CA2251534A1 - Process for treating wood against infection by moulds harmful to wood - Google Patents
Process for treating wood against infection by moulds harmful to wood Download PDFInfo
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- CA2251534A1 CA2251534A1 CA 2251534 CA2251534A CA2251534A1 CA 2251534 A1 CA2251534 A1 CA 2251534A1 CA 2251534 CA2251534 CA 2251534 CA 2251534 A CA2251534 A CA 2251534A CA 2251534 A1 CA2251534 A1 CA 2251534A1
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- Prior art keywords
- wood
- fenpropimorph
- acid
- acetone
- mixture
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/343—Heterocyclic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/38—Aromatic compounds
- B27K3/40—Aromatic compounds halogenated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/50—Mixtures of different organic impregnating agents
Abstract
In a process for treating wood against the infection by moulds which are harmful to wood, the wood is treated with a mixture which contains (a) fenpropimorph and (b) a triazole compound, with the exception of epoxyconazol, in a synergistically effective amount against said moulds.
Description
CA 022~1~34 1998-10-14 Treatment of wood against attack by wood-injurious fungi The present invention relates to a method for treating wood 5 against attack by wood-injurious fungi.
The fungicial action of fenpropimorph (4-[3-{4-tert-butylphenyl}-2-methylpropyl]-2,6-cis-dimethylmorpholine) is generally known (cf. DE-A 26 56 747).
It is furthermore known to employ triazole compounds in wood preservation [propiconazole: US-A 4 079 062; tebuconazole: EP-A
40 345 and EP-A 52 424; cyproconazole: EP-A 131 684 and EP-A 555 15 186].
WO-A 95/16349 discloses fungicidal mixtures and compositions comprising them for crop preservation, which as active substances contain fenpropimorph and a triazole compound.
EP-A 72 156 discloses the synergistic action of a mixture of fenpropimorph and prochloraz against phytopathogenic fungi.
Synergistic mixtures of triazole compounds are also familiar in 25 wood preservation [propiconazole + tebuconazole: EP-A 393 746].
DE-A 43 40 853 describes a synergistic mixture for use in wood preservation, which beside a copper compound and an Al kAnolamine contains a triazole compound and a further fungicide, for example 30 fenpropimorph.
Furthermore, EP-A 425 857 discloses the synergistic action of a mixture of fenpropimorph and epoxyconazole against harmful fungi on materials.
Fenpropimorph, the triazole compounds and the known synergistic mixtures which contain these active compounds, however, do not have a satisfactory action against wood-injurious fungi, in particular wood-discoloring fungi.
It is an object of the present invention to remedy this deficiency.
. _ _ .. ..
CA 022~1~34 1998-10-14 We have found that this object is achieved by a method for treating wood against attack by wood-injurious fungi, the wood being treated with a mixture which comprises 5 a) fenpropimorph and b) a triazole compound with the exception of epoxyconazole 10 in an amount which is synergistically active against these fungi.
The term nwoodn here is also inten~e~ to include secondary wood products, such as wood cuttings, celluloses and other industrial products or alternatively cellulose-contAin;ng materials which 15 are accessible to fungal attack, eg. intermediates in paper manufacture and also woody annual plants (bargasse [sic], rape).
The active compounds mentioned herein, in particular fenpropimorph and the triazole compounds, are known to the person 20 skilled in the art (cf. for example "The Pesticide Manualn, 10th Edition, The British Crop Protection Council, Farnham, Great Britain).
Suitable triazole compounds are, for example:
25 2-(1-chlorocyclopropyl-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)propan-2-ol, 1-butyl-1-(2,4-dichlorophenyl)-2-(1,2,4-triazol-1-yl)ethanol (hexaconazole)~
1-(2-chlorophenyl)methyl)-1-(1,1-dimethyl)-2-(l~2~4-triazol-l-yl-ethanol~ 1-(4-fluorophenyl)-1-(2-fluoro-30 phenyl)-2-(1,2,4-triazol-1-yl)- ethanol (flutriafol), (RS)-4-(4-chlorophenyl)-2-phenyl-2-(lH-1,2,4-triazol-1-yl-methyl) butyronitrile, 1-(2 RS,4 RS; 2 RS,4 SR)-4-bromo-2-(2,4-dichlorophenyl)tetrahydrofurfuryl)-lH-1,2,4- triazole, 3-(2,4-dichlorophenyl)-2-(lH-1,2,4-triazol-1-yl)quinazolin-4(3H)-35 one, (RS)-2,2-dimethyl-3-(2-chlorobenzyl)-4-(lH-1,2,4-triazol-l-yl)butan-3-ol, bitertanol, triadimefon, triadimenol, cyproconazole, dichlobutrazole, difenoconazole, diniconazole, etaconazole, flusilazole, penconazole, tetraconazole, bromoconazole, metconazole, fenbendazole, fensilazole, 40 1-(2-(2,4,-dichlorophenyl)-1,3-dioxolan-2-yl-methyl)-lH-1,2,4-triazole (azaconazole), 1-(2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl-methyl)-lH-1,2,4-triazole (propiconazole), (RS)-1-p-chlorophenyl-4,4-dimethyl-3-(lH-1,2,4-triazol-1-ylmethyl)-pentan-3-ol (tebuconazole) and mixtures thereof.
CA 022~1534 1998-10-14 Propiconazole~ penconazole, cyproconazole, hexaconazole, tebuconazole and mixtures thereof are used with particular advantage as the triazole compound.
5 Fenpropimorph and the triazole compounds can in each case be present in the form of the free base or in the form of a metal salt complex or as an acid addition salt.
The salts are prepared by reacting the respective active compound 10 with the appropriate acids, eg. hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydriodic acid or sulfuric acid, phosphoric acid, phosphorous acid, nitric acid or organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, 15 glycolic acid, lactic acid, succinic acid, citric acid, malic acid, tartaric acid, benzoic acid, cinn~;c acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid and 1,2-naphthalenedisulfonic acid.
The metal complexes are prepared from fenpropimorph or the underlying triazole compound and an inorganic or organic metal salt, for example the h~ es, nitrates, sulfates, phosphates, 25 acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates and benzoates of the metals of the second main group of the Periodic Table such as calcium and magnesium and the third and fourth main groups, such as aluminum, tin or lead, and the first to eighth subgroup, such as chromium, 30 manganese, iron, cobalt, nickel copper and zinc. The subgroup elements of the 4th period and in particular copper are preferred. The metals can be present here in the various valencies befitting them. The metal complexes can contain one or more organic molecule components as ligands.
Particularly preferred within the meaning of the present invention is the use of a mixture of fenpropimorph and propiconazole, to be specific in each case in the form of the free base.
The mixing ratio of fenpropimorph and triazole compound in the mixtures used according to the invention is between 0.25 : 1 to [sic] 5 : 1, in particular 1 : 1 to 4 : 1, parts by weight.
CA 022~1~34 1998-10-14 ~, 097 5 /00099 The mixtures of fenpropimorph and one or more triazole compounds are generally formulated before their use with customary formulation auxiliaries. Preferably, because of the better handling ability, liquid wood preservatives are prepared.
