NZ280865A - Wood preservative; composition comprising a preservative compound and an aliphatic organic acid as permeability improving agent - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £80865 TO BE ENTERED AFTER ACCEPTANCE AND PUBLICATION Priority dates: 23.01.1995; Complete Specification Filed: 23.01.1996 Classification:^) B27K3/52,22,38; A01N43/647; A01N25/00 Publication date: 24 November 1937 Journal No.: 1422 New Zealand No. 280865 International No. PCT/ NO DRAWINGS NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION $ Title of Invention: Wood preservative composition and method for improving the permeability of the same Name, address and nationality of applicant(s) as in international application form: SDS BIOTECH K.K., a Japanese company of 12-7, Higashi Shimbashi 2-chome, Minato-ku, Tokyo, 105 Japan 28086 Patents Form No. 5 Our Ref: DT205897 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION WOOD PRESERVATIVE COMPOSITION AND METHOD POR IMPROVING THE PERMEABILITY OF THE SAME We, SDS BIOTECH K. K., a Japanese company of 12-7, Higashi Shimbashi 2-chome, Minato-ku, Tokyo 105, Japan hereby declare the invention, for which We pray that a patent may be granted to us and the method by which it is to be performed, to be particularly described in and by the following statement: \ PT0503478 (followed by page la) SPECIFICATION 280 Wood Preservative Composition and Method for Improving the Permeability of the Same FIELD OF THE INVENTION This invention relates to a wood preservative, that is, a chemical which prevents or suppresses decay of wood. More 10 specifically, this invention relates to a wood preservative composition having improved permeability which protects wood from decay, reproduction of fungi and damage by insects, as well as relating to a method of improving the permeability of a hard-permeating wood preservative.

BACKGROUND OF THE INVENTION Since old times, wood has been utilized in various applications as furniture, buildings, etc. Also, great effort has been made to obviate damage by human causes, such as fires and mechanical destruction, and reduction in its economical value due to deterioration under such natural conditions as decay and contamination by microorganisms, as well as damage by insects. investigation has been made intensively into the kind of microbes to cause decay or contamination of wood and reproduction conditions for them, as well as the kind of insects to eat wood and their ecology. Also on prevention (followed by page 2) 2808 of wood from damage of such causes, intensive investigation has been made, and hence, various antiseptic agents, mildewproofing agents and insecticides are developed and put into practical use. Further, various methods have been 5 devised to apply those chemicals to wood.

Each of those chemicals has its advantages and disadvantages, depending upon its kind; ie what active ingredients it contains, what compositions it is made of, 10 whether or not, and what auxiliary components such as solvents and surfactants are involved in it, wha'^ kind of formulation, what shape, how it is applied to, etc. It is pointed out that they have various characteristics not only in that the chemicals themselves have strong potency but 15 also in that their potency is durable, they are stable, they are easy to handle and use, they are safe to humans and cattle and natural environment, they are economically advantageous, and so on.

One of the fundamental problems in chemical treatment for preserving wood lies on permeability of the chemicals into wood. In order to attain a long-term protection of wood from damage by microorganisms and insects, it is a very important technique to let the chemicals to permeate not 25 only on the surface of wood, but also into the interior of wood, so that also the chemicals (wood preservative) remain effective for a long period of time. 2 280865 Such treatment of wood with chemicals is carried out mainly by surface treatments such as coating, spraying and dipping, and pressurization treatment or vacuum treatment. In order to treat a large amount of wood efficiently, barks are 5 removed from timbers after they are cut down, and optionally the timbers are roughly sawed into long lumbers and dried if necessary, and the long lumbers are contacted with a chemical solution as they are. In any one of the above-mentioned methods, it is necessary to have the chemical 10 solution permeated in the direction perpendicular to the direction of the axis of the trunk and the direction of fibers, that is, from the periphery toward the interior.

The permeability of chemical solutions to the timbers differ 15 depending on the kind of wood. However, generally, as compared with conifer timbers, broadleaf tree timbers are relatively less permeable by chemicals, no matter whether in the direction of the fibers or in the direction perpendicular to the direction of the fibers. The 20 permeability differs also depending on whether they are sapwood or heartwood.

Recently, an aqueous solution of a water-soluble salt of copper-chromium-arsenic (CCA agent) has been used widely 25 because of its high potency, low cost and easiness of use, as well as its suitableness for a pressurized treatment, which requires a short treatment time and hence efficient. However, there has been a keen desire for the development of substitutes for CCA agent because of the toxicity of arsenic 3 280865 and chromium. It is energetically tried to develop organic chemicals which are free of toxicity problems but have a high potency. However, organic chemicals have hydrophobic group and high fat-solubility but relatively low water-5 solubility. There are a great number of difficulties in increasing the permeability of organic chemicals from technical viewpoints.

Water borne or hydrophilic formulations, to be specific, 10 enter the timber relatively easily from an end surface (a plane perpendicular to the axis of the trunk) in the direction of the trunk or fibers, whereas they enter the timber with difficulty in the direction through the surface along the axis of the trunk, particularly in the direction 15 through a flat grain plane, presumably because the solution must permeate perpendicularly through the annual growth ring of the timber where cells exist densely. Organic chemicals having a (high) hydrophobic group show decreased permeability even if they are formulated into aqueous 20 systems such as emulsifiable concentrates, emulsion concentrates and microemulsions because of adsorption and other reasons.

SUMMARY OF THE INVENTION The present inventors have investigated intensively to improve the permeability of an organic hard-permeating wood preservative into wood. As a result they have found that the desired object can be attained by adding a small amount 4 280 865 of an aliphatic organic acid to the wood preservative, thus completing this invention.

