GB1590069A

GB1590069A - Agent for the preservation of wood and wood materials

Info

Publication number: GB1590069A
Application number: GB40820/77A
Authority: GB
Original assignee: Desowag Bayer Holzschutz GmbH
Current assignee: Desowag Materialschutz GmbH
Priority date: 1976-09-30
Filing date: 1977-09-30
Publication date: 1981-05-28
Also published as: SE425470B; SE7710901L; IT1086098B; NO147405B; JPS6224241B2; NO773254L; DK147038C; BE859030A; AR221831A1; CA1078104A; DE2644077C2; DK431177A; FR2366110A1; NL7710148A; FI60807C; ES462725A1; NO147405C; DE2644077B1; JPS5344604A; FR2366110B1

Abstract

A composition for preserving (conserving) wood and woodbase materials comprises 0.5-7% by weight of a component A consisting of at least one insecticidal alkoxyphenyl N-alkylcarbamate and/or alkylphenyl N-alkylcarbamate soluble in an organochemical, sparingly volatile, oily or oil-like solvent having an evaporation number above 35 and a flashpoint above 30 DEG C, and at least one insecticidal halogenated or halogen-free thionophosphoric or thionophosphonic ester that is soluble in an organochemical, sparingly volatile, oily or oil-like solvent having an evaporation number above 35 and a flashpoint above 30 DEG C and has formula <IMAGE> where the substituents are each as defined in Claim 1, the mixture of insecticides containing the carbamate or carbamate mixture in a weight ratio relative to the thionophosphoric or thionophosphonic ester or mixtures of from 3:1 to 1:3, and 0.3-10% by weight of a component B consisting of a fungicide or fungicide mixture that is soluble in an organochemical, sparingly volatile, oily or oil-like solvent having an evaporation number above 35 and a flashpoint above 30 DEG C, and also more than 64% by weight of a component C consisting of a sparingly volatile, oily or oil-like, organochemical solvent having an evaporation number above 35 and a flashpoint above 30 DEG C, of which from 0.5 to 20% by weight can be replaced by the same amount of one or more organochemical binders and/or fixatives.

Description

(54) AGENT FOR THE PRESERVATION OF WOOD AND WOOD MATERIALS (71) We, DESOWAG-BAYER HOLZSCHUTZ GMBH, a body corporate organised under the laws of the German Federal Republic, of 76 Ross Strasse, 4000 Dusseldorf 30, German Federal Republic, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following.

statement: This present invention relates to an agent for the preservation of wood and wood materials, which consists of certain amounts by weight of an insecticide mixture, an alkoxy-phenyl-N-alkylcarbamate and/or alkylphenyl-N-alkylcarbamate and at least one halogenated or halogen-group-free thiophosphoric acid ester and/or insecticidal thionophosphoric acid ester and a fungicide as well as more than 64 per cent by weight of a low-volatility oily or oleaginous organic-chemical solvent with an evaporation number above 35 and a flash point above 30"C.

Various carbamates and thiophosphoric acid esters are known to have a good insecticidal effect. These compounds are therefore preferably used as pesticides, as plant protection agents, and in compositons for spraying for the direct or indirect control of harmful insects. When used as plant protection agents, it is frequently required that these insecticides should be degraded after a certain time in order that no damage to humans or animals occurs with the uptake of nutriment. It is also desirable that these insecticides should be able to be washed off plants with water so that vegetables and fruit which have been treated with these insecticides can, before consumption, be treated by rinsing with water.

Numerous very effective insecticides used on plants, even when used as directed on the plants, no longer exhibit, after a certain period, the necessary effect, so that, depending on the individual case, further treatments may be necessary. As far as possible, most insecticides, e.g. in the form of solutions, emulsions, spray concentrates and the like, should not penetrate deeply into the plants but, instead, should develop their effect only on the surface where, after a certain time, they can be washed off or degraded. However, although systemic insecticides do penetrate into the plants, they are degraded afte a certain time, e.g.

within 3 weeks. Pulverulent insecticides in the form of dusting agents frequently exhibit little adhesion to plants and are readily washed off.

In addition, most insecticides are required to be selective in their action and should not harm beneficial or creatures, such as bees, birds and the like. This has led to many insecticides only being able to be used successfully against specific pests, e.g. against mites and the like, whereas they frequently do not have any effect on other insects. We have tested numerous insecticides for their suitability in wood-preserving agents and have found that many highly effective insecticides with a broad spectrum of insecticidal activity, e.g. insecticidal phosphoric acid esters and the like, are not suitable for use in wood preservatives.

