AU736300B2

AU736300B2 - Wood preservatives for incorporation into binders

Info

Publication number: AU736300B2
Application number: AU50511/98A
Authority: AU
Inventors: Hans-Ulrich Buschhaus; Otto Exner; Seiko Fushiki
Original assignee: KEMIHOLZ CO Ltd; Bayer AG
Current assignee: KEMIHOLZ CO Ltd; Lanxess Deutschland GmbH
Priority date: 1996-10-31
Filing date: 1997-10-20
Publication date: 2001-07-26
Anticipated expiration: 2017-10-20
Also published as: EP0935416A1; AU5051198A; KR20000049019A; JP2001508406A; DE19644008A1; CA2269948A1; NZ335434A; JP4223558B2; WO1998018328A1; CN1235515A

Description

WO 98/18328 PCT/EP97/05776 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.

15 Using the wood preservatives known until now, however, this was not possible until S.I. now as these compositions decompose or evaporate under the process conditions necessary for the manufacture of the sheets.

*1I* The compositions according to the invention do not have these disadvantages.

The application therefore relates to compositions comprising at least one compound of .the formula (I) oooo

(Z)

c.

II

X-E

in which R represents hydrogen, optionally substituted radicals of the group consisting of acyl, alkyl, aryl, aralkyl, heteroaryl and heteroarylalkyl; WO 98/18328 PCT/EP97/05776 2 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 it being possible for the radical -CH= to be linked to the radical Z instead of a H atom; Z represents a monofunctional group from the series consisting of alkyl, -O-R,

-S-R,

R

-N

R

or represents a bifunctional group which is linked to the radical A or the radical X, and at least one binder or adhesive selected from the group consisting of urea/formaldehyde, urea/melamine, isocyanates, phenol/formaldehyde, phenol/resorcinol/formaldehyde and urea/resorcinol/formaldehyde.

Particularly preferred compounds of the formula are those in which the radicals have the following meaning: R represents hydrogen and optionally substituted radicals from the series acyl, alkylary-aralkylheteroaryl- hteroarylallyl- Acyl radicals which may be mentioned are formyl, alkylcarbonyl, arylcarbonyl, alkylsulphonyl, arylsulphonyl, (alkyl-)-(aryl-)-phosphoryl, which for their part can be substituted.

P:IWPDOCS CRNMSPEC72222.baymd=-24oc-IMY -2a- Akyl which may be mentioned is CI-0-alkyl, in particular C1alkyl, specifically methl. 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.

WO 98/18328 PCT/EP97/05776 3 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 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 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 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 methylamino, 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 carbomethoxyand carboethoxy; sulpho.

(-SO

3 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.

A particularly represents hydrogen and optionally substituted radicals from the series acyl, alkyl, aryl, which preferably have meanings given in the case of R.

WO 98/18328 PCT/EP97/05776 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-1,3,5-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 1,5-halogeno-C 1 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

C-

WO 98/18328 PCT/EP97/05776 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 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-methylpiperazine.

Very particularly preferred compounds which may be mentioned are compounds of the general formulae (II) and (III): Subst. H (CH 2 N C (II) I I

X-E

Subst.H-

(A)

(CH2 C (III),

II

X--E in which n represents 1 or 2, Subst. represents one of the abovementioned substituents, in particular halogen, very particularly chlorine, WO 98/18328 6 AZ, X and E have the meanings given above.

The following compounds may be mentioned specifically: PCT/EP97/05776 /i CHi--N NH N0 2 NH 2 11 N-NO 2 (IVa) (IVb) I/

-I

CH--N S

N-N

NO 2 (IVc) 1 CHF- N

CH

3

NN)

.N,,,N-CH

3 CH2 C1xLS N -N0 (IVd) 0 -N HOC 2

H,

N S-CH-CHA NO 2 CH 3 (IVe) (IVf) /14_ -CH--N NH

NC

/I H C -CH-N NHCH 3

N-NO

2 (1Vi)(Ij (lVj) WO 98/18328 WO 9818328PCTIEP97/05776 I/ N c I CHT-N s N ci '\CH-N

S

N2> N- O2 (IVh) c ICH--N

NH

CH

NO 2 (lVI)

N(CH)

