Insecticide composition for crops with reduced phytotoxicity

Abstract

An aqueous composition comprising: diafenthiuron as a first insecticide, optionally flonicamid as a second insecticide, a phosphate ester surfactant, an acrylic copolymer, and water.

Description

INSECTICIDE COMPOSITION FOR CROPS WITH REDUCED PHYTOTOXICITY

[0001] The present invention pertains to an aqueous composition comprising at least one insecticide, wherein the insecticide is diafenthiuron, and at least two synergistic chemical compounds that together act as a safener, reducing the phytotoxicity of the diafenthiuron. Further, the aqueous composition may optionally comprise another insecticide, such as flonicamid. This innovative formulation is designed to mitigate or prevent phytotoxicity, safeguarding crops against potential damage while demonstrating high pest control efficacy of the combined insecticides.BACKGROUND

[0002] Pesticides and insecticides are commonly used in commercial agriculture and have greatly boosted crop yields and improved product quality. Their widespread use has led to substantial economic gains and made agricultural practices more efficient and manageable.

[0003] To optimize pest control, insecticidal formulations may include at least one active ingredient, where the active ingredient is an insecticide designed to target a broad spectrum of pests. While a single insecticide can effectively control both chewing and sucking insects and address resistance issues, combinations of two or more insecticides can offer synergistic effects. These combinations enhance pest control by simultaneously targeting multiple pests and prolonging the residual efficacy of treatments.

[0004] Several insecticidal combinations are well known in the art. For example, the CN103271051A patent discloses a tolfenpyrad-diafenthiuron composite insecticide, which exhibits synergism. This composition, containing both tolfenpyrad and diafenthiuron, has shown enhanced pest control through the interaction of its active ingredients. However, reports have highlighted potential issues with phytotoxicity, where insecticides or their combinations can harm the plants themselves.

[0005] Phytotoxicity, which refers to the toxic effect of chemicals on plants, is a significant concern when formulating insecticidal compositions. It may manifest in symptoms such as leaf scorching, necrotic spots, chlorosis, or stunted growth. These effects can vary depending on plant species, environmental factors, and the specific chemicals used. Phytotoxicity is particularly problematic when insecticides intended to protect plants end up damaging them instead, resulting in reduced yields and quality.

[0006] Therefore, there remains a critical need for insecticidal formulations that not only maintain their effectiveness against pests but also demonstrate low phytotoxicity.

[0007] It is an aim of the present invention to address one or more of the disadvantages associated with the prior art.BRIEF SUMMARY

[0008] Aspects and embodiments of the invention provide an aqueous composition comprising at least one agrochemical active ingredient and at least two chemical compounds, commonlyemployed as dispersing agents. However, when combined in the aqueous composition, these chemical compounds function synergistically as a safener, providing enhanced protection to crops from potential agrochemical damage. Specifically, the combination of both chemical compounds acts as a safener for diafenthiuron, exhibiting a synergistic effect in reducing or even preventing its phytotoxicity. The present invention also relates to the use of this aqueous composition for the treatment of crops or plants against pests. Additionally, this invention involves the use of a combination of twochemical compounds to reduce or prevent the phytotoxicity caused by diafenthiuron. The invention also includes a method for controlling insects on crops of useful plants.

[0009] According to an aspect of the present invention, there is provided an aqueous composition comprising diafenthiuron as a first insecticide, a phosphate ester surfactant, an acrylic copolymer, and water. In an embodiment there is provided a formulated aqueous composition comprising diafenthiuron as a first insecticide, a phosphate ester surfactant, an acrylic copolymer, and water.

[0010] In an embodiment, the aqueous composition may further comprise a second insecticide, wherein the second insecticide is flonicamid.

[0011] In an embodiment of the present invention, there is provided an aqueous composition comprising: diafenthiuron, flonicamid, a phosphate ester surfactant a, an acrylic copolymer, and water.

[0012] In an embodiment, the weight ratio of diafenthiuron to flonicamid in the aqueous composition is in the range of from 7:1 to 1:7, preferably in the range of from 6:1 to 1:6, more preferably 5:1 to 1:5, even more preferably in the range of from 5:1 to 2:1.

[0013] In an exemplary embodiment the weight ratio of diafenthiuron to flonicamid in the aqueous composition is in the range of 3:1.

[0014] In an embodiment, diafenthiuron is present in the range of from 10 % to 40 % by weight based on the total weight of the aqueous composition, preferably in the range of from 15% to 25 % by weight, based on the total weight of the aqueous composition.

[0015] In an embodiment, flonicamid is present in the range of from 3 % to 13 % by weight relative to the total weight of the aqueous composition, preferably in the range of from 5 % to 10 % weight relative to the total weight of the aqueous composition.

[0016] In an embodiment, the phosphate ester surfactant is anionic alkoxylated polyarylphenol.

[0017] In a further embodiment, the phosphate ester surfactant is an is an amine salt of polyarylphenyl ether phosphate. In an embodiment, the amine salt of polyarylphenyl ether phosphate is present in the range of from 0.5% to 5% by weight, based on the total weight of the aqueous composition.

[0018] In an embodiment, wherein the acrylic copolymer is a modified styrene-acrylic copolymer.

[0019] In an embodiment, the modified styrene-acrylic copolymer is present in the range of from 10 % to 25 % by weight, based on the total weight of the aqueous composition, preferably in the range of from 12 % to 20 % by weight, based on the total weight of the aqueous composition.

[0020] In an embodiment, the weight ratio between the phosphate ester surfactant and the acrylic copolymer in the aqueous composition is in the range of from 1 :15 to 15:1 , preferably in the range of from 1:6 to 1:12, more preferably in the range of from 1:7 to 1:11, even more preferably in the range of from 1:8 to 1:10.

[0021] The aqueous composition may further comprise at least one formulation auxiliary selected from the group consisting of anti-freezing agents, anti-foaming agents, solvents, co-solvents, rheology / viscosity modifiers, fillers, preservatives, biocides, stabilizers, buffers and solubilizers, or any combinations thereof, wherein the at least one formulation auxiliary is present in the range of from 1 % to 15 % by weight relative to the total aqueous composition.

