Insecticide formulations with built-in adjuvants

Abstract

The present invention provides an agrochemical suspension in the form of a concentrate comprising at least one ketoenol insecticide; an amount of at least one adjuvant; at least one steric and / or static stabilizer; at least one rheology modifier; and water.

Description

Technical Field

[0001] The present disclosure relates to insecticide formulations, more particularly insecticide formulations comprising adjuvants and being stable in concentrated form. Background Art

[0002] The use of various insecticides to reduce insect infestation of commercially grown crops has been carried out for many years. Various insecticides are known and can be used alone or in combination with one or more adjuvants to enhance their effectiveness.

[0003] The insecticide active ingredient and adjuvant are combined in water or other carrier liquids, typically in the field shortly before or just before use (called "tank mix"), because stock formulations containing both insecticide and adjuvant are known to be physically unstable (e.g., characterized by phase separation). Such physical instability has an impact on the ability to control the concentration of the active ingredient added to water from the stock formulation, which may result in insufficient or excessive application of the insecticide. In addition, such stock formulations are known to have relatively high viscosities, hindering the manufacturing and packaging processes, and making such stock formulations difficult to apply and apply in the field.

[0004] General Description

[0005] The present disclosure relates to stock (i.e., concentrated) formulations of insecticides and adjuvants that are stable in concentrated form for extended periods of time and have a suitable viscosity for in situ dilution prior to application in the field. The inventors have surprisingly discovered that the combination of insecticide, adjuvant, and carefully selected steric and / or static stabilizers results in a physically and chemically stable concentrate formulation, thereby allowing its long-term storage, while also achieving a sufficiently low viscosity to obtain a formulation that can be easily diluted prior to use.

[0006] Thus, according to one aspect of the present disclosure, there is provided an agrochemical suspension in the form of a concentrate comprising:

[0007] a) at least one ketoenol insecticide;

[0008] b) from about 2 wt % to about 20 wt % of at least one adjuvant;

[0009] c) at least one steric and / or static stabilizer;

[0010] d) at least one rheology modifier; and

[0011] e) Water.

[0012] The suspension formulations of the present disclosure provide long-term stability under storage conditions in a concentrated form that can be easily diluted before use. The unique combination of physical and chemical interactions between the formulation components allows the formulation to be stabilized to prevent phase separation and provides reduced viscosity for accurate and easy application.

[0013] The formulation is in the form of a concentrate, i.e., the formulation has a higher concentration of active ingredients than the concentration to be applied to the crop. Unlike ready-to-use mixtures (which are pre-diluted form formulations) or tank mixes (which are mixtures prepared in situ by simply mixing the ingredients into an application container just before application), the formulations of the present disclosure are designed to maintain their physical stability for long-term storage conditions and can be easily diluted before application.

[0014] The formulation is in the form of a suspension, ie, a liquid formulation comprising droplets or particles dispersed substantially uniformly within a continuous liquid phase.

[0015] The term insecticide or insecticidal refers to a composition having activity in reducing or eliminating animal pests (typically insect populations) in agricultural or horticultural crops. The term includes insecticides having insecticidal activity against various insect types and at various developmental stages of insects (e.g., eggs, larvae, pupae, nymphs and adults).

[0016] The suspension comprises at least one ketoenol insecticide.Ketoenols are compounds that exhibit keto-enol tautomerism, wherein the compound exists in chemical equilibrium between the keto form (carbonyl structure containing an alpha-hydrogen) and the enol form (double bond adjacent to the alcohol, -C=C-OH) of the compound.

[0017] According to some embodiments, the at least one ketoenol insecticide is selected from spirotetramat, dispirotetramat, methoxyfenethyl, spirodiclofen, spiromesifen, and combinations thereof.

[0018] By some embodiments, the at least one ketoenol insecticide is spirotetramat.

[0019] Spirotetramat is known to be active primarily against piercing-sucking insects such as aphids, mites and whiteflies by acting as an ACC inhibitor, interrupting lipid biosynthesis in insects. Spirotetramat, or 3-(2,5-dimethylphenyl)-4-(ethoxycarbonyloxy)-8-methoxy-1-azaspiro[4.5]dec-3-en-2-one, exists in cis and trans forms, as shown in formula (I) and (II), respectively:

[0020]

[0021] According to some embodiments, the spirotetramat is cis-spirotetramat or is in the form of a mixture of cis / trans isomers thereof.

[0022] According to some embodiments, the concentration of the at least one ketoenol insecticide in the suspension is at least 2 wt %. According to some other embodiments, the concentration of the at least one ketoenol insecticide in the suspension ranges between about 2 wt % and 30 wt %.

[0023] As noted, the inventors have discovered that when one or more ketoenol insecticides are combined with one or more adjuvants, improved insecticidal activity can be obtained compared to using the ketoenol insecticide without such one or more adjuvants.

[0024] The term adjuvant is intended to mean a substance which, by itself, has no pesticide activity, but which, once combined therewith, enhances the effectiveness of the pesticide. In its broadest definition, an adjuvant may be a spreader, penetrant, compatibilizer and / or drift inhibitor.

[0025] In the suspension of the present disclosure, the at least one auxiliary agent is selected from C8-C16 fatty alcohol alkoxylates, which are prepared by alkoxylating fatty alcohols and / or fatty acids.

