KR20000049019A - Wood preservatives for incorporation into binders - Google Patents

Abstract

PURPOSE: Wood preservative(s) for incorporation into binders is prepared, which is safe in mixing active compounds with the adhesive free of biocide efficacy problems, especially when the biocide is decomposed in the adhesive by hydrolyzation or other chemical reactions. CONSTITUTION: Wood preservatives for incorporation into binders 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 present application relates to wood preservatives that can be used to make plywood and timber materials.

Timber materials such as plywood and cardboard are generally treated with wood preservatives in two ways. Firstly, the wood is treated with wood preservatives prior to processing to obtain timber material, and secondly, the surface of the final timber material is impregnated with wood preservatives, for example by compression. Deformation and expansion generally occur in sheets treated by both methods. On the other hand, methods for making plywood sheets are known to be most effective if pesticides, termite remedies and fungicides can be incorporated directly into the adhesive during sheet manufacture.

However, this is not yet possible as these compositions decompose or evaporate under the process conditions necessary for sheet production with the use of wood preservatives known to date.

The composition according to the invention does not have this disadvantage.

Accordingly, the present application relates to a mixture of a compound of formula (I) with a binder or adhesive that can be used to prepare plywood and timber materials:

Where

R represents hydrogen or an optionally substituted radical selected from the group consisting of acyl, alkyl, aryl, aralkyl, heteroaryl and heteroarylalkyl,

A represents a monofunctional group selected from the group consisting of hydrogen, acyl, alkyl and aryl, or represents a bifunctional group bonded to radical Z,

E represents an electron-withdrawing group,

X represents radical -CH = or = N-, wherein radical -CH = can be bonded to radical Z instead of H atom,

Z is alkyl, -OR, -SR and Represents a monofunctional group selected from the group consisting of or a bifunctional group bonded to radical A or radical X.

Particularly preferred compounds of formula (I) are those in which the radicals have the following meanings:

R represents hydrogen or an optionally substituted radical selected from the group consisting of acyl, alkyl, aryl, aralkyl, heteroaryl and heteroarylalkyl.

Acyl radicals may include formyl, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, (alkyl-)-(aryl-)-phosphoryl, some of which may be substituted.

Alkyl may be mentioned C _1-10 -alkyl, in particular C _1-4 -alkyl, in particular methyl, ethyl, i-propyl, sec- or t-butyl, some of which may be substituted.

As aryl, mention may be made of phenyl, naphthyl, in particular phenyl.

Aralkyl may be mentioned phenylmethyl, phenylethyl.

Heteroaryls may be mentioned with up to 10 ring atoms and heteroaryls having N, O, S, in particular N, as hetero atoms. Specifically mention may be made of thienyl, furyl, thiazolyl, imidazolyl, pyridyl, benzothiazolyl.

Heteroarylalkyl may be mentioned heteroarylmethyl having up to 6 ring atoms and N, O, S, in particular N, heteroarylethyl as hetero atoms.

Substituents which may be mentioned as preferred are preferably alkyl 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; Preferably alkoxy having 1 to 4, especially 1 or 2 carbon atoms, such as methoxy, ethoxy, n- and i-propyloxy and n-, i- and t-butyloxy; Preferably alkylthio having 1 to 4, especially 1 or 2 carbon atoms, such as methylthio, ethylthio, n- and i-propylthio and n-, i- and t-butylthio; Preferably 1 to 4, in particular 1 to 2 carbon atoms and 1 to 5, in particular 1 to 3, identical or different halogen atoms such as trifluoromethyl, wherein the halogen atoms are preferably fluorine, chlorine or Halogenoalkyl with bromine, especially fluorine; Hydroxy; Halogen, preferably fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine; Cyano; Nitro; Amino; Monoalkyl- and dialkylamino having preferably 1 to 4, in particular 1 or 2 carbon atoms per alkyl group such as methylamino, methylethylamino, n- and i-propylamino and methyl-n-butylamino; Carboxyl; Carboalkoxy, preferably having 2 to 4, especially 2 or 3 carbon atoms, such as carbomethoxy and carboethoxy; Sulfo (-SO ₃ H); Alkylsulfonyl having preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methylsulfonyl and ethylsulfonyl; Arylsulfonyl, preferably having 6 or 10 aryl carbon atoms, such as phenylsulfonyl; And heteroarylamino and heteroarylalkylamino such as chloropyridylamino and chloropyridylmethylamino.