[0022] According to another aspect of the present invention there is provided a method of controlling insects on crops or useful plants comprising applying an effective amount of the aqueous composition comprising diafenthiuron as a first agrochemical active ingredient, flonicamid as a second agrochemical active ingredient, a phosphate ester surfactant, an acrylic copolymer, and water to insects or to the crop, or the location of the insects or the crop.

[0023] Another aspect of the invention provides a use of an aqueous composition comprising: diafenthiuron as a first insecticide, optionally flonicamid as a second insecticide, a phosphate ester surfactant, an acrylic copolymer, and water, for treatment of crops or plants against agricultural pests, including mites, aphids, thrips, and whiteflies, cotton bollworms, leafhoppers.

[0024] In another aspect of the present invention there is provided a use of a combination of an amine salt of polyarylphenyl ether phosphate and an anionic styrene-acrylic copolymer to reduce or prevent the phytotoxicity of diafenthiuron

[0025] Within the scope of this application, it is expressly intended that the various aspects, embodiments, examples and alternatives set out in the preceding paragraphs, in the claims and / or in the following description and drawings, and in particular the individual features thereof, may be taken independently or in any combination. That is, all embodiments and / or features of any embodiment can be combined in any way and / or combination, unless such features are incompatible. Terms and Definitions

[0026] The term "aqueous" denotes a composition that is water-based.

[0027] Throughout this disclosure, all parts and percentages are by weight (wt% or mass% based on the total weight) and all temperatures are in °C unless otherwise indicated.

[0028] As used herein, the term "pest" includes, but is not limited to, unwanted phytopathogenic harmful fungi, unwanted insect, unwanted nematode, and weed.

[0029] 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.

[0030] 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. Thisterm 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.

[0031] As used herein the term "ha" refers to hectare.

[0032] The term “safeners” refers to substances or preparations, which are added to a plant protection product (pesticide) to eliminate or reduce phytotoxic effects of the plant protection product (pesticide) on certain plants. In the context of the present invention, the term "safener" refers to substances that mitigate or protect crops against the negative effects, such as phytotoxicity, caused by diafenthiuron.

[0033] As used herein, the verb "comprise" as is used in this description and in the claims and its conjugations are used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. As used herein, the term "about" when used in connection with a numerical value includes ±10% from the indicated value. In addition, all ranges directed to the same component or property herein are inclusive of the endpoints, are independently combinable, and include all intermediate points and ranges. It is understood that where a parameter range is provided, all integers within that range, and tenths thereof, are also provided by the invention.DETAILED DESCRIPTION

[0034] The present disclosure relates to an aqueous composition comprising a diafenthiuron and optionally flonicamid as agrochemical active ingredients (Al) for controlling pest populations, also referred to as insecticides. While diafenthiuron is primarily an insecticide designed to control pests like aphids, whiteflies, and mites, it can indeed cause unintended harm to certain plants, such as leaf scorching or necrotic spots. This plant damage, or phytotoxicity, occurs because the chemical can interfere with plant cells or physiological processes, even though its main target is pests.Therefore, to reduce or prevent phytotoxicity caused by diafenthiuron, the aqueous composition incorporates two chemical compounds. The two chemical compounds, despite their primary function as dispersing agents, synergistically contribute to the reduction and even prevention of phytotoxicity, essentially acting as safeners, reducing the potential for plant damage and providing a balanced solution for agricultural use.

[0035] The invention thus pertains to an aqueous composition comprising at least one insecticide, wherein the at least one insecticide comprises diafenthiuron, also referred to as the first insecticide, a phosphate ester surfactant, an acrylic copolymer, and water. In addition, the aqueous composition of the present invention may further comprise an additional insecticide, namely flonicamid, hereinreferred to as the second insecticide. The insecticide, whether used alone or in combination, enhances pest control efficacy. However, when the first and second insecticides are combined, they exhibit a synergistic effect, further improving pest control at reduced doses, thereby diminishing environmental impact and reducing costs. This insecticidal formulation offers improved pest management while safeguarding crop health.

[0036] The aqueous composition(s) described in the invention are intended to control insects, mites, and ticks on crops, and is an insecticidal composition. These aqueous compositions are effective against various orders, including Lepidoptera, Coleoptera, Homoptera, Diptera, and others. Specifically, they are useful in combating sucking insects, mites, and whitefly. They have shown effectiveness against species such as Tetranychus urticae (spider mites), Aphis gossypii (aphids), and Bemisia tabaci (whitefly). These compositions can be applied directly to insects, plants, or their surrounding environment to ensure protection and control.

[0037] Crops of useful plants in which compositions and formulations of the invention may be used to control insects, and / or in which phytotoxicity may be reduced or prevented, include cotton and vegetables. Preferably said crop is a cotton crop.

[0038] The term "crops" is to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering, as well as those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt cotton (resistant to cotton boll weevil e.g. NuCOTIN33B® (cotton), Bollgard® (cotton). Any suitable method of application may be employed to effect application of compositions or formulations of the invention to crops of useful plants, insects, or the location of insects / crop plants. These include large and small spray application methods (e.g. spray application via boom bar, spray from knapsack with si ngle / tri pie nozzle etc.) with which the skilled man will be familiar.

[0039] Diafenthiuron (1-te / Y-butyl-3-[4-phenoxy-2,6-di(propan-2-yl) phenyl]thiourea), referred to as the first insecticide, is an aromatic ether that is 1, 3-diisopropyl-5-phenoxybenzene in which the hydrogen atom at position 2 is substituted by a (tert-butylcarbamothioyl) nitrilo group. An agricultural proinsecticide which is used to control mites, aphids and white fly in cotton. It has a role as an oxidative phosphorylation inhibitor and a proinsecticide. It is a thiourea acaricide, a thiourea insecticide and an aromatic ether. It derives from a diphenyl ether. Diafenthiuron comes under category of insecticide, acaricide and miticide. Diafenthiuron is an insecticide with novel mode of action of inhibiting mitochondrial ATPase and acaricidal action. Further it has a broad spectrum, contact and stomach action with some ovicidal activity, acts by inhibiting oxidative phosphorylation.

