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WO2024154135A1 - Aqueous fungicidal suspension - Google Patents

Aqueous fungicidal suspension Download PDF

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Publication number
WO2024154135A1
WO2024154135A1 PCT/IL2024/050073 IL2024050073W WO2024154135A1 WO 2024154135 A1 WO2024154135 A1 WO 2024154135A1 IL 2024050073 W IL2024050073 W IL 2024050073W WO 2024154135 A1 WO2024154135 A1 WO 2024154135A1
Authority
WO
WIPO (PCT)
Prior art keywords
suspension concentrate
species
weight
composition
prothioconazole
Prior art date
Application number
PCT/IL2024/050073
Other languages
French (fr)
Inventor
Jenny Lerner Yardeni
Joseph ENGLANDER
Hanan Sertchook
Original Assignee
Adama Makhteshim Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Adama Makhteshim Ltd. filed Critical Adama Makhteshim Ltd.
Publication of WO2024154135A1 publication Critical patent/WO2024154135A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647Triazoles; Hydrogenated triazoles
    • A01N43/6531,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/541,3-Diazines; Hydrogenated 1,3-diazines

Definitions

  • the present invention relates to agrochemical suspension concentrate comprising: a) from 1.0 to 50% per weight of prothioconazole; b) from 2% to 20% per weight of nonionic steric stabilizer; c) optionally one or more additional fungicides, preferably strobilurins, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
  • agrochemicals as crop protection agents in generally based on the nature of active agrochemicals, such as their mode of action, permeability, physico-chemical parameters of interaction with plants and/or soil, toxicity to the target disease or organism and breakdown of agrochemical to metabolites.
  • active agrochemical could be formulated in different ways, which is expected to affect the final behavior of the pesticide, based on chemical stability, safety of use and biological efficacy.
  • the pesticide industry continuously targets the development of new formulations, focusing on the search for greater chemical and physical stability, optimization of biological activity, differentiation, and greater safety in use.
  • Liquid formulations have the advantage over powder and/or granular compositions formulations, that upon the reconstitution of a spray liquid, typically by adding water, they do not produce dust.
  • Preferred liquid formulations are aqueous suspension concentrates, defined as a suspension of solid active ingredients in a liquid (mostly water).
  • Aqueous suspension concentrates avoid the use of high content of an organic, mostly aromatic solvents, or other heavy organic solvent systems which unfavorable on toxicological and environmental grounds.
  • the challenge for preparation of aqueous suspension concentrates of active pesticides is stabilization of certain amount of finely divided solid particles of said organic hydrophobic active pesticide in water.
  • US 2008/274154 recites suspension concentrates of certain fungicides and bactericides containing acrylic graft copolymer surfactant and an ionic alkoxylated polyarylphenol phosphate ester surfactant, said suspension concentrates are shown to be stable over time at high concentrations of active materials.
  • WO 2009/082939 teaches that, concentrated suspensions of certain fungicides may be formed by stabilizing an agrochemical active ingredient with one non-ionic dispersing agent and one anionic dispersing agent or, in certain cases, only with anionic dispersants.
  • prothioconazole is an important member of triazoles class fungicides known for ability to inhibit ergosterol biosynthesis in fungi. Along with prothioconazole extensive use, this compound tends to chemical degradation, leading to loss of efficacy and formation of toxic metabolites. Aqueous dispersions of prothioconazole , especially when formulated at ready-to-use concentrations, significantly reducing their shelf life. Losses of ten to fifteen percent by weight of prothioconazole over time have been observed for certain products.
  • the present invention provides an agrochemical suspension concentrate comprising: a) from 1.0 to 50% per weight of prothioconazole; b) from 2% to 20% per weight of nonionic steric stabilizer; c) optionally one or more additional fungicides, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
  • the present invention is referred to a method of stabilizing the suspension concentrate comprising prothioconazole by means of addition of from 2% to 20% per weight of nonionic steric stabilizer, wherein the nonionic steric stabilizer is a mixture of polyacrylate polymers and of tristyrylphenol alkoxylates, and wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
  • the present invention is referred to a method for controlling and/or preventing pests comprising applying an effective amount of the agrochemical suspension concentrate comprising: a) from 1.0 to 50% per weight of prothioconazole; b) from 2% to 20% per weight of nonionic steric stabilizer; c) optionally one or more additional fungicides, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants, to a locus where the pest is to be controlled and/or prevented so as to thereby control and/or prevent the pest, wherein the pest is a phytopathogenic harmful fungi.
  • the present invention further provides a method of controlling phytopathogenic harmful fungi in a field of crop comprising applying an effective amount of the composition agrochemical suspension concentrate comprising: a) from 1.0 to 50% per weight of prothioconazole; b) from 2% to 20% per weight of nonionic steric stabilizer; c) optionally one or more additional fungicides, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants, to a field of crop so as to thereby control the phytopathogenic harmful fungi in the field of crop.
  • agrochemical suspension concentrate comprising: a) from 1.0 to 50% per weight of prothioconazole; b) from 2% to 20% per weight of nonionic steric stabilizer; c) optionally one or more additional fungicides, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants, to a field of crop so as to thereby control the phytopathogenic harmful fungi in the field of crop.
  • the term "effective amount” refers to an amount of the active component that is commercially recommended for use to control and/or prevent pest.
  • the commercially recommended amount for each active component often specified as application rates of the commercial formulation, may be found on the label accompanying the commercial formulation.
  • the commercially recommended application rates of the commercial formulation may vary depending on factors such as the plant species and the pest to be controlled.
  • the term "pest” includes, but is not limited to, unwanted phytopathogenic harmful fungi, unwanted insect, unwanted nematode, and weed.
  • the term "pesticide” broadly refers to an agent that can be used to prevent, control and/or kill a pest.
  • the term is understood to include but is not limited to fungicides, insecticides, nematicides, herbicides, acaricides, parasiticides or other control agents.
  • fungicides insecticides, nematicides, herbicides, acaricides, parasiticides or other control agents.
  • specific compounds of each class see "The Pesticide Manual Thirteenth Edition” (British Crop Protection Council, Hampshire, UK, 2003), as well as “The e-Pesticide Manual, Version 3" (British Crop Protection Council, Hampshire, UK, 2003-04), the contents of each of which are incorporated herein by reference in their entirety.
  • suspension concentrate is referred to a suspension of solid active ingredients in a liquid intended for dilution with water before use.
  • aqueous as used herein, is meant that the solvent used in the composition is mainly water. Hence, “aqueous” and “water-based” may be considered synonyms. Water-based formulations generally have the advantage that they require little or no organic solvent fraction.
  • 'stable composition' refers to a liquid formulation which is stable physically and chemically.
  • 'chemical stability' as used herein refers to a composition containing one or more active ingredients wherein the active ingredient/s does not chemically degrade or decompose beyond acceptable limit.
  • 'physical stability' as used herein represents a formulation containing one or more active ingredients wherein there is no settling of solid particles occurs during/after storage.
  • active ingredient an ingredient that is chemically active and/or biologically active in origin, in particular, prothioconazole and/or its mixture with at least one additional fungicide.
  • locus includes not only areas where the pest may already be developed, but also areas where pests have yet to emerge, and also to areas under cultivation. Locus includes the plant or crop and propagation material of the plant or crop. Locus also includes the area surrounding the plant or crop and the growing media of the plant or crop, such as soil and crop field.
  • plant or “crop” includes reference to whole plants, plant organs (e.g. leaves, stems, twigs, roots, trunks, limbs, shoots, fruits etc.), plant cells, or plant seeds. This term also encompasses plant crops such as fruits, spores, corms, bulbs, rhizomes, sprouts basal shoots, stolons, and buds and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.
  • plant organs e.g. leaves, stems, twigs, roots, trunks, limbs, shoots, fruits etc.
  • plant cells or plant seeds. This term also encompasses plant crops such as fruits, spores, corms, bulbs, rhizomes, sprouts basal shoots, stolons, and buds and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.
  • ha refers to hectare
  • the present invention provides agrochemically suspension concentrate which is chemically and physically stable.
  • the subject of the present invention is agrochemical suspension concentrate of prothioconazole, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
  • Nonionic surfactants have an advantage to ionic surfactants, given the fact that anionic surfactants are broadly suggested as potent irritants to human and animal skin. Cationic surfactants have similar irritating properties, but suggested to be more cytotoxic than anionic, while the irritation potential of non-ionic surfactants is ranked the lowest.
  • the present invention provides an agrochemical suspension concentrate comprising: a) from 1.0 to 50% per weight of prothioconazole; b) from 2% to 20% per weight of nonionic steric stabilizer; c) optionally one or more additional fungicides, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
  • the agrochemical suspension concentrate comprises from 1.0 to 30 % per weight of prothioconazole.
  • the agrochemical suspension concentrate comprises from 20 to 50 % per weight of prothioconazole.
  • the agrochemical suspension concentrate comprises from 15 to 30 % per weight of prothioconazole. In another embodiment, the agrochemical suspension concentrate comprises from 1.0 to 25 % per weight of prothioconazole.
  • the agrochemical suspension concentrate comprises from 1.0 to 20 % per weight of prothioconazole.
  • the agrochemical suspension concentrate comprises from 1.0 to 15 % per weight of prothioconazole.
  • the agrochemical suspension concentrate comprises from 1.0 to 10 % per weight of prothioconazole.
  • the agrochemical suspension concentrate comprises b) nonionic steric stabilizer selected from polyacrylate polymers, tristyrylphenol alkoxylates and the mixtures thereof.
  • the agrochemical suspension concentrate comprises b) from 2% to 20% per weight of nonionic steric stabilizer selected from polyacrylate polymers, tristyrylphenol alkoxylates and the mixtures thereof.
  • the agrochemical suspension concentrate comprises b) from 2% to 15% per weight of nonionic steric stabilizer selected from polyacrylate polymers, tristyrylphenol alkoxylates and the mixtures thereof.
