WO1997039865A1 - 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 PDF

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Publication number
WO1997039865A1
WO1997039865A1 PCT/EP1997/001911 EP9701911W WO9739865A1 WO 1997039865 A1 WO1997039865 A1 WO 1997039865A1 EP 9701911 W EP9701911 W EP 9701911W WO 9739865 A1 WO9739865 A1 WO 9739865A1
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WO
WIPO (PCT)
Prior art keywords
wood
acid
fenpropimorph
fungi
triazole compound
Prior art date
Application number
PCT/EP1997/001911
Other languages
German (de)
French (fr)
Inventor
Reimer Goettsche
Hans Borck
Reiner Kober
Original Assignee
Dr. Wolman Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dr. Wolman Gmbh filed Critical Dr. Wolman Gmbh
Priority to EP97919373A priority Critical patent/EP0898506A1/en
Priority to AU23872/97A priority patent/AU2387297A/en
Publication of WO1997039865A1 publication Critical patent/WO1997039865A1/en

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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

Definitions

  • the present invention relates to a method for treating wood against infestation by wood-damaging fungi.
  • fenpropimorph (4- [3- ⁇ 4-tert-butylphenyl ⁇ -2-methylpropyl] -2,6-c ⁇ s-dimethylmorpholm) is generally known (cf. DE-A 26 56 747).
  • WO-A 95/16349 discloses fungicidal mixtures and agents for crop protection containing them, which contain fenpropimorph and a tnazole compound as active substances.
  • DE-A 43 40 853 teaches a synergistic mixture for use in wood protection which, in addition to a copper compound and an alkanolamine, contains a tazole compound and a further fungicide, for example fenpropimorph.
  • Fenpropimorph, the tnazole compounds and the known synergistic mixtures which contain these active ingredients do not have a satisfactory effect against wood-damaging, wood-fungal fungi.
  • the object of the present invention was therefore to remedy this deficiency.
  • wood is also intended to include wood secondary products such as woodcuts, cellulose and other technical products or materials containing cellulose that are susceptible to fungal attack, e.g. Intermediates in papermaking and woody annual plants (bar alley, rapeseed) are included.
  • Suitable triazole compounds are: 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-l-yl) ethanol (hexaconazole), 1- (2-chlorophenyl) methyl) -l- (1, 1- dimethyl) -2- (1,2, 4-triazol-l-ylethanol, 1- (4-fluorophenyl) -1- (2-fluorophenyl) -2- (1,2,4-triazol-l-yl) ethanol (Flutriafol), (RS) -4- (4-chlorophenyl) -2-phenyl-2- (1H-1,2,4-triazol-l-yl-methyl) butyronitrile, 1- (2 RS, 4 RS; 2 RS, 4 SR) -4
  • Propiconazole, penconazole, cyproconazole, hexaconazole, tebuconazole and mixtures thereof are used with particular advantage as the triazole compound.
  • Fenpropimorph and the triazole compounds can each be 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 produced by reacting the respective active ingredient with the corresponding acids, e.g. Halogenwasserstoff Text ⁇ ren cloth acid 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, Propions ⁇ acid, glycolic acid, lactic acid, succinic acid, citric acid, malic acid, tartaric acid, Benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid and 1,2-naphthalene disulfonic acid.
  • the corresponding acids e.g. Halogenwasserstoff Text ⁇ ren cloth acid such as hydrofluoric acid, hydroch
  • the metal complexes are produced from fenpropimorph or the underlying triazole compound and an inorganic or organic metal salt, for example the halides, nitrates, sulfates, phosphates, 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 group such as aluminum, tin or lead and the first to eighth subgroups such as chromium, manganese, iron, cobalt, nickel, copper, zinc.
  • the sub-group elements of the 4th period and in particular copper are preferred.
  • the metals can be present in the various valences which they can assume.
  • the metal complexes can contain one or more organic molecular moieties as ligands.
  • the mixing ratio of fenpropimorph and triazole compound in the mixtures used according to the invention is between 0.25: 1 to 5: 1, in particular 1: 1 to 4: 1 parts by weight.
  • the mixtures of fenpropimorph and one or more triazole compounds are generally formulated with conventional formulation auxiliaries to form wood preservatives before they are used. Liquid wood preservatives are preferably produced because of the better handling.
  • the mixture is used in such a way that the wood to be protected is treated with fenpropimorph and one or more triazole compounds simultaneously, together or separately, or in succession.
  • the mixture of fenpropimorph and one or more triazole compounds is preferably used in an amount of 0.05 to 5 kg per cubic meter of wood.
  • the mixtures used according to the invention are partly liquid. Regarding their use in wood protection, they are preferably formulated in liquid form, for example
  • Water and solvents serve to improve the handling of the mixtures or the agents by facilitating the setting of the viscosity and / or accelerating the dissolution of the emulsion concentrates in water.
  • the organic solvents are partly at the same time required to dissolve the triazole compounds.
  • the emulsion concentrates can be in liquid, homogeneous form, but also in paste form in solid form.
  • Preferred organic solvents for such formulations 5 are water-soluble or water-miscible polar solvents, e.g. Glycols (ethylene glycol, propylene glycol), glycol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, phenylglycol), glycol ether acetates (butylglycol acetate), lactic acid esters (lactic acid ethyl ester, lactic acid propyl ester), N-alkylpyrrolidone-0-nolonol-n-acetone, methyl-n-acetone hol, dimethylformamide, diethylformamide, dimethyl sulfoxide, N, N'-dimethylpropyleneurea and mixtures thereof.
  • Glycols ethylene glycol, propylene glycol
  • glycol ethers ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, phenylglycol
  • wood preservatives containing eg 0.1-5% by weight of the fenpropimorph / triazole compound mixture, preferably 0.25-2.5% by weight and especially 0.5-2% by weight,
  • organic solvent if appropriate for dissolving the triazole compound and / or as a penetration aid, the remainder being 100% by weight of aliphatic and / or aromatic hydrocarbons.
  • Suitable water-thinnable wood preservatives exist e.g. out
  • the proportions of the components of these agents should add up to 100% by weight.
  • Non-ionic, cationic and anionic emulsifiers can be used as emulsifiers. Quaternary ammonium compounds and alkoxylated, especially ethoxylated: fatty alcohols, oxo alcohols and oils (castor oil, fish oil) are preferred.
  • fatty amines have been found as an emulsifier, which are alkoxylated with from 2 to 25 moles of ethylene oxide, such as Ethomen ® C 15, Ethomen® T23 or S20 Ethomen® (Akzo Chemicals GmbH, Duren 52355, Germany).
  • the water-dilutable emulsion concentrates form clear to opaque emulsions when diluted in water.
  • these wood preservatives also contain piperidine derivatives and / or further morpholine derivatives, preferably one or more of the fungicidal active substances from the group fenpropidine, (N- (3 (4-tert.-Bu- tylphenyl) -2-methylpropyl) piperidine, tridemorph (N-tridecyl-2, 6-dimethylmorpholine) or their salts.
  • piperidine derivatives and / or further morpholine derivatives preferably one or more of the fungicidal active substances from the group fenpropidine, (N- (3 (4-tert.-Bu- tylphenyl) -2-methylpropyl) piperidine, tridemorph (N-tridecyl-2, 6-dimethylmorpholine) or their salts.
  • solvent-containing formulations or emulsion concentrates can be used withn active ingredients are combined, which in the latter case are incorporated with suitable additional emulsifiers.
