Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N3/00—Preservation of plants or parts thereof, e.g. inhibiting evaporation, improvement of the appearance of leaves or protection against physical influences such as UV radiation using chemical compositions; Grafting wax
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
  • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
  • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
  • B27K3/16—Inorganic impregnating agents
  • B27K3/22—Compounds of zinc or copper
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
  • A01N43/647—Triazoles; Hydrogenated triazoles
  • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
  • A01N59/16—Heavy metals; Compounds thereof
  • A01N59/20—Copper
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L9/00—Disinfection, sterilisation or deodorisation of air
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
  • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
  • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
  • B27K3/34—Organic impregnating agents
  • B27K3/343—Heterocyclic compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
  • B65D85/70—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines
  • C08G73/0206—Polyalkylene(poly)amines
  • C08G73/0213—Preparatory process
  • C08G73/0226—Quaternisation of polyalkylene(poly)amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/02—Polyamines
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
  • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
  • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
  • B27K3/02—Processes; Apparatus
  • B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents

Definitions

• the present invention relates to a wood preservative composition and a method of treating wood and other cellulosic material with the wood preservative composition.
• a typical industrial treatment plant will consist of a storage tank to hold the treatment composition and an autoclave. Wood or other cellulosic material is charged into the autoclave and the autoclave is then flooded with treatment composition. Combinations of vacuum and pressure are applied to achieve the required penetration of treatment composition into the wood or other cellulosic material. During the treatment process, an amount of treatment composition is consumed by way of being absorbed into the wood or other cellulosic material. The amount of the treatment composition absorbed typically represents a relatively small amount of the total volume of treatment composition used to flood the autoclave. This generates a scenario whereby treatment composition is repeatedly exposed to wood or cellulosic material and becomes "aged" due to repeated use.
• the average age of a treatment composition increases as a function of solution refresh rates. This can extend from several days to many months. As a result, the treatment composition is repeatedly exposed to wood being treated increasing the average age of the composition. [0006] It has been observed that the ability of the preservative to penetrate into the wood substrate or cellulosic substrate, as the treatment solution is repeatedly exposed to wood or cellulosic material, can deteriorate very significantly with each and every treatment. This can have significant consequences to the useful service life of the treated wood or cellulosic article. Although not wishing to be bound to theory, it is believed that disruptive substances from wood or cellulosic extractives increase in the preservative composition after each and every treatment.
• cationic polymers, enzymes, organic polymers and quaternary ammonium compounds have been found that are not only compatible with anionic dispersion and/or emulsion phases but are also very effective at stabilizing these phases against charge fluctuations during subsequent treatment cycles and improving penetration of the dispersed and/or emulsified phase.
• the present invention provides wood preservative compositions containing a dispersed and/or emulsified phase comprising a wood preservative component; and a stabilizer.
• the stabilizer is a cationic polymer, an enzyme, an organic polymer, a quaternary ammonium compound and/or a mixture thereof.
• the stabilizer is present in an amount effective to stabilize the dispersed and/or emulsified phase of the preservative composition which will allow the wood preservative component to effectively penetrate a wood substrate intended to be protected by the wood preservative composition.
• the dispersed and/or emulsified phase contains a biocidal agent, colorant, water repellent, fire retardant, binder, emulsifier, co-solvent, dispersant, UV inhibitor, antioxidant, or a combination thereof.
• the biocidal component contains a biocidal metal compounds; boron containing biocides, organic fungicides such as of amides; anilides; anilinopyrimidine; aromatic compounds; fungicidal heterocyclic compounds; strobilurins; azoles; isothiazolones; cyclohexylhydroxydiazene 1 -oxide, potassium salt, pyrion compounds; quaternary ammonium compounds or mixtures thereof.
• a biocidal metal compounds boron containing biocides, organic fungicides such as of amides; anilides; anilinopyrimidine; aromatic compounds; fungicidal heterocyclic compounds; strobilurins; azoles; isothiazolones; cyclohexylhydroxydiazene 1 -oxide, potassium salt, pyrion compounds; quaternary ammonium compounds or mixtures thereof.
• the biocidal agent is dispersed zinc and/or dispersed copper.
• the dispersed zinc or copper may be micronized zinc or micronized copper dispersed in a solvent.
• the cationic polymer is chitosan, cationic derivative of natural polymers selected from guar gum, starch, cellulose or hydroxycellulose, a polymer or copolymer having one or more of the following repeating units of formula (I), (II) or (I II) described below or mixtures of the cationic polymers.