This invention provides: 1) A wood preservative composition comprising a -triazole derivative ' an aliphatic organic acid as essential ingredients and optionally another fungicidal component, another insecticidal component, a color forming component, a surfactant, and/or a solvent; 2) The wood preservative composition as described in 1) above, wherein the triazole derivative is a azaconazole, bromoconazole, cyproconazole, hexaconazole, propiconazole, tebuconazole or flusilazole; 3) The wood preservative composition as described in 1) above, wherein the another fungicidal component is at least one compound selected from the group consisting of sulfonamides, benzimidazoles, thiocyanates, quaternary ammonium salts, morpholine derivatives, phenols, organic iodine compounds, organic bromine derivatives, isothiazolines, benzisothiazolines, pyridines, metal soaps, 280 8 6 5 organic tin derivatives, dialkyldithiocarbamates, nitriles, activated halogen atom-containing anti-microbial agents, 2-mercaptobenzothiazoles, benzothiazoles, guinolines and formaldehyde-releasing compounds; 4) The vraod preservative composition as described in 1) above, wherein another insecticide component is selected from the group consisting of boron compounds, phosphates, carbamates, pyrethroids, nitroimines, and nitromethylenes; ) The wood preservative composition as described in 1) above, wherein the coloring agent is selected from zinc salts, copper salts and boric acid; 6) The wood preservative composition as described in 1) above, wherein the aliphatic organic acid is blended in a dosage of not smaller than 50 *^pm; 7)- A method for improving the permeability of a wood preservative composition containing a triazole derivative, comprising the step of adding a small amount of an aliphatijc organic acid to the wood preservative; 8) A method for improving the permeability of a wood preservative composition containing a metal naphthenate, comprising the step of adding a small amount of an aliphatic organic acid to the wood preservative; and 9) The method for improving the permeability as described in 7) or 8) above, wherein insecticide is used in combination with the wood preservative. 280865 The wood preservative composition and method for improving the permeability of the wood preservative according to this invention use a mixture of a wood preservative having low toxicities to humans and cattle with a small amount of an 5 aliphatic organic acid. The method of this invention significantly increases not only the permeability of the wood preservative but also the permeability of other fungicidal components, insecticidal components, color forming components, surfactants and/or solvents into timber, 10 so that decay of timber, coloring of its surface and interior due to growth of fungi, and damage by termites can be all prevented simultaneously.

Furthermore, since it is possible to use it in combination 15 with conventional antiseptic and mildewproofing agents, the wood preservative composition of this invention has antiseptic and mildewproofing properties against a wide variety of fungi. In addition, the wood preservative composition of this invention is considerably useful because 20 of its capability of being prepared as aqueous formulations, its high stability, its easiness and reliability to carry out anti-rotting treatment for wood.

DETAILED DESCRIPTION OF THE INVENTION Hereafter, this invention will be described in more detail. 7 28 n 8 6 5 The wood preservative composition, of this invention comprises a triazole derivative and an aliphatic organic 10 acid as essential ingredients.

Specific examples of triazole derivative include the following compounds: azaconazole, etaconazole, propiconazole, bromoconazole, cyproconazole, diphenoconazole, itraconazole, flutriafol, myclobutanil, 15 fenethanil, penconazole, tetraconazole, hexaconazole, tebuconazole, imibenconazole, flusilazole, ribavirin, triamiphos, isazophos, triazophos, idinfos, fluortimazole, triadimefon, triadimenol, diclobutrazol, diniconazole, diniconazole M, bitertanol, epoxiconazole, triticonazole, 20 metconazole, ipconazole, furconazole, and furconazole-cis.

Among the above-cited, preferable triazole derivatives are ■ azaconazole, propiconazole, bromoconazole, cyproconazole, hexaconazole, and tebuconazole. i Specific examples of metal naphthenate include coppei naphthenate and zinc naphthenate.

The present inventors have found the method of this invention, which improves the permeability of a triazole 8 23 0 8 6 E derivative into timber by using a small amount of an aliphatic organic acid together with the triazole derivative.

Further, the present inventors have been successful in developing a wood preservative composition Qf 5 this invention which contains, in addition thereto, another fungicidal components and another insecticidal components, color forming components, surfactants and/or solvents if necessary, and has an improved permeability into timber. wood-rotting fungi against which the triazole derivatives and metal naphthenate are effective include the following species: Basidiomycetes including Coniophora puteana, Coriolus versicolor, Poria placenta, Poria vaporaria, Poria vaillantii, Gloeophylium sepiarium, Gloeophylium adoratum, 15 Gloeophylium abietinum, Gloeophylium trabeum, Gloeophylium protactum, Lentinus lepideus, Lentinus edodes, Lentinus cyathiformes, Lentinus squarrolosus, Paxillus panuoides, Tyromyces palustris, Pleurotus ostreatus, Donkioporia expansa, Serpula lacrymans, Serpula himantoides, and 20 Glenospora graphii; Deuteromycetes including Cladosporium herbarum; and Ascomycetes including Chaetomium globosum, Chaetomium alba-arenulum, Petriella setifera, Trichurus * spiralis, and Humicola grisea.

Wood discoloring fungi against which the triazole compounds are effective include the following species: Deuteromycetes including Aureobasidium pullans, Sclerophoma pithyophila,^ ^ E N r c I Scopular phycomyces, Aspergillus niger, PeniciIlium " - 3 FIT bj7 / variabile, Trichoderma viride, Trichoderma rignorum, and \ . J* VC E \ \ 9 t 280865 Dactyleum fusarioides; Ascomycetes including Caratocystis minor; and Zygomycetes including Mucor spinosus.

In the method and wood preservative composition of this 5 invention, the combination of the above-described wood preservative and the aliphatic organic acid is effective.

It is also possible to further combine therewith known fungicidal components (antiseptic or mildewproofing agent) and/or insecticidal components to enhance the effect of the 10 chemical or to broaden the spectrum of the activity.

