A composition comprising flonicamid and spirotetramat

Abstract

The invention relates to the field of pesticides, and in particular to a composition comprising a combination of flonicamid and spirotetramat and uses thereof, lire invention further relates to a composition comprising: at least one tetronic and / or tetramic acid insecticide; at least one insecticide selected from flonicamid; at least one-star shaped polymer; a non-aqueous continuous phase; and optionally one or more additives.

Description

[0001] A COMPOSITION COMPRISING FLONICAMID AND SPIROTETRAMAT

[0002] FIELD OF THE INVENTION

[0003] The invention relates to the field of pesticides, and in particular to a composition comprising a combination of flonicamid and spiroietramat and uses thereof.

[0004] BACKGROUND OF THE INVENTION

[0005] Flonicamid is a low toxicity picolinamide class insect growth regulator, IGR insecticides. The chemical name of flonicamid is N-cy anogen methyl-(trifluoromethyl) vitamin PP, and its chemical structural formula is

[0006] Spirotetramat is active against piercing-sucking insects, such as aphids, mites, and white flies, by acting as an ACC inhibitor, interrupting lipid biosynthesis in the insects. It is a systemic insecticide that penetrates plant leaves when sprayed on. It is ambimobile, being transported both upwards and downwards through vascular bundles. In plants, it is hydrolyzed to the enol form by cleavage of the central ethoxycarbonyl group. This enol is more stable due to double bond being in a ring and the conjugation with the amide group and the benzene ring.

[0007] Its chemical structural formula is

[0008]

[0009] An oil-based dispersant (OD) is a high-efficiency and environment-friendly green formulation which is proposed by the Food and Agriculture Organization (FAO) of the United nations in recent years, and is a liquid preparation which takes environment-friendly oil as a medium and stably suspends effective components in the oil. However, it was found that when formulating OD composition of spirotetramat and flonicamid the content of spirotetramat was reduced by more than 5 and evenlO-25% precents and further particle growth and crystallization tend to appear.

[0010] Thus, there is a need for developing an OD formulation that contains a combination of spirotetramat and flonicamid, wherein the amount of both active material remain stable during storage.

[0011] SUMMARY OF THE INVENTION

[0012] The invention relates to a composition comprising flonicamid, tetronic and / or tetramic acid insecticide and a one-star shaped polymer in a non-aqueous continuous phase. The application further relates to a method for controlling animal pests by applying an effective amount of the composition according to the invention.

[0013] DETAILED EMBODIMENTS OF THE INVENTION

[0014] In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the invention. However, it will be understood by those skilled in the art that the present invention may be practiced without these specific details. In other instances, well- known methods, procedures, and components have not been described in detail so as not to obscure the present invention. Definitions

[0015] 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.

[0016] 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.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] As used herein, the term “pest” includes, but is not limited to, unwanted phytopathogenic harmful fungi, unwanted insect, unwanted nematode, and weed.

[0021] 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. 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. The ’’plant” or “crop” can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or cannot be protected by plant breeders' rights.

[0022] As used herein the term “ha” refers to hectare.

[0023] As used herein, the term "adjuvant" is broadly defined as any substance that itself is not a pesticide, but which enhances or is intended to enhance the effectiveness of the pesticide with which it is used.

[0024] As used herein the term “dispersion of solid particles” includes a system in which distributed solid particles of an active ingredient are dispersed in a liquid continuous phase. The continuous phase may be part of the formulated product or derived by the addition of external tank mix aids.

[0025] As used herein, the phrase "tank mix" refers to organic solvents, water and / or adjuvants that are added separately before the use and must be mixed in the sprayer tank.

[0026] As used herein, the term "agriculturally acceptable carrier" means carriers which are known and accepted in the art for the formation of compositions / formulations for agricultural or horticultural use.

[0027] As used herein the term “soluble” refers to the ability of a liquid and / or solid adjuvant to mix with the emulsification system thus forming a single-phase solution.

[0028] Spirotetramat and flonicamid are chemically incompatible, flonicamid induces the degradation of spirotetramat especially in contact with water. The inventors developed a formulation which minimizes the degradation of spirotetramat to less than 5% after storage at 54 Celsius degree for 2 weeks (54C2W). In some embodiments, the oil used is mineral oil which has low solubility of both spirotetramat and flonicamid. In some embodiments, a pH regulator, such as without limitation, citric acid, is added to the formulation. The pH of the composition of the invention is 7 or less, 6, 5, 4, 3 or 2 or less. In some embodiments, the pH is about 4. In some embodiments, the moisture of the formulation is 1% or less.

