WO2007031198A1 - Use of triclosan for wood protection - Google Patents

Use of triclosan for wood protection Download PDF

Info

Publication number
WO2007031198A1
WO2007031198A1 PCT/EP2006/008510 EP2006008510W WO2007031198A1 WO 2007031198 A1 WO2007031198 A1 WO 2007031198A1 EP 2006008510 W EP2006008510 W EP 2006008510W WO 2007031198 A1 WO2007031198 A1 WO 2007031198A1
Authority
WO
WIPO (PCT)
Prior art keywords
wood
triclosan
optionally
mixture according
destruction
Prior art date
Application number
PCT/EP2006/008510
Other languages
German (de)
French (fr)
Inventor
Rainer Bruns
Martin Kugler
Thomas Jaetsch
Original Assignee
Lanxess Deutschland 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 Lanxess Deutschland Gmbh filed Critical Lanxess Deutschland Gmbh
Priority to EP06791752A priority Critical patent/EP1926368A1/en
Publication of WO2007031198A1 publication Critical patent/WO2007031198A1/en

Links

Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/16Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27KPROCESSES, 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
    • B27K3/00Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34Organic impregnating agents
    • B27K3/343Heterocyclic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27KPROCESSES, 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
    • B27K3/00Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34Organic impregnating agents
    • B27K3/38Aromatic compounds
    • B27K3/40Aromatic compounds halogenated
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27KPROCESSES, 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
    • B27K3/00Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34Organic impregnating agents
    • B27K3/50Mixtures of different organic impregnating agents

Definitions

  • the present invention relates to the use of triclosan for the protection of wood and wood-based materials against attack and / or destruction " by soft rot fungi, as well as new fungicidal " agents and new, synergistic mixtures based on the active ingredient triclosan, and their use for the protection of industrial materials from infestation , Damage and / or destruction by microorganisms.
  • the skilled person distinguishes between a structural destruction of the wood by Basidiomyceten and - if the wood is exposed to a high humidity or earth contact environment - by soft rot fungi, and a visual impairment of the wood by wood-discoloring fungi.
  • Tar oils Active ingredients for the protection of wood against the destruction by fungi have been known for a long time, for example, tar oils were used to protect the wood. Tar oils are characterized by good permeability and high leaching resistance, but have significant disadvantages due to their persistence, their odor and their toxicologically unfavorable properties, so that their use in wood preservation today is very limited.
  • active ingredients based on chromium, copper and arsenic salts have been used for permanent wood preservation, but these are subject to substitution pressure due to their toxicological and in particular ecotoxicological disadvantages.
  • triazole fungicides such as tebuconazole or propiconazole, may be mentioned by way of example.
  • wood preservatives for this hazard class still inorganic wood preservatives such as boron compounds, silicofluorides, chromium and fluorine-containing salts, chromium- and copper-containing salts with and without arsenic, chromium and copper-containing salts with and without boron compounds and betaine preparations based on polymeric betain in Combination with boron and copper salts, and highly water-soluble quaternary ammonium compounds used.
  • fungicides against Basidiomycete infestation today include triazole fungicides such as e.g. Tebuconazole, propiconazole or cyproconazole used. Furthermore, the fungicides IPBC, Cabendazim, Folpet as well as Dichlofluanid and Tolylfluanid are used for protection against wood-discolouring fungi. However, both the triazoles and the mentioned fungicides with activity against fungal trees in the test against soft rot fungi according to ENV 807 completely fail or have only an insufficient effect.
  • Triclosan belongs to the class of diphenyl ethers and is already used as a chemical disinfectant and preservative. Triclosan is used, among other things, as an additive in sports and functional textiles, shoes and carpets to prevent unpleasant odors. Further fields of application are the use of triclosan in toothpastes, cleaners, household sponges or plastic dishes as well as in cosmetics, shampoos, soaps, deodorants or lotions. In hospitals and medical practices, triclosan-containing solutions are used for disinfection.
  • Triclosan is characterized by a low acute toxicity, the LD50 value against rats (oral administration) is e.g. at 3700 - 4500 mg / kg. Triclosan is as a pure substance only moderately irritating, also there are no signs of sensitization or photosensitizing potential. Triclosan is an inhibitor of bacterial fatty acid biosynthesis. Triclosan is not used in wood preservation. This may be due to the fact that triclosan is degraded by wood-destroying basidiomycetes (see Hundt et al., Applied and Environmental Microbiology, September 2000, page 4157-4160, Vol. 66, No. 9).
  • triclosan has an excellent action against soft rot fungi.
  • the present invention thus relates to the use of triclosan (5-chloro-2- (2,4-dichlorophenoxy) phenol) for the protection of wood, wood-based materials and wood-plastic composites from infestation and / or destruction by soft rot fungi.
  • the use according to the invention substantially and decisively enriches the state of the art because ecotoxicologically hazardous heavy metal-containing wood preservatives protect wood with permanent soil contact or in environments with high humidity, i. For example, in hazard class 4, can be substituted. As a result, the environmental impact of heavy metals is significantly reduced.
  • Triclosan shows a broad activity against soft rot fungi such as. contrary to ENV 807 (Test method for the determination of the limit of activity against soft rot and others erdbe passende microorganisms, German version of 2001) described fungi such as Chaetomium globosum, Glenospora graphii, Humicola gisea, Petriella setifera, Trichurus spiralis and Lecythophora mutabilis and against Trichoderma viride, Stachybotrys cartarum, Chephaporium sp. and Acremonium sp ..
  • triclosan against soft rot can optionally be extended by adding at least one further microbicidal compound to increase the spectrum of action or to achieve special effects.
  • the activity spectrum can be supplemented by the addition of further fungicides and / or termiticides.
  • triazole fungicides examples include: azaconazoles, azocyclotin, bitertanol, bromuconazoles; Cyproconazole, diclobutrazole, difenoconazole, dinuconazole, epoxyconazole, etconazole, fenbuconazole, fenchlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol, furconazole, hexaconazole, imibenconazole, ipconazole, izofos, myclobutanil, metconazole, paclobutrazole, penconazole, propiconazole, (+ / -) - cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol, 2- (1-tert-butyl) -1 - (2- chloroph
  • triclosan in combination with one or more of the following fungicidal components is preferred: chlorothalonil, captan, dichlofluanid, tolylfluanid, carbenzimine, thiabendazole, fenpropimorph, bethoxazine, folpet, fluorolipet, thiocyanato-methylthiobenzothiazole, 3-iodo 2-propynyl-n-butylcarbamate, zinc pyrithione, copper pyrithione, dichloroctylisothiazolinone, n-octylsisothiazolinone, N- (3-aminopropyl) -N-dodecylpropane-1,3-diamine and also boric acid compounds such as boric acid, boric acid ester, borax.
  • boric acid compounds such as boric acid, boric acid ester, borax.
  • triclosan in combination with one or more of the following fungicidal components: clorthalonill, dichlofluanid, tolylfluanid, bethoxazine, 3-iodo-2-propynyl-butylcarbamate, dichloroctylisothiazolinone, n-octylsisothiazolinone, folpet, zinc and copper pyrithione ,
  • triclosan in a mixture with one or more of the following termiticidal components:
  • triclosan in combinations with one or more of the following termiticidal components:
  • triclosan in combinations with one or more of the following termiticides:
  • triclosan if appropriate in combination with one or more of the above-mentioned mixing partners, can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and very fine encapsulations in polymeric substances.
  • Another object of this invention are agents containing triclosan for the protection of wood and wood-based materials and wood plastic composites before infestation and or destruction by soft rot fungi.
  • compositions of the invention comprise triclosan and at least one diluent or solvent, optionally further auxiliaries and additives and optionally at least one further microbicidal component, preferably from the series of the above-mentioned fungicides and termiticides.
  • the formulations can be prepared in a known manner, for example by mixing the active substance triclosan and optionally further active compounds with extenders, ie liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active agents, ie emulsifiers and / or dispersants - greed and / or foaming agents.
  • extenders ie liquid solvents, liquefied gases under pressure and / or solid carriers
  • surface-active agents ie emulsifiers and / or dispersants - greed and / or foaming agents.
  • organic solvents can also be used as auxiliary solvents.
  • Suitable liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, aliphatic hydrocarbons such as cyclohexane or paraffins, eg petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or Cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • liquefied gaseous extenders or carriers are meant liquids which are at normal temperature and are under normal pressure gaseous, for example, aerosol propellants, such as halogenated hydrocarbons and
  • Suitable solid carriers are: e.g. ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates.
  • Suitable solid carriers for granules are: e.g. Cracked and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks.
  • Suitable emulsifiers and / or foam-formers are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylarylpolyglycolether, alkyl sulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates.
  • Suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex polymers may be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids.
  • Other additives may be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • inorganic pigments e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • compositions according to the invention generally contain between 0.005 and 95% by weight of triclosan, preferably between 0.1 and 50% by weight of triclosan, and optionally between 0.005 and 50% by weight of said microbicidal components, preferably between 0.1 and 30% by weight.
  • microbicidal agents or concentrates used to protect the technical materials contain the active ingredient triclosan or the combination of triclosan with another microbicidal active ingredient in a concentration of 0.005 and 95 wt .-%, in particular 0.1 to 50 weight percent.
  • the use concentrations of the active substance triclosan to be used according to the invention or the active substance combination of triclosan with at least one further microbicidal active ingredient depends on the nature and occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimum amount used can be determined by test series. In general, the use concentrations of triclosan or the combination of triclosan with at least one other microbicidal active ingredient in the Range of 0.001 to 5 weight percent, preferably from 0.01 to 1.5 weight percent, based on the material to be protected.
  • compositions according to the invention exhibit good stability and advantageously have a broad spectrum of activity.
  • triclosan has excellent activity against soft rot fungi, but is resistant to wood-destroying basidiomycetes, e.g. Gloeophyllum trabeum, Coniophora souna, Poria placenta, Lentinus tigrinus, Coriolus versicolor and Stereum sanguinolentum are insufficiently effective and can be degraded by them.
  • basidiomycetes e.g. Gloeophyllum trabeum, Coniophora souna, Poria placenta, Lentinus tigrinus, Coriolus versicolor and Stereum sanguinolentum are insufficiently effective and can be degraded by them.
  • compositions comprising a synergistically effective amount of triclosan and at least one triazole fungicide, fungicidal compositions based on these mixtures and the use of these mixtures and agents for the protection of industrial materials, in particular wood and wood-based materials, from infestation, damage and / or Destruction by microorganisms.
  • the triazole fungicides to be used according to the invention are preferably azaconazoles, azocyclotin, bitertanol, bromuconazoles; Cyproconazole, diclobutrazoles, difenoconazole, diniconazole, epoxyconazole, etconazole, fenbuconazole, fenchlorazole, fenethanil, fluquinocynazole, flusilazole, flutriafol, furconazole, hexaconazole, imibenconazole, ipconazole, izofos, myclobutanil, metconazole, paclobutrazole, penconazole, propiconazole, (+/- ) -cis-1- (4-chlorophenyl) -2- (1H-l, 2,4-triazol-1-yl) cycloheptanol, 2- (1-tert-butyl) -1- (2-chlor
  • mixtures of triclosan with at least one triazole fungicide from the series propiconazoles, tebuconazoles, cyproconazoles, hexaconazoles and triadimefon, which are distinguished by pronounced synergism against wood-destroying basidiomycetes.
  • the mixtures according to the invention generally contain triclosan and at least one triazole fungicide in a weight ratio of from 1:99 to 99: 1, preferably from 1:10 to 10: 1.
  • the mixtures according to the invention may contain further active ingredients from the series of fungicidal and / or termiticides for increasing the activity and / or achieving particular effects.
  • the mixtures according to the invention preferably contain one or more of the following fungicidal components: clorthalonil, carbendazim, thiabendazole, dichloroctylisothiazolinone, n-octylisothazolinone, folpet, dichlofluanid, tolylfluanid, bethoxazine, 3-iodo-2-propynyl-butylcarbamate, zinc or Copper pyrithione, bifenthrin, chlorfenapyr, clothianidin, cyfluthrin, cypermethrin, deltamethrin, etofenprox, imidacloprid, permethrin, thiacloprid, thiamethoxam.
  • Captan carbendazim, fenpropimorph, bethoxazine, fluoro-folpet, thiocyanato-methylthiobenzothiazole, dichloroctylisothiazolinone, n-octylsisothiazolinone, N- (3-aminopropyl) -N-dodecylpropane-l, 3-diamine and boric acid compounds such as boric acid, boric acid ester, borax.
  • boric acid compounds such as boric acid, boric acid ester, borax.
  • the mixtures according to the invention particularly preferably comprise one or more of the following fungicidal components: clorthalonill, dichlofluanid, tolylfluanid, bethoxazine, 3-iodo-2-propynyl-butylcarbamate, dichloroctylisothiazolinone, n-octylsisothiazolinone, folpet, zinc pyrithione and copper pyrithione.
  • fungicidal components clorthalonill, dichlofluanid, tolylfluanid, bethoxazine, 3-iodo-2-propynyl-butylcarbamate, dichloroctylisothiazolinone, n-octylsisothiazolinone, folpet, zinc pyrithione and copper pyrithione.
  • the mixtures according to the invention generally contain 0.01-85% by weight of triclosan, 0.01-85% by weight of one or more triazole fungicides, optionally 0.01-80% by weight of at least one further microbicidal active ingredient from the series of fungicides, insecticides and termiticides.
  • the mixtures according to the invention are outstandingly suitable for the protection of industrial materials, in particular wood and wood-based materials, against infestation, damage and or destruction by microorganisms.
  • the mixtures according to the invention can be prepared by a generally known process by mixing a synergistically effective amount of the active substances triclosan and one or more triazole fungicides and optionally further active compounds from the series of fungicides, insecticides and termiticides and optionally adjuvants and additives in a suitable apparatus, ground, granulated, emulsified or dispersed.
  • Another object of this invention are protected against attack and / or destruction by soft rot fungi wood and wood-based materials and wood-plastic composites containing triclosan or an agent based on triclosan.
  • Wood, wood-based materials and wood-plastic composites which can be protected by the active substance mixtures according to the invention or agents contained in them, are exemplary understand: timber, wooden beams, railway sleepers, bridge parts, boat bridges, wooden vehicles,
  • Crates pallets, containers, telephone poles, wood cladding, wooden windows and doors, plywood, medium density fibreboard (MDF), chipboard, Oriented Strand Board (OSB), waferboard, laminated veneer lumber (LVL) or wood products commonly used in house building or in the joinery and wood plastic composites.
  • MDF medium density fibreboard
  • OSB Oriented Strand Board
  • LTL laminated veneer lumber
  • Another object of the invention is a method for the protection of wood, wood-based materials and wood-plastic composites against the infestation by soft rot fungi.
  • the active ingredient triclosan can be used as such, in the form of formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, pastes, soluble powders.
  • the application is usually carried out by treating the wood, the wood-based material or the wood-plastic composite with the active substance triclosan, optionally in combination with one or more microbicidal agents, or with an agent prepared therefrom in the form of a formulation or form of application, e.g. by spray, brush, dip and large scale impregnation methods, e.g. Vacuum, double vacuum or pressure method as well as by addition to the glue or masterbatch as well as via the compounder or mixer.
  • spray, brush, dip and large scale impregnation methods e.g. Vacuum, double vacuum or pressure method as well as by addition to the glue or masterbatch as well as via the compounder or mixer.
  • Particularly effective wood protection is provided by large scale impregnation methods, e.g. Achieved vacuum, double vacuum or printing process.
  • a method for the protection of wood is particularly preferred wherein the wood with an effective amount of triclosan and at least one diluent or solvent, optionally further auxiliaries and additives and optionally one or more microbicidal agents, preferably from the series of termiticides and fungicides Vacuum, double vacuum, pressure or dipping method is impregnated.
  • agar prepared using malt extract was added with triclosan in concentrations of 1 mg / l to 500 mg / l. After solidification of the agar, contamination was carried out with pure cultures of the soft rot fungi listed in Table 1. After 2 weeks of incubation at 26 ° C, the MIC was determined. MIC is the lowest concentration of active substance in which no fouling by soft rot fungi occurs., It is given in Table 1.
  • triclosan (A), tebuconazole (B) and mixtures (AB) of the two active substances mentioned were tested against the wood destroying basidiomycete Lentinus tigrinus.
  • Mycelium pieces were punched out of a colony of the wood destructor and incubated on a malt extract-peptone containing nutrient agar at 26 ° C.
  • radial hyphae growth was compared with and without addition of active ingredient.
  • the minimum inhibitory concentration (MIC) was given as the lowest active ingredient concentration in succession, which completely suppresses radial growth.
  • Qa concentration of substance A, which represents the MIC
  • Qb concentration of substance B, which represents the MIC
  • QB concentration of substance B in the concentration of A / B that inhibits microbial growth
  • SI> 1 means antagonism
  • SI ⁇ 1 means synergism
  • Table 2 MIC values and synergistic index of triclosan and tebuconazole (test fungus Lentinus tigrinus)
  • Table 3 MIC values and synergistic index of triclosan and cyproconazole (test fungus Gloephyllum trabeum)
  • Example 2 As described in Example 1, various concentrations of triclosan (A), propiconazole (B) and mixtures (AB) of the two active substances mentioned were tested against the moder rot causative agent Trichurus spiralis. According to the KuIl et al. (FCKuli, PC Eismann, HDSylvestrowicz, RL Mayer, Applied Microbiology 9, 538-541, 1961), the synergism was determined analogously to Example 2.
  • Table 3 MIC values and synergistic index of triclosan and propiconazole (test fungus Trichurus spiralis9