[0026] By some embodiments, the adjuvant is a C8-C16 fatty alcohol alkoxylate. According to some embodiments, the adjuvant is at least one linear branched C8-C10 alcohol ethoxylate, C8-C10 alcohol propoxylate, C9-C11 alcohol ethoxylate, C9-C11 alcohol propoxylate, C12-C15 alcohol ethoxylate, C12-C15 alcohol propoxylate, isodecyl alcohol ethoxylate, isodecyl alcohol propoxylate, isoundecanol ethoxylate, isoundecanol propoxylate, isotridecanol ethoxylate, isotridecanol propoxylate, and polyethylene glycol trimethyl nonyl ether.

[0027] According to some other embodiments, the at least one adjuvant is selected from trimethyl nonyl ethoxylate (TergitolTM N-6), C9 / C11 alcohol ethoxylate / propoxylate (Atplus245) and mixtures thereof.

[0028] According to some embodiments, the suspension comprises at least about 2 wt% of the adjuvant.By other embodiments, the concentration of the at least one adjuvant in the suspension ranges between about 2 wt% and about 20 wt%.

[0029] By some embodiments, the suspension comprises between about 5 wt % and about 8 wt % Tergitol TMN-6. By other embodiments, the suspension comprises between about 12 wt % and about 14 wt % Atplus 245.

[0030] As noted, most commercial formulations comprising ketoenol insecticides and adjuvants are physically unstable and exhibit significant phase separation, making such formulations unsuitable for long-term storage and accurate dosing. The inventors of the present invention have surprisingly discovered that incorporation of carefully selected steric and / or static stabilizers significantly improves the stability of the suspension, thereby minimizing or even preventing phase separation for a period of at least 1 year, making these formulations suitable for long-term storage, while also allowing for increased concentrations of the one or more adjuvants in the suspension (i.e., concentrations of the one or more adjuvants in the suspension up to about 20 wt %).

[0031] The term steric stabilizer is intended to denote a compound or substance which stabilizes colloidal particles / droplets within a suspension or dispersion by creating steric hindrance between these particles / droplets, thereby preventing coalescence and aggregation. In other words, a steric stabilizer inhibits coagulation and aggregation of a suspension or dispersion.

[0032] The term static stabilizer refers to compounds or substances which generate surface charge and / or surface potential in aqueous suspensions, thereby preventing particle / droplet aggregation by inducing repulsive forces.

[0033] In the present disclosure, steric stabilizers and / or static stabilizers are selected to interact physically and / or chemically with components in the suspension (typically with the one or more adjuvants) to obtain steric stabilization of the adjuvant in the suspension, and to maintain the adjuvant in a suspended (or dispersed) form. The steric and / or static stabilizers used in the suspension of the present disclosure are selected to have one or more hydrophobic parts that can be physically interlocked with the at least one adjuvant, so that the adjuvant in the suspension is stable and allows high-load adjuvants to enter the suspension with minimal risk of phase separation. In other words, steric and / or static stabilizers are selected to allow their hydrophobic parts to mechanically entangle with the adjuvant, so that the adjuvant is kept in the suspension. The steric and / or static stabilizers can be nonionic, anionic, cationic, zwitterionic or amphoteric.

[0034] By some embodiments, the at least one steric stabilizer is selected from the group consisting of ethylene oxide / propylene oxide copolymers, acrylate / methacrylate copolymers, C10-C14 fatty alcohol ethoxylates, and any combination thereof.

[0035] By way of other embodiments, the static stabilizer is selected from alcohol sulfates, alcohol sulfonates, alkyl sulfates, aryl sulfates, alkylaryl sulfates, alkyl ether sulfates, aryl sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty acid sulfonates (e.g., lauryl sulfonate), mono-, di- or tristyrylphenol ethoxylate sulfates, taurates (N-methyloleoyl taurate), isethionates (cocoyl isethionate), and combinations thereof.

[0036] According to some embodiments, the at least one steric and / or static stabilizer is selected from ethoxylated tristyrylphenol ammonium sulfate salt (e.g., Tersperse 2218), isotridecanol ethoxylate (e.g., Alkont IT60), acrylic graft copolymers (e.g., Tersperse 2500), ethoxylated tristyrylphenol phosphate (e.g., Soprophor 3D33R), polyalkylene oxide block copolymers (e.g., Atlas G5002L), and combinations thereof.

[0037] According to some embodiments, the total concentration of steric and / or static stabilizers in the suspension is between about 1 wt % and about 9 wt %.

[0038] According to some embodiments, the weight ratio (w / w) of the at least one adjuvant to the steric and / or static stabilizer ranges between about 1:5 and about 5: 1. The inventors have further discovered that incorporating the at least one steric and / or static stabilizer into the concentrated suspension enables, on the one hand, physical interlocking of the adjuvant within the hydrophobic portion of the steric and / or static stabilizer, and on the other hand, controlling the viscosity of the suspension by controlling the balance between hydrogen bonds formed between the hydrophilic portion of the steric and / or static stabilizer and the adjuvant, and obtaining a lubricating effect by relative sliding of the hydrophobic portion of the steric and / or static stabilizer.

