WO2022248293A1

WO2022248293A1 - New method for controlling pests

Info

Publication number: WO2022248293A1
Application number: PCT/EP2022/063366
Authority: WO
Inventors: Markus FIESS; Dieter Strobel; Christian Sowa; Simon Nord; Matthias Bratz
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2021-05-26
Filing date: 2022-05-18
Publication date: 2022-12-01
Anticipated expiration: 2023-11-26
Also published as: EP4346404A1

Abstract

New method for controlling pestsMethod for controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, comprising the following steps i) Providing a formulation F comprising one or more pesticides P, said pesti-cide P being insoluble in water and said pesticide P being dissolved in a wa-ter immiscible solvent S; ii) Preparing a mixture of formulation F, water and an adjuvant A, wherein said adjuvant A is not miscible with water and wherein said one or more pesticides P have a solubility in said adjuvant A of below 10 g/l at 20 °C; iii) allowing the resulting mixture obtained in step ii) to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment.

Description

New method for controlling pests

The present invention is directed to a method for controlling phytopathogenic fungi and/or unde sired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, comprising the following steps i) Providing a formulation F comprising one or more pesticides P, said pesti cide P being insoluble in water and said pesticide P being dissolved in a wa ter immiscible solvent S; ii) Preparing a mixture of formulation F, water and an adjuvant A, wherein said adjuvant A by itself is not miscible with water and wherein said one or more pesticides P have a solubility in said adjuvant A of below 10 g/l; iii) allowing the resulting mixture obtained in step ii) to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment.

There is a constant need for agrochemical formulations with high efficacies. Especially pesti- cidal active ingredients with a low solubility in standard solvents are very difficult to formulate. One problem with the application of agrochemical formulations is that when such formulations are applied in the field prior to rainfall, the pesticide contained therein may be washed away by the rain.

One approach to overcome this issue is the use of uptake enhancers like alcohol alkoxylates that can act as rain fastness enhancers since they accelerate penetration of active ingredients into the plant. Upon penetration of the plant the active ingredients cannot be washed away by a rain event anymore.

WO2012001068 and WO2012003060 discloses the use of certain polymer dispersions for im proving the rain fastness of pesticide formulations.

It was the objective of the present invention to provide agrochemical formulations and methods of using agrochemical formulations that lead to excellent efficacies for controlling pests and that in particular lead to excellent rain fastness properties.

This objective was achieved by a method for controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, comprising the following steps i) Providing a formulation F comprising one or more pesticides P, said pesti cide P being insoluble in water and said pesticide P being dissolved in a wa ter immiscible solvent S; ii) Preparing a mixture of formulation F, water and an adjuvant A, wherein said adjuvant A by itself is not miscible with water and wherein said one or more pesticides P have a solubility in said adjuvant A of below 10 g/l at 20°C; iii) allowing the resulting mixture obtained in step ii) to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment.

All solubilities given herein are, unless stated otherwise, given for a temperature of 20 °C.

The term pesticide refers to at least one active substance selected from the group of the fungi cides, insecticides, nematicides, herbicides, safeners, biopesticides and/or growth regulators. Preferred pesticides P are fungicides, insecticides, herbicides and growth regulators. In one em bodiment pesticides P are selected from fungicides, insecticides and herbicides. Especially pre ferred pesticides P are fungicides. Mixtures of pesticides of two or more of the abovementioned classes may also be used.