Abstract

The invention relates to triclosan, in addition to novel fungicides and novel, synergistic mixtures based on the active substance triclosan which are particularly suitable for protecting technical materials against attacks, damage, and/or destruction by micro-organisms, in particular, for protecting wood and wood materials against attacks and/or destruction by lignivorous fungi.

Description

Verwendung von Triclosan für den HolzschutzUse of triclosan for wood preservation
Die vorliegende Erfindung betrifft die Verwendung von Triclosan zum Schutz von Holz und Holzwerkstoffen vor Befall und/oder Zerstörung" durch Moderfäulepilze, sowie neue fungizide" Mittel und neue, synergistische Mischungen auf Basis des Wirkstoffs Triclosan, sowie deren Verwendung zum Schutz von technischen Materialien vor Befall, Schädigung und /oder Zerstörung durch Mikroorganismen.The present invention relates to the use of triclosan for the protection of wood and wood-based materials against attack and / or destruction " by soft rot fungi, as well as new fungicidal " agents and new, synergistic mixtures based on the active ingredient triclosan, and their use for the protection of industrial materials from infestation , Damage and / or destruction by microorganisms.
Grundsätzlich unterscheidet der Fachmann zwischen einer strukturellen Zerstörung des Holzes durch Basidiomyceten und - sofern das Holz einer Umgebung mit hoher Feuchtigkeit oder Erdkontakt ausgesetzt ist - durch Moderfäulepilze, und einer optischen Beeinträchtigung des Holzes durch Holz verfärbende Pilze.Basically, the skilled person distinguishes between a structural destruction of the wood by Basidiomyceten and - if the wood is exposed to a high humidity or earth contact environment - by soft rot fungi, and a visual impairment of the wood by wood-discoloring fungi.
Wirkstoffe zum Schutz von Holz vor der Zerstörung durch Pilze sind seit langer Zeit bekannt, so wurden zum Beispiel Teeröle zum Schutz des Holzes verwendet. Teeröle zeichnen sich durch gute Permeabilität und hohe Leachingresistenz aus, haben jedoch aufgrund ihrer Persistenz, ihres Geruchs und ihrer toxikologisch ungünstigen Eigenschaften deutliche Nachteile, so dass ihre Verwen- düng im Holzschutz heute stark limitiert ist.Active ingredients for the protection of wood against the destruction by fungi have been known for a long time, for example, tar oils were used to protect the wood. Tar oils are characterized by good permeability and high leaching resistance, but have significant disadvantages due to their persistence, their odor and their toxicologically unfavorable properties, so that their use in wood preservation today is very limited.
Als Alternative wurden für den permanenten Holzschutz Wirkstoffe auf Basis von Chrom-, Kupfer- und Arsensalzen eingesetzt, die jedoch aufgrund ihrer toxikologischen und insbesondere ökotoxikologischen Nachteile unter Substitutionsdruck geraten sind.As an alternative, active ingredients based on chromium, copper and arsenic salts have been used for permanent wood preservation, but these are subject to substitution pressure due to their toxicological and in particular ecotoxicological disadvantages.
Vor diesem Hintergrund wurden moderne Holzschutzmittel auf Basis organischer Wirkstoffe ent- wickelt. Beispielhaft seien die Triazolfungizide wie Tebuconazol oder Propiconazol genannt.Against this background, modern wood preservatives based on organic substances were developed. The triazole fungicides, such as tebuconazole or propiconazole, may be mentioned by way of example.
Es zeigt sich jedoch in der Praxis, dass solche modernen organischen Wirkstoffe zum Schutz von Holz mit permanentem Bodenkontakt oder in Umgebungen mit hoher Feuchtigkeit, d.h. in der Gefährdungsklasse 4, nicht ausreichend wirksam sind und eine Wirkungslücke gegen Moderfäulepilze haben, so dass die eingangs beschriebenen Wirkstoffe wie Tebuconazol oder Propiconazol für diese Anwendung mit Metallen oder Metallsalzen, insbesondere Kupfersalzen, kombiniert werden müssen. Weiterhin werden in Holzschutzmitteln für diese Gefährdungsklasse immer noch anorganische Holzschutzmittel wie Bor-Verbindungen, Silicofluoride, chrom- und fluorhaltige Salze, chrom - und kupferhaltige Salze mit und ohne Arsen, chrom- und kupferhaltige Salze mit und ohne Borverbindungen sowie Betainpräparate auf Basis polymeren Betains in Kombination mit Bor- und Kupfersalzen, sowie stark wasserlösliche quaternäre Ammoniumverbindungen eingesetzt.However, it has been shown in practice that such modern organic actives protect wood with permanent soil contact or in high humidity environments, e.g. in hazard class 4, are not sufficiently effective and have an inefficiency against soft rot fungi, so that the agents described above such as tebuconazole or propiconazole for this application with metals or metal salts, especially copper salts, must be combined. In addition, wood preservatives for this hazard class still inorganic wood preservatives such as boron compounds, silicofluorides, chromium and fluorine-containing salts, chromium- and copper-containing salts with and without arsenic, chromium and copper-containing salts with and without boron compounds and betaine preparations based on polymeric betain in Combination with boron and copper salts, and highly water-soluble quaternary ammonium compounds used.
Die Verwendung von schwermetallhaltigen Holzschutzmitteln ist aber aus ökologischer Sicht als bedenklich zu beurteilen. Es bestand also weiterhin Bedarf an verbesserten Holzschutzmitteln, die auf Wirkstoffen beruhen, die ohne Zusatz von Schwermetallen ausreichenden Schutz von Holz gewährleisten.However, the use of wood preservatives containing heavy metals is environmentally questionable. There was therefore still a need for improved wood preservatives that based on active substances which ensure adequate protection of wood without the addition of heavy metals.
Im Holzschutz werden heute als Fungizide gegen Befall durch Basidiomyceten Triazolfungizide wie z.B. Tebuconazole, Propiconazole oder Cyproconazole eingesetzt. Weiterhin werden die Fun- gizide IPBC, Cabendazim, Folpet sowie Dichlofluanid und Tolylfluanid zum Schutz vor holzverfärbende Pilze verwendet. Jedoch versagen sowohl die Triazole als auch die erwähnten Fungizide mit Wirkung gegen verbläuende Pilze in der Prüfung gegen Moderfäulepilze nach ENV 807 völlig oder habe eine nur unzureichende Wirkung.In wood preservation, fungicides against Basidiomycete infestation today include triazole fungicides such as e.g. Tebuconazole, propiconazole or cyproconazole used. Furthermore, the fungicides IPBC, Cabendazim, Folpet as well as Dichlofluanid and Tolylfluanid are used for protection against wood-discolouring fungi. However, both the triazoles and the mentioned fungicides with activity against fungal trees in the test against soft rot fungi according to ENV 807 completely fail or have only an insufficient effect.
Triclosan gehört zur Klasse der Diphenylether und findet bereits als chemisches Desinfektions- und Konservierungsmittel Verwendung. Triclosan wird unter anderem als Additiv in Sport- und Funktionstextilien, Schuhen und Teppichen eingesetzt, um unangenehme Gerüche zu unterbinden. Weitere Anwendungsgebiete sind der Einsatz von Triclosan in Zahncremes, Reinigern , Haushalts- schwämmen oder Plastikgeschirr sowie in Kosmetika, Shampoos, Seifen, Deodorants oder Lotionen. In Krankenhäusern und Arztpraxen werden Triclosan-haltige Lösungen zur Desinfektion verwendet.Triclosan belongs to the class of diphenyl ethers and is already used as a chemical disinfectant and preservative. Triclosan is used, among other things, as an additive in sports and functional textiles, shoes and carpets to prevent unpleasant odors. Further fields of application are the use of triclosan in toothpastes, cleaners, household sponges or plastic dishes as well as in cosmetics, shampoos, soaps, deodorants or lotions. In hospitals and medical practices, triclosan-containing solutions are used for disinfection.
Triclosan zeichnet durch eine geringe akute Toxizität aus, der LD50-Wert gegen Ratten (orale Applikation) liegt z.B. bei 3700 - 4500 mg/kg. Triclosan ist als reiner Stoff nur mäßig irritierend, zudem liegen keine Hinweise auf Sensibilisierungs- oder Photosensibilisierungspotenz vor. Triclosan ist ein Inhibitor der bakteriellen Fettsäurebiosynthese. Triclosan findet im Holzschutz keine Verwendung. Gründe hierfür dürften in der Tatsache liegen, daß Triclosan durch holzzerstörende Basidiomyceten abgebaut wird (vgl. Hundt et al., Applied and Environmental Microbiology, September 2000, Seite 4157 -4160, Vol. 66, No. 9)Triclosan is characterized by a low acute toxicity, the LD50 value against rats (oral administration) is e.g. at 3700 - 4500 mg / kg. Triclosan is as a pure substance only moderately irritating, also there are no signs of sensitization or photosensitizing potential. Triclosan is an inhibitor of bacterial fatty acid biosynthesis. Triclosan is not used in wood preservation. This may be due to the fact that triclosan is degraded by wood-destroying basidiomycetes (see Hundt et al., Applied and Environmental Microbiology, September 2000, page 4157-4160, Vol. 66, No. 9).
Überraschenderweise wurde nun gefunden, dass Triclosan eine hervorragende Wirkung gegen Moderfäulepilze hat. Gegenstand der vorliegenden Erfindung ist somit die Verwendung von Triclosan (5-Chloro-2-(2,4-dichlorophenoxy)phenol) zum Schutz von Holz, Holzwerkstoffen und Holz-Plastik-Verbundstoffen vor dem Befall und oder der Zerstörung durch Moderfäulepilze.Surprisingly, it has now been found that triclosan has an excellent action against soft rot fungi. The present invention thus relates to the use of triclosan (5-chloro-2- (2,4-dichlorophenoxy) phenol) for the protection of wood, wood-based materials and wood-plastic composites from infestation and / or destruction by soft rot fungi.