[0040] Diafenthiuron for use in the invention may be obtained as described in US4328247 or, it may be obtained as a commercial product (e.g. as POLO® 50 WP, POLO® 500SC or PEGASUS®; available from Syngenta Crop Protection AG Basel).

[0041] In an embodiment, the aqueous composition comprises diafenthiuron present in the range of from 10 % to 40 % by weight relative to the total weight of the aqueous composition, preferably of from 10 % to 30 % by weight, more preferably in the range of from 15% to 25 % by weight, most preferably in the range of from 18 % to 22 % by weight relative to the total weight of the aqueous composition.

[0042] Flonicamid (A / -(cyanomethyl)-4-(trifluoromethyl) pyridine-3-carboxamide), referred to as the second insecticide, is a pyridinecarboxamide. It is a derivative of nicotinamide that is substituted by a trifluoromethyl group at position 4 and a cyanomethyl group at the carbamoyl nitrogen atom. It has a role as a xenobiotic, an environmental contaminant and an insecticide. It is a pyridinecarboxamide, a nitrile and an organofluorine compound. It derives from a nicotinamide. Flonicamid rapidly inhibits the feeding behavior of aphids and has better action through ingestion than by contact. Its mode of action is different from other insecticides such as neonicotinoids, pymetrozine and pyri-uquinazon. Flonicamid belongs to I RAC 10 Group 29 and is the only insecticide in this class. Flonicamid also has a good toxicological, environmental and ecotoxicological profile.

[0043] In an embodiment, the aqueous composition comprises flonicamid present in an amount in the range of from 3 % to 13 % by weight relative to the total weight of the aqueous composition, preferably in the range of from 5 % to 10 % weight.

[0044] The weight ratio between diafenthiuron and flonicamid in the aqueous composition can range from 7:1 to 1:7, with a preferred range of 6:1 to 1:6, more preferably 5:1 to 1:5, even more preferably 4:1 to 1:4, and most preferably 3:1 to 1:3.

[0045] In an embodiment, the weight ratio of diafenthiuron to flonicamid in the aqueous composition according to the inventioncan be in the range of from 7:1 to 2:1 , preferably in the range of 6:1 to 2:1 , preferably in the range of from 5:1 to 2:1. In an exemplary embodiment, the weight ratio of diafenthiuron to flonicamid in the aqueous composition is 3:1.

[0046] The present invention is further based on the unexpected finding that the synergistic combination of two chemical compounds added as dispersing agents: a phosphate ester surfactant and an acrylic coploymer, generally can effectively reduce and even prevent the phytotoxicity caused by diafenthiuron. Thus, the combination of these two chemical compounds functions as a safener This synergistic effect ensures that diafenthiuron, when used together with these compounds, becomes less harmful to non-target plants, enhancing its safety profile in agricultural applications. Phytotoxicity refers to the toxic effects of a substance on plants, in this case diafenthiuron, which can result in damage to plant tissues, stunted growth, leaf discoloration, wilting, or even plant death.

[0047] The aqueous composition described in the present invention comprises a phosphate ester surfactant. The phosphate ester surfactant is formed through the phosphorylation of alkoxylated polyarylphenols, resulting in a molecule that combines a hydrophobic polyaryl core with hydrophilicphosphate and ethoxy groups, making it highly effective in a variety of industrial applications, including as a dispersant.

[0048] For example, ethoxylation of triphenyl vinyl phenol phosphate can be carried out by reacting tristyrylphenol ethoxylates with phosphorus pentoxide dissolved in phosphoric acid. The tristyrylphenol ethoxylates are synthesized by treating triphenyl vinyl phenol with an alkali (such as sodium hydroxide or potassium hydroxide), followed by the addition of the required equivalent of oxirane (ethylene oxide). Triphenyl vinyl phenol is commercially available or can be synthesized using well-established methods and conventional chemical knowledge. Additionally, mixtures of different phenols, such as triphenyl vinyl phenol and diphenylethylene phenol, can also be used as raw materials to prepare the phosphate ester surfactants in this invention.

[0049] Examples of phosphate ester surfactants are ethoxylated triphenyl phosphate, ethoxylated tetraphenyl phosphate, propoxylated triphenyl phosphate, amine salt of polyarylphenyl ether phosphate, sodium alkyl polyoxyethylene phosphate, ammonium lauryl phosphate.

[0050] Examples of suitable phosphate ester surfactants include Rhodafac RS-610, Chemphos TR-421 , Zelec UN, Stepan CPE, IGEPAL CO-660, Atrasien 500 SC, and SOPROPHOR™ surfactants from Rhodia.

[0051] In an embodiment, the phosphate ester surfactant is anionic alkoxylated polyarylphenol. For example, the anionic alkoxylated polyarylphenol can be alkoxylated polyarylphenol phosphate.

[0052] In a further embodiment, the phosphate ester surfactant is an amine salt of polyarylphenyl ether phosphate.

[0053] The amine salt of polyarylphenyl ether phosphate with the IUPAC name: Ethanol, 2,2',2"-nitrilotris-, compound with a-[2, 4, 6-tris(1 -phenylethyl) phenyl]-w-hydroxypoly(oxy-1 ,2-ethanediyl) phosphate, can have the molecular formula: C6Hi5N03.x(C2H40)nC3oH3o0.xH304P. The structural formula (Formula I) further illustrates the configuration and functional groups within the molecule.OHO P — OHIOHFormula I

[0054] The amine salt of polyarylphenyl ether phosphate is a specific type of phosphate ester salt that functions as an anionic surfactant, soluble in water. Further it may have a density in the range of 1.10 to 1.15 g / cm3at 50°C. Without wishing to be bound by a theory, this chemical compound (Formula I) may feature a large hydrophobic region (the tris(phenylethyl)phenyl group), a polyethylene glycol segment for solubility, and a phosphate group complexed with triethanolamine for stability or reactivity.