The skilled worker is familiar with such pesticides, which can be found, for example, in the Pes ticide Manual, 16th Ed. (2013), The British Crop Protection Council, London. Suitable insecti cides include insecticides from the class of the carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosins, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin compounds nereistoxin analogs, benzo- ylureas, diacylhydrazines, METI acarizides, and insecticides such as chloropicrin, pymetrozin, flonicamid, clofentezin, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorofenapyr, DNOC, buprofezine, cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenone, or their derivatives. Suitable fungicides include fungicides from the clas ses of dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, ben- zenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, ben- zotriazines, benzyl carbamates, carbamates, carboxamides, carboxylic acid diamides, chloroni- triles cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy-(2-amino)pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganic substances, isobenzofuranones, methoxyacrylates, meth- oxycarbamates, morpholines, N-phenylcarbamates, oxazolidinediones, oximinoacetates, oximi- noacetamides, peptidylpyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyr- roles, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, pipera zines, piperidines, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, pyrim- idinamines, pyrimidines, pyrimidinonehydrazones, pyrroloquinolinones, quinazolinones, quino lines, quinones, sulfamides, sulfamoyltriazoles, thiazolecarboxamides, thiocarbamates, thi- ophanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines, triazoles. Suitable herbicides include herbicides from the classes of the acetamides, amides, aryloxyphe- noxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dini- trophenol, diphenyl ether, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N- phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl(thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, tria- zolocarboxamides, triazolopyrimidines, triketones, uracils, ureas.

Pesticides P are insoluble in water, meaning that pesticide P have a solubility in water of less than 10 g/l at 20 °C. Preferably, pesticides P have a solubility in water of less thanl g/l, and in particular less than 0.5 g/l, in each case at 20 °C.

In one preferred embodiment, pesticide P is selected from prothioconazole, pyraclostrobin, flufenoxadiazam, metyltetraprol, mefentrifluconazol, florylpicoxamid, pydiflumetofen or mixtures thereof.

In one preferred embodiment, pesticide P is selected from prothioconazole, flufenoxadiazam, metyltetraprol, mefentrifluconazol, florylpicoxamid, pydiflumetofen or mixtures thereof.

In one embodiment, pesticide P comprises a mixture of metyltetraprol and mefentrifluconazol.

Formulations of the invention normally comprise a pesticidally effective amount of a pesticide. The term "effective amount" denotes an amount of the composition or of the pesticide, which is sufficient for controlling harmful pests on or around cultivated plants or in the protection of mate rials and which does not result in a substantial damage to the treated plants upon use and, if applicable after dilution with water. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific pesticide used.

According to the invention, formulation F comprises pesticide P dissolved in a solvent S that is water immiscible.

The term “water immiscible” as used herein in relation to solvents and adjuvants A shall mean that a solvent that is “immiscible” with water has a solubility in water of less than 10 % by weight at 20 °C, preferably less than 1 wt% at 20 °C and more preferably of less than 0.5 wt% at 20 °C. Unless stated otherwise, all solubilities or miscibilities given herein are at 20 °C.

Solvent S may comprise one solvent or of a mixture of solvents. In case solvent S comprises a mixture of different solvents, at least 70 wt% of the components of solvent S shall be water im miscible. For example, solvent S can be a mixture comprising 70 - 95 wt% of water immiscible solvent like Solvesso, benzyl acetate or capric acid dimethylamide and further comprising 5 to 30 wt% of a water miscible solvent like N-alkylpyrrolidone, N-methylpyrrolidone, N-butylpyrroli- done, propylene carbonate, lactic acid N,N-dimethylamide or DMSO.

In principle all water immiscible solvents in which the solubility of pesticides P is sufficiently high are suitable as solvents S. Typically, the solubility of pesticides P in solvent S needs to be at least 10 g/l, preferably at least 20 g/l at 20 °C.

Examples of suitable solvents S include: ketones, e.g. acetophenone; carbonates, e.g. dibutyl carbonate; esters, e.g. benzyl acetate, benzyl lactate, 2-phenoxyethyl propionate, alkyl benzoates like me thyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate; lactates, e.g. 2-ethylhexyl lactate; fatty acid esters, fatty acids; phosphonates; fatty acid amines; pyrrolidones, such as N-octylpyrrolidone, N-ethyl pyrrolidone, N-docedyl pyrrolidone; fatty acid amides, e.g. N,N-dimethyloctanamide, N,N-dimethylnonaneamide, N,N-dimethylde- canamide, N,N-Dimethyl 9-decenamide, lauryl N,N-dimethylamide, lauryl N,N-dimethylamide, and mixtures thereof.

