composition

Abstract

The invention relates to an aqueous composition comprising (A) a compound of formula:; (B) a compound of formula:; (C) a metal lignosulfate salt; (D) a bis(2-ethylhexyl) sulfosuccinate metal salt; and (E) water.

Description

[0001] 83092-FF

[0002] COMPOSITION

[0003] The present invention relates to compositions for use in agricultural and non-agricultural pest control applications, such as control of insects.

[0004] There is an abundance of insect pest species that can infect or infest a wide variety of environments and host organisms, posing a serious threat to number of commercially important crops, in particular cereal crops such as rice. Planthoppers, including Nilaparvata lugens (brown planthopper; BPH), Laodelphax striatellus (small brown planthopper) and Sogatella furcifera (white-backed planthopper) are particularly major pests of rice in many parts of Asia. Feeding by hopper nymphs and adults at the base of the plant causes rapid wilting and chlorosis of the plant, which eventually leads to a drying of the plant, also described as "hopper- burn". Adult hoppers also lay their eggs in the midribs of the leaf sheath, blocking the xylem and phloem and thus preventing water and nutrient transportation. Planthoppers have also been shown to be vectors of plant viruses, for example brown planthoppers transmit the economically damaging plant viruses: rice grassy stunt tenuivirus and rice ragged stunt oryzavirus, whilst Laodelphax striatellus is implicated in the transmission of rice stripe virus.

[0005] Various insecticides have been employed over the years for planthopper control. However, this has resulted in the development of resistance in planthopper species to many classes of insecticides, such as to pyrethroid, organophosphate, organochlorine, carbamate, buprofezin, and more recently, neonicotinoids.

[0006] Hence, the emergence of cross- and / or multiply-resistant insects presents a major threat to the cultivation of rice and other crops that are host to planthoppers and leafhoppers. Accordingly, the use of combinations of insecticides with different modes of action is being contemplated.

[0007] In addition, there is a strong emergence of precision agriculture and smart farming. In order to accomplish the tasks of precision crop health management, the use of drones is gaining popularity, in particular for pesticide delivery to cereals, and in particular rice paddies, since rice is cultivated in larger areas in contiguous blocks where drone application is feasible. This however requires adaptation and optimisation of pesticidal compositions for drone-based spraying, such as concentrations, droplet size, spread, density, uniformity, deposition, and penetrability, which requires in particular water borne emulsions and dispersions with relatively high concentrations of active ingredients.

[0008] Accordingly, there is a need to prepare storage stable and readily dispersible aqueous suspensions comprising at least two active ingredients with complementary modes of action, suitable for use with drones, which can effectively control planthoppers and leafhopper infections. Furthermore, there is a need to provide such compositions that can be thinned with water without phase separation or coagulation, and retain the biological activity over a suitably long period. 83092-FF

[0009] It has now been surprisingly and unexpectedly discovered that storage stable and readily dispersible aqueous suspensions may be prepared comprising triflumezopyrim and pymetrozine.

[0010] Both triflumezopyrim and pymetrozine have stability problems relating to the properties of the active ingredients and attempts to formulate liquid compositions containing these active ingredients have thus far encountered issues with physical stability and viscosity.

[0011] There has therefore been the problem of how to prepare a commercially viable, liquid, stable, efficacious, applicable formulation combining these active ingredients in order to treat the full spectrum of pests and manage resistance. These technical problems are addressed by the present invention.

[0012] Thus, in a first aspect, the present invention relates to an aqueous composition comprising: (A) a compound of formula:

[0013] (C) a metal lignosulfate salt;

[0014] (D) a bis(2-ethylhexyl) sulfosuccinate metal salt; and

[0015] (E) water.

[0016] The present invention relates to the compositions comprising such compounds for combating invertebrate pests, as well as their uses. .

[0017] The present invention also provides a method of controlling or preventing infestation of a plant by an insect of the order Hemiptera, Lepidoptera or Coleoptera, which comprises applying, on the plant, the locus thereof or its propagation material, a composition comprising as component (A), a compound of formula: 83092-FF and, as component (B), a compound of formula:

[0018] A reference to compounds of formula (A) and formula (B) also includes agrochemically acceptable ionic forms, salts, solvates, isomers, including geometric and stereochemical isomers, tautomers, N- oxides, esters, prodrugs, isotopes and protected forms thereof.

[0019] Preferably, a reference to compounds of formula (A) and formula (B) also includes the salts, polymorphs or tautomers or isomers or N-oxides or solvates such as hydrates or anhydrides thereof; and more preferably, the salts or tautomers or N-oxides or solvates thereof, even more preferably the salts or tautomers or solvates thereof, as well as any polymorphs, and mixtures thereof. Optionally, the compositions of the present invention further comprise one or more auxiliaries and / or diluents.

[0020] In another aspect, the present invention relates to the use of the compositions of the invention for the control of invertebrate pest on plants.

[0021] In another aspect, the present invention relates to a method for the preparation of the compositions according to the invention.

[0022] Among insecticides that to date effectively can control planthopper infections, pymetrozine and triflumezopyrim each have independently shown significant effect when employed separately against brown planthoppers. However, compositions comprising a single active ingredient may result in emergence of cross- and / or multiply-resistant pest populations. Without wishing to be bound to any particular theory, it is considered that issues have been found in formulating active ingredients into water borne suspensions . This is further enhanced if a second active ingredient is added, resulting in an unpredictability and complex nature of such mixtures, with potential chemical and physical incompatibilities. Hence such mixtures, even if not reacting chemically, may form agglomerates due to, e.g., coagulation, flocculation, gelling, or precipitation of crystals. This presents difficulties since the malfunctioning mixture may plug spray filters and nozzles, resulting in inaccurate spray volumes. This is in particular cumbersome where drone application is envisaged. 83092-FF

[0023] Triflumezopyrim, having IUPAC name 4-oxo-l-(pyrimidin-5-ylmethyl)-3-[3- (trifluoromethyl)phenyl]pyrido[l,2-a]pyrimidin-l-ium-2-olate, and CAS number 1263133-33- 0, has been described in US9474277B2, and which belongs to the calls of mesoionic insecticides, and has shown high efficiency at a low dosage for the control of various hopper species.

