NO147405B - Means for the preservation of wood and wood materials. - Google Patents

Description

The present invention relates to an agent for preserving wood and wood materials, consisting of specific weight amounts of an insecticide mixture, an alkoxy-phenyl-N-alkyl carbamate and/or alkylphenyl-N-alkyl carbamates and at least one halogenated or halogen group-free insecticide thiophosphoric acid ester, and/or thionophosphonic acid ester and a fungicide, as well as more than 60% by weight of a low-volatile oily or oily organic chemical solvent with an evaporation number above 35 and a flash point above 30°C.

It is already known that numerous carbamates and thiophosphoric acid esters exhibit good insecticidal activity. These compounds are therefore above all used as pesticides, as plant protection agents (see e.g. DE-PS 1,137,895), as sprays and the like for direct or indirect control of pests. As a plant protection agent, for these insecticides there is often the necessity and the requirement that they must be broken down after a certain time, so that no harm occurs to humans or animals when nutrients are absorbed., It is also desirable that these insecticides can be washed down from the plants with water so that vegetables and fruit that have been treated with these insecticides can be treated with water before they are eaten.

Numerous, highly effective insecticides used for plant protection therefore no longer have the required effect after a certain period of time, even when used correctly on plants, so that in individual cases, as needed, post-treatment may be necessary. As far as possible, the insecticides, e.g. in the form of solutions, emulsions, spray concentrates and the like, do not penetrate the internal plant parts, but only unfold their activity on the surface,

where after a certain time they are washed off or broken down. In contrast, the systemic insecticides very often penetrate into the interior of the plant, but are built up there after a certain time, e.g. during. 3 weeks. Furthermore, the powdery insecticides in the form of dusting agents often exhibit too poor adhesion, so that they are easily washed off.

In addition, most insecticides must often have a selective effect requirement, so e.g. beneficial animals such as bees, birds and the like are not put at risk. This has led to the fact that many insecticides can only be used successfully against certain pests, e.g. mites and the like, while with other insects they often show no effect.

Within the framework of the present invention, numerous insecticides were therefore tested with a view to their usability as three preservatives, whereby it was determined that even numerous highly effective insecticides with a broad insecticidal spectrum of action, e.g. insecticide phos-for acid esters and the like, are not suitable as wood preservatives.

Namely, there are requirements for wood preservatives which in some cases differ greatly from the requirements for insecticides in their usual areas of application, e.g. when it comes to plant protection agents or pest control agents. While the insecticides, e.g. in the case of plant protection, degrades after a certain time, is washed away or the like, long-term effects are required when it comes to wood preservatives. The wood preservative must therefore not only stick to the surface and kill the animals that come into contact with it, on the contrary, they must penetrate as far as possible into the wood and protect it against later attack. Even in the case of climatic stresses, there must be no particular reduction in effectiveness, nor any significant reduction in the preservative effect. Furthermore, as the wood is not only attacked by numerous pests, insects and their larvae, but also by plants, such as fungi and the like, the effective wood preservative must also show a corresponding fungicidal action, whereby it is important that the fungicidal and the insecticidal action are not adversely affected by each other.

The aim and task of the present invention is thus to find a wood preservative with good effect which, even after a long time, exhibits a sufficient insecticidal and fungicidal wood protection effect, and which protects the tree, or the wooden materials for a long time without degrading their quality. The wood preservative must also be used after exposure to climate and the like, i.e. after exposure to rain. snow, frost and sun, exhibit a sufficient preservative effect. The agent should, at the same time as preserving the wood with a good fungicidal and insecticidal long-term effect, also be usable as a wood protective primer or coloring or glazing agent and be able to penetrate far into the wood or the wood material.

According to the invention, it has been established that these targets

and tasks are found in an agent for the preservation of wood and wood materials, consisting of oil-soluble or in oily solvents soluble organic chemical insecticides and fungicides, highly volatile solvents and possibly aqueous additives, and these agents for preservation are characterized by the fact that the preservative consists of 0.5 to 7% by weight, preferably 2 to 5% by weight, calculated on the basis of the finished mixture, of a mixture consisting of at least one in an organic-chemical heavy-volatile or oily solvent with an evaporation number above 35 and a flash point above 30° C soluble insecticide alkoxy-phenyl-N-alkyl carbarnate and/or alkylphenyl-N-alkyl carbarnate and at least one in an organic-chemical heavy-volatile or oily solvent with an evaporation number above 35 and a flash point above 30°C soluble insecticide halogenated or without halogen group in thionophosphoric acid ester and /or thionophosphonic acid ester with the general formula:

