LIQUID PESTICIDAL COMPOSITION CONTAINING A CRYSTAL GROWTH INHIBITOR
Field of the Invention
The present invention relates to the field of pesticidal compositions, particularly to the use of polyvinyl alcohol as a crystal growth inhibitor in said compositions.
Background of the Invention
Perhaps the most prevalent practice for applying pesticides to plants is by spraying a liquid composition onto the plant. Some technical difficulties are associated with this practice when predominantly aqueous compositions of pesticides which are essentially water insoluble, are employed. In such cases, often certain parts of the spraying equipment, e.g. filters and nozzles, are clogged as a result of crystal growth of the water-insoluble pesticide in said parts. A particular method for overcoming this problem is by inhibiting or preventing the crystal growth of the pesticide in the sprayer parts by employing a crystal growth inhibitor in the pesticidal composition. U.S. 5,206,225 describes the employment of alkylcarboxylic acid dimethylamides as crystallization inhibitors of azole fungicides. EP 637,202 describes a liquid pesticidal composition containing as a crystallization inhibitor benzene which contains two or three hydroxy groups and substituted by one or more lower alkyl groups. Notwithstanding, the prior art crystallization inhibitors are organic substances which are essentially insoluble in an aqueous medium. Hence, it is necessary to employ an organic co-solvent in which the pesticide and crystal growth inhibitor are soluble. This may present difficulties in terms of environmental safety and phytotoxicity. The current practice in pest control is to reduce the use of organic solvents.
WO 00/35284 describes an aqueous suspension concentrate of triazole fungicides which contains a tristyrylphenol-ethoxylate, phosphate or sulfate thereof, with a vinylpyrrolidon polymer or copolymer thereof, as a crystal growth inhibitor. However, in order to inhibit crystal growth according to WO 00/35284 it is necessary to employ a mixture of crystallization inhibitors; at least a binary mixture thereof.
Furthermore, the crystal growth inhibitors disclosed in the prior publications do not offer
a solution for all needs, practices and conditions employed in agriculture. The crystal growth inhibitor may vary in accordance with the active ingredient. Thus, there is an ongoing need to develop further crystal growth inhibitors which overcome the shortcomings of the prior art.
It is therefore a purpose of the present invention to provide a pesticidal composition with a new crystal growth inhibitor.
A further purpose of the present invention is to present the new use of a compound as a crystal growth inhibitor.
Other objects of the invention will become apparent as the description proceeds.
Summary of the Invention The present invention provides a liquid pesticidal composition comprising one or more azole fungicides and polyvinyl alcohol (PVA) as a crystal growth inhibitor.
Further provided by the present invention is the use of polyvinyl alcohol (PNA) as a crystal growth inhibitor in pesticidal liquid compositions comprising azole fungicides.
The present invention further provides a method for inhibiting crystal growth of azole fungicides which are present in liquid pesticidal compositions comprising of adding PVA, as a crystal growth inhibitor, to liquid azole-containing fungicidal compositions.
Detailed Description of the Invention
The following description is illustrative of embodiments of the invention. The following description is not to be construed as limiting, it being understood that the skilled person may carry out many obvious variations to the invention.
Throughout the description, percentages of components are by weight, unless specifically noted differently. Furthermore, throughout the description "polyvinyl alcohol (PVA)" refers to a polymer of vinyl alcohol with an average molecular weight in the range of 200
to 200,000. Throughout the specification the term "azole" or "azole fungicide" also means mixtures thereof.
It has surprisingly been found that polyvinyl alcohol (PNA) is effective as a crystal growth inhibitor in liquid pesticidal compositions of azoles.
According to an embodiment of the present invention there is provided a liquid pesticidal composition comprising 1% to 60% of an azole fungicide selected from among a group consisting of epoxiconazole, tebuconazole, cyproconazole, prochloraz (Zn, Cu and Mn complexes), penconazole, definoconazole, flusilazole, metconazole, triadimenol, hexaconazole, flutriafol, triflumizole, fenbuconazole, bromuconazole, fluquinconazole, azaconazole, triticonazole, triadimefon, tetraconazole and imibenconazole; and 0.1% to 30% of PNA, wherein PVA is a crystal growth inhibitor. According to the present invention the weight ratio between the azole fungicide and PVA is 50:1 to 1:10. According to a preferred embodiment of the invention, the weight ratio between the azole fungicide and PVA is 20: 1 to 1 : 1.