[0029] In some embodiments of the invention, there is provided a composition comprising: a) at least one tetronic and / or tetramic acid insecticide; b) flonicamid; c) at least one-star shaped polymer; d) a non-aqueous continuous phase; and e) optionally one or more additives.

[0030] In some embodiments, the tetramic acid insecticide is selected from the group consisting of spirotetramat, spidoxamat, spiropidion, and any combination thereof.

[0031] In some embodiments, the tetronic acid insecticide is selected from the group consisting of spirodiclofen, spiromesifen and any combination thereof.In some embodiments, the composition comprises spirotetramat and flonicamid.

[0032] In some embodiments, as used herein, the spirotetramat is cis-spirotetramat or in the form of its cis / trans isomeric mixture.

[0033] In some embodiments, the composition is in the form of an oil dispersion.

[0034] In some embodiments, the ratio between spirotetramat and flonicamid in the composition is between 10:1-1:10. In some embodiments, the ratio between spirotetramat and flonicamid in the composition is between 7: 1-1:7. In some embodiments, the ratio between spirotetramat and flonicamid in the composition is between 5: 1-1:5. In some embodiments, the ratio between spirotetramat and flonicamid in the composition is between 3: 1-1:3. In some embodiments, the ratio between spirotetramat and flonicamid in the composition is between 2: 1-1:2. In some embodiments, the ratio between spirotetramat and flonicamid is about 1:1. In some embodiments, the amount of each spirotetramat and flonicamid in the composition is about 20% by weight, based on the total weight of the composition. In some embodiments, the amount of each spirotetramat and flonicamid in the composition is about 15% by weight, based on the total weight of the composition. In some embodiments, the amount of each spirotetramat and flonicamid in the composition is about 10% by weight, based on the total weight of the composition. In some embodiments, the amount of each spirotetramat and flonicamid in the composition is about 5% by weight, based on the total weight of the composition. In some embodiments, the star shaped polymer is a non-ionic polymer. In some embodiments, the star shaped polymer is a sorbitol based ethoxylate, which may, in some embodiments, further reacted with polymerized fatty acid. In some embodiments, the star shaped polymer has HLB of between 4-8 optionally, about 6. The term “HLB” refers to the hydrophilic-lipophilic balance (HLB) which is a measure of its degree of hydrophilicity or lipophilicity, determined by calculating percentages of molecular weights for the hydrophilic and lipophilic portions of the molecule, as described by Griffin’s method.

[0035] According to some embodiments, the star shaped polymer is Atlox™ 4916 having the following structure:

[0036] In some embodiments, Atlox 4916 has superior anchorage at the oil / water / particle interface providing unrivalled stability even in the most challenging formulation conditions. For example, enhancing emulsion stability through increased steric hindrance of irreversible flocculation. The star consists of a sorbitol base reacted with ethylene oxide (EO). This product is then further reacted with a polymerised fatty acid resulting in between 2-6 polymerised fatty acid chains randomly distributed across the star shape.

[0037] According to some embodiments, the composition further comprises a nonionic block copolymer. The nonionic block copolymer is in some embodiments, ABA polyhydroxyester-PEG- polyhydroxyester, which may be in some embodiments, a polyhydroxystearic acid / polyethylene oxide / polyhydroxystearic acid. In some embodiments, the nonionic block copolymer is selected from Hypermer™ B246, Zephrym™, Atlox 4912, Atlox 4914, PD 2206 or any combination thereof.

[0038] In some embodiments, the total amount of the dispersant / s in the composition is between 0.5-10% by weight of the composition. In some embodiments, the total amount of the dispersant / s in the composition is between 1-8% by weight of the composition. In some embodiments, the total amount of the dispersant / s in the composition is between 2-6% by weight of the composition. In some embodiments, the total amount of the dispersant / s in the composition is between about 2, 3, 4, 5, or 6% by weight of the composition.

[0039] In some embodiments, the amount of tetronic and / or tetramic acid insecticide and floniciamid in is between 1 -50% by weight based on the total weight of the composition, the amount of the star shaped polymer is between 0.1%-20% by weight and the amount of the non aqueous continuous phase in the composition is about 30% to about 70% by weight, based on the total weight of the composition. The composition further comprising one or more additives are selected from the group consisting of emulsifiers, adjuvants, dispersants, stabilizers, anti-foam agents, rheology modifiers, surfactants, pH regulators, thickeners, spreading agents, anti-freeze agents and any combination thereof.

