CA1305835C - Wood preservatives and process for using same - Google Patents

Abstract

Abstract of The Disclosure The present invention provides for a composi-tion for preserving wood comprising (A) at least one metal salt of an organic carboxylic acid containing at least about 6 carbon atoms; (B) an effective amount of at least one oil to disperse and/or dissolve said salt in said oil; and (C) an effective amount of at least one thickener to provide said composition with a grease-like consistency. Optional ingredients include (D) solvent/-diluents; (E) surfactants; and/or (F) wood-stabilizing agents. The invention further provides for a method for treating wood using the foregoing composition; this method is particularly suitable for treating wood that is already in place such as standing poles (e.g., util-ity poles).

Description

)5835 Technical Field This invention relates to novel compositions and to a process for preserving wood using said composi-tions. The compositions comprise certain metal salts dispersed in oil having a thickened grease-like consist-ency. The inventive process involves treating wood using these compositions and is particùlarly suitable for the ground-line treatment of standing poles, such as utility poles and the like.
Backqround of ~he Inven~ion There are many methods of applying preserva-tives to wood prior to the time the wood is put in use.
The compositions of the present invention also have utility in this respect, such as treatment of new or used utility poles in storage prior to installation~
The inventive compositiona are intended primarily for use on wood already in place,i such as poles, posts, sills, toe plates, stair risers, etc.: and the present invention will be described primarily in connection with this use.
One of the chief uses for the present invention is in extending the usable life of poles already in line. Some of these poles may have been in place many years and the application of the present composition thereto adds extra years of life to the pole~ Those poles which were poorly pretreated or pretreated with inferior preservatives may be again treated, while in 1305~33S

place, with the inventive composition along the pole.
Poles which are removed from one location to be set in another, usually at a different depth, can be advan-tageously treated with the composition of the invention.
The inventive composition is a grease, or a grease-like material, which may be applied by hand-spreading, by a mechanical grease gun, or on a paper or plastic film or bandage. On poles it is applied at the ground line area, where deterioration is most likely to occur.
There are at present several wood preservative greases that are in commercial use. Chapman Chemical a Company markets a grease under the name ~Pol-Nu" which is believed to contain 81% solvent, 9.2% pentachloro-phenol, 1.1~ other chlorinated phenols and 8.7% inerts.
Androc Chemical Company m~a~kets a grease under the name "Androc Penta--Creo ~aste" which is believed to contain 15% creosote, 10% pentachlorophenol, 10~ sodium fluoride and the remainder consisting of oil, thickeners and fil-lers. Osmose Wood Preserving~Company markets a grease under the name "Osomplastic" which is believed to con-tain 46% sodium fluoride, 3.4% dinitrophenol, 2~ potas-sium dichromate, 0.8% pentachlorophenol, 33% coal tar, 2.9% asbestos, and 11.9% solvent and thickener. Wood Preserva Produc~ts markets a grease under the name ~Preserva Life" which is believed to contain 21.5%
sodium fluoride, 13.4% dinitro phenol, 12.2% of a mixture of water, tar and oil, 9.6~ arsenious anhydride, 4.3% pentachlorophenol, 0.6% other chlorophenols, 3.8~
aromatic petroleum solvents, and the remainder consist-ing of solvents, binders, cohesives and blending agents.
While each of these wood preservatives are believed to be meritorous, none are entirely satisfactory.

