitrile; UV stabilizers such as hindered amine light stabilizers (HALS); and antioxidants such as amines, imidiazoles, or complex hindered phenols.

[0233] In another embodiment of the present invention, the functional additive may be included in an amount of 10 parts by weight or less, preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the entire nano sol solution.

[0234]

[0235] The water may be additionally added to adjust the viscosity of the aqueous wood preservative depending on the intended use of the aqueous wood preservative, and the content thereof is not particularly limited as long as it does not impede the purpose of the present invention. The water may be, for example, distilled water, and may be included as a remainder to satisfy 100 parts by weight of the entire nano-sol solution, but is not limited thereto.

[0236] The above-mentioned water-based wood preservative includes the above-mentioned nano-sol solution, and the above-mentioned water-based wood preservative may be, but is not limited to, the above-mentioned nano-sol solution.

[0237]

[0238] <Method for manufacturing a water-based wood preservative>

[0239] Another aspect of the present invention relates to a method for producing an aqueous wood preservative, comprising the steps of forming a dispersion by mixing an aqueous solution of a copper salt and a dispersant containing an aliphatic amine, and adding a base dropwise to the dispersion to obtain an aqueous wood preservative comprising a nano-sol solution in which an inorganic biocide containing a sparingly soluble copper compound having an average particle size of 1 to 1000 nm is dispersed.

[0240] The above-described dispersant, sparingly soluble copper compound, inorganic biocide, and nano sol solution containing the above-described aliphatic amine can be applied.

[0241] In another embodiment of the present invention, the inorganic biocide may contain a copper compound having an average particle size of 1 to 300 nm.

[0242]

[0243] Although we do not wish to be limited by theory, moisture movement within wood occurs through the margo of the flexible wall.

[0244] In the case of wood, penetrability is a critical factor in wood preservation, but large metal compounds can interfere with the penetrability of preservatives within the wood. Wood tissue consists of numerous cells, and for a wood preservative to penetrate these cells, the size of the cell wall's flexible boreholes (margo) must be smaller than the size of the cell wall's flexible boreholes (approximately 400 to 600 nm) and the window pits (approximately 10,000 nm).

[0245] However, the conventional top-down method is a method of crushing ㎛-sized metal compound particles into nano-sized particles by applying physical force through a crushing medium. In this case, large metal compound particles are inevitably mixed in, which makes it difficult to inject wood preservatives.

[0246] The method for manufacturing a water-based wood preservative according to the present invention has the advantage of being able to manufacture a water-based wood preservative that is easy to inject into even difficult-to-inject wood, since the metal compound is manufactured in a build-up manner rather than a conventional top-down manner.

[0247]

[0248] Furthermore, the water-based wood preservative according to the present invention has the advantage of being easily manufactured using a low-cost manufacturing method. Conventional water-based wood preservatives have been manufactured using complex processes, resulting in high processing costs. However, the water-based wood preservative according to the present invention offers the advantage of easily obtaining a nano-sol solution that is easy to inject into wood, particularly into difficult-to-inject wood, at a reasonable cost.

[0249]

[0250] A method for manufacturing a water-based wood preservative according to the present invention comprises a step of forming a dispersion by mixing a copper salt aqueous solution and a dispersant containing an aliphatic amine.

[0251] Specifically, the copper salt aqueous solution may include a copper salt. The copper salt has superior biological activity compared to other metal salts, such as salts of cobalt, nickel, tin, silver, and / or zinc, and has the advantage of superior binding ability to wood components compared to other metals when treated by an appropriate method, making it preferable.

[0252] When a dispersant containing an aliphatic amine is mixed into the above copper salt aqueous solution and then neutralized with a base, particles of a sparingly soluble metal compound having excellent dispersion stability in the aqueous solution are produced.

[0253]

[0254] The anion corresponding to the copper cation of the above copper salt may be, but is not limited to, a salt of a C1 to C8 carboxylic acid such as a chloride salt, a nitrate salt, a carbonate salt, a sulfate salt, a fluoride salt, a bromide salt, a hydroxide salt, a borate salt, an oxide salt, or copper formate, copper acetate, or copper propionate. Preferably, the anion may be a chloride salt.

