DK162146B - PESTICID AGENT FOR TREATMENT OF TREES - Google Patents

Description

DK 162146 B

The present invention relates to a pesticidal agent for treating wood, e.g. of building timber or wood for carpentry, containing a water-insoluble pesticide component, a synthetic resin which can be diluted with water, a water-soluble emulsifier and an amino group-containing compound. In particular, the invention relates to such agents which are in concentrated form and which can be diluted with water before they are put into use, as well as such agents which are diluted with water and are ready for use.

U.S. Patent No. 3,281,318 discloses pesticidal agents of this kind, which consist of aqueous emulsions of mixtures of a polychlorophenol, a wax, a fatty acid, a nonionic emulsifier, and an alkanolamine. The nonionic emulsifier has in these known pesticidal agents to enhance the homogeneity of the emulsion, and the alkanolamine, which is preferably ethanolamine, is intended to facilitate the dispersion of the fatty acid and of the polychlorophenol. These known pesticidal agents, due to the presence of a wax species which has the function of acting as a fixing agent for the polychlorophenol, exhibit the disadvantage that they can only be used with difficulty to impregnate in sufficient depth of the treated articles 25 of wood, and the protection which they ensure is of short duration. The stability of these pesticides is otherwise uncertain.

In order to alleviate these drawbacks, German Patent Publication No. DE-A-3 004 319 has proposed pesticidal agents in aqueous emulsions, in order to ensure the fixation of the active ingredients to the wood, a synthetic resin which can be diluted with water, together with an amine, the emulsifier used being also non-ionic.

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The present invention has for its object to provide pesticidal agents of this kind. Surprisingly, it has been found that by using a special anionic emulsifier and a special amino group-containing compound, agents are obtained which, after dilution with water, appear as an actual solution, having in particular the transparency provided with excellent stability and having a high penetration ability into the wood.

For this purpose, the invention relates to pesticidal agents for treating wood consisting of a water-insoluble pesticide, a water-soluble synthetic resin, a water-soluble emulsifier, and an amino group-containing compound, the agent of which is claimed. l's characteristic part stated.

The aforementioned pesticide active ingredient may in the composition of the invention be any water-insoluble pesticide agent, as is commonly used in pesticidal wood treatment compositions. It can be a water-insoluble fungicide or an insoluble water-insecticide. The pesticidal compositions of the invention may contain, as needed, more water-insoluble fungicides or more water-insoluble insecticides or a mixture of one or more water-insoluble fungicides and one or more water-insoluble insecticides.

Examples of water-insoluble insecticides used in the pesticidal composition of the invention include pyrethrum, pyrethroids (such as pyrethrin, allethrin, cyclethrin, furethrin, tetramethrin, decamethrin and bioresmethrin), insecticidal carbamates. (such as propoxur), esters of phosphonic acid, phosphoric acid, thiophosphoric acid, dithiophosphoric acid or thionophosphoric acid, chlorinated hydrocarbons such as methoxychlor, lindane, chlorine, heptachlor, aldrin and di-3

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eldrin.

Examples of 1 water-insoluble fungicides which can be used in the present pesticide include 5 organic compounds of tetravalent tin (such as tributyltin benzoate, tris (tributyltin) phosphate and the oxide of bis (tributyltin), 1-trityl The 1,2,4-triazole compounds of the general formula: 10 N in / o

Rn 20 wherein R represents a fluorine atom, a chlorine atom or a bromine atom, a trifluoromethyl group, a nitro group or cyano group, or an alkyl group containing up to 4 25 carbon atoms and wherein n represents one of the numbers 1 or 2, as well as organic or inorganic acid addition salts thereof (e.g., trifluoromethyl-triphenylmethyl triazole), hexachlorobenzene, pentachlorobenzene, chelates with fungicidal action of tris (N-cyclohexyldiazenium dioxide) metal, especially those containing aluminum and found in a product known under designation "Xyligen A1" (BASF), N, N-dimethyl-N'-phenyl-N '- (fluorodichloromethylthio) sulfamide, Ν, Ν-dimethyl-N'-p-tolyl-N' - (dichlorofluorobenzyl) methylthio) sulfamide, chlorinated naphthalenes, copper and zinc naphthenates, the mercaptobenzothiazole compounds and their salts, 8-hydroxyquinoline and their salts, organo boro esters, quaternary ammonium compounds as derivatives 4