13()5~5 U.S. Patent 2,904,467 discloses a wood preserv-ative material which is described as being useful for the ground-line treatment of poles and comprises at least 2~ pentachlorophenol, 50-95% mineral oil, and a compound of bentonite and an organic-nitrogen base in an amount sufficient to impart a grease-like consistency to the preservative material.
Summ~ry of the Invention The present invention provides for a composi-tion for preserving wood comprising (A) at least one metal salt of an organic carboxylic acid containing at least about 6 carbon atoms; (B) an effective amount of at least one oil to disperse and/or dissolve said salt in said oil; and (C) an effective amount of at least one thickener to provide said composition with a grease-like consistency. Optional ingredients include (D) solvent/-diluents; (E) surfactants; and/or (F) wood-stabilizing agents. The invention further provides for a method for treating wood using the foregoing composition; this method is particularly suitable for treating wood that is already in place such as standing poles (e.g., util-ity poles), posts, sills, toe plates, stair risers, etc.
~ &~iE~ion of the-Preferred ~m~Q~imç~s The compositions of the present invention comprise certain metal salts dispersed in oil having a thickened grease-like consistency.
(A): Metal_Salts The compositions of the present invention contain a preservative-effective amount of at least one metal salt of an organic carboxylic acid containing at least about 6 carbon atoms. Preferably, the metal salt is soluble in oil. The oil-solubility of the metal salts used in the mixture is believed to contribute to 13058;~;

the advantageous and desirable results which are obtained. Since these salts are oil-soluble and essen-tially hydrophobic, they do not have a tendency to be extracted or leached from the treated wood even over an extended period of time.
Particularly preferred types of oil-soluble metal salts which are useful in the compositions of the present invention are the acid, neutral and basic salts of organic carboxylic acids. These salts also are known in the art as ~soaps", and the two terms are used inter-changeably in this specification and in the claims.
The choice of metal contained in the salts will depend upon the properties which are desired to be imparted to the wood being treated, availability, cost and effectiveness. For example, copper salts such as copper naphthenate are fungicides as well as insecti-cides. Certain metals are more commonly used in the method o~ the invention, and these include, copper, zinc, zirconium, chromium, iron, antimony, lead and mercury. Salts containing a mixture of the ions of two or more of tbese metals also can be used.
As mentioned, the salts can be acid, neutral or basic. The acid salts contain insufficient metal cation to neutrali~e the acid. The neutral salts contain an amount of metal cation just sufficient to neutralize the acidic groups present in the salt anion. The basic salts contain an excess of metal cation and are often referred to as overbased, h~perbased or superbased salts. These acid, basic and neutral salts preferably are of oil-soluble organic carboxylic acids and mixtures of such acids.
The carboxylic acids from which suitable acid, neutral and basic salts can be prepared include alipha-~305~3~;

tic, cycloaliphatic and aromatic mono- and polybasic carboxylic acids containing 6 or more carbon atoms. The organic carboxylic acids can be either natural or syn-thetic or mixtures thereof. The examples of natural acids, although usually refined, include straight and branched chain carboxylic acids and mixtures such as tall oil acids and cyclic carboxylic acids such as naphthenic acids. A variety of synthetic carboxylic acids, and particularly aliphatic carboxylic acids or mixtures thereof is useful.
The metal salts or soaps can be prepared by fusion or precipitation methods. The soaps normally are prepared in an inert liquid medium such as a hydrocarbon oil or solvent. The organic carboxylic acids generally will have at least 6 carbon atoms and as many as 30 carbon atoms, but when more than one carboxylic acid is employed, carboxylic acids containing as few as 2 carbon atoms may be employed as one of the acids of th* mix-ture. Examples of useful organic carboxylic acids include acetic acid, propionic acid, butyric acid, isopentanoic acid, hexanoic acid, 2-ethyl butyric acid, nonanoic acid, decanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, neodecanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, naphthenic acid, and commercially avail-able mixtures of two or more carboxylic acids such as naphthenic, tall oil acids, rosin acids, etc.
Examples of acid salts are acid copper salts containing less than a stoichiometric equivalent of copper per acid equivalent. For metals other than copper, the basic salts or soaps are preferred since these contain higher amounts of metal. For example, solutions of normal zinc salts of monocarboxylic acids ~30583S

such as neodecanoic acid contain about 6% zinc by weight whereas a solution of a basic zinc neodecanoate can contain up to about 16% by weight or more of zinc.
Basic metal salts or soaps of carboxylic acids also can be prepared by methods well known in the art.
Examples of neutral and basic salts and of metal salt complexes as well as their preparation can be found in, for example, U.S. Patents 2,251,798; 2,955;949;