[0039] Further control over the viscosity of the suspension is obtained by adding at least one rheology modifier to the suspension.The term rheology modifier or rheomodifier is intended to mean a compound or substance that is capable of modulating (eg increasing or decreasing) the viscosity of a suspension.

[0040] According to some embodiments, the at least one rheology modifier is selected from polysaccharides, silicate compounds, water-soluble or colloidal water-soluble polymers.

[0041] According to some embodiments, the at least one rheology modifier is selected from magnesium aluminum silicate, magnesium aluminum metasilicate, cellulose ethers (e.g., hydroxyethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose), polyvinyl alcohol, polyquaternium-10, guar gum, hydroxypropyl guar gum, xanthan gum, carrageenan, starch, gelatin, ghatty gum, gum arabic, pectin, polyvinyl pyrrolidone, copolymers containing pyrrolidone, carboxyvinyl polymers, and combinations thereof.

[0042] By some embodiments, the at least one rheology modifier is selected from magnesium aluminum silicate, xanthan gum, and combinations thereof.

[0043] According to some embodiments, the suspension comprises between about 0.05 wt % and 1.5 wt % of one or more rheology modifiers.

[0044] According to some embodiments, the suspension has a viscosity of at most 14,500 cP (centipoise). In some embodiments, the suspension has a viscosity ranging between about 1,100 and about 14,500 cP.

[0045] In order to enhance the pesticide activity of the suspension or increase its effective range, one or more additional insecticides may be added. By some embodiments, the additional insecticide is selected from diafenthiuron, diflubenzuron, flufenuron, lufenuron, and any combination thereof. By some other embodiments, the additional insecticide is diafenthiuron.

[0046] According to some embodiments, the at least one additional insecticide is present in the suspension at a concentration of at least 5 wt%.By some embodiments, the additional insecticide is present in the suspension at a concentration ranging between about 5 wt% and about 50 wt%.

[0047] By some embodiments, the weight ratio (w / w) of the at least one ketoenol insecticide to the at least one additional insecticide in the suspension ranges between about 1:1 and 1:5. By other embodiments, the weight ratio (w / w) of the at least one ketoenol insecticide to the at least one additional insecticide in the suspension is about 1:3.

[0048] By way of some embodiments, the suspension may further comprise one or more additives such as defoamers, buffers, solvents, antifreeze agents, colorants, odorants, antioxidants, UV stabilizers, thickeners, stickers, and dispersants.

[0049] By some embodiments, the suspension has a pH between about 3 and 6.

[0050] As noted, the agrochemical suspensions of the present disclosure are designed to be in the form of a stable concentrate. Thus, by some embodiments, the suspension comprises up to 50 wt% water.

[0051] By another aspect of the present disclosure, there is provided an agrochemical suspension in the form of a concentrate comprising:

[0052] a) spirotetramat,

[0053] b) from about 2 wt % to about 20 wt % of at least one adjuvant,

[0054] c) at least one steric and / or static stabilizer,

[0055] d) at least one rheology modifier, and

[0056] e) Water.

[0057] By another aspect of the present disclosure, there is provided an agrochemical suspension in the form of a concentrate comprising:

[0058] a) spirotetramat,

[0059] b) from about 2 wt% to about 20 wt% of at least one auxiliary agent selected from C8-C16 fatty alcohol alkoxylates,

[0060] c) at least one steric stabilizer selected from the group consisting of ethylene oxide / propylene oxide copolymers, acrylate / methacrylate copolymers, C10-C14 fatty alcohol ethoxylates, and any combination thereof; and / or at least one static stabilizer selected from the group consisting of alcohol sulfates, alcohol sulfonates, alkyl sulfates, aryl sulfates, alkylaryl sulfates, alkyl ether sulfates, aryl sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty acid sulfonates (e.g., lauryl sulfonate), mono-, di- or tristyrylphenol ethoxylate sulfates, taurates (N-methyloleoyl taurate), isethionates (cocoyl isethionate), and combinations thereof,

[0061] d) at least one rheology modifier, and

[0062] e) Water.

[0063] By yet another aspect of the present disclosure, there is provided an agrochemical suspension in the form of a concentrate comprising:

[0064] a) spirotetramat and diafenthiuron,

[0065] b) from about 2 wt% to about 20 wt% of at least one auxiliary agent selected from C8-C16 fatty alcohol alkoxylates,

[0066] c) at least one steric stabilizer selected from the group consisting of ethylene oxide / propylene oxide copolymers, acrylate / methacrylate copolymers, C10-C14 fatty alcohol ethoxylates, and any combination thereof; and / or at least one static stabilizer selected from the group consisting of alcohol sulfates, alcohol sulfonates, alkyl sulfates, aryl sulfates, alkylaryl sulfates, alkyl ether sulfates, aryl sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty acid sulfonates (e.g., lauryl sulfonate), mono-, di- or tristyrylphenol ethoxylate sulfates, taurates (N-methyloleoyl taurate), isethionates (cocoyl isethionate), and combinations thereof,

[0067] d) at least one rheology modifier, and

[0068] e) Water.

[0069] By way of another aspect, the present disclosure provides a pesticide composition comprising a suspension as described herein and an agriculturally acceptable liquid carrier.