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thereof, condensation compounds derived from diphenylamines and acetone, N-cyclohexyl, N-methoxy, 2,5-dimethylfuran-3-carboxamide found in the product known as "Xyligen B" (BASF), N- (trichloromethyl) 5-thio) -phthalimide, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, 2- (3-thiazolyl) -benzimidazole, 5-n-butyl-2-dimethylamino-4-hydroxy -6-methyl-pyrimidine, ortho-phenylphenol and paraphenylphenol.

The pesticide active agent of the pesticidal agents concerned is selected from chlorinated phenols in a particularly advantageous embodiment of the invention. The preferred chlorinated phenols are polychlorophenols, tetrachlorophenol, and pentachlorophenol have been found to be particularly advantageous.

The water-dilutable synthetic resin present in the pesticidal agent of the invention is preferably an alkyd resin which is soluble in water thanks to the formation of a salt having an amino group-containing compound or a acrylic modified alkyd resin, such as that known by the trademark Hydrorob (Robbe).

The emulsifier of the present compounds is an anionic emulsifier and selected from ammonium and alkali metal alkylbenzenesulfonates of the general formula: R - SO3 - M 30 wherein M represents the amino group or an alkali metal group, e.g. sodium and wherein R represents an alkylbenzene group.

The alkylbenzenesulfonates may be straight-chain alkylbenzene sulfonates or branched alkylbenzenesulfonates; preferred are the straight-chain alkylbenzene sulfonates, commonly referred to as "LAS". Particularly advantageous equal-

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chain alkylbenzene sulfonates are those whose alkyl chain contains from 8 to 18 carbon atoms, especially from 12 to 14 carbon atoms; the dodecylbenzenesulfonates, especially the sodium salt of dodecylbenzenesulfonate, are particularly suitable.

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The anionic surfactant can be used in the present compositions, as is present, or in the form of a dispersion or solution in an organic solvent or in water, if it is desired to decrease its viscosity. In general, emulsified products containing 30 to 80 parts by weight of ammonium or alkali metal alkyl benzene sulfonates containing 10-14 carbon atoms in the alkyl chain are obtained, and 20 to 70 parts by weight of one or more organic solvents and / or water. . The best results are usually obtained with such emulsifying products which contain from 40 to 60 parts by weight of alkyl benzene sulfonate (s) and sections. 30 to 50 parts by weight of organic solvent (s) and / or water.

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The alkanolamines included in the subject pesticide may be conventional products wherein the alkanol group consists of 2-4 carbon atoms and is obtained by reaction between ammonia and ethylene oxide, propylene oxide or butene oxide such as monoethanolamine, diethanolamine, tri -ethanolamine, monoisopropanolamine, diisopropanolamine, tri-isopropanolamine, mono-sec-butanol, di-sec-butanolamine and tri-sec-butanolamine. However, such alkanolamines are preferred where the alkanol group consists of 2 to 4 carbon atoms and is substituted by at least one alkyl group or phenyl group preferably consisting of 1 to 8 carbon atoms, especially to such alkanolamines substituted by two alkyl groups, preferably contains 1-4 carbon atoms. Examples of such alkanolamines are, on the one hand, methylethanolamine, butylethanolamine, phenylethylethanolamine, methyldiethanolamine, ethyl diethanolamine and phenyldiethanolamine, on the other

DK 162146B

6 ethanolamine, diethylethanolamine, diisopropylethanolamine, dibutylethanolamine and dimethylisopropanolamine. The best results have been obtained with alkanolamines whose solidification point is lower than -25 ° C, preferably lower than -50 ° C, and especially with diethylethanolamine.