  • the agrochemical suspension concentrate comprises b) from 2% to 10% per weight of nonionic steric stabilizer selected from polyacrylate polymers, tristyrylphenol alkoxylates and the mixtures thereof.
  • the agrochemical suspension concentrate comprises b) from 2% to 8% per weight of nonionic steric stabilizer selected from polyacrylate polymers, tristyrylphenol alkoxylates and the mixtures thereof.
  • the agrochemical suspension concentrate comprises b) from 2% to 6% per weight of nonionic steric stabilizer selected from polyacrylate polymers, tristyrylphenol alkoxylates and the mixtures thereof. Any nonionic polyacrylate polymer may be used.
  • nonionic acrylate polymers are selected from polyfmethyl acrylate polymers and copolymers), polyfmethyl methacrylate polymers and copolymers), polyfethyl methacrylate polymers and copolymers), (styrene/(meth)acrylic acid copolymers), (methyl methacrylate/methacrylic acid/methoxy (polyethyleneglycol) methacrylate copolymers), methacrylatepolyethylene oxide graft copolymers, graft copolymer of acrylic ester and oxyalkylene.
  • the nonionic polyacrylate polymer is a methyl methacrylate/methacrylic acid/monomethoxypolyethylene glycol (PEG) methacrylate graft copolymer (eg, AtloxTM 4913, Uniqema Surfactants Ltd, UK).
  • PEG methyl methacrylate/methacrylic acid/monomethoxypolyethylene glycol
  • the nonionic tristyrylphenol alkoxylates including those prepared from tristyryl phenol and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof).
  • the nonionic tristyrylphenol alkoxylates are tristyrylphenol ethoxylates having from 10 to 54 units of ethylene oxide.
  • the agrochemical suspension concentrate comprises b) the nonionic steric stabilizer, which is a mixture of polyacrylate polymers and tristyrylphenol alkoxylates.
  • the agrochemical suspension concentrate comprises the nonionic steric stabilizer, which is a mixture of from 1 % to 10 % per weight of polyacrylate polymers and from 0.5 % to 10 % per weight of tristyrylphenol alkoxylates.
  • the agrochemical suspension concentrate comprises the nonionic steric stabilizer, wherein the weight ratio of polyacrylate polymers to tristyrylphenol alkoxylates in said steric stabilizer is from 1.5 :1 to 5:1.
  • the agrochemical suspension concentrate comprises the nonionic steric stabilizer, wherein the weight ratio of polyacrylate polymers to tristyrylphenol alkoxylates in said steric stabilizer is from 1.5:1 to 3:1. In another embodiment, the agrochemical suspension concentrate comprises the nonionic steric stabilizer, wherein the weight ratio of polyacrylate polymers to tristyrylphenol alkoxylates in said steric stabilizer is from 1.5:1 to 2:1.
  • the weight ratio of polyacrylate polymers to prothioconazole is from 1:100 to 1:0.83.
  • the weight ratio of polyacrylate polymers to prothioconazole is from 1:20 to 1:0.83.
  • the weight ratio of polyacrylate polymers to prothioconazole is from 1:10 to 1:0.83.
  • the weight ratio of polyacrylate polymers to prothioconazole is from 1:5 to 1:0.83.
  • the weight ratio of polyacrylate polymers to prothioconazole is from 1:4.5 to 1:0.83.
  • the weight ratio of tristyrylphenol alkoxylates to prothioconazole is from 1: 166 to 1:5.
  • the weight ratio of tristyrylphenol alkoxylates to prothioconazole is from 1: 100 to 1:5.
  • the weight ratio of tristyrylphenol alkoxylates to prothioconazole is from 1: 50 to 1:5.
  • the weight ratio of tristyrylphenol alkoxylates to prothioconazole is from 1: 30 to 1:5.
  • the weight ratio of tristyrylphenol alkoxylates to prothioconazole is from 1: 20 to 1:5.
  • the weight ratio of tristyrylphenol alkoxylates to prothioconazole is from 1: 10 to 1:5. In an embodiment, the weight ratio of tristyrylphenol alkoxylates to prothioconazole is from 1: 8 to 1:5.
  • the weight ratio of tristyrylphenol alkoxylates to prothioconazole is from 1: 7 to 1:5.
  • the agrochemical suspension concentrate comprises c) one or more additional fungicide.
  • the agrochemical suspension concentrate comprises c) one or more additional fungicide, wherein the amount of the one or more additional fungicides is of about 1% to about 50% by weight, based on the total weight of the composition.
  • the agrochemical suspension concentrate comprises c) one or more additional fungicide, wherein the amount of the one or more additional fungicides is of about 1% to about 10% by weight, based on the total weight of the composition.
  • the agrochemical suspension concentrate comprises c) one or more additional fungicide, wherein the amount of the one or more additional fungicides is of about 5% to about 10% by weight, based on the total weight of the composition.
  • the agrochemical suspension concentrate comprises c) one or more additional fungicide, wherein the amount of the one or more additional fungicides is of about 10% to about 20% by weight, based on the total weight of the composition.
  • the agrochemical suspension concentrate comprises c) one or more additional fungicide, wherein the amount of the one or more additional fungicides is of about 20% to about 30% by weight, based on the total weight of the composition.
  • the agrochemical suspension concentrate comprises c) one or more additional fungicide, wherein the amount of the one or more additional fungicides is of about 30% to about 40% by weight, based on the total weight of the composition. In an embodiment, the agrochemical suspension concentrate comprises c) one or more additional fungicide, wherein the amount of the one or more additional fungicides is of about 40% to about 50% by weight, based on the total weight of the composition.
  • the agrochemical suspension concentrate comprises c) one or more additional fungicide selected from the triazole fungicides including azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazol, diniconazole, diniconazole-M, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furconazole, furconazole-cis, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazol, penconazole, quinconazole, simeconazole, tetraconazole, triadimenol, triadimefon, triticonazole, uniconazole, uniconazole-P, voriconazole, difenoconazole, propiconazole, triazo
  • the agrochemical suspension concentrate comprises c) one or more additional fungicide selected from the strobilurin family including azoxystrobin, kresoxim- methyl, picoxystrobin, fluoxastrobin, oryzastrobin, dimoxystrobin, pyraclostrobin, trifloxystrobin and the mixtures thereof.
  • said additional fungicide is azoxystrobin.
  • the agrochemical suspension concentrate comprises of about 1% to about 50% by weight of azoxystrobin, as an additional fungicide c), based on the total weight of the composition.
  • the agrochemical suspension concentrate comprises of about 1% to about 10% by weight of azoxystrobin, as an additional fungicide c) based on the total weight of the composition.
  • the agrochemical suspension concentrate comprises of about 5% to about 10% by weight of azoxystrobin, as an additional fungicide c), based on the total weight of the composition. In an embodiment, the agrochemical suspension concentrate comprises of about 10% to about 20% by weight of azoxystrobin, as an additional fungicide c), based on the total weight of the composition.
  • the agrochemical suspension concentrate comprises of about 20% to about 30% by weight of azoxystrobin, as an additional fungicide c), based on the total weight of the composition.
  • the agrochemical suspension concentrate comprises of about 30% to about 50% by weight of azoxystrobin, as an additional fungicide c), based on the total weight of the composition.
  • the agrochemical suspension concentrate comprises of about 40% to about 50% by weight of azoxystrobin, as an additional fungicide c), based on the total weight of the composition.
  • the present invention provides a method for controlling and/or preventing pests comprising applying an effective amount of the agrochemical suspension concentrate comprising: a) from 1.0 to 50% per weight of prothioconazole; b) from 2% to 20% per weight of nonionic steric stabilizer; c) optionally one or more additional fungicides, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants, to a locus where the pest is to be controlled and/or prevented so as to thereby control and/or prevent the pest, wherein the pest is a phytopathogenic harmful fungi.
  • the locus is a crop field.
  • the present invention further provides a method of controlling phytopathogenic harmful fungi in a field of crop comprising applying an effective amount of the agrochemical suspension concentrate comprising: a) from 1.0 to 50% per weight of prothioconazole; b) from 2% to 20% per weight of nonionic steric stabilizer; c) optionally one or more additional fungicides, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants, to a field of crop so as to thereby control the phytopathogenic harmful fungi in the field of crop.
  • the crop is selected from the group consisting of cotton, flax, grapevines, fruit, vegetables, such as Rosaceae sp. (for example pome fruit such as apples and pears, but also stone fruit such as apricots, cherries, almonds and peaches, and berry fruits such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp.
  • Rosaceae sp. for example pome fruit such as apples and pears, but also stone fruit such as apricots, cherries, almonds and peaches, and berry fruits such as strawberries
  • Rosaceae sp. for example pome fruit such as apples and pears, but also stone fruit such as a
  • Rubiaceae sp. for example coffee
  • Theaceae sp. Sterculiceae sp.
  • Rutaceae sp. for example lemons, organs and grapefruit
  • Solanaceae sp. for example tomatoes
  • Liliaceae sp. for example lettuce
  • Umbelliferae sp. for example lettuce
  • Alliaceae sp. for example leeks, onions
  • main crop plants such as Gramineae sp. (for example maize, turfgrass, cereals such as wheat, rye, rice, barley, oats, sorghum/millet and triticale), Asteraceae sp. (for example sunflowers), Brassicaceae sp. (for example white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, Pak Choi, kohlrabi, radishes, and rapeseed, mustard, horseradish and cress), Fabacae sp. (for example beans, peanuts), Papilionaceae sp. (for example soya beans), Solanaceae sp.
  • Gramineae sp. for example maize, turfgrass, cereals such as wheat, rye, rice, barley, oats, sorghum/millet and triticale
  • Asteraceae sp. for example sunflowers
  • Brassicaceae sp. for example white cabbage, red cabbage, broccoli
  • the crop is selected from the group consisting of wheat, rye, rice, barley, oats, sorghum/millet, triticale, maize, rapeseed, beans, peanuts and sunflowers.
