JPS6224241B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to preservatives for wood or wood-based materials using organic chemical pesticides and fungicides that are oil-soluble or soluble in oily solvents and refractory solvents. It is known that a large number of carbamates and thionophosphates have a good insecticidal effect.
Therefore, these compounds are used in particular as pest control agents, plant protection agents, in the form of sprays, etc. for the direct or indirect control of pests. As plant protection agents, the need and requirement often arises for these pesticides that they should be degraded after a certain period of time so that they are not harmful to humans or animals upon ingestion. Furthermore, the pesticides on these plants can be washed off with water, and it is therefore desirable to be able to treat vegetables and fruits treated with these pesticides by washing them with water before consumption. Therefore, a large number of insecticides that are used very effectively in the botanical field themselves no longer have the necessary effect after a certain experimental time when used for a specific purpose on plants and are therefore classified as special Post-processing may be required in each case. Also, most insecticides do not penetrate deeply into the plant parts, acting only on the surface of the plant, as much as possible, for example in the form of solutions, emulsions, spray concentrates, etc., and are washed away or degraded after a certain period of time. Should. Systemic insecticides, on the other hand, penetrate the plant parts, but are then degraded within a certain time, for example within three weeks. Powdered insecticides in powder form also often have low adhesion strength and are easily washed off. Furthermore, selective effects are often required for most insecticides. For example, useful animals such as hives, birds, etc. should not be harmed. This has the consequence that many insecticides can only be used effectively against certain pests, such as mites, while being ineffective against other insects. Therefore,
During the research process of this invention, a number of insecticides were tested for their properties in wood preservatives, and the results showed that a number of resistant insecticides with a wide spectrum of action, such as insecticidal phosphate esters, can themselves be used in wood preservatives. It turned out to be inappropriate to do so. That is, requirements are set for wood or wood-based material preservatives that significantly deviate from the requirements for insecticides in normal uses such as pest control agents, for example in plant protection. For example, insecticides used in plant protection should be decomposed and washed away after a certain period of time, while long-term effects are desired for preservatives. In this case, the preservative should not only immediately eradicate animals that adhere to the surface and come into contact with it, but also penetrate the wood as deeply as possible and protect the wood against later outbreaks of parasitic diseases. It is.
Exposure to the open air should not result in significant loss of effectiveness or deterioration of the preservative effect of the wood protectant. It is an effective wood preservative because wood or wood-based materials are not only attacked and decomposed by numerous wood pests, insects, or their larvae, but are also damaged by degrading plant species (fungi, etc.). They should also have a corresponding fungicidal action, in which case the action of the insecticides used should not be impaired by the fungicides or vice versa. Therefore, the object and problem of the present invention is to provide an effect that has sufficient insecticidal and bactericidal wood protection effects even after a long period of time, and permanently protects wood or wood materials without deteriorating their quality. The goal was to find a wood preservative with a high quality. The wood preservative should maintain sufficient preservative action even after exposure to the open air, ie, under the action of rain, snow, frost and sunlight. In this case, this agent should be usable for wood preservation with very good bactericidal and insecticidal sustained action and as a wood preservation primer or wood preservation stain or transparent varnish primer. and should be able to penetrate into wood or wood-based materials. The above-mentioned problem is solved according to the present invention in a preservative for wood or wood materials using organic chemical insecticides and fungicides that are oil-soluble or soluble in an oily solvent and a refractory solvent, in which the preservative is volatile according to DIN 53170. at least one alkoxyphenyl N-alkyl carbamate and/or alkylphenyl N-alkyl carbamate soluble in a hardly volatile oily or oily organic solvent having a temperature >35 and a flash point >30° C. according to DIN 51758; Soluble in the above organic solvent, general formula: (In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms, R ₂ represents an alkyl group, an alkoxy group, or a phenyl group having 1 to 4 carbon atoms, and X represents a hydrogen atom or a halogen atom. A mixture with at least one thionophosphoric acid ester or thionophosphonic acid ester which is halogenated or does not have a halogen substituent represented by