  • Suitable mixture partners include the following compounds :
  • Fenulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet;
  • Benzimidazoles such as carbendazim, benomyl, fuberidazole, thiabendazole or their salts;
  • Thiocyanates such as thiocyanatomethylthiobenzothiazol, methylene bisthiocyanate
  • quaternary ammonium compounds such as benzyldimethyletradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethylammonium chloride;
  • Iodine derivatives such as diiodomethyl p-tolysulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2, 3-di-iodo-2-propenylethyl carbonate, 2,3, 3-triiodallyl alcohol, 3-bromo-2, 3-di-iodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butyl carbamate, 3-iodo-2-propynyl-n-hexyl carbamate, 3-iodo-2-propi nyl-cyclohexyl carbamate, 3-iodo-2-propynylphenyl carbamate, 0-1- (6-iodo-3-oxo-hex-5-ynyl) butyl carbamate, 0-1- (6-iodo-3-oxo-hex
  • Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol;
  • Bromine derivatives such as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-2-bromomethyl-glutaronitrile;
  • Isothiazolinones such as N-methylisothiazolin-3-one, 5-chloro-N-methyl-isothiazolin-3-one, 4,5-dichloro-N-octylisothiazoline-3-one, N-octyl-isothiazolin-3- on;
  • Benzisothiazolinones such as 4, 5-trimethylisothiazol-3-one
  • Pyridines such as l-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine; Metal soaps such as tin, copper, zinc naphthenate, octate, 2-ethylhexanoate, oleate, phosphate, benzoate.
  • Organotin compounds e.g. Tributyl (TBT) tin compounds, dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethylthiuram disulfide;
  • TBT Tributyl
  • dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethylthiuram disulfide
  • Nitriles such as 2,4, 5, 6-tetrachloroisophthalonitrile
  • Morpholine derivatives such as aldemorph.
  • Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl,
  • Organosilicon compounds preferably dimethyl (phenyl) silylmethyl-3-phenoxybenzyl ether such as dimethyl (4-ethoxyphenyl) silylmethyl-3-phenoxybenzyl ether or (dimethylphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as dimethyl ( 9-ethoxy -phenyl ) silylmethyl-2-phenoxy-6-pyridylmethyl ether or (phenyl-3- (3-phenoxyphenyl (propyl) dimethylsilane such as (4-ethoxyphenyl) - (3- (4-fluoro-3-phenoxyphenyl-propyl) di- methylsilane;
  • Pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin, cycloprothin, cyfluthrin, decamethrin, cyhalothrin, cypermethrin, deltamethrin, a-cyno-3-phenyl-2-methyl-ben-zyl-2,2-dimethyl-3- (2 -chlor-2-trifluoromethylvinyl) cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flu- cythrinate, flumethrin, fluvalinate, permethrin, resemethrin and tralomethrin;
  • Nitroimines and nitromethylenes such as 1- ((6-chloro-3-pyridinyl ) methyl) -4, 5-dihydro-N-nitro-lH-imidazol-2-amine (midacloprid ) , N- (( 6- Chloro-3-pyridyl ) methyl ) -N'-cyano-N'-methylacetamide;
  • Suitable water-soluble organic acids are e.g. 8-hydroxyquinoline, or an aliphatic or aromatic mono- or polycarboxylic acid, e.g.
  • an aliphatic unbranched monocarboxylic acid with 5 to 20 carbon atoms such as hexanoic acid, heptanoic acid, octane acid, nonanoic acid and decanoic acid
  • an aliphatic branched monocarboxylic acid with 5 to 20 carbon atoms such as 2-ethylpentanoic acid, 2-ethylhexanoic acid, 2-ethylheptanoic acid, isooonanoic acid, isooonanoic acid and versatic acid, or neocarboxylic acid (more strongly branched monocarboxylic acids), or an aliphatic dicarboxylic acid with 5 to 20 carbon atoms such as sebacic acid and decanedicarboxylic acid, or an aromatic or aromatic / aliphatic carboxylic acid such as naphthenic acid and benzoic acid.
  • the solvent-containing wood preservatives or aqueous dilutions of the emulsion concentrates can additionally contain binders, e.g. ollosable or water-thinnable alkyd resins, acrylate dispersion, or in the case of primers, which contain approx. 2 to 10% by weight of solid resin or glazes, which contain approx. 10 to 25% solid resin, also inorganic or organic pigment preparations, water-based and olless dyes, "water repellants" such as metal stearates or waxes and / or other auxiliaries such as dryers, wetting agents and penetration aids are added.
  • binders e.g. ollosable or water-thinnable alkyd resins, acrylate dispersion, or in the case of primers, which contain approx. 2 to 10% by weight of solid resin or glazes, which contain approx. 10 to 25% solid resin, also inorganic or organic pigment preparations, water-based and olless dyes,
  • the application for protecting the wood can e.g. depending on the risk to the wood:
  • the concentration of the fungicidal mixture in the respective wood preservative mostly depends on the degree of danger to the wood to be treated by the fungi and, in addition, on the selected application method.
  • undiluted concentrates e.g. plywood, chipboard, bagasse panels.
  • the mixtures and wood preservatives used in accordance with the invention provide particularly effective protection against wood-discoloring fungi, in particular blue fungi and, in particular, Aureobasidium pullulans and Sclero phoma pityophila, which are included in the Ascomycetes.
  • Basidiomycetes e.g. Serpula lacrymans, Coniophora quina
  • mold e.g. Aspergillus niger
  • mold rot e.g. Chaetomium globosum
  • Pine sapwood blocks measuring 40 x 15 x 4 mm 3 were impregnated by vacuum impregnation with fungicide solutions in one concentration row. For this, the test blocks were 30 min. exposed to a vacuum of 30 mbar in a drinking vessel. The fungicide solution was then sucked into the drinking container by means of the vacuum, and the test blocks secured against floating were flooded in this way. After pressure equalization, the test blocks were then left under the solution for 1 h.
  • the amount of solution taken up by the test blocks was determined by weighing the blocks before and after the drinking, and from this the uptake of active substance or formulation was then calculated.
  • test blocks were soaked with water by vacuum impregnation and washed out with a 5-fold volume of water for 1 week. One water change was carried out per day. After drying again and sterilizing the blocks were then in the Clean room bank placed in petri dishes on agar culture medium and inoculated with a spore mixture of the blue fungi Aureobasidium pullulans and Sclerophoma pityophila (test fungi according to EN 152).
  • the fogging was assessed on the inside using the following scale:
  • the emulsifier Ethomen ® C 15 is a coconut fatty amine alkoxylated with an average of 5 moles of ethylene oxide from Akzo Chemicals GmbH, 52355 Duren, Germany.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

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

Verfahren zur Behandlung von Holz gegen den Befall durch holz- schadigende Pilze Process for treating wood against infestation by wood-damaging fungi
5 Beschreibung5 Description
Die vorliegende Erfindung betrifft ein Verfahren zur Behandlung von Holz gegen den Befall durch holzschädigende Pilze.The present invention relates to a method for treating wood against infestation by wood-damaging fungi.
^Q Die fungizide Wirkung von Fenpropimorph (4-[3-{4-tert.-butylphe- nyl}-2-methylpropyl] -2,6-cιs-dιmethylmorpholm) ist allgemein be¬ kannt (vgl. DE-A 26 56 747).^ Q The fungicidal activity of fenpropimorph (4- [3- {4-tert-butylphenyl} -2-methylpropyl] -2,6-cιs-dimethylmorpholm) is generally known (cf. DE-A 26 56 747).
Es ist ferner bekannt, Tnazolverbindungen im Holzschutz einzu¬It is also known to include tnazole compounds in wood preservation
15 setzen [Propiconazol: US-A 4 079 062; Tebuconazol: EP-A 40 345 bzw. EP-A 52 424; Cyproconazol: EP-A 131 684 bzw. EP-A 555 186].15 [Propiconazole: US-A 4,079,062; Tebuconazole: EP-A 40 345 or EP-A 52 424; Cyproconazole: EP-A 131 684 or EP-A 555 186].
Aus der WO-A 95/16349 sind fungizide Mischungen und sie enthal¬ tende Mittel für den Pflanzenschutz bekannt, welche als Wirksub¬ stanzen Fenpropimorph und eine Tnazolverbmdung enthalten.WO-A 95/16349 discloses fungicidal mixtures and agents for crop protection containing them, which contain fenpropimorph and a tnazole compound as active substances.