Herein, “C8 dimethylamide” and “N,N-dimethyl octaneamide” shall be understood to mean ”C8 fatty acid N,N-dimethylamide” (analogously for other chain lengths).

“Fatty acid” herein shall denote a linear or branched carboxylic acid with a saturated or unsatu rated aliphatic chain.

Preferred solvents S comprise tris hexyl trimellitate, bis(2-ethylhexyl)terephthalate, di-n-butyl terephthalate, phenyl ethyl acetate, tris(2-butoxyethyl)phosphate, phenoxyethyl isobutyrate, branched C11-14 alcohol, oleyl alcohol, N,N-dimethyldecanamide, benzyl acetate, alkylnaph- thalenes, diethyl phthalate, 1-octanol, N,N-dimethyldodecanamide, N,N-dimethyloctanamide, 2- octyldodecan-1-ol, 2-hexyldecan-1-ol, 1-decyl alcohol, isononyl alcohol, 2-octanol, dioctyl ether, ethyl cinnamate, benzyl isovalerate, benzyl isobutyrate, benzyl propionate, propylene glycol dibenzoate, isodecyl benzoate, hexyl benzoate, butyl benzoate, ethyl benzoate, methyl benzo ate, tetrabutyl urea, isopropyl palmitate, coco caprylate, ethylhexyl cocoate, 2-ethylhexyl oleate, ethyl octanoate, n-hexadecane, C11-C14 alkyl acetate, n-decyl acetate, C8-C10 alkyl acetate, 2-ethylhexyl lactate, ethylhexyl stearate, dibutyl sebacate, diethylhexyl sebacate, diisotridecyl adipate, diisodecyl sebacate, diisopropl adipate, diisobutyl adipate, dibutyl adipate, di-isononyl- cyclohexane-1 ,2-dicarboxylate, tributyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, oleic acid, dibutyl carbonate, isopropyl myristate, ethyl decanoate, isobornyl acetate and mixtures thereof. Depending on the pesticide P, some of the solvents listed above may not always be suitable if the solubility in such solvent is not high enough.

Thus, in one embodiment of the invention, the present invention is directed to methods for con trolling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite at tack and/or for regulating the growth of plants, comprising the following steps i) Providing a formulation F comprising one or more pesticides P, said pesti cide P being insoluble in water and said pesticide P being dissolved in a wa ter immiscible solvent S, where the solubility of pesticide P in solvent S is 10 g/l or higher at 20°C; ii) Preparing a mixture of formulation F, water and an adjuvant A, wherein said adjuvant A is not miscible with water and wherein said one or more pesticides P have a solubility in said adjuvant A of below 10 g/l at 20 °C; iii) allowing the resulting mixture obtained in step ii) to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment.

Preferably, formulation F is an emulsifiable concentrate (EC) formulation of pesticide P.

In one embodiment, formulation F is a suspoemulsion (SE) comprising pesticide P dissolved in the oil phase of the suspoemulsion.

Typically, pesticide P is comprised in formulation F in an amount of 1 to 700 g/l, preferably 10 to 500 g/l. In one embodiment, pesticide P is comprised in formulation F in an amount of 10 to 200 g/l or 10 to 100 g/l.

Typically, formulation F comprises less then 10 wt%, preferably less than 2 wt%, more prefera bly less than 1 wt% and especially preferably less than 0.1 wt% of adjuvant A, in each case based on the formulation. In one embodiment, formulation F comprises no adjuvant A.

Formulations F may comprise auxiliaries as they are customarily used in agrochemical formula tions. Examples for suitable auxiliaries are surfactants, dispersants, emulsifiers, wetters, fur ther adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thick eners, repellents, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, color ants, tackifiers and binders.

Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective col loid, or adjuvant. Examples of surfactants are listed in McCutcheon’s, Vol.1 : Emulsifiers & Detergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Ed. or North Ameri can Ed.).

Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of con densed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylate surfactants, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylate surfactants are compounds such as alcohols, alkylphenols, amines, amides, ar ylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably eth ylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Ex amples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or poly- ethyleneamines.

Suitable further adjuvants are compounds, which have a neglectable or even no pesticidal ac tivity themselves, and which improve the biological performance of the pesticide on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.

Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazoli- nones and benzisothiazolinones.

Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.

Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.

Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

In many cases, formulations F comprise one or more suitable surfactants or emulsifiers to facili tate its emulsification in water. Preferably, formulation F comprises one or more nonionic and/or anionic surfactants.

According to the invention, a mixture of formulation F, water and adjuvant A is prepared. Adjuvant A is typically liquid at 20 °C.

Adjuvant A by itself is immiscible with water and said one or more pesticides P have a solubility in adjuvant A of below 10 g/l, preferably below 5 g/l or below 1 g/l, in each case at 20 °C.

In case the solubility of a pesticide P in an adjuvant is higher, such adjuvant is not suitable as adjuvant A according to the invention for this particular pesticide P.

Examples of suitable adjuvants A may include paraffinic oils, aliphatic oils, aromatic oils, vege table oil alkyl esters, fatty acid alkyl esters, polyether modified siloxanes, C8-C18 branched or linear alcohol alkoxylates, alkyl phosphates and mixtures thereof.

Examples of suitable adjuvants A may include paraffinic oils, aliphatic oils, aromatic oils, vege table oil alkyl esters, alkyl phosphates and mixtures thereof.

Examples of Adjuvants A may include the following:

Fatty acid alkyl esters:

Polyether modified siloxanes:

Preferred examples of adjuvant A are vegetable oil methyl ester, tris(2-ethylhexyl) phosphate and mixtures thereof. Preferably, adjuvant A is used in combination with suitable emulsifiers. This helps to facilitate its emulsification upon mixing with water. In one embodiment, said emulsifiers comprise alkylben- zene sulfonate salts, polyalkoxylated plant oils and/or polyalkoxylated sorbitan esters. In one embodiment, said emulsifiers comprise alkylbenzene sulfonate salts, polyalkoxylated plant oils and polyalkoxylated sorbitan esters. The choice of the emulsifier is normally not critical for the invention and not problematic for the skilled person. In one embodiment, adjuvant A is added in step ii) in combination with one or more emulsifiers.

In one embodiment, adjuvant A is applied as a mixture comprising 0.1 to 50 wt% of emulsifiers, preferably 0.3 to 45 wt%. In one embodiment adjuvant A is applied as a mixture comprising 0.5 to 10 wt% of emulsifiers, in each case based on the combined amount of adjuvant A and emul sifiers. “Applied” in this context means “added to the aqueous mixture in step ii)”.

In one embodiment, adjuvant A added in step ii) as a mixture comprising an alkylbenzene sul fonate salt, a polyalkoxylated plant oil and/or a polyalkoxylated sorbitan ester.

In one embodiment, adjuvant A is applied as a mixture comprising 0.1 to 5 % w/w of an al kylbenzene sulfonate salt, 0.1 to 10 % w/w of a polyalkoxylated plant oil and/or 0.1 to 10 % of a polyalkoxylated sorbitan ester, in each case based on the combined amount of adjuvant A and the emulsifiers.

Since formulation F comprises pesticide P in relatively high concentrations, it is very common to dilute such concentrated formulations with water, i.e. to emulsify formulation F in water, before its application on the crop. The preparation of such diluted emulsions with water is often re ferred to as “spray solution”. Such spray solutions typically comprise 0.03 to 16 grams of pesti cides P per liter.