and about 0.3 to 10% by weight of a fungicide or fungicide mixture soluble in the organic solvent and >64% by weight of the organic solvent, and a carbamate or carbamate mixture, thionophosphoric acid in the pesticide mixture. ester or thionophosphonic acid ester or a mixture thereof in a weight ratio of 3:1 to 1:3. According to one advantageous embodiment, one component of the insecticide mixture has the general formula: (wherein R ₄ represents an alkyl group having 1 to 4 carbon atoms and R ₅ represents an alkyl group having 1 to 5 carbon atoms) and/or Or general formula: (wherein R ₆ represents an alkyl group having 1 to 4 carbon atoms and R ₇ represents an alkyl group having 1 to 5 carbon atoms) . According to another advantageous embodiment, the other component in the insecticide mixture has the general formula: (wherein, -thiophosphoryloxyimino)-2-chlorophenylacetonitrile. As the sterilizing agent, a sterilizing agent which is dissolved in a predetermined weight in a known per se, hardly volatile oily or oily organic solvent is used. Preferably, as a fungicide a fungicidal chlorphenol, preferably penta- and/or tetrachlor or a fungicidal tetravalent tin organic compound or a fungicidal tetravalent tin organic compound of the general formula: 1-trityl- (wherein R' represents a fluorine, chlorine or bromine atom, a trifluoromethyl group, a nitro group or a cyano group or an alkyl group having up to 4 carbon atoms, and n represents 1 or 2) 1・2・4
-triazoles and their salts of organic or inorganic acids, preferably trifluoromethyl-triphenylmethyltriazoles or mixtures of one or more of the abovementioned fungicides are used. According to one particularly advantageous embodiment, one component of the insecticide mixture is 2-isopropoxy-phenyl N
- methyl carbamate and/or butylphenyl N-methyl carbamate, and the other component is of the formula: (wherein, X represents a hydrogen atom or a halogen atom, and n is 0 or 1) A halogenated or non-halogen-substituted thionophosphate ester, such as (diethoxy-thiophosphoryloxyimino)- Phenylacetonitrile and/or
or (diethoxy-thiophosphoryloxyimino)-2-chlorophenyl-acetonitrile. In preliminary experiments a number of insecticides with a broad spectrum of action, such as O.O-diethyl-O
-[(2-isopropyl-4-methyl)-6-pyrimidyl]-thionophosphate, O.O-dimethyl-O-2.2-dichlorovinyl-phosphate, diethylvinylphosphate and bis(dimethylamino)-phosphoryl Within the scope of the present invention, insecticidal alkoxy-
When phenyl N-alkyl carbamate and/or alkylphenyl N-alkyl carbamate is used in combination with at least one halogenated or halogen substituent-free thionophosphoric acid ester or thionophosphonic acid ester of an insecticide, the action and effect can be improved. It was found that the wood preservative's long-lasting effect was imparted along with an increase in the insecticidal effect.In this case, even when a fungicidal active substance was added, no decrease in the insecticidal effect was observed. The wood preservatives according to the invention penetrate well into wood or wood-based materials and therefore also impart a certain deep preservation effect and penetrating action.
When tested in the field, the preservative was found to remain effective and retain wood-protective bactericidal and insecticidal properties even on long-term exposure, yet does not harm the wood. According to one particularly advantageous embodiment, said volatility>
0.5 to 20% by weight of a refractory oily or oily organic solvent or solvent mixture having a flash point of >30°C and a flash point of >30°C;
Advantageously 2 to 15% by weight is replaced by one or more organic binders and/or fixing agents, with the organic binder and/or fixing agent being dispersed or dispersed in the oily or oily solvent or solvent mixture. Emulsifying, preferably dissolving, emulsifying agents are used. In a particularly preferred embodiment, the binder used is a synthetic resin in the form of an emulsion, dispersion or solution, preferably an alkyd resin or a modified alkyd resin or a phenolic resin and/or an indene-coumarone resin. As binder it is possible to use up to 10% by weight of bitiumen or similar substances. Furthermore, dyes, pigments, water repellents, deodorants, inhibitors or corrosion protectants, etc. known per se can be used. As a water repellent, use paraffin, wax, wool fat, etc. at a rate of 0.2~
A weight amount of 5% by weight is used, preferably 0.5-2% by weight. As fixing agents or softeners, in particular binders are used which additionally prevent volatilization and/or crystallization or precipitation of the active ingredient. Advantageously, (a) softeners, such as alkyl, aryl or aralkyl phthalates, preferably dibutyl,
dioctyl- and benzylbutyl phthalate,
Alkyl phosphates or phosphoric acid esters, preferably tributyl phosphate, adipate, preferably di-(2-ethyl-hexyl)-adipate, stearates and oleates, such as alkyl stearates or alkyl oleates, preferably butyl oleate. ates, butyl stearates or amyl stearates, bis-(dimethylbenzyl) ethers, p-toluenesulfonic acid esters, glycerin esters, glycerin ethers or polymeric glycol ethers and/or (b) oils, such as linseed oil, castor oil, tall oil and their esters and/or (c) ketones and/or polyvinyl alkyl ethers, such as ketones with alkyl, aryl or aralkyl groups, preferably benzophenone, ethylbenzophenone; polyvinyl alkyl ethers, preferably uses a fixing agent based on polyvinyl methyl ether. As refractory oily or oily organic solvents with a volatility >35 according to DIN 53170 and a flash point >30 °C, preferably >45 °C according to DIN 51758, water-insoluble or hardly water-soluble solvents are used. It is advantageous to do so. Solvents of this type include the corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white split, petroleum oils, gas oils and/or alkylbenzenes. Mineral oil with a boiling range of 170-220℃, 170-220
White Split, with a boiling range of 250 °C
Spindle oil with boiling range of ~350℃, 160~
It is advantageous to use petroleum or aromatics, turpentine, etc. with a boiling range of 280°C. In one embodiment, a high-boiling mixture of aromatic and aliphatic hydrocarbons and/or spindle oils and/or monochloronaphthalene, preferably alpha-monochloronaphthalene, having a boiling range of 180 to about 220 DEG C. was used. Slightly volatile oily or oily organic solvents with a volatility >35 according to DIN 53170 and a flash point >30 °C, preferably >45 ° according to DIN 51775 are partially replaced by easily volatile or moderately volatile organic solvents. Solvents can be substituted, provided that in that case the solvent mixture likewise has a volatility >35 and a flash point >30°C, preferably 45°C.