The mixture is applied such that the wood to be preserved with fenpropimorph and one or more triazole compounds is treated simultaneously, to be specific together or separately, or in succession.
Preferably, the mixture of fenpropimorph and one or more triazole compounds is applied in an amount of from 0.05 to 5 kg per cubic meter of wood.
Some of the mixtures used according to the invention are liquid.
With a view to their use in the preservation of wood, they are preferably formulated independently thereof in liquid form, for example a) as a solution in an organic solvent, to be specific ready-to-use or as a dilutable preconcentrate, b) as an additive to wood perservatives, which are formulated in organic solvents and which can be applied as such or after addition of further organic solvents or c) in water-dilutable wood preservatives which contain organic solvents and, if necessary, water (emulsion concentrates).
Water and solvents in this context serve to improve the handling of the mixtures or of the compositions by facilitating the adjustment of the viscosity andtor accelerating the dissolution 35 of the emulsion concentrates in water. The organic solvents are in some cases needed at the same time for dissolving the triazole compounds. The emulsion concentrates can be present in liquid homogeneous form or as a paste, but also in solid form.
40 Preferred organic solvents for formulations of this type are water-soluble or water-miscible polar solvents, eg. glycols (ethylene glycol, propylene glycol), glycol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, phenyl glycol), glycol ether acetates (butyl glycol acetate), lactic 45 acid esters (ethyl lactate, propyl lactate)~ N-alkylpyrrolidones (N-methylpyrrolidone, N-octylpyrrolidone), alcohols, diacetone CA 022~1~34 1998-10-14 alcohol, dimethylformamide, diethylformamide, dimethyl sulfoxide, ~,N'-dimethylpropyleneurea, and mixtures thereof.
Suitable solvent-containing wood preservatives which are usually 5 ready-to-use as such contain, for example 0.1 - 5% by weight of the mixture fenpropimorph/triazole compound, to be specific preferably to 0.25 - 2.5 and especially to 0.5 - 2% by weight, 0 - 10% by weight of the organic solvents, if necessary for dissolving the triazole compound and/or as a penetration aid, 15 as the remainder to of aliphatic and/or aromatic 100% by weight hydrocarbons.
Suitable water-dilutable wood preservatives (emulsion concentrates) consist, for example, of 1 - 90% by weight of an emulsifier, 1 - 50% by weight of the mixture fenpropimorph/triazole compound, to be specific preferably to 5 - 40 and especially to 10 to 35% by weight, 0 - 60% by weight of an organic solvent and 0 - 60% by weight of water, where the proportions of the constituents of these compositions should make up to 100% by weight.
Emulsifiers which can be used are nonionic, cationic and anionic 35 emulsifiers. Those preferred are quaternary ammonium compounds as well as alkoxylated, in particular ethoxylated, fatty alcohols, oxoalcohols and oils (castor oil, fish oil).
Emulsifiers which have proven to be very particularly 40 advantageous are fatty amines which are alkoxylated with from 2 to 25 mol of ethylene oxide, such as Eth- -n~ C 15, Ethomen~ T23 or Ethomen~ S20 l-(Akzo Chemicals GmbH, 52355 Duren, Germany).
On dilution in water, the water-dilutable emulsion concentrates 45 form clear to opaaue emulsions.
CA 022~1~34 1998-10-14 - ~ 097 5 /00099 To improve the fungicidal action, it may be advantageous for these wood preservatives additionally to contain piperidine derivatives and/or other morpholine derivatives, preferably one or more of the fungicidal active compounds from the group 5 consisting of fenpropidine, (N-(3(4-tert-butylphenyl)-2-methyl-propyl)piperidine [sic], tridemorph (N-tridecyl-2,6-dimethyl-morpholine) or salts thereof.
To widen the spectrum of action or to achieve particular effects, 10 eg. additional protection against insects including termites, the abovementioned solvent-containing formulations or emulsion concentrates can be combined with further active compounds which, in the latter case, are incorporated using suitable additional emulsifiers.
Suitable mixing components are, for example, the following compounds:
- sulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorofolpet;
- benzimidazoles such as carbendazim, benomyl, fuberidazole, thiabendazole or salts thereof;
- thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate - quaternary ammonium compounds such as benzyldimethyletra-decylammonium chloride, benzyldimethyldodecylammoniumchloride, didecyldimethylammonium chloride;
- quaternary phosphonium compounds;
- iodine derivatives such as diiodomethyl-p-toly [sic] sulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2, 3-diiodo-2-propenyl ethyl carbonate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butyl carbamate, 3-iodo-2-propynyl-n-hexyl carbamate, 3-iodo-2-propynylcyclohexyl carbamate, 3-iodo-2-propynylphenyl carbamate, 0-1-(6-iodo-3-oxohex-5-ynyl)butyl [sic] carbamate, 0-1-(6-iodo-3-oxohex-5-ynyl)phenyl lsic] carbamate, Napcocide;
CA 022~1~34 1998-10-14 ~ 0975/OOO99 - phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol;
5 - bromine derivatives such as as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-2-bLc ~~hylglutaronitrile;
- isothiazolinones such as N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octylisothiazolin-3-one;
- benzisothiazolinones such as 4,5-trimethylisothiazol-3-one [sic];
- pyridines such as l-hydroxy-2-pyridinethione (and its Na, Fe, Mn and Zn salts), tetrachloro-4-methylsulfonylpyridine;
- metal soaps such as tin, copper and zinc naphthenates, octates [sic], 2-ethylhexanoates, oleates, phosphates and benzoates.
- organotin compounds, eg. tributyl (T3T) tin [sic] compounds, dialkyl dithiocarbamates such as Na and Zn salts of dialkyl dithiocarbamates, tetramethylthiuram disulfide;
- nitriles such as 2,4,5,6-tetrachloroisophthalonitrile;
30 - benzothiazoles such as 2-mercaptobenzothiazole;
- quinolines such as 8-hydroxyquinoline and their Cu salts;
35 - tris-N-(cyclohexyldiazeniumdioxy)aluminum, N-(cyclohexyldiazeniumdioxy)tributyltin or K salts, bis-N-(cyclohexyldiazeniumdioxy)copper;
- morpholine derivatives such as aldemorph.