• the cation copolymer may have a molecular weight between 1 ,000 and 100,000.
• the composition may contain between about 0.001 and 10% by weight of the cationic polymer, more specifically between 0.01 % and 4% by weight of the cationic polymer.
• the wood preservative composition contains a quaternary ammonium compound wherein the quaternary ammonium compound is trimethyl alkyl quaternary ammonium compounds; dialkyldimethyl quaternary ammonium compounds; alkyl dimethyl or alkyl diethyl benzyl ammonium compounds; polyethoxylated quaternary ammonium; N-substituted pyridinium compounds, monoalkyl methyl bisalkoxylated quaternary ammonium compounds, dialkyl bisalkoxylated quaternary ammonium compounds, a protonated amine, a protonated dialkylamine or a protonated trialkylamine, protonated monoalkyl bisalkoxylated amine, a complex of one or more of the forgoing quaternary ammonium compounds with a complexing agent, or mixtures thereof.
• the quaternary ammonium compound is trimethyl alkyl quaternary ammonium compounds; dialkyldimethyl
• the quaternary ammonium compound is dialkyldimethyl quaternary ammonium compound selected from the group consisting of didecyl dimethyl ammonium chloride, didecyl dimethyl ammonium carbonate, didecyl dimethyl ammonium bicarbonate, dioctyl dimethyl ammonium chloride and octyl decyl dimethyl ammonium chloride, or a mixtures thereof.
• the stabilizer may be an enzyme, wherein the enzyme comprises a lipase, lipoxygenase, esterase, laccase, peroxidase, pectinase, protease, amylase, cellulase and/or xylanase.
• the stabilizer may be an organic polymer, wherein the organic polymer is an acrylamide polymer or copolymer, a polyethylene oxide or copolymer, an alkyl polyglucoside, or a mixture thereof.
• a method of preserving wood or other cellulosic material which contains applying to the wood or other cellulosic material a wood preservative composition of any of the previous embodiments of the present invention.
• a wood treatment system containing a storage tank adapted to receive the wood to be treated and in said tank a volume of treatment solution comprising a wood preservative composition of any of the previous embodiments of the present invention.
• the wood preservative compositions described herein are effective in treating wood and other cellulosic substrates, even after multiple applications of the wood treatment composition on to different wood or cellulosic substrates.
• the term "preservative" as used herein means a composition that renders the material to which it is applied more resistant to insect, fungal and microbial attack than the same material without having the composition applied.
• the wood preservative contains a dispersed and/or emulsified phase and a stabilizer.
• the dispersed and/or emulsified phase is selected from the group consisting of biocidal agents, colorants, water repellents, fire retardants, binders, emulsifiers, co-solvents, dispersants, UV inhibitors, or mixtures or combinations thereof.
• the stabilizer is selected from the group consisting of cationic polymers, enzymes, organic polymers, quaternary ammonium compounds and mixtures thereof.
• stabilizing agents allow the wood preservative composition containing dispersed and/or emulsified phases to be used to treat wood or cellulosic substrates, while maintaining the stability of the dispersed and/or emulsified phases.
• the biocidal agent is able to effectively penetrate the wood or cellulosic substrate even after the preservative composition is used to treat several batches of wood or cellulosic substrates. That is, the preservative composition of the present invention does not agglomerate, settle or separate over time and retains its ability to penetrate wood or cellulosic substrates even after the wood preservative has been used to treat multiple batches of wood or cellulosic substrates.
• the wood preservative composition contains a biocidal agent and a stabilizer.
• the stabilizer allows the wood preservative composition to be used to treat multiple wood or cellulosic substrates, while allowing the biocidal agent to effectively penetrate the wood or cellulosic substrate even after the preservative composition is used to treat several wood or cellulosic substrates. That is, the preservative composition of the present invention does not appreciably lose its ability to penetrate wood or cellulosic substrates even after the wood preservative has been used to treat multiple batches of wood or cellulosic substrates.