Durch die erfindungsgemäße Verwendung wird der Stand der Technik wesentlich und entscheidend bereichert, weil ökotoxikologisch bedenkliche schwermetallhaltige Holzschutzmittel zum Schutz von Holz mit permanenten Bodenkontakt oder in Umgebungen mit hoher Feuchtigkeit, d.h. zum Beispiel in der Gefährdungsklasse 4, substituiert werden können. Hierdurch wird die Umweltbelastung durch Schwermetalle erheblich reduziert.The use according to the invention substantially and decisively enriches the state of the art because ecotoxicologically hazardous heavy metal-containing wood preservatives protect wood with permanent soil contact or in environments with high humidity, i. For example, in hazard class 4, can be substituted. As a result, the environmental impact of heavy metals is significantly reduced.
Triclosan zeigt eine breite Wirksamkeit gegen Moderfäulepilze wie z..B. gegen die in ENV 807(Prüfverfahren für die Bestimmung der Grenze der Wirksamkeit gegen Moderfäule und andere erdbewohnende Mikroorganismen, deutsche Fassung von 2001) beschriebenen Pilze wie Chaetomium globosum, Glenospora graphii, Humicola gisea, Petriella setifera, Trichurus spiralis und Lecythophora mutabilis sowie gegen Trichoderma viride, Stachybotrys cartarum, Chepha- losporium sp. und Acremonium sp..Triclosan shows a broad activity against soft rot fungi such as. contrary to ENV 807 (Test method for the determination of the limit of activity against soft rot and others erdbewohnende microorganisms, German version of 2001) described fungi such as Chaetomium globosum, Glenospora graphii, Humicola gisea, Petriella setifera, Trichurus spiralis and Lecythophora mutabilis and against Trichoderma viride, Stachybotrys cartarum, Chephaporium sp. and Acremonium sp ..
Die erfindungsgemäße Verwendung von Triclosan gegen Moderfäule kann gegebenenfalls durch Zusatz mindestens einer weiteren mikrobiziden Verbindung zur Vergrößerung des Wirkungsspektrums oder Erzielung besonderer Effekte erweitert werden. Insbesondere kann das Wirkspektrum durch Zusatz von weiteren Fungiziden und/oder Termitiziden ergänzt werden.The use according to the invention of triclosan against soft rot can optionally be extended by adding at least one further microbicidal compound to increase the spectrum of action or to achieve special effects. In particular, the activity spectrum can be supplemented by the addition of further fungicides and / or termiticides.
Bevorzugt ist die Verwendung von Triclosan in Kombination mit mindestens einem Triazolfungi- zid.Preference is given to the use of triclosan in combination with at least one triazole fungicide.
Als Beispiele für erfindungsgemäß einzusetzende Triazolfungizide seien genannt: Azaconazole, Azocyclotin, Bitertanol, Bromuconazole; Cyproconazole, Diclobutrazole, Difenoconazole, Dinico- nazole, Epoxyconazole, Etconazole, Fenbuconazole, Fenchlorazole, Fenethanil, Fluquinconazole, Flusilazole, Flutriafol, Furconazole, Hexaconazole, Imibenconazole, Ipconazole, Izofos, Myclobu- tanil, Metconazole, Paclobutrazol, Penconazole, Propiconazole, (+/-)-cis-l-(4-chlorphenyl)-2-(lH- 1 ,2,4-triazol- 1 -yl)cycloheptanol, 2-( 1 -tert.-B utyl)- 1 -(2-chlorphenyl)3-( 1 ,2,4-triazol- 1 -yl)-propan-2- ol, Simeconazole, Tebuconazole, Tetraconazole, Triadimefon, Triadimenol, Triapenthenol, Triflumizole, Triticonazole; Uniconazole sowie deren Metallsalze und Säureaddukte.Examples of triazole fungicides to be used according to the invention include: azaconazoles, azocyclotin, bitertanol, bromuconazoles; Cyproconazole, diclobutrazole, difenoconazole, dinuconazole, epoxyconazole, etconazole, fenbuconazole, fenchlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol, furconazole, hexaconazole, imibenconazole, ipconazole, izofos, myclobutanil, metconazole, paclobutrazole, penconazole, propiconazole, (+ / -) - cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol, 2- (1-tert-butyl) -1 - (2- chlorophenyl) 3- (1, 2,4-triazol-1-yl) -propan-2-ol, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimol, tri-pentanol, triflumizole, triticonazole; Uniconazole and its metal salts and acid adducts.
Weiterhin bevorzugt ist die Verwendung von Triclosan in Kombination mit einer oder mehrerer der folgenden fungiziden Komponenten: Chlorthalonil, Captan, Dichlofluanid, Tolylfluanid, Car- bendazim, Thiabendazol, Fenpropimorph, Bethoxazin, Folpet, Fluorfolpet, Thiocyanato-methyl- thiobenzothiazol, 3-Iod-2-propinyl-n-butylcarbamat, Zink-Pyrithion, Kupfer-Pyrithion, Dichloroctylisothiazolinon, n-Octylsisothiazolinon, N-(3-aminopropyl)-N-dodecylpropan- 1 ,3-dia- min sowie Borsäurverbindungen wie Borsäure, Borsäurester, Borax.Furthermore, the use of triclosan in combination with one or more of the following fungicidal components is preferred: chlorothalonil, captan, dichlofluanid, tolylfluanid, carbenzimine, thiabendazole, fenpropimorph, bethoxazine, folpet, fluorolipet, thiocyanato-methylthiobenzothiazole, 3-iodo 2-propynyl-n-butylcarbamate, zinc pyrithione, copper pyrithione, dichloroctylisothiazolinone, n-octylsisothiazolinone, N- (3-aminopropyl) -N-dodecylpropane-1,3-diamine and also boric acid compounds such as boric acid, boric acid ester, borax.
Insbesondere bevorzugt ist die Verwendung von Triclosan in Kombination mit einer oder mehrerer der folgenden fungiziden Komponenten: Clorthalonill, Dichlofluanid, Tolylfluanid, Bethoxazin, 3-Iod-2-propinyl-butylcarbamat, Dichloroctylisothiazolinon, n-Octylsisothiazolinon, Folpet, Zink- und Kupfer-Pyrithion.Especially preferred is the use of triclosan in combination with one or more of the following fungicidal components: clorthalonill, dichlofluanid, tolylfluanid, bethoxazine, 3-iodo-2-propynyl-butylcarbamate, dichloroctylisothiazolinone, n-octylsisothiazolinone, folpet, zinc and copper pyrithione ,
Bevorzugt ist die Verwendung von Triclosan in einer Mischungen mit einer oder mehrerer der folgenden termitiziden Komponenten:Preferred is the use of triclosan in a mixture with one or more of the following termiticidal components:
Acetamiprid, Allethrin, Alpha-cypermethrin, Beta-cyfluthrin, Bifenthrin, Bioallethrin, 4-Chlor-2- (2-chlor-2-methylpropyl)-5-[(6-iod-3-pyridinyl)methoxy]-3(2H)- pyridazinone (CAS-RN: 120955- 77-3), Chlorfenapyr, Chlorpyrifos, Clothianidin, Cyfluthrin, Cyhalothrin, Cypermethrin, Delta- methrin, Etofenprox, Fenoxycarb, Fipronil, Flufenoxuron, Hexaflumuron, Imidacloprid, Nitenpyram, Permethrin, Pyriproxifen, Silafluofen, Tebufenozide, Thiacloprid, Thiamethoxam, Tralomethrin, Triflumuron.Acetamiprid, allethrin, alpha-cypermethrin, beta-cyfluthrin, bifenthrin, bioallethrin, 4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H ) - pyridazinone (CAS-RN: 120955-77-3), chlorfenapyr, chlorpyrifos, clothianidin, cyfluthrin, cyhalothrin, cypermethrin, deltamethrin, etofenprox, fenoxycarb, fipronil, flufenoxuron, hexaflumuron, imidacloprid, Nitenpyram, permethrin, pyriproxifen, silafluofen, tebufenozide, thiacloprid, thiamethoxam, tralomethrin, triflumuron.
Besonders bevorzugt ist die Verwendung -von Triclosan in Kombinationen mit einem oder mehreren der folgenden termitiziden Komponenten:Particularly preferred is the use of triclosan in combinations with one or more of the following termiticidal components:
Bifenthrin, Chlorfenapyr, Clothianidin, Cyfluthrin, Cypermethrin, Deltamethrin, Etofenprox, Imidacloprid, Permethrin, Thiacloprid, Thiamethoxam.Bifenthrin, Chlorfenapyr, Clothianidin, Cyfluthrin, Cypermethrin, Deltamethrin, Etofenprox, Imidacloprid, Permethrin, Thiacloprid, Thiamethoxam.
Insbesondere bevorzugt ist die Verwendung von Triclosan in Kombinationen mit einem oder mehreren der folgenden Termitizide:Especially preferred is the use of triclosan in combinations with one or more of the following termiticides:
Bifenthrin, Clothianidin, Imidacloprid, Permethrin, Thiacloprid. Für die erfindungsgemäße Verwendung kann Triclosan, gegebenenfalls in Kombination mit einem oder mehreren der oben genannten Mischungspartner, in die üblichen Formulierungen überführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Schäume, Pasten, Granulate, Aerosole und Feinstverkapselungen in polymeren Stoffen.Bifenthrin, clothianidin, imidacloprid, permethrin, thiacloprid. For the use according to the invention, triclosan, if appropriate in combination with one or more of the above-mentioned mixing partners, can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and very fine encapsulations in polymeric substances.
Ein weiterer Gegenstand dieser Erfindung sind Mittel enthaltend Triclosan zum Schutz von Holz und Holzwerkstoffen sowie Holzplastikverbundstoffen vor dem Befall und oder der Zerstörung durch Moderfäulepilze.Another object of this invention are agents containing triclosan for the protection of wood and wood-based materials and wood plastic composites before infestation and or destruction by soft rot fungi.
Die erfindungsgemäßen Mittel enthalten Triclosan sowie mindestens ein Verdünnungs- oder Lösungsmittel, gegebenenfalls weitere Hilfs- und Zusatzstoffe sowie gegebenenfalls mindestens eine weitere mikrobizide Komponente, vorzugsweise aus der Reihe der oben genannten Fungizide und Termitizide.The compositions of the invention comprise triclosan and at least one diluent or solvent, optionally further auxiliaries and additives and optionally at least one further microbicidal component, preferably from the series of the above-mentioned fungicides and termiticides.