As insecticides, the following are preferably added:
- phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, 1-(4-chlorophenyl)-4-(o-ethyl, S-propyl)-phosphoryloxypyrazole, chloropyrifos, coumaphos, demeton,demeton-S-methyl, diazinone, dichlorovos, dimethoate, ethoprophos, etrimfos, fenitrothion, fenthion, heptenophos, CA 022~1~34 1998-10-14 ~ 097 5 /O0099 parathion, parathion-methyl, phosalone, phoxim, pirimiphos-ethyl, pirimiphos-methyl, profenofos, prothiofos, sulfprofos, triazophos and trichloron;
- carbamates such as aldocarb, bendiocarb, 2-(1-methyl-propyl)phenylmethyl carbamate, butocarboxim, carbaryl,carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, primicarb, promecarb, propoxur and thiocarb;
10 ~ organosilicon compounds, preferably dimethyl(phenyl)-silylmethyl 3-phenoxybenzyl ethers such as dimethyl(4-ethoxyphenyl)silylmethyl 3-phenoxybenzyl ether or (dimethylphenyl)silylmethyl [sic] 2-phenoxy-6-pyridylmethyl ethers such as dimethyl(9-ethoxy-phenyl)silylmethyl 2-phenoxy-6-pyridylmethyl ether or (phenyl-3-(3-phenoxyphenyl)propyl)dimethylsilanes such as, for example, (4-ethoxyphenyl)-(3-(4-fluoro-3-phenoxyphenylpropyl)dimethyl-silane;
20 ~ pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin, cycloprothin, cyfluthrin, decamethrin, cyhalothrin, cypermethrin, deltamethrin, a-cyno-3-phenyl-2-methylbenzyl-2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl) [sic] cyclopropanecarboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin, resemethrin and tralomethrin;
- nitroimines and nitromethylenes such as 1-((6-chloro-3-pyridinyl)methyl)-4,5-dihydro-N-nitro-lH-imidazole-2-amine (midacloprid [sic]), N-((6-chloro-3-pyridyl)methyl)-N'-cyano-N'-methylacetamide;
- molting inhibitors such as Flurox and Farox.
Addition of water-insoluble acids to the mixtures or wood preservatives can also improve the activity of the active substances fenpropimorph and triazole compound. Suitable 40 water-insoluble organic acids are, for example, 8-hydroxyquinoline, or an aliphatic or aromatic mono- or polycarboxylic acid, eg. an aliphatic unbranched monocarboxylic acid having 5 to 20 C atoms such as hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid and decanoic acid, or an aliphatic branched monocarboxylic acid havinq 5 to 20 C atoms 45 such as 2-ethylpentanoic acid, 2-ethylhexanoic acid, 2-ethylheptanoic acid, isooctanoic acid, isononanoic acid and versatic acid, or neocarboxylic acid [sic] (more highly branched CA 022~1~34 1998-10-14 monocarboxylic acids), or an aliphatic dicarboxylic acid having 5 to 20 C atoms such as sebacic acid or decanedicarboxylic acid, or an aromatic or aromatically [sic]/aliphatic carboxylic acid such as naphthenic acid or benzoic acid.
Binders, eg. oil-soluble or water-dilutable alkyd resins, acrylate dispersions or, in the case of primers which contain from about 2 to 10% by weight of solid resin or glazes which contain from about 10 to 25% of solid resin, alternatively 10 inorganic or organic pigment preparations, water- and oil-soluble dyes, "water repellants" such as metal stearates or waxes and/or other aids such as dryers, wetting agents and penetration aids.
Application for protecting the wood can be carried out, for 15 example, depending on the danger to the wood:
a) by spraying the wood with the impregnation solution, 20 b) by dipping the wood in the impregnation solution (brief immersion to trough impregnation)~
c) by impregnating the wood with the aid of pressure differences, eg. boiler pressure or double vacuum impregnation, d) by painting the wood or flooding it.
The concentration of the fungicidal mixture in the respective 30 wood preservative usually depends on the degree of endangering of the wood to be treated by the fungi and in addition on the application process selected. In the case of secondary wood products and cellulose, for example, undiluted concentrates are usually employed (e.g. for plywood, chipboards, bagasse sheets).
The success of the treatment with the fungicidal mixtures or the ready-to-use wood preservatives, in particular with the emulsion concentrates, also generally depends on the application process.
The mixtures and wood preservatives used according to the invention protect particularly effectively against wood-discoloring fungi, in particular blue stain fungi and especially Aureobasidium pullans and Sclerophoma pityophila, 45 which are counted among the Ascomycetes.
CA 022~1~34 1998-10-14 In addition, it was found that the mixtures and wood preservatives also protect wood against a) Basidiomycetes (eg. Serpula lacrymans, Coniophora puteana) and b) other Ascomycetes such as mold fungi (eg. Aspergillus niger) and soft rot (eg. Chaetomium globosum).
Examples Pine sapwood blocks measuring 40 x 15 x 4 mm3 were impregnated with fungicide solutions in a concentration series by vacuum 15 impregnation. To this end, the test blocks were exposed to a vacuum of 30 mbar in an impregnation vessel for 30 min. The fungicide solution was then sucked into the impregnation container by means of the vacuum, and the test blocks, which were protected against floating, were thus flooded. After pressure 20 equalization, the test blocks were then left under the solution for 1 h.
The amount of solution absorbed by the test blocks was determined by weighing the blocks before and after impregnation, and the 25 absorption of active compound or formulation was then calculated from this.
After an evaporation and fixing time of 2 weeks, the test blocks were fully impregnated with water by vacuum impregnation and 30 leached with a 5-fold volume of water for 1 week. During the course of this, one change of water was carried out per day.
After drying and sterilizing again, the blocks were then placed on agar nutrient medium in Petri dishes on the clean room bench and inoculated with a spore mixture of the blue stain fungi 35 Aureobasidium pullulans and Scherlophoma pityophila (test fungi according to EN 152).
The Petri dishes cont~ining the test blocks were then installed in the test room at 20~C and about 70% atmospheric humidity for 40 6 weeks. After this period, the growth on the surface of the block and, after splitting open the block, the discoloration (blue staining) in the interior of the block was determined visually.
45 The assessment of the growth (outside) due to the fungus was carried out according to the following scale:
CA 022~1~34 1998-10-14 O Not covered 1 Covered to 5%
2 Covered to 25%
5 3 Covered to 50%
The fungicial action of fenpropimorph (4-[3-{4-tert-butylphenyl}-2-methylpropyl]-2,6-cis-dimethylmorpholine) is generally known (cf. DE-A 26 56 747).
It is furthermore known to employ triazole compounds in wood preservation [propiconazole: US-A 4 079 062; tebuconazole: EP-A
40 345 and EP-A 52 424; cyproconazole: EP-A 131 684 and EP-A 555 15 186].
WO-A 95/16349 discloses fungicidal mixtures and compositions comprising them for crop preservation, which as active substances contain fenpropimorph and a triazole compound.
EP-A 72 156 discloses the synergistic action of a mixture of fenpropimorph and prochloraz against phytopathogenic fungi.
Synergistic mixtures of triazole compounds are also familiar in 25 wood preservation [propiconazole + tebuconazole: EP-A 393 746].
DE-A 43 40 853 describes a synergistic mixture for use in wood preservation, which beside a copper compound and an Al kAnolamine contains a triazole compound and a further fungicide, for example 30 fenpropimorph.
Furthermore, EP-A 425 857 discloses the synergistic action of a mixture of fenpropimorph and epoxyconazole against harmful fungi on materials.
Fenpropimorph, the triazole compounds and the known synergistic mixtures which contain these active compounds, however, do not have a satisfactory action against wood-injurious fungi, in particular wood-discoloring fungi.
It is an object of the present invention to remedy this deficiency.
. _ _ .. ..