2 11 CH-N0 2 (IVm) (IVn) c N NH C 1NO 2 (IVo) CI

OH

2 N Y -H N-NO 2 (IVq)

CH

3 CI ~CH-N

N(CH

3 2

N-NO

2 (IVp) N NN2 (IVr)

CH

3 Cf

CH

2 N -OHs

NO

2 (lVt)

CH

3 I/

I

(IVs) WO 98/18328 PCTIEP97/05776 8 2

H

Cl CH -N -C-NHCH CI CH

H

3

CNO

2

I

N CN (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, 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- *o* i 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 15 buffering agents prior to the application to the wood particles, flakes or veneers. In addition to the active compounds of the formula further biocides, such as, for example, other insecticides, and in particular fungicides having an action against Basio- diomycetes and moulds, can be incorporated into the bonding agent.

20 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 acut pieces of wood and a binderunderpressure-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.

WO 98/18328 PCT/EP97/05776 9 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,_g!ycol 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, WO 98/18328 PCT/EP97/05776 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 IIa) to IIi), these mixtures have particularly good activities and stabilities.

The following examples substantiate the invention without limiting it to these examples.

0 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 Layer structure Dosage Binder_ Manufacturing process Radiata pine 1.5 mm 3.0 mm 1.5 mm (3 layers) a) 1.5 kg/m 3 b) 2.0 kg/m 3 c) 2.5 kg/m 3 a) Phenol resin adhesive A b) Phenol resin adhesive B Quantity of paste 40 g/900 cm 2 125 0 C, 10 kg/cm 2 6 minutes Example 1 Dose rate Blank 1.5 kg 2.0 kg 2.5 kg g ai)/m 3 kg (40 g ai)/m 3 (50 g ai)/m 3 Phenol resin A 250.0 g 250.0 g 250.0 g 250.0 g Flour -4.2 g 4.2 g 4.2 g 4.2 g Walnut powder 20.8 g 20.8 g 20.8 g 20.8 g Sodium 3.3 g 3.3 g 3.3 g 3.3 g WO 98/18328 PCT/EP97/05776 carbonate Curing agent 5.8 g 5.8 g 5.8 g 5.8 g Wood 6.3 g 8.5 g 10.7 g preservative Example 2 Dose rate Blank 1.5 kg 2.0 kg 2.5 kg g ai)/m 3 (40 g ai)/m 3 (50 g ai)/m 3 Phenol resin B 250.0 g 250.0 g 250.0 g 250.0 g Flour 30.0 g 30.0 g 30.0 g 30.0 g Sodium 20.0 g 20.0 g 20.0 g 20.0 g carbonate Curing agent 5.0 g 5.0 g 5.0 g 5.0 g Wood 6.3 g 8.5 g 10.7 g preservative 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) Dose rate weight loss mortality Blank 14.20 16.0 kg (30 g ai)/m 3 2.50 57.5 kg (40 g ai)/m 3 1.35 100.0 kg (50 g ai)/m 3 1.50 100.0 WO 98/18328 PCT/EP97/05776 12 Example 4 (Phenol resin B) Dose rate weight loss mortality Blank 21.90 20.0 kg (30 g ai)/m 3 0.55 49.0 kg (40 g ai)/m 3 0.00 100.0 kg (50 g ai)/m 3 0.00 100.0 Example Various sheets consisting of chips are manufactured: Type of wood: Chip-size: Albizzia (broad leaf tree produced in Indonesia) 5-10 mesh 9% 10-20 mesh 40 20-40 mesh 30 40-60 mesh 9% 60-80 mesh 5 mesh 6% Manufacturing process: Sheet size Sheet thickness Composition of the sheet Pressure conditions 30 x 30 x cm 0.7 Chip 500 g Urea resin 50 g Curing agent 0.85 g Wood preservative (see Table) 30 kg/cm 2 for 5 minutes kg/cm 2 for 5 minutes WO 98/18328 WO 9818328PCT/EP97/05776 Mechanical strength of the sheets Dose rate Blank 13 9 g/cm' 208 g/m' 833 g/m 3 Specific gravity 0.75 0.73 0.71 0.75 Peeling strength 6.0 5.0 5. 1 (kg/cm 2 Flectural strength (kg/cm 2 80.0 72.0 65.0 86.0 Anti-termite action Chemical name Dose rate weight loss mortality Worker Soldier termite termite Blank 5.73 22.0 76.7 Chiorpyriphos 350 g/M 3 0.07 100.0 100.0 520 g/M 3 0.17 100.0 100.0 690 g/Fm 3 0.07 100.0 100.0 Imidacloprid 70 g/m 3 0.00 100.0 100.0 104 g/m 3 0.00 100.0 100.0 138 g/Im 3 0.00 100.0 100.0 Imidacloprid 70 g/m 3 0.00 100.0 100.0 [BC 104 g/m 3 0.00 100.0 100.0 138 g/m n 3 0.00 100.0 100.0 K11 WO 98/18328 PCT/EP97OS776 14 Viscosity of the mixture of resin and active compound 4 9* 999 I 9 a.

