NZ261112A - Synergistic composition comprising benzoylurea derivative and a triazole for protecting industrial materials, especially wood - Google Patents

Abstract

The present invention relates to an agent for protecting technical materials, especially timber and timber materials, from damage or destruction by biological pests, especially timber-eating insects, based on at least one active insecticidal agent with at least one diluent or solvent and possibly at least one organic chemical binder, possibly at least one further agent and possibly other processing auxiliaries and additives, in which the active insecticidal agent (component I) is at least one benzoyl-urea compound of the general formula (1) and is contained in the agent mixed with a quantity generating a synergetic action of at least one triazole fungicide (component II). The present invention also relates to a process for protecting technical materials, especially timber and timber materials, from damage or destruction by biological pests, especially timber-eating insects, and the use of the timber protective agent of the invention.

Description

-I " New Zealand No. 261112 International No. PCT/EP94/00185 Priority Date(s): .1.??.

Complete Spscfficaiion .2Sl|.U<iAk Class: (0) Publication Date: 2.9..Q.CJ. 19.96 I P.O. .,'ouMo: *:±93.

NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION Title of Invention: Agent for protecting technical materials, especially timber and timber materials Name, address and nationality of applicant(s) as in international application form: DESOWAG GmbH, of Rossstrasse 76, D-40476 Dusseldorf, Federal Republic of Germany A. Cerhoon 26 11 -Ift- Compositions for protecting Industrial materials, especially timber and timber materials The present invention relates to compositions for protecting industrial materials, especially timber and 5 timber materials, against damage or destruction by biological pests, especially wood-eating insects, which compositions are based on at least one insecticidal active compound, in addition to at least one diluent and/ox solvent and, if desired, at least one organic 10 chemical binder, together if desired with at least one further active compound and, if desireid, further processing auxiliaries and additives. The present invention relates furthermore to a method of protecting industrial materials, especially timber c.nd timber 15 materials, against damage or destruction by biological pests, especially wood-eating insects, and to the use of the timber-protecting composition according to the invention.

In plant protection, a new group of active 20 compounds, the so-called chitin synthesis inhibitors, has been used successfully for some time for the control of sucking and biting insects. These compounds are insecticidally acting, substituted benzoylurea compounds, including, in particular, substituted N-aroyl-N'-phenyl-25 urea compounds.

The specific mechanism of action of this class of compound lies in the intervention of the abovementioned substituted benzoylurea compounds as chitin synthesis inhibitors in the development, i.e. especially in the 30 larval stages, of insects. This intervention affects not only the molting stages of the larva of an insect pest but also the metamorphosis with the development of a pupa and/or of the final insect, the morphological alterations at this stage of development leading likewise to the 35 death of the insect. On the basis of this mechanism of action, the chitin synthesis inhibitors in general have no effect on adult organisms.

REPLACEMENT SHEET WO 94/17664 - 2 - PCT/EP94/00185 Because of its intervention in chitin formation, this new group of active compounds differs substantially from conventional insecticides such as, for example, cholinesterase inhibitors, or pyrethroids which damage 5 the nervous system of insects, the substituted benzoylurea compounds in question possessing decisive advantages over these conventional insecticides since they are mostly toxicologically acceptable, highly selective and have little or no adverse effect on useful 10 organisms.

The abovementioned benzoylurea compounds are predominantly stomach insecticides, i.e. they are taken in via the absorption pathway of an insect. At the customary application rates, a contact-insecticidal 15 activity has been found only to a very small extent, and thus the damaging intake of active compound by useful insects which merely come into contact with the insecticide cam be largely ruled out. This property of sparing useful insects, and the essential concentration 20 of the biological action of the chitin synthesis inhibitors on organisms which have a chitin-containing outer skeleton, are the particular advantages of the new active compound group.

Owing in particular to this high selectivity and 25 lack of detectable toxicity to warm-blooded creatures, proposals have already been made to extend the use of chitin synthesis inhibitors above and beyond plant protection alone. For example, as active compounds from the class of compounds consisting of the substituted 30 benzoylurea compounds, the plant protection insecticides Dimilin (diflubenzuron) and Alsystin (triflumuron) have already been tested for their action on various wood pests, although it has not been possible to obtain any satisfactory results in respect of effective application 35 rates and the scope of action of the benzoylureas tested.

Furthermore, it is known from European Patent Application 0 275 132 to employ the insecticidal benzoylurea compound flufenoxuron as chitin synthesis inhibitor REPLACEMENT SHEET against wood-destroying termites.