[Fungicidal Component] Examples of the fungicidal component (antiseptic or mildewproofing agent) which can be used for the purposes 15 include sulfonamides such as dichlorofluanide (euparene), trifluanide (methyleuparene), eyelofluanide, phorpet, and fluorophorpet; benzimidazoles such as carbendazime (MBC), benomil, fuberitazole, and thiabendazole or salts thereof; thiocyanates such as thiocyanatomethylthiobenzothiazole 20 (TCMTB), and metylenebisthiocyanate (MBT); quaternary ammonium salts such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyl-dimethylammonium chloride, and N-alkylbenzylmethylammonium chloride; morpholine derivatives such as 4-Cn~Ci4-alkyl-2,6-25 dimethylmorpholine homologues (tridemorph), (±)-cis-4-[3-(t-butylphenyl) -2-methylpropyl]-2, 6-dimethylmorpholine (phenpropimorph, farimorph), etc.; phenols such as o-phenylphenol, tribromophenol, tetrachlorophenol, pentachlorophenol, 3-methyl-4-chlorophenol, dichlorophenol, 280 chlorophene and salts thereof; organic iodine compounds such as 3-iodo-2-propynyl-n-butylcarbamate (IPBC), 3-iodo-2-propyny1-n-hexylcarbamate, 3-iodo-2-propynyIcyclohexy1-carbamate, 3-iodo-2-propynylphenylcarbamate, 3-iodo-2-5 propynyl-n-butylcarbamate, p-chlorophenyl-3-iodopropargyl-formal (IF-1000), 3-bromo-2,3-diiodo-2-propenylethyl-carbonate (Sunplus), and 1-[(diiodomethyl)-sulfonyl]-4-methylbenzene (Amical); organic bromo derivatives such as bronopor; isothiazolines such as N-methylisothiazoline-3-10 one, 5-chloro-N-methylisothiazoline-3-one, 4,5-dichloro-N-octylisothiazoline-3-one, and N-octylisothiazoline-3-one (Octylinone); benzisothiazolines such as cyclopenta-isothiazoline; pyridines such as l-hydroxyl-2-pyridinethione (or sodium, iron, manganese, zinc, etc., salts thereof), and 15 tetrachloro-4-methylsulfonylpyridine; metal soaps, e.g., napht.hate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate, etc. of tin, copper and zinc; oxides, e.g., TBTO, CU2O, CuO, ZnO, etc.; organic tin derivatives such as tributyltin naphthenate and t-butyltin oxide; 20 dialkyldithiocarbamates, e.g., Na or Zn salt of dialkyldithiocarbamate, and tetramethyldiuram disulfide (TMTD); nitriles such as 2,4,5,6- tetrachloroisophthalonitrile (chlorothalonil); antibiotics having an activated halogen atom such as Cl-Ac, MCA, 25 techtamaer, bronopor, and blumidox; benzothiazoles such as 2-mercaptobenzothiazole and dazomet; quinolines, e.g., 8-hydroxyquinoline; formaldehyde-releasing compounds, e.g., benzyl alcohol mono(poly)hemiformal, oxazolidine, hexahydro-s-triazine, N-methylolchloroacetamide, etc.; and tris-N- 11 280865 (cyclohexyldiazeniumudioxine)-tributyltin or K salts, bis-(N-cyclohexyl)diazonium-dioxine copper or aluminum, etc.

These may be used either alone or in combination.

[Insecticidal Component] Examples of the insecticidal composition (insectfugal component) which can be used in this invention include boron compounds, e.g., sodium octaborate tetrahydrate, boric acid, and borax; fluorine compounds, e.g., sodium fluoride and sodium silicofluoride; esters of phosphoric acid, e.g., azinophos-ethyl, azinophos-methyl, 1-(4-chlorophenyl)-4-(0-ethyl, S~propyl)phosphoryloxypyrazole (TIA-230), chloropyriphos, tetrachlorobinphos, cumaphos, det:omen-S-methyl, diazinone, dichlorobos, dimethoate, ethoprophos, etholimphos, phenitrothione, pyridaphenthione, heptenophos, parathione, parthione-methyl, propetamphos, phosarone, phoxime, pyrimphos-ethyl, pyrimiphos-methyl, prophenophos, prothiophos, sulprophos, triazophos and tolchlorphone, etc.; carbamates, e.g., algicarb, beniocarb, BPMC (2—(1— methylpropy1)phenylmethylcarbamate, butocarboxime, butoxycarboxime, carbaryl, carbofuran, carbosulfan, chloethocarb, isoprocarb, methomil, oxamil, pyrimicarb, promecarb, propoxul, thidicarb, etc.; pyrethroids, e.g., arethrine, alphametrine, biorethmetrine, cycloprotrine, cyfurtrine, decametrine, cyhalotrine, cypermetrine, deltametrine, a-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl- 2-(2-chloro-2-trifluoromethylvinyl)-cyclopropane-1 carboxylate, phenpropatrine, phenfurtrine, phenvalerate, furcitrinate, flumetrine, fluvarinate, permetrine, 12 280865 ethophenprox, and resmetrine; nitroiminos and nitromethylenes, e.g., 1-(6-chloro-3-pyridinylmethyl)-4,5-dihydro-N-nitro-lH-imidazole-2-amine (imidacropuride), etc. These may be used alone or in combination.

Among these, the pyrethroid compounds and organic phosphorus compounds are preferred. For the former, aretrine, permetrine, phenvalerate, cypermetrine, ethophenprox, etc. are preferred. For the latter, chloropyriphos, foxime, 10 pyridaphentione, tetrachlorobinphos, phenitrothione, and propethanphos are preferred. The carbamate compounds are generally weak in their effect while propoxul, BPMC, carbaryl, etc. can be used advantageously. Among them, preferred are those having sustained potency over 10 years 15 or more.

Wood decaying insects against which the wood preservative of this invention acts effectively in combination with such an insectfugal component include the following species: 20 Coleoptera including Hylotrupes bajulus, Chlorophorus pilosus, Anobium punctatum, Xestobium rufovillosum, Ptilinus pectiocornis, Dendrobium pertinex, Ernobius mollis, Puriobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon 25 aequale, Minthea rugicollis, Xyleborus sp., Tryptodendron sp., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon sp., and Dinoderus minutus; Hymenoptera including Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, and Urocerus augur; Termitidae including Kalotermes 13 280865 flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Eeticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, and Coptotermes formosanus.

[Aliphatic Organic Acid] In order to improve the permeability of wood preservatives, the present inventors have studied on the combined use with various acids and derivatives thereof. As a result, they 10 have found that the combined use with aliphatic organic acids, particularly acetic acid, is effective in improving the permeability of the wood preservative, thus completing this invention.

