NZ725411B2 - Wood preservative composition - Google Patents

Abstract

The present invention provides wood preservative composition containing a dispersed and/or emulsified phase comprising a wood preservative component; and a stabilizer. The stabilizer is a cationic polymer, an enzyme, organic polymer, quaternary ammonium compound and/or a mixture thereof. Also provided is a method of preserving wood or other cellulosic material which comprises applying to the wood or other cellulosic material. Wood preservative compositions of the invention can be used repeatedly. ed is a method of preserving wood or other cellulosic material which comprises applying to the wood or other cellulosic material. Wood preservative compositions of the invention can be used repeatedly.

Description

WOOD PRESERVATIVE ITION FIELD OF THE INVENTION The present invention relates to a wood preservative composition and a method of treating wood and other cellulosic material with the wood preservative composition.

BACKGROUND OF THE ION Many types of wood preservative treatments exist on the market today.

These treatments can be surface applied by spray or dip, or impregnated into the wood by vacuum pressure immersion treatments. During industrial ation of preservatives, the wood is typically impregnated with the treatment composition containing the wood preservative composition to achieve either shell or full cell type penetration into the wood substrate. ing on the wood species being treated and the end use, the depth of penetration of the treatment composition into the wood can have a significant bearing on the useful service life of the d wood.

A typical industrial treatment plant will consist of a e tank to hold the treatment composition and an autoclave. Wood or other cellulosic material is charged into the ave and the autoclave is then flooded with treatment composition.

Combinations of vacuum and pressure are d to e 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 ition 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 e age of a treatment composition increases as a function of solution refresh rates. This can extend from several days to many months. As a , the treatment composition is repeatedly exposed to wood being treated increasing the average age of the composition.

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 al, 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 ed that disruptive substances from wood or cellulosic extractives increase in the preservative composition after each and every treatment. This reduces the ability of the preservative to penetrate the wood or cellulosic substrate in uent treatments and over time as the composition is edly used. One remedy to this problem is taught in , assigned to Arch Timber Protection. However, the method described in WO 2013/064798 does not address sed and/or fied phases, which typically contain anionic, nonionic or anionic/nonionic blends of dispersants and emulsifiers.

The stability of systems with dispersants and emulsifiers is a te balance of steric and electrostatic mechanisms. Any significant changes in pH and/or solution charge can irreversibly disrupt this stability. on of acidic compounds to anionic dispersions, for example, can ilize the composition and cause agglomeration and settling of dispersed nds or creaming of fied material. This is commonly observed in wood preservatives systems containing dispersed biocides, emulsified water repellents, dispersed pigments, etc. In the present ion, various stabilizing compounds are disclosed which protect dispersed and/or emulsified phases from the disruptive substances generated during the wood treatment. Unexpectedly, ic polymers, enzymes, c 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.

Accordingly, there is a need in the art for improving both stability and penetration of dispersed and/or emulsified phases in biocidal ations into wood.

The present invention provides an answer to that need.

SUMMARY OF THE INVENTION [0009a] ing to a first aspect of the t invention there is provided a wood preservative composition comprising: a) an emulsified phase including a wood preservative component comprising a biocidal metal and at least one azole; and b) a quaternary ammonium compound xed with a boroncontaining biocide. [0009b] According to a second aspect of the present invention there is provided a wood preservative composition comprising: a) an fied phase including a wood vative component: the wood preservative component comprising a biocidal metal and at least two azoles; and b) a quaternary ammonium compound complexed with a boron containing biocide.

In one form, the present invention provides wood preservative compositions containing a dispersed and/or fied phase comprising a wood preservative ent; and a izer. The stabilizer is a cationic polymer, an enzyme, an organic polymer, a quaternary ammonium compound and/or a mixture thereof. The izer 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.

In r form of the present invention, the dispersed and/or emulsified phase contains a biocidal agent, colorant, water repellent, fire retardant, binder, emulsifier, co-solvent, dispersant, UV inhibitor, idant, or a combination thereof. The al 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.