A wood-protecting composition based on the known benzoylurea compounds and having a broad spectrum of application, however, iB not disclosed in the prior art. The reasons for this are, in particular, as follows: the depth penetration of wood-protecting compositions in the brushing, spraying and dipping method is usually only a few millimeters. An insecticidal active compound must therefore be capable of killing penetrating wood-destroying organisms within this impregnated area of the wood. Conventional insecticides, such as the pyrethroids which are frequently employed to protect timber, are highly active and rapidly effective compounds which, in correct dosage, offer secure protection. Chitin synthesis inhibitors, such as flufenoxuron, are slow-acting stomach poisons which act only on the as yet not fully developed insect and only under the precondition that the pest organism takes in a sufficient quantity of active compound. These properties of the chitin synthesis inhibitors have up to now rendered their use in timber protection impossible. Animals which eat through the thin protective zone without molting or metamorphosis, i.e. without a development stage involving the formation of a new chitin cuticle, are not killed, and continue their damaging feeding unhindered inside the wood.

The object of the present invention was to provide a composition for protecting wood and timber materials, in which composition it is possible to employ the abovementioned substituted benzoylurea compounds, especially substituted N-aroyl-N'-phenyl-urea compounds, as effective insecticides having the advantageous actions described. In this context, furthermore, a formulation shall be found which leads to an improvement in the activity of the novel active compounds against wood-damaging and wood-destroying insects, with the application rates of the chitin synthesis inhibitors being as low as possible.

A composition for protecting industrial REPLACEMENT SHEET 26 1 1 1 2 4 materials, especially wood and timber materials, has now been found with which the abovementioned object is achieved. The invention provides a composition which comprises as insecticidal active compound (component X) 5 at least one benzoylurea compound of the general formula in which the substituents have the following meaning: Rx is a halogen or hydrogen atom, R2 is a halogen atom, X is at each instance a hydrogen atom, a halogen atom, an 10 alkyl group, an alkyl group substituted by at least one halogen atom, an alkoxy group or an alkoxy group which is substituted by at least one halogen atom, halogen being in each case fluorine, chlorine or bromine, m has the value 1, 2 or 3, the substituents X being identical or different.

Y is at each instance a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted by at least one halogen atom, or an alkoxy group, where halogen in each case is fluorine, chlorine or bromine, n has the value 1, 2, 3 or 4, the substituents Y being identical or different, and R3 is a halogen atom or an alkyl group which is substituted by at least one halogen atom, halogen being fluorine, chlorine or bromine, or is a group of the formula -OR in which R is an alkyl group substituted by at least one halogen atom where halogen is fluorine, chlorine or bromine, or R is a substituted phenyl radical of the formula RKPIiACEMENT SHEET WO 94/17664 , 261112* in which each group Z is a hydrogen atom, a halogen atom, an alkyl, haloalkyl, polyhaloalkyl, alkoxy, haloalkoxy and/or polyhaloalkoxy group and p has the value 1, 2, 3 or 4, the substituents Z being identical or different and halogen being fluorine, chlorine or bromine; is a halogen'atom or an alkyl group which is substituted by at least one halogen atom, halogen being fluorine, chlorine or bromine? and Q is the group CH or a nitrogen atom, this insecticidal active compound (component I) being present in the composition in a mixture with at least one triazole fungicide (component II) in a quantity which produces a synergistic effect.

It is particularly preferred to employ as component I at least one benzoylurea compound of the general formula in which the substituents have the following meaning: is a fluorine, chlorine or hydrogen atom, *2 is at each instance a fluorine or chlorine atom, X is at each instance hydrogen, with m having the value 3 Y is a hydrogen, fluorine or chlorine atom, n has the value 1, 2, 3 or 4, the substituents Y'being -identical or different, and EEPXiACEMENT SHEET N.Z patent office 17 JUL 1996 received 261 1 1 2 - 6 R3 Is a fluorine or chlorine atom or a group of the formula -OR in which R Is an alkyl group having up to 6 carbon atoms which is substituted by at least bromine, or R is a substituted phenyl radical of the formul in which each group Z is a hydrogen, fluorine or chlorine atom and p has the value 1, 2, 3 or 4, the substituents Z being identical or different; R4 is an alkyl group having up to 6 carbon atoms which is substituted by at least one halogen atom, the abovementioned halogen atoms being fluorine and/or chlorine; and Q is the group CH or a nitrogen atom.

In this context it has been found that, in order to treat wood against wood-eating insect pests with the abovementioned substituted benzoylurea compounds alone an effective applied quantity of the insecticide of at least 3 g/m2 is required, whereas, on the other hand, by means of the synergistic combination with a triazole fungicide, according to the invention, a surprising increase in action of at least 100% can be achieved, this increase in action being dependent on the quantity of triazole fungicide employed and, in particular, on the chosen fungcidal [sic] triazole compound itself. The inward feeding of the larvae of wood-destroying insects can thereby be prevented in a satisfactory manner. The extent of the synergistic effect is most highly pronounced in the concentration range from 0.6 to 0.8 percent by weight in the case of azaconazole. synergistic activity of the active compound mixture employed in accordance with the invention demonstrated a further surprising effect, namely that the larvae are one halogen atom, halogen being fluorine, chlorine or Z. p The experiments carried out to determine the REPLACEMENT SHEET n 2 patent office 17 JUL 1996 received damaged and killed even in the first stage of their existence, in which no molting with formation of a new chitin cuticle has yet taken place. Investigation of the gastrointestinal tract of the dead and damaged animals gave indications of an adverse effect on the chitin network (peritrophic membrane), which normally surrounds the intestinal contents of timber-destroying insects, in order to protect the intestinal wall against damage by splinters of wood. By the synergistic combination of triazole fungicides with the benzoylurea compounds employed in accordance with the invention, there is a superadditive increase in the activity of the insecticidal component, which has the surprising consequence that - in contrast to the use of, for example, fluf enoxuron alone - the formation of the peritrophic membrane is hindered even at the early larval stage, thereby inflicting early damage to the insect pest by way of the gastrointestinal tract even without molting, so that the penetration capacity of the larvae into the wood and/or their feeding activity can be reduced substantially even in this life phase.