[0024] The structure of triflumezopyrim is depicted as formula (A) and the terms will be used interchangeably herein:

[0025] The structure of pymetrozine is depicted as formula (B) and the terms will be used interchangeably herein:

[0026] Pymetrozine is an azomethine insecticide commonly used in integrated crop management to control aphids, whiteflies and other pests. It is readily taken up by leaves and roots and translocated throughout the plant. Plants are immediately protected upon application because insect feeding stops soon after ingestion of pymetrozine. Pymetrozine exists as an anhydrate and as a dihydrate form. There is a known polymorph conversion from the anhydrate to dihydrate in aqueous formulations. Therefore, conventional formulations of pymetrozine reported thus far are so-called "wettable powders," or "wettable granules" in which the pymetrozine is provided in a finely ground state combined with wetting agents and sometimes bulking agents. For application to plants, the wettable powder is dispersed in a large quantity of water and sprayed over a field. While wettable powders can be advantageous in that the pymetrozine can be provided in concentrated form and thus the weight and volume of a dilute pymetrozine suspension need not be managed until the point of use. However, wettable powders have a serious disadvantage: they can be rather dusty, and can create dust pollution and an acute inhalation hazard to operators. Hence, these are not considered useful for drone, or generally, foliar applications.

[0027] It has surprisingly been found in the present invention that pymetrozine polymorph conversion to the dihydrate polymorph is complete and thus the danger of crystal growth is mitigated in the compositions described herein. 83092-FF

[0028] Component (A) is preferably present in an amount of from 0.5 to 8% by weight, such as from 0.6 to 7% by weight, from 0.8 to 6% by weight, from 0.9 to 5% by weight, from 1.2 to 4% by weight, or from 1.4 to 3% by weight.

[0029] Component (B) is preferably present in amount of from 3 to 20% by weight, such as from 4 to 19% by weight, from 5 to 18% by weight, from 6 to 17% by weight, from 8 to 16% by weight, or from 9 to 14% by weight.

[0030] Advantageously, compounds (A) and (B) are in the form of solid particles.

[0031] Preferably the compositions are in the form of suspension concentrate (SC) formulations.

[0032] The suspension concentrate formulations preferably have a high concentration of active ingredient, have good storage stability, and are easy to use and transport. In particular, because these concentrates are typically diluted with water at the time of use, they must be readily dispersed in water, and have good dispersion stability in the diluted state.

[0033] Physical stability of suspension concentrates, both during storage and during use, is of particular concern with these formulations having a solid particulate phase and a continuous liquid phase.

[0034] Suspension concentrates are inherently unstable in gravitational fields because of difference in density between the solid pesticide and the liquid carrier, which can result in separation of the formulation over time into a pesticide-rich layer and a carrier-rich layer. In extreme cases, phase separation occurs, wherein the solid particulate pesticide, typically the denser phase, settles at the bottom of the liquid phase.

[0035] It is therefore generally necessary to include one or more suspension aid(s) in the formulation to assist in maintaining suspension of the solid and thereby improve the physical stability. If separation occurs, it is preferred that the solid can be readily resuspended with minimum agitation of the formulation.

[0036] Further, a pesticidal suspension concentrate to be used in the agricultural industry is typically diluted with water to prepare a dilute sprayable composition which is then applied by spraying to soil and / or plants in a field, for example by means of conventional spraying equipment. At the time of use, therefore, it is desirable that the suspension concentrate is readily emulsified in water, with no more than a minimal and acceptable amount of segregation of components into distinct layers, and no, or not more than a minimal and acceptable amount of sedimentation.

[0037] In order to accomplish this, one or more surfactants or emulsifiers are therefore also typically included in suspension concentrates to improve dispersibility in water.

[0038] Applicants have now surprisingly found that components (A) and (B) may be co-formulated into a storage stable and readily redispersible suspension concentrate, by employing a combination of two components (C) and (D). Furthermore, these compositions could be 83092-FF thinned without phase separation or coagulation, and retained the biological activity over the tested period, and hence may serve for drone applications. Preferably components (C) and (D) are present in amounts effective to disperse the particles in the water.

[0039] Component (C) is a metal lignosulfate salt. The lignosulfate anion moiety of this component is generally a product of the sulfonation of lignin, e.g., prepared from the lignin of sulphite pulp mill liquors. Lignin is a polymeric substance that can include substituted aromatics found in plant and vegetable matter associated with cellulose and other plant constituents. Illustrative plant and vegetable matter can include, but is not limited to, straw, hemp, sisal, cotton stalk, wheat, bamboo, sabai grass, rice straw, banana leaves, paper mulberry (i.e., bast fibre), abaca leaves, pineapple leaves, esparto grass leaves, fibres from the genus Hesperaloe in the family Agavaceae jute, salt water reeds, palm fronds, flax, ground nut shells, hardwoods, softwoods, or any combination thereof.