where R1 denotes an alkyl residue with 1 to 4 C atoms, R2 an alkyl residue or an alkoxy group with 1 to 4 C atoms or a phenyl residue, and denotes a phenyl residue or one with 1 to 3 halogen atoms or with lower alkyl or alkoxy groups substituted phenyl residue, whereby the carbamate or the carbamate mixture in the insecticide mixture relates to the thiophosphoric acid ester or the thionophosphonic acid ester or the mixture thereof as 3:1 to 1:3, preferably 1:0.75 to 1:2 (by weight), and from 0.3 to 10% by weight, calculated on the basis of the finished mixture

ing, of a fungicide soluble in an organic-chemical heavy-volatile oily or oil-like solvent with an evaporation rate of over 35 and a flash point over 30°C or fungicide mixture as well as more than 64% by weight, preferably more than 72% by weight, calculated on the basis of the finished mixture, of a highly volatile oil-like or oily organic chemical solvent with an evaporation number above 35 and a flash point above 30°C.

The insecticide mixture is thereby used in amounts by weight of 0.5 to 7% by weight, and preferably 2 to 5% by weight.

According to a preferred embodiment, the insecticide mixture contains an alkoxy-phenyl-N-alkyl carbonate with the general formula

and/or an alkylphenyl-N-alkylcarbamate of the general formula 1 '

in which in both cases R-1 means an alkyl radical with 1 to 4 C atoms, preferably a methyl radical, and R 2 means an alkyl radical with 1 to 5 C atoms, preferably an alkyl radical with 3 or 4 C atoms.

Furthermore, the ester with the formula is preferably used as a halogenated or halogen group-free in the thionophosphoric acid ester

preferably (diethoxy-thiophosphoryloxyamino)-phenylacetonitrile or according to newer terminology: 0,0-diethyl-O-(alpha-cyanobenzylidene-amino)thionophosphate and/or (diethoxy-thio-phosphoryloxymono)-2-chlorophenylacetonitrile. Fungicides that are known per se and soluble in the specified solvents are used as fungicides in the specified weight quantities. The fungicide used is preferably a fungicide chlorophenol, preferably penta- and/or tetrachlorophenol or a fungicide tetravalent organotin compound or a 1-trityl-1,2-4-triazole with the general formula in which R denotes a fluorine, chlorine or bromine atom, a trifluoromethyl, nitro or cyano group or an alkyl group with up to 4 carbon atoms, and n denotes one or two, as well as salts thereof with organic or inorganic acids, preferably trifluoromethyl-triphenylmethyltriazole or a mixture of one or more of the above-mentioned fungicides. According to a particularly preferred embodiment, a mixture is used consisting of 2-isopropoxy-phenyl-N-methyl carbarnate and/or butylphenyl-N-methyl carbarnate and an insecticide> halogenated or halogen-free in thionophosphoric acid ester with the formula

preferably (diethoxy-thiophosphoryloxyimino)-phenylacetoni tr il or 0,0-diethyl-0-(alpha-cyanobenzylidene-amino)thionophosphate

and/or (diethoxy-thiophosphoryloxyimino)-2-chlorophenylacetonitrile.

Although numerous insecticides with a broad spectrum of action, e.g. 0,0-diethyl-O-[(2-isopropyl-4-methyl)-6-pyrimidyl]-thionophosphate, 0,0-dimethyl-0-2,2-dichlorovinyl phosphate, diethyl vinyl phosphate and bis(dimethylamino)-phosphoryl fluoro -rid, etc., is not suitable as a wood preservative in preliminary trials, as the effect decreases to a considerable extent after a certain duration of the trial, it was established within the scope of the invention that when using /or alkylphenyl-N-alkylcarbamate and at least one insecticide halogenated or halogen group-free thionophosphoric acid ester or insecticide thionophosphonic acid ester, a long-term effect is achieved for the wood preservative with an increase in the effect, whereby a reduction in the effect of the insecticidal effect could not be determined by the addition of fungicidal active substances. The wood preservative penetrates into the wood and into the wood materials so that a certain depth of conservation and impregnation is also achieved. active even in the case of long climatic stress and retained both its wood-protecting fungicide and insecticidal effect without any tree-damaging effects being identified.