[0255] Specifically, the copper salt may be a soluble salt. When the copper salt is a soluble salt, it is preferable because it has high solubility in water, which makes the process easy, while also allowing the production of a copper compound that exhibits poor solubility at a high concentration.

[0256]

[0257] In another embodiment of the present invention, the copper salt aqueous solution may include at least one selected from the group consisting of copper chloride, copper sulfate, copper nitrate, and copper acetate.

[0258] Specifically, the copper salt aqueous solution according to the present invention may include copper chloride. The copper chloride has the advantage of being a copper salt with relatively high solubility in water.

[0259] The above copper salt aqueous solution may be included so that the concentration of the copper salt is 1 to 50 parts by weight, preferably 5 to 30 parts by weight, and more preferably 15 to 25 parts by weight, based on 100 parts by weight of the entire dispersion.

[0260] When the concentration of the above copper salt satisfies the above range, it is preferable because it has the advantage of forming a stable sol in the dispersion.

[0261]

[0262] The step of forming the above dispersion may further include a step of introducing an auxiliary dispersant.

[0263] Preferably, the auxiliary dispersant is added first before the dispersant containing the aliphatic amine is added.

[0264] Specifically, it is preferable to first add the dispersing agent because a uniform dispersion of the dispersing agent, which is mainly composed of amine, and the sparingly soluble copper-amine compound combined with the water-soluble copper compound is formed.

[0265]

[0266] In another embodiment of the present invention, the step of obtaining the dispersion may be performed for 5 minutes to 1 hour, preferably 5 minutes to 30 minutes, more preferably 10 minutes to 20 minutes, at 100 to 2000 rpm, preferably 200 to 1500 rpm, more preferably 250 to 1000 rpm.

[0267] It is preferable that the step of obtaining the above dispersion is performed within the above time range and at the above stirring speed, so that an inorganic biocide having the desired particle diameter can be obtained.

[0268] If the above dispersant is a solid, waxy or paste-like substance at room temperature, it may be added by heating to liquefy it, but is not limited thereto.

[0269] The step of obtaining the above dispersion can be performed at room temperature without applying a special temperature.

[0270] When mixing the above copper salt aqueous solution and the dispersant containing the aliphatic amine, water may be mixed together, but is not limited thereto. The water may be appropriately added to facilitate the mixing, but is not limited thereto. The water may be included as the remainder based on 100 parts by weight of the total dispersion.

[0271]

[0272] The method for producing an aqueous wood preservative according to the present invention comprises the step of adding a base dropwise to the dispersion to obtain an aqueous wood preservative comprising a nano-sol solution in which an inorganic biocide containing a sparingly soluble copper compound having an average particle size of 1 to 1000 nm is dispersed.

[0273] In short, the above-mentioned water-based wood preservative is in the form of a nano-sol solution in which the above-mentioned inorganic biocide is dispersed.

[0274] In the present invention, "nano sol" refers to a sol in which a sparingly soluble copper compound having an average particle size of nano-size, specifically 1 to 1000 nm, is stably and uniformly present in a medium, and may be a state in which an organic biocide is mixed in the form of a nano or micro emulsion. A water-soluble component may be dissolved in the nano sol.

[0275]

[0276] The base neutralizes the dispersion. Without wishing to be limited by theory, when the base is added dropwise to the dispersion, the acidic copper salt aqueous solution reacts with the base, thereby obtaining a nano-sol solution containing an inorganic biocide dispersed therein, which contains neutralized basic copper compounds (hydroxy cupper compounds) having an average particle size of 1 to 1000 nm.

[0277] The above copper salt dissolves in water and exhibits acidity, but when the base is added to make it neutral or alkaline, the solubility decreases rapidly and it becomes a poorly soluble copper compound.

[0278]

[0279] The method for manufacturing a water-based wood preservative according to the present invention can easily obtain a copper compound having an average particle size of 1 to 1000 nm, specifically 1 to 300 nm, by manufacturing a poorly soluble copper compound by a build-up method rather than a conventional top-down method.