[0055] In the aqueous composition according to the invention, the phosphate ester surfactants can be present in the range of from 0.5% to 5 % by weight relative to the total weight of the aqueous composition. For example, the phosphate ester surfactant can be present in the range of from 1 % to 4 % by weight, or in the range of from 1 % to 3 % by weight relative to the total weight of the aqueous composition, or in the range of from 1.5 wt % and 3 wt %, based on the total weight of the aqueous composition.

[0056] In an embodiment, the amine salt of polyarylphenyl ether phosphate is present in the range of from 0.5% to 5 % by weight relative to the total weight of the aqueous composition, andpreferably in the range of from 1 wt% to 4 wt %, more preferably in the range of from 1 wt % to 3 wt % by weight, based on the total weight of the aqueous composition, most preferably between 1.5 wt % and 3 wt %, based on the total weight of the aqueous composition.

[0057] The aqueous composition comprises at least one acrylic copolymer. Non-limiting examples of suitable acrylic copolymers that can be used, but are not limited to, are those sold under the brand names Hycar 26447 (Lubrizol), Joncryl 77 (BASF)(ammonium salt of modified styrene acrylic polymers), PRIMAL™ AC-261 (Acrylic Emulsion (Dow), TEXICRYL 17-0422( acrylic copolymer). . Further, Neocryl acrylic copolymers sold by Covestro can be advantageous as they act both as dispersing agents and binders. For example, NeoCryl A-2099 (a modified acrylic-styrene copolymer emulsion), NeoCryl A-1120 (modified acrylic-styrene copolymer dispersion), Neocryl A-1090 (an acrylic copolymer), Neocryl BT-9 (styrene-acrylic copolymer emulsion ), Neocryl-BT62 ( a modified styrene-acrylic copolymer, specifically a semi-colloidal modified styrene acrylic copolymer dispersion (40% in water)), Neocryl A-615 (an acrylic copolymer emulsion consisting of 36% acrylic copolymer, 55.2% water, and 8.8% ethyl diglycol), .

[0058] The weight ratio between the amine salt of polyarylphenyl ether phosphate and the modified styrene-acrylic copolymer in the aqueous composition can be in the range between 1:15 and 15:1 , For example the weight ratio between the amine salt of polyarylphenyl ether phosphate and the modified styrene-acrylic copolymer can be in the range between 1:14 and 14:1, or between 1:13 and 13:1, or between 1:12 and 12:1, or between 1:11 and 11:1. The weight ratio between the amine salt of polyarylphenyl ether phosphate and the modified styrene-acrylic copolymer can be 1:4, or 1:5, or 1:6, or 1:7, or 1:8 , or 1:9 , or 1:11, or 1:12.

[0059] In an embodiment, the weight ratio between the phosphate ester surfactant and the acrylic copolymer is in the range of from 1:6 to 1:12, preferably in the range of from 1:7 to 1:11, more preferably in the range of from 1:8 to 1:10.

[0060] In an exemplary embodiment, the weight ratio between the amine salt of polyarylphenyl ether phosphate and the modified styrene-acrylic copolymer in the aqueous composition is 1 :9.

[0061] In the aqueous composition according to the invention, the acrylic copolymer can be present in the range of from 10 wt % to 25 wt% relative to the total weight of the composition. For example, the acrylic copolymer is present in the range of from 12 % to 22 % by weight, based on the total weight of the aqueous composition, and more preferably of from 13 wt % to 20 wt %, based on the total weight of the composition, even more preferably in the range of from 15 wt % to 20 wt %, based on the total weight of the composition,.

[0062] In an embodiment, the acrylic copolymer in the aqueous composition is a modified (anionic) styrene-acrylic copolymer, where the modified styrene-acrylic copolymer is present in the range of from 10 % to 25 % by weight relative to the total weight of the composition, preferably in the range of from 12 % to 22 % by weight and more preferably of from 15 wt % to 20 wt %, based on the total weight of the composition. If the amount of the modified styrene-acrylic copolymerexceeds 25 wt%, it forms a film that can clog the spray nozzles. Conversely, if the amount is below 10 wt%, its effect on reducing phytotoxicity becomes insufficient.

[0063] The synergistic effect of the phosphate ester surfactant and the acrylic copolymer, specifically when the phosphate ester surfactant is an amine salt of polyarylphenyl ether phosphate and the acrylic copolymer is a modified styrene-acrylic copolymer, leads to a reduction, and in some cases prevention, of phytotoxicity, wherein the phytotoxicity is caused by application of diafenthiuron to the crops of useful plants. Without wishing to be bound by theory, this effect could be attributed to the enhanced uniform distribution of the agrochemical active ingredients across the plant surface due to their dispersing action. In addition, it is believed that one or both chemical compounds also may form a protective film on the plant surfaces.

[0064] In an aspect of the present invention, there is provided a use of a combination of an amine salt of polyarylphenyl ether phosphate and an anionic styrene-acrylic copolymer to reduce or prevent the phytotoxicity of diafenthiuron. In an embodiment, the combination of an amine salt of polyarylphenyl ether phosphate and an anionic styrene-acrylic copolymer are formulated with diafenthiuron into an aqueous composition.

[0065] In one embodiment, diafenthiuron and flonicamid are formulated with at least one formulation auxiliary, and subsequently combined with the mixture of amine salt of polyarylphenyl ether phosphate and anionic styrene-acrylic copolymer (which may be formulated, or as obtained from synthesis) prior to spraying.

[0066] In an embodiment, the aqueous composition comprises diafenthiuron as a first agrochemical active ingredient, flonicamid as a second agrochemical active ingredient, a phosphate ester surfactant, wherein the phosphate ester surfactant is an amine salt of polyarylphenyl ether phosphate and an acrylic copolymer, wherein the acrylic copolymer is modified styrene-acrylic copolymer, formulation auxiliary’s and water.