The relative amount of alkanolamine conveniently employed can be readily determined experimentally, and it depends on various factors, among which, in particular, the nature of the alkanolamine, as well as the nature and relative amount of each of the ingredients in the agent, is determined. , as well as the desired concentration of the aqueous emulsion to be formed. As a general rule, it has been found desirable to arrange the weight content of the alkanolamine in such a way that the ratio of the weight of alkanolamine to the weight of the pesticidal action agent is between 0.1 and 2, preferably between 0.25 and 1. 25, having obtained the most advantageous results with a weight ratio of 0.5 to 1.

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All else being equal, the selection of the alkanolamine from those having a solidification point lower than -25 ° C ensures the achievement of very high stability aqueous emulsions capable of withstanding significant temperature variations, especially alternating periods of frost and periods. with ^ thawing, without affecting their stability, their clarity and their penetrating ability into the tree.

As a variation to reduce the diet of the agents corresponding to the preferred embodiment of the invention without damaging the properties of the aqueous emulsions thus obtained, one can substitute a portion of the low solidification alkanolamine with an equivalent amount of alkanolamine with a higher solidification point. In this variant of the invention, the relative amounts of low and high solidification temperature alkanolamines to be used depend on the temperature range which

DK 162146B

It is envisaged that the aqueous emulsions will be exposed, with the relative proportion of low solidification alkanolamine being larger, the greater the temperature range, and the lower the temperature at storage, handling or use. In practice, it is desirable to use at least 10% by weight, preferably at least 20% by weight, of alkanolamine having a solidification point lower than -25 ° C, preferably lower than -50 ° C. In practice, it is not necessary to exceed 75% by weight and 10 most frequently 50% of such an alkanolamine.

The optimum amount of anionic emulsifier to be used in the pesticidal compositions of the invention can also be determined experimentally and it also depends on 15 different factors, in particular the emulsifier chosen, as well as the nature and concentration of the other ingredients.

In general, it has been found desirable to arrange the content of anionic emulsifier in such a way that the ratio between the sum of the weight amounts of 20 emulsifier and of alkanolamine and the sum of the weight amounts of the other constituents of the agent other than water which is normally insoluble in water is between 1 and 2, preferably between 1.25 and 1.50.

The present pesticidal agent may contain, in addition to the water-insoluble pesticide, the synthetic resin which can be diluted with water, the anionic emulsifier and the alkanolamine, and other ingredients, in particular a plasticizer and a so-called co-solvent.

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Any plasticizer that is liquid or paste-like at ambient temperature can be used as a plasticizer. Examples of such plasticizers are fatty acid phosphates and fatty acid esters such as tributyl phosphate, butyl stearate, butyl oleate, di-butyl sebacate and dioctyl phthalate. These plasticizers are preferably esters derived from dicarboxylic acids.

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containing 4 to 10 carbon atoms, such as maleic, adipic and phthalic acids, as well as alcohols containing 2-8 carbon atoms. The best results have been obtained with phthalates of alcohols containing 3 to 6 carbon atoms, especially 5 with dibutyl phthalate.

As the co-solvent, all the co-solvents usually used in water-soluble alkyd resins, especially alcohols, and preferably glycols and glycol ethers containing 2-8 carbon atoms can be used. The best results are obtained with glycols containing 2 to 4 carbon atoms, especially with ethylene glycol. Co-solvent-containing agents are particularly suitable for use at winter temperatures. It is desirable that the weight of the co-sol vent taken into operation does not exceed 20%, preferably 10% by weight of the synthetic resin which can be diluted with water.

The pesticide agent in question may optionally contain a wax species; but in that case it is desirable that this wax species be present in a weight amount not exceeding 0.5% by weight of the total weight of the agent. It is generally preferred that the agent in question be free of wax.

The agent in question is in concentrated form which may optionally contain some dilution water, which is intended to provide the agent with a sufficiently good light flow unit so that it can be easily transferred between storage containers and to facilitate handling thereof when 30 pesticide diluted with water must be prepared and ready for use. The amount of water for dilution is in principle not critical and can be readily determined in each case, depending on the constituents of the concentrate and the desired ease of flow. In practice, good results are generally obtained with concentrates containing an amount of water up to 50% by weight of the total weight of the concentrate, since

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retrieves values greater than 10%, generally between 25 and 30%.