[0280] The above “base” may be, but is not limited to, a weak base or a strong base.

[0281]

[0282] The above copper salt aqueous solution is acidic. The base can neutralize the acidic copper salt aqueous solution. The base can be an alkali metal hydroxide, such as potassium hydroxide or sodium hydroxide, or an alkaline substance, such as ammonia water or an amine. The base can be a primary, secondary, or tertiary amine.

[0283] Specifically, the amine among the bases is diamylamine, diethylamine, diisopropylamine, dimethylethylamine, di-n-butylamine, mono-2-ethylhexylamine, monoamylamine, monoethylamine, monoisopropylamine, mono-n-butylamine, triamylamine, triethylamine, tri-n-butylamine, dibutylaminoethanol, diethylaminoethanol, diethylaminoethoxyethanol, diisopropylaminoethanol, dimethylaminoethanol, dimethylaminoethoxyethanol, ethylaminoethanol, ethylaminoethanol, isopropylaminoethanol, isopropylethylaminoethanol, -n-propylaminoethanol, n-butylaminoethanol, n-butyldiethanolamine, n-butyldiethanolamine, t-butylaminoethanol, t-butyldiethanolamine, monoethanolamine, diethanolamine, triethanolamine, These include, but are not limited to, lower amines such as diisopropanolamine, monoisopropanolamine, triisopropanolamine, aminoethylethanolamine, aminoethylpiperazine, diethylenetriamine, ethylenediamine, piperazine tetraethylenepentamine, triethylenetetramine, 3-methoxypropylamine, cyclohexylamine, and morpholine.

[0284] The amount of base required to neutralize the acidic copper salt, specifically the acidic water-soluble copper salt, is such that the pH of the resulting poorly soluble copper nano-sol solution reaches 4 to 10, preferably 5 to 9, and more preferably 6 to 8.

[0285]

[0286] When the acidic copper compound and the aliphatic amine and the neutralizing agent are selected, the reaction of the neutralizing agent with the theoretical copper compound reaches a pH near 7 when reacting at a set equivalent ratio, so this amount can be easily calculated by those skilled in the art.

[0287]

[0288] The dropping speed of the base may be 0.1 to 5 ml / min, preferably 0.5 to 3 ml / min, more preferably 1 to 2 ml / min, and the dropping time may be 0.1 to 3 hours, preferably 0.5 to 2 hours, more preferably 1 to 1.5 hours.

[0289]

[0290] The above base is preferably used in an amount such that the pH of the dispersion reaches 4 to 10, preferably 5 to 9, and more preferably 6 to 8.

[0291] When the above base is included within the above range, there is an advantage in that the viscosity of the formed sol is low and a stable sol is formed.

[0292]

[0293] In another embodiment of the present invention, the step of obtaining the water-based wood preservative can be performed for 0.1 to 3 hours, preferably 0.5 to 2 hours, and more preferably 1 to 1.5 hours.

[0294] If the step of obtaining the above nano sol solution is performed within the above time range, it is preferable because there is an advantage in that a stable nano sol can be obtained.

[0295]

[0296] A method for producing a water-based wood preservative according to the present invention may include a step of mixing an organic biocide comprising at least one selected from the group consisting of long-chain quaternary ammonium compounds, aromatic quaternary ammonium compounds, and triazole compounds.

[0297] For example, the organic biocide may be mixed with the copper salt aqueous solution and the dispersant.

[0298] The above organic biocide can be applied to the above-mentioned contents.

[0299]

[0300] In another embodiment of the present invention, the step of further mixing at least one selected from the group consisting of an auxiliary dispersant, water, a co-biocide, a neutralizing agent, a rust inhibitor, and a functional additive may be further included.

[0301] The above-mentioned co-biocide, water, rust inhibitor, neutralizer and functional additive can be applied, and can be mixed with a copper salt aqueous solution and a dispersant as needed, or can be added to a nano sol solution.