In a particular ment, 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.

In another embodiment, the cationic polymer is chitosan, cationic derivative of natural polymers selected from guar gum, starch, cellulose or hydroxycellulose, a r or copolymer having one or more of the following ing units of formula (I), (II) or (III) 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 n 0.01% and 4% by weight of the cationic polymer.

In yet a further ment of the present invention, 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 um compounds; hoxylated quaternary ammonium; N-substituted 3a (the next page is page 4) nium compounds, monoalkyl methyl bisalkoxylated quaternary um compounds, dialkyl bisalkoxylated quaternary ammonium compounds, a protonated amine, a protonated dialkylamine or a protonated trialkylamine, protonated kyl bisalkoxylated amine, a complex of one or more of the forgoing quaternary ammonium compounds with a complexing agent, or mixtures thereof.

In another embodiment of the present invention, the quaternary ammonium compound is dialkyldimethyl quaternary ammonium compound selected from the group consisting of didecyl dimethyl um chloride, didecyl dimethyl ammonium carbonate, l dimethyl ammonium bicarbonate, dioctyl dimethyl ammonium chloride and octyl decyl dimethyl ammonium chloride, or a mixtures f.

In a further embodiment, the stabilizer may be an enzyme, wherein the enzyme comprises a lipase, lipoxygenase, esterase, laccase, peroxidase, pectinase, protease, amylase, cellulase and/or xylanase.

In yet a r embodiment, the stabilizer may be an organic polymer, wherein the organic r is an acrylamide r or copolymer, a polyethylene oxide or copolymer, an alkyl polyglucoside, or a mixture f.

In another aspect of the present invention, provided is 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 t invention.

In a further aspect of the present invention provided is a wood treatment system containing a storage tank adapted to receive the wood to be treated and in said tank a volume of treatment on sing a wood preservative ition of any of the previous embodiments of the present invention.

These and other aspects will become apparent when reading the detailed description of the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS It has now been surprisingly found that 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. As used herein, 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 ition appHed.

The wood preservative contains a dispersed and/or emulsified phase and a izer. The dispersed and/or emulsified phase is ed from the group consisting of al agents, nts, water repellents, fire retardants, s, 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.

It has been discovered that such 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 s of wood or osic substrates. That is, the preservative composition of the present invention does not agglomerate, settle or separate over time and retains its ability to ate wood or cellulosic substrates even after the wood preservative has been used to treat le 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 iably lose its ability to ate wood or cellulosic substrates even after the wood preservative has been used to treat multiple s 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 ides including fungicidal amides such as prochloraz, penthiopyrad, fluanid and tolylfluanid; anilide fungicides such as sedaxane and penflufen; anilinopyrimidine ides such as pyrimethanil, cyprodinil or mepanipyrim; fungicidal aromatic compounds such as chlorthalonil, cresol, dicloran, pentachlorophenol, sodium pentachlorophenol, 2—(thiocyanatomethylthio)-1,3- benzothiazole (TCMBC), dichlorophen, xonil and oxyquinoline; fungicidal heterocyclic compounds such as dazomet, fenpropimorph, bethoxazin and dehydroacetic acid; strobilurins such as trobin; azoles; isothiazolones; Potassium HDO (cyclohexylhydroxydiazene 1 -oxide, potassium salt), pyrion compounds such as sodium pyrithione, zinc pyrithione, copper pyrithione, 1-hydroxy- 2—pyridinone and pyrion disulfide; quaternary ammonium compounds, and es thereof.

The azole compound, Le. a compound comprising an azole group, may be an imidazole or a 1,2,4-triazole and is preferably represented by the general formula wherein X denotes CR4 or N; Ft1 denotes hydrogen or a linear, branched, , ic or any combination f, saturated or unsaturated, substituted or unsubstituted 01 to C40 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; R2 denotes hydrogen, 01-08 alkyl, Cz-Cs alkenyl, 06-010 aromatic, 05-010 heteroaromatic or C1-C4 alkyl carbamate; and R3 and R4 denote hydrogen; or together R3 and R4 may provide a benzimidazole group (i.e. R3 and R4 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 WO 68456 or more 1,2,4-triazoles. However, the use 1,2,4-triazoles in the formulations of the invention is of particular interest.