That is, in the wood preservative composition and the method for improving the permeability thereof according to this invention, it is essential to add a small amount of an aliphatic organic acid to the active ingredient of the wood preservative containing the above-described triazole 20 derivative, and optionally another fungicidal component, another insecticidal component (antiseptic or mildewproofing agent). The addition of a small amount of an aliphatic organic acid in combination significantly increases the permeability of the active ingredients of the wood 25 preservative and that of the color forming agent (zinc chloride, etc.) used to confirm the permeation of the active ingredients of the wood preservative into wood. 14 2b U d 6 Here, aliphatic organic acid includes various ones, e.g., lower aliphatic monocarboxylic acids such as formic acid, acetic acid, valeric acid, and butyric acid; lower aliphatic dicarboxylic acids such as oxalic acid and succinic acid; unsaturated carboxylic acids such as sorbic acid; hydroxyacids such as lactic acid, citric acid, and tartaric acid. Among them, acetic acid exhibits extremely specific, excellent effects.

Some prior patents disclose the use of organic acids in wood preservatives. However, they all teach or suggest the use of organic acids as solvents, which is essentially different from the addition or combined use in a small amount in order to improve the permeability of the vraod preservative as in 15 this invention.

The amount of the aliphatic organic acid to add depends on its type and cannot be defined indiscriminately. For example, in the case of acetic acid, the organic acid 20 exhibits its effect in a concentration of 0.5 - 20 weight % of the composition, preferably 2-15 weight %, or in a concentration of 50 ppm or higher, preferably 100 ppm or higher, in the chemical solution to be pressed into.

Although there is no particular upper limit, concentrations 25 on the Cj. dci" (J £ 1,000 ppm will be sufficient. Usually, a base composition is diluted upon use. A suitable dilution rate is about 10 to about 500 times the original. The concentration of the aliphatic organic acid in the base composition is adjusted in accordance therewith. Too high a 280865 concentration is undesirable, since it causes aggravation of operability.

[Color Forming Component] In this invention, the wood preservative composition may contain a color forming component in order to confirm the permeability of the wood preservative component. Such a color forming agent includes zinc salts such as zinc chloride and zinc naphthenate, which develop red color when 10 sprayed with a dithizone solution, boric acid, which develops a color with a curcumin solution, etc.

[Surfactant] As the surfactant, there can be used any of anionic, 15 nonionic, cationic, and amphoteric surfactants. In particular, polyoxyethylene alkyl aryl ethers and polyoxyethylene alkyl ethers are used advantageously.

[Other Components] In this invention, the wood preservative composition may contain known binders in order to increase bonding with the wood or timber. More specifically, the binder includes synthetic resins which can be dissolved or dispersed or emulsified in water or organic solvents used and/or binding, 25 drying oils. For example, there can be cited acrylate resins, polyvinyl acetate, polyester resins, polycondensed or polyadded resins, polyurethane resins, alkyd resins or modified alkyd resins, phenyl resins, hydrocarbon resins, 16 280865 e.g., coumarone and indene resins, silicone resins, drying vegetable oils, etc.

In addition to or in place of the above-described binders, 5 fixing agents and plasticizers may be used. Examples of the fixing agents include polyvinyl alcohol such as polyvinyl methyl ether, and ketones such as benzophenone and ethylbenzophenone. Examples of the plasticizers include phthalic acid esters such as dibutyl phthalate, dioctyl 10 phthalate and benzylbutyl phthalate; phosphoric acid esters such as tributyl phosphate; stearic acid esters such as butyl stearate and amyl stearate,- oleic acid esters such as butyl oleate; glycerol ether; or glycol ether, glycerol ester and p-toluenesulfonic acid ester having a high 15 molecular weight; and so on.

The wood preservative composition of this invention may further contain dyes, pigments, UV stabilizers, antifoaming agents, thickening agents, antifreezing agents, etc.

[Formulation and Solvent of Wood preservative] Formulation of the chemical of this invention is not limited particularly. Usually, it is used in the form of wettable powder, emulsifiable concentrate, emulsion concentrate, 25 soluble concentrate, microemulsion, oil, or paste. The wettable powder can be obtained by mixing the active ingredient and optionally the aliphatic organic acid of this invention with a carrier such as talc, kaolin or diatomaceous earth, excipient, and solubilization or 17 28086 emulsification aid such as a wetting agent, a surfactant or the like and pulverizing the mixture to form powder or granules.

The emulsifiable concentrate, emulsion concentrate, soluble concentrate and microemulsion can be obtained by adding the active ingredient and optionally the aliphatic organic acid of this invention together with the solubilizing or emulsifying agent to a solvent, or by adding the active 10 ingredient and optionally the aliphatic organic acid of this invention to a solvent containing the solubilizing or emulsifying agent, with mixing. The oil and paste can be obtained by mixing the active ingredient with an organic solvent without using such aids.

The active ingredient of this invention basically is an oil-soluble compound and hence it is preferred to use it as emulsifiable concentrates, emulsion concentrates, soluble concentrates, microemulsions and oils. The emulsifiable 20 concentrates, emulsion concentrates, soluble concentrates and microemulsions can be diluted with water or an aqueous solution containing an aliphatic organic acid to form an aqueous treating solution, which is suitable for permeation under pressure into timbers. The oils are suitable for 25 permeation into timbers after dilution. From the viewpoints of operation and environment, the treatment under pressure that does not require organic solvents upon use is preferred and, hence, emulsifiable concentrates, emulsion 18 concentrates, soluble concentrates and microemulsions are preferred formulations.

Examples of the solvent which can be used for preparing 5 emulsifiable concentrates, emulsion concentrates, soluble concentrates, microemulsions, oils and pastes as well as for diluting oils and pastes include aromatic organic solvents such as toluene, xylene, and methylnaphthalene solvents; halogenated hydrocarbons such as dichloromethane and 10 trichloroethane; alcohols such as isopropyl alcohol, butanol, hexanol, octanol, and decanol; ethylene glycol solvents such as polyethylene glycol and polypropylene glycol; kerosene; N-methylpyrrolidone; phosphoric acid esters, benzoic acid esters; and so on. Instead of the 15 organic solvents, there can be used fatty acid ester derivatives of polyhydric alcohols, surfactants such as polyoxyethylene alkyl aryl ether, etc.