[0302]

[0303] The method for manufacturing an aqueous wood preservative according to the present invention has the advantage of producing an aqueous wood preservative in which an inorganic biocide containing a sparingly soluble metal compound having an average particle size of nano-size, specifically 1 to 1000 nm, is stably dispersed. In particular, since it is a build-up method, it substantially does not contain metal compound particles exceeding 1000 nm, and thus has the advantage of excellent injection performance even in difficult-to-inject wood.

[0304]

[0305] Another aspect of the present invention relates to a method for preserving wood, comprising the step of applying the aforementioned water-based wood preservative to wood or cellulosic material.

[0306] The treatment with the wood preservative can be carried out by techniques commonly practiced in the art, such as dipping, spraying, brushing, other surface coating methods, impregnation such as high pressure or double vacuum impregnation into the body of wood or other materials, etc. Impregnation under pressure is particularly preferred when the substrate is wood or wood composition material that will be wet during its life cycle, such as wood for window frames, wood used on floors exposed to the environment such as decking, and lumber used in contact with the ground or in fresh or salt water environments.

[0307] Another aspect of the present invention relates to a wood treatment system comprising a storage tank for receiving wood or cellulosic material to be treated, and a volume of a treatment solution containing an aqueous wood preservative prepared by the method for preparing an aqueous wood preservative as described above in the storage tank.

[0308] The water-based wood preservative according to the present invention is preferably used in wood immersion treatments, and may be used in specific immersion treatments utilizing vacuum and / or pressure. Optionally, the system may further include an additional autoclave. Furthermore, the system may include, but is not limited to, means for applying vacuum or pressure, such as 25 to 29% of full vacuum, or 8 to 12 bar of pressure.

[0309]

[0310] Hereinafter, preferred embodiments and comparative examples of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

[0311]

[0312] Example 1

[0313] Add 100 g of 50% CuCl2·2H2O solution, 45.0 g of water, and 3.0 g of Tween-20 to a 500 ml round bottom flask and stir well. N-oleyl-1,3-propylene diamine is the main ingredient. (Nouryon's trade name: Duomeen) TM 10.0 g of OL was added and mixed at 100 rpm for 10 minutes. After mixing, 31.5 g of 50% NaOH was slowly injected over 1 hour at a drip rate of 0.5-0.6 g / min. After the injection, the mixture was stirred well for an additional hour and then water was added to make a water-based wood preservative containing a stable nano-sol with a total weight of 200 g.

[0314] The pH of the manufactured water-based wood preservative was 7.44, and the calculated concentration of CuO was 11.7%. The particle size of the solution diluted with distilled water was measured using Zeta-potential & Parcicle size Analyzer ELSZ-2000ZS of Photal OTSUKA ELCTRONIC Co., Ltd. according to ISO 22412:2017 Particle size analysis - Dynamic light scattering (DLS) method. As a result, the average particle size was 139.1 nm, as shown in Table 1. The particle size distribution results are shown in Fig. 1. Specifically, Fig. 1 shows the intensity distribution, volume distribution, and number distribution.

[0315]

[0316] Example 2

[0317] Synthesize in the same manner as in Example 1, but using Tween-20 TM The particle size distribution of an aqueous wood preservative containing a stable nano sol synthesized by adding 1.0 g of 80% DDAC (Didecyldimethyl Ammonium Chloride) after adding 3.0 g was measured, and the average particle size was 93.5 nm, as shown in Table 1. The particle size distribution results are shown in Fig. 2.

[0318]

[0319] Example 3

[0320] Synthesize in the same manner as in Example 1, but using Tween-20 TM The particle size distribution of the aqueous wood preservative containing the stable nano-sol synthesized by adding 3.0 g of 80% DDAC was measured, and the average particle size was 82.1 nm, as shown in Table 1. The particle size distribution results are shown in Fig. 3.

[0321]

[0322] Example 4

[0323] Synthesize in the same manner as in Example 1, but using Tween-20 TM The particle size distribution of the aqueous wood preservative containing the stable nano-sol synthesized by adding 5.0 g of 80% DDAC after adding 3.0 g was measured, and the average particle size was 63.8 nm, as shown in Table 1. The intensity distribution results are shown in Fig. 4.

