WOOD PRESERVATIVES FOR INCORPORATION INTO BINDERS

Abstract: The application relates to mixtures of binders or adhesives which can be employed for the manufacture of plywood and timber materials with compounds of general formula (I) in which R represents hydrogen, optionally substituted radicals of the group consisting of acyl, alkyl, aryl, aralkyl, heteroaryl and heteroarylalkyl; A represents a monofunctional group from the series hydrogen, acyl, alkyl, aryl, or represents a bifunctional group which is linked to the radical Z; E represents an electron-withdrawal radical; X represents the radicals -CH= or =N-, it being possible for the radical -CH= to be linked to the radical Z instead of an H atom; Z represents a monofunctional group from the series alkyl, -O-R, -S-R, (a) or represents a bifunctional group which is linked to the radical A or the radical X; the compound Imidocloprid being particularly preferred.

Description: Wood preservatives for incorporation into binders The application relates to wood preservatives which can be employed in the manufacture of plywood and timber materials. Plywood and timber materials such as, for example, chipboards are in general treated with wood preservatives by two methods. Firstly, by treating the wood with wood preservatives before processing to give timber materials and secondly, by impregnating the surface of the finished timber materials, e.g. by pressure. Both processes in general lead to deformations and swellings in the sheet treated in this way. On the other hand, it is known that a process for the manufacture of plywood sheets would be most efficient if insecticides, termiticides and fungicides could be incorporated directly into the adhesives during sheet manufacture. Using the wood preservatives known until now, however, this was not possible until now as these compositions decompose or evaporate under the process conditions necessary for the manufacture of the sheets. The compositions according to the invention do not have these disadvantages. The application therefore relates to mixtures of binders or adhesives which can be employed for the manufacture of plywood and timber materials with compounds of the general formula (I) ΛA) R — Z) c (I) II X E in which R represents hydrogen, optionally substituted radicals of the group consisting of acyl, alkyl, aryl, aralkyl, heteroaryl and heteroarylalkyl; A represents a monofunctional group from the series hydrogen, acyl, alkyl, aryl, or represents a bifunctional group which is linked to the radical Z; E represents an electron-withdrawal radical; X represents the radicals -CH= or =N-, it being possible for the radical -CH= to be linked to the radical Z instead of an H atom; Z represents a monofunctional group from the series alkyl, -O-R, -S-R, or represents a bifunctional group which is linked to the radical A or the radical X. Particularly preferred compounds of the formula (I) are those in which the radicals have the following meaning: R represents hydrogen and optionally substituted radicals from the series acyl, alkyl, aryl, aralkyl, heteroaryl, heteroarylalkyl. Acyl radicals which may be mentioned are formyl, alkylcarbonyl, arylcarbonyl, alkylsulphonyl, arylsulphonyl, (alkyl-)-(aryl-)-phosphoryl, which for their part can be substituted. Alkyl which may be mentioned is specifically methyl, ethyl, i-propyl, sec- or t-butyl, which for their part can be substituted Aryl which may be mentioned is phenyl, naphthyl in particular phenyl. Aralkyl which may be mentioned is phenylmethyl, phenethyl. Heteroaryl, which may be mentioned is heteroaryl having up to 10 ring atoms and N, O, S, in particular N, as heteroatoms. Thienyl, furyl, thiazolyl, imidazolyl, pyridyl, benzothiazolyl may specifically be mentioned. Heteroarylalkyl which may be mentioned is heteroarylmethyl, heteroarylethyl having up to 6 ring atoms and N, O, S, in particular N, as heteroatoms. Substituents which may preferably be mentioned by way of example are: alkyl preferably having 1 to 4, in particular 1 or 2, carbon atoms, such as methyl, ethyl, n- and i-propyl and n-, i- and t-butyl; alkoxy preferably having 1 to 4, in particular 1 or 2 carbon atoms, such as methoxy, ethoxy, n- and i-propyloxy and n-, i- and t-butyloxy; alkylthio preferably having 1 to 4, in particular 1 or 2 carbon atoms, such as methylthio, ethylthio, n- and i-propylthio and n-, i- and t-butylthio; halogenoalkyl preferably having 1 to 4, in particular 1 to 2 carbon atoms and preferably 1 to 5, in particular 1 to 3 halogen atoms, the halogen atoms being identical or different and, as halogen atoms, are preferably fluorine, chlorine or bromine, in particular fluorine, such as trifluoromethyl; hydroxy; halogen, preferably fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine; cyano; nitro; amino; monoalkyl- and dialkylamino preferably having 1 to 4, in particular 1 or 2 carbon atoms per alkyl group, such as methylarnino, methyl-ethyl-amino, n- and i-propylamino and methyl-n-butylamino; carboxyl; carbalkoxy preferably having 2 to 4, in particular 2 or 3 carbon atoms, such as carbomethoxy and carboethoxy; sulpho (-SO3H); alkylsulphonyl preferably having 1 to 4, in particular 1 or 2 