An ole compound incorporates a five-membered aturated 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 embered 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): H2 H2 I RG—c —c —C—R5 wherein R5 represents a branched or straight chain 01-5 alkyl group (e.g. t- butyl), and R6 represents a phenyl group optionally tuted by one or more substituents selected from halogen (e.g. chlorine, fluorine or bromine) atoms or 01-3 alkyl (e.g. methyl), 01.3 alkoxy (e.g. methoxy), phenyl or nitro groups.

Alternatively, the le compound is advantageously selected from nds of formula (C): wherein R7 is as defined for Ft6 above, and R8 ents a hydrogen atom or a branched or straight chain C1—5 alkyl group (e.g. methyl, ethyl, propyl, etc). ular triazoles include, but are not d to, triadimefon, triadimenol, triazbutil, onazole, cyproconazole, difenoconazole, fluquinconazole, nazole, azole, uniconazole, diniconazole, bitertanol, hexaconazole, azaconazole, flutriafol, epoxyconazoie, tetraconazole, penconazole, ipconazole, oconazole and mixtures thereof.

In one particular embodiment, the biocidal metal is a copper or a zinc metal.

The biocidal metal may be a dispersed or an insoluble metal material. Examples of insoluble copper, such as in the form of submicron or micronized particles are lllustratively, U.S. Patent Application Nos. 2006/0062926 and 2005/0255251 and US Patent No. 8,409,627, the disclosures of which are orated 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 nds 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.

The term "micronized" as used herein means a le size in the range of 0.001 to 25 microns. The term "particle size" refers to the largest axis of the particle, and in the case of a generally spherical particle, the largest axis is the er.

Typically 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 ble 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 nic zinc salts, such as carbonate, bicarbonate, de, hydroxide, borate, oxide or phosphate.

Alternatively, 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- exyl-hydroxylamine- zinc (zinc-HDO), zinc naphthenate or zinc pyrithione (bis(2—pyridylthio)zinc 1,1'- dioxide - CAS number 134637). Other exemplary zinc compounds include zinc oxide, zinc carbonate, zinc chloride, zinc borate and zinc pyrithione.

In another embodiment, 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 W093/02557. 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 xing with copper or zinc cations; aminocarboxylic acids such as glycine, glutamic acid, nediaminetetraacetic acid (EDTA), hydroxyethyldiamine triacetic acid, nitrilotriacetic acid and N-dihydroxy lycine. Where the complexing agents are acidic in nature they may be employed either as free acids or as their alkali metal or ammonium salts. These complexing agents may be used either alone or in ation with each other. Exemplary complexing agents are selected from lamines, such as monoethanolamine, diethanolamine, triethanolamine, 2015/028616 monopropanolamine, dipropanolamine, and tripropanolamine. Ethanolamines are generally used, with monoethanolamine being of particular interest.

The cationic r 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): a. ing units of formula (I) ( CH2)y ( CH2)X “ ( CH2)X b. repeating units of formula (II) N+/Rl R R c. repeating units of formula (III) \ III N (R)z .