[0040] Sulfonated lignins are highly negatively charged polyelectrolytes, due to the presence of fully ionizable sulfonate groups that are pH-independent as to its ionization. Suitable lignin material can include, but is not limited to, lignin in its native or natural state, i.e., nonmodified or unaltered lignin, lignosulfonates, or any combination or mixture thereof. Suitable lignosulfonates can include, but are not limited to, ammonium lignosulfonate, sodium lignosulfonate, potassium lignosulfonate, calcium lignosulfonate, magnesium lignosulfonate, or any combination or mixture thereof. The metal lignosulfate salt may be any salt of a lignosulfonic acid which is effective to disperse the insecticide. Suitable metal counterions include sodium, potassium, lithium, and calcium. Two or more lignosulfate salts may be combined in effective amounts to provide an adequate dispersant. For example, sodium lignosulfate and calcium lignosulfate may be combined in effective amounts. Also included are ammonium lignosulfate salts, e.g., comprising tetra alkyl ammonium or aryl trialkyl ammonium counterions. Examples of these types of dispersants include tetra butyl ammonium lignosulfate and phenyl trimethylammonium lignosulfate.

[0041] The metal content of the metal lignosulfate is generally from 0.2% to 15% by weight if sodium or from 0.1 to 0.9% by weight of calcium. The amount of sulfonation of the lignin polymer is generally from 2 to 10% by weight. The degree of sulfonation is generally from 0.5% to 3% by weight.

[0042] Generally, one or more of the following types of lignin-based dispersants may be used: mono-calcium salt of polymerized aryl alkylsulfonic acids, (lignosulfonate calcium salt); sodium salt of kraft lignin polymer optionally mixed with a modified sulphite lignin; ammonium lignosulfonates; lignin; alkali: and reaction products with sodium bisulphite and formaldehyde.

[0043] It is noted that during the milling of the dispersed active ingredients, at least component (C) may be employed to prevent the re-agglomeration of finely ground particles, and also, like- charge repulsion prevents the cohesive interaction of dispersant molecules and keeps the viscosity of the solution low, aiding grinding or milling.

[0044] Indeed, it is a surprising benefit of the described compositions that milling of the components is possible without high temperatures. 83092-FF

[0045] Preferred component (C) include lignosulfonates under CAS No: 8061-51-6. More preferred are lignosulfonates selected from the group of commercially available sulfonated lignins / lignosulfonate, in particular POLYFON O®, REAX 85A®, POLYFON H®, Vanisperse CB®, Marasperse CBA®, Ufoxane RG®, Ultrazine NA®, and Lignosol SD60®. A particularly preferred component (C) comprises POLYFON H®, a sodium salt of lignin sulfonate commercially available from Ingevity Corp.

[0046] Advantageously, component (C) is present in an amount of from 0.01 to 5% by weight.

[0047] Component (C) is preferably present in an amount of from 0.01 to 5% by weight, such as from 0.05 to 3% by weight, from 0.1 to 2.5% by weight, from 0.3 to 1.9% by weight.

[0048] The second component is a surface-active agent (D), in particular an anionic surfactant comprising a bis(2-ethylhexyl) sulfosuccinate metal salt. Preferably, the surfactant comprises a dioctyl sodium sulfosuccinate and sodium benzoate, such as disodium 2,2-bis(2- ethylhexyl)-3-sulfobutanedioate; as for instance disclosed in GBA587403.

[0049] A particularly preferred anionic surfactant is Aerosol® OT-B, which is commercially available from Cytec Industries Inc., comprises 85 w / w% dioctyl sodium sulfosuccinate and 15 w / w% sodium benzoate.

[0050] Component (D) is preferably present in an amount of from 0.01 to 5% by weight, such as from 0.05 to 3% by weight, from 0.1 to 2.5% by weight, from 0.3 to 1.9% by weight.

[0051] The compositions may further comprise component (F) polyalkylene oxide block copolymer, preferably wherein the copolymer is deionised. An example of such a polymer is ATLAS G- 5000D™.

[0052] Component (F) is preferably present in an amount of from 0.01 to 5% by weight, such as from 0.05 to 3% by weight, from 0.1 to 2.5% by weight, from 0.3 to 1.9% by weight.

[0053] The compositions may further comprise component (G) a copolymer of methyl methacrylate, methacrylic acid and polyethylene glycol methacrylate. An example of such a polymer is ATLOX 4913™.

[0054] Component (G) is preferably present in an amount of from 0.05 to 9% by weight, such as from 0.5 to 8% by weight, from 1 to 7% by weight, from 1.5 to 4.5% by weight.

[0055] Preferably the solids content, calculated on components (A) and (B) is in the range of from 10 to 40% by weight, more preferably from 15 to 30% by weight.

[0056] The water-based formulations according to the present disclosure are considered environmentally benign and safe, as they produce no dust and include little or no aromatic solvent. Microparticulate pymetrozine and triflumezopyrim are suspended in water at relatively high concentrations to produce the suspension concentrate. 83092-FF

[0057] Advantageously the compositions have a viscosity of less than 800 cps, such as less than 750 cps.

[0058] Water-based formulations are considered much more environmentally benign and safe, as they produce no dust and include little or no aromatic solvent. Microparticulate pymetrozine can be suspended in water at relatively high concentrations to produce a suspension concentrate.

[0059] Suspension concentrates can overcome the problems with dust of wettable powders, and can provide a number of additional advantages, such as ease of pouring and measuring. However, it can be difficult to prepare suspension concentrate formulations that are storage stable, e.g., with respect to thickening and particle agglomeration.

[0060] There remains a need for pymetrozine formulations that can address these shortcomings.

[0061] There is a continuing need to provide pesticidal combinations, which provide improved, for example, biological properties, especially for controlling insect, acarina and nematode pests. The benefits may also be an increased safety profile, improved physico-chemical properties, or increased biodegradability.

[0062] It has been found that particular combinations of active ingredients provide unexpected control or prevention of infestation of plants, when the particular combination is applied on the plant, the locus thereof or its propagation material.

[0063] Many agrochemical formulations proposed today are water-borne, e.g. dispersions or emulsions. While this provides for a very efficient, safe and environmentally friendly way of applying the compositions, there are some features that may limit their industrial applicability.