[0070] It should be noted that in the context of the present disclosure, the term suspension refers to the concentrate, whereas the term composition refers to the suspension in diluted form, for example prepared shortly before or immediately prior to administration.

[0071] By some embodiments, the agriculturally acceptable liquid carrier is water.

[0072] By some other embodiments, the composition comprises about 100 g / L spirotetramat.

[0073] By way of other examples, the composition further comprises about 300 g / L diafenthiuron.

[0074] By another aspect, there is provided a method of controlling pest populations in a plant, the method comprising applying a suspension or composition described herein to the plant and / or the soil surrounding the plant.

[0075] By way of another aspect, there is provided a method of protecting a plant from infestation by insects, the method comprising applying a suspension or composition as described herein to the plant and / or the soil surrounding the plant.

[0076] According to some embodiments, the suspension or composition described herein eliminates at least about 10%, 20%, 30%, 40%, 50%, 60%, 70% or even 80% of the insect population compared to the insect population before applying the suspension or composition.

[0077] By another aspect, there is provided a method for controlling and / or preventing animal pests, the method comprising applying an effective amount of a suspension or composition to a location of the animal pest to be controlled and / or prevented, so as to thereby control and / or prevent the animal pest.

[0078] The terms control or controlling of insect populations are meant to encompass any of inhibition or interference with the normal life cycle of the insects (at any stage thereof), growth regulation, or killing.

[0079] The suspension or composition can be used to eliminate or control infestations of animal pests (such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Coleoptera, Hymenoptera) and also other invertebrate pests (for example, mites, nematodes and mollusc pests).

[0080] In some embodiments, the location is a crop field.

[0081] In some embodiments, the suspension or composition is applied in an amount of about 0.6 L / ha (liters per hectare) to about 2 L / ha.

[0082] In some embodiments, the suspension or composition is applied in an amount of about 60 g / ha (grams per hectare) of spirotetramat to about 200 g / ha of spirotetramat.

[0083] In some embodiments, the suspension or composition is applied in an amount of about 180 g / ha of diafenthiuron to about 600 g / ha of diafenthiuron.

[0084] Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as pests. Pests include pests associated with agriculture (i.e. the growth of crops for food and fiber products), horticulture and animal husbandry, forestry and the storage of products of plant origin (such as fruits, grains and wood).

[0085] Non-limiting examples of pest species that can be controlled by the suspensions or compositions disclosed herein include Myzus persicae (aphids), Aphis gossypii (aphids), Aphis fabae (aphids), Lygus spp. (capsid insects), Dysdercus spp. (capsid insects), Nilaparvata lugens (planthoppers), Nephotettixc incticeps (leafhoppers), Nezara spp. (stink bugs), Euschistus spp. (stink bugs), Leptocorisa spp. (stink bugs), Frankliniella occidentalis (thrips), Thrips spp. (thrips), Leptinotarsa ​​decemlineata (potato beetle), decemlineata (Colorado potato beetle), Anthonomus grandis (Boll weevil), Aonidiella spp. (Scale insects), Pseudococcus spp. (Mealybugs), Trialeurodes spp. (Whiteflies), Bemisia tabaci (Whiteflies), Ostrinia nubilalis (European corn borer), Spodoptera littoralis (Cotton leafworm), Heliothis virescens (Tobacco budworm), Helicoverpa armigera (Bollworm), Helicoverpa zea (Bollworm), Sylepta derogata (Cotton leafroller), Pieris cabbage butterfly (Pieridae) brassicae (white butterfly), Plutellaxylostella (diamond back moth), Agrotis spp. (root cutter), Chilo suppressalis (rice borer), Locusta migratoria (locust), Chortiocetesterminifera (locust), Diabrotica spp.) (rootworms), Panonychus ulmi (European red mite), Panonychus citri (Citrus red mite), Tetranychus surticae (two-spotted spider mite), Tetranychus cinnabarinus (cotton spider mite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemus latus (broad mites), Brevipalpus spp. (short-bearded mites), Liriomyza spp. (leaf miners), Meloidogyne spp. (root-knot nematodes), Globodera spp., Heterodera spp. (cyst nematodes), Pratylenchus spp. ( spp.) (rot nematodes), Rhodopholus spp. (banana boring nematodes), Tylenchulus spp. (citrus nematodes), Haemonchus contortus (twisting stomach worms), Caenorhabditis e / egans (vinegar nematodes), Trichostrongylus spp. (gastrointestinal nematodes) and Deroceras reticulatum (slugs); from the order of the Acarina, for example, Acarus siro, Aceriasheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp.), Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp.), Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.; from the order of the Coleoptera, for example, Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp. spp.), Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa ​​decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.; from the order of the Diptera, for example, Aedes spp., Antherigonasoccata, 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 of the Hemiptera, for example, Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistos spp., Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotino-phara spp., and Triatoma spp.; from the order of the Homoptera, for example, Aleurothrixus floccosus, Aleyrodes brassicae), Aonidiella spp., Aphididae, Aphis spp., Aspidiotus 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., Planococcus 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 of the Hymenoptera, for example, Acromyrmex spp., Atta spp., Cephus spp., Diprions spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprions spp., Solenopsis spp. and Vespa spp.; from the order of the 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, Cadracautella, Carposina nipponensis, ChNo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotalis, Cryptophlebialeucotreta, Cydia spp., Diatraea spp., Diparopsis sudanensis castanea), Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedyanubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucopterascitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp.), Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemiss 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 of the Thysanoptera, for example Frankliniella spp.), Hercinothrips spp., Scirtothripsaurantii, Taeniothrips spp., Thrips palmi and Thripstabaci; and from the order of the Thysanura, for example, Lepisma saccharina.