This advantageous increase in action is preferably brought about by an active compound mixture in which the weight ratio of component I to component II is from 1:2 to 1:20,000. The claimed values for the weight ratio of substituted benzoylurea compound to the triazole fungicide vary in dependence on the species of insects to be controlled and on economic considerations relating to the insecticidal concentration of active compound to be employed. Moreover, by means of a certain minimum content of fungicidal component in the wood-protecting composition, it is possible in addition to achieve activity of the composition against wood-discoloring, wood-damaging and wood-destroying fungi. An action of this kind is not necessarily present with the abovementioned weight ratios.

It has been found in particular that, under these considerations, a weight ratio of component I to REPLACEMENT SHEET WO 94/17664 - 8 - PCT/EP94/00185 component II in the composition of from 1:10 to 10:15,000 is preferred.

The synergistic increase in action brings about the additional advantage that, owing to the small quanity of component I to be employed in an effective insecticidal wood-protecting composition according to the present invention, a substantial cost saving can be made in relation to the use of the substituted benzoylurea compound alone.

However, it is also possible for component I to be present in a higher proportion by weight than component II in the composition according to the invention. The synergistic effect is not lost thereby, but such a combination of the two active compounds in a wood-protecting composition would be uneconomic at the current time since the insecticidal benzoylurea compounds employed in accordance with the invention are substantially more expensive than the triazole fungicides conventionally used in timber protection.

In accordance with the invention, the novel wood-protecting composition contains at least one compound corresponding to component I and at least one compound corresponding to component II. However, it is also possible to employ mixtures of different benzoylurea compounds and/or mixtures of different triazole fungicides.

Particularly advantageous effects can be achieved with a composition which comprises as fungicidal component II a triazole fungicide selected from azaconazole (1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl] -methyl]-1H-1,2,4-triazole), tebuconazole (a-[2-(4-chlorophenyl)ethyl]-a-[1,1-dimethyl-ethyl] -1H-1,2,4-triazole-l-ethanol) and/or propiconazole (1-[ [2-(2,4-dichlorophenyl) -4-propyl-l,3-dioxolan-2-yl] -methyl]-1H-1,2,4-triazole).

Furthermore it has been found that, as component I, flufenoxuron (1-[4-(2-chloro-a,a,a-trifluoro-p-tolyloxy)-2-fluorophenyl]-3-(2,6-difluorobenzoyl)-urea), REPLACEMENT SHEET 261112 WO 94/17664 - 9 - PCT/EP94/00185 hexaflumuron (1-(3,5-dichlore-4-(1/1,2,2-tetrafluoro-ethoxy) -phenyl] -3- (2, 6-di-fluorobenzoyl) -urea) and/or trifluxnuron [sic] (1- (4-trifluoromethoxy-phenyl)-3-(2-chloro-benzoyl)-urea) should preferably be employed as 5 chitin synthesis inhibitors in the composition according to the invention. On the basis of the active properties described, the synergistic active compound . mixtures employed in accordance with the invention affect the moltable development stageB of holo- and hemimetabolic 10 wood-damaging insects, in particular from the order Coleoptera (beetles) such as for example Hylotrupes bajulus, Anobium punctatum, powder-post beetles (Lyctidae) and Xestobium rufovillosum, and from the order Isoptera (termites).

Since the class of compounds of the substituted benzoylur' compounds employed in accordance with the invention *ias a very good stability to light and to washing off, no persistency problems are encountered in the treated wood. 2 0 It is already known to combine the novel chitin synthesis inhibitors with customary insecticides and fungicides for ready-to-use formulations in plant protection, without any resulting adverse effects on their activity. It has consequently been found that the 25 synergistic active compound mixture in the wood-protecting composition according to the invention can be admixed with further active compounds, namely fungicides and insecticides which are conventional in timber protection, in order to broaden the spectrum of action. 30 Furthermore, the wood-protecting composition according to the invention comprises at least one diluent and/or solvent, if desired at least one organic chemical binder and, if desired, a further processing auxiliary and additive.

The composition preferably contains up to 99.94995 % by weight of a mixture comprising at least one organic chemical binder and/or plasticizer and/or fixing agent and at least one diluent and/or at least one and/or at least one emulsifier and/or at least o WO 94/17664 - 10 - PCT/EP94/00185 agent.