Typically, the amount of adjuvant A in the spray solution is adjusted such that 50 to 1000 g, preferably 100 to 500 g of adjuvant A per hectare are applied.

Typically, 50 to 300 I of spray solution are applied per hectare.

In one embodiment, the amount of adjuvant A in the spray solution is 0.17 g /I to 20 g/l, prefera bly 0.3 g/l to 10 g/l, more preferably 0.5 g/l to 5 g/l.

In one embodiment, the amount of adjuvant A in the spray solution is 0.1 g to 20 g per liter of spray solution, more preferably 0.2 g to 10 g per liter of spray solution and particularly prefera bly 0.4 to 10 g per liter or 0.5 to 2.5 g per liter of spray solution.

It was now surprisingly found that the addition of a water insoluble adjuvant A, wherein said ad juvant A by itself is not miscible with water at 20 °C and wherein said one or more pesticides have a solubility in said adjuvant A of below 10 g/l at 20 °C, improves the efficacy of pesticides P for controlling pests. In particular, the addition of adjuvant A improves that rain fastness of pesticides P. This may, for example lead to a higher uptake of pesticide P into the plant after rainfall.

Given the fact that pesticides P have a low solubility in water and a low solubility in adjuvant A, it was quite counter intuitive to add adjuvant A to a spray solution of pesticide P. In view of the low solubility of pesticide P in adjuvant A, it was also quite unexpected that the addition of adju vant A had such a remarkable effect on the biological efficacy and the rain fastness of pesti cides P. According to the invention, a mixture of formulation F, adjuvant A and water (also referred to as mixture M) is prepared in step ii). In mixture M, adjuvant A and formulation F are emulsified in water. When it is stated herein that formulation F is emulsified in water, this shall mean that an emulsion of the water immiscible solvent S in water has been prepared that contains pesticide P dissolved in the emulsified droplets of solvent S.

In one less preferred embodiment, adjuvant A is included in formulation F during the manufac ture of formulation F. In another less preferred embodiment, formulation F and adjuvant A are in a first step mixed in the absence of water prior to the emulsification of formulation F in water. In these cases, there is the risk that pesticide P may precipitate due to its low solubility in adjuvant A. In this case, it needs to be ensured that pesticide P does not precipitate, for example by working at sufficiently high temperatures and by carrying out further process step without delay. When adjuvant A is added to formulation F prior to the mixture of formulation F with water, the addition of adjuvant A to formulation F is preferably done less than 1 week, more preferably 24 hours, even more preferably less than 2 hours prior to the mixing of formulation F with water. Preferably, formulation F and adjuvant A are only added to the mixture one after the other with the second of the two being added only when the other has been emulsified in water.

In one embodiment, formulation F is emulsified in water, and to the so obtained emulsion adju vant A is then added and emulsified.

In one embodiment, adjuvant A is emulsified with water and to the so obtained emulsion formu lation F is then added and emulsified.

In one embodiment, adjuvant A and formulation F are mixed with water simultaneously while preferably ensuring that adjuvant A and formulation F are not in direct contact. For example, ad juvant A and formulation F can be added to the water simultaneously through different pipes of inlets under stirring.

The emulsification of formulation F and adjuvant A in water is typically carried by standard methods known to the skilled person, for example by stirring, e.g. with an ultraturrax. In addition, emulsifiers are preferably used to facilitate the emulsification.

Without limiting the invention, it is assumed that at least a part of the emulsified adjuvant A and the emulsified solvent S that contains dissolved pesticide P are present as separate emulsified droplets. Thus, it is assumed that mixture M contains two separate oil phases emulsified in wa ter.

In one aspect of the invention, this invention is directed to oil in water emulsions containing at least two separate oil phases, wherein one oil phase is made up of solvent S that contains dis solved pesticide P and one oil phase is made up of adjuvant A. Optionally, both oil phases may further contain one or more emulsifiers as described above.

