Wood preservative composition

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.

Claims

1. A wood preservative composition comprising a) a wood preservative component comprising an insoluble metal material in a liquid, the insoluble metal material comprising a biocidal metal being dispersed copper or dispersed zinc; b) a stabilizer comprising a cationic polymer; and; c) optionally a boron containing biocide; wherein the stabilizer is present in an amount effective to stabilize the wood preservative component thereby facilitating the wood preservative component to penetrate a wood substrate intended to be protected by the wood preservative composition; and wherein the cationic polymer comprises polymers or copolymers having one or more of the following repeating units of formula (1); (II), (III) or (IV): ##STR00007## 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 z is 3, the nitrogen atom of formula III carries 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″, —CO2H, —CO2R″, —CH2CO2H, —CH2CO2R″, CH2NR″R″, —CH2CH(OH)CH2Cl, —(C═O)NR″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; w is 2 or 3; R′ is a divalent group having one or more of the following groups V1-V8: ##STR00008## in which: R′″ is H, OH, or N(R)x; a is 1 to 20; and X— is any anion selected from chloride, bromide, iodide, fluoride, sulphate, phosphate, carboxylate, carbonate, bicarbonate, nitrate, nitrite, hydroxide, and cyanide; or mixtures of the cationic polymers; wherein the amount of the cationic polymer or copolymer is less than the biocidal metal on a weight to weight basis.

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

3. The wood preservative composition according to claim 1, further comprising at least one azole, wherein the at least one azole comprises thiabendazole, imazalil, carbendazim, prochloraz, triadimefon, triadimenol, triazbutil, propiconazole, cyproconazole, difenoconazole, fluquinconazole, tebuconazole, flusilazole, uniconazole, diniconazole, bitertanol, hexaconazole, azaconazole, flutriafol, epoxyconazoie, tetraconazole, penconazole, ipconazole, prothioconazole or mixtures thereof.

4. The wood preservative composition according to claim 2, further comprising a second azole.

5. The wood preservative composition according to claim 4, wherein the at least one azole and the second azole, comprise tebuconazole and propiconazole.

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

7. The wood preservative composition according to claim 1, wherein the wood preservative composition includes a quaternary ammonium compound.

8. The wood preservative composition according to claim 7, wherein the quaternary ammonium compound is selected from the group consisting of 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 foregoing quaternary ammonium compounds with a complexing agent, or mixtures thereof.

9. The wood preservative composition according to claim 7, wherein 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 mixtures thereof.

10. The wood preservative composition according to claim 1, wherein the wood preservative component further comprises an organic fungicide selected from the group consisting of amides, anilides, anilinopyrimidine, aromatic compounds, fungicidal heterocyclic compounds, strobilurins, isothiazolones, cyclohexylhydroxydiazene 1-oxide, potassium salt, pyrion compounds, or mixtures thereof.

11. The wood preservative composition according to claim 1, wherein the wood preservative component further comprises a colorant, water repellent, fire retardant, binder, emulsifier, co-solvent, dispersant, UV inhibitor, antioxidant, or a combination thereof.

12. The wood preservative composition according to claim 1, wherein the biocidal metal comprises dispersed copper, wherein the dispersed copper comprises micronized copper dispersed in a solvent, or wherein the biocidal metal comprises dispersed zinc, wherein the dispersed zinc comprises micronized zinc dispersed in a solvent.

13. The wood preservative composition according to claim 1, wherein the cationic polymer has a molecular weight between 1,000 and 100,000.

14. The wood preservative composition according to claim 1, wherein the composition contains between about 0.01% and 4% by weight of the cationic polymer.

15. The wood preservative composition according to claim 1, further comprising an organic polymer comprises an acrylamide polymer or copolymer, a polyethylene oxide or copolymer, an alkyl polyglucoside, or a mixture thereof.

16. A method of preserving wood or other cellulosic material which comprises applying to the wood or other cellulosic material a wood preservative composition of claim 1.

17. 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 wood preservative composition as defined in claim 1.

18. A wood preservative composition comprising a) a wood preservative component comprising an insoluble metal material in a liquid, the insoluble metal material comprising a biocidal metal being disposed copper or dispersed zinc; b) a stabilizer, wherein the stabilizer selected from the group consisting of cationic polymers, organic polymers, quaternary ammonium compounds and mixtures thereof, wherein the quaternary ammonium compounds are selected from the group consisting of methyl alkyl quaternary ammonium compounds, dialkyldimethyl quaternary ammonium compounds and polyethoxylated quaternary ammonium compounds; and c) optionally a boron containing biocide; wherein the wood preservative composition further comprises an organic fungicide selected from the group consisting of amides, anilides, anilinopyrimidine, aromatic compounds, fungicidal heterocyclic compounds, strobilurins, azoles, isothiazolones, cyclohexylhydroxydiazene 1-oxide, potassium salt, pyrion compounds, quaternary ammonium compounds and mixtures thereof; wherein the stabilizer is present in an amount effective to stabilize the wood preservative component thereby facilitating the wood preservative component to penetrate a wood substrate intended to be protected by the wood preservative formulation, and wherein the amount of the biocidal metal is greater than the amount of the stabilizer on a weight by weight basis.