3,723,152 and 3,941,606. Some of the basic salts have been referred to as complexes because they are not simple salts. For example, the basic compositions described in U.S. Patent 3,941,606 are referred to as "metal carboxylate-alkoxy alcoholate" complexes. For the purpose of this invention such basic complexes are to be included in the term metal salts or soaps as used in this specification and claims.
Specific examples of the salts or soaps which are useful in the invention include those described below in Table I and the following specific examples.
TABLE I
Carboxylate Metal Salts Metal Content Component Metal(Wt.~) Acid A-l~l Cu 16 neodecanoic A-1-2 Cu 11 neodecano.ic A-1-3 Cu 10 naphthenic A-1-4 Zn 18 2-ethyl hexanoic A-1-5 Zn 8 naphthenic A-1-6 Zn 10 mixture of C
A-1-7 ~b 10 naphthenic 9 13 X

13(~58~5 The preparation of the above-described metal salts is illustrated by the following examples. All parts and percentages in the following examples, and elsewhere in the specification and claims, are by weight, and all temperatures are in degrees centigrade, unless otherwise stated.
Example A-l-l A mixture of 260 parts of crude neodecanoic acid, 103 parts of propionic acid, 400 parts of mineral spirits, 172 parts of copper powder, 91 parts of Methyl Cellosolve, 14 parts of dipropylene glycol, 70 parts of water, 10 parts of octyl-phenoxy polyethoxy ethanol (Triton X-15 ~rom Rohm & Haas Company) and 3 parts of Santoflex-77 is prepared and sparged with air while heating to a temperature of about 80C. Reaction under these conditions continues for about 6 hours. A small amount of boric acid (7 parts) is added and the heating is continued at 80C with air sparging. The reaction is continued at this temperature until about 1.8 equiva-lents of metal are reacted per equivdlent of acid (total, 14 hours). The mixture is heated for an addi-tional 2 hours at a temperature of about 150C until about 1.9 equivalents of metal are reacted per equiva-lent of acid. The air blowin~ i8 terminated, and an inert nitrogen atmosphere i~ employed while the mixture is slowly heated to about 150C over a period of 8 hours while excess water is removed.
Four approximately equal proportions of amyl phosphate totalling 176 parts are added at 3-hour inter~
vals while maintaining a temperature of about 145C and a nitrogen atmosphere. The mixture then is cooled to about 125C, settled to remove excess copper and fil-tered.

130~;~335 The filtered product is heated under vacuum to a temperature of about 150C in order to remove the mineral spirits to yield the desired concentration of metal.
The compositions of Examples A-1-2 through A-1-7 in Table I can be prepared by methods similar to those described above for A-l-l or by alternative procedures known in the art.
Example A-1-8 A mixture of 840 parts of distilled naphthenic acid, 176 parts of 2-ethyl hexanoic acid, 512 parts of mineral spirits, 48 parts of Carbitol (a diethylene glycol ether available commercially from Union Carbide Corp.), 4.8 parts of acetic acid, 1.6 parts of water and 10.9 parts of an anti-foam agent is charged to a reactor, and the mixture is heated with agitation to a temperature of about 65C. The mixture is sparged with carbon dioxide and 214.4 parts of zinc oxide are added to the mixture which is then heated to a temperature of about 105C. The reaction is continued at this temper-ature while periodic checks are made for percent zinc, the acid value and percent water. If ne~essary, the acid value is adjusted to minus 33 to minus 38 for 10%
zinc. If the water conten~ is over 0.4~, the mixture is dehydrated. About 100 parts of filter aid are added with stirring to the mixture which is then filtered.
The filtrate is a clear liquid which is adjusted to a zinc content of 10~ using mineral spirits to form the desired product.
Mineral spirit solutions of metal carboxylate salts of the type described above are available commer-cially such as from Mooney Chemicals, Inc., Cleveland, Ohio, 44113, under the general trade designations TEN-13~5F~3S