[0086] The term plant is intended to mean any of the whole plant, plant parts (leaves, stems, branches, roots, tubers, bulbs, trunks, buds, seedlings, flowers, inflorescences, buds, fruits, seeds etc.), and propagation material.

[0087] The term crop means agricultural, cultivated or horticultural crops, including seasonal, annual, semi-perennial and perennial crops.

[0088] Non-limiting examples of suitable crops include cereals (e.g., wheat, barley, rye, oats, rice, maize, sorghum), beets (e.g., sugar beets, fodder beets), fruits (e.g., pome, stone or soft fruit, such as apples, pears, avocados, plums, peaches, apricots, cherries, berries (e.g., strawberries, raspberries, blackberries)), cinnamon, camphor, citrus fruits (e.g., oranges, lemons, grapefruits, tangerines), melons (e.g., pumpkins, cucumbers, melons) , vegetables (such as spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato or pepper, chili, okra, eggplant), leguminous crops (such as beans, lentils, peas, soybeans), oil crops (such as rapeseed, mustard, poppy, olive, sunflower, coconut, castor, cocoa beans, peanuts), fiber plants (such as cotton, flax, hemp, jute), tobacco, nuts, coffee, sugar cane, tea, grapevine, hops, Plantaginaceae, latex plants, ornamental plants and Lauraceae.

[0089] As used herein, the term about is intended to encompass deviations of ±10% from the specifically mentioned parameter value (eg, concentration, temperature, etc.).

[0090] Unless specifically stated otherwise, concentrations are provided in wt %, ie as weight percent of the total weight of the formulation / composition.

[0091] Whenever a numerical range is indicated herein, it is meant to include any cited numeral (fractional or integer) within the indicated range. The phrases range between a first indicated numeral and a second indicated numeral and "range from" a first indicated numeral "to" a second indicated numeral are used interchangeably herein and are meant to include the first indicated numeral and the second indicated numeral and all fractions and integers therebetween.

[0092] Unless the context requires otherwise, the word "comprise" and variations such as "comprises" and "comprising", will be understood to imply the inclusion of stated integers or steps or groups of integers or steps but not the exclusion of any integer or step or group of integers and steps.

[0093] It should generally be noted that the term "... at least one... " as applied to any component of the compositions of the present invention should be read to cover one, two, three, four, five or more different occurrences of said component in the formulations described herein.

[0094] It should be appreciated that certain features of the disclosure described in the context of separate embodiments for the sake of clarity may also be provided in combination in a single embodiment. Conversely, various features of the disclosure described in the context of a single embodiment for the sake of simplicity may also be provided in any other described embodiment of the disclosure, either individually or in any suitable sub-combination or where appropriate. Certain features described in the context of various embodiments are not considered essential features of those embodiments, unless the embodiment is ineffective without those elements. DETAILED DESCRIPTION

[0095] Exemplary Formulations

[0096] Exemplary suspension formulations according to the present disclosure are provided in Table 1-1 and Table 1-2.

[0097] Table 1-1: Exemplary formulations of stable suspensions with Tergitol TMN-6

[0098]

[0099]

[0100] *Accelerated aging protocol, related to 2 years at ambient conditions

[0101] Table 1-2: Exemplary formulations of stable suspensions with Atplus245

[0102]

[0103]

[0104] Exemplary formulations were prepared according to the following general preparation method:

[0105] Vangel B is slowly added to water (90% of the total water content of the preparation) and mixed until completely dissolved. Then, propylene glycol (80% of the total required amount), Tergitol TMN 6, SAG 1572 (50% of the total required amount) and Tersperse 2218 are added successively, and propeller agitator is used to stir 10min at 700-800RPM, and then glacial acetic acid and sodium acetate are added under continuous stirring. Add spirotetramat and diafenthiuron and homogenize 5min at 4000-6000rpm, then grind 30-45min at 2500RPM in EMI bead mill, until particle size is less than 8 microns. The suspension slurry ground is stirred with the defoamer of residual amount, and continues to stir at 1000-1200RPM. Later, an amount of rheology modifier (xanthan gum) gel solution is added to the suspension ground to obtain a viscosity of about 1200-2000cP.

[0106] The rheology modifier (xanthan gum) gel solution was prepared the day before by mixing water (remaining 10% of the amount), xanthan gum, Proxel GXL and propylene glycol (remaining 20% ​​of the amount) under continuous stirring for 3-4 hours and kept ready for use.

[0107] The effects of various steric stabilizers on the stability of the formulations were evaluated as detailed in Table 2-1 and Table 2-2. Acceptable stability results are considered to be less than 5% phase separation.