The diluent and/or solvent preferably comprises an organic chemical solvent or solvent mixture, preferably an oily or oil-like, organic chemical solvent 5 or solvent mixture of low volatility or a mixture of water and/or at least one organic chemical solvent, preferably at least one oily or oil-like, organic chemical solvent or solvent mixture of low volatility, and/or at least one emulsifier and/or wetting agent, or 10 the diluent and/or solvent comprises one or more of these constituents.

The solvents employed are polar or nonpolar organic chemical solvents or solvent mixtures or mixtures of polar and nonpolar organic chemical solvents or 15 mixtures of water and an organic chemical solvent, preferably a polar organic chemical solvent or solvent mixture, and at least one emulsifier and/or solubilizer.

As polar organic chemical solvents or solvent mixtures it is preferred to employ solvents or solvent 2 0 mixtures containing hydroxyl and/or ether groups and/or keto groups and/or ester groups. Those preferably employed are alcohols, glycols, glycol ethers, diacetone alcohol, water-soluble polyols and esters thereof.

As nonpolar solvents or solvent mixtures it is 25 possible to employ aliphatic or aromatic hydrocarbons or a solvent mixture comprising aromatic and aliphatic HCs.

However, it is also possible in particular to employ oily or oil-like solvents of low volatility having an evaporation number of more than 35 and a flash point 30 of greater than 30°C, preferably greater than 45°C. Compounds used as water-insoluble, oily or oil-like solvents of this kind, of low volatility, are appropriate mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, 35 spindle oil, petroleum, terpentine oil, terpene hydrocarbons, nonaromatic petroleum fractions and/or alkylbenzenes, etc.

The organic chemical binders used in the context REPLACEMENT SHEET WO 94/17664 - 11 - PClVEP94/00185 of the present Invention are synthetic resins and/or binding drying oils which are known per se and are dilutable in water and/or soluble or dispersib&e and/or emulsifiable in the organic chemical solvents eptployed, especially binders consisting of or comprising acrylic resin, a vinyl resin# for example polyvinyl acetate, polyester resin, condensation or addition polymer resin, polyurethane resin, alkyd resin, silicone resin, drying vegetable oils and/or drying [sic] oils and/or physically drying binders based on a natural and/or synthetic resin.

As binders it is possible in particular to use synthetic resins in the form of an emulsion, dispersion or solution, preferably alkyd resins and/or modified alkyd resins or phenolic resins and/or hydrocarbon resins, preferably indene-coumarone resins. It is also possible to employ as binder bitumen or bituminous substances in proportions of up to 10 % by weight.

The organic chemical binder or binder mixture can be replaced wholly or partially by at least one fixing agent and/or by at least one plasticizer.

As emulsifying agent the wood-protecting composition according to the invention receives [sic] anionic or cationic emulsifiers or emulsifier mixtures. Examples of anionic emulsifiers are alkyl-, aryl- and/or alkylarylsulionates or partial esters of phosphoric acid. As cationic emulsifiers it is possible to employ quaternary ammonium compounds.

It is preferred to employ nonionic emulsifiers or emulsifier mixtures, for example alkyl polyglycol ethers or esters and/or alkylaryl polyglygol ethers or esters, alkylphenol polyglycol ethers, polyoxyethylene derivatives, polyethylene glycol carboxylates, alkylolamides, ethoxylated phenols containing a side group, preferably ethoxylated nonylphenol and/or an ethoxylated fatty acid, fatty acid esters of polyhydroxy compounds, especially mono- and difatty acid esters of glycerol, polygycerol or glycerol polyethylene ■ or polypropylene glycol ethers.

REPLACEMENT SHEET WO 94/176S4 The emulsifiers can also be combined with wetting agents, for example with wetting agents based on organic phosphorus amine compounds.

For the preparation of emulsifiable concentrates or water-containing wood-protecting compositions in particular, the organic chemical solvents are mixed in particular with solvents, preferably solubilizers or solvents containing hydroxyl or ether groups.

As organic chemical polar solvents, organic chemical solvents containing hydroxyl groups and/or ether groups and/or keto groups are used.

As organic chemical solvents containing hydroxyl groups and/or ether groups and/or keto groups it is preferred to employ ethylene glycol (2-hydroxyethanol), diethylene glycol (2,2-dihydroxy-diethyl ether), ethyl-glycol (2-hydroxy-diethyl ether), butylglycol (1-hydroxy-2-n-butoxy-ethane) and/or ethyldiglycol (2-hydroxy-2-ethoxy-diethyl ether) and/or diacetone alcohol.

As solubilizers, use is made of anionic or cationic, but preferably nonionic, surfactants, which dissolve the active compounds and form a stable emulsion together with water.

