NO158713B - PESTICID PREPARATION FOR TREATMENT OF TREE AND CONTAINING A WATERLESS PESTICID AGENT, A SYNTHETIC RESIN, A WATERLESS EMULSATING AGENT, AND AN AMINE COMPOUND. - Google Patents

Description

The present invention relates to pesticide preparations for the treatment of wood, for example construction or carpentry timber, comprising a water-insoluble pesticide, a synthetic resin that can be diluted with water, a water-soluble emulsifier and an amino compound. It concerns more particularly preparations of this type which are presented in concentrated form and can be diluted with water before use, and also preparations of this type which have been diluted with water and are ready for use.

US patent A 3,281,381 (Chapman Chemical Company) has described pesticidal preparations of this type which consist of aqueous emulsions of a mixture of a polychlorophenol, a wax, a fatty acid, a nonionic emulsifier and an alkanolamine. In these known pesticide preparations, the purpose of the non-ionic emulsifier is to improve the homogeneity of the emulsion, and the purpose of the alkanolamine, which is preferably ethanolamine, is to facilitate the dispersion of the fatty acid and the polychlorophenol. Due to the presence of a wax which acts as a fixing agent for the polychlorophenol, these known pesticide preparations have the disadvantage that they are quite unsuitable for impregnating the treated wooden elements to a sufficient depth, and the protection they provide is short-lived. Furthermore, the stability of these pesticide preparations is uncertain.

To overcome these disadvantages it is in patent application

DE A 3 004 319 (Desowag Bayer Holzschutz GmbH) proposed pesticide preparations in aqueous emulsions in which a synthetic resin is used that can be diluted with water, together with an amine, to ensure fixation of the active agents in the wood, as the emulsifier is also not -ionic.

The aim of the present invention is to provide pesticide preparations of this type which, after dilution with water, appear as a real solution and in particular have the transparency of a real solution, which have excellent stability and which have high wood penetration.

The invention thus relates to a pesticide preparation for: treatment of wood. The preparation with preferred embodiments is specified in the claims, and reference is made to these.

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In the preparations according to the invention, the pesticide can be any water-insoluble pesticide which is generally used in pesticide preparations for treating wood. It can be a water-insoluble fungicide (fungicide) or a water-insoluble insecticide. If desired, the pesticide preparations according to the invention can contain several water-insoluble fungicides, several water-insoluble insecticides or a mixture of one or more water-insoluble fungicides with one or more water-insoluble insecticides.

Examples of water-insoluble insecticides that can be used in the pesticidal preparations according to the invention are pyrethrum, pyrethroids (such as pyrethrin, allethrin, cyclethrin, furethrin, tetramethrin, decamethrin and bioresmethrin), insecticidal kiarbamates (such as methoxychlor, lindane, chlordane, heptachlor, aldrin and dieldrin).

Examples of water-insoluble fungicides that can be used in

the pesticidal preparations according to the invention are organic compounds of tetravalent tin (such as tributyl tin benzoate, tris (tributyl tin) phosphate and bis (tributyl tin) oxide), the 1-trityl-1,2,4-triazoles with the general formula:

where 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 the number 1 or 2, and also their salts with organic or inorganic acids (for example, trifluoromethyl-triphenylmethyltriazole), hexachlorobenzene, pentachlorobenzene, fungicidal chelates of tris-(N-cyclohexyldiazenium dioxide) metal, especially the aluminum chelate, found in the product known as Xyligen Al (BASF), N,N -dimethyl-N'-(fluorodichloromethylthio)-sulfamide, N,N-dimethyl-N'-(dichlorofluoromethylthio)-sulfamide, chloronaphthalenes, copper naphthenate and zinc naphthenate, mercaptobenzothiazole and its salts, 8-hydroxyquinoline and its salts, organoboric acid esters , quaternary ammonium compounds and their derivatives, diphenylamine/acetone condensation derivatives, N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide, which is found in the product known as Xyligen B (BASF), N-(trichloromethylthio)-phthalimide,. 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, 2-(thiazol-4-yl)-benzimidazole, 5-n-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, orthophenyl-phenol and paraphenylphenol.

In a particularly advantageous embodiment of the invention, the pesticide in the preparations is selected from among chlorophenols. Preferred chlorophenols are polychlorophenols, and tetrachlorophenol and pentachlorophenol prove particularly advantageous.