  • the crop is selected from the group consisting of wheat, rye, rice, barley, oats, sorghum/millet and triticale.
  • Non-limiting examples of pathogens of fungal diseases which may be treated in accordance with the invention include: diseases caused by powdery mildew pathogens, for example Blumeria species, for example Blumeria graminis, Podosphaera species, for example Podosphaera leucotricha, Sphaerotheca species, for example Sphaerotheca fuliginea, Uncinula species, for example Uncinula necator, for example Erysiphe species; diseases caused by rust disease pathogens, for example Gymnosporangium species, for example Gymnosporangium sabinae ; Hemileia species, for example Hemileia vastatrix; Phakopsora species, for example Phakopsora pachyrhizi or Phakopsora meibomiae Puccinia species, for example Puccinia recondita, Puccinia graminis oder Puccinia striif ormis, Uromyces species
  • brassicaer Phytophthora species, for example Phytophthora inf estans, Plasmopara species, for example Plasmopara viticola, Pseudoperonospora species, for example Pseudoperonospora humuli or Pseudoperonospora cubensis, Pythium species, for example Pythium ultimunv, leaf blotch diseases and leaf wilt diseases caused, for example, by Alternaria species, for example Alternaria solanv, Cercospora species, for example Cercospora beticola, Cladiosporium species, for example Cladiosporium cucumerinunr, Cochliobolus species, for example Cochliobolus sativus (conidial form: Drechslera, syn: Helminthosporium) or Cochliobolus miyabeanus, Colletotrichum species, for example Colletotrichum linde
  • Pseudomonas species for example Pseudomonas syringae pv. lachrymans, Erwinia species, for example Erwinia amylovora, Liberibacter species, for example Liberibacter asiaticus, Xyella species, for example Xylella f astidiosa, Ralstonia species, for example Ralstonia solanacearum, Dickeya species, for example Dickeya solanv, Clavibacter species, for example Clavibacter michiganensis, Streptomyces species, for example Streptomyces scabies, diseases of soya beans: fungal diseases on leaves, stems, pods and seeds caused, for example, by Alternaria leaf spot (Alternaria spec atrans tenuissima), Anthracnose (Colletotrichum gloeosporoides dematium var.
  • phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophora gregata), pythiumrot (Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctonia root rot, stem decay, and damping-off (Rhizoctonia solani), sclerotinia stem decay (Sclerotinia sclerotiorum), sclerotinia southern blight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).
  • the phytopathogenic harmful fungi is selected from Septoria species, Fusarium species, Puccinia species, Erisyphe species, Drechslera species, Ramularia species, Mycosphaerella species and Rhynchosporium species.
  • the phytopathogenic harmful fungi is selected from Puccinia recondita, Septoria tritici, Fusarium culmorum, Pyrenophora teres and Rhynchosporium secal is. In an embodiment, the phytopathogenic harmful fungi is selected from Pyrenophora teres, Rhynchosporium secalis, Cochliobolus sativus, Puccinia hordei, Blumeria graminis f. sp.
  • the agrochemical suspension concentrate of invention is applied in an amount from about 0.2 L/ha to about 2 L/ha.
  • the agrochemical suspension concentrate of invention is applied in an amount of from about 20 g/ha of prothioconazole to about 500 g/ha of prothioconazole.
  • the agrochemical suspension concentrate of invention is applied in an amount of from about 75 g/ha of prothioconazole to about 150 g/ha of prothioconazole.
  • the agrochemical suspension concentrate of invention comprises strobilurin as an additional fungicide c); and said agrochemical suspension concentrate is applied in an amount of from about 20 g/ha of strobilurin to about 500 g/ha of strobilurin.
  • the agrochemical suspension concentrate of invention comprises azoxystrobin as an additional fungicide c); and said agrochemical suspension concentrate is applied in an amount of from about 20 g/ha of azoxystrobin to about 500 g/ha of azoxystrobin.
  • the present invention provides a method of stabilizing of the suspension concentrate comprising from 1.0 to 50 % per weight of prothioconazole by means of addition of from 2% to 20% per weight of nonionic steric stabilizer, wherein the nonionic steric stabilizer is a mixture of polyacrylate polymers and of tristyrylphenol alkoxylates, and wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
  • prothioconazole exist in the form of solid particles.
  • the present invention provides a method of stabilizing of the suspension concentrate comprising from 1.0 to 50 % per weight of prothioconazole by means of addition of from 2% to 20% per weight of nonionic steric stabilizer, wherein the nonionic steric stabilizer is a mixture of polyacrylate polymers and of tristyrylphenol alkoxylates, and wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
  • the present invention provides a method of stabilizing of the suspension concentrate comprising from 1.0 to 50 % per weight of prothioconazole by means of addition of from 2% to 20% per weight of nonionic steric stabilizer, which is a mixture of from 1 % to 10 % per weight of polyacrylate polymers and from 0.5 % to 10 % per weight of tristyrylphenol alkoxylates, and wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
  • the present invention provides a method of stabilizing of the suspension concentrate comprising from 1.0 to 50 % per weight of prothioconazole by means of addition of from 2% to 20% per weight of nonionic steric stabilizer, which is a mixture of from 1 % to 10 % per weight of polyacrylate polymers and from 0.5 % to 10 % per weight of tristyrylphenol alkoxylates, wherein the weight ratio of polyacrylate polymers to tristyrylphenol alkoxylates is from 1.5 :1 to 5:1, and wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
  • the present invention provides a method of stabilizing of the suspension concentrate comprising from 1.0 to 50 % per weight of prothioconazole by means of addition of from 2% to 20% per weight of nonionic steric stabilizer, which is a mixture of from 1 % to 10 % per weight of polyacrylate polymers and from 0.5 % to 10 % per weight of tristyrylphenol alkoxylates, wherein the weight ratio of polyacrylate polymers to tristyrylphenol alkoxylates is from 1.5:1 to 3:1, and wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
  • the present invention provides a method of stabilizing of the suspension concentrate comprising from 1.0 to 50 % per weight of prothioconazole by means of addition of from 2% to 20% per weight of nonionic steric stabilizer, which is a mixture of from 1 % to 10 % per weight of polyacrylate polymers and from 0.5 % to 10 % per weight of tristyrylphenol alkoxylates, wherein the weight ratio of polyacrylate polymers to tristyrylphenol alkoxylates is from 1.5:1 to 2:1, and wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
  • All the suspension concentrates of the invention may comprise further additives such as emulsifiers, penetrants, wetting agents, spreading agents and/or retention agents.
  • Suitable substances are all of those which can typically be used for this purpose in agrochemicals.
  • Suitable additives are, for example, organomodified polysiloxanes, e.g. BreakThru® OE444, BreakThru® S240, Silwett® L77, Silwett® 408; tristyrylphenol ethoxylate, e.g. POE-16 POLYSTEP® TSP-16;; polyalkoxylated butyl ether, e.g. WitconolTM NS 500 LQ; Sorbitan monolaurate ethoxylated (20EO), e.g. Tween® 20 and the like.
  • organomodified polysiloxanes e.g. BreakThru® OE444, BreakThru® S240, Silwett® L77, Silwett® 408
  • Additional suitable additives which may be present in all the compositions of the invention are defoamers, preservatives, antioxidants, pH modifiers, dyes and inert fillers.
  • Suitable defoamers are all substances which can typically be used for this purpose in agrochemicals. Preference is given to silicone oils, silicone oil formulations, magnesium stearate, phosphinic acids and phosphonic acids. Examples are Silcolapse® 482 from Bluestar Silicones, Silfoam® SCI 132 from Wacker [dimethylsiloxanes and -silicones, CAS No. 63148-62-9], SAG 1538 or SAG 1572 from Momentive [dimethylsiloxanes and - silicones, CAS-Nr. 63148-62-9] or Fluowet® PL 80.
  • Suitable pH modifiers are all substances which can be used for achieving the desirable pH of final suspension concentrate of from 4 to 8, in particular, alkali metal hydroxides, such as NaOH or KOH, or water- miscible amines such as triethanolamine, diethanolamine and the like.
  • preservatives are all substances which can typically be used for this purpose in agrochemicals. Suitable preservatives are, for example, formulations comprising 5-chloro- 2-methyl-4-isothiazolin-3-one [CIT; CAS No. 26172-55-4], 2-methyl-4-isothiazolin-3-one [MIT, CAS No. 2682-204] or l,2-benzisothiazol-3(2H)-one [BIT, CAS No. 2634-33-5], Examples include Preventol® D7 (Lanxess), Kathon® CG/ICP (Rohm & Haas), Acticide® SPX (Thor GmbH) and Proxel® GXL (ArchChemicals).
  • Suitable antioxidants are all substances which can typically be used for this purpose in agrochemicals. Preference is given to butylhydroxytoluene [3,5-di-tert-butyl-4- hydroxytoluene, CAS No. 128-37-0] and citric acid.
  • Possible dyes are all substances which can typically be used for this purpose in agrochemicals. Examples include titanium dioxide, carbon black, zinc oxide, blue pigments, red pigments and Permanent Red FGR.
  • Suitable inert fillers are all substances which can typically be used for this purpose in agrochemicals and which do not function as thickeners. Preference is given to inorganic particles such as carbonates, silicates and oxides, and also organic substances such as urea-formaldehyde condensates. Examples include kaolin, rutile, silicon dioxide ("finely divided silica”), silica gel and natural and synthetic silicates, and additionally talc.
  • the composition may comprise additional nonionic surfactants.
  • Suitable nonionic surfactants are surfactants from the classes of the alkoxylates, block polymers, N alkylated fatty acid amides, amine oxides, esters or sugar-based surfactants.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters that have been alkoxylated.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters that have been alkoxylated.