According to a particularly preferred embodiment of the invention, 0.5 to 20% by weight, preferably 2 to 15% by weight, of the organic highly volatile, oil-like or oily solvent is replaced or mixture of solvents with an evaporation rate of more than 35 and a flash point of more than 30°C with the same amount of one or more organic chemical binders and/or fixing agents, whereby the organic chemical binding agents and/or fixing agents used are those that can be distributed respectively emulsified and preferably dissolved in the said solvent.

According to a particularly suitable embodiment, synthetic resin in the form of an emulsion, dispersion or solution, preferably alkyd resin or modified alkyd resins or phenolic resins and/or indene-coumarone resins. Bitumen or bitumen can also be used as a binder

minous substances are used in an amount of up to 10% by weight.

In addition, per se known dyes, pigments, water repellents, odor additives and inhibitors or corrosion protection agents and the like can be added. Paraffins and wax are used as water repellants. wool grease and the like in amounts by weight of 0.2 to 5% by weight and preferably 0.5 to 2% by weight, calculated for the wood preservative.

As a fixing agent or plasticizers are used above all such compounds which are also intended to prevent evaporation of the active substances and/or crystallization or precipitation of these. Preferably used

a) plasticizers, e.g. alkyl, aryl or aralkyl phthalates, preferably dibutyl, dioctyl and benzylbutyl phthalates, alkyl phosphates or phosphoric acid ester, preferably tributyl phosphate/ adipates, preferably di-2-ethylhexyl adipate, stearates and oleates, e.g. alkyl stearates and alkyl oleates, preferably butyl oleate, butyl stearate or amyl stearate, bis-dimethyl benzyl ether, p-toluene sulfonic acid ethyl ester, glycerin esters, glycerin ethers or higher molecular glycol ethers, and/or b) oils, e.g. linseed oil, castor oil, tallow oil and esters thereof and/or c) fixing agents based on ketones and/or polyvinyl alkyl ethers, e.g. ketones with alkyl, aryl or

aralkyl groups, preferably benzophenone. ethyl benzophenone polyvinyl alkyl ether, preferably polyvinyl methyl ether.

Water-insoluble or slightly water-soluble solvents are preferably used as organically volatile oily or oil-like solvents with an evaporation number above 35 and a flash point above 30°C, preferably above 45°C. Corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably test petrol, petroleum, gas oil and/or alkylbenzene, are used as the type of solvent.

Preferably, mineral oil with a boiling range of 170 to 220°C, test gasoline with a boiling range of 170 to 220°C, spindle oil with a boiling range of 250 to 350°C, petroleum with respectively aromatics with a boiling range of 160

to 280°C or turpentine oil and the like.

In one embodiment, high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range of 180 to 220°C and/or spindle oil and/or monochloronaphthalene, preferably α-monochloronaphthalene, are also used.

The organic heavy-volatile oil-like or oily solvent with an evaporation number above 35 and a flash point above 30°C, preferably above 45°C, can be partially replaced by light or medium-volatile organic chemical solvents, provided that the solvent mixture retains 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. Thereby, the insecticide-fungicide mixture should at least be as soluble as in the previously mentioned solvents. It has been established that, depending on the evaporation rate and flash point of the oil-like or oily solvents used, these can be replaced with up to 20% by weight, preferably up to 5% by weight, of a solvent with a lower evaporation rate.

As regards the fungicidally active substances, it has been shown that it must be used in different concentrations depending on the type of fungicide. Using 3 to 8% by weight of chlorophenol, preferably penta- and/or tetrachlorophenol, has proven to be particularly advantageous with regard to the fungicidal effect. Surprisingly, it has been shown that the tetravalent fungicide organotin compounds and the fungicide 1-trityl-1,2,4-triazoles give the wood preservative a very good fungicidal effect already in concentrations of 0.2 to 2% by weight. Preferably, 0.3 to 2% by weight of a fungicide tetravalent organotin compound and/or 1-trityl-1,2,4-triazole of the general formula I in which R is a fluorine, chlorine - or bromine atom, a trifluoromethyl, nitro or cyano group or an alkyl group with up to 4 carbon atoms, and n is 1 or 2, as well as alters thereof with organic or inorganic acids, preferably trifluoromethyl-tri-phenylmethyltriazole or a mixture of one or more of the above-mentioned fungicides.