• the wood preservative composition may comprise as a biocidal agent, inter alia, one or more of the following active agents; biocidal metal compounds (in which the metal ion is the active biocidal agent); boron containing biocides such as boric acid, oxides and salts thereof and organic fungicides including fungicidal amides such as prochloraz, penthiopyrad, dichlofluanid and tolylfluanid; anilide fungicides such as sedaxane and penflufen; anilinopyrimidine fungicides such as pyrimethanil, cyprodinil or mepanipyrim; fungicidal aromatic compounds such as chlorthalonil, cresol, dicloran, pentachlorophenol, sodium pentachlorophenol, 2-(thiocyanatomethylthio)-1 ,3- benzothiazole (TCMBC), dichlorophen, fludioxonil and 8-hydroxyquinoline; fung
• the azole compound i.e. a compound comprising an azole group, may be an imidazole or a 1 ,2,4-triazole and is preferably represented by the general formula (A)
• X denotes CP. 4 or N ;
• R 1 denotes hydrogen or a linear, branched, cyclic, aromatic or any combination thereof, saturated or unsaturated, substituted or unsubstituted Ci to C o group; wherein any of the carbon atoms other than those bound to the nitrogen atom shown in formula (A) may be replaced with an optionally substituted hetero atom;
• R 2 denotes hydrogen, Ci -Cs alkyl, C2-C8 alkenyl, Ce-Cio aromatic, C5-C10 heteroaromatic or C1 -C4 alkyl carbamate;
• R 3 and R 4 denote hydrogen; or together R 3 and R 4 may provide a benzimidazole group (i.e. R 3 and R 4 may combine to form -(CH) 4 - linkage).
• the formulations of the invention may contain one or more azole compounds, such as mixtures of an imidazole and a 1 ,2,4-triazole, or mixtures of two or more 1 ,2,4-triazoles.
• one or more azole compounds such as mixtures of an imidazole and a 1 ,2,4-triazole, or mixtures of two or more 1 ,2,4-triazoles.
• the use 1 ,2,4-triazoles in the formulations of the invention is of particular interest.
• An imidazole compound incorporates a five-membered di-unsaturated ring composed of three carbon atoms and two nitrogen atoms at non-adjacent positions.
• the imidazole compound may be a benzimidazole.
• Preferred compounds include thiabendazole, imazalil, carbendazim and prochloraz.
• a 1 ,2,4-triazole compound incorporates a five-membered di-unsaturated ring composed of three nitrogen atoms and two carbon atoms at non-adjacent positions.
• An exemplary triazole compounds include a triazole compound selected from compounds of formula (B):
• R 5 represents a branched or straight chain C1-5 alkyl group (e.g. t- butyl), and
• R 6 represents a phenyl group optionally substituted by one or more substituents selected from halogen (e.g. chlorine, fluorine or bromine) atoms or C1-3 alkyl (e.g. methyl), Ci s alkoxy (e.g. methoxy), phenyl or nitro groups.
• halogen e.g. chlorine, fluorine or bromine
• C1-3 alkyl e.g. methyl
• Ci s alkoxy e.g. methoxy
• the triazole compound is advantageously selected from compounds of formula (C):
• R 7 is as defined for R 6 above, and
• R 8 represents a hydrogen atom or a branched or straight chain C1-5 alkyl group (e.g. methyl, ethyl, propyl, etc).
• triazoles include, but are not limited to, triadimefon, triadimenol, triazbutil, propiconazole, cyproconazole, difenoconazole, fluquinconazole, tebuconazole, flusilazole, uniconazole, diniconazole, bitertanol, hexaconazole, azaconazole, flutriafol, epoxyconazoie, tetraconazole, penconazole, ipconazole, prothioconazole and mixtures thereof.
• the biocidal metal is a copper or a zinc metal.
• the biocidal metal may be a dispersed or an insoluble metal material.
• insoluble copper such as in the form of submicron or micronized particles are Illustratively, U.S. Patent Application Nos. 2006/0062926 and 2005/0255251 and US Patent No. 8,409,627, the disclosures of which are incorporated herein by reference in their entireties. These applications describe methodologies for making submicron- sized biocidal particulate slurries, such as particulate copper slurries, and their use as wood preservatives.
• the micronized copper based composition is suitably prepared by using conventional grinding methodology, or other means known in the small particle production industry.
• the composition comprises one or more of micronized elemental copper or copper-containing compounds and a liquid carrier medium, such as water or an organic solvent in which the micronized copper is insoluble.
• the exemplary copper containing compounds include copper carbonates, copper oxides, copper hydroxides, copper chlorides, copper aromatic or aliphatic carboxylates, copper aminocarboxylates, and combinations thereof.
• the copper containing compound can also be any other suitable copper compounds known to those skilled in the art.