Examples of anionic surfactants are alkyl-, aryl-and/or alkylarylsulfonates, while cationic surfactants include quaternary ammonium compounds. Examples of nonionic surfactants are alkyl polyglycol ethers or esters and/or alkylaryl polyglycol ethers or esters, polyoxyethylene derivatives, ethoxylated nonylphenol, fatty acid esters of polyhydroxy compounds, such as, in particular, mono- and difatty acid esters of glycerol, polyglycerol or glycerol polyethylene or polypropylene glycol ethers.

The composition according to the invention may additionally comprise dyes, pigments, hydrophobic agents, odor correctants and odor inhibitors and/or corrosion inhibitors known per se and the like. A further additive which may be present in the composition according to the invention is an amino alcohol for regulating the pH REPLACEMENT SHEET WO 94/17664 - 13 - PCT/EP94/00185 and/or as a co-emulsifier, preferably monoethanolamine.

For particular formulations it may be expedient to add antifoams such ae silicone defoaming agents or alkyl phosphates, preferably n-butyl phosphate.

In addition, other additives such as, for example, UV stabilizers, thickeners and siccatives may be added. As siccatives (driers), which are employed preferably in combination with a binder based on a vegetable oil, use is preferably made of cobalt, zinc, cerium and/or manganese octoate and/or naphthenate.

As rediluting agents for the preparation of ready-to-use compositions from concentrates, the abovementioned diluents or diluent mixtures are employed, if desired in combination with binders, additives, processing auxiliaries, dyes, color pigments, UV stabilizers, corrosion inhibitors and the like.

In addition the wood-protecting composition according to the invention may contain a stabilizer or stabilizer mixture based on at least one phenol which carries aryl, alkyl or arylalkyl groups, on a bisphenol or bisphenol derivative, on a bis-hydroxyarylalkane or bis-hydroxyarylalkane derivative, on a polyoxypolyphenyl-alkane and/or on at least one phosphatide.

With the aid of the stabilizer or stabilizer mixture it is possible to stabilize the active compounds chemically and/or physically in the wood-protecting composition, even if the proportion of aliphatic hydrocarbons is very high.

The wood-protecting composition according to the invention may be in the form of a concentrate or a ready-to-use composition, for example as a coating composition in the form of a varnish, especially a stain, or as an impregnating composition, with the ready-to-use composition comprising an appropriate quantity of at least one diluent and, if dedired, further processing auxiliaries and additives.

According to a preferred embodiment of the present invention, the composition according to the REPLACEMENT SHEET invention/ as ready-to-use composition, comprises from 0.00005 to 0.5 % by weight preferably from 0.0001 to 0.2 % by weight, of component X, from 0.05 to 2 % by weight preferably from 0.25 to 1.5 % by weight, of component XI, from 0.9 to 40 % by weight preferably from 3 to 33 % by weight, of at least one organic chemical binder and/or plasticizer and/or fixing agent, from 0 to 8 % by weight preferably from 0.1 to 4 % by weight of at least one water-soluble and/or water-insoluble dye, 15 colored pigment and/or corrosion inhibitor, siccative and/or stabilizer and from 44 to 99 % by weight preferably from 58 to 95 % by weight, of a diluent, consisting of eui organic chemical solvent 20 or solvent mixture or of a mixture of water and at least one emulsifier and/or wetting agent.

According to another preferred embodiment of the present invention, the composition according to the invention, as a concentrate, comprises from 0.002 to 5 % by weight preferably from 0.003 to 2 % by weight.

REPLACEMENT SHEET 26 1 1 1 WO 94/17664 ^ - 15 - PCT/EP94/00185 of component I, f from 0.01 to 20 % by weight preferably from 1 to 8 % by weight, of component II and from 2 to 85 % by weight preferably from 8 to 60 % by weight, of at least one organic chemical binder and/or plasticizer and/or fixing agent and a residual component consisting of an organic chemical solvent or solvent mixture or of a mixture of water and at least one organic chemical solvent and at least one emulsifier and/or wetting agent and, if desired, one or more dyes, color pigments, corrosion inhibitors, siccatives and/or stabilizers The present invention relates furthermore to a method of protecting industrial materials, especially wood and tinker materials, against damage or destruction by biological pests, especially wood-eating insects, in which the wood or the timber material is treated with an effective quantity of the composition according to the invention.

The treatment of the wood is carried out by applying the composition according to the invention to the wood by known methods, such as, for example, brushing, spraying, squirting, or using impregnating methods such as, for example, dipping, pressure, vacuum or double-vacuum methods.

The wood or the timber material is preferably treated with a quantity of from 0.5 to 2000 g, based on the synergistic active confound combination, per cubic meter of timber.

The composition according to the invention is used for controlling larval stages of wood-damaging and/or wood-destroying insects in industrial materials, especially wood and timber materials, which are already REPLACEMENT SHEET jn.z. patent office 47 JUL 199R RECEIVED 26 1 1 1 WO 94/17664 % - 16 - PCT/EP94/00185 infested by wood pests.

However, it can also be employed for tlie preventive protection against infestation of industrial materials/ especially wood and timber materials, by controlling larval stages; of wood-damaging and/or wood-destroying insects.