19. The wood preservative composition according to claim 18, wherein the biocidal metal comprises a biocidal copper compound, and further comprises an azole.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(1) 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 composition applied.

(2) 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.

(3) 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 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.

(4) 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.

(5) 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; fungicidal heterocyclic compounds such as dazomet, fenpropimorph, bethoxazin and dehydroacetic acid; strobilurins such as azoxystrobin; 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 mixtures thereof.

(6) 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)

(7) ##STR00001##
wherein X denotes CR.sup.4 or N; R.sup.1 denotes hydrogen or a linear, branched, cyclic, aromatic or any combination thereof, saturated or unsaturated, substituted or unsubstituted C.sub.1 to C.sub.40 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.sup.2 denotes hydrogen, C.sub.1-C.sub.8 alkyl, C.sub.2-C.sub.8 alkenyl, C.sub.6-C.sub.10 aromatic, C.sub.5-C.sub.10 heteroaromatic or C.sub.1-C.sub.4 alkyl carbamate; and R.sup.3 and R.sup.4 denote hydrogen; or together R.sup.3 and R.sup.4 may provide a benzimidazole group (i.e. R.sup.3 and R.sup.4 may combine to form —(CH).sub.4— linkage).

(8) 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. However, the use 1,2,4-triazoles in the formulations of the invention is of particular interest.

(9) 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.

(10) 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.

(11) An exemplary triazole compounds include a triazole compound selected from compounds of formula (B):

(12) ##STR00002##
wherein R.sup.5 represents a branched or straight chain C.sub.1-5 alkyl group (e.g. t-butyl), and R.sup.6 represents a phenyl group optionally substituted by one or more substituents selected from halogen (e.g. chlorine, fluorine or bromine) atoms or C.sub.1-3 alkyl (e.g. methyl), C.sub.1-3 alkoxy (e.g. methoxy), phenyl or nitro groups.

(13) Alternatively, the triazole compound is advantageously selected from compounds of formula (C):

(14) ##STR00003##
wherein R.sup.7 is as defined for R.sup.6 above, and R.sup.5 represents a hydrogen atom or a branched or straight chain C.sub.1-5 alkyl group (e.g. methyl, ethyl, propyl, etc).

(15) Particular 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.

(16) 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 Illustratively, U.S. Patent Application Nos. 2006/0062926 and 2005/0255251 and U.S. Pat. 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.

(17) The term “micronized” as used herein means a particle 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 diameter. 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 insoluble metal material is referred to herein as dispersed metal.

(18) 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. 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-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.

(19) 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 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. 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 combination with each other. 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.

(20) 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), (Ill) or (IV):

(21) ##STR00004##
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 z is 3, the nitrogen atom of formula III carries a positive charge and a counter ion X.sup.− 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″, —CO.sub.2H, —CO.sub.2R″, —CH.sub.2CO.sub.2H, —CH.sub.2CO.sub.2R″, CH.sub.2NR″R″, —CH.sub.2CH(OH)CH.sub.2Cl, —(C═O)NR″R″, —CN, —(CH.sub.2).sub.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; w is 2 or 3; R′ is a divalent group having one or more of the following groups V.sub.1-V.sub.8:

(22) ##STR00005##
in which; R′″ is H, OH, or N(R).sub.x; a is 0 to 20; and X.sup.− 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 cationic polymers.

(23) 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-co-S.sub.2), 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-SO.sub.2), polyDAAmC-co-maleic acid (DAAmC-co-MA); polyallylamines (polyAAm) including polyDAAmC-co-AAm; polyamines, including 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 imidazole, and quaternized polyvinyl imidazole; polyamides; polyvinyl amides, including polyvinyl pyrrolidone and polyvinyl caprolactam; polyvinyl formamides; poly(acryloyloxy trimethyl ammonium (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 trimethyl 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).

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

(25) 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 contain 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 cationic polymer is in the 0.01 and 1.0%.

(26) 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-4 CAS #92183-41-0); and chitosan (CAS #9012-76-4).