[0064] For instance, water-borne formulations comprising the active ingredients according to the present disclosure may exhibit crystallisation tendency over time, and / or increased crystal size growth, depending on storage and dilution conditions. While this may not be an issue for certain applications, for the industrial applicability it is often necessary that the active ingredients are provided in a form that can be used directly, or within a few days after dilution in water before the actual application, such as field or greenhouse spraying. Hence, solid pesticides such as triflumezopyrim and pymetrozine are commonly formulated as water dispersible granules, or as solvent borne formulations.

[0065] A particular problem for water borne formulations of each of pymetrozine and triflumezopyrim, and in particular combinations are the following known issues: pymetrozine is known to exhibit a polymorph conversion from the anhydrate form to the dihydrate when stored in the presence of water, and hence this compound was hitherto only available as water dispersible granules. On the other hand, given triflumezopyrim's mesoionic structure, the compatibility with pymetrozine in a water borne formulation was hitherto unknown, and no common stabilising systems have thus been reported. 83092-FF

[0066] Active ingredient dispersions should exhibit a sufficiently high phase separation stability not only immediately after dilution with water, but retain this stability for a suitably elongated period to allow for application. Presence of crystals above a certain size may adversely impact filterability and / or spray applicability, whereby obstruction of pumps, lines and spray nozzles may render an effective and homogeneous application difficult.

[0067] Also, where wetting of a target substrate is desired, for instance in the field or greenhouses or other locations such as leaves, in furrow, soil surface or underground soil and surface or underground water reservoirs, it may be desirable to show a specific level of crystallisation. The same applies to (bio)availability, whereby changes in crystal size or form may reduce efficacy and availability. Furthermore, it may be useful to provide such compositions in a form that can be used for dilution in water only before the actual application, such as field or greenhouse spraying. Ideally, such compositions should also be storage stable under a wide range of conditions, without chemically or physically affecting the active ingredient quality, and without inducing crystallising. Considering the variety of conditions and special situations under which pesticides are stored, shipped and used around the world, there remains a need for suspension concentrate premix formulations of pesticides that provide stability benefits under at least some of those conditions and situations.

[0068] Accordingly, there remained a need to provide a substantially storage-stable and dilutionstable suspension concentrate (SC) formulation of combinations of pymetrozine and triflumezopyrim, preferably suspension concentrate (SC) formulations that are storage stable for at least several weeks, preferably for at least one year, and under temperature conditions ranging from - 10°C to + 54°C.

[0069] The room-temperature solid pesticides such as pymetrozine and triflumezopyrim are formulated as suspension concentrate, wherein both pesticidally active ingredients are in a solid particulate state, and suspended in a non-active liquid carrier.

[0070] The liquid carrier in the present composition may be aqueous, or in part non-aqueous, for example comprising a hydrocarbon oil or other organic liquid, and is typically selected such that the solid pesticide has low solubility in the liquid carrier.

[0071] Although increases in food grain production have been due to several factors, including the use of better plant varieties and seeds, irrigation, fertilizers, agrochemicals (pesticides, fungicides and herbicides), and farm machinery, agrochemicals have been an integral part of the process by reducing crop losses caused by insect pests, diseases and weeds. In the developed world, it is generally assumed that about one-third of agricultural production may be attributed to the use of agrochemicals.

[0072] When pesticides are sprayed on crops, only a small amount of the applied pesticide displays a protective role to fight against crop pests and diseases with the danger that the remainder reaches the non-target areas, resulting in environmental pollution, including soil, water and air pollution.

[0073] An unmanned aerial vehicle (UAV), commonly known as a drone, is an aircraft that can operate autonomously or can be operated remotely without a human pilot on board. 83092-FF

[0074] Compared to conventional agricultural manned aircraft, UAVs does not require a special airport and have advantages, such as good mobility, low weight, flexible movement, lower operational cost and complexity, less dependence on weather conditions, higher spatial resolution, and shorter revisit times.

[0075] Compared with ground equipment, the biggest difference is the spray volume of pesticide used per unit area. The average spray volume used in different ground-based sprayers, such as knapsack-type sprayer, boom sprayer, or orchard sprayer and various crop types, such as field crops, vegetables, orchard, plantation crops etc., varies from 300-1000 L / ha, while the average spray volume application by drone ranges from 15-40 L / ha depending on the model and payload capacity.

[0076] The control efficacy on pests and diseases is one of the most important evaluation indices of chemical application by drones. The control efficacy with aerial spraying using drones ideally should be compatible / similar to that of conventional spray application methods, considering the advantages and challenges of drone application.

[0077] Accordingly, it is of paramount importance to be able to formulate the active ingredients in highly concentrated and stable suspensions, in order to allow for the use with drones.

[0078] Conversely, the compositions of the present invention have been found to be suitable for use in Unmanned Aerial Vehicles (UAVs).

[0079] Preferably, the present invention provides a composition comprising as component (A) of formula: and, as component (B), a compound of formula : wherein the ratio by weight of (A) to (B) is from 500:1 to 1:500, 100:1 to 1:100, 50:1 to 1:50 or 20:1 to 1:20, or preferably 10:1 to 1:10, or 1:1 to 1:10, or 1:2 to 1:9 by weight. 83092-FF

[0080] The compositions of the present invention may comprise a compound of formula (A) and the compound of formula (B) in a suitable ratio by weight, examples of which are between 2000:1 to 1:2000, between 1500:1 to 1:1500, between 1000:1 to 1:1000, between 750:1 to 1:750, between 500:1 to 1:500, between 400:1 to 1:400, between 300:1 to 1:300, between 250:1 to 1:250, between 200:1 to 1:200, between 150:1 to 1:150, between 125:1 to 1:125, between 100:1 to 1:100, between 80:1 to 1:80, between 75:1 to 1:75, between 70:1 to 1:70, between 125:2 to 2:125, between 60:1 to 1:60, between 50:1 to 1:50, between 40:1 to 1:40, between 30:1 to 1:30, between 25:1 to 1:25, between 20:1 to 1:20, between 16:1 to 1:16, between 15:1 to 1:15, between 12:1 to 1:12, between 10:1 to 1:10, between 9:1 to 1:9, between 8:1 to 1:8, between 7.5:1 to 1:7.5, or between 7:1 to 1:7 by weight.