As tetravalent organotin compounds, the tetravalent organotin compounds known per se as fungicides can be used. The following tetravalent organotin fungicide compounds have been found to be particularly suitable in the wood preservatives according to the invention: Bis-(tri-butyl-tin) oxide, tri-n-butyltin trichloroacetate, tri-n-butyltin-8-oxyquinoline, tri-n-butyltin pentachlorophenolate . Instead of these, as previously mentioned, preferred fungicides, however, one can use others which are soluble in the stated solvents, or also mixtures of such other fungicides, e.g. fungicide oil-soluble naphthenates, preferably zinc and/or copper naphthenates; 8-oxyquinoline or these fungicide oil-soluble salts or derivatives, preferably phenylmercuric-8-oxyquinolate; fungicide compounds or derivatives or mixtures of chlorophenols, preferably compounds or mixtures of penta- and/or tetrachlorophenol with highly volatile amines, e.g. rosin amine; nitrophenols or nitrochlorophenols and/or nitrochlorobenzenes, preferably 1,2-dinitrotetrachlorobenzene; oil-soluble fungicide metal-organic compounds, e.g. of copper, zinc, manganese, cobalt, chromium or mercury, e.g. in the form of caprylates, naphthenates, oleates and the like; fungicidal salts of N-nitroso-N-cyclohexylhydroxylamine, preferably the aluminum salt of N-nitroso-N-cyclohexylhydroxylamine and/or N-trichloromethylthiotetrahydrophthalimide. When using N-nitroso-N-cyclohexylhydroxylamine and/or the aluminum salt of N-nitroso-N-cyclohexylhydroxylamine, however, one must take into account that these fungicidal compounds are apparently only suitable for certain types of wood, resp. against special wood fungi. Tar oil distillates and/or tar oil can also be incorporated into the fungicide mixtures.

According to another embodiment, the organic chemical heavy-volatile or oily solvent is at the same time a fungicidally active substance - e.g. chironaphthalene, preferably monochloronaphthalene and/or dichloronaphthalene. Thereby, the concentration of fungicide in this exceptional case is exceeded. Preferably, however, monochloronaphthalene and/or dichloronaphthalene are not used as the only fungicidal active substance, but are used together with other solvents and/or fungicides within the scope of the invention.;

Depending on the active substances and the like used, it may be appropriate to use additional emulsifiers and/or crosslinking agents.

With regard to the action of the preservative

and to reduce corrosion, preservatives are used together with mandelic acid and/or benzotriazole. In this combination, discolouration of the wood preservative in tin containers or by impact of the wood preservative on

1

metal or metal parts due to possible corrosion. These corrosion protection agents are preferably used in amounts by weight of 0.05 to 0.2% by weight.

The preservatives are often produced in the form of concentrates which, after transport to the place where they are to be used, are diluted with the specified solvents to the usual concentrations. Thereby, it is possible to produce highly effective wood protection concentrates that can be transported very reasonably.

When the preservatives according to the invention are

it is very advantageous to prepare a concentrate. During the production of the concentrates, of course the specified concentrations shift in such a way that the weight amounts of the insecticide mixtures and fungicides are increased, so that after transport it is possible to achieve the previously mentioned concentrations by adding solvent.

The application quantity of preservatives according to the invention differs depending on the area of application, concentration of active substance and the like. In general, the quantities amount to 100 to 350 g/m 2 , preferably 150 to 200 g/m 2 . The agent can be used on all types of wood or wooden materials, and preferably on dry ones.

Comparison experiment.

Tested preservatives and test methods.

1% impregnating agent solutions of diethoxy-thiophosphoryloxyimino-phenylacetonitrile or 0,0-diethyl-O-α-cyanobenzylidene-amino thionophosphate; diethoxy-thiophosph oryloxy-imino-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 with a side range between 180 and 210°C. As a fixing agent, the impregnating agent also contained tributyl phosphate. They tried the active substances alone and a combination of these in special weight ratios.

For the test, round filters were soaked with the diluted impregnating agent and dried in the open for 8 days. After that, small glass tubes (diam. 2 cm, height 5 cm) which were filled with 2 moist plastic disks (polyurethane foam) were placed on the filter. 50 mg of wood and 30 workers of the termite strain Reticulitermes santonensis were introduced into each tube. The duration of the experiment was 21 days.

During the experiments, the work was done so that this applied effective amount of substance was 20 g/m 2 in a series of experiments and 25

2

g/m at the second.

From these comparison tests, it appears that, subject to compliance with certain quantity ratios, an increase in effectiveness is achieved for the protective agent which is even above the additive effect of the individual substances.