~ 1 7 n 7 ~v~ T )`'I TCEM, C~M-ALL, NAP-ALL, HEX-CEM, LIN-ALL, and NEO-NAP.
These mineral spirit solutions can be used in the compositions of the present invention or can be adopted for use by mixing said mineral spirit solutions with other hydrocarbon solvents, or alternatively, the mineral spirits may be removed and the residue mixed directly with the oil (B).
Mixtures of the carboxylic acid salts such as those described in Table I are easily prepared and utilized in accordance with the invention. For example, a mixture in accordance with the invention is prepared from equal parts of components A-l-l and A-1-6 resulting in a mixture containing 8% copper and 5~ zinc. A
mixture of two parts of component A-l-l with one part of component A-1-6 will contain 10.7% copper and 3.3% of zinc.
The metal salts which are utilized in the compositions of the present invention also may be prepared by conventional procedures such as by the reaction of copper metal or a copper salt with the acid, for example, naphthenic acid. When the acid is a liquid, solvents are not generally required. The metal salts prspared in this manner may be either acid or neutral salts as described above and can be diss~lved or dispersed in the oil ~B) for use in the present inven-tion.
Examples of other neutral and basic salts include lead naphthenate, lead neodecanoate, lead 2-ethyl hexanoate, lead tallate, zinc tallate, chromium 2-ethyl hexanoate, chromium tallate, chromium oleate, antimony octanoate, antimony oleate, iron naphthenate, iron tallate, phenyl mercury oleate, mercury dioleate, etc.

~30583S

Although a wide variety of metal salts can be utilized in the present invention, it generally is preferred that the metal salt utilized in the process is a fungicide, and, accordingly, the metal of the metal salt generally will be at least one of zinc, copper, chromium, zirconium, iron, antimony, lead or mercury.
In addition to the metal salts described above, other metal salts known in the art can be applied to wood in accordance with the process of the present invention.
For example, metal salt compositions are described in U.S. Patent 4,374,854 (this patent being incorporated herein by reference) which are mixtures of salts of primary and/or secondary saturated acyclic carboxylic acids and a tertiary saturated acyclic carboxylic acid with zinc or copper. Such salts are useful in the compositions of the present invention.
(B): Oil The oil that is used in the inventive composi-tion can be a natural or synthetic oil or a mixture thereof. Mineral oils and particularly petroleum oils are preferred.
Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as mineral oils such as liquid petroleum oils and solvent-treated or acid-treated mineral oils of the paraffinic, naph-thenic or mixed paraffinic-naphthenic types. Oils from coal or shale are also useful. Synthetic oils include hydrocarbon oils and halosubstituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc.); poly(l-hexenes), poly(l-octenes), poly(l-decenes), etc. and mixtures ~hereof; al~ylbenzenes (e.g., dodecylbenzenes, ' .

tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes, etc.); polyphenyls (e.g., biphenyls, terphen-yls, alkylated polyphenyls, etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides and the deriva-tives, analogs and homologs thereof and the like.
Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic oils that can be used. These are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methylpolyisopropylene glycol ether having an average molecular weight of about 1000, diphenyl ether of polyethylene glycol having a molecular weight of about 500-1000, diethyl ether of polypropylene glycol having a molecular weight of abo~t 1000-1500, etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixe~
C3-8 fatty acid esters, or the C130xo acid diester of tetraethylene glycol.
Another suitable class of synthetic oils that can be used comprises the esters of dicarboxylic acid~
(e.g., pnthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethyl-ene glycol monoether, propylene glycol, etc.) Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl ~.305~3~5 sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl seba-cate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid and the like.
Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils comprise another useful class of synthetic oils ~e.g., tetraethyl silicate, tetraisopropyl sili-cate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-hexyl)silicate, tetra-(p-tert-butyl-phenyl)-silicate, hexyl-~4-methyl-2-pentoxy)disiloxane, poly(methyl)silox-anes, poly(methylphenyl)siloxanes, etc.). Other synthe-tic oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decane phosphonic acid, etc.), poly-meric tetrahydrofurans and the like.
Unrefined, refined and rerefined oils, either natural or synthetic (as well as mixtures of two or more of any of these) of the type disclosed hereinabove can be used. Unrefined oils are those obtained directly from a natural or s~nthetic source without further puri-fication treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from primary distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined ~30583S

oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purifîcation s~eps to improve one or more properties.
Many such purification techniques are known to those skilled in the art such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used.
Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
(C): Thickene~
A wide variety of thickening agents can be used in the preparation of the compositions of this inven-tion. Included among the thickening agents are alkali and alkaline earth metal soaps of fatty acids and fatty materials having from about 12 to about 30 carbon atoms.
The metals are typified by sodium, lithium, calcium and barium. Examples of fatty materials include stearic acid, hydroxy stearic acid, stearin, oleic acid, palme-tic acid, myristic acid, cottonseed oil acids, and hydrogenated fish oils.
Other thickening agents include salt and salt-soap complexes as calcium stearate-acetate (U.S. Patent 2,197,263), barium stearate acetate (U.S. Patent 2,564,561), calcium stearate-caprylate-acetate complexes (U.S. Patent 2,99g,065), calcium caprylate-acetate (U.S.
Patent 2,999,066), and calcium salts and soaps of low-, intermediate- and high-molecular weight acids and of nut oil acids.

~30583~

Useful thickening agents employed in the grease-like compositions of the invention are essen-tially hydrophilic in character, but which have been converted into a hydrophobic condition by the introduc-tion of long chain hydrocarbon groups onto the surface of the clay particles prior to their use as a component of the grease-like inventive compositions, as, for example, by being subjected to a preliminary treatment with an organic cationic surface-active agent, such as an onium compoundr Typical onium compounds are tetra-alkylammonium chlorides, such as dimethyl dioctadecyl ammonium chloride, dimethyl dibenzyl ammonium chloride and mixtures thereof. This method of conversion, being well known to those skilled in the art, and is believed to require no further discussion. More specifically, the clays which are useful as starting materials in forming the thickening agents to be employed in the inventive compositions, can comprise the naturally occurring chemically unmodified clays. These clays are crystalline complex silicates, the exact composition of which is not subject to precise description, since they vary widely from one natural source to another. These clays can be described as complex inorganic silicates such as aluminum silicates, magnesium silicates, barium silicates, and the like, containing, in addition to the silicate lattice, varying amounts of cation-exchangeable groups such as sodium. ~ydrophilic clays which are particularly useful for conversion to desired thickening agents include montmorillonite clays, such as bentonite, attapulgite, hectorite, illite, saponite, sepiolite, biotite, vermiculite, zeolite clays, and the like.
Examples of commercially available thickenin~
agents that are particularly useful include Cab-O-Sil (a ~;~()58~5 -lS-product of Cabot Corp. identified as colloidal silica particles sintered together in chain-like formations), and HiSil T-600 (a product of PPG Industries, Inc.
identified as a hydrated, amorphous silica).
(D): Solvent/Diluent An optional ingredient that can be included in the compositions of the present invention is at least one solvent/diluent. The solvent/diluent is preferably a hydrocarbon liquid.
Suitable hydrocarbon liquids include aromatic and aliphatic hydrocarbon solvents such as petroleum hydrocarbon solvents, aromatic hydrocarbons, aromatized petroleum distillates, and mixtures of petroleum hydro-carbon solvents and aromatic hydrocarbons. Halogenated hydrocarbon solvents are included within the term ~hydrocarbon solvents~ as utilized in this application and claims. Examples of useful solvents include xylene, toluene, naphtha, light mineral oil, etc. Mineral spirits is particularly useful.
Examples of specific hydrocarbon solvents useful in the present invention include solvents which are principally aliphatic such as No. 2 diesel fuel, Pennzoil 510 oil and 140 Mineral spirits, and solvents which are principally aromatic such as Shell P9 oil (Shell Chemical Co.) and Lilyblad Base L Oil~
(E): Sur~c~tan~
The compositions of the invention also may contain (E) at least one surfactant. Preerably, the surfactants are anionic or nonionic surfactants. Many such surfactants are known in the art. See, for example, McCutcheon's ~Detergents and Emulsifiers", 1979, North American Edition, published by McCutcheon's Division, MC Publishing Corporation, Glen Rock, New 13~5l3.~