and the pesticide/fungicide mixture should be soluble in this solvent mixture. In this case, the insecticide/fungicide mixture should be at least as well soluble as in the oily or oily solvent. up to 20% by weight, preferably up to 15% by weight, of a refractory oily or oily organic solvent, based on the respective volatility and flash point of the oily or oily solvent used;
It has been found that it can be replaced by a solvent with lower volatility. It has been established that the fungicidal substances should be used in different concentrations depending on the particular type of fungicide. With regard to the bactericidal effect, the use of 3 to 8% by weight of chlorphenol, in particular penta- and/or tetrachlorophenol, was particularly advantageous. Surprisingly, it has been found that tetravalent fungicidal tin organic compounds and fungicidal 1-trityl-1,2,4-triazole can impart very good bactericidal action to wood preservatives at concentrations of 0.3 to 2% by weight. found.
Therefore, as a fungicide among wood preservatives, fungicidal tetravalent tin organic compounds and/or (wherein R is a fluorine atom, a chlorine atom or a bromine atom,
1-trityl- of trifluoromethyl, nitro or cyano or an alkyl group having up to 4 carbon atoms and n is 1 or 2
Preference is given to using 1,2,4-triazole as well as salts of organic or inorganic acids, preferably trifluoromethyl-triphenylmethyltriazole or mixtures of one or more of the abovementioned fungicides. As the tetravalent tin organic compound, a known bactericidal tetravalent tin organic compound can be used. The following fungicidal tetravalent tin organic compounds have been found to be particularly advantageous in the wood preservatives of the invention: bis-tributyltin oxide, tri-n-butyltin trichloroacetate, tri-n- Butyltin-8-oxyquinoline, tri-n-butyltin pentachlorophenolate, tri-n-butyltin bisethylenedithiocarbamate, tri-n-butyltin benzoylcyanoacetic acid, tri-n-butyltin dimethyl arsenate, - n-butyltin fluoride, tri-n-butyltin rhodanide, tributyltin dichlorophenolate and tri-n-butyltin acrylate/hexachlorocyclopentadiene adduct. However, instead of the said fungicides which are advantageously used within the scope of the invention, other said oily or oily solvent-soluble fungicides or mixtures of these with said fungicides, such as oil-soluble naphthenates, can be used. , preferably tin naphthenate and/or copper; 8-oxyquinoline or its fungicidal oil-soluble salts or derivatives, advantageously phenyl-mercury-8-oxyquinolate; fungicidal compounds or derivatives or mixtures of chlorphenol. , preferably a compound or mixture of penta- and/or tetrachlorophenol and a refractory amine; nitrophenol or nitrochlorophenol and/or nitrochlorobenzene, especially 1.2
- dinitrotetrachlorobenzene, fungicidal oil-soluble metal-organic compounds, such as compounds of copper, zinc, manganese, cobalt, chromium or mercury in the form of caprates, naphthenates, oleates, etc.; N-nitroso-
It is possible to use the fungicidal salts of N-cyclohexylhydroxylamine, preferably the aluminum salts of N-nitroso-N-cyclohexylhydroxylamine and/or N-trichloromethylthiotetrahydrophthalimide. However, N
- When using nitroso-N-cyclohexylhydroxylamine and/or aluminum salts of N-nitroso-N-cyclohexylhydroxylamine, these fungicidal compounds are clearly only for certain wood species or wood fungi. It should be noted that it is appropriate. The disinfectant mixture may also contain a portion of tall oil distillate and/or tall oil. According to a further embodiment, the hardly volatile or oily organic solvent is at the same time a fungicidal active substance, for example chlornaphthalene, preferably monochlornaphthalene and/or dichlornaphthalene. This increases the concentration of disinfectant in this case. However, it is advantageous within the scope of the invention to use monochlornaphthalene and/or dichlornaphthalene not as the sole fungicidal active substance, but in combination with other solvents and/or fungicides. Depending on the active substance used in each case, it may be advantageous to additionally use emulsifiers and/or wetting agents. Regarding the effects of preservatives and inhibition of corrosion,