The reason for this is that the demands made on wood preservatives differ considerably from those of insecticides in their usual fields of application, e.g. in plant protection, as pesticides and the like. Whereas insecticides used, e.g. for plant protection, should after a certain time be degraded, washed off completely and the like, long-term activity is required for wood preservative. The wood preservative should not adhere to the surface and immediately kill the pests coming into contact therewith but should penetrate as deeply as possible into the wood and protect the wood against later infestation. Even with weathering, no substantial loss of activity and no substantial reduction of the preservative effect of the wood preservative must take place. Since the wood or the wood material may not only be attacked and destroyed by numerous wood pests, insects or their larvae and the like but are also threatened by vegetable destroyers (fungi and the like), the effective wood preservative must also exhibit a corresponding fungicidal activity; it is important that the effectiveness of the insecticidal agent used is not adversely affected by the fungicidal agent or vice versa.

It is, therefore, an object of the present invention to provide an effective wood preservative which, even after a long time, exhibits adequate insecticidal and fungicidal wood-protective activity and protects the wood or the wood materials without impairing their quality. The wood preservative should provide an adequate preservative effect even after weathering and the like, i.e. under the influence of rain, snow, frost and sun. The agent should be capable of being used both for the preservation of wood with a very good fungicidal and insecticidal long-term effect and as a wood-protective primer or as wood-protective paint or varnish and be able to penetrate well into the wood or into the wood materials.

According to the present invention there is provided an agent for the preservation of wood and wood materials, comprising (a) more than 64% by weight of a solvent medium having an evaporation number according to DIN 53170 above 35 and a flash point above 300 C., said solvent medium comprising an organic lowvolatility oily solvent or mixture of solvents, optionally from 0.5 to 20% by weight of said agent being constituted by a binder and/or fixing agent which is distributable or emulsifiable in the solvent(s), (b) from 0.5 to 7% by weight of an insecticide mixture consisting of at least one insecticidal alkoxy-phenyl-N-alkylcarbamate or alkylphenyl-N-alkylcarbamate soluble in said solvent medium and at least one insecticidal, halogenated or halogen-free, thionophosphoric acid ester or thionophosphoric acid ester which is soluble in said solvent medium and has the general formula

where R; is an alkyl radical with 1 to 4 atoms, R2 is an alkyl or alkoxy radical with 1 to 4 C atoms or a phenyl radical, and R3 is a phenyl radical or a phenyl radical substituted with 1 to 3 halogen atoms, or with alkyl or alkoxy radicals with I to 4 C atoms, the ratio by weight in the insecticide mixture of the carbamate(s) to the thionophosphoric acid ester and/or thionophosphonic acid ester being from 3:1 to 1:3, and (c) from 0.3 to 10% by weight of a fungicide or fungicide mixture soluble in said solvent medium.

Preferably said ratio by weight in the insecticide mixture is from 1:0.75 to 1:2.

Preferably more than 72 per cent by weight of the solvent medium is constituted by an organic low-volatility oily solvent with an evaporation number above 35 and a flash point as determined in accordance with German Industrial Standard DIN 53 170 of over 300 C. The insecticide mixture is preferably present in an amount of 2 to 5 per cent by weight.

The insecticide mixture preferably contains an alkoxyphenyl-Nalkylcarbamate of the general formula

and/or an alkylphenyl-N-alkylcarbamate of the general formula

in which each R is an alkyl radical with 1 to 4 C atoms, preferably a methyl radical, and each R2 is an alkyl radical with 1 to 5 C atoms, preferably an alkyl radical with 3 or 4 C atoms.

Furthermore, the halogenated or halogen-free thiono-phosphoric acid ester is preferably an ester of the formula

preferably (diethoxy-thiophosphoryloxyimino)-phenylacetonitrile of O,O-diethyl O-(alpha-cyanobenzylidene-amino) thionophosphate or (diethoxy thiophosphoryloxyimino)-2-chlorophenylacetronitrile .

The fungicide is a fungicide which is known per se and is soluble in the solvent.