[0040] In some embodiments, the emulsifier is selected from the group consisting of one or more alcohol alkoxylates, calcium alkyl benzene sulfonates and any combination thereof. In some embodiments, the alcohol alkoxylate is Cl 6-C 18 polyethylene oxide, C 16-C 18 polypropylene oxide, C 16-C 18 polyethylene oxide / polypropylene oxide, Cl 2-C 15 polyethylene oxide / polypropylene oxide, C12-C15 polyethylene oxide, C12-C15 polypropylene oxide or any combination thereof. In some embodiments, the calcium alkyl benzene sulfonate is calcium dodecylbenzene sulfonate (CaDDBS) or sodium dioctyl sulfosuccinate.

[0041] In some embodiments, the composition further comprises a surfactant. In some embodiments, the amount of the surfactant is between about 5% to about 25% by weight, based on the total weight of the composition.

[0042] According to some embodiments, the non-aqueous continuous phase is paraffin oil, vegetable oil, ester of vegetable oil or any combination thereof. In some embodiments, the amount of the non aqueous continuous phase in the composition is about 30% to about 70% by weight, based on the total weight of the composition. In some embodiments, the amount of the non aqueous continuous phase in the composition is about 20% to about 80% by weight, based on the total weight of the composition. In some embodiments, the amount of the non aqueous continuous phase in the composition is about 40% to about 60% by weight, based on the total weight of the composition. In some embodiments, the amount of the non aqueous continuous phase in the composition is about 20% to about 80% by weight, based on the total weight of the composition. In some embodiments, the amount of the non aqueous continuous phase in the composition is about 30%, 40%, 50%, 60 or about 70% by weight, based on the total weight of the composition.

[0043] In some embodiments, the thickener is silicon dioxide; silane dichlorodimethyl or any other product that reacts with silica.

[0044] In some embodiments, the total amount of thickener / s is about 0.5% to about 5% by weight, based on the total weight of the composition. In some embodiments, the total amount of thickener / s is about 0.1% to about 10% by weight, based on the total weight of the composition. In some embodiments, the total amount of thickener / s is less than about 1%, 2%, 3%, 4%, 5%, 6% or less than 8% by weight, based on the total weight of the composition.

[0045] In some embodiments, the rheology modifier is organo bentonite.

[0046] In some embodiments, the amount of the rheology modifier in the composition is about 0.5% to about 5% by weight, based on the total weight of the composition. In some embodiments, the amount of the rheology modifier in the composition is less than 5%, 4%, 3%, 2% or 1%. In some embodiments, the amount is about 1%. In some embodiments, the amount is about 2%.

[0047] In some embodiment, the pH modifier is citric acid or lactic acid. In some embodiments, the amount of the pH modifier in the composition is about 0.1% to about 1.0% by weight, based on the total weight of the composition. In some embodiments, the amount of the pH modifier in the composition is about 0.1% to about 5.0% by weight, based on the total weight of the composition. In some embodiments, the amount of the pH modifier in the composition is about 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4 or 4.5% by weight, based on the total weight of the composition.

[0048] In some embodiments, the composition comprises CaDDBS, wherein CaDDBS is dissolved in a solvent oil or hydrocarbon. In some embodiments, the CaDDBS is dissolved in naphthalene or on isobutanol. In some embodiments, the amount of the emulsifier comprising CaDDBS dissolved in the solvent oil or aromatic hydrocarbon in the composition is about 0.1% to about 10% by weight, based on the total weight of the composition. In some embodiments, the amount of the emulsifier comprising CaDDBS dissolved in the solvent oil or aromatic hydrocarbon in the composition is about 1% to about 8% by weight, based on the total weight of the composition. In some embodiments, the amount of the emulsifier comprising CaDDBS dissolved in the solvent oil or aromatic hydrocarbon in the composition is about 2% to about 6% by weight, based on the total weight of the composition. In some embodiments, the amount of the emulsifier comprising CaDDBS dissolved in the solvent oil or aromatic hydrocarbon in the composition is about 3% to about 4% by weight, based on the total weight of the composition. In some embodiments, the amount of the emulsifier comprising CaDDBS dissolved in the solvent oil or aromatic hydrocarbon in the composition is about 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 or 10% by weight, based on the total weight of the composition.

[0049] In some embodiments, the total amount of the emulsifier / s in the composition is between 10-40% by weight of the composition.

[0050] In some embodiments, the total amount of the emulsifier / s in the composition is between 15-35% by weight of the composition.

[0051] In some embodiments, the total amount of the emulsifier / s in the composition is between 15-25% by weight of the composition.

[0052] In some embodiments, the total amount of the emulsifier / s in the composition is between 10-25% by weight of the composition.

[0053] In some embodiments, the total amount of the emulsifier / s in the composition is between 15-20% by weight of the composition.

[0054] In some embodiments, the total amount of the emulsifier / s in the composition is about 15, 16, 17, 18, 19, or 20% by weight of the composition.