The chemicals containing these solvents or water and 20 surfactants usually contain the triazole derivative in an amount of 0.1 to 40% by weight in oils, 1 to 20% by weight in emulsifiable concentrates or emulsion concentrates, 1 to 20% by weight in soluble concentrates or microemulsions, or 1 to 70% by weight in pastes. The chemicals may contain the 25 insectfuge suitably in amounts ranging from the same amount to twice as much as the triazole derivative, more particularly, 0.1 to 80% by weight, preferably 1 to 40% by-weight. The other antiseptic and fungiproofing agents optionally added may be present in the chemicals in amounts 19 280865 similar to conventional CCA antiseptic agents, preferably not greater than 80% by weight, and more preferably within the range of 1 to 50% by weight. If necessary, the chemicals may be concentrated so that they contain these components in proportions greater than those described above.

[Application of Wood Preservative] The wood preservative of this invention can be used in the treatment of lumber, timber, woodwork and construction (wood construction and wood building material used partially in non-wood construction). For example, it can be used for interior construction timber such as sill, lumber girder, floor joists, flooring, furring strips, studs, sheathing, braces, fascia rafters, roof sheathing, bathroom framework, floor construction plates, basement materials, etc.; exterior construction timber such as outdoor construction materials, log houses, balcony, terraces, drying space, gate doors, log cabins, bowers, wetted perimeters, deck boards, etc.; civil engineering timber such as ties, snow-fences, electric poles, foundation pillars, mine pillars, sound insulating wall, railroad board, bridge materials, harbor materials, windbreak wall, etc.; park timber such as posts, flower pots, fences, play tools, wooden brick, bench, etc.; horticultural materials such as vinyl resin clad green house, flower bed frames, guide boards, landscape architecture materials, etc.; agricultural materials such as meadow farm fences, barns, etc.; and for other purposes such as shipping materials, container materials, shipbuilding 280865 materials, mosaic materials, cooling tower materials, decks, etc. The shape of timber may be any of log, plate, square cimber, rods, plywood, chip board, etc.

The treatment with the chemical of this invention can be applied to the above-described objects in the same manner as the conventional anti-deterioration treatment applied thereto. More specifically, the treatment includes treatment of timber itself and that of plywood. The 10 treatment of timber itself is carried out usually by coating, spraying, dipping, pressurization, boring, etc. The treatment of plywood usually includes green plate treatment (spraying, dipping, etc.), treatment with an adhesive, finished plate treatment (coating, spraying or 15 pressurization treatment) and the like. With regard to the treatment of base plates, it is possible to inject the chemical into the soil. In particular, soil treatment is sometimes necessary to cope with termites.

DESCRIPTION OF THE PREFERRED EMBODIMENT Hereafter, this invention will be described more concretely by examples and test examples. However, this invention is not limited thereto. In the following description, all "%" 25 and "part" or "parts" are by weight.

Example 1: Combined use test for various acids To blends having the formulation shown in Table 1 was added one of various acids shown in Table 2 to form various 21 26086 5 chemicals. Timbers were treated with these chemicals in the dipping method described below and the permeability of the chemicals into the timbers and the stability of the chemicals were evaluated in the following manner. The results are also shown in Table 2.

Table I Component Blended Proportion Cyproconazole 6% Propetamphos 4% Zinc chloride 6% Alkylbenzene derivative % Nonion/anion mixed surfactant 34% Cyclohexanone % Acid Table 2 Permeability Formic acid O Acetic acid © Valeric acid o Oxalic acid o Succinic acid © Sorbic acid o Lactic acid © Citric acid o Tartaric acid o 22 C. KJ KJ o Timber Treatment: Each chemical was diluted 400 fold with water to prepare a chemical solution for treatment. On the other hand, 90x90x1,000 mm sized square timber of hemlock spruce was placed in a stainless steel vessel. Then, the vessel was kept under vacuum of 600 miuHg or lower. About 410 kg/m3 of the chemical was injected into the vessel and left to stand for 24 hours.

Evaluation of the Permeability: The timber thus treated was sawed roughly in the center thereof in the direction perpendicular to the long axis, and a dithizone solution was sprayed onto a cut surface to 15 develop a color. The state of the color development was visually observed and the permeability of the chemical was evaluated according to the following rating; @ : Color development occurred along a length of at least 11 mm in average from the outer end of the cut surface; 20 O : color development occurred along a length of 10 mm in average from the outer end of the cut surface; A : Color development occurred along a length of 3 to 9 mm in average from the outer end of the cut surface; X : Color development occurred along a length of no 25 greater than 2 mm in average from the outer end of the cut surface.

Evaluation of the Stability of the Chemical: 23 280865 The prepared chemicals were left to stand at 5°C and 40°C for 3 months, and changes of the chemicals from their initial stage were visually observed. Evaluation was made according to the following rating.

O : No change was observed from the initial transparent liquid or transparent paste.

X : Separation or precipitation occurred.

Example 2 A chemical having the formulation shown in Table 3 that contains 10% of acetic acid was prepared. The chemical was diluted 400 folds with water. This was then used to treat timber in the same manner as in Example 1 and the permeability of the chemical into the timber was evaluated in the same manner as in Example 1. Further, concentration gradient of the chemical which permeated into the timber from its surface was evaluated in the following manner. As a result, the chemical permeated about 25 mm and no concentration gradient was observed. 24 Table 3 280865 Component Proportion Cyproconazole 6% Propetamphos Zinc chloride 4% 6% Alkylbenzene derivative % Nonion/anion mixed surfactant 33% Cy c 1 ohexanone 16% Acetic acid % Comparative Example 1 15 An aqueous 100 ppm zinc chloride solution was used to treat timber in the same manner as in Example 1 to develop a color, and the permeability of zinc chloride was evaluated, zinc chloride revealed to have permeated to a depth of about 5 mm from the surface.