  • ethylene oxide and/or propylene oxide preferably ethylene oxide.
  • N-alkylated fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose esters and glucose esters or alkylpolyglucosides.
  • Suitable block polymers are block polymers of the A-B or A-B-A type, comprising blocks of polyethylene oxide and polypropyleneoxide, or of the A-B-C type, comprising alkanol, polyethylene oxide, and polypropylene oxide.
  • Preferred nonionic surfactants are surfactants from the classes of alkoxylates and block polymers, more particularly alkoxylates.
  • compositions and/or combinations of the invention can be applied in undiluted form or diluted with water.
  • they are diluted with at least one part water, preferably with 10 parts water and more preferably with at least 100 parts water, for example with 1 to 10000, preferably 10 to 5000 and more preferably with 50 to 24,000 parts water, based on one part of the formulation.
  • the dilution is achieved by pouring the suspension concentrates of the invention into the water.
  • agitation for example stirring.
  • agitation is generally unnecessary.
  • dilutions are typically conducted at temperatures in the range from 0°C to 50°C, especially at 10 °C to 30 °C or at ambient temperature.
  • the water used for dilution is generally tap water.
  • the water may, however, already contain water soluble or finely dispersed compounds which are used in crop protection, for instance nutrients, fertilizers or pesticides.
  • various kinds of oils, wetting agents, adjuvants, fertilizers or micronutrients and further pesticides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • these may be added to the compositions of the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
  • compositions of the invention are applied mainly by spraying, especially spraying of the leaves.
  • Application can be conducted by spraying techniques known to those skilled in the art, for example using water as carrier and amounts of spray liquid of about 50 to 1000 liters per hectare, for example from 100 to 200 liters per hectare.
  • inventive suspension concentrates have advantageous properties in respect of the treatment of plants; more particularly, they feature good use properties, high stability and high fungicidal activity.
  • composition 1 One exemplary embodiment of the formulation of the present invention is illustrated below as Composition 1:
  • composition 1 Preparation of Inventive Composition 1:
  • Soft water about 90% of the required quantity of soft water
  • prothioconazole about 90% of the required quantity of soft water
  • azoxystrobin about 90% of the required quantity of soft water
  • nonionic stabilizers about 90% of the required quantity of soft water
  • propylene glycol about 90% of the required quantity of soft water
  • anti-foam emulsion was stirred until homogenous dispersion is obtained.
  • compositions 1-3 prepared by similar procedure and having different amounts and ratios of polyacrylate polymers and tristyrylphenol alkoxylates as nonionic steric stabilizer are represented in Table 1 below.
  • Comparative Compositions 4-9 prepared by similar procedure and having different amounts and ratios of polyacrylate polymers and tristyrylphenol alkoxylates as nonionic steric stabilizer are represented in Table 2 below. Table 2. Comparative compositions 4-9.
  • inventive compositions have good flowability after two weeks 54 °C storage and comparative compositions solidify completely under the same

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Abstract

The invention provides an agrochemical suspension concentrate comprising: a) from 1.0 to 50% per weight of prothioconazole; b) from 2% to 20% per weight of nonionic steric stabilizer and c) optionally one or more additional fungicides, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants. Methods for controlling and/or preventing pests, and for controlling and/or preventing phytopathogenic harmful fungi, comprising the application of the composition, are also provided.

Description

TITLE: AQUEOUS FUNGICIDAL SUSPENSION
FIELD OF INVENTION:
The present invention relates to agrochemical suspension concentrate comprising: a) from 1.0 to 50% per weight of prothioconazole; b) from 2% to 20% per weight of nonionic steric stabilizer; c) optionally one or more additional fungicides, preferably strobilurins, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
BACKGROUND:
The efficacy of agrochemicals as crop protection agents in generally based on the nature of active agrochemicals, such as their mode of action, permeability, physico-chemical parameters of interaction with plants and/or soil, toxicity to the target disease or organism and breakdown of agrochemical to metabolites. However, the same active agrochemical could be formulated in different ways, which is expected to affect the final behavior of the pesticide, based on chemical stability, safety of use and biological efficacy. Based on the above, the pesticide industry continuously targets the development of new formulations, focusing on the search for greater chemical and physical stability, optimization of biological activity, differentiation, and greater safety in use.
Moreover, for reasons of economics, ecology and safety, certain formulations are more advantageous than others. Liquid formulations have the advantage over powder and/or granular compositions formulations, that upon the reconstitution of a spray liquid, typically by adding water, they do not produce dust. Preferred liquid formulations, are aqueous suspension concentrates, defined as a suspension of solid active ingredients in a liquid (mostly water). Aqueous suspension concentrates avoid the use of high content of an organic, mostly aromatic solvents, or other heavy organic solvent systems which unfavorable on toxicological and environmental grounds. However, the challenge for preparation of aqueous suspension concentrates of active pesticides is stabilization of certain amount of finely divided solid particles of said organic hydrophobic active pesticide in water.
For example, US 2008/274154 recites suspension concentrates of certain fungicides and bactericides containing acrylic graft copolymer surfactant and an ionic alkoxylated polyarylphenol phosphate ester surfactant, said suspension concentrates are shown to be stable over time at high concentrations of active materials.
WO 2009/082939 teaches that, concentrated suspensions of certain fungicides may be formed by stabilizing an agrochemical active ingredient with one non-ionic dispersing agent and one anionic dispersing agent or, in certain cases, only with anionic dispersants.
US 2009/325808 describes highly concentrated suspension of slightly water-soluble pesticides that are protected from crystal growth by the use of certain polymeric surfactants.
However, none of the above publications recites prothioconazole as active pesticide. Prothioconazole is an important member of triazoles class fungicides known for ability to inhibit ergosterol biosynthesis in fungi. Along with prothioconazole extensive use, this compound tends to chemical degradation, leading to loss of efficacy and formation of toxic metabolites. Aqueous dispersions of prothioconazole , especially when formulated at ready-to-use concentrations, significantly reducing their shelf life. Losses of ten to fifteen percent by weight of prothioconazole over time have been observed for certain products.
There remains a need in the art for improved stable fungicidal suspension aqueous concentrates comprising prothioconazole.
SUMMARY:
The present invention provides an agrochemical suspension concentrate comprising: a) from 1.0 to 50% per weight of prothioconazole; b) from 2% to 20% per weight of nonionic steric stabilizer; c) optionally one or more additional fungicides, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
Furthermore, the present invention is referred to a method of stabilizing the suspension concentrate comprising prothioconazole by means of addition of from 2% to 20% per weight of nonionic steric stabilizer, wherein the nonionic steric stabilizer is a mixture of polyacrylate polymers and of tristyrylphenol alkoxylates, and wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
In addition, the present invention is referred to a method for controlling and/or preventing pests comprising applying an effective amount of the agrochemical suspension concentrate comprising: a) from 1.0 to 50% per weight of prothioconazole; b) from 2% to 20% per weight of nonionic steric stabilizer; c) optionally one or more additional fungicides, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants, to a locus where the pest is to be controlled and/or prevented so as to thereby control and/or prevent the pest, wherein the pest is a phytopathogenic harmful fungi.
The present invention further provides a method of controlling phytopathogenic harmful fungi in a field of crop comprising applying an effective amount of the composition agrochemical suspension concentrate comprising: a) from 1.0 to 50% per weight of prothioconazole; b) from 2% to 20% per weight of nonionic steric stabilizer; c) optionally one or more additional fungicides, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants, to a field of crop so as to thereby control the phytopathogenic harmful fungi in the field of crop.
DESCRIPTION OF THE INVENTION:
Definitions:
Prior to setting forth the present subject matter in detail, it may be helpful to provide definitions of certain terms to be used herein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this subject matter pertains. The following definitions are provided for clarity.
The term "a" or "an" as used herein includes the singular and the plural, unless specifically stated otherwise. Therefore, the terms "a," "an," or "at least one" can be used interchangeably in this application.
As used herein, the verb "comprise" as is used in this description and in the claims and its conjugations are used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded.
As used herein, the term "about" when used in connection with a numerical value includes ±10% from the indicated value. In addition, all ranges directed to the same component or property herein are inclusive of the endpoints, are independently combinable, and include all intermediate points and ranges. It is understood that where a parameter range is provided, all integers within that range, and tenths thereof, are also provided by the invention.
As used herein, the term "effective amount" refers to an amount of the active component that is commercially recommended for use to control and/or prevent pest. The commercially recommended amount for each active component, often specified as application rates of the commercial formulation, may be found on the label accompanying the commercial formulation. The commercially recommended application rates of the commercial formulation may vary depending on factors such as the plant species and the pest to be controlled.
As used herein, the term "pest" includes, but is not limited to, unwanted phytopathogenic harmful fungi, unwanted insect, unwanted nematode, and weed.
As used herein, the term "pesticide" broadly refers to an agent that can be used to prevent, control and/or kill a pest. The term is understood to include but is not limited to fungicides, insecticides, nematicides, herbicides, acaricides, parasiticides or other control agents. For chemical classes and applications, as well as specific compounds of each class, see "The Pesticide Manual Thirteenth Edition" (British Crop Protection Council, Hampshire, UK, 2003), as well as "The e-Pesticide Manual, Version 3" (British Crop Protection Council, Hampshire, UK, 2003-04), the contents of each of which are incorporated herein by reference in their entirety.
The term "suspension concentrate" is referred to a suspension of solid active ingredients in a liquid intended for dilution with water before use.
By the term "aqueous" as used herein, is meant that the solvent used in the composition is mainly water. Hence, "aqueous" and "water-based" may be considered synonyms. Water-based formulations generally have the advantage that they require little or no organic solvent fraction.