[0055] In some embodiments, the composition further comprises a stabilizer. In some embodiments, the stabilizer is butylated hydroxy toluene or butyl hydroxyanisole (BHA).

[0056] In some embodiments, the amount of the stabilizer in the composition is about 0.1% to about 8% by weight, based on the total weight of the composition. In some embodiments, the amount of the stabilizer in the composition is about 0.5% to about 6% by weight, based on the total weight of the composition. In some embodiments, the amount of the stabilizer in the composition is about 1% to about 5% by weight, based on the total weight of the composition. In some embodiments, the amount of the stabilizer in the composition is about 2% to about 4% by weight, based on the total weight of the composition.

[0057] In some embodiments, the pH of the composition is 7 or less than 7, 6, 5, 4, 3 or 2.

[0058] In some embodiments, the composition had a moisture of 1% or less than 1%.

[0059] In some embodiments, there is provided a stable composition comprising flonicamide and spirotetramat, wherein the composition comprises Atlox 4916 and CaDDBS dissolved in a solvent oil or aromatic hydrocarbon or a combination thereof. In some embodiments, the aromatic hydrocarbon is isobutanol or solvesso. In some embodiments, the formulation further comprises one or more of silicon dioxide; silane, di chlorodimethyl, reaction products with silica; polyethylene glycol; C12-15-alkyl ethers; organo bentonite; butylated hydroxy toluene; 3- hydroxy-3-carboxy-l,5-pentanedioic acid; alcohols, C16-18, ethoxylated propoxylated; nonionic block copolymer and white oil (liquid paraffin).

[0060] In some embodiments, the composition is as described in Table 1 below:

[0061] Table 1 In some embodiments, the composition is as set forth below in Table 2.

[0062] Table 2

[0063] In some embodiments, the composition of the invention is prepared as follows:

[0064] Oil is charged into the reactor and mixed; emulsifiers and dispersant are added while mixing until the suspension is homogeneous; spirotetramat, flonicamid tech, thickener and stabilizer are added and the composition is mixed until the suspension is homogeneous; and the suspension is milled; and gradually, another thickener, reology modifier and citric acid are added and the suspension is continued to mill.

[0065] In some embodiments, the composition of as described in Tables 1 and 2 is prepared as follows: Oil is charged into the reactor and mixed;

[0066] Emulsifiers and dispersant, AR 500, ATLOX 6500-LQ-(TH), EMULSOGEN MTP / 070, ATLOX 4916-LQ-(AP), ZEPHRYM PD 2206-LQ-(AP) are added while mixing until the suspension is homogeneous;

[0067] Spirotetramat, Flonicamid tech, AEROSIL® R974 and BHT are added and the composition is mixed until the suspension is homogeneous; and

[0068] The suspension is milled; and

[0069] Gradually, AEROSIL® 380, Bengel 958 and citric acid are added and the suspension is continued to mill.

[0070] The compositions of the invention can be used to combat and control infestations of animal pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Coleoptera, Hymenoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests. Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as pests. The animal pests which may be combated and controlled by the use of the invention compounds include those animal pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, forestry and the storage of products of vegetable origin (such as fruit, grain and timber). Non limiting examples of pest species which may be controlled by the compositions of the invention include Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs Leptocorisa spp. (stinkbugs), Frankliniella occidentalis (thrip), Thrips spp. (thrips), Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis (boll weevil), Aonidiella spp. (scale insects), Pseudococcus SPP. (mealybugs) Trialeurodes spp. (white flies), Bemisia tabaci (white fly), Ostrinia nubilalis (European corn borer), Spodoptera littoralis (cotton leafworm), Heliothis virescens (tobacco budworm), Helicoverpa armigera (cotton bollworm), Helicoverpa zea (cotton bollworm), Sylepta derogata (cotton leaf roller), Pieris brassicae (white butterfly), Plutella xylostella (diamond back moth), Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), Locusta migratoria (locust), Chortiocetes terminifera (locust), Diabrotica spp. (rootworms), Panonychus ulmi (European red mite), Panonychus citri (citrus red mite), Tetranychus urticae (two-spotted spider mite), Tetranychus cinnabarinus (carmine spider mite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemus latus (broad mite), Brevipalpus spp. (flat mites), Liriomyza spp. (leafminer), Meloidogyne spp. (root knot nematodes), Globodera spp. and Heterodera spp. (cyst nematodes), Pratylenchus spp. (lesion nematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulus spp. (citrus nematodes), Haemonchus contortus (barber pole worm), Caenorhabditis e / egans_( vinegar eelworm), Trichostrongylus spp. (gastro intestinal nematodes) and Deroceras reticulatum (slug). From the order Acarina, for example, Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp., Boophi- lus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Derma- nyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Oly- gonychus pratensis, Omithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.; From the order Coleoptera, for example, Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Lepti- notarsa decemLineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp., Otiorhyn- chus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.; From the order Diptera, for example, Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; From the order Heteroptera, for example ,Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Lep- tocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotino- phara spp. and Triatoma spp.; From the order Homoptera, for example Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspi- diotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Parlatoria spp., Pemphigus spp., Pianococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri; From the order Hymenoptera, for example, Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplo- campa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.; From the order Lepidoptera, for example, Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, ChNo spp., Choristoneura spp., Clysia ambi- guella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedy a nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiela, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.; from the order Thysanoptera, for example, Frankliniella spp., Hercinothrips spp., Scirtothrips aurantii, Taeniothrips spp., Thrips palmi and Thrips tabaci; and from the order Thysanura, for example, Lepisma saccharina.