Furthermore, the composition according to the invention may additionally possess fungicidal properties, so that it has a preventive or controlling action against wood-discoloring, and/or wood-damaging and/or wood-destroying fungi, preferably against wood-destroying Basidiomycetes, for example Serpula lacrimals, Oloeophyllum spec., Poria spec., Lentinus spec., Donfcioporia expansa, especially Coniophora puteana, Poria placenta, Gloeophyllum trabeum and Coriolus versicolor, and against other wood-destroying and/or wood-discoloring blue stain fungi, for example Aureobasidium spec., Sclerophoma spec., Ceratocystis spec., Cladosporium spec., and mold fungi, for example Aspergillus spec., Penicillium funicolosum and Trichoderma viride, and soft rot fungi, for example Chaetomium globosum, Glenospora graphii, Humicola grisea, Petriella setifera, Phialophora mutabilis and Trichurus spiralis.

In this case the composition according to the invention preferably contains more than 0.25 % by weight of the fungicidal component II.

As primer coating composition, impregnating coating composition or as a stain, the composition according to the invention is employed preferably at an application rate of from 0.002 to 1 g, based on the synergistic active compound combination, per square meter of timber surface.

As a dipping or impregnating composition, it is employed preferably in an amount of from 30 to 150 g, based on the synergistic active compound combination, per cubic meter of timber.

REPLACEMENT SHEET n.z. patent office 17 JUL 1996 received WO 94/17664 - 17 - PCT/EP94/00185 Notes on the Figure Figure 1: Mortality In % after exposure for 4 weeks for the active compound flufenoxuron and for the active compound 5 combinations of flufenoxuron with the fungicides propiconazole, tebuconazole or azaconazole. The letters denote: D « flufenoxuron with azaconazole (Quantity of fungicide based in each case on the overall weight of the composition tested: 0.6 % by weight, 0.8 % by weight and 1.0 % by weight) A « flufenoxuron (3 g/m3) B a flufenoxuron with propiconazole C a flufenoxuron with tebuconazole Examples 1. Timber treatment composition for control Flufenoxuron Tebuconazole Fixing agent (polyglycols) Solvent (white spirit) 0.03 % by wt 0.7 % by wt. 3.0 % by wt. 96.27 % by wt. 2. Timber treatment composition with primer effect Flufenoxuron Tebuconazole Dichlofluanid 0.05 % by wt 0.9 % by wt. 0.6 % by wt. 12.0 % by wt. 86.45 % by wt Alkyd resin (solid) Solvent (white spirit) 3. Stain-type timber treatment composition Fluf enoxuron Tebuconazole Dichlofluanid 0.05 % by wt. 0.9 % by wt. 0.6 % by wt.

REPLACEMENT SHEET Pigment 3.0 % by wt.

Auxiliaries (wetting agents, siccatives, etc.) 3.0 % by wt.

Alkyd resin (solid) 23.0 % by wt.

Solvent (white spirit) 69.45 % by wt. 4. Synergistic activity of active compound combinations In the appended Fig. 1, the synergistic activity (stomach poison action; feeding test with boards) of the combinations flufenoxuron with propiconazole, 10 flufenoxuron with tebuconazole and flufenoxuron with azaconazole within the weight ratio of component I to component II which is claimed as preferable in accordance with the invention, namely from 1:10 to 1:15,000, against the wood pest Hylotrupes bajulus (house longhom beetle) 15 and (as comparison) the insecticidal activity of flufenoxuron alone against the abovementioned wood pest is shown in diagrammatic form.

In this test, component I, flufenoxuron, was combined with various quantities of the respective 20 triazole fungicides, the percentages indicated ( = percentages by weight) of the fungicidal component II relating to the overall weight of the composition.

The attached Table 1 again illustrates, in table form, the synergistic activity (stomach poison action; 25 feeding test with boards) of the combination flufenoxuron with propiconazole, flufenoxuron with tebuconazole and flufenoxuron with azaconazole within the weight ratio of component I to component II which is claimed as preferred in accordance with the invention, namely from 1:10 to 30 1:15,000, against the wood pest Hylotrupes bajulus (house longhom beetle) and (as comparison) the insecticidal activity of flufenoxuron alone against the abovementioned wood pest. In this test component I, flufenoxuron, was likewise combined with various quantities of the 35 respective triazole fungicides, the percentages indicated ( = percentages by weight) of the active components REPLACEMENT SHEET WO 94/17664 - 19 - PCT/EP94/00185 relating to the overall weight of the composition. The dimensionless numerical values of the table indicate the mortality rates of the insects tested in percent.

A particularly marked synergistic increase in action of the insecticidal benzoylurea compound was found in the tests carried out with a combination of flufenoxuron (0.00063 % by weight) with 0.6 % by weight of azaconazole and with 0.8 % by weight of azaconazole, respectively, and of flufenoxuron (0.00063 % by weight) with 1.0 % by weight of tebuconazole, as shown by the corresponding mortality rates which are reproduced in the table of Fig. 2.