[0081] In an embodiment, the above uses and methods exclude treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body. In an embodiment, the use is a non-therapeutic use. In an embodiment, the method is a non-therapeutic method.

[0082] The compositions according to the aspects of the invention can also have further surprising advantageous properties. Examples of such advantageous properties that may be mentioned are: more advantageous degradability, improved toxicological and / or ecotoxicological behaviour, or improved characteristics of the useful plants including: emergence, crop yields, more developed root system, tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf colour, less fertilizers needed, less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, improved plant vigour, and early germination.

[0083] The compositions of the present invention may be useful for the control of pests, especially insects, in improving the tolerance of crop plants to abiotic stress conditions, and / or in improving the yield of crop plants. The present invention provides a method for controlling insect pests in or on crop plants, improving the tolerance of crop plants to abiotic stress conditions, and / or improving the yield of crop plants, comprising treating the pests, plants, plant part, plant propagation material, or plant growing locus with compositions as described herein.

[0084] The compositions of the present invention may be useful for extending the duration of protection afforded to the plant material. In one embodiment, the compositions of the present invention may show both a fast-acting curative action and a preventative or protective action.

[0085] The compositions of the present invention may be useful for extending the range of crops with which the compositions are useful and / or the range of pests against which the compositions provide effective control. 83092-FF

[0086] Accordingly, the compositions of the present invention provide an enhanced biological profile which may include a more complete activity spectrum and / or complementary modes of activity.

[0087] Where used herein, the indication 'CAS' followed by a sequence of numbers refers to the Chemical Abstracts Registry number of the active ingredient. Where available or known, active ingredients are also referred to by their common name allocated in accordance with 'ISO 1750:1981 - Pesticides and other agrochemicals — Common names'.

[0088] The compositions according to the invention can be used for preventing or controlling, i.e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.

[0089] Examples of the above-mentioned pests are: from the order Coleoptera, for example,

[0090] Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis, Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp, Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus orator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemlineata, Lissorhoptrus spp., Liogenys spp, Maecolaspis spp, Maladera castanea, Megascelis spp, Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp, Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Somaticus spp, Sphenophorus spp, Sternechus subsignatus, Tenebrio spp., TriboHum spp. And Trogoderma spp. from the order Lepidoptera, for example,

[0091] Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp, Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias 12yridin, Cosmophila flava, Crambus spp, Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp., Elasmopalpus lignosellus, Eldana saccharina, Ephestia spp., Epinotia spp, Estigmene acrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella, Euproctis spp., 12yridinel2., Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp, Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexto, Mythimna spp, Noctua spp, Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Papaipema nebris, Pectinophora gossypiela, Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Pseudoplusia spp, Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia 83092-FF spp., Sparganothis spp., Spodoptera spp., Sylepta derogate, Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tuta absoluta, and Yponomeuta spp.;

[0092] The compositions of the invention are particularly suitable for control of a pest of, from the order Lepidoptera, one or more of the species Spodoptera littoralis, Spodoptera frugiperda, Plutella xylostella, Cnaphalocrocis medinalis, Cydia pomonella, Chrysodeixis includens, Chilo suppressalis, Elasmopalpus lignosellus, Pseudoplusia includens, and Tuta absoluta; from the order Coleoptera, the species Diabrotica balteata, Diabrotica virgifera virgifera, Diabrotica undecimpunctata howardi, Diabrotica speciosa, Agriotes lineatus and Leptinotarsa decemlineata.

[0093] From the order Hemiptera, for example,

[0094] Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Amblypelta nitida, Bathycoelia thalassina, Blissus spp., Cimex spp., Clavigralla tomentosicollis, Creontiades spp., Distantiella 13yridinel3, Dichelops furcatus, Dysdercus spp., Edessa spp., Euchistus spp., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp., Margarodes spp., Murgantia histrionic, Neomegalotomus spp., Nesidiocoris tenuis, Nezara spp., Nysius simulans, Oebalus insularis, Piesma spp., Piezodorus spp., Rhodnius spp., Sahlbergella singulars, Scaptocoris castanea, Scotinophara spp., Thyanta spp., , Triatoma spp., Vatiga illudens;

[0095] Acyrthosiumpisum, Adalges spp., Agalliana ensigera, Agonoscena targionii, Aleurodicus spp., Aleurocanthus spp., Aleurolobus barodensis, Aleurothrixusfloccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp., Brachycaudus spp., Brevicoryne brassicae, Cacopsylla spp., Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus conidium, Chrysomphalus dictyospermi, Cicadella spp., Cofana spectra, Cryptomyzus spp., Cicadulina spp., Coccus hesperidum, Dalbulus maidis, Dialeurodes spp., Diaphorina citri, Diuraphis noxia, Dysaphis spp., Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp., Hyperomyzus pallidus, Idioscopus clypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp., Metcalfe 13yridine, Metopolophium dirhodum, Myndus crudus, Myzus spp., Neotoxoptera spp., Nephotettix spp., Nilaparvata spp., in particular Nilaparvata lugens (brown planthopper; BPH), Laodelphax striatellus (small brown planthopper) and Sogatella furcifera (white-backed planthopper); Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter, Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Peregrinus maidis, Perkinsiella spp., Phorodon humuli, Phylloxera spp., Pianococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Sogatella furcifera, Spissistilusfestinus, Tarophagus Proserpina, Toxoptera spp., Trialeurodes spp., Tridiscus sporoboli, Trionymus spp., Trioza erytreae, Unaspis citri, Zygina flammigera, Zyginidia scutellaris ; from the order Hymenoptera, for example,