WO 68456 d. repeating units of formula (IV) wherein 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 2 is 3, the nitrogen atom of formula III s a positive charge and a counter ion X- is present; R groups, which can be identical or different, are each independently hydrogen or a straight chain, branched or cyclic alkyl, alkenyl, alkynyl, alkanoxyl, aryl, -(C=O)H, - (C=O)R", -COzH, -CO2R", -CH2COzH, -CHzCO2R", CH2NRHR", -CH2CH(OH)CH2CI, - R”R”, -CN, -(CH2)w-O-R”, in which; R” groups, which can be identical or different, are hydrogen or a straight chain, branched or cyclic alkyl, alkenyl, alkynyl, alkanoxyl or aryl; wis20r3; R' is a nt group having one or more of the following groups V1- V8; E—O—I WO 68456 +E+ (V2), —NH— (vs), —C— (V4), —0— (V5), C=N— (V6), T T C—N+— (V7), and/or H (vs), 2015/028616 in which; R'” is H, OH, or N(R)x; a is 0 to 20; and X- is any anion selected from chloride, bromide, iodide, fluoride, sulphate, phosphate, carboxylate especially propionate and lactate, carbonate, bicarbonate, nitrate, nitrite, hydroxide, cyanide; or mixtures of the ic polymers.

Exemplary cationic polymers for use in the formulations of the invention include: an, cationic derivatives of l polymers including guar gum, starch, cellulose and hydroxyl cellulose; Polydiallyldimethylammonium chlorides (polyDADMAC), including DMAC-co-sulphones (DADMAC-co-802), DMAC-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-802), polyDAAmC-co-maleic acid (DAAmC-co-MA); polyallylamines (polyAAm) including polyDAAmC-co-AAm; polyamines, ing branched and linear epihalohydrin derivatives of polyamines or polyamidoamines, branched and linear polyethyleneimines (PEI), and polyionenes; polyvinyl amines (PVAm) including vinyl amine/ vinyl formamide copolymers, polyvinyl ole, and quaternized polyvinyl imidazole; polyamides; polyvinyl amides, ing nyl pyrrolidone and polyvinyl actam; polyvinyl formamides; poly(acryloyloxy trimethyl um (polyAcETA) or poly(methacryloyloxyethyl trimethyl ammonium) (polyMacETA) salts including polyMacETA-co-acrylamide (MacETA-co-Am), and polyMacETA-co-vinyl pyrrolidone (MacETA-co-VP); poly(acrylamidopropyl trimethyl ammonium) (polyAmPTA) or poly(methacrylamidopropyl hyl ammonium) (polyMamPTA) salts, including polyMamPTA-co-vinyl pyrrolidone (MamPTA-co-VP) and poly(acrylic acid-co-MamPTA-co-methyl acrylate) (AA-co-MamPTA-co-Mac).

Of particular interest are nylamines, polyDADMACs, polyamines (both high and low MW polyamines), and polyionenes.

Generally the cationic polymer will have a molecular weight of about 1,000 to about 10,000, and typically will be in the range of about 2,000 to about 5,000. The preservative composition will generally n between about 0.001% to about 10% by weight of the cationic polymer; typically between about 0.01% to about 4.0% by weight. A particularly useful range of the ic polymer is in the 0.01 and 1.0%.

Exemplary cationic natural polymers include, for example, Guar Hydroxypropyltrimonium Chloride (Guar gum 2-hydroxy(trimethylammonio) propyl ether de CAS# 65497-29—2); Hydroxypropyl Guar Hydroxypropyltrimonium Chloride (Guar gum, 2-hydroxypropyl 2-hydroxy(trimethylammonio)propyl ether, chloride CAS# 71329—50-5); Starch Hydroxypropyltrimonium chloride (Starch, 2- hydroxy(trimethylammonio)propyl ether, chloride CAS# 56780-58—6); Cellulose, omega-ether with alphahydroxy(trimethylammonio) -omega- hydroxypoly(oxy-1,2-ethanediyl) chloride (Polyquaternium-10, CAS# 686104); Hydroxyethyl cellulose dimethyl diallylammonium chloride mer (Polyquaternium-4 CAS# 921830); and chitosan (CAS# 90124).