• micronized means a particle size in the range of 0.001 to 25 microns.
• particle size refers to the largest axis of the particle, and in the case of a generally spherical particle, the largest axis is the diameter.
• the insoluble micronized copper particles in the copper-based composition typically have a size such that wherein at least 95% of the particles have a particle diameter of from about 0.05 to about 1 .5 microns, preferably from about 0.05 to about 1 micron, and most preferably from about 0.05 to about 0.7 microns. This type of insoluble metal material is referred to herein as dispersed metal.
• the biocidal metal ion may be a biocidal zinc ion.
• the biocidal zinc may advantageously be incorporated into the formulation in the form of inorganic zinc salts, such as carbonate, bicarbonate, chloride, hydroxide, borate, oxide or phosphate.
• the zinc may be in the form of an organozinc compound such as a simple organic salt, such as formate or acetate, or as a complex such as N-nitroso-N- cyclohexyl-hydroxylamine- zinc (zinc-HDO), zinc naphthenate or zinc pyrithione (bis(2-pyridylthio)zinc 1 ,1 '- dioxide - CAS number 13463-41 -7).
• Other exemplary zinc compounds include zinc oxide, zinc carbonate, zinc chloride, zinc borate and zinc pyrithione.
• the metal may be included in the formulation of the invention as a solubilized metal ion, in addition to the dispersed or emulsified metal ions.
• Suitable methods for solubilizing metal ions such as copper and zinc are known in the art, for example from WO93/02557.
• Suitable complexing agents for the copper or zinc ion include, for example, polyphosphoric acids such as tripolyphosphoric acid; ammonia; water soluble amines and alkanolamines capable of complexing with copper or zinc cations; aminocarboxylic acids such as glycine, glutamic acid, ethylenediaminetetraacetic acid (EDTA), hydroxyethyldiamine triacetic acid, nitrilotriacetic acid and N-dihydroxy ethylglycine.
• polyphosphoric acids such as tripolyphosphoric acid; ammonia; water soluble amines and alkanolamines capable of complexing with copper or zinc cations
• aminocarboxylic acids such as glycine, glutamic acid, ethylenediaminetetraacetic acid (EDTA), hydroxyethyldiamine triacetic acid, nitrilotriacetic acid and N-dihydroxy ethylglycine.
• Exemplary complexing agents are selected from alkanolamines, such as monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, and tripropanolamine. Ethanolamines are generally used, with monoethanolamine being of particular interest.
• the cationic polymer used in the preservative composition includes chitosan; cationic derivative of natural polymers such as guar gum, starch, cellulose and hydroxycellulose; a polymer or copolymer having one or more of the following repeating units of formula (I), (II), (III) or (IV):
• n is between 1 to 5000;
• x is an integer equal to 0, 1 or 2;
• y is an integer equal to 0 or 1 ;
• z is an integer equal to 2 or 3 and when z is 3, the nitrogen atom of formula II I carries a positive charge and a counter ion X- is present;
• w 2 or 3;
• R ' is a divalent group having one or more of the following groups Vi- Vs:
• FT is H, OH, or N(R) x ;
• a is 0 to 20;
• X " is any anion selected from chloride, bromide, iodide, fluoride, sulphate, phosphate, carboxylate especially propionate and lactate, carbonate, bicarbonate, nitrate, nitrite, hydroxide, cyanide;
• Exemplary cationic polymers for use in the formulations of the invention include: chitosan, cationic derivatives of natural polymers including guar gum, starch, cellulose and hydroxyl cellulose; Polydiallyldimethylammonium chlorides (polyDADMAC), including polyDADMAC-co-sulphones (DADMAC-C0-SO2), polyDADMAC-co-hydroxyethylcellulose (DADMAC-co-HEC), polyDADMAC-co- acrylamide (DADMAC-co-AM), polyDADMAC-co-acrylic acid (DADMAC-co-AA), and acrylic acid -DADMAC-acrylamide terpolymers (AA-co-DADMAC-AM); Polydiallylmethylamine chlorides (polyDAMAmC), including epichlorohydrin derivatives; Polydiallyamine chlorides (polyDAAmC), including polyDAAmC-co- sulphones (DAAmC-co-SO2), polyDAAmC-co-maleic
• the cationic polymer will have a molecular weight of about 1 ,000 to about 1 0,000, and typically will be in the range of about 2,000 to about 5,000.