[0324]

[0325] Example 5

[0326] Synthesize in the same manner as in Example 1, but using Tween-20 TM The particle size distribution of the aqueous wood preservative containing the stable nano-sol synthesized by adding 7.0 g of 80% DDAC after adding 3.0 g was measured, and the average particle size was 71.7 nm, as shown in Table 1. The particle size distribution results are shown in Fig. 5.

[0327]

[0328] Example 6

[0329] Synthesize in the same manner as in Example 1, but using Tween-20 TM The particle size distribution of an aqueous wood preservative containing a stable nano-sol synthesized by adding only 7.0 g of 80% DDAC without adding silver was measured, and the average particle size was 52.1 nm, as shown in Table 1. The particle size distribution results are shown in Fig. 6.

[0330]

[0331] Example 7

[0332] Synthesize in the same manner as in Example 1, but using Tween-20 TM Minox-L from Miwon Sangsa, which contains 30% Laurylamine oxide as its main ingredient and is free of additives TM The particle size distribution of the aqueous wood preservative containing a stable nano-sol synthesized by adding only 7.5 g was measured, and the average particle size was 90.0 nm, as shown in Table 1. The particle size distribution results are shown in Fig. 7.

[0333]

[0334] Example 8

[0335] Nalgene 500ml capacity TM Add 72.0 g of CuCl2·2H2O and 146.5 g of water to the bottle and shake well. Do not add any other auxiliary surfactants. TM Only 16.0 g of OL was added. After the addition was completed, 45.7 g of 43.3% NaOH was slowly added over 2 hours. After the injection was completed, aging was performed in an 80°C oven for 1 hour, and then 3.5 g of 43.3% NaOH was additionally added to the elastic gel, which rapidly decreased the viscosity and obtained an aqueous wood preservative containing a stable nano-sol with a pH of 6.77. The center particle diameter of this solution was analyzed in the same manner as in Example 1, and the average particle size was 66.5 nm, as shown in Table 1. The particle size distribution results are shown in Fig. 8.

[0336]

[0337] Example 9

[0338] In a 500 ml round bottom flask, add 100 g of 50% CuCl2·2H2O solution, 45.0 g of water, 5.0 g of 80% DDAC, and Tween-80. TM Add 4.0g and stir well. The main ingredient is N-coco-1,3-propylene diamine, which is melted by heating until transparent. (Nouryon's product name is Duomeen) TM 10.0 g of C was added. After the addition was complete, 31.6 g of 50% NaOH was slowly injected over 1 hour. After the injection was complete, the mixture was stirred well for an additional hour, and then additional water was added to produce an aqueous wood preservative containing a stable nano-sol with a total mass of 200 g. The pH of this solution was 7.39, and the calculated CuO concentration was 11.7%.

[0339] The average particle size of this solution was 132.3 nm as shown in Table 1 when measured using the same method as in Example 1. The particle size distribution results are shown in Fig. 9.

[0340]

[0341] Intensity Distribution (nm)Volume Distribution (nm)Number Distribution (nm)Average Particle Size (nm)Example 1 174.28 2.55 9.3 139.1Example 2 100.87 8.66 5.89 3.5Example 396.66 0.54 6.48 2.1Example 476.24 5.93 4.76 3.8Example 5: Peak 1 23.22 2.22 1.47 1.7Example 5: Peak 2 77.76 2.75 2.9Example 662.5 3 7.12 8.15 2.1Example 7 116.35 7.64 0.89 0.0Example 880.74 7.33 5.66 6.5Example 9 146.41 14.99 6.41 32.3

[0342] Example 10

[0343] A synthesis was performed as in Example 6, but using 30.5 g of 28% NH4OH instead of NaOH. The pH of the aqueous wood preservative containing this stable nano-sol was 6.15, and a stable solution could be prepared.

[0344]

[0345] Example 11

[0346] A synthesis was performed as in Example 6, but using 23.2 g of monoethanolamine instead of NaOH. The pH of the aqueous wood preservative containing this stable nano-sol was 5.64, and although the viscosity of the liquid was higher than that of others, a stable liquid could be produced.