In one aspect of the invention, this invention is directed to agrochemical compositions, where said composition comprises one or more pesticide P, said pesticide P being insoluble in water and said pesticide P being dissolved in a water immiscible solvent S, wherein said solvent S is present as emulsified droplets in water; and where said composition further comprises at least one adjuvant A, wherein said adjuvant A is not miscible with water and wherein said one or more pesticides P have a solubility in said adjuvant A of below 10 g/l at 20 °C, and wherein said adjuvant A is present as emulsified drop lets in water, wherein adjuvant A and solvent S form at least partly separate oil phases.

Such compositions typically comprise 0.03 to 16 grams of pesticides P per liter.

In one embodiment, the amount of adjuvant A in such compositions is 0.1 g /I to 20 g/l, prefera bly 0.3 g/l to 10 g/l, more preferably 0.5 g/l to 5 g/l.

When the mixture M has been prepared, it can be applied to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment. In one embodiment, it is applied to the leaves of a crop (foliar application).

In one preferred embodiment, a formulation F comprising metyltetraprol and mefentrifluconazol dissolved in a solvent S is prepared. Said formulation F is mixed with water and an adjuvant A that comprises a mineral oil, a vegetable oil alkyl ester and/or a phosporic acid alkyl ester.

In one preferred embodiment, a formulation F comprising metyltetraprol and mefentrifluconazol dissolved in a solvent S that comprises benzyl acetate, alkyl naphthalenes, N,N-dimethylalkana- mides and/or a water miscible solvent like N-alkylpyrrolidone, N-methylpyrrolidone, N-butylpyr- rolidone, propylene carbonate, lactic acid N,N-dimethylamide or DMSO is prepared. Said formu lation F is mixed with water and an adjuvant A that preferably comprises a mineral oil, a vegeta ble oil alkyl ester and/or a phosporic acid alkyl ester.

Examples of suitable crop plants are cereals, for example wheat, rye, barley, triticale, oats or rice; beet, for example sugar or fodder beet; pome fruit, stone fruit and soft fruit, for example ap ples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, currants or goose berries; legumes, for example beans, lentils, peas, lucerne or soybeans; oil crops, for example oilseed rape, mustard, olives, sunflowers, coconut, cacao, castor beans, oil palm, peanuts or soybeans; cucurbits, for example pumpkins/squash, cucumbers or melons; fiber crops, for ex ample cotton, flax, hemp or jute; citrus fruit, for example oranges, lemons, grapefruit or tange rines; vegetable plants, for example spinach, lettuce, asparagus, cabbages, carrots, onions, to matoes, potatoes, pumpkin/squash or capsicums; plants of the laurel family, for example avoca dos, cinnamon or camphor; energy crops and industrial feedstock crops, for example maize, soybeans, wheat, oilseed rape, sugar cane or oil palm; maize; tobacco; nuts; coffee; tea; bana nas; wine (dessert grapes and grapes for vinification); hops; grass, for example turf; sweetleaf (Stevia rebaudania); rubber plants and forest plants, for example flowers, shrubs, deciduous trees and coniferous trees, and harvested produce of these plants.

When employed in plant protection, the amounts of pesticides P applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.

When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.

Various other types of oils, wetters, adjuvants, fertilizers, or micronutrients, and further pesti cides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to mixture M, if appropriate not until immediately prior to use. These agents can be admixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1 , preferably 1:10 to 10:1.

The user applies mixture M usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, mixture M is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liq uor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the mixture M are applied per hectare of agricultural useful area.

The present invention offers the following advantages:

It is easy and economical to carry out.

By methods of the invention the rain fastness of pesticides can be increased.

The long-term efficacy of pesticide formulations can be improved.

Pesticidal formulations can be stored over extended periods of time.

The physical-chemical stability of pesticide formulations can be improved.