[0071] In some embodiments, the composition is applied in an amount from about 1.8 L / ha to about 28.8 L / ha.

[0072] In some embodiments, the composition is applied in an amount from about 18 g / ha of spirotetramat to about 288 g / ha of spirotetramat. In some embodiments, the composition is applied in an amount from about 18 g / ha of flonicamid to about 288 g / ha of flonicamid. In some embodiments, there is provided a method for controlling animal pests comprising applying an effective amount of the composition of the invention to a locus where the animal pest is to be controlled and / or prevented so as to thereby control and / or prevent the animal pest. In some embodiments, the locus is a crop field.

[0073] In some embodiments, the crop field is selected from pomaceous fruit, stone fruit, soft fruit, apples, pears, avocado, plums, peaches, almonds, cherries, berries, strawberries, raspberries, blackberries, citrus fruit, oranges, lemons, grapefruit, tangerines, cucurbits, pumpkins, cucumbers, melons, lettuce, cabbages, carrots, tomatoes, potatoes, peppers, chilli, okra, eggplants; beans, peas, soya, oilseed rape, olives, sunflowers, ground nuts, cotton, nuts, coffee, grapevines, ornamentals, lauraceae.

[0074] No limiting examples of suitable crops include cereals, such as wheat, barley, rye, oats, rice, maize, sorghum; beet, such as sugar, fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, avocado, plums, peaches, almonds, cherries, berries, for example strawberries, raspberries, blackberries; cinnamonium, camphor citrus fruit, such as oranges, lemons, grapefruit, tangerines; cucurbits, such as pumpkins, cucumbers, melons, vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or peppers, chilli, okra, eggplants; leguminous crops, such as beans, lentils, peas, soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa, ground nuts; fibre plants, such as cotton, flax, hemp, jute; and also tobacco, nuts, coffee, sugarcane, tea, grapevines, hops, the plantain family, latex plants ornamentals and lauraceae.

[0075] In some embodiments, the animal pest is selected from the order of Lepidoptera, Diptera, Hemiptera, Thysanoptera, Coleoptera, Hymenoptera Heteroptera, Homoptera, Thysanoptera, acarine, nematode and mollusc.

[0076] In some embodiments, the invention provides use of the composition of the invention for controlling and / or preventing animal pests, wherein the animal pest is selected from the order of Lepidoptera, Diptera, Hemiptera, Thysanoptera, Coleoptera, Hymenoptera Heteroptera, Homoptera, Thysanoptera, acarine, nematode and mollusc.

[0077] In some embodiments, all the compositions and / or combinations of the invention may comprise further one or more active fungicidal, insecticidal, bactericidal or herbicidal ingredients. EXAMPLES

[0078] The present invention will be further understood by reference to the following non-limiting examples. Specifically, the inventors show that spirotetramat and flonicamid are chemically incompatible. Flonicamid induces the degradation of spirotetramat in general and especially in contact with water. The examples show that the formulation as suggested in Tables 1 and 2 minimizes the degradation of spirotetramat to less than 5% after storage at 54 Celsius degrees for two weeks. “HT” as used in the Examples was 54°C. RT is room temprature

[0079] . The oil which was used was mineral oil which has low solubility for both flonicamid and spirotetramat. A pH regulator was added to the formulation as well. Moreover, ATLOX 4916 is required in order to prevent particle aggregations and phase separation. The inventors further identified that CaDDBS should be dissolved in isobutanol or solvent oil (low naphthalene).

[0080] Example 1

[0081] Solubility of Spirotetramat and Flonicamid in different solvents

[0082] Aim of the experiment:

[0083] To assess the solubility of spirotetramat and flonicamid in different solvents

[0084] Method:

[0085] 5g of each A.I. (active ingredients i.e. spirotetramat or flonicamid) were mixed with 20g solvent (methyel oleate, mineral oil, soy methyl ester or other oils as shown in Table 3 below) for 2 hours and separated to two samples: one was restored at room temperature, the other at 54°C for 12 hours. Samples were filtered through 0.45 |jm filter and A.I. content was analyzed by HPLC to obtain the solubility of A.I. in each specific solvent.