CA 022~1~34 1998-10-14 We have found that this object is achieved by a method for treating wood against attack by wood-injurious fungi, the wood being treated with a mixture which comprises 5 a) fenpropimorph and b) a triazole compound with the exception of epoxyconazole 10 in an amount which is synergistically active against these fungi.
The term nwoodn here is also inten~e~ to include secondary wood products, such as wood cuttings, celluloses and other industrial products or alternatively cellulose-contAin;ng materials which 15 are accessible to fungal attack, eg. intermediates in paper manufacture and also woody annual plants (bargasse [sic], rape).
The active compounds mentioned herein, in particular fenpropimorph and the triazole compounds, are known to the person 20 skilled in the art (cf. for example "The Pesticide Manualn, 10th Edition, The British Crop Protection Council, Farnham, Great Britain).
Suitable triazole compounds are, for example:
25 2-(1-chlorocyclopropyl-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)propan-2-ol, 1-butyl-1-(2,4-dichlorophenyl)-2-(1,2,4-triazol-1-yl)ethanol (hexaconazole)~
1-(2-chlorophenyl)methyl)-1-(1,1-dimethyl)-2-(l~2~4-triazol-l-yl-ethanol~ 1-(4-fluorophenyl)-1-(2-fluoro-30 phenyl)-2-(1,2,4-triazol-1-yl)- ethanol (flutriafol), (RS)-4-(4-chlorophenyl)-2-phenyl-2-(lH-1,2,4-triazol-1-yl-methyl) butyronitrile, 1-(2 RS,4 RS; 2 RS,4 SR)-4-bromo-2-(2,4-dichlorophenyl)tetrahydrofurfuryl)-lH-1,2,4- triazole, 3-(2,4-dichlorophenyl)-2-(lH-1,2,4-triazol-1-yl)quinazolin-4(3H)-35 one, (RS)-2,2-dimethyl-3-(2-chlorobenzyl)-4-(lH-1,2,4-triazol-l-yl)butan-3-ol, bitertanol, triadimefon, triadimenol, cyproconazole, dichlobutrazole, difenoconazole, diniconazole, etaconazole, flusilazole, penconazole, tetraconazole, bromoconazole, metconazole, fenbendazole, fensilazole, 40 1-(2-(2,4,-dichlorophenyl)-1,3-dioxolan-2-yl-methyl)-lH-1,2,4-triazole (azaconazole), 1-(2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl-methyl)-lH-1,2,4-triazole (propiconazole), (RS)-1-p-chlorophenyl-4,4-dimethyl-3-(lH-1,2,4-triazol-1-ylmethyl)-pentan-3-ol (tebuconazole) and mixtures thereof.
CA 022~1534 1998-10-14 Propiconazole~ penconazole, cyproconazole, hexaconazole, tebuconazole and mixtures thereof are used with particular advantage as the triazole compound.
5 Fenpropimorph and the triazole compounds can in each case be present in the form of the free base or in the form of a metal salt complex or as an acid addition salt.
The salts are prepared by reacting the respective active compound 10 with the appropriate acids, eg. hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydriodic acid or sulfuric acid, phosphoric acid, phosphorous acid, nitric acid or organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, 15 glycolic acid, lactic acid, succinic acid, citric acid, malic acid, tartaric acid, benzoic acid, cinn~;c acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid and 1,2-naphthalenedisulfonic acid.
The metal complexes are prepared from fenpropimorph or the underlying triazole compound and an inorganic or organic metal salt, for example the h~ es, nitrates, sulfates, phosphates, 25 acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates and benzoates of the metals of the second main group of the Periodic Table such as calcium and magnesium and the third and fourth main groups, such as aluminum, tin or lead, and the first to eighth subgroup, such as chromium, 30 manganese, iron, cobalt, nickel copper and zinc. The subgroup elements of the 4th period and in particular copper are preferred. The metals can be present here in the various valencies befitting them. The metal complexes can contain one or more organic molecule components as ligands.
Particularly preferred within the meaning of the present invention is the use of a mixture of fenpropimorph and propiconazole, to be specific in each case in the form of the free base.
The mixing ratio of fenpropimorph and triazole compound in the mixtures used according to the invention is between 0.25 : 1 to [sic] 5 : 1, in particular 1 : 1 to 4 : 1, parts by weight.
CA 022~1~34 1998-10-14 ~, 097 5 /00099 The mixtures of fenpropimorph and one or more triazole compounds are generally formulated before their use with customary formulation auxiliaries. Preferably, because of the better handling ability, liquid wood preservatives are prepared.
The mixture is applied such that the wood to be preserved with fenpropimorph and one or more triazole compounds is treated simultaneously, to be specific together or separately, or in succession.
Preferably, the mixture of fenpropimorph and one or more triazole compounds is applied in an amount of from 0.05 to 5 kg per cubic meter of wood.
Some of the mixtures used according to the invention are liquid.
With a view to their use in the preservation of wood, they are preferably formulated independently thereof in liquid form, for example a) as a solution in an organic solvent, to be specific ready-to-use or as a dilutable preconcentrate, b) as an additive to wood perservatives, which are formulated in organic solvents and which can be applied as such or after addition of further organic solvents or c) in water-dilutable wood preservatives which contain organic solvents and, if necessary, water (emulsion concentrates).
Water and solvents in this context serve to improve the handling of the mixtures or of the compositions by facilitating the adjustment of the viscosity andtor accelerating the dissolution 35 of the emulsion concentrates in water. The organic solvents are in some cases needed at the same time for dissolving the triazole compounds. The emulsion concentrates can be present in liquid homogeneous form or as a paste, but also in solid form.
40 Preferred organic solvents for formulations of this type are water-soluble or water-miscible polar solvents, eg. glycols (ethylene glycol, propylene glycol), glycol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, phenyl glycol), glycol ether acetates (butyl glycol acetate), lactic 45 acid esters (ethyl lactate, propyl lactate)~ N-alkylpyrrolidones (N-methylpyrrolidone, N-octylpyrrolidone), alcohols, diacetone CA 022~1~34 1998-10-14 alcohol, dimethylformamide, diethylformamide, dimethyl sulfoxide, ~,N'-dimethylpropyleneurea, and mixtures thereof.
Suitable solvent-containing wood preservatives which are usually 5 ready-to-use as such contain, for example 0.1 - 5% by weight of the mixture fenpropimorph/triazole compound, to be specific preferably to 0.25 - 2.5 and especially to 0.5 - 2% by weight, 0 - 10% by weight of the organic solvents, if necessary for dissolving the triazole compound and/or as a penetration aid, 15 as the remainder to of aliphatic and/or aromatic 100% by weight hydrocarbons.
Suitable water-dilutable wood preservatives (emulsion concentrates) consist, for example, of 1 - 90% by weight of an emulsifier, 1 - 50% by weight of the mixture fenpropimorph/triazole compound, to be specific preferably to 5 - 40 and especially to 10 to 35% by weight, 0 - 60% by weight of an organic solvent and 0 - 60% by weight of water, where the proportions of the constituents of these compositions should make up to 100% by weight.