Exemplary nenes include, for e, 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# 315120), Poly[(dimethyliminio)-1,3-propanediyl e(1:1)] (lonene-3,3; CAS# 87-4), Poly[(dimethyliminio)-1,6-hexanediylbromide (1:1)] (lonene-6,6; CAS# 31622-88—5), Poly[(dimethyliminio)-1,6-hexanediyl(dimethyliminio)-1,10- decanediyldibromide(1:2)] (lonene-6,10; CAS# 28728—57-6), Poly[(dimethyliminio)- 1,2-ethanediyl(dimethyliminio)-1,5—pentanediylbromide(1:2)] (lonene-2,5; CAS# 51325-19—0), [or-[4-[Tris(2-hydroxyethyl)ammonio]butenyl]-(,o-[tris(2- hydroxyethyl)ammonio]poly[(dimethyliminio)butene-1,4-diyl Chloride] Chloride; (Polidronium Chloride; Polyquaternium 1; CAS# 753456), and Poly[bis(2- chloroethyl)ether s[3-(dimethylamino)propyl]urea] quaternized (Polyquaternium 2; CAS# 68555—36-2).

Other stabilizers may be used either in place of or in combination with the ic polymer and/or the quaternary ammonium compound. Such stabilizers include s, organic polymers and mixtures thereof, wherein the stabilizer is t in an amount which will allow the preservative composition to effectively penetrate the wood being protected.

Particular enzymes include for e a lipase, lipoxygenase, se, e, peroxidase, pectinase, protease, amylase, cellulase, and/or xylanase.

Particular organic polymers include for e an acrylamide polymer or copolymers, and/or polyethylene oxide or mer. Further examples of c polymers include alkyl polyglucosides, for example 06-010 alkyl polyglucosides.

Particular quaternary ammonium compounds include trimethylalkyl quaternary ammonium compounds such as cocotrimethyl ammonium chloride; dialkyldimethyl quaternary um compounds such as didecyl dimethyl ammonium chloride, didecyl dimethyl ammonium carbonate, didecyl dimethyl ammonium bicarbonate, dioctyl dimethyl um chloride and octyl decyl dimethyl ammonium chloride, or mixtures thereof; alkyl yl or diethyl benzyl ammonium salts such as konium de and benzalkonium hydroxide; polyethoxylated quaternary ammonium compounds such as N,N-didecyl-N-methyl- poly(oxyethyl) ammonium nate (Bardap 26) or N.N-didecyl-N-methyl-poly(oxyethyl) ammonium lactate; and N-substituted pyridinium compounds such as cetyl pyridinium chloride. Further examples of 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 um 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 , also referred to as a polymeric betaine, having the general formula D ”seepage 'fi‘iffi” fiiz§$§§ .e {3ft smegma, . figs“; ,3 m; . m;‘ v ‘ a: "1 a it {1' m ‘\ . m m{2: {:fiigfifizfi ‘ " 2 " E {Itsfizt (D).

This particular compound has a CAS# 214706. In this case, the complex is a complex of a dialkyl bisalkoxylated quaternary ammonium salts with boric acid.

Other quaternary ammonium nd may also include quaternary amine salts formed by the protonation of monoalkylamines, dialkylamines, trialkylamines, and mono bisalkoxylated amines at pH values below their pKa.

Of these quaternary ammonium nds 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 t from ent 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. It will be understood that "wood" in the t 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 rboard, and cellulosic material such as cotton. Also, leather, e materials and even synthetic fibers, hessian, rope and cordage as well as composite wood materials.

For convenience, the invention is described with reference to the treatment of wood but it will be appreciated that other cellulosic materials may be treated analogously.

Generally, though not exclusively, the formulations are applied to sawn timber, logs or laminated veneer lumber, OSB or MDF.

For convenience, the preservative compositions of the t invention are applied as a liquid ition. They may also be applied as a solid implant or paste.

The application of these formulations may be by one or more of g, ng, spraying, brushing or other surface coating means or by impregnation methods, e.g. high re or double vacuum impregnation into the body of the wood or other material, all being techniques well known to the man skilled in the art. lmpregnation under pressure is ularly 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 ably used in immersion treatments of wood, in particular immersion treatments which utilize a vacuum and/or pressure. Thus, in a r aspect, the present invention provides 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 . Optionally the system further comprises an autoclave. Optionally the system comprises means to apply a vacuum or pressure, e.g. 25-95% of a full vacuum and 8-12 bar re.