Example 3 Timber was treated in the same manner as in Example 2 except that acetic acid was added in an amount of 2%. The permeability of the chemical into the timber and the 25 concentration gradient of the permeated chemical were evaluated. As a result, the chemical revealed to have permeated to a depth of about 20 mm but no concentration gradient was observed.

Example 4 Treatment was made in the same manner as in Example 2 except that instead of hemlock spruc-e sized square timber, there 280865 was used Japanese cryptomeria log of 150 mm in diameter and 1,500 nun in length, and that the amount of the chemical treated was changed to about 365 kg/m3. The chemical revealed to have permeated to a depth of about 15 mm.

[Test Examples] Test Chemical 1 A soluble concentrate (Test Chemical 1) was prepared by blending the compounds described in Table 4 in the described proportions.

Table 4 Component Proportion Cyproconazole parts Permetrine parts N-Me thylpyrro1idone parts Nonionic surfactant parts Polyethylene glycol 70 parts Acetic acid parts Test Chemical 2 An emulsifiable concentrate (Test Chemical 2) was prepared by blending the compounds described in Table 5 in the described proportions. 26 £@086 5 Table 5 Component Proportion Cyproconazole parts Propetamphos parts N-Methylpyrrolidone parts Nonionic/anionic mixed surfactant parts Xylene 60 parts Acetic acid parts Test Chemical 3 An emulsifiable concentrate (Test Chemical 3) was prej by blending the compounds described in Table 6 in the described proportions.

Table 6 Component Proportion Cyproconazole parts Chloropyriphos parts Chlorothalonil parts N-Me thylpyrro1idone parts Nonionic/anionic mixed surfactant parts Xylene 50 parts Acetic acid parts Test Chemical 4 An oil (Test Chemical 4) was prepared by blending the 35 compounds described in Table 7 in the described proportions 27 Table 7 Component Proportion Cyproconazole parts Ethophenprox parts Chlorothalonil parts N-Methylpyrrolidone parts Polypropylene glycol 1 parts Xylene 36 parts Acetic acid 3 parts Test Example 1 For Test Chemicals 1 to 4, antiseptic effects were confirmed according to the method JIS A 9201.

More specifically, 40 normal sound Japanese cryptomeria sapwood test samples (bricks of an end surface: 20x20 mm and a thickness: 10 mm) were classified into 4 groups. Firstly, 4 kinds of treatments shown in Table 8 were made with the chemicals of the above-described examples. The treated test samples were left to stand at room temperature for no shorter than 20 days, and the test samples in each group were further divided into two groups. One group was given weatherproofing treatment and the other was left as is.

Both groups were dried in a circulating air-drier at a temperature of 60°C ± 2°C for 48 hours and then left to stand in a desiccator for about 30 minutes until weighing. Then, the test samples were weighed on the order of 0.01 g. 28 280865 Thereafter, the fungiproofing effect tests were conducted as described below.

Table 8 Treatment Test Chemical Treatment Concentration (Cyproconazole) Diluting Solution Treating Method 1 1 0.02% Water Pressurization 2 2 0.02% Water Pressurization 3 3 0.02% Water Pressurization 4 4 0.2% Xylene Dipping [Weatherproofing Treatment] Weatherproofing treatment was carried out by alternately repeating leaching and volatilization operations 10 times.

The leaching operation was carried out as follows. For the treatments 1 to 4, test samples to have the same treatment were placed together in a beaker having a volume of about 500 ml, and deionized water 10 folds the volume of the test samples was added to the beaker to submerge 'chem. The water 25 was stirred at 25 ± 3°C using a magnetic stirrer at 400 to 450 rpm for 8 hours to effect leaching.

Volatilization operation was carried out by placing in a circulating air-drier kept at a temperature of 60 ± 2°C the 30 test samples immediately after completion of the leaching operation and leaving them to stand for 16 hours to volatilize volatile components. 29 28086 [Fungiproofing Effect Test] The following two strains were used as the test fungi. The test samples were exposed to the test fungi and then left to 5 stand, weight reduction ratio was measured. 1) Coriolus versicolor 2) Tyromyces palustris More specifically, test samples were placed upright, with 10 the direction of fiber being perpendicular, on an about 1 mm thick heat resistant plastic mesh directly in the case of Coriolus versicolor or after sterilization in the case of Tyromyces palustris. They were left to stand in an environment of 26 ± 2°C and a relative humidity of 70% or 15 more for 12 weeks or more. Thereafter, the test samples were taken out and hyphae and other adhering matter were thoroughly removed from their surfaces. Then, the test samples were air-dried for 24 hours and then dried at 60 ± 2°C for 48 hours. After being left to stand for about 30 20 minutes in a desiccator, the samples were weighed to the order of 0.01 g.

The weight reduction ratio was obtained according to the following equation: Weight reduction ratio = [(weight of the test sample before the fungiproofing effect test - Weight of the test sample after the fungiproofing effect test) +■ (Weight of the test sample before the fungiproofing effect test)] x 100 ^u«6 5 Table 9 shows the results obtained.

Table 9 Weatherproofing Weight Reduction Ratio (%) Treatment Tyromyces Coriolus palustris* versicolor* No 1.33 0.98 Treatment 1 Yes 1.86 1.39 NO 0.99 0.84 Treatment 2 Yes ■ 1.51 1.11 No 0.26 0 .12 Treatment 3 Yes 0.45 0.36 NO 1.40 0.99 Treatment 4 Yes 1.56 1.26.

* Test fungus Test samples (Japanese cryptomeria) not treated with the chemical of this invention were tested in the same manner -as described above. As a result, the weight reduction ratio was 29.3% in the case of Coriolus versicolor and 59.8% in the case of Tyromyces palustris. Generally, weight reduction ratios not greater than 3% are considered to be acceptable in practice.

Test Example 2 40 According to Standard No. 1 of Japan Wood Preservation Association (1989), Test Chemicals 1 to 4 were tested to 31 » 280865 confirm their antiseptic effect against Serpula lacrymans (Wulf. ex Fr.) Schroeter) .