Preservatives are advantageously used together with mandelic acid and/or benzotriazole. In this combination, discoloration of the wood preservative due to corrosion, which may occur in tin containers or when the wood preservative acts on metal or wood containing metal parts, is avoided. This corrosion protectant is 0.05-0.2% by weight
It is advantageous to use a weight of . Frequently, preservatives are produced in the form of a concentrate which, after being transported to the point of use, is diluted again to the customary concentration using a non-volatile oily or oily solvent. This makes it possible to produce highly effective wood protection concentrates that can be transported with low transport costs. In the case of the preservatives according to the invention for wood and wood-based materials, it is particularly advantageous to produce concentrates.
Of course, when producing concentrates, the predetermined concentration is
In each case, the weight proportions of the insecticide mixture and the fungicide (homogeneity is advantageous) are increased so that after transport they can be diluted back to the stated concentration (use concentration) by adding oil or oily solvents. be changed. The application amount of the wood preservative according to the invention varies depending on the particular application, active substance concentration, etc.
Generally from about 100 to 350 g/m ² , advantageously from 150 to
It is 200g/ ^m2 . As wood or wood-based materials,
Useful for windows, doors, floors, ceilings, paneling, coverings, fences, walls, and buildings.

【table】

[Table] Comparative experiments have revealed that by adhering to a certain mixing ratio, the effect of the preservative actually increases far more than the added effects of the individual substances. The average value of dead termites in "% mortality" was calculated from three comparative experiments each. Harmful erosion refers to high material decomposition, while perforation erosion is to be understood as partial decomposition or slight damage, such as damage due to the initiation of termite erosion, without further damage occurring. . During the experiment, surprisingly,
It was found that the termite eradication time in the combination was reduced compared to the individual components. Example 1 Penta- and/or tetrachlorophenol
5.0% by weight Isopropoxyphenyl N-methylcarbamate 0.6% by weight (diethoxy-thiophosphoryloxyimino)-phenylacetonitrile 1.8% by weight Alkyd resin (100%) 12.0% by weight Desiccant solution (1 part cerium octoate and octanoic acid solution consisting of 2 parts of zinc) 0.2% by weight Aromatic and aliphatic hydrocarbons (boiling range: 180-212
C) 80.4% by weight 100.0% by weight This preservative is suitable as a wood protective basecoat with a good effect against fungi and insects, including termites. Example 2 Bis-phenyl-(3-trifluoromethylphenyl)-1-(1,2,4-triazolyl)-methane 1.0% by weight 2-s-butylphenyl N-methylcarbamate 1.0% by weight 2-isopropoxyphenyl N-Methyl carbamate 1.0% by weight (diethoxy-thiophosphoryloxyimino)-phenylacetonitrile 1.5% by weight Benzothiazole 0.05% by weight Tributyl phosphate (softener) 6.0% by weight Aromatic and aliphatic hydrocarbons (boiling range: 180- 212
℃) 89.45% by weight 100.0% by weight This wood preservative is a repellent wood preservative that has a good bactericidal effect and at the same time a preventive effect against insects including termites. Example 3 Pentachlorophenol 5.5% by weight 2-s-butylphenyl N-methylcarbamate 1.0% by weight (diethoxy-thiophosphoryloximino)-phenylacetonyl 2.0% by weight Benzotriazole 0.1% by weight Alkyd resin (100%) 4.0% by weight Aromatic and aliphatic solvents (boiling range: 180-212℃)
87.4% by weight 100.0% by weight This mixture is suitable as a preventative wood preservative. Example 4 Bis-phenyl-(trifluoromethylphenyl)-1-(1,2,4-triazolyl)methane
1.5% by weight 2-iso-propoxyphenyl N-methylcarbamate 1.5% by weight (diethoxy-thiophosphoryloxyimino)-phenylacetonitrile 2.0% by weight α-monochlornaphthalene (industrial use) 50.0% by weight Linseed oil 6.0% by weight Spindle oil (Boiling range: 250-320℃)
39.0% by weight 100.0% by weight This wood preservative has good preventive effect against insects, especially termites. It also has excellent penetrating action and long working life even when affected by weather. The antifungal effect of this active substance mixture is likewise very good. Example 5 Bis-phenyl-(3-trifluoromethylphenyl)-1-(1,2,4-triazolyl)methane