The preferred fungicide is a fungicidal chlorophenol, preferably penta- or tetrachlorophenol or a mixture thereof, or a fungicidal tetravalent organo-tin compound or a l-trityl-l,2,4-triazole of the general formula

in which R is a fluorine, chlorine or bromine atom, a tri-fluoromethyl, nitro or cyano group or an alkyl radical with up to 4 carbon atoms, and n is 1 to 2, or a salt thereof with an organic or inorganic acid or a mixture of one or more of the aforesaid fungicides, a preferred fungicide being trifluoromethyltriphenylmethyl-triazole. A particularly advantageous embodiment of the present wood preservative comprises a mixture of 2-isopropoxy-phenyl-N-methylcarbamate and/or butylphenyl-N-methylcarbamate and an insecticidal halogenated or halogen-group-free thionophosphoric acid ester of the aforesaid formula

Although, in preliminary experiments, numerous insecticides with a broad spectrum of activity, e.g. O,O-diethyl-O-[(2-isopropyl-4-methyl)-6-pyrimidyll - thionophosphate; O,O-dimethyl-O-2,2-dichlorovinyl-phosphate; diethylvinyl phosphate and bis-(dimethylamino)-phosphoryl fluoride, etc. were found to be unsuitable for use in wood preservatives, since their effectiveness diminishes to a considerable extent, after a certain period of time, it was found that the use of a.

combination of an insecticidal alkoxy-phenyl-N-alkylcarbamate and/or alkylphenyl-N-alkylcarbamate and at least one insecticidal halogenated or halogen-free thionophosphoric acid ester or thionophosphonic acid ester of the formula defined above produced a long lasting effectiveness of the wood preservative with an increase of activity. It was also found that fungicidal substances produced no reduction of the insecticidal activity. The wood preservative penetrates satisfactorily into wood and wood materials so that a certain depth of preservation and impregnation can be obtained. In tests in the open air it was moreover found that the preservative remained effective even in the case of weathering of long duration and retained both its wood-protective fungicidal and insecticidal properties without wooddamaging influences being able to be found.

Preferably 2 to 15 per cent by weight, of the agent is constituted by one or more organic binders and/or fixing agents, the binder and/or fixing agent preferably being soluble in the low-volatility only solvent.

The binder is preferably a synthetic resin in the form of an emulsion, dispersion or solution, preferably an alkyd resin, a modified alkyd resin, a phenolic resin, an indene-coumarone resin or a mixture of two or more thereof. The binder may also comprise bitumen or a bituminous substances in an amount of up to 10% by weight. In addition, the wood-preservative may include one or more conventional dyestuffs, pigments, water-repelling agents, correctors and inhibitors and anti-corrosion agents. The water-repelling agent may be a paraffin, a wax, wool fat or the like and may be present in an amount by weight of 0.2 to 5% by weight, preferably 0.5 to 2% by weight, based on the weight of the wood-preservative.

The fixing agent is preferably a compound which serves to inhibit or prevent volatilisation of the active substances and/or a crystallisation or precipitation thereof. Preferred fixing agents, which may be used singly or in admixture with one another, include:a) plasticisers, e.g. alkyl, aryl or aralkyl phthalates, preferably dibutyl, dioctyl or benzylbutyl phthalate, alkyl phosphates or phosphoric acid esters, preferably tributyl phosphate, adipates, preferably di(2-ethylhexyl)-adipate, stearates and oleates, e.g. alkyl stearates or alkyl oleates, preferably butyl oleate, butyl stearate or amyl stearate, bis-(dimethylbenzyl) ether, ethyl-p-toluenesulphonate, glyceryl esters, glyceryl ethers or high molecular-weight glycol ethers; b) oils, e.g. linseed oil, castor oil, tall oil and their esters; and c) fixing agents based on ketones and/or polyvinylalkyl ethers, e.g. ketones with alkyl, aryl or aralkyl radicals, preferably benzophenone, ethylbenzophenone; polyvinylalkyl ethers, preferably polyvinylmethyl ether.

The solvent medium with an evaporation number above 35 and a flash point above 30"C., preferably above 45"C., may comprise a water-insoluble or sparingly water-soluble solvent, and such solvents include mineral oils or their aromatic fractions or mineral-oil-containing solvent mixtures, preferably white spirit, petroleum, gas oil and/or alkylbenzene, etc.

The preferred solvents are mineral oils with a boiling range of 170 to 2200C., white spirit with a boiling range of 170 to 2200C., spindle oil with a boiling range of 250 to 3500C., petroleum or aromatics with a boiling range of 160 to 2800C., turpentine oil and the like.