[0086] Results:

[0087] The results are summarized in Table 3:

[0088] Table 3

[0089] Conclusion:

[0090] Mineral oil P0802 provided better results than the other tested solvents with both spirotetramat (less than 0.05%) and flonicamid (not detected). Vegatable oil, methyl oleate, soy methyl ester were also good compared with Solvesso 150 and Solvesso 200. It is noted that if the solubility of the two A.I. in the solvent is too high, it will lead to particle aggregations and sedimentation.

[0091] Example 2

[0092] The formulation below was tested for its stability in room temperature (RT) and in 54 Celsius degrees for 2 weeks (54C2W).

[0093] Table 4

[0094] Results are summarized in Table 5 below.

[0095] Table 5

[0096] Conclusion

[0097] As can be seen the formulation showed no phase separation at room temperature (RT) after two weeks and only 2% phase separation at 54°C (HT) for two weeks. Example 3

[0098] Aim of the experiment:

[0099] The below formulations (Table 6) were prepared in order to assess the effect of pH regulators on the degradation of spirotetramat.

[0100] Results:

[0101] Results are summarized in Table 6.

[0102] Table 6 Results:

[0103] The results are provided in Table 7.

[0104] Table 7:

[0105] Conclusion:

[0106] The degradation rates of spiraotetramat are provided in the forth column. As can be seen, degradation rate was higher in HT conditions (i.e. more than 54°C) and in the presence of acetic acid as opposed to citric acid which is within the acceptable range, i.e. less than 5%.

[0107] Example 4 pH was adjusted was adjusted to alkaline pH with triethylamine.

[0108] Table 8 Results:

[0109] As can be seen below, in Table 9, the degradation of spirotetramat was higher when the pH of the formulation was alkaline (see in parentheses).

[0110] Table 9

[0111] Example 5

[0112] Aim of the experiment:

[0113] To assess whether the effect of an emulsifier containing CaDDBS dissolved in isobutanol or isooctanol has an effect on the appearance and stability of the formulation comprising spirotetramat and flonicamid.

[0114] Formulations (see Table 10) comprising spirotetramat and flonicamid both in an amount of 100 g / L were prepared and 150 ml samples were taken for an assessment. The differences between the formulations were as follows:

[0115] Citric acid was added as pH modifier to adjust to pH of about 4.6 in samples nos. 2023101102 and 20231012.

[0116] CaDDBS was dissolved in isobutanol in samples nos. 2023101101 and 2023101102 and in isooctanol in samples nos. 023101201 and 2023101202.

[0117] Table 10

[0118] Density=0.963 g / cm3

[0119] Results:

[0120] Results are summarized in Tables 1 la and 1 lb below.

[0121] Table 11 a

[0122] Table 11b

[0123] Conclusions:

[0124] The appearance of all samples was flowable under 54 Celsius for two weeks (54C2W), and the active ingredients were stable. The particle size of batch 20231011 remained the same. The formulation of Table 2 after 54C2W was without aggregates when viewed under microscope. The 2023101101 sample after 542W was almost without aggregates, but the 2023101202 sample, i.e. in which the isooctanol was used for dissolving CaDDBS and the pH was adjusted by citric acid after 54C2W was significantly aggregated.

[0125] Example 6

[0126] Aim of the experiment:

[0127] The aim of the experiment was to assess the effect of removing ATLOX 4916 from the formulation and / or replacing it with another dispersant. a. The following formulation without ATLOX 4916 (Table 12) was prepared: Table 12

[0128] Density=0.963 g / cm3

[0129] Results:

[0130] Results are summarized in Table 13.

[0131] Table 13 Conclusions:

[0132] The active ingredients were stable after 54C2W.The appearance of 20231013 sample under room temperature for two weeks (RT2W) showed about 12% phase separation, whereas the appearance of identical formulation with Atlox 4916 (see the results of example 2) at RT did not show any phase separation Although both samples were flowable after 54C2W, the formulation with Atlox 4916 (the formulation of Table 4, example 2) showed separated particles under microscope. In contrast, the 20231013 sample (without Atlox 4916) showed many aggregates after 54C2W when assessed under microscope. b. The following formulations were prepared in which ATLOX 4916 was substituted by ALTOX LP- 1 (poly hydroxystearic acid, sample 2023101701) or WLNO D600 (polyether, sample 2023101702).