Die Formulierungen können in bekannter Weise hergestellt werden, z.B. durch Vermischen des Wirkstoffs Triclosan und gegebenenfalls weiterer Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln, unter Druck stehenden verflüssigten Gasen und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Disper- giermitteln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol oder Alkylnaphthaline, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, Alkohole, wie Butanol oder Glycol sowie deren Ether und Ester, Ketone, wie Aceton, Methylethylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Di- methylformamid und Dimethylsulfoxid, sowie Wasser. Mit verflüssigten gasförmigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und unter Normaldruck gasförmig sind, z.B. Aerosol-Treibgase, wie Halogenkohlenwasserstoffe sowieThe formulations can be prepared in a known manner, for example by mixing the active substance triclosan and optionally further active compounds with extenders, ie liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active agents, ie emulsifiers and / or dispersants - greed and / or foaming agents. In the case of using water as extender, for example, organic solvents can also be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, aliphatic hydrocarbons such as cyclohexane or paraffins, eg petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or Cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water. By liquefied gaseous extenders or carriers are meant liquids which are at normal temperature and are under normal pressure gaseous, for example, aerosol propellants, such as halogenated hydrocarbons and
Butan, Propan, Stickstoff und Kohlendioxid. Als feste Trägerstoffe kommen in Frage: z.B. natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminium- oxid und Silikate. Als feste Trägerstoffe für Granulate kommen in Frage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnußschalen, Maiskolben und Tabakstengel. Als Emulgier und/oder schaumerzeugende Mittel kommen in Frage: z.B. nichtionogene und anionische Emulgatoren, wie PoIy- oxyethylen-Fettsäureester, Polyoxyethylen-Fettalkoholether, z.B. Alkylarylpolyglycolether, Alkyl- sulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate. Als Dispergiermittel kommen in Frage: z.B. Lignin-Sulfitablaugen und Methylcellulose.Butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: e.g. ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates. Suitable solid carriers for granules are: e.g. Cracked and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. Suitable emulsifiers and / or foam-formers are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylarylpolyglycolether, alkyl sulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates. Suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose.
Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulverige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholipide, wie Kephaline und Lecithine, und synthetische Phospholipide. Weitere Additive können mineralische und vegetabile Öle sein.Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex polymers may be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids. Other additives may be mineral and vegetable oils.
Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalocyaninfarbstoffe und Spurennährstoffe, wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Die erfindungsgemäßen Mittel enthalten im allgemeinen zwischen 0,005 und 95 Gew.-% Triclosan, vorzugsweise zwischen 0,1 und 50 Gew.-% Triclosan, und gegebenenfalls zwischen 0,005 und 50 Gew.-% der genannten mikrobiziden Komponenten, vorzugsweise zwischen 0,1 und 30 Gew.-%.The compositions according to the invention generally contain between 0.005 and 95% by weight of triclosan, preferably between 0.1 and 50% by weight of triclosan, and optionally between 0.005 and 50% by weight of said microbicidal components, preferably between 0.1 and 30% by weight.
Die zum Schutz der technischen Materialien verwendeten mikrobiziden Mittel oder Konzentrate enthalten den Wirkstoff Triclosan bzw. die Kombination von Triclosan mit einem weiteren mikrobiziden Wirkstoff in einer Konzentration von 0,005 und 95 Gew.-%, insbesondere 0,1 bis 50 Gewichtsprozent.The microbicidal agents or concentrates used to protect the technical materials contain the active ingredient triclosan or the combination of triclosan with another microbicidal active ingredient in a concentration of 0.005 and 95 wt .-%, in particular 0.1 to 50 weight percent.
Die Anwendungskonzentrationen des erfindungsgemäß zu verwendenden Wirkstoffs Triclosan bzw. der Wirkstoffkombination von Triclosan mit mindestens einem weiteren mikrobiziden Wirk- stoff richtet sich nach der Art und dem Vorkommen der zu bekämpfenden Mikroorganismen sowie nach der Zusammensetzung des zu schützenden Materials. Die optimale Einsatzmenge kann durch Testreihen ermittelt werden. Im allgemeinen liegen die Anwendungskonzentrationen von Triclosan bzw. der Kombination von Triclosan mit mindestens einem weiteren mikrobiziden Wirkstoff im Bereich von 0,001 bis 5 Gewichtsprozent, vorzugsweise von 0,01 bis 1,5 Gewichtsprozent, bezogen auf das zu schützende Material.The use concentrations of the active substance triclosan to be used according to the invention or the active substance combination of triclosan with at least one further microbicidal active ingredient depends on the nature and occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimum amount used can be determined by test series. In general, the use concentrations of triclosan or the combination of triclosan with at least one other microbicidal active ingredient in the Range of 0.001 to 5 weight percent, preferably from 0.01 to 1.5 weight percent, based on the material to be protected.
Die erfindungsgemäße Verwendung von Triclosan ermöglicht in vorteilhafter Weise,- die bisher verfügbaren mikrobiziden Mittel durch effektivere zu ersetzen. Die erfindungsgemäßen Mittel zei- gen eine gute Stabilität und haben in vorteilhafter Weise ein breites Wirkungsspektrum.The use of triclosan according to the invention advantageously makes it possible to replace the previously available microbicidal agents with more effective ones. The compositions according to the invention exhibit good stability and advantageously have a broad spectrum of activity.
Triclosan weist zwar überraschend gegen Moderfäulepilze eine hervorragende Wirksamkeit auf, ist aber gegen holzzerstörende Basidiomceten wie z.B. Gloeophyllum trabeum, Coniophora puteana, Poria placenta, Lentinus tigrinus, Coriolus versicolor und Stereum sanguinolentum unzureichend wirksam und kann durch diese abgebaut werden.Although surprisingly, triclosan has excellent activity against soft rot fungi, but is resistant to wood-destroying basidiomycetes, e.g. Gloeophyllum trabeum, Coniophora puteana, Poria placenta, Lentinus tigrinus, Coriolus versicolor and Stereum sanguinolentum are insufficiently effective and can be degraded by them.
Überraschenderweise wurde gefunden, dass Kombinationen des allein nicht ausreichend wirksamen Triclosan mit Triazolfungiziden sowohl gegen holzzerstörende Basidiomyceten als auch gegen Moderfäulepilze synergistisch wirken, d. h. die fungizide Wirksamkeit der synergistischen Mischungen ist unerwarteter Weise höher als die Summe der fungiziden Wirksamkeit der jeweiligen Fungizide allein.Surprisingly, it has been found that combinations of triclosan alone with triazole fungicides acting both against wood-destroying Basidiomyceten as well as against mold fungi act synergistically, d. H. the fungicidal activity of the synergistic mixtures is unexpectedly higher than the sum of the fungicidal activity of the respective fungicides alone.
Weitere Gegenstände der vorliegenden Erfindung sind daher Mischungen enthaltend eine synergistisch wirksame Menge an Triclosan und mindestens einem Triazolfungizid, fungizide Mittel auf Basis dieser Mischungen sowie die Verwendung dieser Mischungen und Mittel zum Schutz von technischen Materialien, insbesondere Holz und Holzwerkstoffen, vor Befall, Schädigung und oder Zerstörung durch Mikroorganismen.Further objects of the present invention are therefore mixtures comprising a synergistically effective amount of triclosan and at least one triazole fungicide, fungicidal compositions based on these mixtures and the use of these mixtures and agents for the protection of industrial materials, in particular wood and wood-based materials, from infestation, damage and / or Destruction by microorganisms.
Bevorzugt handelt es sich bei den erfindungsgemäß einzusetzenden Triazolfungiziden um Azaco- nazole, Azocyclotin, Bitertanol, Bromuconazole; Cyproconazole, Diclobutrazole, Difenoconazole, Diniconazole, Epoxyconazole, Etconazole, Fenbuconazole, Fenchlorazole, Fenethanil, Fluquinco- nazole, Flusilazole, Flutriafol, Furconazole, Hexaconazole, Imibenconazole, Ipconazole, Izofos, Myclobutanil, Metconazole, Paclobutrazol, Penconazole, Propiconazole, (+/-)-cis-l-(4-chlorphe- nyl)-2-(lH-l,2,4-triazol-l-yl)cycloheptanol, 2-(l-tert.-Butyl)-l-(2-chlorphenyl)3-(l,2,4-triazol-l- yl)-propan-2-ol, Simeconazole, Tebuconazole, Tetraconazole, Triadimefon, Triadimenol, Tria- penthenol, Triflumizole, Triticonazole; Uniconazole sowie deren Metallsalze und Säureaddukte.The triazole fungicides to be used according to the invention are preferably azaconazoles, azocyclotin, bitertanol, bromuconazoles; Cyproconazole, diclobutrazoles, difenoconazole, diniconazole, epoxyconazole, etconazole, fenbuconazole, fenchlorazole, fenethanil, fluquinocynazole, flusilazole, flutriafol, furconazole, hexaconazole, imibenconazole, ipconazole, izofos, myclobutanil, metconazole, paclobutrazole, penconazole, propiconazole, (+/- ) -cis-1- (4-chlorophenyl) -2- (1H-l, 2,4-triazol-1-yl) cycloheptanol, 2- (1-tert-butyl) -1- (2-chlorophenyl ) 3- (l, 2,4-triazol-1-yl) -propan-2-ol, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimol, tri-penthenol, triflumizole, triticonazole; Uniconazole and its metal salts and acid adducts.