For the combination of flufenoxuron (0.00063 % by weight) with 1.0 % by weight of azaconazole, moreover, a decrease in the synergistic effect can already be observed.

REPLACEMENT SHEET Table 1: Propiconazole Tebuconazole Azaconazole Flufenoxuron (0.00063 %) Fungicide (5 %) 0 0 0 Flufenox. + fungicide (0.6 %) 40 70 Flufenox. + fungicide (0.8 %) 50 70 Flufenox. + fungicide (1.0 %) 40 100 (Flufenox. = flufenoxuron) Mortility [sic] in %

Claims (31)

261112 WO 94/17664 - 21 - PCT/EP94/00185 Patent claims

1. A composition for protecting industrial materials 5 against damage or destruction by biological pests, which composition is based on at least one insecticidal active compound in addition to at least one diluent and/or solvent and, if desired, at least one organic chemical binder, 10 together if desired with at least one further active compound and, if desired, further processing auxiliaries and additives, characterized in that the insecticidal active compound (component I) is at least one. benzoylurea compound of the general 15 formula CO—NK—CO —NK—i )—R3 v "n in which the substituents have the following meaning: Rj is a halogen or hydrogen atom, R2 is a halogen atom, X is at each instance a hydrogen atom, a halogen atom, an 20 alkyl group, an alkyl group substituted by at least one halogen atom, an alkoxy group or an alkoxy group which is substituted by at least one halogen atom, halogen being in each case fluorine, chlorine or bromine, 25 m has the value 1, 2 or 3, the substituents X being identical or different, Y is at each instance a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted by at least one halogen atom, or an alkoxy group, where halogen in each 30 case is fluorine, chlorine or bromine, n.z. patent umot REPLACEMENT SHEET 17 M- 1996 ""rbcbved- 26 1 1 1 WO 94/17664 22 PCT/EP94/00185 n has the value 1, 2, 3 or 4, the substituents Y being identical or different, and R3 is a halogen atom or an alkyl group which is substituted by at least one halogen atom, halogen being fluorine, chlorine or bromine, or is a group of the formula -OR in which R is an alkyl group substituted by at least one halogen atom where halogen is fluorine, chlorine or bromine, or.R is a substituted phenyl radical of the formula in which each group Z is a hydrogen atari, a halogen atom:, an • alkyl, haloalkyl, polyhaloalkyl, alkoxy, haloalkoxy and/or polyhaloalkoxy group and p has the value 1, 2, 3 or 4, the substituents Z being identical or different and halogen being fluorine, chlorine or bromine; is a halogen atom or an alkyl group which is substituted by at least one halogen atom, halogen being fluorine, chlorine or bromine; and Q is the group CH or a nitrogen atom, and is present in the composition in a mixture with at least one triazole fungicide (component XX) in a quantity which produces a synergistic effect.

2. , A composition according to claim 1, characterized in that the triazole fungicide is azaconazole, tebuconazole and/or propiconazole.

3. A composition according to claims 1 or 2, characterized in that component X is a benzoylurea -compound of the general formula —— . Z. P n.2. patent office REPLACEMENT SHEET 17 JUL 1996 received WO 94/17664 - 23 - 26 lii2 PCT/EP94/00185 In which the substituents have the following meaning: Ra is a fluorine, chlorine or - hydrogen atom, R2 is a fluorine or chlorine atom, X is at each instance hydrogen ■, with m having the value 3 Y is at each instance a hydrogen, fluorine tsr chlorine atom, n has the value 1, 2, 3 or 4, the substituents Y being identical or different, and r3 is a fluorine or chlorine atom or a group of the formula -OR in which R is an alkyl group having up to 6 carbon atoms which is substituted by at least one halogen atom, halogen being fluorine, chlorine or bromine, or R is a substituted phenyl radical of the formula R4 is in which each group Z is a hydrogen, fluorine or chlorine atom and p has the value 1, 2, 3 or. 4, the substituents Z being identical or different an alkyl group having up to 6 carbon atoms which is substituted by at least one halogen atom, the abovementioned halogen atoms being fluorine and/or chlorine; and Q is the group CH or a nitrogen atom.

A composition according to any one of claims 1 to 3, characterized in that component I is REPLACEMENT SHEET [n.z. patent office 17 JUL 1996 "received - 24 - flufenoxuron, hexaflumuron or triflumuron.

5. A composition according to any one of claims 1 to 4, characterized in that the weight ratio of component I to component II is from 1:2 to 1:20,000.

6. A composition according to claim 5, characterized in that the weight ratio of component I to component II is from 1:10 to 1:15,000.

7. A composition according to any one of claims 1 to 6, characterized in that the composition contains up to 99.94995 % by weight of a mixture comprising at least one organic chemical binder and/or plasticizer and/or fixing agent and at least one diluent and/or at least one solvent and/or at least one emulsifier and/or at least one wetting agent.