Emulsifiers which can be used are nonionic, cationic and anionic 35 emulsifiers. Those preferred are quaternary ammonium compounds as well as alkoxylated, in particular ethoxylated, fatty alcohols, oxoalcohols and oils (castor oil, fish oil).
Emulsifiers which have proven to be very particularly 40 advantageous are fatty amines which are alkoxylated with from 2 to 25 mol of ethylene oxide, such as Eth- -n~ C 15, Ethomen~ T23 or Ethomen~ S20 l-(Akzo Chemicals GmbH, 52355 Duren, Germany).
On dilution in water, the water-dilutable emulsion concentrates 45 form clear to opaaue emulsions.
CA 022~1~34 1998-10-14 - ~ 097 5 /00099 To improve the fungicidal action, it may be advantageous for these wood preservatives additionally to contain piperidine derivatives and/or other morpholine derivatives, preferably one or more of the fungicidal active compounds from the group 5 consisting of fenpropidine, (N-(3(4-tert-butylphenyl)-2-methyl-propyl)piperidine [sic], tridemorph (N-tridecyl-2,6-dimethyl-morpholine) or salts thereof.
To widen the spectrum of action or to achieve particular effects, 10 eg. additional protection against insects including termites, the abovementioned solvent-containing formulations or emulsion concentrates can be combined with further active compounds which, in the latter case, are incorporated using suitable additional emulsifiers.
Suitable mixing components are, for example, the following compounds:
- sulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorofolpet;
- benzimidazoles such as carbendazim, benomyl, fuberidazole, thiabendazole or salts thereof;
- thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate - quaternary ammonium compounds such as benzyldimethyletra-decylammonium chloride, benzyldimethyldodecylammoniumchloride, didecyldimethylammonium chloride;
- quaternary phosphonium compounds;
- iodine derivatives such as diiodomethyl-p-toly [sic] sulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2, 3-diiodo-2-propenyl ethyl carbonate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butyl carbamate, 3-iodo-2-propynyl-n-hexyl carbamate, 3-iodo-2-propynylcyclohexyl carbamate, 3-iodo-2-propynylphenyl carbamate, 0-1-(6-iodo-3-oxohex-5-ynyl)butyl [sic] carbamate, 0-1-(6-iodo-3-oxohex-5-ynyl)phenyl lsic] carbamate, Napcocide;
CA 022~1~34 1998-10-14 ~ 0975/OOO99 - phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol;
5 - bromine derivatives such as as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-2-bLc ~~hylglutaronitrile;
- isothiazolinones such as N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octylisothiazolin-3-one;
- benzisothiazolinones such as 4,5-trimethylisothiazol-3-one [sic];
- pyridines such as l-hydroxy-2-pyridinethione (and its Na, Fe, Mn and Zn salts), tetrachloro-4-methylsulfonylpyridine;
- metal soaps such as tin, copper and zinc naphthenates, octates [sic], 2-ethylhexanoates, oleates, phosphates and benzoates.
- organotin compounds, eg. tributyl (T3T) tin [sic] compounds, dialkyl dithiocarbamates such as Na and Zn salts of dialkyl dithiocarbamates, tetramethylthiuram disulfide;
- nitriles such as 2,4,5,6-tetrachloroisophthalonitrile;
30 - benzothiazoles such as 2-mercaptobenzothiazole;
- quinolines such as 8-hydroxyquinoline and their Cu salts;
35 - tris-N-(cyclohexyldiazeniumdioxy)aluminum, N-(cyclohexyldiazeniumdioxy)tributyltin or K salts, bis-N-(cyclohexyldiazeniumdioxy)copper;
- morpholine derivatives such as aldemorph.
As insecticides, the following are preferably added:
- phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, 1-(4-chlorophenyl)-4-(o-ethyl, S-propyl)-phosphoryloxypyrazole, chloropyrifos, coumaphos, demeton,demeton-S-methyl, diazinone, dichlorovos, dimethoate, ethoprophos, etrimfos, fenitrothion, fenthion, heptenophos, CA 022~1~34 1998-10-14 ~ 097 5 /O0099 parathion, parathion-methyl, phosalone, phoxim, pirimiphos-ethyl, pirimiphos-methyl, profenofos, prothiofos, sulfprofos, triazophos and trichloron;
- carbamates such as aldocarb, bendiocarb, 2-(1-methyl-propyl)phenylmethyl carbamate, butocarboxim, carbaryl,carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, primicarb, promecarb, propoxur and thiocarb;
10 ~ organosilicon compounds, preferably dimethyl(phenyl)-silylmethyl 3-phenoxybenzyl ethers such as dimethyl(4-ethoxyphenyl)silylmethyl 3-phenoxybenzyl ether or (dimethylphenyl)silylmethyl [sic] 2-phenoxy-6-pyridylmethyl ethers such as dimethyl(9-ethoxy-phenyl)silylmethyl 2-phenoxy-6-pyridylmethyl ether or (phenyl-3-(3-phenoxyphenyl)propyl)dimethylsilanes such as, for example, (4-ethoxyphenyl)-(3-(4-fluoro-3-phenoxyphenylpropyl)dimethyl-silane;
20 ~ pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin, cycloprothin, cyfluthrin, decamethrin, cyhalothrin, cypermethrin, deltamethrin, a-cyno-3-phenyl-2-methylbenzyl-2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl) [sic] cyclopropanecarboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin, resemethrin and tralomethrin;
- nitroimines and nitromethylenes such as 1-((6-chloro-3-pyridinyl)methyl)-4,5-dihydro-N-nitro-lH-imidazole-2-amine (midacloprid [sic]), N-((6-chloro-3-pyridyl)methyl)-N'-cyano-N'-methylacetamide;
- molting inhibitors such as Flurox and Farox.
Addition of water-insoluble acids to the mixtures or wood preservatives can also improve the activity of the active substances fenpropimorph and triazole compound. Suitable 40 water-insoluble organic acids are, for example, 8-hydroxyquinoline, or an aliphatic or aromatic mono- or polycarboxylic acid, eg. an aliphatic unbranched monocarboxylic acid having 5 to 20 C atoms such as hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid and decanoic acid, or an aliphatic branched monocarboxylic acid havinq 5 to 20 C atoms 45 such as 2-ethylpentanoic acid, 2-ethylhexanoic acid, 2-ethylheptanoic acid, isooctanoic acid, isononanoic acid and versatic acid, or neocarboxylic acid [sic] (more highly branched CA 022~1~34 1998-10-14 monocarboxylic acids), or an aliphatic dicarboxylic acid having 5 to 20 C atoms such as sebacic acid or decanedicarboxylic acid, or an aromatic or aromatically [sic]/aliphatic carboxylic acid such as naphthenic acid or benzoic acid.
Binders, eg. oil-soluble or water-dilutable alkyd resins, acrylate dispersions or, in the case of primers which contain from about 2 to 10% by weight of solid resin or glazes which contain from about 10 to 25% of solid resin, alternatively 10 inorganic or organic pigment preparations, water- and oil-soluble dyes, "water repellants" such as metal stearates or waxes and/or other aids such as dryers, wetting agents and penetration aids.