2020th
Aus der EP-A 72 156 ist die synergistische Wirkung einer Mischung von Fenpropimorph und Prochloraz gegen phytopathogene Pilze be¬ kannt.The synergistic effect of a mixture of fenpropimorph and prochloraz against phytopathogenic fungi is known from EP-A 72 156.
25 Auch synergistische Mischungen von Tnazolverbindungen sind im Holzschutz geläufig [Propiconazol + Tebuconazol: EP-A 393 746].25 Synergistic mixtures of tnazole compounds are also common in wood preservation [propiconazole + tebuconazole: EP-A 393 746].
Die DE-A 43 40 853 lehrt eine synergistische Mischung zur Verwen¬ dung im Holzschutz, welche neben einer Kupferverbindung und einem ™ Alkanolamin eine Tnazolverbmdung und ein weiteres Fungizid, beispielsweise Fenpropimorph, enthalt.DE-A 43 40 853 teaches a synergistic mixture for use in wood protection which, in addition to a copper compound and an alkanolamine, contains a tazole compound and a further fungicide, for example fenpropimorph.
Weiterhin ist aus der EP-A 425 857 die synergistische Wirkung ei¬ ner Mischung aus Fenpropimorph und Epoxiconazol gegen Schadpilze 35 an Materialien bekannt.Furthermore, the synergistic effect of a mixture of fenpropimorph and epoxiconazole against harmful fungi 35 on materials is known from EP-A 425 857.
Fenpropimorph, die Tnazolverbindungen und die bekannten synergi¬ stischen Mischungen, welche diese Wirkstoffe enthalten, haben je¬ doch keine zufriedenstellende Wirkung gegen holzschadigende, ms- 40 besondere holzverfarbende Pilze.Fenpropimorph, the tnazole compounds and the known synergistic mixtures which contain these active ingredients, however, do not have a satisfactory effect against wood-damaging, wood-fungal fungi.
Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, diesem Mangel abzuhelfen.The object of the present invention was therefore to remedy this deficiency.
55
BESTATIGUNGSKOPIE Demgemäß wurde ein Verfahren zur Behandlung von Holz gegen den Befall durch holzschädigende Pilze gefunden, wobei man das Holz mit einer Mischung, welcheCONFIRMATION COPY Accordingly, a method for treating wood against infestation by wood-damaging fungi has been found, wherein the wood is mixed with a mixture which
a) Fenpropimorph unda) fenpropimorph and
b) eine Triazolverbindung mit Ausnahme von Epoxiconazolb) a triazole compound with the exception of epoxiconazole
in einer gegen diese Pilze Synergistisch wirksamen Menge enthält, behandelt.contains in an amount synergistically effective against these fungi.
Von dem Begriff "Holz" sollen hier auch Holzfolgeprodukte wie Holzschnitte, Zellstoffe sowie weitere technische Produkte oder auch Cellulose enthaltende Materialien, die einem Pilzbefall zugänglich sind, z.B. Zwischenprodukte bei der Papierherstellung sowie verholzte Einjahrespflanzen (Bargasse, Raps) , umfaßt wer¬ den.The term "wood" is also intended to include wood secondary products such as woodcuts, cellulose and other technical products or materials containing cellulose that are susceptible to fungal attack, e.g. Intermediates in papermaking and woody annual plants (bar alley, rapeseed) are included.
Die hierin genannten Wirkstoffe, insbesondere Fenpropimorph und die Triazolverbindungen, sind dem Fachmann bekannt (vgl. z.B.The active substances mentioned here, in particular fenpropimorph and the triazole compounds, are known to the person skilled in the art (cf. e.g.
"The Pesticide Manual", lOth Edition, The British Crop Protection Council, Farnham, Großbritannien)."The Pesticide Manual", 10th Edition, The British Crop Protection Council, Farnham, UK).
Als Triazolverbindungen kommen beispielsweise in Betracht: 2- (1-Chlorcyclopropyl-l- (2-chlorphenyl)-3- (1,2 ,4-tria- zol-l-yl)propan-2-ol, 1-Butyl-l- (2, 4-dichlorphe- nyl)-2- (1,2, 4-triazol-l-yl)ethanol (Hexaconazol) , 1- (2-Chlorphe- nyl)methyl)-l- (1, 1-dimethyl) -2-(1,2, 4-triazol-l-ylethanol, 1- (4-Fluorphenyl)-1- (2-fluorphenyl)-2- (1,2,4-triazol-l-yl)ethanol (Flutriafol) , (RS) -4- (4-Chlorphenyl) -2-phenyl-2-(1H-1, 2, 4-tria- zol-l-yl-methyl)butyronitril, l-(2 RS,4 RS; 2 RS,4 SR)-4-Brom-2- (2,4-dichlorphenyl)-tetrahydrofurfu- ryl) -1H-1,2, 4-triazol, 3- (2, 4-Dichlorphenyl)-2-(1H-1,2,4-tria- zol-l-yl)quinazolin-4 (3H)-on, (RS) -2,2-Dimethyl-3- (2-chlorben- zyl) -4-(1H-1,2,4-triazol-l-yl)butan-3-ol, Bitertanol, Triadime¬ fon, Triadimenol, Cyproconazol, Dichlobutrazol, Difenoconazol, Diniconazol, Etaconazol, Flusilazol, Penconazol, Tetraconazol, Bromoconazol, Metconazol, Fenbendazol, Fensilazol, 1- (2- (2, 4, -Dichlorphenyl)-1, 3-dioxolan-2-yl-me- thyl)-lH-l,2,4-tπazol (Azaconazol) , 1- (2- (2, 4-Dichlorphe- nyl) -4-propyl-l, 3-dioxolan-2-yl-methyl)-1H-1,2, 4-triazol (Propi¬ conazol) , (RS)-l-p-Chlorphenyl-4,4-dimethyl-3- (1H-1, 2 , 4-tria- zol-1-ylmethyl)-pentan-3-ol (Tebuconazol) sowie deren Gemische.Examples of suitable triazole compounds are: 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-l-yl) ethanol (hexaconazole), 1- (2-chlorophenyl) methyl) -l- (1, 1- dimethyl) -2- (1,2, 4-triazol-l-ylethanol, 1- (4-fluorophenyl) -1- (2-fluorophenyl) -2- (1,2,4-triazol-l-yl) ethanol (Flutriafol), (RS) -4- (4-chlorophenyl) -2-phenyl-2- (1H-1,2,4-triazol-l-yl-methyl) butyronitrile, 1- (2 RS, 4 RS; 2 RS, 4 SR) -4-bromo-2- (2,4-dichlorophenyl) tetrahydrofurfuryl) -1H-1,2,4-triazole, 3- (2,4-dichlorophenyl) -2- (1H-1,2,4-triazol-l-yl) quinazolin-4 (3H) -one, (RS) -2,2-dimethyl-3- (2-chlorobenzyl) -4- (1H -1,2,4-triazol-l-yl) butan-3-ol, bitertanol, Triadime¬ fon, triadimenol, cyproconazole, dichlobutrazole, difenoconazole, diniconazole, etaconazole, flusilazole, penconazole, tetraconazole, bromoconazole, metconazole, fenconazole, fen , 1- (2- (2, 4, -Dichlorophenyl) -1, 3-dioxolan-2-yl-methyl) -lH-l, 2,4-tπazole (Azaco nazole), 1- (2- (2,4-dichlorophenyl) -4-propyl-l, 3-dioxolan-2-yl-methyl) -1H-1,2,4-triazole (propi-conazole), (RS) -lp-chlorophenyl-4,4-dimethyl-3- (1H-1,2,4-triazol-1-ylmethyl) pentan-3-ol (tebuconazole) and mixtures thereof.
Mit besonderem Vorteil werden als Triazolverbindung Propiconazol, Penconazol, Cyproconazol, Hexaconazol, Tebuconazol sowie deren Gemische verwendet. Fenpropimorph und die Triazolverbindungen können jeweils in Form der freien Base oder in Form eines Metallsalz-Komplexes oder als Säureadditionssalz vorliegen.Propiconazole, penconazole, cyproconazole, hexaconazole, tebuconazole and mixtures thereof are used with particular advantage as the triazole compound. Fenpropimorph and the triazole compounds can each be in the form of the free base or in the form of a metal salt complex or as an acid addition salt.