High-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range of 180 to 2200C., and/or spindle oil and/or monochloronaphthalene, preferably a-monochloronaphthalene, were also used in some embodiments.

The solvent medium may also comprise a readily volatile or moderately volatile organic solvent, with the proviso that the resulting solvent mixture has an evaporation number above 35 and a flash point above 30"C., preferably above 45"C., and that the insecticide-fungicide mixture is soluble in this solvent mixture.

It was found that, depending upon the evaporation number and flash point of an oily solvent used as the solvent medium, up to 20% by weight, preferably up to 15% by weight of the organic low-volatility oily solvent may be replaced by a solvent with a lower evaporation number.

With regard to the fungicide, it has been found that its concentration may vary in dependence upon the nature of the fungicide. With regard to the fungicidal effect, the use of 3 to 8% by weight of chlorophenol, preferably penta- and/or tetrachlorophenol, was found to be partciularly advantageous. Surprisingly, it was found that fungicidal tetravalent organo-tin compounds and the fungicidal l-trityl-l,2,4- triazoles confer on the wood preservative a very good fungicidal activity even in concentrations of 0.3 to 2% by weight. The fungicide is therefore preferably 0.3 to 2 per cent by weight of a fungicidal tetravalent organo-tin compound and/or a 1 trityl- 1 ,2,4-triazole of the general formula I

in which R is for a fluorine, chlorine or bromine atom, a tri-fluoromethyl; nitro or cyano group or an alkyl radical with up to 4 carbon atoms, and n is 1 or 2, as well as their salts with organic or inorganic acids, preferably trifluoromethyl-triphenylmethyltriazole or a mixture of one or more of the aforesaid fungicides.

The tetravalent organo-tin compound is preferably a known fungicidal tetravalent organo-tin compound. Particularly suitable tetravalent organo-tin compounds for use in the present wood-preservative include bis-(tri-butyl-tin) oxide, tri-n-butyl-tin trichloroacetate, tri-n-butyl-tin-8-oxyquinoline, tri-n-butyl-tin pentachlorophenolate, trin-n-butyl-tin bis-ethylene-dithiocarbamate, tri-n-butyltin benzoylcyanoacetic acid, tri-n-butyl-tin dimethylarsenic acid, tri-n-butyl-tin fluoride, tri-n-butyl tin thiocyanate, tributyl tin dichlorophenolate as well as the adduct tri-n-butyl tin acrylate/hexachlorocyclo-pentadiene.

However, instead of these aforesaid fungicides which are preferred, other fungicides, or mixtures of these with the aforesaid fungicides, which are soluble in the solvent may also be used, e.g. fungicidal oil-soluble naphthenates, preferably zinc and/or copper naphthenate; 8-hydroxyquinoline or its fungicidal oil-soluble salts or derivatives, preferably phenylmercury-8-oxyquinolate; fungicidal compounds or derivatives or mixtures of chlorophenols, preferably compounds or mixtures of penta- and/or tetra-chlorophenol with low-volatility amines, e.g.

rosinamine; nitrophenols or nitrochlorophenols or nitrochlorobenzenes, in particular 1 ,2-dinitrotetrachlorobenzene; oil-soluble fungicidal organometallic compounds. e.g. of copper, zinc, manganese, cobalt, chromlum or mercury, e.g. in the form of caprylates, naphthenates, oleates and the like; fungicidal salts of Nnitroso-N-cyclohexylhydroxyl-amine, preferably of the aluminium salt of Nnitroso-N-cyclo-hexyl-hydroxylamine and/or N-trichloromethylthiotetrahydrophthalimide. In the case of N-nitroso-N-cyclohexyl-hydroxylamine and/or of the aluminium salt of N-nitroso-N-cyclo-hexylhydroxylamine it must, however, be borne in mind that these fungicidal compounds are obviously only suitable for specific kinds of wood or wood fungi. In the fungicide mixtures, tar oil distillate and/or tar oil may in part also be used.

In one embodiment of the present wood-preservative the solvent medium is an organic low-volatility oily solvent which is simultaneously a fungicidal active substance, e.g. chloronaphthalene, preferably monochloro-naphthalene and/or dichloronaphthalene. In this way the concentration of the fungicide in this exceptional case is exceeded. Preferably, however, the monochloronaphthalene and/or dichloro-naphthalene is not used as the sole fungicidal active substance but together with other solvents and/or fungicides.