Application for protecting the wood can be carried out, for 15 example, depending on the danger to the wood:
a) by spraying the wood with the impregnation solution, 20 b) by dipping the wood in the impregnation solution (brief immersion to trough impregnation)~
c) by impregnating the wood with the aid of pressure differences, eg. boiler pressure or double vacuum impregnation, d) by painting the wood or flooding it.
The concentration of the fungicidal mixture in the respective 30 wood preservative usually depends on the degree of endangering of the wood to be treated by the fungi and in addition on the application process selected. In the case of secondary wood products and cellulose, for example, undiluted concentrates are usually employed (e.g. for plywood, chipboards, bagasse sheets).
The success of the treatment with the fungicidal mixtures or the ready-to-use wood preservatives, in particular with the emulsion concentrates, also generally depends on the application process.
The mixtures and wood preservatives used according to the invention protect particularly effectively against wood-discoloring fungi, in particular blue stain fungi and especially Aureobasidium pullans and Sclerophoma pityophila, 45 which are counted among the Ascomycetes.
CA 022~1~34 1998-10-14 In addition, it was found that the mixtures and wood preservatives also protect wood against a) Basidiomycetes (eg. Serpula lacrymans, Coniophora puteana) and b) other Ascomycetes such as mold fungi (eg. Aspergillus niger) and soft rot (eg. Chaetomium globosum).
Examples Pine sapwood blocks measuring 40 x 15 x 4 mm3 were impregnated with fungicide solutions in a concentration series by vacuum 15 impregnation. To this end, the test blocks were exposed to a vacuum of 30 mbar in an impregnation vessel for 30 min. The fungicide solution was then sucked into the impregnation container by means of the vacuum, and the test blocks, which were protected against floating, were thus flooded. After pressure 20 equalization, the test blocks were then left under the solution for 1 h.
The amount of solution absorbed by the test blocks was determined by weighing the blocks before and after impregnation, and the 25 absorption of active compound or formulation was then calculated from this.
After an evaporation and fixing time of 2 weeks, the test blocks were fully impregnated with water by vacuum impregnation and 30 leached with a 5-fold volume of water for 1 week. During the course of this, one change of water was carried out per day.
After drying and sterilizing again, the blocks were then placed on agar nutrient medium in Petri dishes on the clean room bench and inoculated with a spore mixture of the blue stain fungi 35 Aureobasidium pullulans and Scherlophoma pityophila (test fungi according to EN 152).
The Petri dishes cont~ining the test blocks were then installed in the test room at 20~C and about 70% atmospheric humidity for 40 6 weeks. After this period, the growth on the surface of the block and, after splitting open the block, the discoloration (blue staining) in the interior of the block was determined visually.
45 The assessment of the growth (outside) due to the fungus was carried out according to the following scale:
CA 022~1~34 1998-10-14 O Not covered 1 Covered to 5%
2 Covered to 25%
5 3 Covered to 50%
4 Fully covered (over 50%) The assessement of the blue st~ining (inside) due to the fungus 10 was carried out according to the following scale:
O Not stained blue 1 Stained blue to 5%
15 2 Stained blue to 25%
3 Stained blue to 50%
4 Fully stA;neA blue (over 50%) Each test was carried out three times and the mean value for growth or blue stA;n;ng in these three tests was then acquired.
The test results are compiled in the following two Tables A and 25 B. "Amount introducedn designates the amount of the solutions or formulations identified in this way absorbed by the wood (unit [kg/m3]).
The emulsifier Ethomen~ C 15 is a coconut fatty amine alkoxylated 30 with, on average, 5 mol of ethylene oxide from Akzo Chemicals GmbH, 52355 Duren, Germany.
Table A: Examples 1 to 12 (Comparison Examples) ~
o No. Active compound Solvent Amount of active compound Growth Blue for introduced [kg/m3] (outside) staining active ~inside) compound 1 Fenpropimorph Acetone 2.68 4 4 2 Propiconazole Acetone 1.34 2 4 D
3 Tebuconazole Acetone 1.34 4 4 ~~
4 Cyproconazole Acetone 1.34 3-4 3-4 5 Cyproconazole Acetone 2.68 1 1 r 6 Penconazole Acetone 1.34 4 4 7 Penconazole Acetone 2.68 8 Hexaconazole Acetone 0.67 3 3 ,~
O Not stained blue 1 Stained blue to 5%
15 2 Stained blue to 25%
3 Stained blue to 50%
4 Fully stA;neA blue (over 50%) Each test was carried out three times and the mean value for growth or blue stA;n;ng in these three tests was then acquired.
The test results are compiled in the following two Tables A and 25 B. "Amount introducedn designates the amount of the solutions or formulations identified in this way absorbed by the wood (unit [kg/m3]).
The emulsifier Ethomen~ C 15 is a coconut fatty amine alkoxylated 30 with, on average, 5 mol of ethylene oxide from Akzo Chemicals GmbH, 52355 Duren, Germany.
Table A: Examples 1 to 12 (Comparison Examples) ~
o No. Active compound Solvent Amount of active compound Growth Blue for introduced [kg/m3] (outside) staining active ~inside) compound 1 Fenpropimorph Acetone 2.68 4 4 2 Propiconazole Acetone 1.34 2 4 D
3 Tebuconazole Acetone 1.34 4 4 ~~
4 Cyproconazole Acetone 1.34 3-4 3-4 5 Cyproconazole Acetone 2.68 1 1 r 6 Penconazole Acetone 1.34 4 4 7 Penconazole Acetone 2.68 8 Hexaconazole Acetone 0.67 3 3 ,~
9 Hexaconazole Acetone 1.34 1 1 r 10 Emulsion concentrate of: Water 1.4 (emulsion concentrate:4.7) 4 4 30% by weight of fenpropimorph and 70% by weight of Ethomen~ C 15 No. Active compound Solvent Amount of active compound Growth Blue ~
forintroduced [kg/m3] (outside) staining active(inside) ~
compound g 11 Emulsion concentrate of: Water 2.3 (emulsion concentrate:7.5) 3-4 3-4 30% by weight of fenpropimorph and 70% by weight of Ethomen~ C 15 12 Emulsion concentrate of: Water 0.3 (emulsion concentrate:1.2) 1-2 3 D
25% by weight of propiconazole o and 75% by weight of Ethomen~ C 15 w ~
o r Table B: Examples 13 to 44 (according to the invention) ~