Die Salze werden hergestellt durch Umsetzung des jeweiligen Wirk¬ stoffs mit den entsprechenden Säuren, z.B. Halogenwasserstoffsäu¬ ren wie Fluorwasserstoffsaure, Chlorwasserstoffsaure, Bromwasser- stoffsaure und Jodwasserstoffsäure oder Schwefelsaure, Phosphor¬ säure, phosphorige Saure, Salpetersäure oder organischen Sauren wie Essigsaure, Trifluoressigsäure, Trichloressigsaure, Propions¬ aure, Glycolsaure, Milchsaure, Bernsteinsaure, Zitronensäure, Äpfelsaure, Weinsäure, Benzoesäure, Zimtsäure, Oxalsäure, Amei¬ sensaure, Benzolsulfonsaure, p-Toluolsulfonsaure, Methansulfon¬ säure, Salicylsaure, p-Aminosalicylsaure und 1, 2-Naphthalin- disulfonsaure.The salts are produced by reacting the respective active ingredient with the corresponding acids, e.g. Halogenwasserstoffsäu¬ ren cloth acid 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, Propions¬ acid, glycolic acid, lactic acid, succinic acid, citric acid, malic acid, tartaric acid, Benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid and 1,2-naphthalene disulfonic acid.
Die Metallkomplexe werden hergestellt aus Fenpropimorph bzw. der zugrundeliegenden Triazolverbindung und einem anorganischen oder organischen Metallsalz, beispielsweise den Halogeniden, Nitraten, Sulfaten, Phosphaten, Acetaten, Trifluoracetaten, Trichloraceta- ten, Propionaten, Tartraten, Sulfonaten, Salicylaten und Benzoa- ten der Metalle der zweiten Hauptgruppe des Periodensystems wie Calcium und Magnesium und der dritten und vierten Hauptgruppe wie Aluminium, Zinn oder Blei sowie der ersten bis achten Nebengruppe wie Chrom, Mangan, Eisen, Kobalt, Nickel, Kupfer, Zink. Bevorzugt sind die Nebengruppen-Elemente der 4. Periode und insbesondere Kupfer. Die Metalle können dabei in den verschiedenen ihnen zu¬ kommenden Wertigkeiten vorliegen. Die Metallkomplexe können einen oder mehrere organische Molekύlanteile als Liganden enthalten.The metal complexes are produced from fenpropimorph or the underlying triazole compound and an inorganic or organic metal salt, for example the halides, nitrates, sulfates, phosphates, 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 group such as aluminum, tin or lead and the first to eighth subgroups such as chromium, manganese, iron, cobalt, nickel, copper, zinc. The sub-group elements of the 4th period and in particular copper are preferred. The metals can be present in the various valences which they can assume. The metal complexes can contain one or more organic molecular moieties as ligands.
Besonders bevorzugt im Sinne der vorliegenden Erfindung ist die Verwendung einer Mischung von Fenpropimorph und Propiconazol, und zwar jeweils in Form der freien Base.For the purposes of the present invention, particular preference is given to the use of a mixture of fenpropimorph and propiconazole, in each case in the form of the free base.
Das Mischungsverhältnis von Fenpropimorph und Triazolverbindung liegt in den erfindungsgemäß verwendeten Mischungen zwischen 0,25 : 1 bis 5 : 1, insbesondere bei 1 : 1 bis 4 : 1 Gewichtstei¬ len.The mixing ratio of fenpropimorph and triazole compound in the mixtures used according to the invention is between 0.25: 1 to 5: 1, in particular 1: 1 to 4: 1 parts by weight.
Die Mischungen aus Fenpropimorph und einer oder mehreren Triazol¬ verbindungen werden vor ihrer Anwendung in der Regel mit üblichen Formulierungshilfsmitteln zu Holzschutzmitteln formuliert. Vor¬ zugsweise stellt man wegen der besseren Handhabbarkeit flussige Holzschutzmittel her. Man wendet die Mischung so an, daß man das zu schutzende Holz mit Fenpropimorph und einer oder mehreren Triazolverbindungen gleichzeitig, und zwar gemeinsam oder getrennt, oder nacheinander behandelt.The mixtures of fenpropimorph and one or more triazole compounds are generally formulated with conventional formulation auxiliaries to form wood preservatives before they are used. Liquid wood preservatives are preferably produced because of the better handling. The mixture is used in such a way that the wood to be protected is treated with fenpropimorph and one or more triazole compounds simultaneously, together or separately, or in succession.
Vorzugsweise wendet man die Mischung aus Fenpropimorph und einer oder mehreren Triazolverbindungen in einer Menge von 0,05 bis 5 kg pro Kubikmeter Holz an.The mixture of fenpropimorph and one or more triazole compounds is preferably used in an amount of 0.05 to 5 kg per cubic meter of wood.
Die erfindungsgemäß verwendeten Mischungen sind teilweise flus¬ sig. Im Hinblick auf ihre Verwendung im Holzschutz werden sie un¬ abhängig davon vorzugsweise flussig formuliert, beispielsweiseThe mixtures used according to the invention are partly liquid. Regarding their use in wood protection, they are preferably formulated in liquid form, for example
a) als Losung in einem organischen Losungsmittel, und zwar ge- brauchsfertig oder als verdunnbares Vorkonzentrat,a) as a solution in an organic solvent, ready for use or as a dilutable preconcentrate,
b) als Zusatz zu Holzschutzmitteln, welche in organischen Lo¬ sungsmitteln formuliert sind und die als solche oder nach Zu¬ satz von weiterem organischen Losungmittel angewendet werden können oderb) as an additive to wood preservatives which are formulated in organic solvents and which can be used as such or after the addition of further organic solvents, or
c) in wasserverdunnbaren Holzschutzmitteln, welche organisches Losungsmittel und gegebenenfalls Wasser enthalten (Emulsions¬ konzentrate) .c) in water-thinnable wood preservatives which contain organic solvents and, if appropriate, water (emulsion concentrates).
Wasser und Losungsmittel dienen hierbei dazu, die Handhabung der Mischungen bzw. der Mittel zu verbessern, indem sie das Einstel¬ len der Viskosität erleichtern und/oder das Auflosen der Emul¬ sionskonzentrate in Wasser beschleunigen. Die organischen Lo- sungsmittel werden z.T. zugleich zum Losen der Triazolverbindun¬ gen benotigt. Die Emulsionskonzentrate können in flussiger homo¬ gener Form, als Paste aber auch in fester Form vorliegen.Water and solvents serve to improve the handling of the mixtures or the agents by facilitating the setting of the viscosity and / or accelerating the dissolution of the emulsion concentrates in water. The organic solvents are partly at the same time required to dissolve the triazole compounds. The emulsion concentrates can be in liquid, homogeneous form, but also in paste form in solid form.
Bevorzugte organische Losungsmittel für derartige Formulierungen 5 sind wasserlösliche bzw. wassermischbare polare Losungsmittel, z.B. Glykole (Ethylenglykol , Propylenglykol) , Glykolether (Ethy- lenglykolmonomethylether, Ethylenglykolmonoethylether, Phenylgly- kol), Glykoletheracetate (Butylglykolacetat) , Milchsaureester (Milchsaureethylester, Milchsaurepropylester) , N-Alkylpyrrolidone 0 (N-Methylpyrrolidon, N-Oktylpyrrolidon) , Alkohole, Diacetonalko- hol, Dimethylformamid, Diethylformamid, Dimethylsulfoxid, N,N'- Dimethylpropylenharnstoff sowie deren Gemische.Preferred organic solvents for such formulations 5 are water-soluble or water-miscible polar solvents, e.g. Glycols (ethylene glycol, propylene glycol), glycol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, phenylglycol), glycol ether acetates (butylglycol acetate), lactic acid esters (lactic acid ethyl ester, lactic acid propyl ester), N-alkylpyrrolidone-0-nolonol-n-acetone, methyl-n-acetone hol, dimethylformamide, diethylformamide, dimethyl sulfoxide, N, N'-dimethylpropyleneurea and mixtures thereof.