[0067] In a further exemplary embodiment, the aqueous composition comprises diafenthiuron as a first insecticide present in amount ranging of from 10 % to 40 % by weight relative to the total weight of the aqueous composition, flonicamid as a second insecticide present in amount ranging of from 3 % to 13 % by weight relative to the total weight of the aqueous composition, a phosphate ester surfactant, wherein the phosphate ester surfactant is an amine salt of polyarylphenyl ether phosphate present in amount ranging of from 0.5 % to 5% by weight relative to the total weight of the aqueous composition and an acrylic copolymer, wherein the acrylic copolymer is modified styrene-acrylic copolymer present in amount ranging of from 10 % to 25 % by weight relative to the total weight of the aqueous composition, and the rest water.

[0068] Each component of the aqueous composition of the invention may be used in unmodified form, i.e. as obtainable from synthesis. However, each may be formulated (either separately or together) in any suitable manner using standard formulation auxiliaries, such as carriers, solvents and surface-active substances, for example, as described hereinafter. Such formulations can be inthe form of concentrates which are diluted prior to use, although ready-to-use formulations can also be made. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.

[0069] In certain embodiments, diafenthiuron is formulated as a suspension concentrate, and the phosphate ester surfactant and the acrylic copolymer will be in unmodified form or formulated as a liquid.

[0070] In further embodiments, diafenthiuron, flonicamid and standard formulation auxiliary is formulated as a suspension concentrate.

[0071] The total mass fraction of diafenthiuron and flonicamid in the composition can be in the range between 5 wt % and 80 wt%, or in the range between 10 wt % and 50 wt %, or in the range between 20 % and 40 %, based on the total weight of the composition.

[0072] In an embodiment, the aqueous composition is formulated as a suspension concentrate (formulation) that comprises diafenthiuron present in amount ranging of from 10 wt % to 40 wt %, preferably in the range of 10 wt % to 25 wt %; optionally flonicamid present in amount ranging of from 3 % to 13%, preferably in the range of 5 wt % to 10 wt %; an phosphate ester surfactant in an amount in the range of from 0.5 wt% to 5 wt% , preferably of 1 wt% to 4 wt%, more preferably of 1 wt % to 3 wt%, most preferably of 1.5 wt% to 3 wt%; a modified styrene-acrylic copolymer in an amount in the range of 10 wt% to 25 wt%, preferably in the range of from 12 wt% to 22 wt%; more preferably of from 13 wt% to 20 wt%, even more preferably 15 wt% to 20, wt%; one or more other formulation auxiliaries in an amount of 1 wt % to 15 wt%; and the remainder being water.

[0073] In a preferred embodiment, the aqueous composition is formulated as a suspension concentrate (formulation) that comprises diafenthiuron present in amount ranging of from 10 wt % to 40 wt %, preferably in the range of 10 wt % to 25 wt %; flonicamid present in amount ranging of from 3 % to 13%, preferably in the range of 5 wt % to 10 wt %; an amine salt of polyarylphenyl ether phosphate in an amount in the range of from 0.5 wt% to 5 wt% , preferably of 1 wt% to 4 wt%, more preferably of 1 wt % to 3 wt%, most preferably of 1.5 wt% to 3 wt%; a modified styrene-acrylic copolymer in an amount in the range of 10 wt% to 25 wt%, preferably in the range of from 12 wt% to 22 wt%; more preferably of from 13 wt% to 20 wt%, even more preferably 15 wt% to 20, wt%; one or more other formulation auxiliaries in an amount of 1 wt % to 15 wt%; and the remainder being water.

[0074] In an embodiment, the weight ratio between diafenthiuron and flonicamid in the aqueous composition is 5:1 , preferably 3:1.

[0075] The aqueous composition may also comprise various formulation auxiliaries. At least one formulation auxiliarycan be selected from the group consisting of anti-freezing agents, anti-foaming agents, solvents, co-solvents, rheology / viscosity modifiers, fillers, preservatives, bactericides, stabilizers, buffers and solubilizers, or any combinations thereof.

[0076] Formulation auxiliaries that are suitable for the preparation of formulations according to the invention are known per se. As liquid carriers there may be used: water, ethylene glycol, ethylene glycol, propylene glycol, glycerol. Water is generally the carrier of choice for diluting the concentrates. Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, A large number of surface-active substances may advantageously be used in the formulations, especially in those formulations designed to be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.

[0077] In an embodiment, the at least one formulation auxiliary is present in the range of from 1 % to 15 % by weight, the at least one formulation auxiliary is present in the range of from 1 % to 15 % by weight, based on the total weight of the composition, preferably of from 1 wt % to 10 wt %, based on the total weight of the composition.

[0078] The aqueous composition further may comprise at least one wetting agent, wherein the at least one wetting agent is selected from the group consisting of alcohol ethoxylate, organo-modified trisiloxanes or a combination thereof. Non-limiting examples for alcohol ethoxylate are Rhodasurf series by Solvay: Rhodasurf LA 7, Rhodasurf DA 630, Rhodasurf AE 12. Other common alcohol ethoxylates are Genapol C 100, Synperonic 91 / 5, Synperonic A7, Neodol 25-7.

[0079] The aqueous composition of the present invention may comprise at least one rheology modifying agent, for example a viscosity modifier such as a thickener. Examples of suitable thickeners are Rhodopol 23, Bentopharm, Attagel.

[0080] In an embodiment, the thickener is xanthan gum. The amount of the at least one thickener present in the aqueous composition can be in the range between 0.05 wt % and 0.5 wt %, preferably between 0.08 wt % and 0.3 wt % relative to the total weight of the aqueous composition.

[0081] Anti-foaming agents can be added in the aqueous composition, such as silicon -based formulation auxiliaries. An example of a suitable anti-foaming agent used in the composition according to the invention is Xiameter ACP-1000, Xiameter ACP-1500, Sicolapse 454, SAG 100.

[0082] In an embodiment, the anti-foaming agent is a silicon-based defoamer such as polydimethylsiloxane. In a further embodiment, the anti-foaming agent is present in the range of from 0.1 wt % to 0.4 wt %, based on the total weight of the composition.

[0083] The aqueous composition may further comprise one or more bactericides (preservatives). Non-limiting examples of a suitable bactericides (preservative) used in the composition according to the invention are Acticide L, Acticide LG, Acticide M10s, Acticide MV, Acticide BW 33, Acticide BW 20, Acticide MBS, Proxel GXL, Bronopol, Koralone, Kathon.