1.5% by weight 2-isopropoxyphenyl N-methylcarbamate 0.75% by weight (diethoxy-thiophosphoryloximino)-phenylacetonitrile 1.5% by weight Alkyd resin (100%) 15.0% by weight Linseed oil varnish 5.0% by weight Benzotriazole 0.05% by weight % Drying as described in Example 1 + Methyl ethyl ketoxime (anti-stripping agent) 0.3% by weight Aromatic and aliphatic solvents 72.90% by weight Inorganic and organic pigments (transparent iron oxide pigments or monoazo pigments) 3.0% by weight 100.0% by weight Preservation of this wood The agent is effective in staining wood as a clear coat and protects the wood against fungi and insects. Example 6 Penta- and/or tetrachlorophenol
5.0% by weight Phenylmercuric oleate 0.5% by weight Isopropoxyphenyl N-methyl carbamate 0.6% by weight (diethoxy-thiophosphoryloxymono)-phenylacetonitrile 1.8% by weight Alkyd resin (100%) 12.0% by weight Desiccant solution (Example 1) ) 0.2% by weight Aromatic and aliphatic hydrocarbons (boiling range: 180−212
C) 79.9% by weight 100.0% by weight This preservative is suitable as a wood preservative basecoat with good action against fungi, including termites and blue molds. The preservatives for wood or wood-based materials described in Examples 1 to 6 above, when applied to test wood at an application rate of 50 mg/m ² of the preservative, resulted in 100% mortality without any harmful erosion or drilling attack. was able to achieve this rate. In practice, approximately 100-350 g/m 2 of active substance, especially 150-200 g/m ² , taking into account evaporation or wash-off.
A coating weight of g/m ² should be used.

Claims (1)

[Scope of Claims] 1. A preservative for wood or wood materials using an oil-soluble or oily solvent-soluble organic chemical insecticide and bactericide and a hardly volatile solvent, wherein the preservative is
Alkoxyphenyl N- soluble in poorly volatile oily or oily organic solvents with volatility >35 according to DIN 53170 and flash point >30 °C according to DIN 51758
At least one alkyl carbamate and/or alkylphenyl N-alkyl carbamate and a general formula soluble in the above organic solvent: (In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms, R ₂ represents an alkyl group, an alkoxy group, or a phenyl group having 1 to 4 carbon atoms, and X represents a hydrogen atom or a halogen atom. A mixture with at least one thionophosphoric acid ester or thionophosphonic acid ester which is halogenated or does not have a halogen substituent represented by
and about 0.3 to 10% by weight of a fungicide or fungicide mixture soluble in the organic solvent and >64% by weight of the organic solvent, and a carbamate or a mixture of carbamates in the pesticide mixture; A preservative for wood or wood materials, characterized in that it contains a phosphoric acid ester, a thionophosphonic acid ester, or a mixture thereof in a weight ratio of 3:1 to 1:3. 2 One of the insecticide mixtures has the general formula: (wherein R ₄ represents an alkyl group having 1 to 4 carbon atoms and R ₅ represents an alkyl group having 1 to 5 carbon atoms) and/or Or general formula: (wherein R ₆ represents an alkyl group having 1 to 4 carbon atoms and R ₇ represents an alkyl group having 1 to 5 carbon atoms) , the preservative according to claim 1. 3 The other component in the insecticide mixture has the general formula: The preservative according to claim 1, which is a halogenated or thionophosphate ester having no halogen substituent represented by the formula (wherein, X represents a hydrogen atom or a halogen atom). 4 one component of the insecticide mixture is 2-isopropoxyphenyl N-methyl carbamate and/or butylphenyl N-methyl carbamate;
and the other component is the formula: The preservative according to claim 1, which is a halogenated or thionophosphate ester having no halogen substituent represented by the formula (wherein, X represents a hydrogen atom or a halogen atom). 5 Volatility >35 according to DIN53170 and DIN51758
0.5 to 20% by weight of a refractory oily or oily organic solvent with a flash point >30°C based on The preservative according to claim 1, wherein the fixing agent is one that is dispersible, emulsifiable or soluble in an oily or oily solvent or solvent mixture.