Substrates made of wood or cellulosic material which have been d 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.

The present invention is r described in detail by means of the following Examples. All parts and tages are by weight and all temperatures are degrees Celsius unless explicitly stated otherwise.

EXAMPLES The 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 les.

A micronized copper concentrate containing about 60% solids was ed 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 d using a high speed mixer for 30 minutes. The mixture was then transferred into a LabStar bead mill, supplied by h Laboratories, and milled for 90 minutes at 1200 rpm.

An emulsifiable azole concentrate was prepared at 10 weight percent azoles and 1:1 wt. ratio of Tebuconazole and Propiconazole in a surfactant and/or solvent.

Emulsifiable imidacloprid concentrates were prepared at 10.5 wt. t actives with a 1:1:0.1 wt. ratio of Tebuconazole, onazole 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 100 . The composition was calculated to be 0.2 weight percent copper and 0.008 weight percent azoles.

The imidacloprid emulsion control was prepared by adding 217.7 grams of the azole/imidacloprid trate 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 ted into 4 equal samples.

Where indicated in the following examples, 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.

The following treatment solutions were made for Example 1.

Example 1 Control (fresh) - Copper/azole composition without additives.

Control (aged) - Copper/azole composition without additives.

Sample 1 (aged) — Copper/azole composition with 500 ppm didecyl dimethyl ammonium carbonate.

Sample 2 (aged) — Copper/azole composition with 500 ppm didecyl dimethyl um carbonate and 250 ppm of the cationic polymer, methylamine-co- epichlorohydrin.

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 ave and were subjected to a vacuum of 24 inches of Hg for 5 minutes. Then the ent solution was added to the autoclave and subjected to a pressure of 150 psi for a period of 20 2015/028616 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.

TABLE 1 Sample Uptake % lncrease vs. (lbs/cu ft.) Control (aged) l (fresh) 30.5 Control (aged) 27.6 Sample 1 (aged) 28.1 1.8 Sample 2 (aged) 29.9 8.3 Example 2 Control (fresh) - Copper/azole composition without additives. l (aged) - Aged copper composition without additives.

Sample 1 (aged) — Copper/azole composition with 500 ppm didecyl dimethyl um carbonate.

Sample 2 (aged) — Copper/azole composition with 250 ppm of the cationic polymer, polydimethylamine-co-epichlorohydrin.

Sample 3 (aged) - Copper/azole composition with 500 ppm didecyl dimethyl ammonium carbonate and 250 ppm of the cationic polymer, polydimethylamine-co- orohydrin.

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 ted to a vacuum of 24 inches of Hg for 5 minutes. Then the treatment solution was added to the autoclave and ted 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.

TABLE 2 Sample Uptake % lncrease vs. (lbs/cu ft.) Control (aged) Control (fresh) 27.7 l (aged) 17.5 Sample 1 (aged) 21.6 23.4 Sample 2 (aged) 23.8 36.0 Sample 3(aged) 23.9 36.6 Example 3 Control (aged) - Copper/azole composition without additives.

Sample 1 (aged) - Copper/azole ition with 200 ppm polyvinylamine.

Sample 2 (aged) - Copper/azole ition with 200 ppm polyamine low Sample 3 (aged) - Copper/azole composition with 200 ppm polyamine high Sample 4 (aged) - Copper/azole composition with 200 ppm poly(diallyldimethyl ammonium chloride).

Sample 5 (aged) - Copper/azole ition with 200 ppm of polyionene.

Each of the ent solutions 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 ted 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 d 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.

TABLE 3 Sample Uptake % lncrease vs. (lbs/cu ft.) Control (aged) Control (aged) 22 Sample 1 26 18 Sample 2 30 39 Sample 3 31 43 Sample 4 31 44 Sample 5 33 52 Example 4 Control - copper/azole (25/1 w/w) composition t additives.