A preferred pesticidal agent which has been found particularly suitable for the formation of aqueous diluted pesticide emulsions which are ready for use and which have a high stability, are very fine and have a high degree of translucency, has the following composition: 5 to 20 parts by weight of chlorinated phenol, up to 4 parts by weight of a chlorinated hydrocarbon with insecticidal effect, 5 to 20 parts by weight of water-soluble alkyd resin, 5 to 20 parts by weight of plasticizer, 15 to 20 parts by weight of alkanolamine, 5 to 20 parts by weight of straight-chain sodium alkylbenzene sulfonate wherein the alkyl chain contains 10 to 14 carbon atoms, 5 to 20 parts by weight of co-solvent, and up to 50 parts by weight of water, 20 with any residual amount consisting of substances usually present in pesticidal agents intended for the treatment of wood. Such agents may e.g. be anti-UV agents, sicatives or pigments.

The pesticidal agent is diluted before use with water to a degree of dilution selected in each case, which depends on various factors, in particular the nature and the respective concentrations of the constituents contained therein. In general, the degree of dilution suitable for 30 corresponds to one part by weight of the constituents in addition to water per minute. 2 to 6 parts by weight of water in the agent.

Generally, it is sufficient to mix the ingredients 35 together with the preparation of the present pesticidal agent. In practice, it is convenient to carry out the mixture at such temperatures and pressure conditions so as not to stiffen the mixture of the components or

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evaporation of one or more of these components.

One can, for example. carry out the mixture at a temperature of between 15 and 55 ° C, and at pressures of between 0.535 and 1.135 bar, with the preferred temperatures being between 5 and 55 ° C and the preferred pressures being between 0.865 and 1.055 bar.

The present pesticidal agent is in the form of an aqueous emulsion of extremely high fineness, having a appearance as a transparent and homogeneous solution. It has great stability in long to and high resistance to temperature variations as well as to mechanical stresses, such as shocks, falls or centrifuges, without affecting stability.

In the following examples, concentrates of the agent according to the invention are described.

EXAMPLE 1 20

Mix thoroughly at a temperature of approx. 40 ° C pentachlorophenol, aldrin, diisobutyl phthalate, ethylene glycol and the product known under the trade name "Uradil 30100" (Scado N.V.), which is an alkyd resin.

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To the mixture thus obtained, a mixture of diethylethanolamine and monoethanolamine is successively added, and then an emulsifying product containing approx. 1 part by weight of water, one part by weight of isobutanol and 2 parts by weight of a mixture 30 of sodium alkylbenzenesulfonates of straight chain alkyl chain and of the general formula: 35 CnH2n + 1 - SO, Ne 11

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wherein: 10 s n * 14.

5 After dilution with water to obtain sufficient good flow properties to allow the mixture to be poured into storage containers, the concentrate in question has the following weight composition:

Ingredients Weight%

Pentachlorophenol 14

Aldrin 2 15 Resin "Uradil 30100" 13

Diisobutylphthalate 13

Ethylene glycol 1

Diethylethanolamine 4

Monoethanolamine 10 Emulsifier 10

Water 33

This concentrate is dispersed in water in an amount of 1 25 parts by weight of concentrate and 4 parts by weight of water, so as to obtain a dilute pesticide mixture which is ready for use in the treatment of pieces of wood, especially of structural materials such as building timber. Such agents have been found to consist of aqueous emulsions of extremely high degree of fineness, with the individual spheres having a mean diameter less than 0.05 μπι in accordance with the definition in French standard AFN0R T730409. For this reason, they had the appearance of transparent aqueous solutions. When subjected to a centrifugation experiment 2 corresponding to centrifugal force of 98100 m / sec for one hour, they did not undergo any change.

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EXAMPLE 2

Mix thoroughly at a temperature of approx. 40 "C deca-methrin, a fungicide known under the designation" Xyligen B "5 (BASF), which mainly consists of N-cyclohexyl, N-methoxy, 2,5-dimethyl-furan-3-carboxamide, and the a product known by trade name "Hydrorob 2428" (Robbe), which is an acrylic modified alkyd resin, first adding to the mixture thus obtained a mixture of diethanolamine and monoethanolamine, and then the same emulsifier product used in Example 1 .