[0347]

[0348] Example 12

[0349] Synthesize as in Example 6, but instead of DDAC, use 5.84 g of 50% Benzalkonium Chloride and Tergitol (trade name: Dow Chemical) TM-15-S-15 3.0g was mixed and synthesized. The pH of the aqueous wood preservative containing this stable nano-sol was 7.09, and a stable solution could be prepared.

[0350]

[0351] Example 13

[0352] Synthesize as in Example 6, but with Duomeen TM Instead of OL, use Dow Chemical's trade name Tween-20 TM It was synthesized by mixing 3.0 g of ethylene oxide 2 mole adduct with 10.0 g of lauryl amine ethoxylate ether. The pH of the aqueous wood preservative containing this stable nano sol was 7.03, and a stable solution could be prepared.

[0353]

[0354] Example 14

[0355] Synthesize as in Example 6, but use the product name Duomeen from Nouryon TM Instead of OL, 10.0 g of preheated and melted lauryl amine, 5.0 g of 80% DDAC, and Tween-20 TM 3.0 g was mixed and synthesized. The pH of the aqueous wood preservative containing this stable nano-sol was 7.57, and a stable solution could be prepared.

[0356]

[0357] Example 15

[0358] A synthesis was performed as in Example 11, but oleyl amine was mixed and used instead of lauryl amine, which was melted by preheating. The pH of the aqueous wood preservative containing this stable nano-sol was 7.07, and a stable solution could be prepared.

[0359]

[0360] Example 16

[0361] Cyproconazole 0.90g and Tergitol (trade name: Dow Chemical) in advance TM -15-S-7 29.1g was mixed to make a transparent mixed solution with a 3% concentration of Cyproconazole.

[0362] In a 2 L round bottom flask, add 300 g of 50% CuCl2·2H2O solution, 140 g of water, and 30.0 g of a transparent mixed solution with a 3% concentration of Cyproconazole, and stir well. (Duomeen, trade name, Nouryon) TM 30.0 g of OL was added. After the addition was completed, 92.0 g of 50% NaOH was slowly injected over 1 hour. After the injection was completed, the mixture was stirred well for an additional hour, and then additional water was added to produce an aqueous wood preservative with a total volume of 600 g. The aqueous wood preservative containing the synthesized stable nano-sol showed a stable form, and the pH of the solution was 6.66. The calculated concentration of CuO was 11.7% and the concentration of cyproconazole was 0.15%.

[0363]

[0364] Example 17

[0365] Cyproconazole 1.80g and Tergitol (trade name: Dow Chemical) TM An aqueous wood preservative containing a stable nano-sol was prepared by the same method as in Example 13, except that 28.2 g of -15-S-7 was mixed to obtain a clear mixed solution with a 6% concentration of Cyproconazole. The pH of this aqueous wood preservative was 6.70, and the calculated concentration of CuO was 11.7% and the concentration of Cyproconazole was 0.30%.

[0366]

[0367] Example 18

[0368] Nalgene 500ml capacity TMAdd 40.0g of CuCl2 anhydrous, 10.00g of ZnCl2 and 141.4g of water to the bottle and shake well. Add 8.00g of 80% DDAC and Duomeen. TM 12.0 g of OL was added. After the addition was completed, 38.6 g of 50% NaOH was slowly added over 2 hours, resulting in the formation of an aqueous wood preservative containing a stable nano-sol.

[0369]

[0370] Example 19

[0371] Nalgene 500ml capacity TM Add 45.0g of CuCl2 anhydrous, 5.00g of MgCl2 and 139.9g of water to the bottle and shake well. Add 8.00g of 80% DDAC and Duomeen. TM 12.0 g of OL was added. After the addition was completed, 40.5 g of 50% NaOH was slowly added over 2 hours, resulting in the formation of an aqueous wood preservative containing a stable nano-sol.