Besonders bevorzugt sind Mischungen von Triclosan mit wenigstens einem Triazolfungizid aus der Reihe Propiconazole, Tebuconazole, Cyproconazole, Hexaconazole und Triadimefon die sich durch einen ausgeprägten Synergsimus gegen holzerstörende Basidiomyceten auszeichnen.Particular preference is given to mixtures of triclosan with at least one triazole fungicide from the series propiconazoles, tebuconazoles, cyproconazoles, hexaconazoles and triadimefon, which are distinguished by pronounced synergism against wood-destroying basidiomycetes.
Durch die synergistische Wirkungssteigerung ergibt sich der zusätzliche Vorteil, dass durch die anzuwendende geringere Menge an Fungizid in einem Holzschutzmittel gemäß der vorliegenden Erfindung nicht nur ein ökonomischer Vorteil erzielt wird, sondern auch das Sicherheitsrisiko für die Umwelt reduziert wird. Die erfindungsgemäßen Mischungen enthalten im allgemeinen Triclosan und mindestens ein Triazolfungizid im Gewichtsverhältnis von 1 : 99 bis 99 : 1, bevorzugt von 1 : 10 bis 10 : 1.Due to the synergistic increase in activity, there is the additional advantage that the smaller amount of fungicide to be used in a wood preservative according to the present invention not only provides an economic advantage, but also reduces the safety risk for the environment. The mixtures according to the invention generally contain triclosan and at least one triazole fungicide in a weight ratio of from 1:99 to 99: 1, preferably from 1:10 to 10: 1.
Die erfindungsgemäßen Mischungen können weitere wirksame Bestandteile aus der Reihe der fun- gizide und/oder termitizide zur Steigerung der Wirksamkeit und/oder Erzielung besonderer Effekte enthalten.The mixtures according to the invention may contain further active ingredients from the series of fungicidal and / or termiticides for increasing the activity and / or achieving particular effects.
Bevorzugt enthalten die erfindungsgemäßen Mischungen einen oder mehrere der folgenden fungi- ziden Komponenten: Clorthalonil, Carbendazim, Thiabendazol, Dichloroctylisothiazolinon, n- Octylisothazolinon, Folpet, Dichlofluanid, Tolylfluanid, Bethoxazin, 3-Iod-2-propinyl-butylcarba- mat, Zink- oder Kupfer-Pyrithion, Bifenthrin, Chlorfenapyr, Clothianidin, Cyfluthrin, Cyper- methrin, Deltamethrin, Etofenprox, Imidacloprid, Permethrin, Thiacloprid, Thiamethoxam. Captan, Carbendazim, Fenpropimorph, Bethoxazin, Fluorfolpet, Thiocyanato-methyl- thiobenzothiazol, Dichloroctylisothiazolinon, n-Octylsisothiazolinon, N-(3-aminopropyl)-N- dodecylpropan-l,3-diamin sowie Borsäurverbindungen wie Borsäure, Borsäurester, Borax.The mixtures according to the invention preferably contain one or more of the following fungicidal components: clorthalonil, carbendazim, thiabendazole, dichloroctylisothiazolinone, n-octylisothazolinone, folpet, dichlofluanid, tolylfluanid, bethoxazine, 3-iodo-2-propynyl-butylcarbamate, zinc or Copper pyrithione, bifenthrin, chlorfenapyr, clothianidin, cyfluthrin, cypermethrin, deltamethrin, etofenprox, imidacloprid, permethrin, thiacloprid, thiamethoxam. Captan, carbendazim, fenpropimorph, bethoxazine, fluoro-folpet, thiocyanato-methylthiobenzothiazole, dichloroctylisothiazolinone, n-octylsisothiazolinone, N- (3-aminopropyl) -N-dodecylpropane-l, 3-diamine and boric acid compounds such as boric acid, boric acid ester, borax.
Besonders bevorzugt enthalten die erfindungsgemäßen Mischungen eine oder mehrere der folgen- den fungiziden Komponenten: Clorthalonill, Dichlofluanid, Tolylfluanid, Bethoxazin, 3-Iod-2- propinyl-butylcarbamat, Dichloroctylisothiazolinon, n-Octylsisothiazolinon, Folpet, Zink- und Kupfer-Pyrithion.The mixtures according to the invention particularly preferably comprise one or more of the following fungicidal components: clorthalonill, dichlofluanid, tolylfluanid, bethoxazine, 3-iodo-2-propynyl-butylcarbamate, dichloroctylisothiazolinone, n-octylsisothiazolinone, folpet, zinc pyrithione and copper pyrithione.
Die erfindungsgemäßen Mischungen enthalten im allgemeinen 0.01 - 85 Gewichtsprozent Triclosan, 0.01 - 85 Gewichtsprozent eines oder mehrer Triazolfungizide, gegebenenfalls 0.01 - 80 Gewichtsprozent mindestens eines weiteren mikrobiziden Wirkstoffs aus der Reihe der Fungizide, Insektizide und Termitizide enthalten sind.The mixtures according to the invention generally contain 0.01-85% by weight of triclosan, 0.01-85% by weight of one or more triazole fungicides, optionally 0.01-80% by weight of at least one further microbicidal active ingredient from the series of fungicides, insecticides and termiticides.
Die erfindungsgemäßen Mischungen eignen sich hervorragend zum Schutz von technischen Materialien insbesondere Holz und Holzwerkstoffen, vor Befall, Schädigung und oder Zerstörung durch Mikroorganismen.The mixtures according to the invention are outstandingly suitable for the protection of industrial materials, in particular wood and wood-based materials, against infestation, damage and or destruction by microorganisms.
Die erfindungsgemäßen Mischungen können nach allgemein bekanntem Verfahren hergestellt werden indem eine synergistisch wirksame Menge der Wirkstoffe Triclosan und eines oder mehrere Triazolfungizide sowie gegebenenfalls weitere Wirkstoffe aus der Reihe der Fungizide, Insektizide und Termitizide sowie gegebenenfalls Hilfs- und Zusatzstoffe in einer geeigneten Apparatur gemischt, gemahlt, granuliert, emulgiert oder dispergiert werden. Ein weiterer Gegenstand dieser Erfindung sind das vor Befall und/oder Zerstörung durch Moderfäulepilze geschützte Holz und Holzwerkstoffe sowie Holzplastikverbundstoffe enthaltend Triclosan oder ein Mittel basierend auf Triclosan.The mixtures according to the invention can be prepared by a generally known process by mixing a synergistically effective amount of the active substances triclosan and one or more triazole fungicides and optionally further active compounds from the series of fungicides, insecticides and termiticides and optionally adjuvants and additives in a suitable apparatus, ground, granulated, emulsified or dispersed. Another object of this invention are protected against attack and / or destruction by soft rot fungi wood and wood-based materials and wood-plastic composites containing triclosan or an agent based on triclosan.
Unter Holz, Holzwerkstoffen und Holzplastikverbundstoffen, welches durch die erfindungsgemäßen Wirkstoffmischungen bzw. diese enthaltene Mittel geschützt werden kann, ist beispielhaft zu verstehen: Bauholz, Holzbalken, Eisenbahnschwellen, Brückenteile, Bootsstege, Holzfahrzeuge,Wood, wood-based materials and wood-plastic composites, which can be protected by the active substance mixtures according to the invention or agents contained in them, are exemplary understand: timber, wooden beams, railway sleepers, bridge parts, boat bridges, wooden vehicles,
Kisten, Paletten, Container, Telefonmasten, Holzverkleidungen, Holzfenster und -türen, Sperrholz, Mitteldichte Faserplatten (MDF), Spanplatten, Oriented Strand Board (OSB), Waferboard, Lami- nated Veneer Lumber (LVL) oder Holzprodukte, die ganz allgemein beim Hausbau oder in der Bautischlerei Verwendung finden sowie Holzplastik-Verbundstoffe.Crates, pallets, containers, telephone poles, wood cladding, wooden windows and doors, plywood, medium density fibreboard (MDF), chipboard, Oriented Strand Board (OSB), waferboard, laminated veneer lumber (LVL) or wood products commonly used in house building or in the joinery and wood plastic composites.
Weiterer Gegenstand der Erfindung ist ein Verfahren zum Schutz von Holz, Holzwerkstoffen und Holz-Plastik-Verbundwerkstoffen gegen den Befall durch Moderfäulepilze.Another object of the invention is a method for the protection of wood, wood-based materials and wood-plastic composites against the infestation by soft rot fungi.
Der Wirkstoff Triclosan, gegebenenfalls in Kombination mit einem oder mehreren mikrobiziden Wirkstoffen, kann als solcher, in Form von Formulierungen oder den daraus bereiteten Anwen- dungsformen, wie gebrauchsfertige Lösungen, Suspensionen, Pasten, lösliche Pulver angewendet werden. Die Anwendung geschieht in üblicher Weise indem man das Holz, den Holzwerkstoff oder den Holz-Plastik-Verbundwerkstoff mit dem Wirkstoff Triclosan, gegebenenfalls in Kombination mit einem oder mehreren mikrobiziden Wirkstoffen, oder mit einem daraus hergestellten Mittel in Form einer Formulierung oder Anwendungsform behandelt, z.B. durch Sprüh-, Streich-, Tauch- und großtechnische Imprägnierverfahren, z.B. Vakuum-, Doppel vakuum- oder Druckverfahren sowie durch Zugabe zum Leim oder Masterbatch sowie über den Compounder oder Mischer.The active ingredient triclosan, optionally in combination with one or more microbicidal active compounds, can be used as such, in the form of formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, pastes, soluble powders. The application is usually carried out by treating the wood, the wood-based material or the wood-plastic composite with the active substance triclosan, optionally in combination with one or more microbicidal agents, or with an agent prepared therefrom in the form of a formulation or form of application, e.g. by spray, brush, dip and large scale impregnation methods, e.g. Vacuum, double vacuum or pressure method as well as by addition to the glue or masterbatch as well as via the compounder or mixer.