Depending upon the active substances and the like which are used, it may be expedient to include emulsifiers and/or wetting agents in the present woodpreservative.

In order to increase the activity of the preservative and to lessen corrosion, it is desirable to include mandelic acid and/or benzotriazole in the preservative. In this combination, discoloration of the wood-protective agents in tin-plate containers or during the action of the wood preservatives on wood containing metal or metal parts through possible corrosion is prevented. These anti-corrosion agents are preferably used in amounts of 0.05 to 0.2% by weight.

Wood-preservatives are frequently produced in the form of concentrates which, after transport, are diluted at the place of use to the normal concentration, using organic low-volatility oily solvents. In this way it is possible to produce highly effective wood-protective concentrates which can be transported in a costeffective manner.

In the case of the present preservative, the production of a concentrate is also particularly advantageous. In the case of the production of a concentrate, the stated concentrations of course shift in such a manner that in each case the amount by weight of the insecticide mixture and of the fungicide is increased (preferably uniformly) so that, after transport dilution back to the aforesaid concentrations (application concentration) is possible through the addition of the oily solvent.

The application amount of the present wood preservative may vary, depending upon the field of application, active substance concentration and the like. In general, it is about 100 to 350 g./m.2, preferably 150 to 200 g./m.2. The wood or wood materials which can be treated with the present preservative include dry woods, chipboards, plywood, timber, planks, boards, wood for windows, doors, floors, ceilings, casings, fences, walls, roofs, furniture, posts, masts and the like.

Comparative experiments Tested preservatives and test methods.

1% strength impregnating agent solutions of (diethoxy-thiophosphoryloxyimino)-phenylacetonitrile (or O,O-diethyl-O-(alpha-cyanobenzylideneamin)thionophosphate); (diethoxy-thiophosphoryloxyimino)-2-chlorophenylacetonitrile and 2-isopropoxyphenyl-N-methylcarbamate in an organic solvent with an evaporation number above 35 and a flash point above 30"C. and which has a boiling range between 180 to 2100C. were produced. The impregnating agent solution additionally contained tributyl phosphate as a fixing agent. The active substances alone and the combination of the active substances were tested in certain weight ratios.

For the investigation, circular filters were soaked with the diluted impregnating agent and dried for 8 days in the open. Small glass tubes (diameter 2 cm, height 5 cm) which were filled with two moist plastics foam disks (polyurethane foam) were then placed on the filters. Into each tube were placed 50 mg. of fodder wood and 30 workers of Reticulitermes santonensis. The experiments duration was 21 days.

In the tests, the procedure was that in one series of experiments the applied amount of active substance was 20 g./m.2 and in the other series of experiments it was 25 g./m.2.

1. 7 /e Dead Protective agent Amount g/m2 (average value) Damage 1 % (diethoxy-thio- 20 70 only partial phosphoryloxyimino)- destruction or phenylacetonitrile minor damage (or O,O-diethyl-O- (alpha-cyanobenzylidene amino) thionophosphate) 1 % (diethoxy-thiophosphoryl- 20 70 only partial oxyimino)-2-chlorpheny 1- destruction or acetonitrile minor damage 1 % 2-isopropoxyphenyl-N- 20 84 major destruc methylcarbamate tion 0.25 % (diethoxy-thio- 20 90 only partial phosphory loxyimino) - destruction or phenylacetonitrile minor damage (or O,O-diethyl-O-(alpha cyanobenzyl ideneamino) - thionophosphate) + 0.75 % 2-isopropoxyphenyl-N methylcarbamate 0.25 % 2-isopropoxyphenyl- 20 88 only partial N-methylcarbamate + 0.75 % destruction or (diethoxythiophosphory loxy- minor damage imino)-phenylacetonitrile (or O,O-diethyl-O-(alpha cyanobenzylideneamino) thionophosphate) 0.25 % (diethoxythio- 20 86 only partial phosphoryloxy imino)- destruction or 2-chlorophenylacetonitrile minor damage +0.75 % 2-isopropoxyphenyl- N-methylcarbamate 0.25 % 2-isopropoxyphenyl- 20 85 only partial N-methylcarbamate + 0.75 % destruction or (diethoxythiophosphoryloxy- minor damage imino)-2-chlorophenyl acetonitrile