[0108] Table 2-1: Unstable formulations of TergitolTMN6 with different steric stabilizers

[0109]

[0110] Table 2-2: Phase separation and viscosity data

[0111]

[0112] As clearly shown in Tables 1-1 to 1-2, adjuvants, more specifically those selected from the group of C8-C16 fatty alcohol alkoxylates, can be formulated to provide an intrinsically stable product using different types of stabilizers. Formulations AE showed no or minimal phase separation and exhibited desirable viscosity characteristics.

[0113] The formulations in Table 2-1 and Table 2-2 differ only in the type of steric stabilizer added and are intended to be used as comparative data. Various types of steric stabilizers were tested and the desired effect was not achieved due to high levels of phase separation and / or high viscosity.

[0114] The effects of various rheology modifiers on the formulations are provided in Table 3-1 and Table 3-2.

[0115] Table 3-1: Unstable formulation of Atplus 245 without Vangel B

[0116]

[0117] Table 3-2: Unstable formulation of Tergitol TMN-6 without Vangel B

[0118]

[0119]

[0120] Efficacy and phytotoxicity testing protocols and methods

[0121] The formulations of the present disclosure were field tested on various crops to evaluate their efficacy against multiple insect infestations as well as phytotoxicity symptoms. These tests were conducted according to two test protocols as detailed in Table 4-1 and Table 4-2.

[0122] The exact formulation of Spirotetramat 100 + Diafenthiuron 300SC with Tergitol TMN-6 is as described in Formulation A in Table 1-1.

[0123] The exact formulation of Spirotetramat 100 + Diafenthiuron 300SC with Atplus 245 is as described in Formulation C in Table 1-2.

[0124] Table 4-1: Test scenario 1

[0125]

[0126]

[0127] *Commercial product reference

[0128] Table 4-2: Test scenario 2

[0129]

[0130]

[0131] *Commercial product reference

[0132] method

[0133] Mites and Aphids - Five (5) plants were randomly selected in each test plot for observation. The number of mites and aphids was counted on day 0 (before application), 3, 5, 7 and 10 days after the first application. Three (3) leaves were observed for each of the 5 plants (the total number of leaves observed per plot was 45).

[0134] Whitefly Adults - Five (5) plants were randomly selected in each test plot for observation. The number of whitefly adults on the underside of two top leaves and one middle leaf was recorded for each of the 5 plants. The formulations were evaluated for knockdown effect within 4 hours from application and 1 day after the first application (DAA). The total number of leaves observed per plot was 45.

[0135] Whitefly Nymphs - Five (5) plants were randomly selected in each test plot for observation. Nymphs on the top, middle and bottom leaves were circled and counted. The number of live nymphs was recorded before application and at 3, 7 and 10 days after the first application. The total number of leaves observed per plot was 45.

[0136] Mealybugs - Ten (10) plants were randomly selected in each test plot for observation. For each plant, 3 branches were observed (30 branches total per plot). The number of mealybug nymphs (crawlers) and adults per 5 cm of the branch tip shoots before and after application.

[0137] Diamondback moth (DBM) - Five (5) plants were randomly selected in each test plot for observation. The number of L1-2 larvae on the plants was counted. The number of live L1-2 larvae was recorded before application and at 3, 7 and 10 days after the first application.

[0138] In the following tables, letter indices 1-I indicate DMRT levels.

[0139] Example 1: Tomato

[0140] As detailed in Table 5-1, tomato plots were evaluated for efficacy against mites (DAA = days after first application; ROC = reduction relative to control).

[0141] Both formulations with Tergitol TMN-6 and Atplus 245 showed better efficacy than the formulation without adjuvants.

[0142] Table 5-1: Test details, tomato

[0143]

[0144] Table 5-2: Efficacy results, tomato mite (two-spotted spider mite)

[0145]

[0146]

[0147] Example 2: Cotton

[0148] Efficacy against mites was evaluated on cotton plots as detailed in Table 6-1. Efficacy results are detailed in Tables 6-2-1 to 6-2-4 (DAA = days after first application; ROC = reduction relative to control).

[0149] The formulation with Tergitol TMN-6 showed better efficacy than the formulation without adjuvant and compared with the commercial product. The residual effect was 7-10 days.

[0150] The exact formulation of Spirotetramat 100 + Diafenthiuron 300SC with Tergitol TMN-6 is as described in Formulation A in Table 1-1.

[0151] The exact formulation of Spirotetramat 100 + Diafenthiuron 300SC with Atplus 245 is as described in Formulation C in Table 1-2.

[0152] Table 6-1: Test details, cotton

[0153]

[0154]

[0155] Table 6-2-1: Efficacy results, cotton whitefly (Bemisia tabaci), position 1

[0156]

[0157]

[0158] Table 6-2-2: Efficacy results, cotton mealybug (Phenacoccus solenopsis), position 1

[0159]

[0160]

[0161] Table 6-2-3: Efficacy results, cotton aphid (Aphis gossypii), position 1

[0162]

[0163]

[0164] Table 6-2-4: Efficacy results, cotton whitefly nymphs ( Bemisia tabaci ), position 2

[0165]

[0166]

[0167] Example 3: Okra

[0168] As detailed in Table 7-1, efficacy against mites was evaluated on okra plots. Efficacy results are detailed in Table 7-2-1 and Table 7-2-2 (DAA = days after first application; ROC = reduction relative to control).