[0096] Acromyrmex, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium 13yridinel3, Neodiprion spp., Pogonomyrmex spp., Slenopsis 13yridin, Solenopsis spp., and Vespa spp.; from the order Isoptera, for example, 83092-FF

[0097] Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Solenopsis geminate from the order Lepidoptera, for example,

[0098] Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp., Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colics 14yridin, Cosmophila flava, Crambus spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp., Eldana saccharine, Ephestia spp., Epinotia spp., Estigmene acrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella, Euproctis spp., 14yridinel4., Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp., Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Mythimna spp., Noctua spp., Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Papaipema nebris, Pectinophora gossypiela, Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Pseudoplusia spp., Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Sylepta derogate, Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tuta absolute, and Yponomeuta spp.;

[0099] Suitable target crops are, for example, cereals such as wheat, barley, rye, oats, rice, maize, sorghum, maize, millet, and triticale; beet crops such as sugar beet and fodder beet; fruit trees such as apple, pear, plum, peach, almond, cherry, strawberry, raspberry, blackberry, blueberry, cranberry, nectarine, banana, apricot, avocado, citrus (orange, lemon, grapefruit, tangerine), or grape; leguminous crops like beans, lentils, peas, and soybean; oil crops such as oilseed rape (canola), mustard, poppies, olives, sunflowers, coconut, castor, cocoa, ground nuts, and peanuts; cucurbits like pumpkins, cucumbers, and melons; fibre plants including cotton, flax, hemp, jute, and sisal; Lauraceae species such as avocado, cinnamon, and camphor; tobacco; nuts such as almonds, cashews, ground nuts, hazelnuts, pecans, pistachios, and walnuts; coffee; eggplants; sugarcane; tea; pepper; hops; the Plantain family (Banana family); latex plants; grasses such as Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass, and Zoysia grass; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage, and thyme; palms, for example oil palm; ornamentals including flowers, shrubs, and trees; other trees like cacao, coconut, olive, and rubber; and a variety of vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, bell peppers, broccoli, garlic, marrow, okra, pumpkin, and rhubarb. Additionally, vines such as grapes are also suitable target crops.

[0100] In an embodiment, the crop is a cereal, preferably rice.

[0101] Crops are to be understood as being those which are naturally occurring, obtained by conventional methods of breeding, or obtained by genetic engineering. They include crops 83092-FF which contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).

[0102] Crops are to be understood as also including those crops which have been rendered tolerant to herbicides like bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO-inhibitors. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer canola.

[0103] Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I®, and LibertyLink®.

[0104] Crops are also to be understood as being those which naturally are or have been rendered resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria. Examples of toxins which can be expressed include d-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, arachnids, wasps and fungi.

[0105] An example of a crop that has been modified to express the Bacillus thuringiensis toxin is the Bt maize KnockOut (Syngenta Seeds). An example of a crop comprising more than one gene that codes for insecticidal resistance and thus expresses more than one toxin is VipCot® (Syngenta Seeds). Crops or seed material thereof can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification). For example, a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).

[0106] Normally, in the management of a crop a grower would use one or more other agronomic chemicals or biologicals in addition to the composition of the present invention.

[0107] The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.

[0108] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as 6-endotoxins, e.g. CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vipl, Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. Or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, 83092-FF patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize- RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.

[0109] In the context of the present invention there are to be understood by 6-endotoxins, for example CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), for example Vipl, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02 / 15701). Truncated toxins, for example a truncated CrylAb, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G- recognition sequence is inserted into a Cry3A toxin (see WO 03 / 018810).

[0110] Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374753, WO 93 / 07278, WO 95 / 34656, EP-A-0427 529, EP- A-451 878 and WO 03 / 052073.

[0111] The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP-A-0 367 474, EP-A-0401 979 and WO 90 / 13651.

[0112] The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).

[0113] Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bbl toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bbl toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a CrylFa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a CrylAc toxin); Bollgard II® (cotton variety that expresses a CrylAc and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a CrylAb toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Btll corn borer (CB) trait) and Protecta®.

[0114] Further examples of such transgenic crops are: 83092-FF

[0115] 1. Btll maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Btll maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.

[0116] 2. Btl76 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylAb toxin. Btl76 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.

[0117] 3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Maize which has been rendered insectresistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03 / 018810.

[0118] 4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses a Cry3Bbl toxin and has resistance to certain Coleoptera insects.

[0119] 5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0120] 6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize for the expression of the protein CrylF for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.

[0121] 7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 8. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. Strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. Kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.

[0122] Transgenic crops of insect-resistant plants are also described in BATS (Zentrum fur Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http: / / bats.ch).

[0123] The term "crops" is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95 / 33818 and EP-A-0 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. 83092-FF

[0124] Crops may also be modified for enhanced resistance to fungal (for example Fusarium, Anthracnose, or Phytophthora), bacterial (for example Pseudomonas) or viral (for example potato leafroll virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens.

[0125] Crops also include those that have enhanced resistance to nematodes, such as the soybean cyst nematode.

[0126] Crops that are tolerant to abiotic stress include those that have enhanced tolerance to drought, high salt, high temperature, chill, frost, or light radiation, for example through expression of NF-YB or other proteins known in the art.

[0127] Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KPI, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A-0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95 / 33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03 / 000906).

[0128] The term "plants" refers to all physical parts of a plant, seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.

[0129] The term "locus" as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.

[0130] The term "plant propagation material" denotes all generative parts of a plant, for example seeds or vegetative parts of plants such as cuttings and tubers. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes, and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably "plant propagation material" is understood to denote seeds.