Geeignete, zumeist als solche anwendungsfertige losungsmittelhal- c tige Holzschutzmittel enthalten z.B. 0,1 - 5 Gew.-% der Mischung Fenpropimorph/Triazolver- bindung, und zwar vorzugsweise zu 0,25 - 2,5 und vor allem zu 0,5 - 2 Gew.-%,Suitable, mostly as such ready-losungsmittelhal- c term wood preservatives containing eg 0.1-5% by weight of the fenpropimorph / triazole compound mixture, preferably 0.25-2.5% by weight and especially 0.5-2% by weight,
0 - 10 Gew.-% organisches Lösungsmittel gegebenen- falls zum Auflösen der Triazolverbin¬ dung und/oder als Penetrationshilfsmit¬ tel, als Rest zu 100 Gew.-% aliphatische und/oder aromatische Koh¬ lenwasserstoffe.0-10% by weight of organic solvent, if appropriate for dissolving the triazole compound and / or as a penetration aid, the remainder being 100% by weight of aliphatic and / or aromatic hydrocarbons.
Geeignete wasserverdunnbare Holzschutzmittel (Emulsionskonzen¬ trate) bestehen z.B. ausSuitable water-thinnable wood preservatives (emulsion concentrates) exist e.g. out
1 - 90 Gew.-% eines Emulgators, 1 - 50 Gew.-% der Mischung Fenpropimorph/Triazolver- bindung, und zwar vorzugsweise zu 5 - 40 und vor allem zu 10 bis 35 Gew.-%, 0 - 60 Gew.-% eines organischen Losungsmittels und1 - 90% by weight of an emulsifier, 1 - 50% by weight of the fenpropimorph / triazole compound mixture, preferably 5 - 40 and especially 10 to 35% by weight, 0 - 60% by weight. % of an organic solvent and
0 - 60 Gew.-% Wasser,0 - 60% by weight water,
wobei sich die Anteile der Bestandteile dieser Mittel zu 100 Gew.-% erganzen sollen.the proportions of the components of these agents should add up to 100% by weight.
Als Emulgatoren können nicht-ionische, kationische und anionische Emulgatoren verwendet werden. Bevorzugt sind quartare Ammonium¬ verbindungen sowie alkoxylierte, insbesondere ethoxylierte: Fet¬ talkohole, Oxoalkohole und Ole (Ricinusöl, Fischol) .Non-ionic, cationic and anionic emulsifiers can be used as emulsifiers. Quaternary ammonium compounds and alkoxylated, especially ethoxylated: fatty alcohols, oxo alcohols and oils (castor oil, fish oil) are preferred.
Als ganz besonders vorteilhaft haben sich Fettamine als Emulgator erwiesen, welche mit 2 bis 25 Mol Ethylenoxid alkoxyliert sind, wie Ethomen® C 15, Ethomen® T23 oder Ethomen® S20 (Akzo Chemicals GmbH, 52355 Duren, Deutschland).Very particularly advantageous fatty amines have been found as an emulsifier, which are alkoxylated with from 2 to 25 moles of ethylene oxide, such as Ethomen ® C 15, Ethomen® T23 or S20 Ethomen® (Akzo Chemicals GmbH, Duren 52355, Germany).
Die wasserverdύnnbaren Emulsionskonzentrate bilden bei der Ver- dunnung in Wasser klare bis opake Emulsionen.The water-dilutable emulsion concentrates form clear to opaque emulsions when diluted in water.
Zur Verbesserung der fungiziden Wirkung kann es vorteilhaft sein, daß diese Holzschutzmittel noch Piperidinderivate und/oder wei¬ tere Morpholinderivate, vorzugsweise einen oder mehrere der fun¬ giziden Wirkstoffe aus der Gruppe Fenpropidin, (N- (3 (4-tert.-Bu- tylphenyl) -2-methylpropyl)piperidin, Tridemorph (N-Tride- cyl-2, 6-dimethylmorpholin) oder deren Salzen enthalten.To improve the fungicidal activity, it may be advantageous that these wood preservatives also contain piperidine derivatives and / or further morpholine derivatives, preferably one or more of the fungicidal active substances from the group fenpropidine, (N- (3 (4-tert.-Bu- tylphenyl) -2-methylpropyl) piperidine, tridemorph (N-tridecyl-2, 6-dimethylmorpholine) or their salts.
Zur Vergrößerung des Wirkungsspektrums oder zur Erzielung beson¬ derer Effekte, z.B. zusatzlicher Schutz gegen Insekten ein¬ schließlich Termiten, können die vorstehend genannten losungs- mittelhaltigen Formulierungen oder Emulsionskonzentrate mit wei- teren Wirkstoffen kombiniert werden, die im letzteren Fall mit geeigneten zusätzlichen Emulgatoren eingearbeitet werden.To increase the spectrum of activity or to achieve special effects, for example additional protection against insects, including termites, the above-mentioned solvent-containing formulations or emulsion concentrates can be used with teren active ingredients are combined, which in the latter case are incorporated with suitable additional emulsifiers.
Geeignete Mischungspartner sind z.B. die folgenden Verbindungen: Suitable mixture partners include the following compounds :
Ξulfenamide wie Dichlofluanid, Tolylfluanid, Folpet, Fluor- folpet;Fenulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet;
Benzimidazole wie Carbendazim, Benomyl, Fuberidazole, Thi- abendazole oder deren Salze;Benzimidazoles such as carbendazim, benomyl, fuberidazole, thiabendazole or their salts;
Thiocyanate wie Thiocyanatomethylthiobenzothiazol, Methylen- bisthiocyanatThiocyanates such as thiocyanatomethylthiobenzothiazol, methylene bisthiocyanate
- quartare Ammoniumverbindungen wie Benzyldimethyletradecylam- moniumchlorid, Benzyldimethyldodecylammoniumchlorid, Didecyl¬ dimethylammoniumchlorid;quaternary ammonium compounds such as benzyldimethyletradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethylammonium chloride;
quartare Phosphoniumverbindungen;quaternary phosphonium compounds;
Jodderivate wie Dijodmethyl-p-tolysulfon, 3-Jod-2-propinyl- alkohol, 4-Chlorphenyl-3-jodpropargylformal, 3-Brom-2 , 3-di- jod-2-propenylethylcarbonat, 2,3, 3-Trijodallylalkohol, 3-Brom-2 , 3-di-jod-2-propenylalkohol, 3-Jod-2-propinyl-n-bu- tylcarbamat, 3-Jod-2-propinyl-n-hexylcarbamat, 3-Jod-2-propi- nyl-cyclohexylcarbamat, 3-Jod-2-propinyl-phenylcarbamat, 0-1- (6-Jodo-3-oxo-hex-5-inyl)-butylcarbamat, 0-1- (6-Jodo-3-oxo-hex-5-inyl)phenylcarbamat, Napcocide;Iodine derivatives such as diiodomethyl p-tolysulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2, 3-di-iodo-2-propenylethyl carbonate, 2,3, 3-triiodallyl alcohol, 3-bromo-2, 3-di-iodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butyl carbamate, 3-iodo-2-propynyl-n-hexyl carbamate, 3-iodo-2-propi nyl-cyclohexyl carbamate, 3-iodo-2-propynylphenyl carbamate, 0-1- (6-iodo-3-oxo-hex-5-ynyl) butyl carbamate, 0-1- (6-iodo-3-oxo-hex -5-inyl) phenyl carbamate, napcocide;
- Phenolderivate wie Tribromphenol, Tetrachlorphenol, 3-Me- thyl-4-chlorphenol, Dichlorophen, o-Phenylphenol, m-Phenyl- phenol, p-Phenylphenol, 2-Benzyl-4-chlorphenol;- Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol;
Bromderivate wie 2-Brom-2-nitro-l,3-propandiol, 2-Brom-2-brommethyl-glutardinitril;Bromine derivatives such as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-2-bromomethyl-glutaronitrile;
Isothiazolinone wie N-Methylisothiazolin-3-on, 5-Chloro-N-me- thyl-isothiazolin-3-on, 4, 5-Dichloro-N-octylisothiazo- lin-3-on, N-Octyl-isothiazolin-3-on;Isothiazolinones such as N-methylisothiazolin-3-one, 5-chloro-N-methyl-isothiazolin-3-one, 4,5-dichloro-N-octylisothiazoline-3-one, N-octyl-isothiazolin-3- on;
Benzisothiazolinone wie 4, 5-Trimethylisothiazol-3-on;Benzisothiazolinones such as 4, 5-trimethylisothiazol-3-one;
Pyridine wie l-Hydroxy-2-pyridinthion (und ihre Na-, Fe-, Mn-, Zn-Salze) , Tetrachlor-4-methylsulfonylpyridin; Metallseifen wie Zinn-, Kupfer-, zinknaphthenat, -octat, -2-ethylhexanoat, -oleat, -phosphat, -benzoat .Pyridines such as l-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine; Metal soaps such as tin, copper, zinc naphthenate, octate, 2-ethylhexanoate, oleate, phosphate, benzoate.