According to a particular aspect of the present invention, the compositions of the present invention are aqueous compositions which contain more than about 10% water. Νon-limiting examples of such compositions are: suspension concentrates (SC) and emulsion in water (EW) formulations.
Compositions of the present invention may further comprise an additional pesticide which is not an azole fungicide. Said pesticide selected from among a group comprising of strobilurin analogues, e.g. kresoxim-methyl and pyraclostrobin; morpholines, e.g., fenpropidin and fenpropimorph; quinoxyfen, spiroxamine, chlorothalonil, maneb, mancozeb, ziram, thirarn and Ν-thiahalomethyl derivatives, e.g., captan and folpet.
Compositions according to the present invention may further contain organic solvents, surfactant agents, thickeners, anti-foaming agents, dispersing agents and wetting agents.
Suitable organic solvents which may be employed in the present invention can be aromatic or aliphatic, polar or non-polar solvents which are customarily used in the preparation of pesticidal compositions. Non-limiting examples of said solvents include amides such as dimethylformaide, N,N-dimethylacetamide; ketones such as cyclohexanone, methylisobutyl ketone; aromatics such as benzene, toluene, xylene, mineral oil, naphthalenes; aliphatic hydrocarbons such as hexane and cyclohexane; N-pyrrolidone derivatives; ethers; esters; fatty acid esters; alcohols; glycols; sulphoxides and plant oils. The solvent is 0% to 50% of the composition.
0% to 40% of the present composition may be surfactant agents wherein non-limiting examples of suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.
Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds. Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10 -C 2), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained, e.g. from coconut oil or tallow oil. Further suitable surfactants are also the fatty acid methyltaurin salts as well as modified and unmodified phospholipids.
More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkali earth metal salts or unsubstituted or substituted ammonium salts and contain a C8 -C22 alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate, or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium,
calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C8 -C 2 alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)emylammomum bromide, preferably 1% to 5%.
Suitable thickeners for the present invention are, e.g., xanthan gum, polysaccharides and ethoxylated dialkyl phenols which are present in the composition in 0.01% to 2%, preferably 0.1% to 1%.
Anti-foaming agents (AF) suitable for use in the present composition are those customarily employed in pesticidal compositions, wherein non-limiting examples of said agents are silicon oils or silicon oil emulsions in water commercially available as, e.g., Rhodorsil 432, Sag 470 and Dow Corning 1520, wherein 0% to 5% of anti-foaming agent are employed, preferably 0.1% to 1%.
The present composition may further comprise 0% to 10% of a wetting agent wherein said wetting agent may be selected from the non-limiting examples presented under the surface active agents. Preferably, 1% to 3% wetting agent is employed.
According to a particular embodiment of the present invention there is provided a fungicidal composition of epoxiconaole comprising 5% to 25% of epoxiconazole, 1% to 5% PVA, 0.1% to 1% anti-foaming agent, 10% to 50% aromatic solvent, 0.05% to 5% thickener and 10% to 90% water.
The present invention further relates to the use of PVA as a crystal growth inhibitor in pesticidal compositions which contain 1% to 60% of an azole fungicide selected from among a group consisting of epoxiconazole, tebuconazole, cyproconazole, prochloraz, penconazole, definoconazole, flusilazole, metconazole, triadimenol, hexaconazole, flutriafol, triflumizole, fenbuconazole, bromuconazole, fluquinconazole, azaconazole, triticonazole, triadimefon, tetraconazole and imibenconazole, wherein the crystal growth inl ibiting effect of PVA is achieved when said composition contains 0.1% to 30% of PVA. Said effect can also be achieved by maintaining a weight ratio between the azole fungicide and PVA in the range of 50:1 to 1:10. Preferably, the weight ratio between the azole fungicide and PVA is 20: 1 to 1 : 1.
According to a further aspect of the invention, there is provided a method for preventing crystal growth of azole fungicides which are present in liquid pesticidal compositions comprising of adding PVA to liquid azole-containing fungicidal compositions.
According to an embodiment of the method of the present invention, PVA is added to a fungicidal azole-containing pesticidal composition so that the weight ratio between the azole fungicide and the PVA is in the range of 50: 1 to 1 : 10, preferably 20: 1 to 1 : 1.