The term 'stable composition' refers to a liquid formulation which is stable physically and chemically. In particular, 'chemical stability' as used herein refers to a composition containing one or more active ingredients wherein the active ingredient/s does not chemically degrade or decompose beyond acceptable limit. The term 'physical stability' as used herein represents a formulation containing one or more active ingredients wherein there is no settling of solid particles occurs during/after storage.
By the term "active ingredient" as used herein, is meant an ingredient that is chemically active and/or biologically active in origin, in particular, prothioconazole and/or its mixture with at least one additional fungicide.
As used herein, the term "locus" includes not only areas where the pest may already be developed, but also areas where pests have yet to emerge, and also to areas under cultivation. Locus includes the plant or crop and propagation material of the plant or crop. Locus also includes the area surrounding the plant or crop and the growing media of the plant or crop, such as soil and crop field.
As used herein the term "plant" or "crop" includes reference to whole plants, plant organs (e.g. leaves, stems, twigs, roots, trunks, limbs, shoots, fruits etc.), plant cells, or plant seeds. This term also encompasses plant crops such as fruits, spores, corms, bulbs, rhizomes, sprouts basal shoots, stolons, and buds and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.
As used herein the term "ha" refers to hectare.
Subject of invention:
The present invention provides agrochemically suspension concentrate which is chemically and physically stable.
The subject of the present invention is agrochemical suspension concentrate of prothioconazole, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
Nonionic surfactants have an advantage to ionic surfactants, given the fact that anionic surfactants are broadly suggested as potent irritants to human and animal skin. Cationic surfactants have similar irritating properties, but suggested to be more cytotoxic than anionic, while the irritation potential of non-ionic surfactants is ranked the lowest.
In particular, the present invention provides an agrochemical suspension concentrate comprising: a) from 1.0 to 50% per weight of prothioconazole; b) from 2% to 20% per weight of nonionic steric stabilizer; c) optionally one or more additional fungicides, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
In an embodiment, the agrochemical suspension concentrate comprises from 1.0 to 30 % per weight of prothioconazole.
In an embodiment, the agrochemical suspension concentrate comprises from 20 to 50 % per weight of prothioconazole.
In an embodiment, the agrochemical suspension concentrate comprises from 15 to 30 % per weight of prothioconazole. In another embodiment, the agrochemical suspension concentrate comprises from 1.0 to 25 % per weight of prothioconazole.
In another embodiment, the agrochemical suspension concentrate comprises from 1.0 to 20 % per weight of prothioconazole.
In an embodiment, the agrochemical suspension concentrate comprises from 1.0 to 15 % per weight of prothioconazole.
In an embodiment, the agrochemical suspension concentrate comprises from 1.0 to 10 % per weight of prothioconazole.
In an additional embodiment, the agrochemical suspension concentrate comprises b) nonionic steric stabilizer selected from polyacrylate polymers, tristyrylphenol alkoxylates and the mixtures thereof.
In an embodiment, the agrochemical suspension concentrate comprises b) from 2% to 20% per weight of nonionic steric stabilizer selected from polyacrylate polymers, tristyrylphenol alkoxylates and the mixtures thereof.
In an embodiment, the agrochemical suspension concentrate comprises b) from 2% to 15% per weight of nonionic steric stabilizer selected from polyacrylate polymers, tristyrylphenol alkoxylates and the mixtures thereof.
In an embodiment, the agrochemical suspension concentrate comprises b) from 2% to 10% per weight of nonionic steric stabilizer selected from polyacrylate polymers, tristyrylphenol alkoxylates and the mixtures thereof.
In an embodiment, the agrochemical suspension concentrate comprises b) from 2% to 8% per weight of nonionic steric stabilizer selected from polyacrylate polymers, tristyrylphenol alkoxylates and the mixtures thereof.
In an embodiment, the agrochemical suspension concentrate comprises b) from 2% to 6% per weight of nonionic steric stabilizer selected from polyacrylate polymers, tristyrylphenol alkoxylates and the mixtures thereof. Any nonionic polyacrylate polymer may be used. In particular, the nonionic acrylate polymers are selected from polyfmethyl acrylate polymers and copolymers), polyfmethyl methacrylate polymers and copolymers), polyfethyl methacrylate polymers and copolymers), (styrene/(meth)acrylic acid copolymers), (methyl methacrylate/methacrylic acid/methoxy (polyethyleneglycol) methacrylate copolymers), methacrylatepolyethylene oxide graft copolymers, graft copolymer of acrylic ester and oxyalkylene.
In certain embodiments, the nonionic polyacrylate polymer is a methyl methacrylate/methacrylic acid/monomethoxypolyethylene glycol (PEG) methacrylate graft copolymer (eg, Atlox™ 4913, Uniqema Surfactants Ltd, UK).
In an embodiment, the nonionic tristyrylphenol alkoxylates including those prepared from tristyryl phenol and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof).
In an embodiment, the nonionic tristyrylphenol alkoxylates are tristyrylphenol ethoxylates having from 10 to 54 units of ethylene oxide.
In another embodiment, the agrochemical suspension concentrate comprises b) the nonionic steric stabilizer, which is a mixture of polyacrylate polymers and tristyrylphenol alkoxylates.
In an embodiment, the agrochemical suspension concentrate comprises the nonionic steric stabilizer, which is a mixture of from 1 % to 10 % per weight of polyacrylate polymers and from 0.5 % to 10 % per weight of tristyrylphenol alkoxylates.
In further embodiment, the agrochemical suspension concentrate comprises the nonionic steric stabilizer, wherein the weight ratio of polyacrylate polymers to tristyrylphenol alkoxylates in said steric stabilizer is from 1.5 :1 to 5:1.
In another embodiment, the agrochemical suspension concentrate comprises the nonionic steric stabilizer, wherein the weight ratio of polyacrylate polymers to tristyrylphenol alkoxylates in said steric stabilizer is from 1.5:1 to 3:1. In another embodiment, the agrochemical suspension concentrate comprises the nonionic steric stabilizer, wherein the weight ratio of polyacrylate polymers to tristyrylphenol alkoxylates in said steric stabilizer is from 1.5:1 to 2:1.
In an embodiment, the weight ratio of polyacrylate polymers to prothioconazole is from 1:100 to 1:0.83.
In an embodiment, the weight ratio of polyacrylate polymers to prothioconazole is from 1:20 to 1:0.83.
In an embodiment, the weight ratio of polyacrylate polymers to prothioconazole is from 1:10 to 1:0.83.
In an embodiment, the weight ratio of polyacrylate polymers to prothioconazole is from 1:5 to 1:0.83.
In an embodiment, the weight ratio of polyacrylate polymers to prothioconazole is from 1:4.5 to 1:0.83.
In an embodiment, the weight ratio of tristyrylphenol alkoxylates to prothioconazole is from 1: 166 to 1:5.
In an embodiment, the weight ratio of tristyrylphenol alkoxylates to prothioconazole is from 1: 100 to 1:5.
In an embodiment, the weight ratio of tristyrylphenol alkoxylates to prothioconazole is from 1: 50 to 1:5.
In an embodiment, the weight ratio of tristyrylphenol alkoxylates to prothioconazole is from 1: 30 to 1:5.
In an embodiment, the weight ratio of tristyrylphenol alkoxylates to prothioconazole is from 1: 20 to 1:5.
In an embodiment, the weight ratio of tristyrylphenol alkoxylates to prothioconazole is from 1: 10 to 1:5. In an embodiment, the weight ratio of tristyrylphenol alkoxylates to prothioconazole is from 1: 8 to 1:5.
In an embodiment, the weight ratio of tristyrylphenol alkoxylates to prothioconazole is from 1: 7 to 1:5.
In an embodiment, the agrochemical suspension concentrate comprises c) one or more additional fungicide.
In an embodiment, the agrochemical suspension concentrate comprises c) one or more additional fungicide, wherein the amount of the one or more additional fungicides is of about 1% to about 50% by weight, based on the total weight of the composition.
In an embodiment, the agrochemical suspension concentrate comprises c) one or more additional fungicide, wherein the amount of the one or more additional fungicides is of about 1% to about 10% by weight, based on the total weight of the composition.
In an embodiment, the agrochemical suspension concentrate comprises c) one or more additional fungicide, wherein the amount of the one or more additional fungicides is of about 5% to about 10% by weight, based on the total weight of the composition.
In an embodiment, the agrochemical suspension concentrate comprises c) one or more additional fungicide, wherein the amount of the one or more additional fungicides is of about 10% to about 20% by weight, based on the total weight of the composition.
In an embodiment, the agrochemical suspension concentrate comprises c) one or more additional fungicide, wherein the amount of the one or more additional fungicides is of about 20% to about 30% by weight, based on the total weight of the composition.
In an embodiment, the agrochemical suspension concentrate comprises c) one or more additional fungicide, wherein the amount of the one or more additional fungicides is of about 30% to about 40% by weight, based on the total weight of the composition. In an embodiment, the agrochemical suspension concentrate comprises c) one or more additional fungicide, wherein the amount of the one or more additional fungicides is of about 40% to about 50% by weight, based on the total weight of the composition.
In an embodiment, the agrochemical suspension concentrate comprises c) one or more additional fungicide selected from the triazole fungicides including azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazol, diniconazole, diniconazole-M, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furconazole, furconazole-cis, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazol, penconazole, quinconazole, simeconazole, tetraconazole, triadimenol, triadimefon, triticonazole, uniconazole, uniconazole-P, voriconazole, difenoconazole, propiconazole, tebuconazole, mefentrifluconazole and any mixture thereof.
In an embodiment, the agrochemical suspension concentrate comprises c) one or more additional fungicide selected from the strobilurin family including azoxystrobin, kresoxim- methyl, picoxystrobin, fluoxastrobin, oryzastrobin, dimoxystrobin, pyraclostrobin, trifloxystrobin and the mixtures thereof.
In another embodiment, said additional fungicide is azoxystrobin.