OrganozinnVerbindungen z.B. Tributyl (TBT) zinnverbindungen, Dialkyldithiocarbamate wie Na- und Zn-Salze von Dialkyldi- thiocarbamaten, Tetramethylthiuramdisulfid;Organotin compounds e.g. Tributyl (TBT) tin compounds, dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethylthiuram disulfide;
Nitrile wie 2,4, 5, 6-Tetrachlorisophthalodinitril;Nitriles such as 2,4, 5, 6-tetrachloroisophthalonitrile;
- Benzthiazole wie 2-Mercaptobenzothiazol;- benzothiazoles such as 2-mercaptobenzothiazole;
Chinoline wie 8-Hydroxychinolin und deren Cu-Salze;Quinolines such as 8-hydroxyquinoline and their Cu salts;
Tris-N-(cyclohexyldiazeniumdioxy)aluminium, N-(Cyclohexyldia- zeniumdioxy)tributylzinn bzw. K-Salz, Bis-N- (cyclohexyldiaze¬ niumdioxy)-Kupfer;Tris-N- (cyclohexyldiazeniumdioxy) aluminum, N- (cyclohexyldiazeniumdioxy) tributyltin or K-salt, bis-N- (cyclohexyldiazenium dioxide) copper;
Morpholinderivate wie Aldemorph.Morpholine derivatives such as aldemorph.
Als Insektizide werden bevorzugt zugesetzt:The following are preferably added as insecticides:
Phosphorsäureester wie Azinphos-ethyl, Azinphos-methyl,Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl,
1- (4-Chlorphenyl)-4- (o-ethyl, S-propyl)phosphoryloxypyrazol,1- (4-chlorophenyl) -4- (o-ethyl, S-propyl) phosphoryloxypyrazole,
Chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, Diazinon, Dichlorvos, Dimethoate, Ethoprophos, Etrimfos, Fenitro¬ thion,Fenthion, Heptenophos, Parathion, Parathion-methyl, Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Pro- fenofos, Prothiofos, Sulfprofos, Triazophos und Trichloron; Carbamate wie Aldocarb, Bendiocarb, 2- (1-Methylpropyl)phenyl- methylcarbamat, Butocarboxim, Carbaryl, Carbofuran, Carbosul- fan, Cloethocarb, Isoprocarb, Methomyl, Oxamyl, Primicarb, Promecarb, Propoxur und Thiocarb;Chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, Diazinon, Dichlorvos, Dimethoate, Ethoprophos, Etrimfos, Fenitro¬ thion, Fenthion, Heptenophos, Parathion, Parathion-methyl, Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Pro fenofos, prothiofos, sulfprofos, triazophos and trichlorone; Carbamates such as aldocarb, bendiocarb, 2- (1-methylpropyl) phenylmethylcarbamate, butocarboxime, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, primicarb, promecarb, propoxur and thiocarb;
Organosilicumverbindungen, vorzugsweise Dimethyl (phenyl)si- lylmethyl-3-phenoxybenzylether wie Dimethyl(4-ethoxyphe- nyl) silylmethyl-3-phenoxybenzylether oder (Dimethylphenyl) si- lylmethyl-2-phenoxy-6-pyridylmethylether wie Dimethyl- (9-ethoxy-phenyl)silylmethyl-2-phenoxy-6-pyridylmethylether oder (Phenyl-3- (3-phenoxyphenyl(propyl)dimethylsilane wie z.B. (4-Ethoxyphenyl) -(3- (4-fluoro-3-phenoxyphenyl-propyl)di- methylsilan;Organosilicon compounds, preferably dimethyl (phenyl) silylmethyl-3-phenoxybenzyl ether such as dimethyl (4-ethoxyphenyl) silylmethyl-3-phenoxybenzyl ether or (dimethylphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as dimethyl ( 9-ethoxy -phenyl ) silylmethyl-2-phenoxy-6-pyridylmethyl ether or (phenyl-3- (3-phenoxyphenyl (propyl) dimethylsilane such as (4-ethoxyphenyl) - (3- (4-fluoro-3-phenoxyphenyl-propyl) di- methylsilane;
Pyrethroide wie Allethrin, Alphamethrin, Bioresmethrin, By- fenthrin, Cycloprothin, Cyfluthrin, Decamethrin, Cyhalothrin, Cypermethrin, Deltamethrin, a-Cyno-3-phenyl-2-methyl-ben- zyl-2,2-dimethyl-3- (2-chlor-2-trifluormethylvinyl)cyclopro- pancarboxylat, Fenpropathrin, Fenfluthrin, Fenvalerate, Flu- cythrinate, Flumethrin, Fluvalinate, Permethrin, Resemethrin und Tralomethrin;Pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin, cycloprothin, cyfluthrin, decamethrin, cyhalothrin, cypermethrin, deltamethrin, a-cyno-3-phenyl-2-methyl-ben-zyl-2,2-dimethyl-3- (2 -chlor-2-trifluoromethylvinyl) cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flu- cythrinate, flumethrin, fluvalinate, permethrin, resemethrin and tralomethrin;
Nitroimine und Nitromethylene wie 1- ( (6-Chlor-3-pyridi- nyl)methyl)-4, 5-dihydro-N-nitro-lH-imidazol-2-amin (midaclo- prid) , N- ( (6-Chlor-3-pyridyl)methyl)-N'-cyano-N'-methylacet- amid;Nitroimines and nitromethylenes such as 1- ((6-chloro-3-pyridinyl ) methyl) -4, 5-dihydro-N-nitro-lH-imidazol-2-amine (midacloprid ) , N- (( 6- Chloro-3-pyridyl ) methyl ) -N'-cyano-N'-methylacetamide;
Häutungshemmer wie Flurox und Farox.Slough inhibitors like Flurox and Farox.