carbon atoms, such as methylsulphonyl and ethylsulphonyl; arylsulphonyl preferably having 6 or 10 aryl carbon atoms, such as phenylsulphonyl, and heteroarylamino and heterarylalkylamino such as chloropyridylamino and chlorpyridylmethylamino. particularly represents hydrogen and optionally substituted radicals from the series acyl, alkyl, aryl, which preferably have meanings given in the case of R. A furthermore represents a bifunctional group. Optionally substituted alkylene have 1-4, in particular 1-2, C atoms may be mentioned, whereas substituents the substituents listed further above may be mentioned and where the alkylene groups can be interrupted by heteroatoms from the series N, O, S. A and Z, together with the atoms to which they are bonded, can form a saturated or unsaturated cyclic ring. The heterocyclic ring can contain a further 1 or 2 identical or different heteroatoms and/or heterogroups. Heteroatoms are preferably oxygen, sulphur or nitrogen and heterogroups are N-alkyl, alkyl of the N-alkyl group preferably containing 1 to 4, in particular 1 or 2 carbon atoms. Alkyl which may be mentioned is methyl, ethyl, n- and i-propyl and n-, i- and t-butyl. The heterocyclic ring contains 5 to 7, preferably 5 or 6, ring member. Examples of the heterocyclic ring which may be mentioned are imidazolidine, pyrrolidine, piperidine, piperazine, hexamethylenimine, hexahydro-l,3,5-triazine, hexahydrooxodiazine, morpholine, each of which, if appropriate, may preferably be substituted by methyl. E represents an electronic-withdrawing radical, where in particular NO 2 , CN, halogenalkylcarbonyl such as l,5-halogeno-Cι_ 4 -carbonyl, in particular COCF 3 , may be mentioned. X represents -CH= or -N= Z represents optionally substituted radicals alkyl, -OR, -SR, -NRR, R and the substituents preferably having the meaning given above. Z can additionally to the abovementioned ring, together with the atom to which it is bonded and the radical form a saturated or unsaturated heterocyclic ring in the position of X. The heterocyclic ring can contain a further one or two identical or different heteroatom and/or heterogroups. Heteroatoms and preferably oxygen, sulphur or nitrogen and heterogroups are N-alkyl, the alkyl or N-alkyl group preferably containing 1 to 4, in particular 1 or 2, carbon atoms. Alkyl which may be mentioned is methyl, ethyl, n- and i-propyl and n-, i- and t-butyl. The heterocyclic ring contains 5 to 7, preferably 5 or 6, ring members. Examples of the heterocyclic ring which may be mentioned are pyrrolidine, piperidine, piperazine, hexamethylenimine, morpholine and N-methylpiper- azine. Very particularly preferred compounds which may be mentioned are compounds of the general formulae (II) and (III): in which represents 1 or 2, Subst. represents one of the abovementioned substituents, in particular halogen, very particularly chlorine, A, Z, X and E have the meanings given above. The following compounds may be mentioned specifically: (IVa) (IVb) CH, (IVC) (IVd) (IVe) (IVf) (IVi) (IVj) (IVh) (IV1) (IVm) (IVn) (IVo) (IVp) (IVq) (IVr) (IVs) (IVt) (IVu) (IVv) the compound of the formula (IVa), imidacloprid, being particularly preferred. Glues and adhesives are regarded as binders which are employed for the manufacture of plywood sheets and timber material sheets. In the manufacture of wood composites, typically the following bonding agents are used: glues based on urea/formaldehyde, urea/melamine, isocyanates such as MDI, phenol/formaldehyde, phenol/resorcinol/formaldehyde, or urea/resorcinol/form- aldehyde. Normally, the bonding agents are prepared by mixing the glues with water, curing agents, and if desired with water repellents, biocides, extenders and/or buffering agents prior to the application to the wood particles, flakes or veneers. In addition to the active compounds of the formula (II), further biocides, such as, for example, other insecticides, and in particular fungicides having an action against Basi- diomycetes and moulds, can be incorporated into the bonding agent. Timber material sheets in this case are artificial wood sheets, such as, for example, plywood sheets, chipboards and fibreboards, which in general are manufactured from cut pieces of wood and a binder under pressure and with heat treatment. The active compounds are mixed with these binders such that either finished formulations are obtained which can be employed directly in the sheet manufacturing process, or the active compounds are added during or shortly before sheet manufacture. The amount of active compound and binder is calculated from the volume of the manufactured sheets according to generally known methods. The active compounds can be incorporated into a wood composite through a number of routes, for example: 1. Treatment of the flakes/wood particles, before or after drying, using an additional sprayhead or blender system. 2. Mixing the chemical with the adhesive and/or wax which is subsequently applied to the flakes in the blender. 3. Spraying the flakes with a preservative solution or emulsion, or mixing the powdered chemical with the flakes in the blender. 