Pesticidal mixture to control pests

Abstract

The present invention relates to a method of combating and / or controlling a pest selected from the Pentatomidae family, which comprises applying to said pest, to a locus of said pest, to a plant susceptible to attack by said pest, or to a plant propagation material susceptible to attack by said pest, a pesticidal composition comprising isocycloseram as active ingredient A, and ethiprole as active ingredient B.

Description

[0001] PESTICIDAL MIXTURE TO CONTROL PESTSThe present invention relates to compositions of pesticidally active ingredients and to methodsof using the compositions in the field of agriculture.WO2011067272 discloses that certain isoxazoline compounds have insecticidal activity.The present invention provides a method of combating and / or controlling a pest selected fromthe Pentatomidae family, which comprises applying to said pest, to a locus of said pest, to aplant susceptible to attack by said pest, or to a plant propagation material susceptible to attack by said pest, a pesticidal composition comprising isocycloseram as active ingredient A, andethiprole as active ingredient B.It has now been found, surprisingly, that the pesticidal composition, or in other words the activeingredient mixture, according to the invention achieves a synergistic effect to treat a pestselected from the Pentatomidae family, preferably selected from the Euschistus genus such asmore preferably Euschistus heros. The pesticidal composition achieves a high degree of pestcontrol, especially within a short time.Throughout this document, the expression “composition” stands for the various mixtures orcombinations of active ingredients (A) and (B), for example in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the active ingredients (A) and (B) is not essential for working the present invention. Isocycloseram is an insecticidal agrochemical with the following CAS number: 2061933-85-3, and has the following chemical formula:

[0002] Isocycloseram can comprise the isomer (5S,4R) which is 4-[(5S)-5-(3,5-dichloro-4-fluoro- phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo-isoxazolidin-4-yl]-2- methyl-benzamide, and optionally at least one of the isomers selected among isomer (5S,4S), isomer (5R,4R), isomer (5R,4S), and any combinations thereof. In the present invention, the isomer (5S,4S) is 4-[(5S)-5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3- yl]-N-[(4S)-2-ethyl-3-oxo-isoxazolidin-4-yl]-2-methyl-benzamide; the isomer (5R,4R) is 4- [(5R)-5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2- ethyl-3-oxo-isoxazolidin-4-yl]-2-methyl-benzamide; and the isomer (5R,4S) is 4-[(5R)-5-(3,5- dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(4S)-2-ethyl-3-oxo-isoxazolidin-4-yl]-2-methyl-benzamide. When isocycloseram further comprises at least one ofthe isomers selected among isomer (5S,4S), isomer (5R,4R), isomer (5R,4S), and any combinations thereof, isocycloseram can comprise a molar proportion of the isomer (5S,4R) greater than 50%, e.g. at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98% or 99%, over the total amount of the isomers (5S,4R), (5S,4S), (5R,4R) and (5R,4S).The molar proportion of the isomer (5S,4S) can be less than 50%, e.g. at most 30%, 25%, 20%,15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5% or 0.1%, over the total amount of theisomers (5S,4R), (5S,4S), (5R,4R) and (5R,4S). The molar proportion of the isomer (5R,4R) can be less than 50%, e.g. at most 30%, 25%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5% or 0.1%, over the total amount of the isomers (5S,4R), (5S,4S), (5R,4R) and (5R,4S). The molar proportion of the isomer (5R,4S) can be less than 50%, e.g. at most 30%, 25%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5% or 0.1%, over the total amount of the isomers (5S,4R), (5S,4S), (5R,4R) and (5R,4S).The active ingredient B is ethiprole with the following CAS number: 181587-01-9.According to the present invention, the active ingredients (A) and (B) can be present in asynergistically effective amount in the pesticidal composition.In a preferred embodiment, the weight ratio (in grams of active ingredients ) of active ingredient A to active ingredient B can range from 1:1 to 1:100, preferably from 1:1 to 1:50, preferably from 1:1 to 1:20, preferably from 1:1 to 1:10, preferably from 1:1 to 1:5, and more preferably 1:2; 1:3 or 1:4.The active ingredient A according to the present invention can be used to prepare a suspensionconcentrate (SC), a flowable suspension (FS), a suspoemulsion (SE), a suspension concentrate-capsule suspension blend (ZC), water soluble granules (SG), water-dispersible granules (WG),water-dispersible tablets (WT), a dispersible concentrate (DC), an emulsifiableconcentrate (EC), or an oil dispersion (OD). The most preferred formulation type is asuspension concentrate, a dispersible concentrate, or a suspension concentrate-capsule suspension blend.The above-mentioned formulations can be prepared in using ingredients and techniques well-known in the art, such as for example as described in the documents WO2022 / 128912 orWO2023 / 232559.For example, the pesticidal composition according to the present invention, especially for thepreparation of the active ingredient A, can further comprise at least one of the componentsselected among a polyoxyalkylene copolymer, an acrylic graft copolymer, an oxygenatedhydrocarbon, a lignin compound, a lactamide compound, and an ether type solvent, preferablyat least two of said components, preferably at least three of said components, and more preferably preferably at least four of said components. In a particular embodiment to form a suspension concentrate, the pesticidal composition,especially for the preparation of the active ingredient A, can further comprise at least one of thecomponents selected among a polyoxyalkylene copolymer, an acrylic graft copolymer, and anoxygenated hydrocarbon, preferably at least two of said components, and more preferably saidthree components. In a particular embodiment to form a dispersible concentrate, the pesticidal composition,especially for the preparation of the active ingredient A, can further comprise at least one of thecomponents selected among an acrylic graft copolymer, a lignin compound, a lactamidecompound, and ether type solvent, preferably at least two of said components, preferably atleast three of said components, and more preferably said four components. In the present invention, the polyoxyalkylene copolymer can be obtained from at least two different alkylene oxides, such as from ethylene oxide and propylene oxide monomers. The polyoxyalkylene copolymer can be more preferably a polyoxyalkylene block copolymer of the AB, ABA, BAB, or ABABA type. More particularly, the polyoxyalkylene copolymer can be prepared by ring-opening polymerization of the corresponding cyclic ethylene oxide and propylene oxide monomers. Typically, the ring-opening polymerization is initiated by addition of water and alkali hydroxides, such as sodium hydroxide and potassium hydroxide. The block structure of the copolymer is formed by first polymerizing a polymer block using one monomer, before adding a second monomer to form further polymer blocks. In a preferred embodiment, the polyoxyalkylene copolymer can be an ethylene oxide-propylene oxide-ethylene oxide block copolymer (EO-PO-EO block copolymer), or in other words apoly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer or apoly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) block copolymer. The polyoxyalkylene copolymer of the invention, and more particularly the EO-PO-EO block copolymer, can have a molecular weight from 1,000 to 15,000 g / mol, and more preferably from 3,000 to 7,000 g / mol. In the present invention, the expression “a molecular weight” means an average molecularweight (i.e. a molecular weight approximately of). Molecular weight of a polymer, or in otherwords the molar mass, can be easily determined by method well-known in the art, such as gel permeation chromatography (GPC). In a first embodiment, the EO-PO-EO block copolymer can have a polypropylene oxide molecular weight from 900 to 4,000 g / mol, and preferably from 2,000 to 4,000 g / mol. In other words, the polypropylene oxide molecular weight is the molecular weight of the poly(propylene oxide) block of the EO-PO-EO block copolymer. In a second embodiment, the EO-PO-EO block copolymer can have an ethylene oxide content from 10 to 80%, and preferably from 30 to 50%, over the total weight of the copolymer. Inother words, the ethylene oxide content is the percentage of the poly(ethylene oxide) block inthe EO-PO-EO block copolymer. In a third embodiment, the EO-PO-EO block copolymer can have the features of the first embodiment and the features of the second embodiment. Examples include the GENAPOL®PF series (CLARIANT), the PLURONIC®series (BASF), the SYNPERONIC®PE series (CRODA), or the TOXIMUL®series (STEPAN).The acrylic graft copolymer