More specifically, normal sound Japanese red pine sapwood 5 samples (bricks having an edge grain face of 40x20 mm and a thickness of 5 mm, cross section being sealed with an epoxy resin) were classified into 4 groups. Firstly, 4 kinds of treatments shown in Table 10 were conducted with the chemicals of the above-described examples. The treated test 10 samples were left to stand at room temperature for no shorter than 20 days, and the test samples in each group were further divided into two groups. One group was given weatherproofing treatment and the other was left as is.

Thereafter, both groups were dried in a circulating air-15 drier at a temperature of 60°C ± 2°C for 48 hours and left to stand in a desiccator for about 30 minutes. Then, the test samples were weighed on the order of 0.01 g.

Thereafter, the mildewproofing effect tests were conducted as described below.

[Weatherproofing Treatment] The same treatment as the weatherproofing treatment in Test Example 1 was carried out.

[Fungiproofing Effect Test] As the test fungus, there was used Serpula lacrymans (Wulf. ex Fr.) Schroeter. The test samples were exposed to the test fungus and left to stand. Then, its weight reduction ratio was measured. 32 28086 5 More specifically, samples were separately fit in a Teflon plate frame in a number of 3 samples per incubation bottle and sterilized. Thereafter, the samples were placed on the 5 lawn of the test fungus with the 40x5 mm face down and left to stand at a temperature of 20 ± 2°C and a relative humidity of 70% or higher for 8 weeks.

Thereafter, the test samples were taken out and hyphae and 10 other adhering matter were thoroughly removed from their surfaces. Then, the test samples were air-dried for 24 hours and then dried at 60 ± 2°C for 48 hours. After being left to stand for about 30 minutes in a desiccator, the samples were weighed to the order of 0.01 g. Table 10 shows 15 the results obtained. 33 Table 10 2808 Weatherproofing Treatment Weight Reduction Ratio (%} Test fungus: Serpula lacrymans (Wulf. ex Fr.) Schroeter Treatment 1 NO Yes 0.83 1.22 Treatment 2 No Yes 0.74 1.97 Treatment 3 No Yes 1.24 2.06 Treatment 4 No Yes 0.69 1.24 Test samples (Japanese red pine) not treated with the chemical of this invention were tested in the same manner as 30 described above. As a result, the weight reduction ratio was 25.16%. Generally, weight reduction ratios not greater than 3% are considered to be acceptable in practice.

The above results confirmed that the timber treated by the 35 method of this invention, regardless of whether or not weatherproofing treatment was carried out, was superior to those not treated with the chemical of this invention and the chemical of this invention exhibited excellent antiseptic effect far exceeding the practical standard. 40 Test Example 3: Timber Mildewproofing Effect Test 34 280865 Test Chemicals 3 and 4 were tested to evaluate their mildewproofing effect by the method of testing the mildewproofing activity of mildewproofing agents for timber according to Standard No. 2 of Japan Wood Preservation 5 Association (1992).

More specifically, the following procedure was taken.

As the test timber, there were used flat grain timber pieces 10 of beech having a cross section of 20x3 mm and a length of 50 mm. Each timber piece was dipped in a potato soup for 3 minutes so that it could absorb a nutrient. Then, the thus alimented timber piece was dried at 60 ± 2°C. Timber pieces (10 to 20 in number) were stacked up to form a well crib in 15 a 1 liter beaker and a weight was placed on the top. The test chemical was poured in. The chemicals were prepared by diluting the formulations with water in Example 3 or with xylene in Example 4 so that the concentration of cyproconazole was 0.2%. The level of the chemical was set 20 to about 1 cm above the uppermost .end of the timber pieces. After the pouring of the chemical, the dipping was continued for 3 minutes. Then, the timber pieces were taken out and air-dried for 2 days. Also, control samples were prepared in the same manner as above except that the treatment with 25 the chemical was omitted.

Next, those test samples which underwent the same treatment were arranged in a petri dish in parallel to each other so that they did not contact each other and 2 ml of a 2808 suspension of monospores of the test fungus was coated with a brush on the surfaces of the timber pieces. The above-described suspension of monospores was prepared by the method of preparing a spore suspension described in the 5 method for testing the mildewproofing activity of mildewproofing agents for timber according to Standard No. 2 of Japan Wood Preservation Association (1992). That is, sodium dioctyl sulfosuccinate, a wetting agent, was added to potato soup in a concentration of 0.005% and the soup was 10 sterilized and cooled to room temperature. 50 Milliliters of the potato soup thus obtained was poured on the fully grown lawn of the test fungus. The soup was stirred with a platinum loop so that the spores were scraped off and then filtered through sterilized gauze. The test samples were 15 arranged with a 3 mm wide face up.

The test fungi include the following five species. 1) Aspergillus niger van Tieghem IFO 6341=ATCC 6275 2) Penicillium funiculosum Thom IFO 6345=ATCC 9644 20 3) Rhizopus japanicus Takeda IFO 6354 4) Aureobasidium pullulans (de Bary) Arnaud IFO 6353=IAM ) Gliocladium virens Miller, Giddens and Fosteb IFO 6355=ATCC 9645 The test samples coated with the fungal spores together with the Petri dish were left to stand in an environment of a temperature of 26 ± 2°C and a relative humidity of 70 to 80% for 4 weeks to incubate the fungi. Tests were carried out using 6 samples for each test fungus. 36 2808 The state of growth of the fungus after 4 weeks was observed and evaluation values were assigned according to the criteria shown in Table 11. Degree of damage is defined by 5 a ratio of the average evaluation value of the treated samples to that of the control samples.

Table 11 Relationship between the state of growth of the fungus and evaluation value Evaluation State of Growth of Fungus VfllU3 : 0 No growth of fungus on the test sample was observed. 1 slight growth of fungus on the test sample was observed. 2 Growth of fungus over 1/3 or less of the upper 20 surface of the test sample was observed. 3 Growth of fungus over 1/3 or more of the upper surface of the test sample was observed.

The degree of damage was calculated as follows.

Tha't is, an average evaluation value (A) for each fungal species is calculated according to the following equation: Average evaluation value (A) = (ai + a2 + ...+ as) ■+■ 6 wherein ai, a2, ..., ag represent evaluation values of individual test samples.