8. A composition according to any one of claims 1 to 7, characterized in that the diluent and/or solvent comprises an organic chemical solvent or solvent mixture or a mixture of water and/or at least one organic chemical solvent and/or at least one emulsifier and/or wetting agent.

9. A composition according to claim 8, characterized in that the organic chemical solvent .or solvent mixture is oily of low volatility.

10. A composition according to any one of claims 1 to 9, characterized in that the organic chemical binder is replaced wholly or partially by at least one fixing agent and/or at least one plasticizer. 2611 12 - 25 -

11. A composition according to anyone of claims 1 to 10, characterized in that it comprises, as a ready-to-use composition, from 0.00005 to 0.5% by weight of component I, from 0.05 to 2% by weight of component II, from 0.9 to 40 % by weight of at least one organic chemical binder and/or plasticizer and/or fixing agent, from 0 to 8% by weight of at least one water-soluble dye and/or water-insoluble dye, colored pigment and/or corrosion inhibitor, siccative and/or stabilizer and from 44 to 99% by weight of a diluent, consisting of an organic chemical solvent or solvent mixture or of a mixture of water and at least one emulsifier and/or wetting agent.

12. A composition according to claim 11, characterized in that it comprises from 0.0001 to 0.2% by weight of component I.

13. A composition according to claim 11, characterized in that it comprises from 0.25 to 1.5% by weight of component II.

14. A composition according to claim 11, characterized in that it comprises from 3 to 33% by weight of at least one organic chemical binder and/or plasticizer and/or fixing agent.

15. A composition according to claim 11, characterized in that it comprises from 0.l to 4% by weight of at least one water-soluble dye and/or water-insoluble dye, colored pigment and/or corrosion inhibitor, siccative and/or stabilizer. n.z patent office 17 JUL 1996 received 261 1 1 2 - 26-

16. A composition according to claim 11, characterized in that it comprises from 58 to 95% by weight of a diluent, consisting of an organic chemical solvent or solvent mixture or of a mixture of water and at least one emulsifier and/or wetting agent.

17. A composition according to any one of claims 1 to 10, characterized in that, as a concentrate, it comprises from 0.002 to 5% by weight of component I, from 0.01 to 20% by weight of component XI and from 2 to 85% by weight of at least one organic chemical binder and/or plasticizer and/or fixing agent and a residual component consisting of an organic chemical solvent or solvent mixture or of a mixture of water and at least one organic chemical solvent and at least one emulsifier and/or wetting agent and, if desired, one or more dyes, color pigments, corrosion inhibitors, siccatives or stabilizers.

18. A composition according to claim 17, characterized in that it comprises from 0.003 to 2% by weight of component I.

19. A composition according to claim 17, characterized in that it comprises from 1 to 8% by weight of component II.

20. A composition according to claim 17, characterized in that it comprises from 8 to 60% by weight of at least one organic chemical binder and/or plasticizer and/or fixing agent and a residual component consisting of an organic chemical solvent or solvent mixture or of a mixture of water and at least one organic chemical solvent and at least one emulsifier and/or wetting agent and, if desired, one or more dyes, color pigments, 261112 27

21. A method of protecting industrial materials selected from wood and timber material against damage or destruction by biological pests, characterized in that the wood or the timber material is treated with an effective quantity of a composition according to one or more of claims l to 20.,

22. A method according to claim 21, characterized in that the wood or the timber material is treated with a composition according to any one of claims 1 to 20 in a quantity of from 0.5 to 2000 g, based on the synergistic active compound combination, per cubic meter of wood. .

23. Use of the composition according to any one of claims 1 to 20, for controlling larval stages of wood-damaging and/or wood-destroying insects in industrial materials.

24. Use of the composition according to any one of claims 1 to 2 0 for the preventive protection of industrial materials by controlling larval stages of wood-damaging and/or wood destroying insects.

25. Use of the composition according to claim 23 or claim 24, characterized in that the composition additionally possesses fungicidal properties and is employed against wood-diecoloring, and/or wood-damaging and/or wood-destroying fungi. .

26. Use of the composition according to claim 25, characterized in that the composition contains more than 0.25% by weight of the fungicidal component II.

27. Use of the composition according to any one of claims 1 to 2 0 as a primer coating composition, an imnrpcrnat- i-ng l coating composition or as a stain at an applicatioEf^r^e0'*'/^ of from 0.002 to 1 g, based on the synergistic active compound combination, per square meter of wood siMr^'-*® 2fi 1 1 1 2 28

28. Use of the composition according to any one of claims 1 to 20 as a dipping or impregnating composition in a quantity of from 3 0 to 150 g, based on the synergistic active compound combination, per cubic meter of wood.

29. A composition for protecting industrial materials /' according to any one of claims 1 to 20 substantially as herein described with reference to the Examples.

30. A method of protecting industrial materials using a composition of any one of claims 1 to 20 substantially ( as herein described.

31. Use of a composition according to any one of claims 1 to 20 substantially as herein described. n.z. patent ow-t: 17 JUL 1996 received J