has typically a comb- or star-like structure, and preferably a comb-like structure. Graft copolymers are branched copolymers wherein the components forming the side chains are structurally different from the components forming the main chain. Comb-like polymers comprise of a main chain (backbone) which contains branch points from each of which a linear side chain emanates. Star-like polymers comprise of a multifunctional centre from which at least three polymer chains radiate. In a preferred embodiment, the acrylic graft copolymer can be an amphipathic copolymer. More particularly, the acrylic graft copolymer comprises at least one component A, which is solvated by an aqueous medium (hydrophilic part), and at least one other component B which is hydrophobic. Suitable acrylic graft copolymers may comprise polyethylene glycol, mono-methyl ethers of polyethylene glycol, poly(vinyl pyrrolidone), poly(acrylamide) or poly(vinyl alcohol) as hydrophilic side chain, while the hydrophobic backbone may comprise polymers and copolymers of styrene, methyl acrylate, methyl methacrylate, ethyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, or vinyl acetate. Such acrylic graft copolymers can for example be prepared by converting the mono-methyl ether of a polyethylene glycol to the acrylic or methacrylic ester, which is then subjected to radical polymerization with other unsaturated monomers such as styrene, ethyl acrylate, or methyl methacrylate. It is also possible to prepare such acrylic graft copolymers by reacting a hydrophobic polymer backbone, which consists chemically reactive sites such as carboxyl, hydroxy, or amine groups, with monomeric alkylene oxides, such as ethylene oxide and propylene oxide, to form hydrophilic side chains. More preferably, the acrylic graft copolymer is a non-ionic polymer, and more particularly with a comb-like structure. In the present invention, the acrylic graft copolymer can comprise polyethylene glycol and / or mono-ether polyethylene glycol side chains. The acrylic graft copolymer can also comprise a backbone obtained from acrylate and / or methacrylate monomers. Even more preferably, the acrylic graft copolymer can comprise a backbone obtained from acrylate and / or methacrylate monomers, and side chains comprising polyethylene glycol and / or mono-ether polyethylene glycol, giving more particularly the polymer a comb-like structure.For example, the acrylic graft copolymer of the present invention can be Atlox 4913™ suppliedby CRODA, or Tersperse 2500™ supplied by HUNTSMAN.The oxygenated hydrocarbon compound can be selected among alkyl ether compounds, alkyl ester compounds, and any mixture thereof; and preferably among polyethylene glycol alkyl ether, sulfonated alkyl ester compounds, and any mixture thereof. In other words, theoxygenated hydrocarbon compound is preferably different from the polyoxyalkylenecopolymer and from the acrylic graft copolymer. The polyethylene glycol alkyl ether can be obtained by reacting alcohols with ethylene oxide. Suitable alcohols are linear or branched aliphatic alcohols with a chain length from C2 to C15, preferably with a chain length from C7 to C11, and more preferably with a chain length of C9 orC10. An example can be Rhodasurf DA / 630-E™ supplied by SOLVAY-RHODIA,The sulfonated alkyl ester compound can be a sulfosuccinate ester or a salt of a sulfosuccinateester. An example can be Aerosol™ OT-B, supplied by SOLVAY-RHODIA.The lignin compound can have a molecular weight up to 10000 g / mol, and preferably up to 5000 g / mol. In a preferred embodiment, the lignin compound can have a molecular weight of at least 1000 g / mol.The lignin compound can be more particularly a kraft lignin and / or an unsulfonated lignin. In apreferred embodiment, the lignin compound can be an unsulfonated kraft lignin. An unsulfonated kraft lignin can be defined as a lignin separated from cellulose using the Kraft process (also known as sulfate process), namely separation using sodium hydroxide (NaOH) and sodium sulfide (Na2S). The use of this process gives rise to unsulfonated lignins, unlike those produced via an acidic sulfite process.The lactamide compound can be of formula I: CH3CH(OH)C(=O)NR1R2 (I), wherein R1 andR2are each independently hydrogen; or C1-6alkyl, C2-6alkenyl or C3-6cycloalkyl, each of which is optionally substituted by up to three substituents independently selected from phenyl, hydroxy, C1-5 alkoxy, morpholinyl and NR3R4 where R3 and R4 are each independently