In an embodiment, the agrochemical suspension concentrate comprises of about 1% to about 50% by weight of azoxystrobin, as an additional fungicide c), based on the total weight of the composition.
In an embodiment, the agrochemical suspension concentrate comprises of about 1% to about 10% by weight of azoxystrobin, as an additional fungicide c) based on the total weight of the composition.
In an embodiment, the agrochemical suspension concentrate comprises of about 5% to about 10% by weight of azoxystrobin, as an additional fungicide c), based on the total weight of the composition. In an embodiment, the agrochemical suspension concentrate comprises of about 10% to about 20% by weight of azoxystrobin, as an additional fungicide c), based on the total weight of the composition.
In an embodiment, the agrochemical suspension concentrate comprises of about 20% to about 30% by weight of azoxystrobin, as an additional fungicide c), based on the total weight of the composition.
In an embodiment, the agrochemical suspension concentrate comprises of about 30% to about 50% by weight of azoxystrobin, as an additional fungicide c), based on the total weight of the composition.
In an embodiment, the agrochemical suspension concentrate comprises of about 40% to about 50% by weight of azoxystrobin, as an additional fungicide c), based on the total weight of the composition.
In addition, the present invention provides a method for controlling and/or preventing pests comprising applying an effective amount of the agrochemical suspension concentrate comprising: a) from 1.0 to 50% per weight of prothioconazole; b) from 2% to 20% per weight of nonionic steric stabilizer; c) optionally one or more additional fungicides, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants, to a locus where the pest is to be controlled and/or prevented so as to thereby control and/or prevent the pest, wherein the pest is a phytopathogenic harmful fungi.
In an embodiment, the locus is a crop field.
The present invention further provides a method of controlling phytopathogenic harmful fungi in a field of crop comprising applying an effective amount of the agrochemical suspension concentrate comprising: a) from 1.0 to 50% per weight of prothioconazole; b) from 2% to 20% per weight of nonionic steric stabilizer; c) optionally one or more additional fungicides, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants, to a field of crop so as to thereby control the phytopathogenic harmful fungi in the field of crop.
In some embodiments, the crop is selected from the group consisting of cotton, flax, grapevines, fruit, vegetables, such as Rosaceae sp. (for example pome fruit such as apples and pears, but also stone fruit such as apricots, cherries, almonds and peaches, and berry fruits such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (for example banana trees and plantations), Rubiaceae sp. (for example coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (for example lemons, organs and grapefruit); Solanaceae sp. (for example tomatoes), Liliaceae sp., Asteraceae sp. (for example lettuce), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (for example cucumbers), Alliaceae sp. (for example leeks, onions), Papilionaceae sp. (for example peas); main crop plants such as Gramineae sp. (for example maize, turfgrass, cereals such as wheat, rye, rice, barley, oats, sorghum/millet and triticale), Asteraceae sp. (for example sunflowers), Brassicaceae sp. (for example white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, Pak Choi, kohlrabi, radishes, and rapeseed, mustard, horseradish and cress), Fabacae sp. (for example beans, peanuts), Papilionaceae sp. (for example soya beans), Solanaceae sp. (for example potatoes), Chenopodiaceae sp. (for example sugar beet, fodder beet, chard, beetroot); sugarcane, poppies, olives, coconuts, cocoa, tobacco and useful plants and ornamental plants in gardens and forests; and genetically modified varieties of each of these plants, and the seeds of these plants. In a preferred embodiment, the crop is selected from the group consisting of wheat, rye, rice, barley, oats, sorghum/millet, triticale, maize, rapeseed, beans, peanuts and sunflowers. In a more preferred embodiment, the crop is selected from the group consisting of wheat, rye, rice, barley, oats, sorghum/millet and triticale.
Non-limiting examples of pathogens of fungal diseases which may be treated in accordance with the invention include: diseases caused by powdery mildew pathogens, for example Blumeria species, for example Blumeria graminis, Podosphaera species, for example Podosphaera leucotricha, Sphaerotheca species, for example Sphaerotheca fuliginea, Uncinula species, for example Uncinula necator, for example Erysiphe species; diseases caused by rust disease pathogens, for example Gymnosporangium species, for example Gymnosporangium sabinae ; Hemileia species, for example Hemileia vastatrix; Phakopsora species, for example Phakopsora pachyrhizi or Phakopsora meibomiae Puccinia species, for example Puccinia recondita, Puccinia graminis oder Puccinia striif ormis, Uromyces species, for example Uromyces app endiculatus, diseases caused by pathogens from the group of the Oomycetes, for example Albugo species, for example Albugo Candida , Bremia species, for example Bremia laciucaer, Peronospora species, for example Peronospora pisi or P. brassicaer, Phytophthora species, for example Phytophthora inf estans, Plasmopara species, for example Plasmopara viticola, Pseudoperonospora species, for example Pseudoperonospora humuli or Pseudoperonospora cubensis, Pythium species, for example Pythium ultimunv, leaf blotch diseases and leaf wilt diseases caused, for example, by Alternaria species, for example Alternaria solanv, Cercospora species, for example Cercospora beticola, Cladiosporium species, for example Cladiosporium cucumerinunr, Cochliobolus species, for example Cochliobolus sativus (conidial form: Drechslera, syn: Helminthosporium) or Cochliobolus miyabeanus, Colletotrichum species, for example Colletotrichum lindemuthaniunv, Corynespora species, for example Corynespora cassiicola, Cycloconium species, for example Cycloconium oleaginunv, Diaporthe species, for example Diaporthe citrv, Elsinoe species, for example Elsinoe f awcettii, Gloeosporium species, for example Gloeosporium laeticolor, Glomerella species, for example Glomerella cingulata, Guignardia species, for example Guignardia bidwellv, Leptosphaeria species, for example Leptosphaeria maculans, Magnaporthe species, for example Magnaporthe grisea, Microdochium species, for example Microdochium nivaler, Mycosphaerella species, for example Mycosphaerella graminicola (also known as Septoria tritici), Mycosphaerella arachidicola or Mycosphaerella fi j iens , Phaeosphaeria species, for example Phaeosphaeria nodorunr, Pyrenophora species, for example Pyrenophora teres or Pyrenophora tritici rep enth , Ramularia species, for example Ramularia collo-cygni or Ramularia areola, Rhynchosporium species, for example Rhynchosporium secalis, Septoria species, for example Septoria apii or Septoria lycopersicv, Stagonospora species, for example Stagonospora nodorunr, Typhula species, for example Typhula incarnata, Venturia species, for example Venturia inaequal, root and stem diseases caused, for example, by Corticium species, for example Corticium graminearum, Fusarium species, for example Fusarium oxysporum\Gaeumannomyces species, for example Gaeumannomyces graminis, Plasmodiophora species, for example Plasmodiophora brassica, Rhizoctonia species, for example Rhizoctonia solani, Sarocladium species, for example Sarocladium oryzae; Sclerotium species, for example Sclerotium oryzae, Tapesia species, for example Tapesia acuf ormis, Thielaviopsis species, for example Thielaviopsis basicola, ear and panicle diseases (including com cobs) caused, for example, by Alternaria species, for example Alternaria spp.; Aspergillus species, for example Aspergillus flavus, Cladosporium species, for example Cladosporium cladosporioides, Claviceps species, for example Claviceps purpurea, Fusarium species, for example Fusarium culmorunr, Gibberella species, for example Gibberella zeae Monographella species, for example Monographella nivalis, Stagnospora species, for example Stagnospora nodorunr, diseases caused by smut fungi, for example Sphacelotheca species, for example Sphacelotheca reiliana, Tilletia species, for example Tilletia caries or Tilletia controversy, Urocystis species, for example Urocystis occulta, Ustilago species, for example Ustilago nuda, fruit rot caused, for example, by Aspergillus species, for example Aspergillus flavus, Botrytis species, for example Botrytis cinerea, Monilinia species, for example Monilinia lotxa, Penicillium species, for example Penicillium expansum or Penicillium purpurogenum, Rhizopus species, for example Rhizopus stolonifer, Sclerotinia species, for example Sclerotinia sclerotiorum, Verticilium species, for example Verticilium alboatrum, seed- and soil-bome rot and wilt diseases, and also diseases of seedlings, caused, for example, by Alternaria species, for example Alternaria brasside ola Aphanomyces species, for example Aphanomyces euteiches, Ascochyta species, for example Ascochyta lends, Aspergillus species, or example Aspergillus flavus, Cladosporium species, for example Cladosporium herbarum, Cochliobolus species, for example Cochliobolus sativus (conidial form: Drechslera, Bipolaris Syn: Helminthosp orium), Colletotrichum species, for example Colletotrichum coccodes, Fusarium species, for example Fusarium culmorum, Gibberella species, for example Gibberella zeae Macrophomina species, for example Macrophomina p haseolina, Microdochium species, for example Microdochium nivale , Monographella species, for example Monographella nivalis, Penicillium species, for example Penicillium expansum, Phoma species, for example Phoma lingam, Phomopsis species, for example Phomopsis so ae Phytophthora species, for example Phytophthora cactorum, Pyrenophora species, for example Pyrenophora graminea, Pyricularia species, for example Pyricularia oryzac, Pythium species, for example Pythium ultimum, Rhizoctonia species, for example Rhizoctonia solanv, Rhizopus species, for example Rhizopus oryzae; Sclerotium species, for example Sclerotium rolfsii, Septoria species, for example Septoria nodorum, Typhula species, for example Typhula incarnata, Verticillium species, for example Verticillium dahliae, cancers, galls and witches' broom caused, for example, by Nectria species, for example Nectria galligena, wilt diseases caused, for example, by Verticillium species, for example Verticillium longisporunr, Fusarium species, for example Fusarium oxysporurrv, deformations of leaves, flowers and fruits caused, for example, by Exobasidium species, for example Exobasidium vexans, Taphrina species, for example Taphrina deformans, degenerative diseases in woody plants, caused, for example, by Esca species, for example Phaeomoniella chlamydospora, Phaeoacremonium aleophilum or Fomitiporiamediterranean Ganoderma species, for example Ganoderma boninense, diseases of plant tubers caused, for example, by Rhizoctonia species, for example Rhizoctonia solanv, Helminthosporium species, for example Helminthosporium solanv, diseases caused by bacterial pathogens, for example Xanthomonas species, for example Xanthomonas campestris pv. oryzae, Pseudomonas species, for example Pseudomonas syringae pv. lachrymans, Erwinia species, for example Erwinia amylovora, Liberibacter species, for example Liberibacter asiaticus, Xyella species, for example Xylella f astidiosa, Ralstonia species, for example Ralstonia solanacearum, Dickeya species, for example Dickeya solanv, Clavibacter species, for example Clavibacter michiganensis, Streptomyces species, for example Streptomyces scabies, diseases of soya beans: fungal diseases on leaves, stems, pods and seeds caused, for example, by Alternaria leaf spot (Alternaria spec atrans tenuissima), Anthracnose (Colletotrichum gloeosporoides dematium var. truncatum), brown spot (Septoria glycines), cercospora leaf spot and blight (Cercospora kikuchii), choanephora leaf blight (Choanephora infundibulifera trispora (Syn.j), dactuliophora leaf spot (Dactuliophora glycines), downy mildew (Peronospora manshurica), drechslera blight (Drechslera glycini), frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot (Leptosphaerulina trifolii), phyllostica leaf spot (Phyllosticta sojaecola), pod and stem blight (Phomopsis sojae), powdery mildew (Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines), rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), mst (Phakopsora pachyrhizi, Phakopsora meibomiae), scab (Sphaceloma glycines), stemphylium leaf blight (Stemphylium botryosum), sudden death syndrome (Fusarium virguliforme), target spot (Corynespora cassiicola). Fungal diseases on roots and the stem base caused, for example, by black root rot (Calonectria crotalariae), charcoal rot (Macrophomina phaseolina), fusarium blight or wilt, root rot, and pod and collar rot (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris), neocosmospora (Neocosmospora vasinfecta), pod and stem blight (Diaporthe phaseolorum), stem canker (Diaporthe phaseolorum var. caulivora), phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophora gregata), pythiumrot (Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctonia root rot, stem decay, and damping-off (Rhizoctonia solani), sclerotinia stem decay (Sclerotinia sclerotiorum), sclerotinia southern blight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).