Ein besonders effektiver Holzschutz wird durch großtechnische Imprägnierverfahren, z.B. Vakuum, Doppelvakuum oder Druckverfahren erzielt.Particularly effective wood protection is provided by large scale impregnation methods, e.g. Achieved vacuum, double vacuum or printing process.
Besonders bevorzugt ist daher ein Verfahren zum Schutz von Holz wobei das Holz mit einer wirksamen Menge Triclosan und mindestens einem Verdünnungs- oder Lösungsmittel, gegebenenfalls weiteren Hilfs- und Zusatzstoffe sowie gegebenenfalls einem oder mehreren mikrobiziden Wirkstoffen, vorzugsweise aus der Reihe der Termitizide und Fungizide, mittels Vakuum, Doppelvakuum, Druck- oder Tauchverfahren imprägniert wird.Therefore, a method for the protection of wood is particularly preferred wherein the wood with an effective amount of triclosan and at least one diluent or solvent, optionally further auxiliaries and additives and optionally one or more microbicidal agents, preferably from the series of termiticides and fungicides Vacuum, double vacuum, pressure or dipping method is impregnated.
Die folgenden Beispiele dienen zur Erläuterung der vorliegenden Erfindung ohne diese jedoch einzuschränken. Beispiel 1The following examples serve to illustrate the present invention without, however, limiting it. example 1
Zum Nachweis der Wirksamkeit von Triclosan gegen in EN 807 beschriebene Moderfäulepilze wurde die minimalen Hemmkonzentrationen (MHK) ermittelt. -To demonstrate the efficacy of triclosan against soft rot fungi described in EN 807, the minimum inhibitory concentrations (MIC) were determined. -
Ein Agar, der unter Verwendung von Malzextrakt hergestellt wurde, wurde mit Triclosan in Kon- zentrationen von 1 mg/1 bis 500 mg/1 versetzt.. Nach Erstarren des Agars erfolgte eine Kontamination mit Reinkulturen der in Tabelle 1 aufgeführten Moderfäulepilze. Nach 2-wöchiger Inkubation bei 26°C wurde die MHK ermittelt. MHK ist die niedrigste Konzentation an Wirkstoff, bei der keinerlei Bewuchs durch Moderfäulepilze erfolgt., sie ist in Tabelle 1 angegeben.An agar prepared using malt extract was added with triclosan in concentrations of 1 mg / l to 500 mg / l. After solidification of the agar, contamination was carried out with pure cultures of the soft rot fungi listed in Table 1. After 2 weeks of incubation at 26 ° C, the MIC was determined. MIC is the lowest concentration of active substance in which no fouling by soft rot fungi occurs., It is given in Table 1.
Tabelle 1 Minimale Hemmkonzentrationen von Triclosan gegen ModerfäulepilzeTable 1 Minimum inhibitory concentrations of triclosan against soft rot fungi
Figure imgf000010_0001
Figure imgf000010_0001
Beispiel 2Example 2
Verschiedene Konzentrationen von Triclosan (A), Tebuconazole (B) und Mischungen (AB) der beiden genannten Wirkstoffe wurden gegen den holzzerstörenden Basidiomyceten Lentinus tigrinus geprüft. Aus einer Kolonie des Holzdestruenten wurden Mycelstücke ausgestochen und auf einem Malzextrakt-peptonhaltigen Nähragar bei 26°C inkubiert. In der Folge wurde das radiale Hyphenwachstum mit und ohne Wirkstoffzusatz verglichen. Als minimale Hemmkonzentration (MHK) wurde die niedrigste Wirkstoffkonzentration in Folge angegeben, welche das radiale Wachstum völlig unterdrückt.Various concentrations of triclosan (A), tebuconazole (B) and mixtures (AB) of the two active substances mentioned were tested against the wood destroying basidiomycete Lentinus tigrinus. Mycelium pieces were punched out of a colony of the wood destructor and incubated on a malt extract-peptone containing nutrient agar at 26 ° C. Subsequently, radial hyphae growth was compared with and without addition of active ingredient. The minimum inhibitory concentration (MIC) was given as the lowest active ingredient concentration in succession, which completely suppresses radial growth.
Nach der von KuIl et al. (F.C.Kull, P.C. Eismann, H.D.Sylvestrowicz, R.L.Mayer, Applied Microbiology 9, 538 bis 541,1961) beschriebenen Methode wurde dann der Synergismus ermittelt. Dabei gelten folgende Beziehungen:According to the KuIl et al. Synergism was then determined (F.C. Kull, P.C. Eismann, H.D. Sylvestrowicz, R. L. Mayer, Applied Microbiology 9, 538-541, 1961). The following relationships apply:
QA/ Qa + QB/ Qb = SIQA / Qa + QB / Qb = SI
Qa = Konzentration von Substanz A, welche die MHK darstellt Qb = Konzentration von Substanz B, welche die MHK darstelltQa = concentration of substance A, which represents the MIC Qb = concentration of substance B, which represents the MIC
QA = Konzentration von Substanz A in der Konzentration von A/B, die das Mikroben Wachstum unterbindet - — - _ - _ _ - -QA = Concentration of substance A in the concentration of A / B that inhibits microbial growth - - - _ - _ _ - -
QB = Konzentration von Substanz B in der Konzentration von A/B, die das Mikroben Wachstum unterbindetQB = concentration of substance B in the concentration of A / B that inhibits microbial growth
SI = Synergistischer IndexSI = synergistic index
SI = 1 bedeutet AdditivitätSI = 1 means additivity
SI > 1 bedeutet AntagonismusSI> 1 means antagonism
SI < 1 bedeutet SynergismusSI <1 means synergism
Tabelle 2: MHK- Werte und Synergistsicher Index von Triclosan und Tebuconazole (Prüfpilz Lentinus tigrinus)Table 2: MIC values and synergistic index of triclosan and tebuconazole (test fungus Lentinus tigrinus)
Figure imgf000011_0001
Figure imgf000011_0001
Aus den ermittelten Index-Daten geht hervor, dass die erfindungsgemäße Kombination von Triclosan mit Tebuconazole über weite Bereiche hinweg einen ausgeprägten Synergismus gegen den holzzerstörenden Basidomyceten Lentinus tigrinus aufweist. Beispiel 3From the index data determined, it appears that the combination of triclosan with tebuconazole according to the invention has a pronounced synergism against the wood-destroying basidomycete Lentinus tigrinus over a wide range. Example 3
Verschiedene Konzentrationen von Triclosan (A), Cyproconazole (B) und Mischungen (AB) der beiden genannten Wirkstoffe wurden gegen den holzzerstörenden Basidiomyceten Gloephyllum trabeum geprüft. Aus einer Kolonie des Holzdestruenten wurden Mycelstücke ausgestochen und auf einem Malzextrakt-peptonhaltigen Nähragar bei 26°C inkubiert. In der Folge wurde das radiale Hyphenwachstum mit und ohne Wirkstoffzusatz verglichen. Als minimale Hemmkonzentration (MHK) wurde die niedrigste Wirkstoffkonzentration in Folge angegeben, welche das radiale Wachstum völlig unterdrückt.Various concentrations of triclosan (A), cyproconazole (B) and mixtures (AB) of the two active substances mentioned were tested against the wood destroying basidiomycete Gloephyllum trabeum. Mycelium pieces were punched out of a colony of the wood destructor and incubated on a malt extract-peptone containing nutrient agar at 26 ° C. Subsequently, radial hyphae growth was compared with and without addition of active ingredient. The minimum inhibitory concentration (MIC) was given as the lowest active ingredient concentration in succession, which completely suppresses radial growth.
Nach der von KuIl et al. (F.C.Kuli, P.C. Eismann, H.D.Sylvestrowicz, R.L.Mayer, Applied Microbiology 9, 538 bis 541,1961) beschriebenen Methode wurde analog zu Beispiel 2 der Synergismus ermittelt.According to the KuIl et al. (F.C. Kuli, P. C. Eismann, H.D. Sylvestrowicz, R. L. Mayer, Applied Microbiology 9, 538 to 541, 1961), the synergism was determined analogously to Example 2.
Tabelle 3: MHK-Werte und Synergistsicher Index von Triclosan und Cyproconazole (Prüfpilz Gloephyllum trabeum)Table 3: MIC values and synergistic index of triclosan and cyproconazole (test fungus Gloephyllum trabeum)
Figure imgf000012_0001
Figure imgf000012_0001
Aus den ermittelten Index-Daten geht hervor, dass die erfindungsgemäße Kombination von Triclosan mit Cyproconazole über weite Bereiche hinweg einen ausgeprägten Synergismus gegen den holzzerstörenden Basidomyceten Gloeophyllum trabeum aufweistIt emerges from the index data determined that the combination of triclosan with cyproconazole according to the invention has a pronounced synergism with the wood-destroying basidomycete Gloeophyllum trabeum over a wide range
Beispiel 4Example 4
Wie in Beispiel 1 beschrieben wurden verschiedene Konzentrationen von Triclosan (A), Propiconazole (B) und Mischungen (AB) der beiden genannten Wirkstoffe wurden gegen den Moderfäuleverursacher Trichurus spiralis geprüft. Nach der von KuIl et al. (F.C.Kuli, P.C. Eismann, H.D.Sylvestrowicz, R.L.Mayer, Applied Microbiology 9, 538 bis 541,1961) beschriebenen Methode wurde analog zu Beispiel 2 der Synergismus ermittelt.As described in Example 1, various concentrations of triclosan (A), propiconazole (B) and mixtures (AB) of the two active substances mentioned were tested against the moder rot causative agent Trichurus spiralis. According to the KuIl et al. (FCKuli, PC Eismann, HDSylvestrowicz, RLMayer, Applied Microbiology 9, 538-541, 1961), the synergism was determined analogously to Example 2.
Tabelle 3: MHK-Werte und Synergistsicher Index von Triclosan und Propiconazole (Prüfpilz Trichurus spiralis9Table 3: MIC values and synergistic index of triclosan and propiconazole (test fungus Trichurus spiralis9
Figure imgf000013_0001
Figure imgf000013_0001
Aus den ermittelten Index-Daten geht hervor, dass die erfmdungsgemäße Kombination von Triclosan mit Propiconazole einen ausgeprägten Synergismus gegen den Moderfäulepilz Trichurus spi- ralis aufweist From the index data determined, it appears that the combination of triclosan with propiconazole according to the invention has pronounced synergism with the soft rot fungus Trichurus spiralis