Auch ein Zusatz von wasserunlöslichen Sauren zu den Mischungen oder Holzschutzmitteln kann die Wirksamkeit der Wirksubstanzen Fenpropimorph und Triazolverbindung verbessern. Geeignete wasse¬ runlösliche organische Sauren sind z.B. 8-Hydroxychinolin, oder eine aliphatische oder aromatische Mono- oder Polycarbonsaure, z.B. eine aliphatische unverzweigte Monocarbonsaure mit 5 bis 20 C-Atomen wie Hexansaure, Heptansaure, Octansaure, Nonansaure und Decansaure, oder eine aliphatische verzweigte Monocarbonsaure mit 5 bis 20 C-Atomen wie 2-Ethylpentansaure, 2-Ethylhexansaure, 2-Ethylheptansaure, Isooctansaure, Isononansäure und Versatic- saure, oder Neocarbonsaure (starker verzweigte Monocarbonsauren) , oder eine aliphatische Dicarbonsäure mit 5 bis 20 C-Atomen wie Sebacinsaure und Decandicarbonsaure, oder eine aromatische oder aromatisch/aliphatische Carbonsaure wie Naphthensäure und Benzoe- saure.Adding water-insoluble acids to the mixtures or wood preservatives can also improve the effectiveness of the active substances fenpropimorph and triazole compound. Suitable water-soluble organic acids are e.g. 8-hydroxyquinoline, or an aliphatic or aromatic mono- or polycarboxylic acid, e.g. an aliphatic unbranched monocarboxylic acid with 5 to 20 carbon atoms such as hexanoic acid, heptanoic acid, octane acid, nonanoic acid and decanoic acid, or an aliphatic branched monocarboxylic acid with 5 to 20 carbon atoms such as 2-ethylpentanoic acid, 2-ethylhexanoic acid, 2-ethylheptanoic acid, isooonanoic acid, isooonanoic acid and versatic acid, or neocarboxylic acid (more strongly branched monocarboxylic acids), or an aliphatic dicarboxylic acid with 5 to 20 carbon atoms such as sebacic acid and decanedicarboxylic acid, or an aromatic or aromatic / aliphatic carboxylic acid such as naphthenic acid and benzoic acid.
Den losungsmittelhaltigen Holzschutzmitteln oder wäßrigen Verdün¬ nungen der Emulsionskonzentrate können zusatzlich Bindemittel, z.B. ollosliche oder wasserverdunnbare Alkydharze, Acrylatdisper- sion, oder im Falle von Grundierungen, welche ca. 2 bis 10 Gew.-% Festharz enthalten oder Lasuren, welche ca. 10 bis 25% Festharz enthalten, auch anorganische oder organische PigmentZubereitun¬ gen, wasser- und ollosliche Farbstoffe, "waterrepellants" wie Me- tallstearate oder Wachse und/oder sonstige Hilfsmittel wie Trock¬ ner, Netzmittel und Penetrationshilfsmittel zugesetzt werden.The solvent-containing wood preservatives or aqueous dilutions of the emulsion concentrates can additionally contain binders, e.g. ollosable or water-thinnable alkyd resins, acrylate dispersion, or in the case of primers, which contain approx. 2 to 10% by weight of solid resin or glazes, which contain approx. 10 to 25% solid resin, also inorganic or organic pigment preparations, water-based and olless dyes, "water repellants" such as metal stearates or waxes and / or other auxiliaries such as dryers, wetting agents and penetration aids are added.
Die Anwendung zum Schutz des Holzes kann z.B. je nach Gefahrdung des Holzes erfolgen:The application for protecting the wood can e.g. depending on the risk to the wood:
a) durch Besprühen des Holzes mit der Impragnierlosung,a) by spraying the wood with the impregnation solution,
b) durch Tauchen des Holzes in die Impragnierlosung (Kurztauchen bis Trogtranken) ,b) by dipping the wood into the impregnation solution (short dives to trough tendrils),
c) durch Tränkung des Holzes mit Hilfe von Druckunterschieden, z.B. Kesseldruck- oder Doppelvakuumtrankung, d) durch Streichen des Holzes oder Fluten.c) by impregnating the wood with the aid of pressure differences, for example boiler pressure or double vacuum drinking, d) by painting the wood or flooding.
Die Konzentration der fungiziden Mischung im jeweiligen Holz¬ schutzmittel richtet sich meist nach dem Grad der Gefahrdung des zu behandelnden Holzes durch die Pilze und daneben nach dem ge¬ wählten Anwendeverfahren. Bei Holzfolgeprodukten und Cellulose werden beispielsweise zumeist unverdünnte Konzentrate eingesetzt (z.B. bei Sperrholz, Spanplatten, Bagasseplatten) .The concentration of the fungicidal mixture in the respective wood preservative mostly depends on the degree of danger to the wood to be treated by the fungi and, in addition, on the selected application method. For wood secondary products and cellulose, for example, mostly undiluted concentrates are used (e.g. plywood, chipboard, bagasse panels).
Auch der Erfolg der Behandlung mit den fungiziden Mischungen oder den gebrauchsfertigen Holzschutzmitteln, insbesondere mit den Emulsionskonzentrate, hangt in der Regel vom Anwendeverfahren ab.The success of the treatment with the fungicidal mixtures or the ready-to-use wood preservatives, especially with the emulsion concentrates, usually depends on the application procedure.
Die erfindungsgemaß verwendeten Mischungen und Holzschutzmittel schützen besonders wirksam gegen holzverfärbende Pilze, insbeson¬ dere Blauepilze und vor allem Aureobasidium pullulans und Sclero¬ phoma pityophila, welche zu den Ascomyceten gezahlt werden.The mixtures and wood preservatives used in accordance with the invention provide particularly effective protection against wood-discoloring fungi, in particular blue fungi and, in particular, Aureobasidium pullulans and Sclero phoma pityophila, which are included in the Ascomycetes.
Daneben wurde gefunden, daß die Mischungen und Holzschutzmittel Holz auch gut schützen gegenIt has also been found that the mixtures and wood preservatives also protect wood well
a) Basidiomyceten (z.B. Serpula lacrymans, Coniophora puteana) unda) Basidiomycetes (e.g. Serpula lacrymans, Coniophora puteana) and
b) weitere Ascomyceten wie Schimmelpilze (z.B. Aspergillus ni- ger) und Moderfaulepilze (z.B. Chaetomium globosum) .b) other ascomycetes such as mold (e.g. Aspergillus niger) and mold rot (e.g. Chaetomium globosum).
BeispieleExamples
Kiefernsplintholzklotzchen der Abmessung 40 x 15 x 4 mm3 wurden durch Vakuumimpragnierung mit Fungizidlosungen m einer Kon¬ zentrationsreihe imprägniert. Hierzu wurden die Prüfklotzchen 30 min. einem Vakuum von 30 mbar in einem Trankgefaß ausgesetzt. Dann wurde die Fungizidlosung mittels des Vakuums in den Trankbe¬ hälter gesaugt, und es wurden so die gegen Aufschwimmen gesicher¬ ten Prüfklotzchen geflutet. Nach Druckausgleich wurden die Pruf- klotzchen dann 1 h unter der Losung belassen.Pine sapwood blocks measuring 40 x 15 x 4 mm 3 were impregnated by vacuum impregnation with fungicide solutions in one concentration row. For this, the test blocks were 30 min. exposed to a vacuum of 30 mbar in a drinking vessel. The fungicide solution was then sucked into the drinking container by means of the vacuum, and the test blocks secured against floating were flooded in this way. After pressure equalization, the test blocks were then left under the solution for 1 h.
Die von den Prüfklötzchen aufgenommene Menge an Losung wurde durch Verwiegen der Klotzchen vor und nach der Trankung ermit¬ telt, und daraus wurde dann die Aufnahme an Wirkstoff bzw. Formu¬ lierung berechnet.The amount of solution taken up by the test blocks was determined by weighing the blocks before and after the drinking, and from this the uptake of active substance or formulation was then calculated.
Nach einer Abdunstungs- und Fixierzeit von 2 Wochen wurden die Prüfklotzchen mit Wasser durch Vakuum-Imprägnierung vollgetrankt und mit einem 5-fachen Volumen an Wasser 1 Woche ausgewaschen. Es wurde dabei pro Tag ein Wasserwechsel durchgeführt . Nach erneutem Abtrocknen und Sterilisieren wurden die Klotzchen dann in der Reinraumbank in Petrischalen auf Agarnährboden gelegt und mit ei¬ nem Sporengemisch der Bläuepilze Aureobasidium pullulans und Sclerophoma pityophila beimpft (Prüfpilze gemäß EN 152).After an evaporation and fixing time of 2 weeks, the test blocks were soaked with water by vacuum impregnation and washed out with a 5-fold volume of water for 1 week. One water change was carried out per day. After drying again and sterilizing the blocks were then in the Clean room bank placed in petri dishes on agar culture medium and inoculated with a spore mixture of the blue fungi Aureobasidium pullulans and Sclerophoma pityophila (test fungi according to EN 152).