[0084] In an embodiment, at least one bactericide is selected from 1 ,2-benzisothiazolin-3-one, a 20% aqueous dipropylene glycol solution of 1 ,2-benzisothiazolin-3-one, 2-bromo-2-nitro-1 ,3-propanediol, or a combination thereof. The amount of the at least one bactericide present in theaqueous composition can be in the range between 0.01 wt % and 0.5 wt %, or between 0.02 wt % and 0.4 wt %, relative to the total weight of the aqueous composition.

[0085] At least one buffer may also be added to the aqueous composition of the present invention. Examples of suitable buffers include acids such as sulfuric acid, phosphoric acid, citric acid, hydrochloric acid. The amount of the buffer present in the aqueous composition can be in the range between 0 wt % and 1 wt %, preferably between 0.05 wt % and 0.5 wt %, more preferably between 0.05 wt % and 0.2 wt % relative to the total weight of the aqueous composition. In an embodiment, the buffer is an inorganic acid, such as sulfuric or hydrochloric acid.

[0086] The aqueous composition may further comprise an antifreeze (anti-freezing agent) to reduce the freezing point of the mixture, such as 1 ,2-propylene glycol, glycerol, ethylene glycol, diethylene glycol. In an embodiment, the anti-freezing agent is 1 ,2-propylene glycol. The amount of the antifreeze (anti-freezing agent) present in the aqueous composition can be in the range between 3 wt % and 10 wt %, preferably between 3 wt % and 6 wt %, more preferably between 0.05 wt % and 0.2 wt % relative to the total weight of the aqueous composition.

[0087] In an exemplary embodiment, the aqueous composition comprises diafenthiuron present in amount ranging of from 10 % to 40 %, flonicamid present in amount ranging of from 3 % to 13 % by weight , an amine salt of polyarylphenyl ether phosphate present in amount ranging of from 0.5 % to 5% by weight, modified styrene-acrylic copolymer present in amount ranging of from 10 % to 25 % by weight, and the remainder being water, based on the total weight of the composition.

[0088] In an embodiment, the aqueous composition comprises diafenthiuron present in amount ranging of from 10 % to 30 %, flonicamid present in amount ranging of from 5 % to 10 % by weight , an amine salt of polyarylphenyl ether phosphate present in amount ranging of from 1 % to 4 % by weight, modified styrene-acrylic copolymer present in amount ranging of from 15 % to 20 % by weight, at least one formulation auxiliary present in the range of from 1 % to 15 % by weight, and the remainder being water, based on the total weight of the composition.

[0089] In a further embodiment, the aqueous composition comprises diafenthiuron present in amount ranging of from 10 % to 40 %, flonicamid present in amount ranging of from 3 % to 13 % by weight , an amine salt of polyarylphenyl ether phosphate present in amount ranging of from 0.5 % to 5% by weight, modified styrene-acrylic copolymer present in the range of from 10 % to 25 % by weighty ,2-propylene glycol present in the range of from 3 wt % to 8 wt %, thickener present in the range of from 0.05 wt % to 0.3 wt %, one or more biocides present in the range of from 0.02 wt % to 0.3 wt %, polydimethylsiloxane 0.1 wt % to 0.4 wt %, inorganic acid in the range of from 0 wt % to 0.3 wt % and the rest water, based on the total weight of the composition.

[0090] In a further embodiment, the aqueous composition comprises diafenthiuron present in amount ranging of from 10 wt % to 40 wt %, flonicamid present in amount ranging of from 3 wt % to 13 wt %, an amine salt of polyarylphenyl ether phosphate present in amount ranging of from 0.5 % to 5% by weight, 1 ,2-propylene glycol present in amount ranging of from 3 wt % to 8 wt %,thickener present in the range of from 0.05 wt % to 0.3 wt %, one or more biocides present in the range of from 0.02 wt % to 0.3 wt %, polydimethylsiloxane present in the range of from 0.1 wt % to 0.4 wt %, , sulfuric acid of from 0 wt % to 0.3 wt %, at least one alcohol ethoxylate present in amount of from 1 wt % to 10 wt % and the rest water, based on the total weight of the composition.

[0091] The aqueous composition of the present invention is used for treatment of crops or plants against agricultural pests, including mites, aphids, thrips, and whiteflies, cotton bollworms, leafhoppers.

[0092] In yet another aspect, the invention provides a method of reducing or preventing phytotoxicity in crops of useful plants, wherein the phytotoxicity is caused by application of diafenthiuron to the crops of useful plants, the method comprising applying an aqueous composition by spraying an effective amount of the aqueous composition onto the target insects, the crops, or the surrounding area where the insects or crops are located. The composition is designed to control or repel insects, providing protection for the crops or useful plants. The phytotoxic effect on plants may be assessed visually as a function of the percentage of reddening of the leaves and / or the appearance of necrosis.

[0093] Various aspects and embodiments of the present invention will now be illustrated in more detail by way of example. It will be appreciated that modification of detail may be made without departing from the scope of the invention. For the avoidance of doubt, literary reference, patent application, or patent, is cited within the text of this application, the entire text of said citation is herein incorporated by referenceEXAMPLES

[0094] As will be appreciated by those skilled in the art, the following examples are representative of the present invention. All compositions herein described may be further optimized, as all such further development should be considered within the scope of the present invention.

[0095] The aqueous composition was prepared through the separate preparation of diafenthiuron and flonicamid millbases (concentrated mixture of raw materials) using an attritor milling process.

[0096] Example 1

[0097] Method of preparation of diafenthiuron millbase

[0098] A diafenthiuron millbase composition was prepared comprising the following ingredients based on the total aqueous composition, where each individual material was charged in this order: 55 wt % of diafenthiuron as an active ingredient (insecticide), followed by addition of 5.5 wt % 1 ,2-propylene glycol, 0.27 wt % silicon-based anti-foaming agent, 2.20 wt % of amine salt of polyarylphenyl ether phosphate as a dispersing agent, 0.07 wt % biocideand the rest water based on the total weight of the aqueous composition.. Once all components were added, the obtained premix was homogenized using a Silverson mixer. The homogenized premix was then milled to the required particle size (D50 ~5 pm) using an attritor.