Claims

Patentansprüche claims
1. Verwendung von Triclosan (5-Chloro-2-(2,4-dichlorophenoxy)phenol) zum Schutz von Holz, Holzwerkstoffen und Holz-Plastik-Verbundstoffen vor dem Befall und/oder der Zerstörung durch Moderfäulepilze.1. Use of triclosan (5-chloro-2- (2,4-dichlorophenoxy) phenol) for the protection of wood, wood-based materials and wood-plastic composites from infestation and / or destruction by soft rot fungi.
2. Verwendung gemäß Anspruch 1, dadurch gekennzeichnet, dass Triclosan in Kombination mit mindestens einem weiteren mikrobiziden Wirkstoff ausgewählt aus der Reihe der Fungizide, Insektizide und Termitizide eingesetzt wird.2. Use according to claim 1, characterized in that triclosan is used in combination with at least one further microbicidal active ingredient selected from the series of fungicides, insecticides and termiticides.
3. Mikrobizides Mittel enthaltend Triclosan sowie mindestens ein Verdünnungs- oder Lösungsmittel, gegebenenfalls weitere Hilfs- und Zusatzstoffe sowie gegebenenfalls eine oder mehrere mikrobizide Wirkstoffe.3. Microbicidal agent containing triclosan and at least one diluent or solvent, optionally further auxiliaries and additives and optionally one or more microbicidal active substances.
4. Verwendung eines Mittels gemäß Anspruch 3 zum Schutz von Holz, Holzwerkstoffen und Holz-Plastik-Verbundstoffen vor Befall und Zerstörung durch Moderfäulepilze.4. Use of an agent according to claim 3 for the protection of wood, wood-based materials and wood-plastic composites from attack and destruction by soft rot fungi.
5. Verfahren zum Schutz von Holz, Holzwerkstoffen und Holz-Plastik-Verbundstoffen vor Befall und/oder Zerstörung durch Mikroorganismen, dadurch gekennzeichnet, dass man das Holz, den Holzwerkstoff oder den Holz-Plastik-Verbundstoff mit Triclosan und mindestens einem Verdünnungs- oder Lösungsmittel, gegebenenfalls weiteren Hilfs- und Zusatzstoffe sowie gegebenenfalls einem oder mehreren bioziden Wirkstoffen mittels Streich-, Sprüh-, Vakuum-, Doppelvakuum-, Druck- oder Tauchverfahren oder durch Zugabe zum Leim oder Masterbatch sowie über den Compounder oder Mischer sowie über Masterbatches imprägniert.5. A method for the protection of wood, wood-based materials and wood-plastic composites from attack and / or destruction by microorganisms, characterized in that the wood, the wood-based material or the wood-plastic composite with triclosan and at least one diluent or solvent , optionally further auxiliaries and additives and optionally one or more biocidal active substances by means of coating, spraying, vacuum, double vacuum, pressure or dipping method or by addition to the glue or masterbatch and impregnated via the compounder or mixer and masterbatches.
6. Holz, Holzwerkstoffe und Holz-Plastik-Verbundstoffe enthaltend Triclosan .6. Wood, wood-based materials and wood-plastic composites containing triclosan.
7. Mischungen enthaltend eine synergistisch wirksame Menge an Triclosan und mindestens einem Triazolfungizid.7. Mixtures containing a synergistically effective amount of triclosan and at least one triazole fungicide.
8. Mischung gemäß Anspruch 7, dadurch gekennzeichnet, dass als Triazolfungizid einer oder mehrere Wirkstoffe aus der Reihe Propiconazole, Tebuconazole, Cyproconazole,8. Mixture according to claim 7, characterized in that as triazole fungicide one or more active substances from the series Propiconazole, Tebuconazole, Cyproconazole,
Hexaconazole und Triadimefon enthalten ist.Hexaconazole and triadimefon is included.
9. Mischung gemäß wenigstens einem der Ansprüche 7 und 8„ dadurch gekennzeichnet dass das Gewichtsverhältnis von Triclosan zu Triazolfungiziden 1:99 bis 99: 1 beträgt.9. Mixture according to at least one of claims 7 and 8 "characterized in that the weight ratio of triclosan to Triazolfungiziden 1:99 to 99: 1.
10. Mischung gemäß wenigstens einem der Ansprüche 7 bis 9, dadurch gekennzeichnet, dass mindestens ein weiterer mikrobizider Wirkstoff aus der Reihe der Fungizide, Insektizide, und Termitizide enthalten ist. 10. Mixture according to at least one of claims 7 to 9, characterized in that at least one further microbicidal active ingredient from the series of fungicides, insecticides, and termiticides is included.
11. Mischung gemäß wenigstens einem der Ansprüche 7 bis 10, dadurch gekennzeichnet, dass als weiterer mikrobizider Wirkstoff mindestens eine Verbindung aus der Reihe Clorthalonil, Carbendazim, Thiabendazol, Dichloroctylisothiazolinon, n- Octylisothazolinon, Folpet, Dichlofluanid, Tolylfluanid, Bethoxazin, 3-Iod-2-propinyl- butylcarbamat, Zink- oder Kupfer-Pyrithion, Bifenthrin, Chlorfenapyr, Clothianidin,11. Mixture according to at least one of claims 7 to 10, characterized in that as further microbicidal active ingredient at least one compound from the series clorthalonil, carbendazim, thiabendazole, dichloroctylisothiazolinone, n-octylisothazolinone, folpet, dichlofluanid, tolylfluanid, bethoxazine, 3-iodo 2-propynyl butyl carbamate, zinc or copper pyrithione, bifenthrin, chlorfenapyr, clothianidin,
Cyfluthrin, Cypermethrin, Deltamethrin, Etofenprox, Imidacloprid, Permethrin, Thiacloprid, Thiamethoxam, Captan, Carbendazim, Fenpropimorph, Bethoxazin, Fluorfolpet, Thiocyanato-methylthiobenzothiazol, Dichloroctylisothiazolinon, n- Octylsisothiazolinon, N-(3-aminopropyl)-N-dodecylpropan-l,3-diamin, Borsäure, Borsäurester, Borax enthalten ist.Cyfluthrin, cypermethrin, deltamethrin, etofenprox, imidacloprid, permethrin, thiacloprid, thiamethoxam, captan, carbendazim, fenpropimorph, bethoxazine, fluorfolpet, thiocyanato-methylthiobenzothiazole, dichloroctylisothiazolinone, n-octylsisothiazolinone, N- (3-aminopropyl) -N-dodecylpropan-1, 3-diamine, boric acid, boric acid ester, borax is included.
12. Mischung gemäß wenigstens einem der Ansprüche 7 bis 11, dadurch gekennzeichnet, dass 0.01 - 85 Gewichtsprozent Triclosan, 0.01 - 85 Gewichtsprozent eines oder mehrer Triazolfungizide gegebenenfalls 0.01 - 80 Gewichtsprozent mindestens eines weiteren mikrobiziden Wirkstoffs aus der Reihe der Fungizide, Insektizide und Termitizide enthal- ten sind.12. Mixture according to at least one of claims 7 to 11, characterized in that 0.01 to 85 weight percent triclosan, 0.01 to 85 weight percent of one or more Triazolfungizide optionally 0.01 to 80 weight percent of at least one further microbicidal active ingredient from the range of fungicides, insecticides and termiticides enthal - th are.
13. Mikrobizides Mittel zum Schutz von technischen Materialien enthaltend eine Mischung gemäß wenigstens einem der Ansprüche 7 bis 12 und mindestens ein Lösungs- oder Verdünnungsmittel sowie gegebenenfalls Verarbeitungshilfsmittel und gegebenenfalls weitere antimikrobiell wirksame Stoffe.13. A microbicidal agent for the protection of industrial materials containing a mixture according to any one of claims 7 to 12 and at least one solvent or diluent and optionally processing aids and optionally other antimicrobial active substances.
14. Verwendung einer Mischung gemäß wenigstens einem der Ansprüche 7 bis 12 oder eines Mittels gemäß Anspruch 13 zum Schutz von technischen Materialien vor Befall und Zerstörung durch biologische Schädlinge.14. Use of a mixture according to any one of claims 7 to 12 or an agent according to claim 13 for the protection of industrial materials from attack and destruction by biological pests.
15. Verwendung gemäß Anspruch 14, dadurch gekennzeichnet, dass es sich bei den technischen Materialien um Holz, Holzwerkstoffe und Holz-Plastik-Verbundstoffe handelt.15. Use according to claim 14, characterized in that the technical materials are wood, wood-based materials and wood-plastic composites.
16. Verfahren zum Schutz von Holz und Holzwerkstoffen sowie Holz-Plastikverbundstoffen vor Befall und Zerstörung durch biologische Schädlinge, dadurch gekennzeichnet, dass man das Holz oder den Holzwerkstoff oder den Holzplastikverbundstoff mit einer synergistisch wirksame Menge an Triclosan und Traizolfungiziden und mindestens einem Ver- dünnungs- oder Lösungsmittel, gegebenenfalls weiteren Hilfs- und Zusatzstoffe sowie ge- gebenenfalls mindestens einem weiteren bioziden Wirkstoff mittels Streich-, Sprüh-, Vakuum-, Doppelvakuum-, Druck- oder Tauchverfahren oder durch Zugabe zum Leim oder durch Zugabe über den Compounder oder Mischer sowie über Materbatches imprägniert.16. A method of protecting wood and wood-based materials and wood-plastic composites against attack and destruction by biological pests, characterized in that the wood or the wood-based material or the wood-plastic composite with a synergistically effective amount of triclosan and Traugolfungiziden and at least one diluting or solvent, if appropriate further auxiliaries and additives and, if appropriate, at least one further biocidal active substance by means of coating, spraying, vacuum, double vacuum, pressure or dipping processes or by addition to the glue or by addition via the compounder or mixer and via Materbatches impregnated.
17. Technische Materialien enthaltend eine Mischung gemäß wenigstens einem der Ansprüche 7 bis 12 . 17. Technical materials containing a mixture according to at least one of claims 7 to 12.
PCT/EP2006/008510 2005-09-13 2006-08-31 Use of triclosan for wood protection WO2007031198A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP06791752A EP1926368A1 (en) 2005-09-13 2006-08-31 Use of triclosan for wood protection