[0169] The exact formulation of Spirotetramat 100 + Diafenthiuron 300SC with Tergitol TMN-6 is as described in Formulation A in Table 1-1.

[0170] The exact formulation of Spirotetramat 100 + Diafenthiuron 300SC with Atplus 245 is as described in Formulation C in Table 1-2.

[0171] Table 7-1: Test details, okra

[0172]

[0173] Table 7-2-1: Effect results, okra whitefly nymph (Bemisia tabaci)

[0174]

[0175]

[0176] Table 7-2-2: Efficacy results, okra mite (two-spotted spider mite)

[0177]

[0178]

[0179] The formulation with Tergitol TMN-6 showed improved control of okra whitefly population, and higher control of okra mite population. The formulation with Tergitol showed results that were also superior to the commercial product.

[0180] Example 4: Cauliflower

[0181] As detailed in Table 8-1, cauliflower plots were evaluated for efficacy against aphids and DBM. The efficacy results are detailed in Table 8-2-1 and Table 8-2-2 (DAA = days after first application; ROC = reduction relative to control).

[0182] It was found that formulations with Tergitol and Atplus provided improved control of cauliflower DBM and aphids.

[0183] The exact formulation of Spirotetramat 100 + Diafenthiuron 300SC with Tergitol TMN-6 is as described in Formulation A in Table 1-1.

[0184] The exact formulation of Spirotetramat 100 + Diafenthiuron 300SC with Atplus 245 is as described in Formulation C in Table 1-2.

[0185] Table 8-1: Test details, cauliflower

[0186]

[0187] Table 8-2-1: Efficacy results, broccoli DMB (diamond back moth)

[0188]

[0189]

[0190] Table 8-2-2: Effect results, cauliflower aphids (cabbage aphids ( B revicoryne brassicae

[0191]

[0192]

[0193]

[0194] Example 5: Eggplant

[0195] As detailed in Table 9-1, eggplant plots were evaluated for efficacy and phytotoxicity against mites. The efficacy results are detailed in Table 9-2.

[0196] The exact formulation of Spirotetramat 100 + Diafenthiuron 300SC with Tergitol TMN-6 is as described in Formulation A in Table 1-1.

[0197] The exact formulation of Spirotetramat 100 + Diafenthiuron 300SC with Atplus 245 is as described in Formulation C in Table 1-2.

[0198] Table 9-1: Test details, Eggplant

[0199]

[0200] Table 9-2: Efficacy results, eggplant mite (two-spotted spider mite)

[0201]

[0202]

[0203] It was found that formulations with Tergitol TMN-6 and Atplus 245 provided improved efficacy against eggplant mites and whiteflies. The residual effect was 7-10 days.

[0204] In all of the above examples 1-6, formulations with built-in adjuvants achieved superior efficacy compared to formulations without adjuvants and / or commercial products. Built-in formulations with reduced pesticide application rates (g Ai\Ha) also had better efficacy compared to formulations without adjuvants.

Claims

1. An agrochemical suspension in the form of a concentrate, comprising: a) at least one ketoenol insecticide; b) from about 2 wt % to about 20 wt % of at least one adjuvant; c) at least one steric and / or static stabilizer; d) at least one rheology modifier; and e) Water.

2. The agrochemical suspension according to claim 1, wherein The at least one auxiliary agent is selected from C8-C16 fatty alcohol alkoxylates.

3. The agrochemical suspension according to claim 1 or 2, wherein: The auxiliary agent is selected from linear or branched C8-C10 alcohol ethoxylates, C8-C10 alcohol propoxylates, C9-C11 alcohol ethoxylates, C9-C11 alcohol propoxylates, C12-C15 alcohol ethoxylates, C12-C15 alcohol propoxylates, isodecyl alcohol ethoxylates, isodecyl alcohol propoxylates, isoundecanol ethoxylates, isoundecanol propoxylates, isotridecanol ethoxylates, isotridecanol propoxylates, and polyethylene glycol trimethyl nonyl ether.

4. The agrochemical suspension according to any one of claims 1 to 3, wherein: (a) the steric stabilizer is selected from ethylene oxide / propylene oxide copolymers, acrylate / methacrylate copolymers, C10-C14 fatty alcohol ethoxylates and any combination thereof, and / or (b) The static stabilizer is selected from alcohol sulfates, alcohol sulfonates, alkyl sulfates, aryl sulfates, alkyl aryl sulfates, alkyl ether sulfates, aryl sulfonates, alkyl aryl sulfonates, lignin sulfonates, fatty acid sulfonates (e.g., lauryl sulfonate), mono-, di- or tristyrylphenol ethoxylate sulfates, taurates (N-methyl oleyl taurate), isethionates (cocoyl isethionate) and combinations thereof.

5. The agrochemical suspension according to any one of claims 1 to 4, wherein The steric and / or static stabilizer is present in the suspension in a concentration ranging between about 1 wt% and 9 wt%.

6. The agrochemical suspension according to any one of claims 1 to 5, wherein The weight ratio (w / w) of the at least one adjuvant to the steric and / or static stabilizer ranges between about 1:5 and about 5:

1.