[0099] Example 2

[0100] Method of preparation of flonicamid millbase

[0101] A flonicamid millbase composition was prepared using ordinary techniques, such as intimately mixing all components with water, where each individual component was charged in this order: 48 wt % of flonicamid as an active ingredient (insecticide) , 6.6 wt% of 1 ,2-propylene glycol, 0.10 wt % silicon-based anti-foaming agent, 3.8 wt % of amine salt of polyarylphenyl ether phosphate, 0.07 wt % biocide and the rest water, based on the total weight of the aqueous composition. Once all components were added, the obtained premix was homogenized using a Silverson mixer. The homogenized premix was then milled to the required particle size (D50 ~5 pm) using an attritor.

[0102] Example s

[0103] The final aqueous composition was prepared by mixing the diafenthiuron millbase, as prepared in Example 1, with the flonicamid millbase, as prepared in Example 2. Additionally, other formulation auxiliaries were incorporated to the final formulation, as shown in Table 1.

[0104] Table 1 presents examples of different aqueous compositions Examples A-F.

[0105] Examples A and B represent an aqueous composition according to the invention comprising diafenthiuron and flonicamid as active ingredients or insecticides, and the synergistic combination of amine salt of polyarylphenyl ether phosphate and modified styrene-acrylic copolymer, showing 0% phytotoxicity at both 250 L / ha and 500 L / ha application rates. Although Examples C to F demonstrate a reduction in phytotoxicity to certain levels, they do not completely eliminate phytotoxicity, as presented in Table 2. Example C is a comparative example demonstrating the aqueous composition without the inclusion of the modified styrene-acrylic copolymer. As a result, the phytotoxicity of the aqueous composition in Example C was reduced to 4% when applied at a rate of 250 L / ha.

[0106] Table 1Component Ex. A Ex. B Ex. C Ex. D Ex.E Ex. F1 diafenthiuron 22.50 21.39 22.50 22.50 22.50 22.502 flonicamid 7.50 7.13 7.50 7.50 7.50 7.50amine salt ofpolyarylphenyl ether3 phosphate (anionic 2 1.90 2 3.70 3.70 3.70 tristyrylphenolphosphate)modified styrene- 4 18 17.11 0 0 0 0 acrylic copolymer5 1 ,2-propylene glycol 5 4.76 5 5 5 56 biocide(s) 0.23 0.22 0.23 0.12 0.13 0.217 thickener 0.2 0.2 0.2 0.1 0.1 0.28 inorganic acid buffer 0.1 0 0.1 0.1 0.1 0.111 anti-foaming agent 0.29 0.28 0.29 0.29 0.29 0.2912 alcohol ethoxylate 0 0 0 5 5 0alcohol ethoxylate (CO13 0 0 0 0 0 3 CH)organomodified14 0 0 0 3 0 0 trisiloxanes15 water Rest Rest Rest Rest Rest Rest0107] Table 2 presents the phytotoxicity data for various Examples A-F from Table 1.

[0108] Table 2Ex.Phytotoxicity Ex .A Ex. B Ex. C Ex. E Ex. F Dwater volume= 500 l / ha 0 % 0% 1.5 % 0 % 0.5 % 0.5 %water volume =250 l / ha 0 % 0% 4 % 3 % 3 % 3 %

[0109] Table 3 presents the particle size distribution (dvso and dvgo, pm) of the aqueous composition which is linked to the crystal growth, dvso (Median Particle Size) represents the particlediameter at which 50% of the sample's total volume consists of particles smaller than this size, dvgo (90th Percentile Particle Size) represents the particle diameter at which 90% of the sample’s total volume consists of particles smaller than this size. As crystals form and grow in an aqueous composition, they can influence the overall particle size distribution. If crystal growth is not well-controlled, larger crystals will develop, leading to higher dv50 and dv90 values. Crystal growth can block the nozzles of the applicator spray, affecting the uniform distribution of the product and potentially reducing its effectiveness. Table 3 shows insignificant crystal growth across Examples A-F from Table 1.

[0110] Table 3Particle size Ex. A Ex. B Ex. C Ex. D Ex. E Ex. Fdv50, pm 4.24 4.24 4.01 6.39 6.29 6.14dv90, pm 15.7 15.7 16.9 15.7 18.8 15.6

[0111] Example 4

[0112] Measuring phytotoxicity (field trial methodology)

[0113] Symptoms of phytotoxic reactions are chlorosis (appears as spots or as tip, margin or leaf yellowing), leaf distortion (appears as curling, crinkling or cupping of the leaf), stunting (the entire plant is reduced in size or certain parts (fruit, flowers, roots) are smaller while the rest of the plant appears normal), abnormal growth (excessive growth on either certain parts (aerial roots, suckering) or the entire plant.

[0114] Cotton was used as the crop in this trial. The seeds were sown in a fertile field and cultivated using standard agronomic practices. When the cotton plants reached 45-60 days of age, they were used in field trials to assess the phytotoxicity (crop safety) of the test products (aqueous compositions of Ex. A and Ex. B, Table 1).

[0115] Trial design includes:

[0116] Randomized Complete Block Design (RCBD) with 2 to 3 replications, depending on the quantity of test product available.

[0117] Plot Size: Each treatment plot measures 30 to 40 square meters, with 30 to 40 plants per plot.

[0118] Number of Treatments: 10 to 20 treatments.

[0119] Number of Replications: 2 to 3 replications per treatment.

[0120] The trial evaluated a range of products, including various formulations (Ex. A-F, Table 1).

[0121] When the cotton crop was around 45-60 days old, the field trials were conducted to test the crop safety of Ex. A-F formulations under typical cotton growing conditions.