The expression "% dead" indicates the mean value of the termites killed from three comparison trials. Damage indicates greater material destruction, while attack only indicates partial destruction or a small damage, e.g. due to incipient attacks without widespread damage. During these experiments, it was further very surprisingly determined that the time it took for the termites to die was shortened for the combinations compared to the individual substances.

in

This preservative is suitable as a wood protective primer with a good effect against fungi and insects including te rini tie.

This wood preservative is suitable for combating insects and termites with simultaneous preventive action and good fungicidal action at the same time.

This mixture is suitable as a preventive wood preservative.

This wood preservative has a good preventive effect against insects, especially against termites. It has an excellent penetration ability and a long duration of action, even in the case of climatic stresses.

The resistance to fungi is also very good for this mixture.

The wood preservative causes a lacy coloring of the wood and protects it against fungi and insects.

This preservative is suitable as a wood-protecting agent with a good effect against fungi and insects, including termites and powdery mildew.

Claims (5)

1. Means for the preservation of wood and wood materials, consisting of oil-soluble or oily solvent-soluble organic chemical insecticides and fungicides, highly volatile solvents and possibly common additives, characterized in that the preservative comprises 0.5 to 7% by weight, preferably 2 to 5% by weight, calculated on the basis of the finished mixture, of a mixture consisting of at least one in an organic-chemical heavy-volatile or oily solvent with an evaporation number above 35 and a flash point above 30°C soluble insecticide alkoxy-phenylrN-alkylcarbamate and/or alkylphenyl-N-alkylcarbamate and at least one insecticide halogenated or halogen-free thionophosphoric acid ester and/or thionophosphonic acid ester with the general formula where R2 denotes an alkyl radical with 1 to 4 C atoms, R2 an alkyl radical or an alkoxy group with 1 to 4 C atoms or a phenyl radical, and R^ denotes a phenyl radical or one with 1 to 3 halogen atoms or with lower alkyl or Alkoxy groups substituted phenyl residue, whereby the carbamate or the carbamate mixture in the insecticide mixture relates to the thionophosphoric acid ester or the thionophosphonic acid ester or mixture thereof as 3:1 to 1:3, preferably 1:0.75 to 1:2 (by weight), and from 0.3 to 10% by weight calculated on the basis of the finished mixture, of a i an organic-chemical heavy-volatile oily or oil-like solvent with an evaporation rate of over 35 and a flash point over 30°C insoluble fungicide or fungicide mixture as well as more than 64% by weight, preferably more than 72% by weight, calculated on the basis of the finished mixture, of a highly volatile oil-like or oily organic chemical solvent with an evaporation number above 35 and a flash point above 30°cJ 2. Means for preserving wood and wood materials according to claim 1, characterized in that the insecticide mixture contains an alkoxyphenyl-N-carbamate with the general formula and/or an alkylphenyl-N-alkylcarbamate of the general formula whereby in both cases eh means an alkyl residue with 1 to 4 carbon atoms, preferably a methyl residue, and R 2 in both cases means an alkyl residue with 1 to 5 carbon atoms, preferably an alkyl residue with 3 or 4 carbon atoms. 3. Agent according to claim 1, characterized in that it contains an ester with the formula as a halogenated or halogen group-free thionophosphoric acid ester preferably diethoxy-thiophosphoryloxyimino-phenylacetonitrile or according to recent terminology 0,0-diethyl-0-(α-cyanobenzylidene-amino)thionophosphate and/or (diethoxy-thiophosphoryloxyimino)-2-chlorophenylacetonitrile. 4. Agent according to claims 1 to 3, characterized in that it contains a mixture of 2-isopropoxyphenyl-N-methylcarbamate and/or butylphenyl-N-methylcarbamate and an insecticide halogenated or halogen-free thionophosphoric acid ester with the formula preferably (diethoxy-thiophosphoryloxyimino)-phenylacetonitrile or 0,0-diethyl-O-(ct-cyanobenzylidene-amino)thionophosphate and/or (diethoxy-thiophosphoryloxyamino)-2-chloro-phenyl-acetonitrile. 5. Agent according to claims 1 to 4, characterized in that 0.5 to 20% by weight, preferably 2 to 15% by weight, of the organic highly volatile oil-like or oily solvent or solvent mixture with an evaporation rate above 35 and a flash point above 30°C, is replaced with the same amount of one or more organic-chemical binders and/or fixing agents, whereby organic-chemical binders and/or fixing agents are used which can be distributed respectively . emulsified in the oily or oil-like solvent or the mixture of these, but which are preferably soluble therein.