9 9 9 9 4*9 4 9 9.

4 9 999 9 999999 9 4* 9 9 999 9 *999 4

S

9.94 9 4* 9 9.

9.

i 9 Temp. Just I day 5 days 10 days 15 days 20 days 25.days after--F das Blank 5 0 C 11.0 11.1 11.5 12.0 12.4 13.2 13.5 0 C 2.0 2.3 2.5 3.1 4.0 5.0 1.1 1.4 2.2 4.8 12.3 N/T NIT Imid- 5 0 C 11.0 11.2 11.5 12.2 12.6 132 13.6 acloprid 20 0 C 2.2 2.3 2.5 2.9 4.0 5.3 6.4 300(C 1.1 -1.6 2.5 4.7 12.5 N/T N/T Imid- -50(2 10.8 11.0 11.4 12.1 12.1 13.1 13.5 acloprid 200C2 2.2 2.3 2.6 3.0 4.2 5.0 6.7 .300C2 1.0 1.0 2.3 5.0 12.3 N/T N/T Irnid- 50(2 11.0. 11.1 11.5 12.2 12.4 13.1 13.5 acloprid 200C2 2.2 2.4 2.7 3.2 4.1 5.2 (15) 300C2 1.1 1-4 2.3 4.8 12.4 NIT N/T Imnid- 50C2 11.0 11.3 11.6 12.4 12.9 13.6 14.0 acloprid 20 0 C 2.2 2.3 2-6 3.2 4.0 4.9 6.6 300C2 1.1 1.4 2.5 4.8 12.7 N/T N/T The reference to any prior art in this specification is not, and should not be taken as, an -acknowledgement or any form of suggestion that the prior art forms part of the c--0Mommofgeneral-knowedgenAstrali Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers or steps but not the exclusion of any other integer or group of integers or steps.

Claims

1. Compositions comprising at least one compound of the formula (1) R-N X-E 'I 10 0 0 .@S Go 0 *00 *0 0 0006 in which R represents hydrogen. optionally substituted radicals of the group consisting of acyl, alkyl, aryl, aralkyl, heteroaryl and heteroarylalkyl; A represents a monoflinctional group from the series hydrogen, acyl, ailkyl, aryl, or represents a bifuinctional group which is linked to the radical Z; Erepresents an electron-withdrawing radical; X represents the radicals -CH= or it being possible for the radical -C.H=to belinkced to the radical. Z instead of a H atom;1 Z represents a inonofunictiona] group from the series consisting of alkyl, -OR1,- -N or represents a bifijnctionil -group which islinked to the radical A or the radical X and at least one binder or adhesive selected from the group of urea/formaldehyde, urea/melamine, isocyanates, phenol/formaldehyde, phenol/resorcinol/formaldehyde and urea/resorcinol/formaldehyde. WO 98/18328 PCT/EP97/05776 16

2. Use of compositions according to claim 1 for the manufacture of plywood and timber materials.

3. Plywood and timber materials manufactured by employing compositions according to Claim 1.

4. Compositions containing at least one compound of the formula uses thereof or plywood and timber materials manufactured by employing said compositions, substantially as hereinbefore described with reference to the Examples. S 10 DATED this 29th day of September, 2000 BAYER AKTIENGESELLSCHAFT AND KEMIHOLZ CO LIMITED By their Patent Attorneys DAVIES COLLISON CAVE S 20 S WO 98/18328 PCT/EP97/05776 3. Chipboards and timber materials comprising a compound of the formula (1) according to Claim 1.