Sample 1 - copper/azole/Cs alkyl glucoside (44 ppm) composition.

Sample 2 - copper/azole/ Cs alkyl glucoside (88 ppm) composition.

Sample 3 - copper/azole/ Cs alkyl glucoside (176 ppm) ition.

Sample 4 - copper/azole/Ce alkyl glucoside (44 ppm) composition.

Sample 5 - copper/azole/Ce alkyl glucoside (88 ppm) composition.

Sample 6 - copper/azole/Ce alkyl glucoside (176 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 s. 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 l.

TABLE 4 Sample Uptake % se (IbS/CU ft') vs. Control l 28.2 Sample 1 28.8 2.3 Sample 2 28.8 2.0 Sample 3 29.7 5.3 Sample 4 29.1 3.0 Sample 5 30.0 6.2 Sample 6 31.2 10.5 Waters (2 inch x 6 inch x 0.5 inches) were taken from each board and cut into 3 zones: Zone 1 (exterior 1/4”), Zone 2 (second 1/4”), and Zone 3 (core). Each zone was ground into sawdust and ed for copper and azoles. The relative wt. % copper and azoles in each zone are shown in Tables 5 and 6. Improved penetration gradients for copper and azole preservatives were observed for all samples in Zone 2 and/or Zone 3.

TABLE 5 Sample Cu, as % of Zone 1 Zone 2 Zone 3 Zone1 Change % Change vs. Control vs. l Control 100 Sample 1 100 Sample 2 100 Sample 3 100 Sample 4 100 Sample 5 100 Sample 6 100 TABLE 6 Sample Azole, as % of Zone 1 Zone 2 Zone 3 Zone1 Change % Change vs. Control vs. Control Control 100 Sample 1 100 Sample 2 100 Sample 3 100 Sample 4 100 Sample 5 100 Sample 6 100 Example 5 Control - Azole/lmidacloprid emulsion without ves.

Sample 1 - Azole/lmidacloprid/polyamine low MW (50 ppm) emulsion.

Sample 2 - Azole/lmidacloprid/polyamine low MW (100 ppm) emulsion.

Sample 3 - lmidacloprid/polyamine low MW (150 ppm) emulsion.

Sample 4 - Azole/lmidacloprid/polyamine low MW (200 ppm) emulsion.

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 ted to a vacuum of 24 inches of Hg for 5 minutes. Then the treatment solution was added to the ave 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.

] TABLE 7 Sample Uptake % lncrease (IbS/CU ft') vs. Control Control 26.0 Sample 1 35.5 36.7 Sample 2 36.4 40.0 Sample 3 34.4 32.2 Sample 4 35.5 36.7 Waters (2 inch x 6 inch x 0.5 inches) were taken from each board and cut into 3 zones: Zone 1 ior 1/4”), Zone 2 (second 1/4”), and Zone 3 (core). Each zone was ground into sawdust and analyzed for azole and imidacloprid concentration. The relative azole and imidacloprid concentrations in each zone are shown in Tables 8 and 9. Improved ation gradients for azole and imidacloprid preservatives were observed for all samples vs. control in Zone 2 and/or Zone 3.

TABLE 8 Sample Azoles, as % of Zone 1 Zone 2 Zone 3 Zone1 Change % Change VS' Control vs. Control Control 100 Sample 1 100 Sample 2 100 Sample 3 100 Sample 4 100 TABLE 9 loprid, as % of Zone 1 Zone 2 Zone 3 % Change % Change vs. Control vs. Control Control 100 Sample 1 100 60.0 Sample 2 100 60.0 Sample 3 100 77.8 Sample 4 100 80.0 While the invention has been described above with references to specific embodiments thereof, it is apparent that many changes, modifications and variations can be made without departing from the ion concept disclosed herein. ingly, it is intended to embrace all such changes, modifications, and variations that fall within the spirit and broad scope of the appended claims.