The synthetic resin which can be diluted with water and is present in the preparations according to the invention is preferably an alkyd resin which is soluble in water due to the formation of a salt with the amino compound, or an acrylic modified alkyd resin such as that known under the trademark Hydrorob ( Robbe).

The emulsifier in the pesticidal preparations according to the invention is an anionic emulsifier which consists of ammonium or alkali metal alkylbenzene sulphonates and is soluble in water.

The alkylbenzenesulfonates can be straight chain alkylbenzenesulfonates or branched alkylbenzenesulfonates; straight chain alkylbenzenesulfonates, commonly referred to as "LAS" (linear alkylbenzenesulfonates), are preferred. Particularly advantageous straight-chain alkylbenzene sulfonates are those where the alkyl chain; contains from 8 to 18 carbon atoms and nine especially from 10 to 14 carbon atoms; dodecylbenzenesulfonates, especially sodium dodecylbenzenesulfonate, are particularly suitable.

In the preparations according to the invention, the anionic surfactant can be used as it is or in the form of a

in dispersion or a solution in an organic solvent or water, if it is desired to reduce its viscosity. Very good results are generally achieved by using, according to the invention, emulsification products containing from 30 to 80 parts by weight of ammonium or alkali metal alkylbenzene sulphonates with from 10 to 14 carbon atoms in the alkyl chain and from 20 to 70 parts by weight of one or more organic solvents and/ or water; the best results are usually obtained with emulsification products of this type containing from 40 to 60 parts by weight of alkylbenzene sulfonate(s) and from 30 to 50 parts by weight of organic solvent(s) and/or water.

The alkanolamines in the pesticide preparations according to

the invention can be the conventional products where the alkanol radical contains from 2 to 4 carbon atoms and which are obtained by reacting ammonia gas with ethylene oxide, propylene oxide or butene oxide, such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, mono-sec.-butanolamine, di-sec.-butanolamine and tri-sec.-butanol-amine. However, preferred are alkanolamines substituted with at least one alkyl radical containing from 1 to 8 carbon atoms, and more particularly alkanolamines substituted with two alkyl radicals preferably containing from 1 to 4 carbon atoms

atoms. Examples of such alkanolamines are, on the one hand, methylethanolamine, butylethanolamine, methyldiethanolamine and ethyldiethanolamine, and, on the other hand, dimethylethanolamine, diethylethanolamine, diisopropylethanolamine, dibutylethanolamine and dimethylisopropanolamine. The best results have been obtained with alkanolamines with a freezing point of below -25°C and preferably below -50°C, and more particularly with diethylethanolamine.

The relative amount of alkanolamine that should be used,

can be easily determined experimentally and depends on various factors, including in particular the nature of the alkanolamine and also the nature and relative amount of each component in the preparation and the desired concentration of the aqueous emulsion to be prepared.

As a general rule, it has been found desirable to adjust the weight proportion of the alkanolamine so that the ratio between the weight of the alkanolamine and the weight of the pesticide is between 0.1 and 2, preferably between 0.25 and 1.25, the most advantageous results being obtained with weight ratio of between 0.5 and 1.

All other things being equal, selection of the alkanolamine from those having a freezing point below -25°C ensures that aqueous emulsions of very high stability are obtained which can withstand large temperature variations, especially periods of freezing alternating with periods of thawing, without their stability , their clarity and their ability to penetrate wood are thereby affected.

In order to reduce the costs of the preparations according to this preferred embodiment of the invention without impairing the properties of the obtained aqueous emulsions,

is it possible - as a variant - to replace part of the alkanolamine with a low freezing point with an equivalent one

amount of an alkanol rain with a higher freezing point. In this variant of the invention, the relative amounts to be used of alkanolamines with a low and high freezing point depend on the temperature differences that can be predicted that the aqueous emulsions will be exposed to, as the relative proportion of the alkanolamine with a low freezing point is increased the greater these temperature differences are even more! it is likely that the storage, handling or application temperatures will drop to low values. In practice, it is desirable to use at least 10% by weight, and preferably at least 20% by weight, of alkanolamine with a freezing point of below

- 2 5°C and preferably below - 50°C. In practice, it is not necessary to exceed 75% by weight and most often 50% by weight

of such an alkanolamine.