5 Anschließend wurden die Petrischalen mit den Prüfklotzchen bei 20 °C und ca. 70% Luftfeuchte im Prüfraum über 6 Wochen eingebaut. Nach diesem Zeitraum wurde der Bewuchs auf der Oberflache des Klötzchens und nach Aufspalten des Klotzchens die Verfärbung (Verblauung) im Inneren des Klötzchens visuell bestimmt. 05 The Petri dishes with the test blocks were then installed in the test room at 20 ° C and approx. 70% humidity for 6 weeks. After this period, the growth on the surface of the block and after splitting the block, the discoloration (blueing) inside the block was determined visually. 0
Die Bewertung des Bewuchses (außen) durch den Pilz erfolgte nach folgender Skala:The evaluation of the growth (outside) by the fungus was based on the following scale:
Figure imgf000012_0001
0
Figure imgf000012_0001
0
Die Bewertung der Verblauung (innen) durch den Pilz erfolgte nach folgender Skala:The fogging was assessed on the inside using the following scale:
0
Figure imgf000012_0002
0
Figure imgf000012_0002
Jeder Versuch wurde dreimal ausgeführt und danach der Mittelwert für Bewuchs bzw. Verblauung in diesen drei Versuchen gebildet.Each test was carried out three times and then the mean for fouling or bluing in these three tests was formed.
5 Die Versuchsergebnisse sind in den beiden folgenden Tabellen A und B zusammengestellt. "Einbringmenge" bezeichnet die vom Holz aufgenommenen Menge der derart gekennzeichneten Lösungen bzw. Formulierungen (Einheit [kg/m']).5 The test results are summarized in the following two tables A and B. "Contribution amount" means the amount of the solutions or formulations (unit [kg / m ']) absorbed by the wood.
« Bei dem Emulgator Ethomen® C 15 handelt es sich um ein mit im Mittel 5 Mol Ethylenoxid alkoxyliertes Cocosfettamin der Firma Akzo Chemicals GmbH, 52355 Duren, Deutschland.«The emulsifier Ethomen ® C 15 is a coconut fatty amine alkoxylated with an average of 5 moles of ethylene oxide from Akzo Chemicals GmbH, 52355 Duren, Germany.
5 vo5 vo
Tabelle A: Beispiele 1 bis 12 (Vergleichsbeispiele ) vo oeTable A: Examples 1 to 12 (comparative examples) before
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Tabelle B: Beispiele 13 bis 44 (erfindungsgemäß) ui vo oe cnTable B: Examples 13 to 44 (according to the invention) ui vo oe cn
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Claims

Patentansprüche claims
1. Verfahren zur Behandlung von Holz gegen den Befall durch holzschädigende Pilze, dadurch gekennzeichnet, daß man das Holz mit einer Mischung, welche1. A method of treating wood against infestation by wood-damaging fungi, characterized in that the wood with a mixture which
a) Fenpropimorph unda) fenpropimorph and
b) eine Triazolverbindung mit Ausnahme von Epoxiconazolb) a triazole compound with the exception of epoxiconazole
in einer gegen diese Pilze synergistisch wirksamen Menge ent¬ halt, behandelt.contained in a synergistically effective amount against these fungi.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Triazolverbindung (b) Propiconazol einsetzt.2. The method according to claim 1, characterized in that propiconazole is used as the triazole compound (b).
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Gewichtsverhaltnis von Fenpropimorph (a) zu der Triazol- Verbindung (b) 1:1 bis 4:1 betragt.3. The method according to claim 1 or 2, characterized in that the weight ratio of fenpropimorph (a) to the triazole compound (b) is 1: 1 to 4: 1.
4. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekennzeich¬ net, daß man Fenpropimorph (a) und die Triazolverbindung (b) gleichzeitig, und zwar gemeinsam oder getrennt, oder nachein- ander anwendet.4. The method according to claims 1 to 3, characterized gekennzeich¬ net that fenpropimorph (a) and the triazole compound (b) at the same time, namely together or separately, or in succession.
5. Verfahren nach den Ansprüchen 1 bis 4, dadurch gekennzeich¬ net, daß man die Mischung gemäß Anspruch 1 in einer Menge von 0,05 bis 5 kg pro Kubikmeter Holz anwendet.5. The method according to claims 1 to 4, characterized gekennzeich¬ net that one uses the mixture according to claim 1 in an amount of 0.05 to 5 kg per cubic meter of wood.
6. Verwendung von Mischungen enthaltend Tnazole mit der Aus¬ nahme von Epoxiconazol und Fenpropimorph zur Behandlung von Holz gegen holzschadigende Pilze. 6. Use of mixtures containing Tnazole with the exception of epoxiconazole and fenpropimorph for the treatment of wood against wood-damaging fungi.
PCT/EP1997/001911 1996-04-19 1997-04-17 Process for treating wood against infection by moulds harmful to wood WO1997039865A1 (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998054969A1 (en) * 1997-06-04 1998-12-10 Basf Aktiengesellschaft Fungicidal mixture
WO1999044424A1 (en) * 1998-03-05 1999-09-10 Buckman Laboratories International, Inc. Microbicidal compositions and methods using synergistic combinations of propiconazole and 2-mercaptobenzothiazole
WO2000005955A1 (en) * 1998-07-28 2000-02-10 Dr. Wolman Gmbh Method for treating wood against the attack of harmful fungi
US6110950A (en) * 1998-03-05 2000-08-29 Buckman Laboratories International Inc. Microbicidal compositions and methods using synergistic combinations of propiconazole and 2-mercaptobenzothiazole
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
EP3639663A1 (en) 2018-10-18 2020-04-22 Technische Universität Dresden Composition and method for improving resistance to mildew and / or reducing water uptake and a material comprising said composition

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BRPI0409100B1 (en) 2003-04-09 2014-08-05 Osmose Inc Wood product, and method for conserving a wood product
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
JP4971790B2 (en) 2003-06-17 2012-07-11 オズモウズ，インコーポレーテッド Fine particle wood preservative and method for producing the same
US20050252408A1 (en) 2004-05-17 2005-11-17 Richardson H W Particulate wood preservative and method for producing same
EP1799776B1 (en) 2004-10-14 2013-01-02 Osmose, Inc. Micronized wood preservative formulations in organic carriers

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DE3736651A1 (en) * 1987-10-29 1989-05-11 Bayer Ag Fungicidal active substance combinations
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DE4441672A1 (en) * 1994-11-23 1996-05-30 Basf Ag Wood preservatives

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998054969A1 (en) * 1997-06-04 1998-12-10 Basf Aktiengesellschaft Fungicidal mixture
US6369090B1 (en) 1997-06-04 2002-04-09 Basf Aktiengesellschaft Fungicidal mixture
EA002383B1 (en) * 1997-06-04 2002-04-25 Басф Акциенгезельшафт Fungicidal mixture
WO1999044424A1 (en) * 1998-03-05 1999-09-10 Buckman Laboratories International, Inc. Microbicidal compositions and methods using synergistic combinations of propiconazole and 2-mercaptobenzothiazole
US6110950A (en) * 1998-03-05 2000-08-29 Buckman Laboratories International Inc. Microbicidal compositions and methods using synergistic combinations of propiconazole and 2-mercaptobenzothiazole
AU746012B2 (en) * 1998-03-05 2002-04-11 Buckman Laboratories International, Inc. Microbicidal compositions and methods using synergistic combinations of propiconazole and 2-mercaptobenzothiazole
WO2000005955A1 (en) * 1998-07-28 2000-02-10 Dr. Wolman Gmbh Method for treating wood against the attack of harmful fungi
US6558685B1 (en) 1998-07-28 2003-05-06 Dr. Wolman Gmbh Method for treating wood against the attack of harmful 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
EP3639663A1 (en) 2018-10-18 2020-04-22 Technische Universität Dresden Composition and method for improving resistance to mildew and / or reducing water uptake and a material comprising said composition

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