THE

Claims (18)

CLAIMS DEFINING THE ION ARE AS FOLLOWS:-

1. A wood preservative composition comprising: a) an emulsified phase ing a wood preservative 5 component comprising a biocidal metal and at least one azole; and b) a quaternary ammonium compound complexed with a boron-containing biocide.

2. The wood preservative ition according to claim 1, wherein the 10 quaternary ammonium is present in an amount less than the biocidal metal on a weight to weight basis.

3. The wood preservative composition according to claim 1, wherein the at least one azole comprises an imidazole, a 1,2,4-triazole, or mixtures thereof.

4. The wood preservative composition according to claim 1, wherein the at least one azole comprises thiabendazole, imazalil, dazim, prochloraz, triadimefon, triadimenol, triazbutil, propiconazole, cyproconazole, conazole, fluquinconazole, tebuconazole, flusilazole, uniconazole, 20 nazole, bitertanol, hexaconazole, azaconazole, flutriafol, epoxyconazoie, tetraconazole, penconazole, ipconazole, prothioconazole or mixtures thereof.

5. The wood preservative composition according to claim 1, further comprising a second azole.

6. The wood preservative composition according to claim 5, wherein the at least one azole and the second azole, comprise nazole and propiconazole. 30

7. The wood preservative composition according to claim 1, wherein the wood preservative component further includes imidacloprid.

8. The wood preservative composition according to claim 1, wherein the biocidal metal comprises zinc, copper, or both zinc and copper.

9. The wood preservative composition according to claim 8, wherein the 5 zinc, the copper, or both the zinc and the copper comprises micronized zinc or micronized .

10. The wood preservative composition according to claim 1, wherein the wood preservative composition es a second quaternary ammonium 10 compound.

11. The wood preservative composition according to claim 10, wherein the second quaternary ammonium compound is selected from the group consisting of trimethyl alkyl quaternary ammonium compounds; dialkyldimethyl 15 quaternary ammonium compounds; alkyl dimethyl or alkyl diethyl benzyl ammonium nds; polyethoxylated quaternary ammonium; N-substituted nium compounds, monoalkyl methyl oxylated quaternary ammonium compounds, dialkyl bisalkoxylated quaternary ammonium compounds, a ated amine, a protonated dialkylamine or a protonated trialkylamine, 20 protonated monoalkyl bisalkoxylated amine, a complex of one or more of the foregoing quaternary ammonium compounds with a xing agent, or mixtures thereof.

12. The wood preservative composition ing to claim 10, wherein 25 the second quaternary ammonium compound is dialkyldimethyl nary ammonium compound selected from the group consisting of didecyl dimethyl ammonium de, didecyl dimethyl ammonium carbonate, didecyl dimethyl ammonium bicarbonate, dioctyl dimethyl ammonium chloride and octyl decyl dimethyl um de, or mixtures thereof.

13. The wood preservative composition according to claim 1, wherein the emulsified phase further comprises organic fungicides selected from the group consisting of amides, anilides, anilinopyrimidine, aromatic compounds, fungicidal heterocyclic compounds, strobilurins, azolones, exylhydroxydiazene 1 -oxide, potassium salt, pyrion compounds, or mixtures thereof.

14. The wood preservative composition according to claim 1, further sing a cationic polymer, an enzyme, an organic polymer, or mixtures thereof. 10 15. The wood preservative composition according to claim 1, wherein the biocidal metal comprises a biocidal copper compound, and wherein the wood preservative composition further comprises tebuconazole, propiconazole, and imidacloprid.

15

16. The wood preservative composition according to claim 1, further comprising copper or zinc complexed with an amino compound.

17. A wood preservative composition comprising: a) an fied phase ing a wood preservative component: 20 the wood preservative component comprising a biocidal metal and at least two ; and b) a quaternary ammonium compound complexed with a boron containing biocide. 25

18. The wood preservative composition according to claim 17, n the biocidal metal comprises a biocidal copper compound, and wherein the wood preservative composition further includes tebuconazole, onazole, and imidacloprid.