o No. Active compound mixture Solvent for Amount of active compoundGrowth Blue [weight ratio] active preparation introduced(outside) staining compound [kg/m3] ~inside) mixture 13 Fenpropimorph + propiconazole Acetone 0.33 0 0 [1: 1]
forintroduced [kg/m3] (outside) staining active(inside) ~
compound g 11 Emulsion concentrate of: Water 2.3 (emulsion concentrate:7.5) 3-4 3-4 30% by weight of fenpropimorph and 70% by weight of Ethomen~ C 15 12 Emulsion concentrate of: Water 0.3 (emulsion concentrate:1.2) 1-2 3 D
25% by weight of propiconazole o and 75% by weight of Ethomen~ C 15 w ~
o r Table B: Examples 13 to 44 (according to the invention) ~
o No. Active compound mixture Solvent for Amount of active compoundGrowth Blue [weight ratio] active preparation introduced(outside) staining compound [kg/m3] ~inside) mixture 13 Fenpropimorph + propiconazole Acetone 0.33 0 0 [1: 1]
14 Fenpropimorph + propiconazole Acetone 0.33 0 0 D
[2 : 1] o Fenpropimorph + propiconazole Acetone 0.33 0 0 [3 : 1]
,16 Fenpropimorph + propiconazole Acetone 0.33 0 0 [4 : 1]
17 Fenpropimorph + tebuconazole Acetone 0.67 0-1 0-1 [1: 1]
18 Fenpropimorph + tebuconazole Acetone 1.34 0 0 r [1: 1]
18 Fenpropimorph + tebuconazole Acetone 0.67 0-1 0-1 [2 : 1]
Fenpropimorph + tebuconazole Acetone 1.34 0 0 [2 : 1]
21 Fenpropimorph + tebuconazole Acetone 0.67 1-2 1-2 [3 : 1]
22 Fenpropimorph + tebuconazole Acetone 1.34 0 0 [3 : 1]
No. Active compound mixture Solvent for Amount of active compound Growth Blue O
[weight ratio] active preparation introduced(outside) st~ining compound [kg/m3] (inside) ~
mixture ~
23 Fenpropimorph + tebuconazole Acetone 0.67 1-2 1-2 [4 : 1]
24 Fenpropimorph + tebuconazole Acetone 1.34 0 0 [4 : 1]
Fenpropimorph + cyproconazole Acetone 0.67 0-1 0-1 [1: 1]
26 Fenpropimorph + cyproconazole Acetone 1.34 0 0 o [1: 1]
27 Fenpropimorph + cyproconazole Acetone 1.34 0 0 12 : 1] . r 28 Fenpropimorph + cyproconazole Acetone 1.34 0 0 [3 : 1]
29 Fenpropimorph + cyproconazole Acetone 0.67 0-1 0-1 0 [4 : 1]
Fenpropimorph + cyproconazole Acetone 1.34 0 0 [4 : 1]
31 Fenpropimorph + penconazole Acetone 0.67 0 0 [1: 1]
32 Fenpropimorph + penconazole Acetone 0.67 0 0 [2 : 1]
33 Fenpropimorph + penconazole Acetone 0.33 0-1 0-1 [3 : 1]
34 Fenpropimorph + penconazole Acetone 0.67 0 0 [3 : 1]
No. Active compound mixture Solvent for Amount of active compound Growth Blue ~
[weight ratiol active preparation introduced (outside) staining compound [kg/m3] (inside) mixture Fenpropimorph + penconazole Acetone 0.33 0-1 0-1 w [4 : 1] w 36 Fenpropimorph + penconazole Acetone 0.67 0 0 [4 : 1]
37 Fenpropimorph + hexaconazole Acetone 0.33 0-1 0-1 [1: 1] D
38 Fenpropimorph + hexaconazole Acetone 0.67 0 0 o [2 : 1]
39 Fenpropimorph + hexaconazole Acetone 0.33 0-1 0-1 [2 : 1] r Fenpropimorph + hexaconazole Acetone 0.67 0 0 [3 : 1]
41 Fenpropimorph + hexaconazole Acetone 0.33 0 0 0 [3 : 1] r 42 Fenpropimorph + hexaconazole Acetone 0.33 0 0 [4 : 1]
No. Active compound mixture Solvent for Amount of active compound Growth Blue ~
[weight ratio] active preparation introduced(outside) staining compound [kg/m3] (inside) ~
mixture g 43 Emulsion concentrate of Water 0.28 (emulsion 0 0 37.5% by weight of the mixture concentrate:0.75)of fenpropimorph +
propiconazole [2 : 1] and 62.5% by weight of Ethomen~
44 Emulsion concentrate of Water 0.28 (emulsion 0 0 O
37.5% by weight of the mixture concentrate:0.75)of fenpropimorph +
propiconazole [3 : 1] and r 62.5% by weight of Ethomen~
o
[2 : 1] o Fenpropimorph + propiconazole Acetone 0.33 0 0 [3 : 1]
,16 Fenpropimorph + propiconazole Acetone 0.33 0 0 [4 : 1]
17 Fenpropimorph + tebuconazole Acetone 0.67 0-1 0-1 [1: 1]
18 Fenpropimorph + tebuconazole Acetone 1.34 0 0 r [1: 1]
18 Fenpropimorph + tebuconazole Acetone 0.67 0-1 0-1 [2 : 1]
Fenpropimorph + tebuconazole Acetone 1.34 0 0 [2 : 1]
21 Fenpropimorph + tebuconazole Acetone 0.67 1-2 1-2 [3 : 1]
22 Fenpropimorph + tebuconazole Acetone 1.34 0 0 [3 : 1]
No. Active compound mixture Solvent for Amount of active compound Growth Blue O
[weight ratio] active preparation introduced(outside) st~ining compound [kg/m3] (inside) ~
mixture ~
23 Fenpropimorph + tebuconazole Acetone 0.67 1-2 1-2 [4 : 1]
24 Fenpropimorph + tebuconazole Acetone 1.34 0 0 [4 : 1]
Fenpropimorph + cyproconazole Acetone 0.67 0-1 0-1 [1: 1]
26 Fenpropimorph + cyproconazole Acetone 1.34 0 0 o [1: 1]
27 Fenpropimorph + cyproconazole Acetone 1.34 0 0 12 : 1] . r 28 Fenpropimorph + cyproconazole Acetone 1.34 0 0 [3 : 1]
29 Fenpropimorph + cyproconazole Acetone 0.67 0-1 0-1 0 [4 : 1]
Fenpropimorph + cyproconazole Acetone 1.34 0 0 [4 : 1]
31 Fenpropimorph + penconazole Acetone 0.67 0 0 [1: 1]
32 Fenpropimorph + penconazole Acetone 0.67 0 0 [2 : 1]
33 Fenpropimorph + penconazole Acetone 0.33 0-1 0-1 [3 : 1]
34 Fenpropimorph + penconazole Acetone 0.67 0 0 [3 : 1]
No. Active compound mixture Solvent for Amount of active compound Growth Blue ~
[weight ratiol active preparation introduced (outside) staining compound [kg/m3] (inside) mixture Fenpropimorph + penconazole Acetone 0.33 0-1 0-1 w [4 : 1] w 36 Fenpropimorph + penconazole Acetone 0.67 0 0 [4 : 1]
37 Fenpropimorph + hexaconazole Acetone 0.33 0-1 0-1 [1: 1] D
38 Fenpropimorph + hexaconazole Acetone 0.67 0 0 o [2 : 1]
39 Fenpropimorph + hexaconazole Acetone 0.33 0-1 0-1 [2 : 1] r Fenpropimorph + hexaconazole Acetone 0.67 0 0 [3 : 1]
41 Fenpropimorph + hexaconazole Acetone 0.33 0 0 0 [3 : 1] r 42 Fenpropimorph + hexaconazole Acetone 0.33 0 0 [4 : 1]
No. Active compound mixture Solvent for Amount of active compound Growth Blue ~
[weight ratio] active preparation introduced(outside) staining compound [kg/m3] (inside) ~
mixture g 43 Emulsion concentrate of Water 0.28 (emulsion 0 0 37.5% by weight of the mixture concentrate:0.75)of fenpropimorph +
propiconazole [2 : 1] and 62.5% by weight of Ethomen~
44 Emulsion concentrate of Water 0.28 (emulsion 0 0 O
37.5% by weight of the mixture concentrate:0.75)of fenpropimorph +
propiconazole [3 : 1] and r 62.5% by weight of Ethomen~
o
Claims (6)
1. A method for treating wood against attack by wood-injurious fungi, which comprises treating the wood with a mixture which comprises a) fenpropimorph and b) a triazole compound with the exception of epoxyconazole in an amount which is synergistically active against these fungi.