The optimal amount of anionic emulsifier to be used in the pesticidal preparations according to the invention can also be determined experimentally and also depends on various factors, especially on the emulsifier chosen and the nature and concentrations of the other ingredients. In general, it has been found desirable to adjust the proportion of anionic emulsifier so that the ratio between the sum of the weights of the emulsifier and the alkanolamine, and the sum of the weights of the other ingredients in the preparation, apart from water, which are usually water insoluble,

is between 1 and 2, preferably between 1.25 and 1.50.

In addition to the water-insoluble pesticide, the synthetic resin that can be diluted with water, the anionic emulsifier and the alkanolamine, the pesticidal preparations according to the invention may contain other ingredients, especially a plasticizer and a co-solvent.

Any plasticizer which is liquid or pasty at ambient temperature is suitable as a plasticizer. Examples of such plasticizers that can be mentioned are phosphates and fatty acid esters, such as tributyl phosphate, butyl stearate, butyl oleate, dibutyl sebacate and dioctyl phthalate. Preferably, these softeners are esters derived from dicarboxylic acid containing from 4 to 10 carbon atoms,

such as maleic, adipic and phthalic acids, and from alcohols containing

containing from 2 to 8 carbon atoms. The best results have been obtained with the phthalates of alcohols containing from 3 to 6 carbon atoms, and more particularly with dibutyl phthalate.

Any co-solvent commonly used in connection with water-soluble alkyd resins is suitable as co-solvent, especially alcohols and preferably glycols and glycol ethers containing from 2 to 8 carbon atoms. The best results have been obtained with glycols containing from 2 to 4 carbon atoms, and more particularly with ethylene glycol. The preparations containing a co-solvent are particularly suitable for use at winter temperatures. It is desirable that the weight of co-solvent used does not exceed 20%, and preferably 10%, of the weight of the synthetic resin which can be diluted with water.

If it is appropriate, the preparations according to the invention may contain a wax, but in this case it is desirable that the amount by weight of the wax does not exceed 0.5% of the weight of the preparation; in general, the preparations according to the invention are preferably wax-free.

If appropriate, they can pesticide preparations

according to the invention, which are in concentrated form, contain a small amount of diluting water, the purpose of which is to give them sufficient fluidity so that they can be transferred to storage containers and that they can be handled when the ready-to-use pesticide preparations diluted with water are prepared. In principle, the quantity of diluting water is not decisive, and it can be easily determined in each particular case according to the constituents of the concentrate and the desired fluidity. In practice, good results are usually achieved with concentrates containing a quantity of water in the range of up to 50% of the total weight of the concentrate, favoring values of more than 10% and usually of between 25 and 40%.

Pesticide preparations according to the invention which have proven particularly suitable for obtaining ready-to-use diluted pesticide aqueous emulsions with very high stability, with a very high degree of fineness and with a high degree of clarity,

are those that consist of:

- 5-20 parts by weight of a chlorophenol,

- up to 4 parts by weight of a chlorohydrocarbon insecticide,

- 5-20 parts by weight of water-soluble alkyd resin,

- 5-20 parts by weight of plasticizer,

- 5-20 parts by weight alkanolamine,

- 5-20 parts by weight of straight-chain sodium alkylbenzene sulphonate in which the alkyl chain contains from 10 to 14 carbon atoms,

- 5-20 parts by weight co-solvent and

- up to 50 parts by weight water,

as any residue consists of substances that are generally present in pesticide preparations for treating wood. These substances can, for example, be UV inhibitors, drying agents or pigments.

The ready-to-use pesticide preparations which are diluted with water, according to the invention, have a dilution factor which is chosen in each particular case and which depends on various factors, especially on the nature and the respective concentrations of their constituents. As a general rule, suitable dilution factors are those equivalent to one part by weight of ingredients other than water, per two to six parts by weight of water in the preparation.

For the production of the pesticidal preparations according to the invention, it is generally sufficient to mix their constituents. In practice, the mixing should be carried out at temperatures and pressures where there is no risk of solidification of the mixture of the constituents or evaporation of one or more of these constituents. For example, it is possible to carry out the mixing at a temperature of between 15 and 75°C and at a pressure of between 0.535 and 1.135 bar, the preferred temperatures being between 30 and 55°C and the preferred pressures between 0.865 and 1.055 bar.