In some embodiments, the phytopathogenic harmful fungi is selected from Septoria species, Fusarium species, Puccinia species, Erisyphe species, Drechslera species, Ramularia species, Mycosphaerella species and Rhynchosporium species.
In some embodiments, the phytopathogenic harmful fungi is selected from Puccinia recondita, Septoria tritici, Fusarium culmorum, Pyrenophora teres and Rhynchosporium secal is. In an embodiment, the phytopathogenic harmful fungi is selected from Pyrenophora teres, Rhynchosporium secalis, Cochliobolus sativus, Puccinia hordei, Blumeria graminis f. sp. Hordei, Septoria tritici, Pyrenophora tritici-repentis, Puccinia recondata, Puccinia triticina, Septoria avenae, Puccinia coronate, Puccinia striiformis, Septoria spp., Puccinia spp, Sclerotinia sclerotiorum, Leptosphaeria maculans, Alternaria brassicae, Alternaria raphanin, Phakopsora pachyrhizi, Cercospora sojina, Microsphaera diffusa, Erysiphe pisi, E. polygon!, Cercospora kikuchii, Ascochyta spp., Mycosphaerella pinodes, Colletotrichum spp., and Aureobasidium zeae.
In an embodiment, the agrochemical suspension concentrate of invention is applied in an amount from about 0.2 L/ha to about 2 L/ha.
In an embodiment, the agrochemical suspension concentrate of invention is applied in an amount of from about 20 g/ha of prothioconazole to about 500 g/ha of prothioconazole.
In an embodiment, the agrochemical suspension concentrate of invention is applied in an amount of from about 75 g/ha of prothioconazole to about 150 g/ha of prothioconazole.
In an embodiment, the agrochemical suspension concentrate of invention comprises strobilurin as an additional fungicide c); and said agrochemical suspension concentrate is applied in an amount of from about 20 g/ha of strobilurin to about 500 g/ha of strobilurin.
In an embodiment, the agrochemical suspension concentrate of invention comprises azoxystrobin as an additional fungicide c); and said agrochemical suspension concentrate is applied in an amount of from about 20 g/ha of azoxystrobin to about 500 g/ha of azoxystrobin.
In addition, the present invention provides a method of stabilizing of the suspension concentrate comprising from 1.0 to 50 % per weight of prothioconazole by means of addition of from 2% to 20% per weight of nonionic steric stabilizer, wherein the nonionic steric stabilizer is a mixture of polyacrylate polymers and of tristyrylphenol alkoxylates, and wherein the agrochemical suspension concentrate is substantially free of ionic surfactants. In particular, prothioconazole exist in the form of solid particles.
In an embodiment, the present invention provides a method of stabilizing of the suspension concentrate comprising from 1.0 to 50 % per weight of prothioconazole by means of addition of from 2% to 20% per weight of nonionic steric stabilizer, wherein the nonionic steric stabilizer is a mixture of polyacrylate polymers and of tristyrylphenol alkoxylates, and wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
In an embodiment, the present invention provides a method of stabilizing of the suspension concentrate comprising from 1.0 to 50 % per weight of prothioconazole by means of addition of from 2% to 20% per weight of nonionic steric stabilizer, which is a mixture of from 1 % to 10 % per weight of polyacrylate polymers and from 0.5 % to 10 % per weight of tristyrylphenol alkoxylates, and wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
In an embodiment, the present invention provides a method of stabilizing of the suspension concentrate comprising from 1.0 to 50 % per weight of prothioconazole by means of addition of from 2% to 20% per weight of nonionic steric stabilizer, which is a mixture of from 1 % to 10 % per weight of polyacrylate polymers and from 0.5 % to 10 % per weight of tristyrylphenol alkoxylates, wherein the weight ratio of polyacrylate polymers to tristyrylphenol alkoxylates is from 1.5 :1 to 5:1, and wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
In an embodiment, the present invention provides a method of stabilizing of the suspension concentrate comprising from 1.0 to 50 % per weight of prothioconazole by means of addition of from 2% to 20% per weight of nonionic steric stabilizer, which is a mixture of from 1 % to 10 % per weight of polyacrylate polymers and from 0.5 % to 10 % per weight of tristyrylphenol alkoxylates, wherein the weight ratio of polyacrylate polymers to tristyrylphenol alkoxylates is from 1.5:1 to 3:1, and wherein the agrochemical suspension concentrate is substantially free of ionic surfactants. In an embodiment, the present invention provides a method of stabilizing of the suspension concentrate comprising from 1.0 to 50 % per weight of prothioconazole by means of addition of from 2% to 20% per weight of nonionic steric stabilizer, which is a mixture of from 1 % to 10 % per weight of polyacrylate polymers and from 0.5 % to 10 % per weight of tristyrylphenol alkoxylates, wherein the weight ratio of polyacrylate polymers to tristyrylphenol alkoxylates is from 1.5:1 to 2:1, and wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
All the suspension concentrates of the invention may comprise further additives such as emulsifiers, penetrants, wetting agents, spreading agents and/or retention agents. Suitable substances are all of those which can typically be used for this purpose in agrochemicals. Suitable additives are, for example, organomodified polysiloxanes, e.g. BreakThru® OE444, BreakThru® S240, Silwett® L77, Silwett® 408; tristyrylphenol ethoxylate, e.g. POE-16 POLYSTEP® TSP-16;; polyalkoxylated butyl ether, e.g. Witconol™ NS 500 LQ; Sorbitan monolaurate ethoxylated (20EO), e.g. Tween® 20 and the like.
Additional suitable additives which may be present in all the compositions of the invention are defoamers, preservatives, antioxidants, pH modifiers, dyes and inert fillers.
Suitable defoamers are all substances which can typically be used for this purpose in agrochemicals. Preference is given to silicone oils, silicone oil formulations, magnesium stearate, phosphinic acids and phosphonic acids. Examples are Silcolapse® 482 from Bluestar Silicones, Silfoam® SCI 132 from Wacker [dimethylsiloxanes and -silicones, CAS No. 63148-62-9], SAG 1538 or SAG 1572 from Momentive [dimethylsiloxanes and - silicones, CAS-Nr. 63148-62-9] or Fluowet® PL 80.
Suitable pH modifiers are all substances which can be used for achieving the desirable pH of final suspension concentrate of from 4 to 8, in particular, alkali metal hydroxides, such as NaOH or KOH, or water- miscible amines such as triethanolamine, diethanolamine and the like.
Possible preservatives are all substances which can typically be used for this purpose in agrochemicals. Suitable preservatives are, for example, formulations comprising 5-chloro- 2-methyl-4-isothiazolin-3-one [CIT; CAS No. 26172-55-4], 2-methyl-4-isothiazolin-3-one [MIT, CAS No. 2682-204] or l,2-benzisothiazol-3(2H)-one [BIT, CAS No. 2634-33-5], Examples include Preventol® D7 (Lanxess), Kathon® CG/ICP (Rohm & Haas), Acticide® SPX (Thor GmbH) and Proxel® GXL (ArchChemicals).
Suitable antioxidants are all substances which can typically be used for this purpose in agrochemicals. Preference is given to butylhydroxytoluene [3,5-di-tert-butyl-4- hydroxytoluene, CAS No. 128-37-0] and citric acid.
Possible dyes are all substances which can typically be used for this purpose in agrochemicals. Examples include titanium dioxide, carbon black, zinc oxide, blue pigments, red pigments and Permanent Red FGR.