A represents in particular hydrogen, or optionally substituted radicals selected from the group consisting of acyl, alkyl and aryl, preferably having the meanings given for R.

A also represents a bifunctional group. Alkylene of 1 to 4, in particular 1 to 2, carbon atoms optionally substituted by them may be mentioned, wherein the substituents mentioned above may be mentioned and the alkylene group is a group consisting of N, O and S It can be blocked by a hetero atom selected from among.

A and Z together with the atoms to which they are attached may form a saturated or unsaturated cyclic ring. Heterocyclic rings may further have one or two identical or different heteroatoms and / or hetero groups. The hetero atom is preferably oxygen, sulfur or nitrogen and the hetero group is N-alkyl, wherein the alkyl of the N-alkyl group preferably contains 1 to 4, in particular 1 or 2 carbon atoms. Alkyl may be mentioned methyl, ethyl, n- and i-propyl and n-, i- and t-butyl. Heterocyclic rings have 5 to 7, preferably 5 or 6 member members.

Examples of heterocyclic rings are imidazolidine, pyrrolidine, piperidine, piperazine, hexamethyleneimine, hexahydro-1,3,5-tri, each optionally optionally substituted by methyl Azine, hexahydrooxodiazine, morpholine may be mentioned.

E represents an electron-withdrawing radical, in particular a halogenoalkylcarbonyl such as NO ₂ , CN, 1,5-halogeno-C _1-4 -carbonyl, in particular COCF ₃ .

X represents -CH = or -N =.

Z represents optionally substituted radical alkyl, —O—R, —S—R or —NRR, wherein R and substituents preferably have the meanings mentioned above.

Z is, in addition to the above-mentioned rings, the atoms and radicals to which they are attached And may form a saturated or unsaturated heterocyclic ring at the position of X. Heterocyclic rings may further have one or two identical or different heteroatoms and / or hetero groups. The hetero atom is preferably oxygen, sulfur or nitrogen and the hetero group is N-alkyl, wherein the alkyl of the N-alkyl group preferably contains 1 to 4, in particular 1 or 2 carbon atoms. Alkyl may be mentioned methyl, ethyl, n- and i-propyl and n-, i- and t-butyl. Heterocyclic rings have 5 to 7, preferably 5 or 6 ring members.

Examples of heterocyclic rings may be mentioned pyrrolidine, piperidine, piperazine, hexamethyleneimine, morpholine and N-methylpiperazine.

Very particularly preferred compounds may be mentioned compounds of the general formulas (II) and (III):

Where

n represents 1 or 2,

Subst. Represents one of the aforementioned substituents, in particular halogen, very particularly chlorine,

A, Z, X and E have the meanings mentioned above.

The following compounds may be mentioned specifically, among which the imidacloprid compound of formula (IVa) is particularly preferred:

Glues and adhesives are considered as binders that can be used in the manufacture of plywood sheets and timber material sheets.

The following binders are generally used to prepare wood composites: urea / formaldehyde, urea / melamine, isocyanates such as MDI, phenol / formaldehyde, phenol / resosocinol / formaldehyde or urea / resosocinol Glue based on formaldehyde. Typically, the binder is prepared by mixing the glue with water, a hardener and, optionally, a water repellent, biocides, extenders and / or buffers before application to wood particles, flakes or veneers. In addition to the active compounds of formula (II), further biocides can be impregnated with the binder, for example other insecticides, and fungicides which act in particular on Basodiomycetes and molds.

Timber material sheets in this case are artificial wood sheets, such as plywood sheets, cardboard and fibreboard, which are generally produced by heat treatment of wood chips and binders under pressure.

The active compound is mixed with these binders to obtain a final formulation that can be used directly in the sheet making process, or the active compound is added during or immediately before the sheet making process. The amount of active compound and binder is generally estimated from the volume of the sheet prepared according to known methods.

The active compound may be impregnated into coarse wood, for example, via several routes:

1. Treat flake / wood particles using an additional sprayhead or blender system before or after drying.

2. Mix the chemical with the adhesive and / or wax and continue to apply the flakes in the blender.

3. Spray the flakes with a preservative solution or emulsion, or mix the powdered chemical with the flakes in the blender.

4. Weigh the powdered preservative and add it to the dried flakes just before blending. The powder is then mixed with the flakes in a blender.