(27) Exemplary polyionenes include, for example, Poly[(dimethyliminio)-1,3-propanediyl(dimethyliminio)-1,6-hexanediylbromide (1:2)] (Hexadimethrine Bromide, Ionene-6,3 Bromide; CAS #28728-55-4), Poly[(dimethyliminio)-1,3-propanediyl(dimethyliminio)-1,6-hexanediylchloride (1:2)] (Hexadimethrine Chloride, Ionene-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 bromide(1:1)] (Ionene-3,3; CAS #31622-87-4), Poly[(dimethyliminio)-1,6-hexanediylbromide (1:1)] (Ionene-6,6; CAS #31622-88-5), Poly[(dimethyliminio)-1,6-hexanediyl(dimethyliminio)-1,10-decanediyldibromide (1:2)] (Ionene-6,10; CAS #28728-57-6), Poly[(dimethyliminio)-1,2-ethanediyl(dimethyliminio)-1,5-pentanediylbromide(1:2)] (Ionene-2,5; CAS #51325-19-0), [α-[4-[Tris(2-hydroxyethyl)ammonio]-2-buten-1-yl]-ω-[tris(2-hydroxyethyl)ammonio]poly[(dimethyliminio)-2-butene-1,4-diyl Chloride] Chloride; (Polidronium Chloride; Polyquaternium 1; CAS #75345-27-6), and Poly[bis(2-chloroethyl)ether 1,3-bis[3-(dimethylamino)propyl]urea] quaternized (Polyquaternium 2; CAS #68555-36-2).

(28) Other 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.

(29) Particular enzymes include for example a lipase, lipoxygenase, esterase, laccase, peroxidase, pectinase, protease, amylase, cellulase, and/or xylanase.

(30) Particular organic polymers include for example an acrylamide polymer or copolymers, and/or polyethylene oxide or copolymer. Further examples of organic polymers include alkyl polyglucosides, for example C.sub.6-C.sub.10 alkyl polyglucosides.

(31) 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-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 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

(32) ##STR00006##

(33) This particular compound has a CAS #21470-34-6. In this case, 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.

(34) Of these 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.

(35) 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. It will be understood that “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. 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.

(36) For convenience, the preservative compositions of the present invention are applied as a liquid composition. They may also be applied as a solid implant or paste. The application of these formulations may be by one or more of dipping, deluging, spraying, brushing or other surface coating means or by impregnation methods, e.g. high pressure 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. 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.

(37) 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. Thus, in a further 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 herein. 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 pressure.

(38) 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.

(39) The present invention is further described in detail by means of the following Examples. All parts and percentages are by weight and all temperatures are degrees Celsius unless explicitly stated otherwise.

EXAMPLES

(40) 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 particles.

(41) 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.

(42) 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 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.

(43) 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 pounds. The composition was calculated to be 0.2 weight percent copper and 0.008 weight percent azoles.

(44) 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.

(45) 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.

(46) The following treatment solutions were made for Example 1.

Example 1

(47) Control (fresh)—Copper/azole composition without additives.

(48) Control (aged)—Copper/azole composition without additives.

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

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

(51) Each of the treatment solutions were used to treat six southern yellow pine boards (2 inch×6 inch×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.

(52) TABLE-US-00001 TABLE 1 Uptake % Increase vs. Sample (lbs/cu ft.) Control (aged) Control (fresh) 30.5 — Control (aged) 27.6 — Sample 1 (aged) 28.1 1.8 Sample 2 (aged) 29.9 8.3

Example 2

(53) Control (fresh)—Copper/azole composition without additives.

(54) Control (aged)—Aged copper composition without additives.

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

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

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

(58) Each of the treatment solutions were used to treat six southern yellow pine boards (2 inch×6 inch×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.

(59) TABLE-US-00002 TABLE 2 Uptake % Increase vs. Sample (lbs/cu ft.) Control (aged) Control (fresh) 27.7 — Control (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

(60) Control (aged)—Copper/azole composition without additives.

(61) Sample 1 (aged)—Copper/azole composition with 200 ppm polyvinylamine.

(62) Sample 2 (aged)—Copper/azole composition with 200 ppm polyamine low MW.

(63) Sample 3 (aged)—Copper/azole composition with 200 ppm polyamine high MW.

(64) Sample 4 (aged)—Copper/azole composition with 200 ppm poly(diallyldimethyl ammonium chloride).

(65) Sample 5 (aged)—Copper/azole composition with 200 ppm of polyionene.

(66) Each of the treatment solutions were used to treat a southern yellow pine board (2 inch×6 inch×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.