Suitable inert fillers are all substances which can typically be used for this purpose in agrochemicals and which do not function as thickeners. Preference is given to inorganic particles such as carbonates, silicates and oxides, and also organic substances such as urea-formaldehyde condensates. Examples include kaolin, rutile, silicon dioxide ("finely divided silica"), silica gel and natural and synthetic silicates, and additionally talc.
The composition may comprise additional nonionic surfactants. Suitable nonionic surfactants are surfactants from the classes of the alkoxylates, block polymers, N alkylated fatty acid amides, amine oxides, esters or sugar-based surfactants. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters that have been alkoxylated. For the alkoxylation it is possible to use ethylene oxide and/or propylene oxide, preferably ethylene oxide. Examples of N-alkylated fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose esters and glucose esters or alkylpolyglucosides. Suitable block polymers are block polymers of the A-B or A-B-A type, comprising blocks of polyethylene oxide and polypropyleneoxide, or of the A-B-C type, comprising alkanol, polyethylene oxide, and polypropylene oxide. Preferred nonionic surfactants are surfactants from the classes of alkoxylates and block polymers, more particularly alkoxylates.
All the compositions and/or combinations of the invention can be applied in undiluted form or diluted with water. In general, they are diluted with at least one part water, preferably with 10 parts water and more preferably with at least 100 parts water, for example with 1 to 10000, preferably 10 to 5000 and more preferably with 50 to 24,000 parts water, based on one part of the formulation.
The dilution is achieved by pouring the suspension concentrates of the invention into the water. For rapid mixing of the concentrate with water, it is customary to use agitation, for example stirring. However, agitation is generally unnecessary. Even though the temperature for the dilution operation is an uncritical factor, dilutions are typically conducted at temperatures in the range from 0°C to 50°C, especially at 10 °C to 30 °C or at ambient temperature.
The water used for dilution is generally tap water. The water may, however, already contain water soluble or finely dispersed compounds which are used in crop protection, for instance nutrients, fertilizers or pesticides. It is possible to add various kinds of oils, wetting agents, adjuvants, fertilizers or micronutrients and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) to the suspension of the invention in the form of a premix or, if appropriate, not until shortly before use (tankmix). These may be added to the compositions of the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
The generally diluted compositions of the invention are applied mainly by spraying, especially spraying of the leaves. Application can be conducted by spraying techniques known to those skilled in the art, for example using water as carrier and amounts of spray liquid of about 50 to 1000 liters per hectare, for example from 100 to 200 liters per hectare. The inventive suspension concentrates have advantageous properties in respect of the treatment of plants; more particularly, they feature good use properties, high stability and high fungicidal activity.
The invention is illustrated by the following examples without limiting it thereby. EXPERIMENTAL PART:
One exemplary embodiment of the formulation of the present invention is illustrated below as Composition 1:
Composition 1:
Figure imgf000024_0001
Preparation of Inventive Composition 1:
1. Soft water (about 90% of the required quantity of soft water), prothioconazole, azoxystrobin, nonionic stabilizers, propylene glycol and anti-foam emulsion were mixed and the obtained mixture was stirred until homogenous dispersion is obtained.
2. The homogenous dispersion as previously prepared was milled until particle size range d90 < 15pm obtained.
3. Xanthan Gum solution and the rest of processing soft water were added, and the final composition was mixed until homogenous dispersion is obtained. Final pH was adjusted with NaOH.
Inventive compositions 1-3 prepared by similar procedure and having different amounts and ratios of polyacrylate polymers and tristyrylphenol alkoxylates as nonionic steric stabilizer are represented in Table 1 below.
Table 1. Inventive compositions 1, 2, 3:
Figure imgf000025_0001
Comparative Compositions 4-9 prepared by similar procedure and having different amounts and ratios of polyacrylate polymers and tristyrylphenol alkoxylates as nonionic steric stabilizer are represented in Table 2 below. Table 2. Comparative compositions 4-9.
Figure imgf000026_0001
As shown in Tables 1, 2 above, inventive compositions have good flowability after two weeks 54 °C storage and comparative compositions solidify completely under the same
5 conditions. 5

Claims

CLAIMS:
1. An agrochemical suspension concentrate comprising: a) from 1.0 to 50% per weight of prothioconazole; b) from 2% to 20% per weight of nonionic steric stabilizer c) optionally one or more additional fungicides, wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
2. An agrochemical suspension concentrate according to claim 1 wherein nonionic steric stabilizer is selected from polyacrylate polymers, tristyrylphenol alkoxylates and the mixtures thereof.
3. An agrochemical suspension concentrate according to claim 2 wherein the nonionic steric stabilizer is a mixture of polyacrylate polymers and tristyrylphenol alkoxylates.
4. An agrochemical suspension concentrate according to claim 2 wherein the nonionic steric stabilizer is a mixture of from 1 % to 10 % per weight of polyacrylate polymers and from 0.5 % to 10 % per weight of tristyrylphenol alkoxylates.
5. An agrochemical suspension concentrate according to claims 2-4, wherein the weight ratio of polyacrylate polymers to tristyrylphenol alkoxylates is from 1.5 :1 to 5:1.
6. An agrochemical suspension concentrate according to claim 2, wherein the weight ratio of polyacrylate polymers to tristyrylphenol alkoxylates is from 1.5:1 to 3:1.
7. An agrochemical suspension concentrate according to claim 2, wherein the weight ratio of polyacrylate polymers to tristyrylphenol alkoxylates is from 1.5: 1 to 2:1.
8. The composition according to any one of claims 1-7, comprising one or more additional fungicide.
9. The composition according to any one of claims 1-8, wherein the one or more additional fungicide is selected from the strobilurin family.
10. The composition according to claim 9, wherein the strobilurin is azoxystrobin.
11. The composition according to any one of claims 1- 10, wherein the amount of the one or more additional fungicides is of about 1% to about 50% by weight, based on the total weight of the composition.
12. The composition according to any one of claims 1-11, wherein the amount of the strobilurin is of about 1% to about 50% by weight, based on the total weight of the composition.
13. The composition according to any one of claims 1-12, wherein the amount of azoxystrobin is about 1% to about 50% by weight, based on the total weight of the composition.
14. A method for controlling and/or preventing pests comprising applying an effective amount of the composition according to any one of claims 1-13 to a locus where the pest is to be controlled and/or prevented so as to thereby control and/or prevent the pest.
15. The method of claim 14, wherein the pest is a phytopathogenic harmful fungi.
16. A method for controlling and/or preventing phytopathogenic harmful fungi comprising applying an effective amount of the composition according to any one of claims 1-13 to a locus where the phytopathogenic harmful fungi is to be controlled so as to thereby control the phytopathogenic harmful fungi.
17. The method according to any one of claims 14-16, wherein the locus is a crop field.
18. A method of controlling phytopathogenic harmful fungi in a field of crop comprising applying an effective amount of the composition according to any one of claims 1-13 to a field of crop so as to thereby control the phytopathogenic harmful fungi in the field of crop.
19. The method according to any one of claims 14- 18, wherein the crop is selected from the group consisting of wheat, barley, rye, triticale, oats, pearl millet, buckwheat, canola and soybean.
20. The method according to any one of claims 14-19, wherein the phytopathogenic harmful fungi is selected from Pyrenophora teres, Rhynchosporium secalis, Cochliobolus sativus, Puccinia hordei, Blumeria graminis f. sp. Hordei, Septoria tritici, Pyrenophora tritici-repentis, Puccinia recondata, Puccinia triticina, Septoria avenae, Puccinia coronate, Puccinia striiformis, Septoria spp., Puccinia spp, Sclerotinia sclerotiorum, Leptosphaeria maculans, Alternaria brassicae, Alternaria raphanin, Phakopsora pachyrhizi, Cercospora sojina, Microsphaera diffusa, Erysiphe pisi, E. polygon!, Cercospora kikuchii, Ascochyta spp., Mycosphaerella pinodes, Colletotrichum spp., and Aureobasidium zeae.
21. The method according to any one of claims 13-20, wherein the composition is applied in an amount from about 0.2 L/ha to about 2 L/ha.
22. The method according to any one of claims 13-21, wherein the composition is applied in an amount from about 20 g/ha of prothioconazole to about 500 g/ha of prothioconazole.
23. The method according to claim 22, wherein the composition is applied in an amount from about 75 g/ha of prothioconazole to about 150 g/ha of prothioconazole.
24. The method according to any one of claims 13-23, wherein the composition is applied in an amount from about 20 g/ha of strobilurin to about 500 g/ha of strobilurin.
25. The method according to claim 24, wherein the strobilurin is azoxystrobin.
26. Use of the composition according to any one of claims 1-13 for controlling and/or preventing pests.
27. Use of the composition according to any one of claims 1-13 for controlling or preventing phytopathogenic harmful fungi.
28. A method of stabilizing the suspension concentrate comprising prothioconazole by means of addition of from 2% to 20% per weight of nonionic steric stabilizer, wherein the nonionic steric stabilizer is a mixture of polyacrylate polymers and of tristyrylphenol alkoxylates, and wherein the agrochemical suspension concentrate is substantially free of ionic surfactants.
29. A method according to claim 28, wherein the nonionic steric stabilizer is a mixture of from 1 % to 10 % per weight of polyacrylate polymers and from 0.5 % to 10 % per weight of tristyrylphenol alkoxylates.
30. A method according to claims 28-29, wherein the weight ratio of polyacrylate polymers to tristyrylphenol alkoxylates is from 1.5 :1 to 5:1.
31. A method according to claims 28-29, wherein the weight ratio of polyacrylate polymers to tristyrylphenol alkoxylates is from 1.5 :1 to 3:1.
32. A method according to claims 28-29, wherein the weight ratio of polyacrylate polymers to tristyrylphenol alkoxylates is from 1.5:1 to 2:1.
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