Adding chemicals as a mixture with adhesives or waxes is probably the most convenient for the manufacturer. However, mixing the active compound with the adhesive can cause problems with the biocide efficacy, particularly if the biocide is degraded by hydrolysis or other chemical reactions in the adhesive. It is safer to impregnate the wax, but often the wax distribution is not as good as that of the adhesive. This may also affect the effectiveness of the biocide.

The active compound is added to the glue as such, or is pre-diluted in a preformulated form, for example in a solvent such as glycol, glycol ethers, aliphatic and / or aromatic hydrocarbons, esters, alcohols or ketones, or in water It can be added by emulsification or dispersion. In addition, the active compounds or their preparations can be applied to wood particles, flakes or venia separately from the glue, to the wood particles before or after mixing with the glue, or even after the glueing process, ie to the final granulated wood.

The invention also relates to a method of impregnating plywood and timber material sheets with other active compounds, for example other insecticides, and especially fungicides which act on basidiomycetes, in addition to the active compounds and the binders of the general formula (II).

Preferred fungicides are IF-1000, IPBC and azoles such as tebuconazole, propiconazole and cyproconazole. When combined with the active compounds of the formulas (IIa) to (IIi) these mixtures exhibit particularly good activity and stability.

The following examples illustrate the invention but are not limited thereto.

The results represent experiments on termites, where cardboard made using a formulation of strongly alkaline phenolic resin containing the compound of formula (IVa) was used.

Plywood Wood Type Radiata Pine

Layer structure 1.5 mm + 3.0 mm + 1.5 mm (3 layers)

Usage a) 1.5 ㎏ / ㎥

b) 2.0 kg / ㎥

c) 2.5 kg / m 3

Binder a) Phenolic Resin Adhesive A

b) phenolic resin adhesive B

Manufacturing process paste amount 40 g / 90 cm 2

125 ° C., 10 kg / cm 2, 6 minutes

Example 1

Example 2

evaluation

The test was conducted according to JWPA Standard No. 11. 150 white workers and 15 white soldiers were placed in a container containing cardboard specimens for 21 days.

Example 3 (phenol resin A)

Example 4 (phenol resin B)

Example 5

Several sheets were prepared comprising the following chips:

Wood type: Albizzia (large tree produced in Indonesia)

Chip size: 5 to 10 mesh 9%

10 to 20 mesh 40%

20 to 40 mesh 30%

40 to 60 mesh 9%

60 to 80 mesh 5%

80 mesh 6%

Manufacturing Process: Sheet Size 30 x 30 x 1 cm

Sheet thickness 0.7

500 g of sheet composition chips

50 g of urea resin

0.85 g of hardener

Wood preservative (see table)

30 kg / ㎠ for 5 minutes under pressure conditions

10 kg / ㎠ for 5 minutes

Mechanical strength of sheet

Anti-termite action

Viscosity of mixtures of resins and active compounds

Claims (3)

A composition containing at least one compound of formula (I) below and a binder or adhesive that can be used to prepare plywood and timber materials: Where R represents hydrogen or an optionally substituted radical selected from the group consisting of acyl, alkyl, aryl, aralkyl, heteroaryl and heteroarylalkyl, A represents a monofunctional group selected from the group consisting of hydrogen, acyl, alkyl and aryl, or represents a bifunctional group bonded to radical Z, E represents an electron-withdrawing group, X represents a monofunctional group selected from the group consisting of alkyl, -O-R and -S-R, Z is alkyl, -OR, -SR and Represents a monofunctional group selected from the group consisting of or a bifunctional group bonded to radical A or radical X. Use of the compound of formula (I) for preparing plywood and timber materials: Where R represents hydrogen or an optionally substituted radical selected from the group consisting of acyl, alkyl, aryl, aralkyl, heteroaryl and heteroarylalkyl, A represents a monofunctional group selected from the group consisting of hydrogen, acyl, alkyl and aryl, or represents a bifunctional group bonded to radical Z, E represents an electron-withdrawing group, X represents radical -CH = or = N-, wherein radical -CH = can be bonded to radical Z instead of H atom, Z is alkyl, -OR, -SR and Represents a monofunctional group selected from the group consisting of or a bifunctional group bonded to radical A or radical X. Plywood and timber material containing a compound of formula (I) according to claim 1.