7. The agrochemical suspension according to any one of claims 1 to 6, wherein The rheology modifier is selected from magnesium aluminum silicate, magnesium aluminum metasilicate, cellulose ethers (e.g., hydroxyethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose), polyvinyl alcohol, polyquaternium-10, guar gum, hydroxypropyl guar gum, xanthan gum, carrageenan, starch, gelatin, gum ghatti, gum arabic, pectin, polyvinyl pyrrolidone, copolymers containing pyrrolidone, carboxyvinyl polymers, and combinations thereof.

8. The agrochemical suspension according to any one of claims 1 to 7, wherein The rheology modifier is present in the suspension at a concentration ranging between about 0.05 wt % and about 1.5 wt %.

9. An agrochemical suspension as claimed in any one of claims 1 to 8 comprising up to 50 wt% water.

10. The agrochemical suspension according to any one of claims 1 to 9, wherein The at least one ketoenol insecticide is selected from the group consisting of spirotetramat, dispirotetramat, methoxyfenethyl, spirodiclofen, spiromesifen, and combinations thereof.

11. The agrochemical suspension according to claim 10, wherein: The at least one ketoenol insecticide is spirotetramat.

12. The agrochemical suspension according to claim 11, wherein The spirotetramat is cis-spirotetramat or a cis / trans isomer mixture thereof.

13. The agrochemical suspension according to any one of claims 1 to 12, wherein The suspension comprises between about 2 wt % and about 30 wt % of the at least one ketoenol insecticide.

14. Agrochemical suspension according to any one of claims 1 to 13, further comprising at least one additional insecticide.

15. The agrochemical suspension according to claim 14, wherein The at least one additional insecticide is diafenthiuron.

16. The agrochemical suspension according to claim 14 or 15, wherein The additional insecticide is present in the suspension at a concentration ranging between about 5 wt % and about 50 wt %.

17. The agrochemical suspension according to any one of claims 14 to 16, wherein The weight ratio (w / w) of the at least one ketoenol insecticide to the at least one additional insecticide ranges between about 1:1 and 1:

5.

18. The agrochemical suspension as claimed in any one of claims 1 to 17, further comprising one or more additives selected from the group consisting of defoamers, buffers, solvents, antifreeze agents, colorants, odorants, antioxidants, UV stabilizers, thickeners, stickers and dispersants.

19. An agrochemical suspension in the form of a concentrate comprising: a) Spirotetramat; b) from about 2 wt % to about 20 wt % of at least one adjuvant; c) at least one steric and / or static stabilizer; d) at least one rheology modifier; and e) Water.

20. An agrochemical suspension in the form of a concentrate comprising: a) Spirotetramat; b) from about 2 wt % to about 20 wt % of at least one adjuvant selected from C8-C16 fatty alcohol alkoxylates; c) at least one steric stabilizer selected from the group consisting of ethylene oxide / propylene oxide copolymers, acrylate / methacrylate copolymers, C10-C14 fatty alcohol ethoxylates, and any combination thereof; and / or at least one static stabilizer selected from the group consisting of alcohol sulfates, alcohol sulfonates, alkyl sulfates, aryl sulfates, alkylaryl sulfates, alkyl ether sulfates, aryl sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty acid sulfonates (e.g., lauryl sulfonate), mono-, di- or tristyrylphenol ethoxylate sulfates, taurates (N-methyloleoyl taurate), isethionates (cocoyl isethionate), and combinations thereof; d) at least one rheology modifier; and e) Water.

21. An agrochemical suspension in the form of a concentrate comprising: a) spirotetramat and diafenthiuron; b) from about 2 wt % to about 20 wt % of at least one adjuvant selected from C8-C16 fatty alcohol alkoxylates; c) at least one steric stabilizer selected from the group consisting of ethylene oxide / propylene oxide copolymers, acrylate / methacrylate copolymers, C10-C14 fatty alcohol ethoxylates, and any combination thereof; and / or at least one static stabilizer selected from the group consisting of alcohol sulfates, alcohol sulfonates, alkyl sulfates, aryl sulfates, alkylaryl sulfates, alkyl ether sulfates, aryl sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty acid sulfonates (e.g., lauryl sulfonate), mono-, di- or tristyrylphenol ethoxylate sulfates, taurates (N-methyloleoyl taurate), isethionates (cocoyl isethionate), and combinations thereof; and d) Water.

22. A pesticide composition comprising the agrochemical suspension of any one of claims 1 to 21 and an agriculturally acceptable liquid carrier.

23. The pesticide composition of claim 22, comprising about 100 g / L spirotetramat.

24. The pesticide composition of claim 23, further comprising about 300 g / L diafenthiuron.

25. A method of controlling pest populations in plants, the method comprising applying a suspension as claimed in any one of claims 1 to 21 or a composition as claimed in any one of claims 22 to 24 to the plants and / or the soil surrounding the plants.

26. A method for protecting plants from infestation by insects, the method comprising applying a suspension as claimed in any one of claims 1 to 21 or a composition as claimed in any one of claims 22 to 24 to the plants and / or the soil surrounding the plants.

27. A method for controlling and / or preventing animal pests, the method comprising applying an effective amount of a formulation as claimed in any one of claims 1 to 21 or a composition as claimed in any one of claims 22 to 24 to the location of the animal pests to be controlled and / or prevented, so as to thereby control and / or prevent the animal pests.

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