• the preservative composition will generally contain between about 0.001 % to about 1 0% by weight of the cationic polymer; typically between about 0.01 % to about 4.0% by weight.
• a particularly useful range of the cationic polymer is in the 0.01 and 1 .0%.
• Exemplary cationic natural polymers include, for example, Guar Hydroxypropyltrimonium Chloride (Guar gum 2-hydroxy-3-(trimethylammonio) propyl ether chloride CAS# 65497-29-2); Hydroxypropyl Guar Hydroxypropyltrimonium Chloride (Guar gum, 2-hydroxypropyl 2-hydroxy-3-(trimethylammonio)propyl ether, chloride CAS# 71329-50-5); Starch Hydroxypropyltrimonium chloride (Starch, 2- hydroxy-3-(trimethylammonio)propyl ether, chloride CAS# 56780-58-6); Cellulose, omega-ether with alpha-2-hydroxy-3-(trimethylammonio) propyl-omega- hydroxypoly(oxy-1 ,2-ethanediyl) chloride (Polyquaternium-10, CAS# 68610-92-4); Hydroxyethyl cellulose dimethyl diallylammonium chloride copolymer (Polyquaternium
• Exemplary polyionenes include, for example, Poly[(dimethyliminio)-1 ,3- propanediyl(dimethyliminio)-1 ,6-hexanediylbromide (1 :2)] (Hexadimethrine Bromide, lonene-6,3 Bromide; CAS# 28728-55-4), Poly[(dimethyliminio)-1 ,3- propanediyl(dimethyliminio)-1 ,6-hexanediylchloride (1 :2)] (Hexadimethrine Chloride, lonene-6,3 Chloride; CAS# 68393-49-7), Poly[oxyethylene (dimethyliminio) ethylene (dimethylimino) ethylene dichloride] (Polixetonium chloride, Polyquaternium 42; CAS# 31512-74-0), Poly[(dimethyliminio)-1 ,3-propanediyl
• stabilizers may be used either in place of or in combination with the cationic polymer and/or the quaternary ammonium compound.
• Such stabilizers include enzymes, organic polymers and mixtures thereof, wherein the stabilizer is present in an amount which will allow the preservative composition to effectively penetrate the wood being protected.
• Particular enzymes include for example a lipase, lipoxygenase, esterase, laccase, peroxidase, pectinase, protease, amylase, cellulase, and/or xylanase.
• organic polymers include for example an acrylamide polymer or copolymers, and/or polyethylene oxide or copolymer.
• organic polymers include alkyl polyglucosides, for example Ce-Cio alkyl polyglucosides.
• Particular quaternary ammonium compounds include trimethylalkyl quaternary ammonium compounds such as cocotrimethyl ammonium chloride; dialkyldimethyl quaternary ammonium compounds such as didecyl dimethyl ammonium chloride, didecyl dimethyl ammonium carbonate, didecyl dimethyl ammonium bicarbonate, dioctyl dimethyl ammonium chloride and octyl decyl dimethyl ammonium chloride, or mixtures thereof; alkyl dimethyl or diethyl benzyl ammonium salts such as benzalkonium chloride and benzalkonium hydroxide; polyethoxylated quaternary ammonium compounds such as N,N-didecyl-N-methyl- poly(oxyethyl) ammonium propionate (Bardap 26) or N.N-didecyl-N-methyl-poly(oxyethyl) ammonium lactate; and N-substi
• quaternary ammonium compounds may include monoalkylmethyl bisalkoxylated quaternary ammonium salts such as cocoalkylmethyl bis(hydroxyethyl) ammonium chloride, ethoxylated; dialkyl bisalkoxylated quaternary ammonium salts such as didecyl bis(hydroxyethyl) ammonium hydroxide, ethoxylated.
• Other quaternary ammonium compounds may include quaternary ammonium compounds described herein which are complexed with an additional compound, such as a boron containing compound, for example, boric acid.
• An example of such a quaternary ammonium complex is didecyl bis(hydroxyethyl) ammonium borate, also referred to as a polymeric betaine, having the general formula D
• This particular compound has a CAS# 21470-34-6.
• the complex is a complex of a dialkyl bisalkoxylated quaternary ammonium salts with boric acid.
• Other quaternary ammonium compound may also include quaternary amine salts formed by the protonation of monoalkylamines, dialkylamines, trialkylamines, and mono bisalkoxylated amines at pH values below their pKa.