(67) TABLE-US-00003 TABLE 3 Uptake % Increase vs. Sample (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

(68) Control—copper/azole (25/1 w/w) composition without additives.

(69) Sample 1—copper/azole/C.sub.8 alkyl glucoside (44 ppm) composition.

(70) Sample 2—copper/azole/C.sub.8 alkyl glucoside (88 ppm) composition.

(71) Sample 3—copper/azole/C.sub.8 alkyl glucoside (176 ppm) composition.

(72) Sample 4—copper/azole/C.sub.6 alkyl glucoside (44 ppm) composition.

(73) Sample 5—copper/azole/C.sub.6 alkyl glucoside (88 ppm) composition.

(74) Sample 6—copper/azole/C.sub.6 alkyl glucoside (176 ppm) composition.

(75) Each of the treatment solutions were used to treat six end-sealed southern yellow pine boards (2 inch×6 inch×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.

(76) TABLE-US-00004 TABLE 4 Uptake % Increase Sample (lbs/cu ft.) vs. Control Control 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

(77) Wafers (2 inch×6 inch×0.5 inches) were taken from each board and cut into 3 zones: Zone 1 (exterior ¼″), Zone 2 (second ¼″), and Zone 3 (core). Each zone was ground into sawdust and analyzed 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.

(78) TABLE-US-00005 TABLE 5 Zone 2 Zone 3 Cu, as % of Zone 1 % Change % Change Sample Zone 1 Zone 2 Zone 3 vs. Control vs. Control Control 100 76.7 69.9 — — Sample 1 100 82.1 81.1 7.1 16.0 Sample 2 100 74.0 71.0 −3.5 1.6 Sample 3 100 84.2 88.4 9.8 26.5 Sample 4 100 85.2 89.1 11.0 27.5 Sample 5 100 76.8 77.8 0.2 11.3 Sample 6 100 73.9 76.6 −3.7 9.6

(79) TABLE-US-00006 TABLE 6 Zone 2 Zone 3 Azole, as % of Zone 1 % Change % Change Sample Zone 1 Zone 2 Zone 3 vs. Control vs. Control Control 100 43.6 29.0 — — Sample 1 100 45.6 33.3 4.7 14.8 Sample 2 100 43.9 31.6 0.7 8.8 Sample 3 100 45.8 37.3 5.1 28.4 Sample 4 100 50.8 41.0 16.7 41.2 Sample 5 100 46.2 33.8 6.0 16.6 Sample 6 100 45.4 31.8 4.4 9.6

Example 5

(80) Control—Azole/Imidacloprid emulsion without additives.

(81) Sample 1—Azole/Imidacloprid/polyamine low MW (50 ppm) emulsion.

(82) Sample 2—Azole/Imidacloprid/polyamine low MW (100 ppm) emulsion.

(83) Sample 3—Azole/Imidacloprid/polyamine low MW (150 ppm) emulsion.

(84) Sample 4—Azole/Imidacloprid/polyamine low MW (200 ppm) emulsion.

(85) Each of the treatment solutions were used to treat six southern yellow pine boards (2 inch×6 inch×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.

(86) TABLE-US-00007 TABLE 7 Uptake % Increase Sample (lbs/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

(87) Wafers (2 inch×6 inch×0.5 inches) were taken from each board and cut into 3 zones: Zone 1 (exterior ¼″), Zone 2 (second ¼″), 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 penetration gradients for azole and imidacloprid preservatives were observed for all samples vs. control in Zone 2 and/or Zone 3.

(88) TABLE-US-00008 TABLE 8 Zone 2 Zone 3 Azoles, as % of Zone 1 % Change % Change Sample Zone 1 Zone 2 Zone 3 vs. Control vs. Control Control 100 33.9 16.6 — — Sample 1 100 48.4 29.5 0.0 0.0 Sample 2 100 48.0 30.6 −0.8 3.7 Sample 3 100 55.0 35.1 13.6 18.8 Sample 4 100 53.9 34.6 11.4 17.0

(89) TABLE-US-00009 TABLE 9 Zone 2 Zone 3 Imidacloprid, as % of Zone 1 % Change % Change Sample Zone 1 Zone 2 Zone 3 vs. Control vs. Control Control 100 43.8 31.3 — — Sample 1 100 61.1 50.0 39.7 60.0 Sample 2 100 55.6 50.0 27.0 60.0 Sample 3 100 61.1 55.6 39.7 77.8 Sample 4 100 68.8 56.3 57.1 80.0

(90) 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 invention concept disclosed herein. Accordingly, it is intended to embrace all such changes, modifications, and variations that fall within the spirit and broad scope of the appended claims.