[0133] Table 14

[0134] Results

[0135] Results are shown in Table 15.

[0136] Table 15

[0137] Conclusion:

[0138] The active ingredients in the two formulations were stable after 54C2W.

[0139] In sample 2023101701, the appearance under RT2W showed about 12% phase separation and after 54C2W significant crystal growth was shown.

[0140] In sample 2023101702, many aggregates were found under RT2W and the sample was aggregated severely under 54C2W. c. The following formulations were prepared in which ATLOX 4916 was substituted by YUS-EP60P (Calcium sulfosuccinate, sample 2023101901) or ZEPHRYM PD 7000 (Polyoxyalkylene amine derivative, sample 2023101902).

[0141] Table 16

[0142] Results:

[0143] Results are shown in Table 17 below.

[0144] Table 17: Conclusions:

[0145] The active ingredients in the two samples were stable under 54C2W.

[0146] In sample 2023101901 the appearance under 54C2W showed about 8% phase separation and the sample was aggregated severely in both RT2W or 54C2W under microscope.

[0147] In sample 2023101902 both in RT2W or 54C2W the samples were aggregated severely under microscope.

[0148] Table 18 below summarizes the conclusions from examples 5 and 6:

[0149] Table 18

[0150] While certain features of the invention have been illustrated and described herein, many modifications, substitutions, changes, and equivalents will now occur to those of ordinary skill in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the invention.

Claims

What is claimed is:

1. A composition comprising: a. at least one tetronic and / or tetramic acid insecticide; b. flonicamid; c. at least one-star shaped polymer; d. a non-aqueous continuous phase; and e. optionally one or more additives.

2. The composition according to claim 1 , wherein the tetramic acid insecticide is selected from the group consisting of spirotetramat, spidoxamat, spiropidion, and any combination thereof.

3. The composition according to claim 1 or 2, wherein the tetronic acid insecticide is selected from the group consisting of spirodiclofen, spiromesifen and any combination thereof.

4. The composition according to claim 3, wherein the star shaped polymer is a non-ionic polymer.

5. The composition according to any one of claims 1-4, wherein the star shaped polymer is a sorbitol based ethoxylate.

6. The composition according to claim 5, wherein the sorbitol based ethoxylate is further reacted with polymerized fatty acid.

7. The composition according to any one of claims 1-6, wherein the star shaped polymer has HLB of between 4-8.

8. The composition according to claim 7, wherein the star shaped polymer has HLB of about 6.

9. The composition according to any one of claims 1-8, wherein the star shaped polymer is Atlox™ 4916.

10. The composition according to any one of claims 1-9, further comprises a nonionic block copolymer.

11. The composition according to claim 10, wherein the nonionic block copolymer is ABA polyhydroxyester- PEG-polyhydroxyester.

12. The composition according to claim 11, wherein the ABA polyhydroxyester-PEG- polyhydroxyester is a polyhydroxystearic acid / polyethylene oxide / polyhydroxystearic acid.

13. The composition according to any one of claims 10-12, wherein the nonionic block copolymer is selected from Hypermer™ B246, Zephrym™, Atlox 4912, Atlox 4914, PD 2206 or any combination thereof.

14. The composition according to any one of claims 1-13, comprising spirotetramat, and flonicamid.

15. The composition according to any one of claims 1-14, wherein a) the amount of the tetronic and / or tetramic acid insecticide in the composition is about 1% to about 25% by weight, based on the total weight of the composition; b) the amount of the additional insecticide in the composition is about 1% to about 25% by weight, based on the total weight of the composition; c) the amount of the star shaped polymer in the composition is about 0.1% to about 10% by weight, based on the total weight of the composition; d) the amount of the non aqueous continuous phase in the composition is about 30% to about 70% by weight, based on the total weight of the composition.

16. The composition according to any one of claims 1-15, wherein the one or more additives are selected from the group consisting of emulsifiers, adjuvants, dispersants, stabilizers, anti-foam agents, rheology modifiers, surfactants, pH regulators, thickeners, spreading agents, anti-freeze agents and any combination thereof.

17. The composition according to any one of claims 1-16, wherein the emulsifier is selected from the group consisting of one or more alcohol alkoxylates, calcium alkyl benzene sulfonates and any combination thereof.

18. The composition according to claim 17, wherein the alcohol alkoxylate is C16-C18 polyethylene oxide, Cl 6-C 18 polypropylene oxide, Cl 6-C 18 polyethylene oxide / polypropylene oxide, C12-C15 polyethylene oxide / polypropylene oxide, C12-C15 polyethylene oxide, C12-C15 polypropylene oxide or any combination thereof.