II. % Dead Protective agent Amount g/m2 (average value) Damage 1 % (diethoxy-thiophosphoryl- 25 90 only partial oxyimino)-phenylacetonitrile destruction or (or O,O-diethyl-O-(alpha- minor damage cyanobenzylideneamino) thionophosphate 1 % (diethoxy-thiophosphoryl- 25 90 only partial oxyimino)-2-chlorophenyl- destruction or acetonitrile minor damage 1 % 2-isopropoxyphenylN- 25 93 major destruc methylcarbamate tion 0.25 gO (diethoxy-thiophos- 25 100 only partial phoryloxyimino)-phenyl- destruction or acetonitrile (or O,O-diethyl- minor damage O-(alpha-cyanobenzylidene amino)thionophosphate + 0.75 % 2-isopropoxyphenyl N-methylcarbanate 0.25 % 2-isopropoxyphenyl- 25 100 only partial N-methylcarbamate + 0.75 % destruction or (diethoxy-thiophosphoryloxy. minor damage imino)-phenylacetonitrile (or O,O-diethyl-O-(alpha cyanobenzylideneamino) thionophosphate) 0.25 % (diethoxy-thiophos- 25 94 only partial phoryloxyimino)-2-chlor- destruction or phenylacetonitrile + 0.75 % minor damage 2-isopropoxyphenyl-N methylcarbamate Solvent (without active 25 28 1 major destruc substances but with tion fixing agent)

From the comparative experiments, it can be seen that, when certain mixture ratios are used, there occurs an increase in the activity of the protective agent, which increase even goes beyond the additive activity of the individual substances.

Under "% Dead" there is entered the average value of the termites killed from, in each case, three comparative experiments. By "major destruction" was designated a greater destruction of material whereas, by "only partial destruction or minor damage" is meant e.g. damage points caused by incipient eating-in by the termites without extensive damage. Within the tests it was, moreover, surprisingly found that the kill time for the termites in the combination is shortened compared to the individual components.

The invention will now be illustrated by the following Examples.

EXAMPLE 1.

Penta- and/or tetrachlorophenol 5.0% by weight Isopropoxyphenyl-N-methylcarbamate 0.6% by weight O-O-diethyl-O-(α-cyanobenzylidene-amino)- thionophosphate or (diethoxy-thiophosphoryl oxyimino)-phenylacetonitrile Alkyd resin (100%) 12% by weight Siccative solution 0.2% by weight Aromatic and aliphatic hydrocarbons 80.4% by weight (boiling range: 180 to 2120C) 100.0% by weight This preservative is suitable as wood-protective primer with good activity against fungi and insects, including termites.

EXAMPLE 2.

B is-phenyl-(3-trifluoromethylphenyl)- 1 (1 ,2,4-triazolyl)-methane 1.0% by weight 2-sec.-butylphenyl-N-methylcarbamate 1.0% by weight 2-isopropoxyphenyl-N-methylcarbamate 1.0% by weight O-O-diethyl-O-(a-cyanobenzylidene-amino) thiono-phosphate or (diethoxy-thiophosphoryl oxyimino).phenylacetronitrile 1.5% by weight Benzotriazole 0.05% by weight Organic phosphates (plasticisers) 6.0% by weight Aromatic and aliphatic hydrocarbons 89.45% by weight (boiling range: 180 to 2120C) 100.0% by weight This wood preservative represents a controlling wood-protective agent with, simultaneously, a preventive effect against insects, including termites, and with good fungicidal effectiveness.

EXAMPLE 3.

Pentachlorophenol 5.5% by weight 2-sec.-butylphenyl-N-methylcarbamate 1.0% by weight O-O-diethyl-O-(α-cyanobenzylidene-amino)- 2.0% by weight thionophosphate or (diethoxy-thiophosphoryl oxyimino)-phenylacetonitrile Benzotriazole 0. 1% by weight Alkyd resin (100%) 4.0% by weight Aromatic and aliphatic solvents 87.4% by weight (of the boiling range 180 to 212"C) 100.0% by weight This mixture is suitable as preventive wood preservative.

EXAMPLE 4.

B is-phenyl-(3-trifluoromethylphenyl- 1 (1 ,2,4-triazolyl)methane 1.5% by weight 2-iso-propoxyphenyl-N-methylcarbamate 1.5% by weight O,O-diethyl.O.(a.cyanobenzylidene-amino)- 2.0% by weight thionophosphate or (diethoxy-thiophosphoryl oxyimino)-phenylacetonitrile a.monochloronaphthalene, technical grade 50.0% by weight Linseed oil 6.0% by weight Spindle oil 39.0% by weight (boiling range 250 to 3200 C) 100.0% by weight This wood preservative possesses a good preventive effect against insects, in particular against termites. It has excellent penetration and a long duration of activity, even under the influence of the weather.