2. A method as claimed in claim 1, wherein as a triazole compound (b) propiconazole is employed.
3. A method as claimed in claim 1 or 2, wherein the weight ratio of fenpropimorph (a) to the triazole compound (b) is from 1:1 to 4:1.
4. A method as claimed in claims 1 to 3, wherein fenpropimorph (a) and the triazole compound (b) are applied simultaneously, to be specific together or separately, or in succession.
5. A method as claimed in claims 1 to 4, wherein the mixture as set forth in claim 1 is applied in an amount of from 0.05 to 5 kg per cubic meter of wood.
6. The use of mixtures comprising triazoles, with the exception of epoxyconazole, and fenpropimorph for treating wood against wood-injurious fungi.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19615530 | 1996-04-19 | ||
| DE19615530.4 | 1996-04-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2251534A1 true CA2251534A1 (en) | 1997-10-30 |
Family
ID=7791773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2251534 Abandoned CA2251534A1 (en) | 1996-04-19 | 1997-04-17 | Process for treating wood against infection by moulds harmful to wood |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0898506A1 (en) |
| AU (1) | AU2387297A (en) |
| CA (1) | CA2251534A1 (en) |
| WO (1) | WO1997039865A1 (en) |
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| US8409627B2 (en) | 2003-06-17 | 2013-04-02 | Osmose, Inc. | Particulate wood preservative and method for producing the same |
| US8460759B2 (en) | 2003-04-09 | 2013-06-11 | Osmose, Inc. | Micronized wood preservative formulations |
| US8637089B2 (en) | 2003-04-09 | 2014-01-28 | Osmose, Inc. | Micronized wood preservative formulations |
| US8747908B2 (en) | 2003-04-09 | 2014-06-10 | Osmose, Inc. | Micronized wood preservative formulations |
| US9775350B2 (en) | 2004-10-14 | 2017-10-03 | Koppers Performance Chemicals Inc. | Micronized wood preservative formulations in organic carriers |
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|---|---|---|---|---|
| CZ298787B6 (en) * | 1997-06-04 | 2008-01-30 | Basf Aktiengesellschaft | Fungicidal mixture |
| ATE324785T1 (en) * | 1998-03-05 | 2006-06-15 | Buckman Labor Inc | MICROBIOCIDAL METHODS USING COMBINATIONS OF PROPICONAZOLE AND 2-MERCAPTOBENZOTHIAZOLES |
| US6110950A (en) * | 1998-03-05 | 2000-08-29 | Buckman Laboratories International Inc. | Microbicidal compositions and methods using synergistic combinations of propiconazole and 2-mercaptobenzothiazole |
| DE19834028A1 (en) * | 1998-07-28 | 2000-02-03 | Wolman Gmbh Dr | Process for treating wood against infestation by wood-damaging fungi |
| FR2939068A1 (en) * | 2008-12-01 | 2010-06-04 | Intace Internat Sarl | Process for fighting against bluing of wood, comprises contacting the wood with cis-4-(3-(p-tert-butylphenyl)-2-methylpropyl)-2,6-dimethyl morpholine, where bluing is provoked by e.g. Aspergillus niger |
| DE102018125851B3 (en) | 2018-10-18 | 2020-04-16 | Technische Universität Dresden | Composition and method for improving the resistance to mold and / or reducing water absorption, and a material comprising this composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62212307A (en) * | 1986-03-06 | 1987-09-18 | チバ−ガイギ− アクチエンゲゼルシヤフト | Fungicidal composition and use |
| DE3736651C2 (en) * | 1987-10-29 | 1995-11-23 | Bayer Ag | Fungicidal active ingredient combinations |
| DE4343176A1 (en) * | 1993-12-17 | 1995-06-22 | Basf Ag | Fungicidal mixture |
| DE4441672A1 (en) * | 1994-11-23 | 1996-05-30 | Basf Ag | Wood preservatives |
-
1997
- 1997-04-17 EP EP97919373A patent/EP0898506A1/en not_active Withdrawn
- 1997-04-17 WO PCT/EP1997/001911 patent/WO1997039865A1/en not_active Application Discontinuation
- 1997-04-17 AU AU23872/97A patent/AU2387297A/en not_active Abandoned
- 1997-04-17 CA CA 2251534 patent/CA2251534A1/en not_active Abandoned
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8460759B2 (en) | 2003-04-09 | 2013-06-11 | Osmose, Inc. | Micronized wood preservative formulations |
| US8637089B2 (en) | 2003-04-09 | 2014-01-28 | Osmose, Inc. | Micronized wood preservative formulations |
| US8747909B2 (en) | 2003-04-09 | 2014-06-10 | Osmose, Inc. | Micronized wood preservative formulations |
| US8747908B2 (en) | 2003-04-09 | 2014-06-10 | Osmose, Inc. | Micronized wood preservative formulations |
| US8778407B2 (en) | 2003-04-09 | 2014-07-15 | Osmose, Inc. | Micronized wood preservative formulations |
| US9079328B2 (en) | 2003-04-09 | 2015-07-14 | Koppers Performance Chemicals Inc. | Micronized wood preservative formulations |
| US8409627B2 (en) | 2003-06-17 | 2013-04-02 | Osmose, Inc. | Particulate wood preservative and method for producing the same |
| US8871277B2 (en) | 2003-06-17 | 2014-10-28 | Osmose, Inc. | Particulate wood preservative and method for producing the same |
| US8158208B2 (en) | 2004-05-17 | 2012-04-17 | Osmose, Inc. | Method of preserving wood by injecting particulate wood preservative slurry |
| US8722198B2 (en) | 2004-05-17 | 2014-05-13 | Osmose, Inc. | Method of preserving wood by injecting particulate wood preservative slurry |
| US9314030B2 (en) | 2004-05-17 | 2016-04-19 | Koppers Performance Chemicals Inc. | Particulate wood preservative and method for producing same |
| US9775350B2 (en) | 2004-10-14 | 2017-10-03 | Koppers Performance Chemicals Inc. | Micronized wood preservative formulations in organic carriers |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0898506A1 (en) | 1999-03-03 |
| AU2387297A (en) | 1997-11-12 |
| WO1997039865A1 (en) | 1997-10-30 |
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