• quaternary ammonium compounds of particular interest are benzalkonium chloride, didecyl dimethyl ammonium chloride and didecyl dimethyl ammonium carbonate. Of these quaternary ammonium compounds, didecyl dimethyl ammonium carbonate has been found to be particularly effective.
• Types of wood which can benefit from treatment with the formulations of the invention include sawn timber, logs, glulam (glued laminated lumber), plywood, laminated veneer lumber (LVL), wood based composite products such as oriented strand board (OSB), medium density fiberboard (MDF), fiberboard, hardboard and particle board.
• OSB laminated veneer lumber
• MDF medium density fiberboard
• wood in the context of this invention does not encompass living trees or other plants.
• Other cellulosic materials which can benefit from treatment with the formulations of the invention are lignocellulosic substrates, wood plastic composites, cardboard and cardboard faced building products such as plasterboard, and cellulosic material such as cotton. Also, leather, textile materials and even synthetic fibers, hessian, rope and cordage as well as composite wood materials.
• the invention is described with reference to the treatment of wood but it will be appreciated that other cellulosic materials may be treated analogously.
• the formulations are applied to sawn timber, logs or laminated veneer lumber, OSB or MDF.
• the preservative compositions of the present invention are applied as a liquid composition. They may also be applied as a solid implant or paste.
• Impregnation under pressure is particularly advantageous when the substrate is wood or a wood composite material which is made to become wet during its life, for example, wood for window frames, timber used above ground in exposed environments such as decking and timber used in ground contact or fresh water or salt water environments.
• the preservative compositions of the invention are preferably used in immersion treatments of wood, in particular immersion treatments which utilize a vacuum and/or pressure.
• a wood treatment system comprising a storage tank adapted to receive the wood to be treated and in said tank a volume of treatment solution comprising a dispersed and/or emulsified phase and a stabilizer as defined herein.
• the system further comprises an autoclave.
• the system comprises means to apply a vacuum or pressure, e.g. 25-95% of a full vacuum and 8-12 bar pressure.
• Substrates made of wood or cellulosic material which have been treated with a formulation or product or by a method according to the invention as described herein, comprise further aspects of the present invention. Additionally, substrates made of wood or other cellulosic material containing a dispersed and/or emulsified phase and a stabilizer (e.g. a formulation) according to the invention comprise a further aspect of the present invention.
• a stabilizer e.g. a formulation
• micronized copper-based dispersion was prepared by micronizing basic copper carbonate (BCC) from a single source using a commercial grinding apparatus, and adding dispersing agents to prevent agglomeration of the micronized particles.
• BCC basic copper carbonate
• a micronized copper concentrate containing about 60% solids was prepared by mixing basic copper carbonate with water, a polycarboxylate dispersant, and a lignosulfonate dispersant wherein the dispersants were used in a 10:1 mixture, respectively. The mixture was mechanically stirred using a high speed mixer for 30 minutes. The mixture was then transferred into a LabStar bead mill, supplied by Netzsch Laboratories, and milled for 90 minutes at 1200 rpm.
• An emulsifiable azole concentrate was prepared at 1 0 weight percent azoles and 1 :1 wt. ratio of Tebuconazole and Propiconazole in a surfactant and/or solvent.
• Emulsifiable azole/imidacloprid concentrates were prepared at 10.5 wt. percent actives with a 1 :1 :0.1 wt. ratio of Tebuconazole, Propiconazole and Imidacloprid in a surfactant and/or solvent.
• the copper/azole composition was prepared by adding 272.7 grams of the micronized copper concentrate and 36.6 gram of the azole concentrate to water. The final weight of the wood treating solution was brought up to 1 00 pounds. The composition was calculated to be 0.2 weight percent copper and 0.008 weight percent azoles.
• the azole/imidacloprid emulsion control was prepared by adding 217.7 grams of the azole/imidacloprid concentrate to water. The final weight of the wood treating solution was brought up to 100 pounds. The emulsion was calculated to be 0.005 weight percent azoles and 0.0025 weight percent imidacloprid. The emulsion was made 4 times and mixed together and then separated into 4 equal samples.
• preservative treatment solutions were aged to replicate commercial treatment plant solutions by the addition of Southern pine sawdust at 3.5% w/w and stirring for 1 hour. Solutions were then filtered to remove sawdust prior to wood treatment.