The anti-fungal action of this active substance mixture is likewise very good.

EXAMPLE 5.

B is-phenyl-(3-trifluoromethylphenyl- 1- 1.5% by weight (1,2,4-triazolyl)methane 2-isopropoxyphenyl-N-methylcarbamate 0.75% by weight O,O-diethyl-O-(a.cyanobenzylidene-amino). 1.5% by weight thionophosphate or (diethoxy-thiophosphoryl oxyimino).phenylacetonitrile Alkyd resin (100%) 15.0% by weight Linseed oil varnish 5.0% by weight Benzotriazole 0.05% by weight Siccative 'ranti-skinning agent 0.3% by weight Aromatic and aliphatic solvents 72.90% by weight Inorganic and organic pigments 3.0% by weight 100.0% by weight The wood preservative causes a glaze coloration of the wood and protects the wood ag

Claims

WHAT WE CLAIM IS:

-I. An agent for the preservation of wood and wood materials comprising (a) more than 64 ó by weight of a solvent medium having an evaporation number according to DIN 53 170 above 35 and a flash point above 30"C., said solvent medium comprising an organic low-volatility oily solvent or mixture of solvents, optionally from 0.5 to 20% by weight of said agent being constituted by a binder and/or fixing agent which is distributable or emulsifiable in the solvent(s), (b) from 0.5 to 7% by weight of an insecticide mixture consisting of at least one insecticidal alkoxy-phenyl-N-alkylcarbamate or alkylphenyl-N-alkylcarbamate soluble in said solvent medium and at least one insecticidal, halogenated or halogen-free thionophosphoric acid ester or thionophosphonic acid ester which is soluble in said solvent medium and has the general formula

where R is an alkyl radical with 1 to 4 C atoms, R2 is an aikyl or alkoxy radical with 1 to 4 C atoms or a phenyl radical, and R3 is a phenyl radical or a phenyl radical substituted with 1 to 3 halogen atoms, or with alkyl or alkoxy radicals with 1 to 4 C atoms, the ratio by weight in the insecticide mixture of the carbamate(s) to the thionophosphoric acid ester and/or thionophosphonic acid ester being from 3:1 to 1:3, and (c) from 0.3 to 10% by weight of a fungicide or fungicide mixture soluble in said solvent medium.
2. An agent as claimed in claim 1, wherein the agent comprises more than 72% by weight of said solvent medium.
3. An agent as claimed in claim 1 or 2, wherein the agent comprises from 2 to 5% by weight of said insecticide mixture.
4. An agent as claimed in any preceding claim, wherein said ratio by weight in the insecticide mixture is from 1:0.75 to 1:2.
5. An agent as claimed in any preceding claim, wherein the alkyoxyphenyl-Nalkylcarbamate has the general formula

and the alkylphenyl-N-alkylcarbamate has the general formula

where each R1 i an alkyl radical with 1 to 4 C atoms, and each R2 is an alkyl radical with I to 5 C atoms.
6. An agent as claimed in claim 5, wherein R1 is a methyl radical and R2 is an alkyl radical with 3 or 4 carbon atoms.
7. An agent as claimed in any preceding claim, wherein the halogenated or halogen-free thiono-phosphoric acid ester has the formula

where Hal is halogen.
8. An agent as claimed in claim 7, wherein said ester is (diethoxy-thiophosphoryloxyimino)-phenylacetonitrile (or O,O-diethyl-O-(alpha-cyanobenzylidene- amino)-thiono-phosphate) or (diethoxy-thiophoxphoryloxyimino).2.chloro.phenyl.

acetonitrile.
9. An agent as claimed in claim 7 or 8, wherein the insecticide mixture is a mixture of 2-isopropoxyphenyl-N-methylcarbamate and/or butyl-phenyl-N-methylcarbamate and said ester.
10. An agent as claimed in any preceding claim, wherein from 2 to 15% by weight of said agent is constituted by said binder and/or fixing agent.
11. An agent as claimed in any preceding claim, wherein the binder and/or fixing agent is soluble in the solvent(s).
12. An agent for the preservation of wood and wood materials substantially as hereinbefore described in any one of the foregoing Examples.