[0131] The term "regulating or improving the growth of a crop" means an improvement in plant vigour, an improvement in plant quality, improved tolerance to stress factors, and / or improved input use efficiency.

[0132] Further areas of use of the compositions according to the invention are the protection of stored goods and store rooms and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.

[0133] Where a range of numbers is disclosed herein (for example, 1 to 10), this is intended to include all numbers and intervening values within that range (for example, 1, 1.1, 2, 3, 3.9, 4, 5, 6, 6.5, 7, 8, 9 and 10) and also any sub-range of numbers and intervening values within 83092-FF that range (for example, 2 to 8, 1.5 to 5.5 and 3.1 to 4.7). Additionally, it is intended that the both the upper and lower limits specified are included within the range.

[0134] Where ranges or values used herein are preceded by the term "about", this term is intended to provide support for both the exact number that it precedes, and also a number that is near to or approximately the number that it precedes. In determining whether a number is near to or approximately a specifically recited number, the near or approximating number may be a number, which would be rounded to or be substantially equivalent to the specifically recited number. For example, the term "about 5" includes 5.0, 4.5, 5.4, 4.92, 5.01, and so on.

[0135] The composition can be in the form of concentrates which are diluted prior to use, although ready-to-use compositions can also be made. The final dilution is usually made with water, but can be made instead of, or in addition to, water, with, for example, liquid fertilisers, micronutrients, biological organisms, oil or solvents.

[0136] Tank-mix compositions are generally prepared by diluting with a solvent (for example, water) the one or more pre-mix compositions containing different pesticides, and optionally further auxiliaries. Suitable carriers and adjuvants can be solid or liquid and are the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Generally, a tank-mix formulation for foliar or soil application comprises 0.1 to 20%, especially 0.1 to 1%, of the desired ingredients, and 99.9 to 80%, especially 99.9 to 85%, of a solid or liquid auxiliaries (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 20%, especially 0.1 to 15%, based on the tank-mix formulation.

[0137] The rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.

[0138] The rates of application of compositions of the present invention may vary within wide limits and depend on the nature of the soil, the method of application (pre- or postemergence, seed dressing, application to the seed furrow, no tillage application etc.), the crop plant, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.

[0139] For foliar or drench application, the compositions of the present invention are generally applied at a rate of from 1 to 2000 g / ha, especially from 10 to 1000 g / ha.

[0140] In certain examples, the rate of application of component (A) is from 5 to 100 g / ha. In some examples, the rate of application of component (A) is from 10 to 50 g / ha.

[0141] In certain examples, the rate of application of component (B) is from 40 to 200 g / ha. In some examples, the rate of application of component (B) is from 50 to 150 g / ha. 83092-FF

[0142] The application is generally made by spraying (A) and (B) together (i.e. the composition), typically by tractor mounted sprayer for large areas, or by drone.

[0143] The compositions according to the invention can be used in combination with other pesticides, including other pesticides such as insecticides, acaricides, nematicides, fungicides, or agents that enhance the activity of the composition according to the invention, in for example chemical treatment or pest control programs. The combination may have further surprising advantages.

[0144] In an embodiment, the target insect is selected from Planthoppers, including Nilaparvata lugens (brown planthopper; BPH), Laodelphax striatellus (small brown planthopper) and Sogatella furcifera (white-backed planthopper).

[0145] Unless otherwise stated all percentages are given as percentages by total weight and all embodiments and preferred features may be combined in any combination.

[0146] The invention is described by the following non-limiting Examples.

[0147] Examples

[0148] Suspension Concentrate (SC) compositions 1 to 5 were prepared with the components as set out in Table 1 (all % are %w / w). Compositions 1 and 4 are according to the present invention.

[0149] Table 1

[0150] The prepared compositions were tested for a wide range of properties, with the results presented in the Tables below. 83092-FF

[0151] Chemical Stability

[0152] Samples of the compositions were stored in 30 mL vials in conditions, varying from two weeks at 54°C to 12 months at room temperature. The tests below are performed before and after storage to determine shelf life and stability. Time is given in weeks (w).

[0153] Table 2

[0154] It can be seen that the compositions do not exhibit any issues with chemical stability with no significant active ingredient degradation being demonstrated.

[0155] Physical Stability

[0156] However, issues when assessing physical stability of the composition differences were seen between the formulations. The results of serum formation and sedimentation after 2 weeks at 54 °C are set out in Table 3.

[0157] Table 3

[0158] It can be seen that Compositions 2 and 3 demonstrate significant serum formation during the storage test conditions.

[0159] Composition 1 was selected for the further testing set out below. 83092-FF

[0160] Viscosity

[0161] Viscosity was measured directly in vials containing composition with Brookfield® Viscosimeter. Measurement was performed with Spindle 63, at 30 rpm, value was taken after 1 minute.

[0162] Viscosity has been measured on newly prepared samples of Composition 1 at room temperature (25 °C) and under varying storage conditions. The results are set out in Table 4 below.

[0163] Table 4

[0164] It can be seen that viscosity does not vary beyond the acceptable range for such a formulation.

[0165] Particle Size Distribution (PSD)

[0166] Particle size distribution was measured on Cilas 1064 Laser Diffraction Particle Size Analyzer. Droplets of sample composition were dispersed until getting about 15-20% obscuration. Ultrasound was applied before and during measurement (60 seconds each).

[0167] Dv(50) and Dv(90) are percentiles values. These are statistical parameters that can be read from the cumulative size distribution. Dv(50) (also known as the median) and Dv(90) respectively indicate the size below 50% and 90% of all particles are found.