[0122] All the test products were applied as foliar spray on cotton plants using a Knapsack sprayer with a water volume of 500 l / ha and 250 l / ha according to PP1 / 135 standard for phytotoxicity assessment for field trials coinciding with pest occurrence window. Two applications of test products were given at 10 days interval as per normal recommendations in the field. Different application rates of the products were tested to compare their effectiveness and safety against the recommended application rate of diafenthiuron at 180 g a.i. / ha and flonicamid at 60 g a.i. / ha (total 240 g.ai / ha).

[0123] Assessment:

[0124] Observations on phytotoxicity (crop safety) were recorded visually on absolute per cent criteria on whole plot basis, cumulating all type of symptoms like reddening, necrosis, scorching, modification in colour. This is according to EPPO Standards (Efficacy evaluation of plant protection products, especially of herbicides and plant growth regulators) of PP1 / 135 (phytotoxicity assessment). Phytotoxicity result from visual estimates of the intensity, for example, of deformation or discoloration. In this case, the effect is often scored by reference to a scale preferably 0 % to 100%, as shown in Table 4. The degree of phytotoxicity was assessed as a function of the percentage of reddening or necrosis of the cotton leaves in comparison to untreated cotton (control data). Necrosis is the local death of tissues or organs, generally appearing first as a discoloration.

[0125] The observations / assessment were recorded at 3,7 & 10 days after each application (2 applications at 10 days interval), as shown in Table 4. Ex. A exhibits zero phytotoxicity on crops even at a volume of 250 L / ha, confirming its safety for use on crops.

[0126] DA1 refers to the assessment of phytotoxicity following the first application, while DA2 refers to the assessment of phytotoxicity after the second application.

[0127] 3DA1 refers to the assessment of phytotoxicity 3 days after the first application, 7DA1 refers to the assessment 7 days after the first application, and 10DA1 refers to the assessment 10 days after the first application. 3DA2 refers to the assessment of phytotoxicity 3 days after the second application, 7DA2 refers to the assessment 7 days after the second application, and 10DA2 refers to the assessment 10 days after the second application.

[0128] Table 4Dos Prod Wat % Phytotoxicity e uct erTr. Prod rate dose voluNo. uct (g.ai rate me 3DA 7 DA 10 3 7 DA 10 / ha) (ml / (L / h 1 1 DA1 DA2 2 DA2 ha) a)Ex.1 240 800 500 0 0 0 0 0 0 AEx.2 240 800 250 0 0 0 0 0 0 AEx.3 240 800 500 0 1 1 2 2 2 CEx.4 240 800 250 0 4 4 5 5 5 CEx.5 240 800 500 0 0 0 0 0 0 DEx.6 240 800 250 0 3 3 4 4 4 DEx.7 240 800 500 0 0 0 0.25 0.25 0.25 EEx.8 240 800 250 0 2 2 2 2 2 EEx.9 240 800 500 0 0 0 0.25 0.25 0.25 FEx.10 240 800 250 0 2 2 3 3 3FIt will be appreciated that various changes and modifications can be made to the present invention without departing from the scope of the present application.

Claims

CLAIMS1. An aqueous composition comprising:diafenthiuron as a first insecticide,a phosphate ester surfactant,an acrylic copolymer,and water.

2. The aqueous composition according to claim 1 , further comprising a second insecticide, wherein the second insecticide is flonicamid.

3. The aqueous composition according to any of claims 1or 2, wherein the phosphate ester surfactant is an amine salt of polyarylphenyl ether phosphate.

4. The aqueous composition according to any of the preceding claims, wherein the acrylic copolymer is a modified styrene-acrylic copolymer.

5. The aqueous composition according to claim 4, wherein the modified styrene-acrylic copolymer is present in the range of from 10 % to 25 % by weight, based on the total weight of the aqueous composition, preferably in the range of from 12 % to 20 % by weight, based on the total weight of the aqueous composition.

6. The aqueous composition according to any of the preceding claims, wherein the weight ratio of diafenthiuron to flonicamid is in the range of from 7:1 to 1:7, preferably in the range of from 6:1 to 1:6, more preferably 5:1 to 1:5, even more preferably in the range of from 5:1 to 2:1.

7. The aqueous composition according to any of the preceding claims, wherein the weight ratio between the phosphate ester surfactant and the acrylic copolymer is in the range of from 1:15 to 15:1, preferably in the range of from 1:6 to 1:12.

8. The aqueous composition of any of the preceding claims, wherein diafenthiuron is present in the range of from 10 % to 40 % by weight, based on the total weight of the aqueous composition, preferably in the range of from 15% to 25 % by weight, based on the total weight of the aqueous composition.

9. The aqueous composition according to any one of claims 2 to 7, wherein flonicamid is present in the range of from 3 % to 13 % by weight, based on the total weight of the aqueous composition, preferably in the range of from 5 % to 10 % weight, based on the total weight of the aqueous composition.

10. The aqueous composition according to any one of claims 4to 9, wherein the amine salt of polyarylphenyl ether phosphate is present in the range of from 0.5% to 5% by weight, based on the total weight of the aqueous composition, preferably present in the range of from 1 % to 4 % by weight, based on the total weight of the aqueous composition.

11. The aqueous composition according to any of the preceding claims, further comprising at least one formulation auxiliary selected from the group consisting of anti-freezing agents, anti-foamingagents, solvents, co-solvents, rheology / viscosity modifiers, fillers, preservatives, bactericides, stabilizers, buffers and solubilizers, or a combination thereof12. The aqueous composition according to claim 11, wherein the at least one formulation auxiliary is present in the range of from 1 % to 15 % by weight of the total aqueous composition.

13. Use of an aqueous composition defined in any one of claims 1 to 12, for treatment of crops or plants against agricultural pests, including mites, aphids, thrips, and whiteflies, cotton bollworms, leafhoppers.

14. Use of a combination of an amine salt of polyarylphenyl ether phosphate and anionic styrene-acrylic copolymer to reduce or prevent the phytotoxicity of diafenthiuron.

15. A method of controlling insects on crops or useful plants comprising applying an effective amount of an aqueous composition defined in any one of any one of claims 1 to 15 to insects or to the crop, or the location of the insects or the crop.

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