Jersey, U.S.A., particularly pages 15-20.
In general, the nonionic surfactants such as those containing ether linkages are particularly useful. Examples of such ether-containing surfactants are those having the general formula Rl-O-[(CEI2)n] H

wherein Rl is an aryl or alkyl group containing from about 6 to about 20 carbon atoms, n is 2 or 3, and x is an integer between 2 and 100. Such surfactants are produced generally by treating fatty alcohols or alkyl-substituted phenols with excess ethylene oxide or propylene oxide. The alkyl carbon chain may contain from about 14 to about 24 carbon atoms and may be derived from a long ehain fatty alcohol such as oleyl alcohol or stearyl alcohol.
Nonionic polyoxyethylene compounds of this type are described in U.S. Patent No. 3,855,085. Such polyoxyethylene compounds are available eommereially under the general trade designations "Surfynol"TM by Air Products and Chemicals, Inc. of Allentown, Pennsylvania, and under the designation "Pluronic"TM or "Tetronic" by BASF Wyandotte Corp. of Wyandotte, Michigan. Examples oE speeiEie polyoxyethylene eondensation produets inelude "Surfynol 465" whieh is a product obtained by reaeting about 10 moles of ethylene oxide with 1 mole of tetramethyldeeynediol. "Surfynol 485" is the produet obtained by reaeting 30 moles of ethylene oxide with tetramethyldeeynediol. "Pluronic L
35" is a product . ~ ;,..
.~

~30~83S

obtained by reacting 22 moles of ethylene oxide with polypropylene glycol obtained by the condensation of 16 A moles of propylene oxide. Also useful is Atlox 1045A
from ICI America, Inc. which is a polyoxyalkylene sorbitol oleate-laurate mixture.
Amine, long chain fatty amine, long chain fatty acid, alkanol amines, diamines, amides, alkanol amides and polyglycol-type surfactants known in the art are also useful. One type found particularly useful is the group obtained by the addition of a mixture of propylene oxide and ethylene oxide to diamines. More specifical-ly, compounds formed by the addition of propylene oxide to ethylene diamine followed by the addition of ethylene oxide are useful and are available commercially from BASF Wyandotte Inc. Chemical Group under the general trade designation ~Tetronicn.
Carbowax-type wetting ageants which are poly-ethyolene glycols having different molecular weigbts have been found to give good results. For example Carbowax ~o. 1000 has a molecular weight range of from about 950 to 1050 and contains from 20 to 24 ethoxy units per molecule. Carbowax No. 4000 has a molecular weight rangle of from about 3000 to 3700 and contains from 68 to 85 ethoxy units per molecule. Other known nonionic glycol derivatives such as polyalkylene glycol ethers and methoxy polyethylene glycols which are available commercially can be utilized as surfactants in the compositions of the invention.
A particularly preferred nonionic surfactant class useful with the present invention are the alkylene oxide-treated alkyl phenols such as the ethylene oxide alkyl phenol condensates sold by the Rohm and Haas Company. A specific example of these is Triton X-100 1~1D5~335 which contains an average of 9-10 ethylene oxide units per molecule, has an HLB value of about 13.5 and a molecular weight of about 628~ Many other suitable nonionic surfactants are known; see, for example, the aforementioned McCutcheon's as well as the treatise "Non-Ionic Surfactants" edited by Martin J. Schick, M.
Dekker Co, New York, 1967.
Anionic surfactants also are useful in the aqueous systems of the invention. Among the useful anionic surfactants are the widely-known metal carboxylate soaps, organo sulfates, sulfonates, sulfocarboxylic acids and their salts, and phosphates.
Various anionic surfactants are readily available commercially, and further informatlon about anionic surfactants can be found in the text "Anionic Surfactants" Parts II and III, edited by W. M.
Linfield, published by Marcel Dekker, Inc., New York, 1976. Examples of commercially available anionic surfactants include those available from Rohm & Haas Company under the names "Triton 770" (a dioctyl sodium sulfosuccinate), "Triton H-55" (a phosphate surfactant, potassium salt), "Triton W-30" and "Triton X-200"
(sodium salts of alkyl aryl polyether sulfonates).
Mixtures of the nonionic and anionic surfactants can be utilized in the compos:itions of the present invention.
(F): Wood-Stabilizing Agents . _ _ Wood-stabilizing agents may be included in the compositions of the invention to provide the wood with improved dimensional stability. Such agents remain in the cell walls, and this bulking action prevents the wood from shrinking. Various chemicals have been 13()583~ii suggested for this purpose in the art of wood treating.
A useful group of stabilizing agents are the polyalkyl-ene glycols, and more particularly, the polyethylene glycols (e.g., diethylene glycol). The polyethylene glycols having molecular weights of up to about 6000 are preferred. Various of these polyethylene glycols are available commercially.
The inventive compositions are preferably formulated by initially dispersing the transition metal salt (A) in the oil (B). The order of addition of the remaining ingredients in not critical with the exception that it is preferable to add the thickening agent (C) last. Preferably the inventi-ve compositions have a metal content of from about 1 to about 3% by weight, more preferably from about 1.5 to about 2.5~ by weight.
Typically, these compositions contain from about 10 to about 30% by weight, more preferably from about 15 to about 25% by weight of the metal salt (A). The level of addition of the oil (B) should be sufficient to disperse and/or dissolve the metal salt (A) in said oil (B).
These compositions preferably contain from about 3S to about 87X by weight, more preferably from about 45 to about 78% by weight of said oil tB)~ The level of addition of the thickener tC) should be sufficient to provide the inventive composition with a grease-like consistency. Preferably, the inventive composition contains from about 3 to about 15% by weight, more preferably from about 5 to about 10% by weight of the thickener tC). When employed, the solvent/diluents tD) are preferably employed at a level of up to about 15% by weight, more preferably from about 1 to 10~ by weight.
The surfactants tE) are preferably employed at a level of up to about 5% by weight, more preferably in the iL3~)58~S