The above-described average evaluation values (A) are obtained for 5 kinds of fungal species. They are summed for 35 each treatment, and degree of damage (D) is obtained according to the following equation. 37 280865 Degree of damage (D) = (Sum S of average evaluation values of test samples which underwent treatment i) + (Sum S' of average evaluation 5 values of control samples) x 100 Here, treatment i indicates the above-described treatment with the chemical of Example 3 or 4.

Table 12 shows the results obtained.

Table 12 Average Evaluation Value Test of fungus Chemical AN PF RJ AP GV Sum of Average Evaluation Value Degree of Damage 3 4 No Treatment 0.7 0.3 0.3 0.0 0.0 0.8 0.5 0.3 0.0 0.0 3.0 3.0 3.0 3.0 3.0 1.3 1.6 15.0 9 11 1) AN: Aspergillus niger 2) PF: Penicillium funiculosum 3) RJ: Rhizopus japanicus 4) AP: Aureobasidium pullulans ) GV: Gliocladium virens in practice, acceptable degree of damage is considered to.be 30 or less, the results of the tests confirmed that the chemicals of this invention has excellent mildewproofing effects.

Test Example 4: Test for Termiteproofing Effect of Timber 38 280865 Test Chemicals 1 to 4 were tested for their termiteproofing effect by the field testing method (2) of the termiteproofing effect test of termiteproofing agents for timber according to Standard No. 11 of Japan Wood 5 Preservation Association (1992). The field termiteproofing test was conducted by burying treated timber in the soil where house termites (Coptotermes formosanus SHIRAI) live and examining whether or not timbers are eaten thereby.

The timber used for the test was pine sapwood with 3 to 5 annual rings per 10 mm, in the form of a two-way radial cut rectangle of 350 ± 0.5 (L) mm X 30 ± 0.5 (R) mm X 30 ± 0.5 (T) mm, each face smoothly and precisely plane finished. One of the ends of the timber was sharpened along a length 15 of 50 mm to form a pile. Test samples were grouped into treated test samples and control test samples. The former group contained 5 piles and the latter 25 piles.

On the surfaces of the treated test samples were coated 20 uniformly with test solutions prepared differently depending on the kinds of the chemicals used as shown in Table 13 .

Treatment Test Chemical Table 13 Treating Concentration (Cyproconazole) Diluting Solution 6 7 8 1 2 3 4 0.2% 0.2% 0.2% 0.2% Water Water water Xylene 39 280865 The amount of coating was 200 g/m2. After the coating, the test samples were left to stand at room temperature over 10 days or more.

The location of test was a field a habitat of house termites where nests were confirmed. 5 Treated test samples were arranged around the nests at a distance of 70 cm from each other. Around each tested sample, there were arranged 5 10 non-treated test samples in a circle of 10 cm in radius around each tested sample.

At the predetermined positions, each test sample was buried perpendicularly to a depth of 30 cm from the soil surface.

Test term was 2 year. After 1 year past, the treated samples were pulled out and observation was made as to whether or not the test samples were eaten by the termites. Tests were stopped for the test samples that were eaten. 20 Additional 1 year test were subsequently conducted for those test samples which did not underwent eating by the termites.

Presence or absence of the eating of the non-treated test samples was confirmed after 3 months from the active period 25 of house termites. When there was observed no eating, the test locations were changed. 40 280865 The test results obtained were judged as follows and expressed by Degree of eating A to C depending on presence or absence of eating.

Degree of eating A: No eating for 2 years. 5 B: Eating was observed for 1 to 2 years.

C: Eating was observed within 1 year.

Table 14 shows the results obtained.

Table 14 Treatment Treatment Treatment Treatment No 6 7 8 Treatment Degree of A A A A C Eating As described above, timber pieces treated with the chemicals 20 of this invention showed no eating by termites arid it was confirmed that the chemicals of this invention exhibited excellent effects. 41 2 8~0 8 j6 5

Claims (10)

WHAT WE CLAIM IS:

1. A wood preservative composition comprising a triazole derivative and an aliphatic organic acid as essential ingredients and optionally another fungicidal component, another insecticidal component, a color forming component, a surfactant, and/or a solvent.

2. The wood preservative composition as claimed in claim 1, wherein the triazole derivative is a azaconazole, bromoconazole, cyproconazole, hexaconazole, propiconazole, tebuconazole or flusilazole.

3. The wood preservative composition as claimed in claim 1, wherein the another fungicidal component is at *lea£t one compound selected from the group consisting of sulfonamides, benzimidazoles, thiocyanates, quaternary ammonium salts, morpholine derivatives, phenols, organic iodine compounds, organic bromine derivatives, isothiazolines, benzisothiazolines, pyridines, metal soaps, organic tin;42;*280 865 derivatives, dialkyldithiocarbamates, nitriles, activated halogen atom-containing anti-microbial agents, 2-mercaptobenzothiazoles, benzothiazoles, quinolines and formaldehyde-releasing compounds.

4. The wood preservative composition as claimed in claim 1, wherein another insecticide component is selected from the group consisting of boron compounds, phosphates, carbamates, pyrethroids, nitroimines, and nitromethylenes.

5. The wood preservative composition as claimed in claim 1, wherein the coloring agent is selected from zinc salts and boric acid.

6. The wood preservative composition as claimed in claim 1, wherein the aliphatic organic acid is blended in a dosage of not smaller than 50 ppm.

7. A method for improving the permeability of a wood preservative composition containing a triazole derivative, comprising the step of adding a small amount of an aliphatic organic acid to the wood preservative. 43 28.9965

8. A method for improving the permeability of a wood preservative composition containing a metal naphthenate, comprising the step of adding a small amount of an aliphatic organic acid to the wood preservative.

9. The method for improving the permeability as claimed in claim 7 or claim 8, wherein insecticide is used in combination with the wood preservative.

10. A wood preservative composition substantially as herein described with reference to any one of Examples 1 to 4. :y END OF CLAIMS ~ 3 SEP 1.997