[0168] The results are set out in Table 5 below. 83092-FF

[0169] Table 5

[0170] Compositions in accordance with the present invention exhibit the below features:

[0171] • Delta Dv(50), defined as (highest Dv(50) - initial Dv(50)) / initial Dv(50), < 10%;

[0172] • Delta Dv(90), defined as (highest Dv(90) - initial Dv(90)) / initial Dv(90), < 10%.

[0173] It can be seen that there is narrow variation in particle size despite the range of storage conditions.

[0174] Wet sieve Residue - 44 pm

[0175] 10 g of composition was poured into 100 mL of water and was stirred for up to 30 seconds until obtaining a homogeneous suspension and the resulting suspension was then poured over a 44 pm fine mesh sieve. The sieve was rinsed for up to 1 minute under tap water. The residue on the sieve was collected, dried and weighed. The result is presented as a percentage against the initial 10 g.

[0176] Table 5

[0177] It can be seen that composition 1 leaves minimal residues. 83092-FF

[0178] Biological trials

[0179] The composition described below were applied to rice plants TN11 rice variety.

[0180] Composition 1 was compared to commercially available solo formulations of the individual active ingredients.

[0181] Single application applied with CO2 powered backpack mounted single nozzle sprayer (hollow cone nozzle) at 500 L / ha water volume. Rice plants had a natural infestation of the brown planthopper (Nilaparvata lugens) with the following average infestation level at the time of the assessments: 3DAA = 40 nymphs per hill. 28 DAA = 127 nymphs per hill.

[0182] Experimental design was randomised complete block (RCB) with four replicate blocks per treatment. Plot size of 12 m2. Assessment of the number of nymphs per hill with eight subsamples per plot measured.

[0183] The results are set out in Table 6 below.

[0184] Table 6

[0185] It can be seen that Composition 1, at 20 g ai / ha, exhibits comparative or improved biological control compared to the commercial standard of 25g ai / ha Triflumezopyrim alone.

[0186] UAV Application

[0187] The sprayability and performance of Composition 1 was tested DJI AGRAS MG1-P Drone Spray Rig.

[0188] 4.5 litres of tap water was added into a S-Pac pre-mix bottle. The required quantity of the product was then added before closing the cap and inverting 5 times. The cap was reopened and the bottle filled to the end volume of 9 litres. Cap closed and inverted a further 5 times. 83092-FF

[0189] The spray mix was then added into the drone spray tank through the inlet basket filter for application.

[0190] Results

[0191] — Initial Dispersion: Good initial dispersion, blooms well; no foam formation

[0192] — After 5 pack inversions: Homogenous cream dispersion; no foam formation

[0193] — After filling up and further 5 pack inversions: Homogenous cream dispersion; no foam formation

[0194] — Application time: 9 minutes

[0195] — Nozzle blockages: None

[0196] — Spray tank after spraying: Traces of yellowish residues were found on the base, the walls and on the ledges of the drone spray tank

[0197] — Outer filter (300 pm): Clean

[0198] — Inner filter(150 pm) : Clean

[0199] — Ease of Cleaning: Easy to rinse, no residues were observed in the drone spray tank after rinsing with 3 portions of fresh tap water

[0200] Composition 1 was therefore suitable for UAV application.

[0201] The invention is defined by the claims.

Claims

83092-FFCLAIMS1. An aqueous composition comprising (A) a compound of formula:and(B) a compound of formula :(C) a metal lignosulfate salt;(D) a bis(2-ethylhexyl) sulfosuccinate metal salt; and(E) water, wherein compounds (A) and (B) comprise any polymorphs, hydrates, agriculturally acceptable salts, tautomers and N-oxides thereof.

2. The composition according to claim 1, wherein component (A) is present in an amount of from 0.5 to 8% by weight.

3. The composition according to claim 1 or 2, wherein component (B) is present in amount of from 3 to 20% by weight.

4. The composition according to any of the previous claims, wherein component (C) is present in an amount of from 0.01 to 5% by weight.

5. The composition according to any of the previous claims, wherein component (D) is present in an amount of from 0.01 to 5% by weight.

6. The composition according to any of the previous claims, wherein component (E) is present in an amount of from 50 to 96% by weight.

7. The composition according to any of the previous claims, wherein the ratio by weight of (A) to (B) is in the range of from 500:1 to 1:500, preferably of from 100:1 to 1:100, more preferably of from 50:1 to 1:50 or 20:1 to 1:20, or preferably from 10:1 to 1:10, or from 1:1 to 1:10 by weight .83092-FF8. The composition according to any of the previous claims further comprising (F) a polyalkylene oxide block copolymer.

9. The composition according to claim 7, wherein component (F) is present in an amount of from 0.01 to 5% by weight10. The composition according to any of the previous claims further comprising (G) a copolymer of methyl methacrylate, methacrylic acid and polyethylene glycol methacrylate.

11. The composition according to claim 10, wherein component (G) is present in an amount of from 0.5 to 8% by weight.

12. The composition according to any of the previous claims where the composition is a suspension concentrate (SC) formulation.

13. Use of a composition according to any one of claims 1 to 7, for controlling or preventing infestation of a plant by an insect of the order Hemiptera, Lepidoptera or Coleoptera.

14. A method for preventing or controlling pathogens in crops of useful plants, comprising treating the plants, plant parts, plant propagation materials or locus thereof with an agrochemically effective amount of a water-diluted spray composition formed when the composition according to any one of claims 1 to 12 is added to an aqueous liquid carrier.

15. The method according to claim 14, wherein the rate of application of component (A) and component (B) each is from 1 to 2000 g / ha, preferably from 10 to 1000 g / ha.

16. A process for the preparation of the composition according to anyone of claims 1 to 12 comprising: i) providing ingredients (A) and (B), ii) milling the ingredients (A) and (B) to a desired particle size and particle size distribution in the presence of at least component (C) and water, and iii) adding component (D), and any other additive and water to the desired composition.

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