range of about 0.5 to about 4% b~ weight. The wood-stabilizing agents (F) are preferably employed at a level of up to about 5% by weight, more preferably in the range of about 2 to about 4% by weight.
The inventive compositions may contain other additives depending on the intended use for the composi-tion. When the compositions of the invention are to be used in preserving wood, other additives can be included which impart desirable properties to the treated wood.
For example, the compositions may contain antioxidants, flame retardant compositions, insecticides, odorants, moldicides, etc. The amount of such optional additives included in the compositions of the invention may vary over a wide range although amounts of from about 0.01 to about 5% of these compositions are generally satisfac-tory.
Fire-retardant compositions are particularly useful in the compositions of the invention. Examples of inorganic materials include metal oxides which are well known in the art such as antimony oxide, etc.
Examples of organic fire retardants include a number of halogenated and organophosphorus compounds which may be dispersed in the solutions.
Insecticides also can be included in the compo-sitions of the invention, and it is preferable that the insecticide be soluble in oil. Examples of such insec ticides include Dursban TC (a product of Dow Chemical Co. identified as 0,0-diethyl-0-3,5,6-trichloro-2-pyri-dyl phosphorothioate).
The following are specific examples of the compositions of the invention. All parts and percen-tages are by weight.

1305~ 5 Ex~mp~e A Amoun f~
Copper Naphthenate 20 Petroleum oil 65O5 Cab-O~Sil 8 Mineral spirits 5 Triton X-100 1.5 Example B
Copper Naphthenate 20 Petroleum oil 60.5 HiSil T-600 12 Mineral spirits 5 Diethylene glycol 2.5 The inventive compositions are useful in treat-ing wood that is already in place such as standing poles, sills, toe plates, stair risers, etc. These com-positions are particularly useful in treating standing poles along the ground-line using conventional techni-ques. In this regard, the inventive composition can be directly applied to the area of the pole to be treated, and preferably a wrap, such as a polyethylene wrap, is placed over the composition. Alternatively, the inven-tive composition can be used with any of the currently available commercial bandages. In areas of rainfall of about 15 inches or more a year, the inventive composi-tion is preferably applied to an area on the pole extending from about 6 inches above the ground line to about 20 inches below. In arrid regions, the inven-tive composition is perferably applied to the pole from approximately the ground-line to as much as three or more feet below the ground-line. The inventive composi-tion can also be applied to the exposed tops of poles.