19. The composition according to claim 17, wherein the calcium alkyl benzene sulfonate is calcium dodecylbenzene sulfonate (CaDDBS) or sodium dioctyl sulfosuccinate.

20. The composition according to any one of claims 17-19, wherein the amount of the emulsifier in the composition is about 5% to about 25% by weight, based on the total weight of the composition.

21. The composition according to any one of claims 1-20, wherein the non-aqueous continuous phase is paraffin oil, vegetable oil, ester of vegetable oil or any combination thereof.

22. The composition according to claim 21 , wherein the amount of the non aqueous continuous phase in the composition is about 30% to about 70% by weight, based on the total weight of the composition.

23. The composition according to any one of claims 1-22, wherein the composition is in the form of an oil dispersion.

24. The composition of any one of claims 1-23, the thickener is silicon dioxide, silane, dichlorodimethyl or any other product that reacts with silica.

25. The composition according to claim 24, wherein the amount of the thickener in the composition is about 0.5% to about 5% by weight, based on the total weight of the composition.

26. The composition of any one of claims 1-25, wherein the rheology modifier is organo bentonite.

27. The composition according to claim 26, wherein the amount of the rheology modifier in the composition is about 0.5% to about 5% by weight, based on the total weight of the composition.

28. The composition according to any one of claims 1-27, wherein the pH modifier is citric acid or lactic acid.

29. The composition according to any one of claims 28, wherein the amount of the pH modifier in the composition is about 0.1 % to about 1.0% by weight, based on the total weight of the composition.

30. The composition according to claim 14, wherein the ratio between spirotetramat and flonicamid is between 10: 1-1:10.

31. The composition according to claim 30, wherein the ratio between spirotetramat and flonicamid is about 1: 1.

32. The composition according to claim 31 wherein the amount of each spirotetramat and flonicamid in the composition is about 10% by weight, based on the total weight of the composition.

33. The composition according to claim 19, wherein CaDDBS is dissolved in a solvent oil.

34. The composition according to claim 19, wherein CaDDBS is dissolved in aromatic hydrocarbon.

35. The composition of any one of claims 33 or 34, wherein the amount of emulsifier comprising CaDDBS dissolved in the solvent oil or aromatic hydrocarbon in the composition is about 0.1% to about 10% by weight, based on the total weight of the composition.

36. The composition according to claim 35, wherein the aromatic hydrocarbon or solvent oil is naphthalene.

37. The composition according to claim 35, wherein the aromatic hydrocarbon or solvent oil is isobutanol.

38. The composition according to claim 18, wherein the stabilizer is butylated hydroxy toluene or butyl hydroxyanisole (BHA).

39. The composition according to claim 35, wherein the amount of the stabilizer in the composition is about 0.1% to about 8% by weight, based on the total weight of the composition.

40. A method for controlling animal pests comprising applying an effective amount of the composition according to any one of claims 1 -39 to a locus where the animal pest is to be controlled and / or prevented so as to thereby control and / or prevent the animal pest.

41. The method according to claim 40, wherein the locus is a crop field.

42. The method according to claim 40, wherein the crop field is selected from pomaceous fruit, stone fruit, soft fruit, apples, pears, avocado, plums, peaches, almonds, cherries, berries, strawberries, raspberries, blackberries, citrus fruit, oranges, lemons, grapefruit, tangerines, cucurbits, pumpkins, cucumbers, melons, lettuce, cabbages, carrots, tomatoes, potatoes, peppers, chilli, okra, eggplants; beans, peas, soya, oilseed rape, olives, sunflowers, ground nuts, cotton, nuts, coffee, grapevines, ornamentals, lauraceae.

43. The method according to any one of claims 40-42, wherein the animal pest is selected from the order of Lepidoptera, Diptera, Hemiptera, Thysanoptera, Coleoptera, Hymenoptera Heteroptera, Homoptera, Thysanoptera, acarine, nematode and mollusc.

44. The method according to any one of claims 40-43, wherein the composition is applied in an amount from about 1.8 L / ha to about 28.8 L / ha.

45. The method according to any one of claims 40-44, wherein the composition is applied in an amount from about 18 g / ha of spirotetramat to about 288 g / ha of spirotetramat.

46. The method according to any one of claims 40-45, wherein the composition is applied in an amount from about 18 g / ha of flonicamid to about 288 g / ha of flonicamid.

47. Use of the composition according to any one of claims 1-39 for controlling and / or preventing animal pests.

48. The use according to claim 47, wherein the animal pest is selected from the order of Lepidoptera, Diptera, Hemiptera, Thysanoptera, Coleoptera, Hymenoptera Heteroptera, Homoptera, Thysanoptera, acarine, nematode and mollusc.

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