After dilution with water, the concentrate showed the following weight composition: 15

Ingredients Weight%

Decamethrin 0.2 Fungicide "Xyligen B" 0.6

Resin "Hydrorob 2428" 12.0

Diethanolamine 1.0

Monoethanolamine 1.0

Emulsifier 10.0 25 Water 69.8

This concentrate was dispersed in water in an amount of one part by weight of concentrate and four parts by weight of water in such a way as to obtain a dilute pesticide ready for use in treating wood pieces, especially structural materials such as building timber. These agents were also found to consist of aqueous emulsions of extremely high fineness, with the individual spheres having a mean diameter lower than 0.05 µm in accordance with the definition in French standard AFNOR T73-409. For this reason, they showed an appearance as transparent water 13

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solid solutions. Undergoing a spin 2 experiment corresponding to a centrifugal force of 98100 m / sec for one hour, they did not undergo any changes.

EXAMPLE 3 (Comparative Example)

Aqueous emulsion pesticide agents of the type described in U.S. Patent No. 3,281,318 as mentioned above, when compared to the same centrifugation test, were found to be separated in two successive phases after 15 minutes. centrifugation.

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Claims (12)

1. A pesticidal agent for treating wood and containing a water-insoluble pesticide component, a water-soluble synthetic resin, a water-soluble emulsifier and an amino group-containing compound, characterized in that the emulsifier is anionic and consists of ammonium or and that the amino group-containing compound is an alkanol amine having from 2 to 4 carbon atoms which may be substituted by at least one alkyl group containing from 1 to 8 carbon atoms. Pesticide agent according to claim 1, characterized in that the alkanolamine has a solidification point below -50 ° C. Pesticide composition according to claim 1 or 2, characterized in that the alkanolamine is substituted with two 20 alkyl groups each containing 1-4 carbon atoms. Pesticide agent according to claim 3, characterized in that the alkanolamine is diethylethanolamine. A pesticide agent according to any one of claims 1-4, characterized in that the weight ratio of the alkanolamine to the pesticide component is 0.50-1. A pesticide composition according to any one of claims 2-5, 30, characterized in that it contains a mixture of an alkanolamine having a setting point below -50 ° C and an alkanolamine having a setting point above +10 ° C. Pesticide composition according to claim 6, characterized in that the mixture contains 20-50% by weight of an alkanolamine with a solidification point below -50 ° C. DK 162146 B Pesticide agent according to claim 7, characterized in that the anionic emulsifier is selected from straight chain alkali metal alkylbenzenesulfonates containing 10-14 carbon atoms in the alkyl chain. 5 Pesticide composition according to any one of claims 1-8, characterized in that the water-insoluble pesticide is selected from chlorinated phenols. Pesticide agent according to any one of claims 1-9, characterized in that it further contains a plasticizer which is a phthalic acid ester of an alcohol containing 3-6 carbon atoms, and a co-solvent which is a glycol or a glycol ether. containing from 2 to 8 carbon atoms. Pesticide composition according to claim 10, characterized in that the ratio between the sum of the weight amounts of the emulsifier, the co-solvent and the alkanolamine and the sum of the weight amounts of the other non-water-soluble constituents is between 1.25 and 1.50 . Pesticide composition according to claim 11 or 30, characterized in that it consists of: 5-20 parts by weight of a chlorinated phenol, up to 4 parts by weight of a chlorinated hydrocarbon with insecticide action, 5-20 parts by weight of a water-soluble alkyd resin, 5-20 parts by weight of a plasticizer, 5-20 parts by weight of a straight chain sodium alkylbenzenesulfonate, the alkyl chain of which contains 10-14 carbon atoms, 5-20 parts by weight of an alkanolamine 5-20 parts by weight of a co-solvent and 35 up to 50 parts by weight water, the residual amount being made up of pesticidal agents for the treatment of wood, usually present ingredients.