~30S8~5 The inventive compositions are particularly useful in treating poles which show evidence of decay or termite attack at or below the ground-line, but which have a sufficient amount of sound wood to remain in plant for additional use. These compositions are also useful in treating salvaged poles that are reused, poles that are moved to a new location, poles where the ground-line has been raised by road grading or filling, poles held in stock for unusually long periods of time (e.g., one year or longer), and incised butt-treated poles where the treated layer has been damaged so that the untreated wood is exposed.
While the invention has been e~plained in relation to its preferred embodiments, it is to be understood that various modifications thereof will hecome apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Claims (25)

1. A composition comprising:
(A) from about 10 to about 30% by weight of at least one metal salt of an organic carboxylic acid containing at least about 6 carbon atoms;
(B) from about 35 to about 87% by weight of at least one oil to disperse and/or dissolve said salt in said oil;
(C) from about 3 to about 15% by weight of at least one thickener to provide said composition with a grease-like consistency; and (E) up to about 5% by weight of at least one anionic or nonionic surfactant;
wherein more than one carboxylic acid is employed in the composition and carboxylic acids containing as few as 2 carbon atoms are used in the composition.

2. The composition of claim 1, wherein said composition further comprises:
(d) at least one solvent/diluent.

3. The composition of claim 1, wherein said composition further comprises:
(F) at least one wood-stabilizing agent.

4. The composition of claim 1, wherein the metal is zinc, copper, chromium, iron, antimony, lead, or a mixture thereof.

5. The composition of claim 1, wherein the metal is copper or zinc.

6. The composition of claim 1, wherein the organic carboxylic acid is at least one aliphatic or alicyclic monocarboxylic acid containing from about 6 to about 30 carbon atoms.

7. The composition of claim 1, wherein component (A) comprises copper naphthenate.

8. The composition of claim 1, wherein component (B) comprises at least one mineral oil.

9. The composition of claim 1, wherein component (B) comprises at least one petroleum oil.

10. The composition of claim 1, wherein component (C) comprises colloidal silica particles.

11. The composition of claim 1, wherein component (C) comprises amorphous silica.

12. The composition of claim 2, wherein component (D) comprises at least one hydrocarbon solvent.

13. The composition of claim 2, wherein component (D) comprises mineral spirits.

14. The composition of claim 1, wherein component (E) comprises at least one anionic or nonionic surfactant or mixture thereof.

15. The composition of claim 1, wherein component (E) comprises at least one alkylene oxide-treated alkyl phenol.

16. The composition of claim 3, wherein component (F) comprises diethylene glycol.

17. The composition of claim 2, wherein said composition comprises up to about 15% by weight of component (D).

18. The composition of claim 1, wherein said composition comprises up to about 5% by weight of component (E).

19. The composition of claim 3, wherein said composition comprises up to about 5% by weight of component (F).

20. The composition of claim 1, wherein the metal content of said composition is from about 1 to about 3% by weight.

21. A composition having a grease-like consistency comprising:
(A) from about 10 to about 30% by weight of copper naphthenate;
(B) from about 35 to about 87% by weight of at least one petroleum oil;
(C) from about 3 to about 15% by weight of at least one thickener;
(D) up to about 15% by weight of at least one hydrocarbon solvent; and (E) up to about 5% by weight of at least one anionic or nonionic surfactant;
wherein more than one carboxylic acid is employed in the composition and carboxylic acids containing as few as 2 carbon atoms are employed in the composition.

22. A method of preserving wood which comprises contacting said wood with the composition of claim 1.

23. A method of preserving wood which comprises contacting said wood with the composition of claim 21.

24. A method for the ground-line treatment of a pole comprising contacting said pole with the composition of claim 1.

25. A method for the ground-line treatment of a pole comprising contacting said pole with the composition of claim 21.