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The pesticidal preparations according to the invention have been shown to be particularly fine aqueous emulsions which act as transparent and homogeneous solutions. They have high stability in terms of time and high resistance to temperature variations and mechanical stresses such as shocks, falls or centrifugation, without their

stability is thereby affected.

Examples of concentrates according to the invention are described below.

Example 1

Pentachlorophenol, aldrin, diisobutyl phthalate, ethylene glycol and the product known as "Uradil 30100" (Scado N.V.), which is an alkyd resin, were thoroughly mixed at a temperature of approx. 40°C.

The following were added successively to the resulting mixture: a mixture of diethylethanolamine and monoethanolamine, followed by an emulsification product containing about one part by weight of water, one part by weight of isobutanol, and 2 parts by weight of a mixture of sodium alkylbenzene sulfonates with a straight chain alkyl chain, of the general formula:

where 10 ^ n « 14.

After dilution with water to render the concentrate sufficiently fluid for transfer to storage containers, the concentrate had the following composition by weight:

This concentrate was dispersed in water at a ratio of one part by weight of concentrate to four parts by weight of water, to obtain a ready-to-use diluted pesticide preparation for the treatment of pieces of wood, especially building materials such as building timbers. These preparations proved to be particularly fine aqueous emulsions in which the small spheres had an average diameter of less than 0.05 µm according to the definition according to AFNOR Standard T73-409. They therefore had the appearance of transparent aqueous solutions. When subjected to a centrifugation test corresponding to a centrifugal acceleration of 98,100 m/second<2>

for one hour they did not undergo any deterioration.

Example 2

Decamethrin, the fungicide known under the name: "Xyligen B" (BASF), which consists mainly of N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide, and the product known under the name "Hydrorob 2428" (Robbe), which is an acrylic-modified alkyd resin, was thoroughly mixed at a temperature of approx. 40°C. The following was added to the resulting mixture: first a mixture of diethanolamine and monoethanolamine and then the emulsifying product used in Example 1.

After dilution with water, the concentrate therein had the following weight composition:

The concentrate was dispersed in water in a ratio of one part by weight of concentrate to four parts by weight of water, to obtain a ready-to-use diluted pesticide preparation for the treatment of pieces of wood, especially building material such as building timber. These preparations also proved to be particularly fine emulsions in which the small spheres had an average diameter of less than 0.05 μm according to the definition according to AFNOR Standard T73-409. They therefore also had an appearance

as transparent aqueous solutions. When subjected to a centrifugation test corresponding to a centrifugal acceleration of 98,100 m/second for one hour, they did not undergo any deterioration.

Example 3 (reference)

For comparison, pesticide preparations in aqueous emulsion of the type described in US patent A 3,281,318, discussed above, were divided into two phases on top of each other after fifteen minutes of centrifugation, when they were subjected to the same centrifugation test.

Claims (9)

1. Pesticide preparation for the treatment of wood and which contains a water-insoluble pesticide, a synthetic resin that can be diluted with water, a water-soluble emulsifier and an amine compound, characterized in that the water-soluble emulsifier is anionic and consists of ammonium or alkali metal alkylbenzene sulfonates, and that the amine compound consists of an alkanolamine with 2-4 carbon atoms, which can be substituted with at least one alkyl group containing 1-8 carbon atoms. 2. Preparation according to claim 1, characterized in that the alkanolamine has a freezing point below -50°C. 3. Preparation according to claim 1 or 2, characterized in that the alkanolamine is substituted with two alkyl groups with 1-4 carbon atoms. 4. Preparation according to claim 3, characterized in that the alkanolamine is diethylethanolamine. 5. Preparation according to one or more of the preceding claims, characterized in that the weight ratio between alkanolamine and pesticide is between 0.5 and 1. 6. Preparation according to one or more of claims 2-5, characterized in that it contains a mixture of an alkanolamine with a freezing point below -50°C and an alkanolamine with a freezing point above +10°C. 7. Preparation according to claim 6, characterized in that the mixture contains 20-50 weight* of alkanolamine with a freezing point below -50°C. 8. Preparation according to one or more of the preceding claims, characterized in that the anionic emulsifier is an unbranched alkali metal alkylbenzene sulfonate with 10-14 carbon atoms in the alkyl chain. 9. Preparation according to one or more of the preceding claims, characterized in that the water-insoluble pesticide is a chlorinated phenol.