Examples

HPLC-MS analysis of the uptake of metyltetraprol and mefentrifluconazol in the plant was done by a process that comprised harvesting of wheat leaves, washing of residual dried spray solu tion from the leaf surface with a suitable solvent, maceration of the washed wheat leaves, ex traction of metyltetraprol and mefentrifluconazol with a suitable solvent, centrifugation and sub sequent dilution of the supernatant for injection into HPLC device.

Adjuvant A1 : mixture of vegetable oil methyl ester and 8 wt% of emulsifiers

Adjuvant A2: mixture of tris(ethylhexyl)phosphate and 40 wt% emulsifiers

Adjuvant A3: mixture of mineral oil and 8 wt% emulsifiers

Example 1 : Preparation of EC Formulations F1 to F3

For the preparation of emulsifiable concentrate (EC) formulations F1 to F3, all components were weighed into a glass or metal beaker of suitable size and were stirred until all active ingredient was completely dissolved. After all components were dissolved, the formulation so obtained was filtered over a 150 pm sieve. In formulation F3, Adjuvant A3 was included in the formulation F3 less than one week prior to the mixing of formulation F3 with water. The compositions of for mulations F1 to F3 are given in table 1. Table 1

Example 2 (Comparative Example)

2 liter of a formulation F1 were mixed with 200 liters of water. The resulting spray solution was sprayed on one wheat plant. The applied use rates was adjusted to equal 80 g/ha for metyltetraprol, 100 g/ha for mefentrifluconazol and 300 g/ha for the fatty alcohol alkoxylates. 2 hours after spray application the applied wheat plant was artificially irrigated with 20 mm of wa ter within 30 min in a rain chamber. 24 hours after spray application the amount of metyltetrap rol and mefentrifluconazol in the leaves was quantitatively analyzed via high pressure liquid chromatography coupled with mass spectrometry (HPLC-MS). The result is given in Table 2.

Example 3:

2 liter of a formulation F1 were first mixed with 200 liters of water and subsequently mixed with 0.25 liter of adjuvant A1. The resulting spray solution was sprayed on one wheat plant. The ap- plied use rates were adjusted to equal 80 g/ha for metyltetraprol, 100 g/ha for mefentriflucona zol and 300 g/ha for the fatty alcohol alkoxylates. 2 hours after spray application the applied wheat plant was artificially irrigated with 20 mm of water within 30 min in a rain chamber. 24 hours after spray application the amount of metyltetraprol and mefentrifluconazol in the leaves was quantitatively analyzed via HPLC-MS. The result is given in Table 2.

Example 4: (Comparative Example)

2 liter of a formulation F2 were mixed with 200 liters of water. The resulting spray solution was sprayed on one wheat plant. The applied use rates were adjusted to equal 80 g/ha for metyltetraprol, 100 g/ha for mefentrifluconazol and 75 g/ha for the fatty alcohol alkoxylates. 2 hours after spray application the applied wheat plant was artificially irrigated with 20 mm of wa ter within 30 min in a rain chamber. 24 hours after spray application the amount of metyltetrap rol and mefentrifluconazol in the leaves was quantitatively analyzed via HPLC-MS. The result is given in Table 2.

Example 5

2 liter of a formulation F2 were first mixed with 200 liters of water and subsequently mixed with 0.25 liter of adjuvant A1. The resulting spray solution was sprayed on one wheat plant. The ap plied use rates were adjusted to equal 80 g/ha for metyltetraprol and 100 g/ha for mefentriflu conazol and 75 g/ha for the fatty alcohol alkoxylates. 2 hours after spray application the applied wheat plant was artificially irrigated with 20 mm of water within 30 min in a rain chamber. 24 hours after spray application the amount of metyltetraprol and mefentrifluconazol in the leaves was quantitatively analyzed via HPLC-MS. The result is given in Table 2.