• Sample 1 (aged) - Copper/azole composition with 500 ppm didecyl dimethyl ammonium carbonate.
• Each of the treatment solutions were used to treat six southern yellow pine boards (2 inch x 6 inch x 24 inches).
• the boards were placed in an autoclave and were subjected to a vacuum of 24 inches of Hg for 5 minutes. Then the treatment solution was added to the autoclave and subjected to a pressure of 150 psi for a period of 20 minutes. The treatment solution was removed from the autoclave and then the boards were subject to 24 inches of Hg vacuum for 30 minutes. The boards were removed from the autoclave.
• the solution uptake for each of the solutions was determined and is reported in Table 1 . As can be seen, gains in preservative solution uptake of 1 .8 to 8.3% were seen with the presence of stabilizing additives.
• Sample 1 (aged) - Copper/azole composition with 500 ppm didecyl dimethyl ammonium carbonate.
• Each of the treatment solutions were used to treat six southern yellow pine boards (2 inch x 6 inch x 24 inches).
• the boards were placed in an autoclave and were subjected to a vacuum of 24 inches of Hg for 5 minutes. Then the treatment solution was added to the autoclave and subjected to a pressure of 150 psi for a period of 10 minutes. The treatment solution was removed from the autoclave and then the boards were subject to 24 inches of Hg vacuum for 30 minutes. The boards were removed from the autoclave.
• the solution uptake for each of the solutions was determined and is reported in Table 2. Stabilizing additives resulted in a 23-36% increase in solution uptakes.
• Sample 1 (aged) - Copper/azole composition with 200 ppm polyvinylamine.
• Sample 3 (aged) - Copper/azole composition with 200 ppm polyamine high MW.
• Sample 4 (aged) - Copper/azole composition with 200 ppm poly(diallyldimethyl ammonium chloride).
• Sample 5 (aged) - Copper/azole composition with 200 ppm of polyionene were used to treat a southern yellow pine board (2 inch x 6 inch x 24 inches). The boards were placed in an autoclave and were subjected to a vacuum of 24 inches of Hg for 5 minutes. Then the treatment solution was added to the autoclave and subjected to a pressure of 150 psi for a period of 25 minutes. The treatment solution was removed from the autoclave and then the boards were subject to 24 inches of Hg vacuum for 30 minutes. The boards were removed from the autoclave. The solution uptake for each of the solutions was determined and is reported in Table 3. Gains of up to 50% in solution uptake were seen when stabilizing additives when included in the treatments.
• Sample 1 copper/azole/Cs alkyl glucoside (44 ppm) composition.
• Sample 4 copper/azole/Ce alkyl glucoside (44 ppm) composition.
• Sample 5 copper/azole/Ce alkyl glucoside (88 ppm) composition.
• Each of the treatment solutions were used to treat six end-sealed southern yellow pine boards (2 inch x 6 inch x 8 inches).
• the boards were placed in an autoclave and were subjected to a vacuum of 24 inches of Hg for 5 minutes. Then the treatment solution was added to the autoclave and subjected to a pressure of 150 psi for a period of 10 minutes. The treatment solution was removed from the autoclave and then the boards were subject to 24 inches of Hg vacuum for 30 minutes. The boards were removed from the autoclave.
• the solution uptake for each of the solutions was determined and is reported in Table 4. All samples had increased solution uptakes vs. the control.
• Zone 1 exitterior 1 ⁇ 4"
• Zone 2 second 1 ⁇ 4"
• Zone 3 core
• Tables 5 and 6 Improved penetration gradients for copper and azole preservatives were observed for all samples in Zone 2 and/or Zone 3.
• Each of the treatment solutions were used to treat six southern yellow pine boards (2 inch x 6 inch x 24 inches).
• the boards were placed in an autoclave and were subjected to a vacuum of 24 inches of Hg for 5 minutes. Then the treatment solution was added to the autoclave and subjected to a pressure of 150 psi for a period of 10 minutes. The treatment solution was removed from the autoclave and then the boards were subject to 24 inches of Hg vacuum for 30 minutes. The boards were removed from the autoclave.
• the solution uptake for each of the solutions was determined and is reported in Table 7.
• Zone 1 exitterior 1 ⁇ 4"
• Zone 2 second 1 ⁇ 4"
• Zone 3 core
• Tables 8 and 9 Improved penetration gradients for azole and imidacloprid preservatives were observed for all samples vs. control in Zone 2 and/or Zone 3.

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