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005043428.2 2005-09-13
DE200510043428 DE102005043428A1 (en) 2005-09-13 2005-09-13 Use of triclosan for wood preservation

Publications (1)

Publication Number Publication Date
WO2007031198A1 true WO2007031198A1 (en) 2007-03-22

Family

ID=37401185

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/008510 WO2007031198A1 (en) 2005-09-13 2006-08-31 Use of triclosan for wood protection

Country Status (3)

Country Link
EP (1) EP1926368A1 (en)
DE (1) DE102005043428A1 (en)
WO (1) WO2007031198A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101579873A (en) * 2008-05-09 2009-11-18 朗盛德国有限责任公司 Method of producing wood materials
WO2016133479A1 (en) * 2015-02-19 2016-08-25 Yeditepe Universitesi Coating formulation for seed and surface sterilization

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0555186A1 (en) * 1992-02-05 1993-08-11 Sandoz Ltd. Fungicidal compositions
US6057274A (en) * 1997-08-22 2000-05-02 Henkel Corporation Antibacterial composition having enhanced tactile properties
WO2002030194A1 (en) * 2000-10-12 2002-04-18 Duraban Oy Antimicrobial polyalphaolefin composition
EP1205287A1 (en) * 2000-11-13 2002-05-15 Sun Technochemicals Co., Ltd. Wood preservative additive composition
DE20215292U1 (en) * 2002-04-22 2003-06-05 F W Barth & Co Gmbh Cleaner-conditioner for wood and plastics surfaces, especially floor, including parquet or laminate, contains additive developing permanent antimicrobial action in liquid polymer dispersion, preferably of acrylate or polyurethane
WO2004011682A1 (en) * 2002-07-26 2004-02-05 Microban Products Company Durable antimicrobial leather
EP1410714A1 (en) * 2002-10-17 2004-04-21 Bayer Chemicals AG Fungicidal mixtures
WO2004080176A2 (en) * 2003-03-06 2004-09-23 Buckman Laboratories International, Inc. Microbicidal compositions including an ionene polymer and 2,4,4’-trichloro-2’-hydroxydiphenyl ether, and methods of using the same
US20040234492A1 (en) * 2003-05-23 2004-11-25 Stockel Richard F. Wood preservative compositions

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0555186A1 (en) * 1992-02-05 1993-08-11 Sandoz Ltd. Fungicidal compositions
US6057274A (en) * 1997-08-22 2000-05-02 Henkel Corporation Antibacterial composition having enhanced tactile properties
WO2002030194A1 (en) * 2000-10-12 2002-04-18 Duraban Oy Antimicrobial polyalphaolefin composition
EP1205287A1 (en) * 2000-11-13 2002-05-15 Sun Technochemicals Co., Ltd. Wood preservative additive composition
DE20215292U1 (en) * 2002-04-22 2003-06-05 F W Barth & Co Gmbh Cleaner-conditioner for wood and plastics surfaces, especially floor, including parquet or laminate, contains additive developing permanent antimicrobial action in liquid polymer dispersion, preferably of acrylate or polyurethane
WO2004011682A1 (en) * 2002-07-26 2004-02-05 Microban Products Company Durable antimicrobial leather
EP1410714A1 (en) * 2002-10-17 2004-04-21 Bayer Chemicals AG Fungicidal mixtures
WO2004080176A2 (en) * 2003-03-06 2004-09-23 Buckman Laboratories International, Inc. Microbicidal compositions including an ionene polymer and 2,4,4’-trichloro-2’-hydroxydiphenyl ether, and methods of using the same
US20040234492A1 (en) * 2003-05-23 2004-11-25 Stockel Richard F. Wood preservative compositions

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE CAPLUS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 1980, J. SZOSTAK-KOTOWA: "Evaluation of biocides used to protect cotton fabrics. II", XP002408437, retrieved from STN accession no. 1980:141630 Database accession no. 92:141630 *
J. SZOSTAK-KOTOWA: "Evaluation of biocides used to protect cotton fabrics. II Resistance of impregnated fabric to the effects of pure strains of cellulolytic fungi.", PRZEGLAD WLOKIENNICZY, vol. 33, no. 11, 1979, pages 634 - 636 *
K. HUNDT, D. MARTIN, E. HAMMER, U. JONAS, M. K. KINDERMANN & F. SCHAUER: "Transformation of Triclosan by Trametes versicolor and Pycnoporus cinnabarinus", APPL. ENVIRON. MICROBIOL., vol. 66, no. 9, 2000, pages 4157 - 4160, XP002408439 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101579873A (en) * 2008-05-09 2009-11-18 朗盛德国有限责任公司 Method of producing wood materials
WO2016133479A1 (en) * 2015-02-19 2016-08-25 Yeditepe Universitesi Coating formulation for seed and surface sterilization
US20170135339A1 (en) * 2015-02-19 2017-05-18 Yeditepe Universitesi Coating formulation for seed and surface sterilization
AU2016220556B2 (en) * 2015-02-19 2017-09-21 Yeditepe Universitesi Coating formulation for seed and surface sterilization
JP2017537872A (en) * 2015-02-19 2017-12-21 イェディテペ・ウニヴェルシテシYeditepe Universitesi Coating formulation for seed and surface sterilization

Also Published As

Publication number Publication date
DE102005043428A1 (en) 2007-03-15
EP1926368A1 (en) 2008-06-04

Similar Documents

Publication Publication Date Title
EP1885532B1 (en) Fungicidal mixtures
EP1689232B1 (en) Method for the protection of materials
EP0533017B1 (en) Water based, solvent- and emulsifier-free microbicidal combination of active agents
DE4113158A1 (en) MICROBICIDAL COMBINATIONS OF ACTIVE SUBSTANCES
US8334312B2 (en) Fungicidal mixtures for wood preservation
EP0533016B1 (en) Water based, solvent- and emusifierfree microbicidal combination of active agents
EP1883512A1 (en) Use of prochloraz for wood protection
EP0269817B1 (en) Agent or concentrate for the preservation of wood and wooden materials
EP1926368A1 (en) Use of triclosan for wood protection
EP1926578A2 (en) Synergistic mixtures
EP0682473B1 (en) Agent for protecting technical materials, especially timber and timber materials
EP1937449A1 (en) Use of diclosan for wood protection

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2006791752

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

WWP Wipo information: published in national office

Ref document number: 2006791752

Country of ref document: EP