The fungicidal azole suitable for the present method is selected from among a group consisting of epoxiconazole, tebuconazole, cyproconazole, prochloraz (Zn, Cu and Mn complexes), penconazole, definoconazole, flusilazole, metconazole, triadimenol, hexaconazole, flutriafol, triflumizole, fenbuconazole, bromuconazole, fluquinconazole, azaconazole, triticonazole, triadimefon, tetraconazole and imibenconazole.
The present method may further be employed by adding PVA to a liquid pesticidal composition which contains 1% to 60% of an azole fungicide selected from among a group consisting of epoxiconazole, tebuconazole, cyproconazole, prochloraz (Zn, Cu and Mn complexes), penconazole, definoconazole, flusilazole, metconazole, triadimenol, hexaconazole, flutriafol, triflumizole, fenbuconazole, bromuconazole, fluquinconazole, azaconazole, triticonazole, triadimefon, tetraconazole and imibenconazole; so that the pesticidal composition then contains 0.1% to 30% PVA.
Examples
Example 1: Preparation of Epoxiconazole Suspension Concentrate
Composition
Epoxiconazol (A.I.) 125 kg. (as 100%)
Poly vinyl alcohol (Crystal growth inhibitor) 35 kg. Silicon oil 1 kg.
Solvesso 200 (Organic solvent) 1 400 kg.
Rhodopol MC (thickener) 2 0.75 kg.
AF 10% emulsionJ 1 kg. Water complete to 1000 liters
= methylnaphthalene fraction = xanthan gum
3 = Sag 470
Preparation:
Dissolve the PVA and the antifoam 100% in the water using a high shear agitator until the solution is homogeneous. Disperse the Epoxiconazole in the solution using the high shear agitator until the dispersion is homogeneous. Add the Solvesso slowly keeping the dispersion under high shear mixing and mill it in a pearl-mill. Dissolve the Rhodopol in the suspension using a high shear agitator and add the antifoam 10%.
Example 2: Preparation of Prochloraz Suspension Concentrate
Composition
Prochloraz-Zn complex (A.I.) 450 kg. (as 100% Prochloraz)
Poly vinyl alcohol (Crystal growth inhibitor) 10 kg.
Witconol NS-500 LQ (surfactant agent) 4 15 kg
Iso propyl alcohol (Organic solvent) 100 kg
Silicon oil 1 kg. succinoglycan gum (thickener) 1.5 kg.
AF 10% emulsion5 1.5 kg.
Water complete to 1000 liters ethylene oxide/propylene oxide block copolymer Sag 470
Example 3: Preparation of Tebuconazole Suspension Concentrate
Composition
Tebuconazole (A.I.) 250 kg. (as 100%)
Poly vinyl alcohol (Crystal growth inhibitor) 25 kg.
Silicon oil 1 kg.
Rhodopol MC (thickener) 2.5 kg.
AF 10% emulsion 1 kg.
Water complete to 1000 liters
Example 4: Preparation of Triadimenol Suspension Concentrate
Composition
Triadiminol (A.I.) 150 kg. (as 100%) Poly vinyl alcohol (Crystal growth inhibitor) 12 kg.
Atlox 4913 (surfactant agent) 6 10 kg
AF 100% 1 kg. elzan (thickener) 7 3 kg.
AF 10% emulsion 1.5 kg. Water complete to 1000 liters.
= acrylic copolymer solution = xanthan gum
Example 5: Test of crystal growth inhibition
The formation of crystals in spraying solutions is determined in various conditions in order to assure no crystal formation in various spraying conditions. 10 liters of spraying solutions are prepared using hard water (CIPAC standard water D, 342 ppm) in 3 different concentrations: 0.5, 1, 2 times the recommended spraying concentration for each formulation. Each sample is placed at 3 different temperatures: 2°C, 15°C and 30°C for 24 hours to allow crystal growth. The solutions are sprayed using a personal spraying machine and using two filters (~8 gr. each): 100 and 50 mesh. After spraying the filters are dried and weighed. A weight difference of the filter before and
after spraying of less than 0.05 gr. indicates essentially no crystal growth. Hence, there will not be filter blocking.
While embodiments of the invention have been described by way of illustration, it will be apparent that the invention may be carried out with many modifications, variations and adaptations, without departing from its spirit or exceeding the scope of the claims.