Example 6

2 liter of a formulation F2 were first mixed with 200 liters of water and subsequently mixed with 0.25 liter of adjuvant A2. The resulting spray solution was sprayed on one wheat plant. The ap plied use rates were adjusted to equal 80 g/ha for metyltetraprol and 100 g/ha for mefentriflu conazol, 75 g/ha for the fatty alcohol alkoxylates. 2 hours after spray application the applied wheat plant was artificially irrigated with 20 mm of water within 30 min in a rain chamber. 24 hours after spray application the amount of metyltetraprol and mefentrifluconazol in the leaves was quantitatively analyzed via HPLC-MS. The result is given in Table 2.

Example 7:

2 liter of formulation F3 were mixed with 200 liters of water. The resulting spray solution was sprayed on one wheat plant. The applied use rates were adjusted to equal 80 g/ha for metyltetraprol, 100 g/ha for mefentrifluconazol, 75 g/ha for the fatty alcohol alkoxylates and 225 g/ha for adjuvant A3. 2 hours after spray application the applied wheat plant was artificially irri gated with 20 mm of water within 30 min in a rain chamber. 24 hours after spray application the amount of metyltetraprol and mefentrifluconazol in the leaves was quantitatively analyzed via HPLC-MS. The result is given in Table 2. Table 2

Examples in which an adjuvant A was added showed significantly higher amounts of the pesti- cide P in the plant.

Claims

1. Method for controlling phytopathogenic fungi and/or undesired plant growth and/or unde sired insect or mite attack and/or for regulating the growth of plants, comprising the fol lowing steps i) Providing a formulation F comprising one or more pesticides P, said pesti cide P being insoluble in water and said pesticide P being dissolved in a wa ter immiscible solvent S; ii) Preparing a mixture of formulation F, water and an adjuvant A, wherein said adjuvant A is not miscible with water and wherein said one or more pesticides P have a solubility in said adjuvant A of below 10 g/l at 20 °C; iii) allowing the resulting mixture obtained in step ii) to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment.

2. Method according to claim 1, wherein formulation F comprises less than 10 wt% of adju vant A.

3. Method according to any of claims 1 to 2, wherein adjuvant A is comprised in the mixture obtained in step ii) in an amount of 0.1 g to 20 g per liter of spray solution.

4. Method according to any of claims 1 to 3, wherein said adjuvant A is selected from par affinic oils, aliphatic oils, aromatic oils, vegetable oil alkyl esters and alkyl phosphates or mixtures thereof.

5. Method according to any of claims 1 to 4, wherein adjuvant A comprises a vegetable oil methyl ester and/or tris(2-ethylhexyl) phosphate.

6. Method according to any of claims 1 to 5, wherein said pesticide P is selected from fun gicides, herbicides and insecticides.

7. Method according to any of claims 1 to 6, wherein said pesticide P is selected from prothioconazole, flufenoxadiazam, metyltetraprol, mefentrifluconazol, florylpicoxamid, pyd- iflumetofen or mixtures thereof.

8. Method according to any of claims 1 to 7, wherein said pesticide P comprises a mixture of metyltetraprol and mefentrifluconazol.

9. Method according to any of claims 1 to 8, wherein said formulation F comprises one or more surfactant, preferably one or more nonionic and/or anionic surfactant.

10. Method according to any of claims 1 to 9, wherein said adjuvant A is added in step ii) in combination with one or more emulsifiers.

11. Method according to any of claims 1 to 10, wherein said adjuvant A added in step ii) as a mixture comprising an alkylbenzene sulfonate salt, a polyalkoxylated plant oil and/or a polyalkoxylated sorbitan ester.

12. Agrochemical composition, where said composition comprises one or more pesticides P, said pesticide P being insoluble in water and said pesticide P being dissolved in a water immiscible solvent S, wherein said solvent S is present as emulsified droplets in water; and where said composition further comprises at least one adjuvant A, wherein said ad juvant A is not miscible with water and wherein said one or more pesticides P have a solubility in said adjuvant A of below 10 g/l at 20 °C, and wherein said adjuvant A is pre sent as emulsified droplets in water, wherein adjuvant A and solvent S form at least partly separate oil phases.