[0372]

[0373] Experimental Example 1

[0374] A treatment solution (5 L) was prepared by diluting the nano-sol solution obtained in Example 4 with a commercially available Ammoniacal Copper Quat (ACQ)-Type D solution to a preservative with a CuO content of 0.85%. This treatment solution was injected into a radiata pine sapwood sample according to the now-obsolete AWPA Standard A3-15, "Standard Method for Determining Penetration of Preservatives and Fire Retardants."

[0375] The appearance of the treated wood was as shown in Fig. 10. Fig. 10 a shows the appearance of wood treated with the water-based wood preservative of the present invention, showing a color similar to the natural color of the wood due to the properties of the water-based wood preservative, while Fig. 10 b shows wood treated with ACQ, showing that the wood has blackened due to the influence of ionic copper.

[0376] When the cut surfaces of the treated wood were treated with a dithiooxamide solution, both samples showed a uniform blue color, confirming that copper was uniformly distributed throughout the cross-section.

[0377] In addition, as shown in Fig. 11, the fracture surfaces of these two wood specimens were observed using a scanning electron microscope (SEM), and it was confirmed that the preservative components were uniformly distributed within the wood. In addition, it was confirmed that these components were copper and chlorine compounds using SEM-Energy Dispersed X-ray Analysis (EDXA).

[0378] Through the above results, it was found that the copper nano sol preservative of Example 4, which is in the form of particles of the present invention, has no difference in injectability from the ionic preservative ACQ, which is a commercially available second-generation wood preservative.

[0379]

[0380] Experimental Example 2

[0381] A treatment solution was prepared by diluting the copper nano sol solution prepared in Example 8 to a CuO content of 0.85%. After applying this diluted solution to the sapwood of domestic pine wood, termites were inoculated according to AWPA Standard E1-17, "Laboratory Methods for Evaluating the Termite Resistance of Wood-based Materials: Choice and No-choice Tests."

[0382] The results of the termite experiment showed that all the inoculated termites died within one week, and the weight loss of the cube blocks was less than 2.0% over a three-week period, while the weight loss of the untreated cube blocks was approximately 45%, proving that the treated copper nano-sol solution is also effective in repelling insects.

[0383]

[0384] Experimental Example 3

[0385] The water-based wood preservative manufactured in Example 16 was diluted to make a 5 kg solution with a CuO concentration of 1.0%.

[0386] The diluted solution was injected into radiata pine sapwood wood cube blocks measuring 19 mm × 19 mm × 19 mm. The treated cube blocks were inoculated with white-rot and brown-rot fungi to evaluate the biological efficacy of the preservative formulations according to the method described in AWPA Standard E10-22 “Laboratory Method for Evaluating the Decay Resistance of Wood-Based Materials Against Pure Basidiomycete Cultures: Soil / Block Test.”

[0387] The results of the post-mortem test showed that the weight loss of the cube blocks was less than 2.0%, while the weight loss of the untreated cube blocks was approximately 50%, demonstrating that the treated water-based wood preservative was effective against decay fungi.

[0388]

[0389] Experimental Example 4

[0390] The aqueous wood preservative prepared in Example 6 was diluted to a CuO concentration of 0.50%. The diluted solution was applied to red pine sapwood. The treated wood samples, dried in air at room temperature for three weeks, showed that copper was uniformly distributed throughout the entire cross-section and exhibited antiseptic and insect repellent effects.

[0391]

[0392] The present invention is not limited to the above-described embodiments, but can be manufactured in a variety of different forms. Those skilled in the art will appreciate that the present invention can be implemented in other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

Claims

1. An aqueous wood preservative comprising a nano-sol solution containing an inorganic biocide containing a sparingly soluble copper compound having an average particle size of 1 to 1000 nm; and a dispersant containing an aliphatic amine.

2. In paragraph 1, An aqueous wood preservative wherein the above-mentioned insoluble copper compound has an average particle size of 1 to 300 nm.

3. In paragraph 1, An aqueous wood preservative comprising at least one selected from the group consisting of copper hydroxide, copper oxide, basic copper carbonate, copper oxychloride, basic copper sulfate, basic copper nitrate, and basic copper acetate.