4. Metering a powdered preservative onto the dried flakes immediately before the blender. The powder is then mixed with the flakes in the blender Adding the chemical as a mixture with the adhesive or wax is probably the most convenient from the manufacturer's viewpoint. However, mixing the active compounds with the adhesive can cause biocide efficacy problems, especially, when the biocide is decomposed in the adhesive by hydrolyzation or other chemical reactions. Incorporation with the wax is safer, but often the wax distribution is not as good as that of the adhesive. This in turn may also influence the effectiveness of the biocide. The active compounds can either be added as they are to the glue or in a preformulated form, for example prediluted in solvents, e.g. glycols, glycol ethers, aliphatic and/or aromatic hydrocarbons, esters, alcohols or ketones, or emulsified or dispersed in water. Alternatively, the active compounds or formulations thereof can be applied to the wood particles, flakes or veneers separately from the glue either to the wood particles before blending with the glue or after blending with the glue or even after the gluing process, i.e. to the finished wood composite. The invention furthermore also relates to incorporating, additionally to the active compounds of the formula (II) and the binder, still further active compounds such as, 1 for example, other insecticides, but in particular fungicides having action against Basidiomycetes, into the plywood and timber material sheets. Preferred fungicides are IF- 1000, IPBC and azoles such as tebuconazole, propiconazole and cyproconazole. In combination with the active compounds of the formulae Ila) to Hi), these mixtures have particularly good activities and stabilities. The following examples substantiate the invention without limiting it to these examples. The results show experiments against termites, chipboard being employed which are manufactured using a formulation of a strongly alkaline phenolic resin containing the compound of the formula (IVa) Type of wood for plywood Radiata pine Layer structure 1.5 mm + 3.0 mm + 1.5 mm (3 layers) Dosage a) 1.5 kg/m 3 b) 2.0 kg/m 3 c) 2.5 kg/m 3 Binder a) Phenol resin adhesive A b) Phenol resin adhesive B Manufacturing process Quantity of paste 40 g/900 cm 2 125°C, 10 kg/cm 2 , 6 minutes Example 1 Example 2 Assessment The test is carried out in accordance with JWPA Standard No. 11. 150 termite workers and 15 termite soldiers were put for 21 days into a container which contains a test piece of chipboard. Example 3 (Phenol resin A) Example 4 (Phenol resin B) Example 5 Various sheets consisting of chips are manufactured: Type of wood: Albizzia (broad leaf tree pro Chip size: 5-10 mesh 9 % 10-20 mesh 40 % 20-40 mesh 30 % 40-60 mesh 9 % 60-80 mesh 5 % 80 - mesh 6 % Manufacturing process: Sheet size 30 x 30 x 1 cm Sheet thickness 0.7 Composition of the sheet Chip 500 Urea resin 50 g Curing agent 0.85 g Wood preservative (see Table) Pressure conditions 30 kg/cm 2 for 5 minutes 10 kg/cm 2 for 5 minutes Mechanical strength of the sheets Anti-termite action Viscosity of the mixture of resin and active compound

Claims: Patent claims 1. Compositions containing at least one compound of the formula (I) ,(A) R- -N - (Z) \ c (I), II x- in which R represents hydrogen, optionally substituted radicals of the group consisting of acyl, alkyl, aryl, aralkyl, heteroaryl and heteroarylalkyl; A represents a monofunctional group from the series hydrogen, acyl, alkyl, aryl, or represents a bifunctional group which is linked to the radical Z; E represents an electron-withdrawing radical; X represents a monofunctional group from the series alkyl, -O-R, -S-R, Z represents a monofunctional group from the series consisting of alkyl, -O-R, -S-R, -N R or represents a bifunctional group which is linked to the radical A or the radical X, and binders or adhesives which can be employed for the manufacture of chipboards and timber material. 2. Use of compounds of the general formula (I) .(A) R- -N - (Z) \ X E (I), in which R represents hydrogen, optionally substituted radicals of the group consisting of acyl, alkyl, aryl, aralkyl, heteroaryl and heteroarylalkyl; A represents a monofunctional group from the series hydrogen, acyl, alkyl, aryl, or represents a bifunctional group which is linked to the radical Z; E represents an electron-withdrawing radical;; X represents the radicals -CH= or =N-, it being possible for the radical -CH= to be linked to the radical Z instead of an H atom; Z represents a monofunctional group from the series alkyl, -O-R, -S-R, / R -N R or represents a bifunctional group which is linked to the radical A or the radical A or the radical X, for the manufacture of chipboards and timber materials.. 3. Chipboards and timber materials comprising a compound of the formula (I) according to Claim 1.

Inventors: BUSCHHAUS HANS-ULRICH, EXNER OTTO, FUSHIKI SEIKO, BUSCHHAUS, HANS-ULRICH, EXNER, OTTO, FUSHIKI, SEIKO
Applicants: BAYER AG, BUSCHHAUS HANS ULRICH, EXNER OTTO, FUSHIKI SEIKO, KEMIHOLZ CO LTD, BAYER AKTIENGESELLSCHAFT, BUSCHHAUS, HANS-ULRICH, EXNER, OTTO, FUSHIKI, SEIKO, KEMIHOLZ CO. LTD.
Application year: 1997
Main classification: A01N51
IPC codes: A01N43, A01N51, B27D1, B27N3, C09J11, C09J201