4. In paragraph 3, An aqueous wood preservative wherein the above-mentioned insoluble copper compound is copper oxychloride.

5. In paragraph 1, An aqueous wood preservative wherein the above-mentioned inorganic biocide is dispersed in the form of the above-mentioned nanosol solution.

6. In paragraph 1, An aqueous wood preservative, wherein the above-mentioned aliphatic amine comprises at least one selected from the group consisting of primary amines, secondary amines, tertiary amines and ethoxylated aliphatic amines.

7. In paragraph 6, The above aliphatic amines are N-coco-1,3-propylene diamine, N-oleyl-1,3-propylene diamine, N-tallow-1,3-propylene diamine, N-tallow-dipropylene triamine, N-coco-dipropylene triamine, N-oleyl-dipropylene triamine, N-tallow-dipropylene triamine, N-coco-dipropylene triamine, N-oleyl-dipropylene triamine, cocamine ethoxylate, cocamine A water-based wood preservative, wherein at least one is selected from the group consisting of ethoxylate propoxylate, laurylamine ethoxylate, laurylamine ethoxylate propoxylate, tallowamine ethoxylate, tallowamine ethoxylate propoxylate, oleylamine ethoxylate, oleylamine ethoxylate propoxylate, stearylamine ethoxylate, stearylamine ethoxylate propoxylate, myristylamine ethoxylate, myristylamine ethoxylate propoxylate, cetylamine ethoxylate, and cetylamine ethoxylate propoxylate.

8. In paragraph 1, An aqueous wood preservative further comprising an organic biocide comprising at least one selected from the group consisting of long-chain quaternary ammonium compounds, aromatic quaternary ammonium compounds and triazole compounds.

9. In paragraph 1, An aqueous wood preservative further comprising at least one auxiliary dispersant selected from the group consisting of cationic and nonionic surfactants, water, a co-biocide, a neutralizing agent, a rust inhibitor, and a functional additive.

10. In paragraph 1, An aqueous wood preservative, wherein the inorganic biocide is contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of the entire nano-sol solution.

11. In paragraph 1, An aqueous wood preservative, wherein the dispersant is contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of the entire nano-sol solution.

12. A step of forming a dispersion by mixing a copper salt aqueous solution and a dispersant containing an aliphatic amine, and A step of adding a base dropwise to the above dispersion to obtain an aqueous wood preservative comprising a nano-sol solution in which an inorganic biocide containing a sparingly soluble copper compound having an average particle size of 1 to 1000 nm is dispersed, A method for producing a water-based wood preservative comprising:

13. In paragraph 12, A method for producing an aqueous wood preservative, wherein the step of obtaining the above dispersion is performed for 5 minutes to 1 hour.

14. In paragraph 12, A method for producing an aqueous wood preservative, wherein the step of obtaining the above-mentioned aqueous wood preservative is performed for 0.1 to 3 hours.

15. In paragraph 12, A method for producing an aqueous wood preservative, wherein the above copper salt aqueous solution contains at least one selected from the group consisting of copper chloride, copper sulfate, copper nitrate, and copper acetate.

16. In paragraph 15, A method for producing an aqueous wood preservative, wherein the above copper salt aqueous solution contains copper chloride.

17. In paragraph 12, A method for producing an aqueous wood preservative, wherein the above-mentioned inorganic biocide contains a sparingly soluble copper compound having an average particle size of 1 to 300 nm.

18. In paragraph 12, A method for producing an aqueous wood preservative, further comprising a step of mixing an organic biocide comprising at least one selected from the group consisting of long-chain quaternary ammonium compounds, aromatic quaternary ammonium compounds and triazole compounds.

19. In paragraph 12, A method for producing an aqueous wood preservative, further comprising the step of mixing at least one selected from the group consisting of an auxiliary dispersant, water, a co-biocide, a neutralizing agent, a rust inhibitor, and a functional additive.

20. A wood preservation method comprising a step of treating wood or cellulosic material with a water-based wood preservative according to any one of claims 1 to 11.

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