C1-3 alkyl; or phenyl optionally substituted by up to three substituents independently selected from C1-3 alkyl; or R1 and R2 together with the nitrogen atom to which they are attached form a morpholinyl, pyrrolidinyl, piperidinyl or azepanyl ring, each of which is optionally substituted by up to three substituents independently selected from C1-3 alkyl. In a preferred embodiment,R1 and R2 of the lactamide compound of formula I can be each independently hydrogen or C1-6alkyl, and more preferably hydrogen or C1-3alkyl such as lactic acid dimethyl amide or lactic acid diethyl amide.The ether type solvent can be selected among dialkyl ethers, dialkyl amide ethers, glycol ethers,aliphatic ethers, and cyclic ethers. For example, the ether type solvent can be methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, tetrahydrofuran or dibutyl ether. In the present invention, the composition may further comprise water. The composition of the present invention may further comprise one or more formulation additives well-known in the art. In particular, the formulation additives can be selected among an anti-freeze agent, an anti-foam agent, an anti-bacterial agent (or biocide), a viscosity modifier (or thickener), a pH modifier, and any mixture thereof. In a preferred embodiment, the composition of the present invention can further comprise at least a silicone compound as anti-foam agent. Examples of silicone compounds can be polydimethylsiloxane. Other suitable formulation additives include amongst others known to the person skilled in the art, antioxidant, emulsifying agent, colourant (or pigment), perfume, adjuvant, attractant, binder, buffer, solid support (carrier), coating agent, deodorant, emetic agent, inorganic filler, safener, organic solvent, photo-protecting agent, and any mixture thereof.In a particular embodiment when the active ingredient A is prepared to form a formulation ascited above, and more particularly a suspension concentrate or a flowable suspension, theformulation may comprise:- from 0.01% to 50.0% by weight of the active ingredient A, and preferably from 0.1% to 40.0%by weight of the active ingredient A, over the total weight of the formulation,- a polyoxyalkylene copolymer, preferably from 0.0005% to 50.0% by weight ofpolyoxyalkylene copolymer, and more preferably from 0.002% to 25.0% by weight of polyoxyalkylene copolymer, over the total weight of the formulation,- an acrylic graft copolymer, preferably from 0.0005% to 20.0% by weight of the acrylic graftpolymer and more preferably from 0.001% to 10.0% by weight of the acrylic graft polymer, over the total weight of the formulation,- an oxygenated hydrocarbon compound, preferably from 0.0001% to 10.0% by weight of theoxygenated hydrocarbon compound, and more preferably from 0.001% to 5.0% by weight of the oxygenated hydrocarbon compound, over the total weight of the formulation, and- optionally water.In a particular embodiment when the the active ingredient A is prepared to form a formulationas cited above, such as a dispersible concentrate, the formulation may comprise:(a) from 0.01% to 70.0% by weight of the active ingredient A, and preferably from 0.1% to50.0% by weight of the active ingredient A, over the total weight of the formulation,(b) a lignin compound, preferably from 0.01% to 30.0% by weight of the lignin compound, and preferably 0.1% to 20.0% by weight of the lignin compound, over the total weight of the formulation, (c) optionally acrylic graft copolymer, preferably from 0.01% to 30.0% by weight of the acrylicgraft copolymer, and preferably from 0.1% to 20.0% by weight of the acrylic graft copolymer,over the total weight of the formulation,(d) optionally a lactamide compound, preferably from 10.0% to 90.0% by weight of thelactamide compound, and preferably from 20% to 80% by weight of the lactamide compound,over the total weight of the composition, and(e) optionally an ether type solvent, preferably from 1.0% to 70.0% by weight of the ether typesolvent, and preferably from 1.0% to 60.0% by weight of the ether type solvent, over the total weight of the composition. In said particular embodiment, the active ingredient A, the polyoxyalkylene copolymer, theacrylic graft copolymer, the oxygenated hydrocarbon, the lignin compound, the lactamidecompound, and the ether type solvent are the compounds described in the present invention.The active ingredient B according to the present invention can be used to prepare a suspensionconcentrate or a flowable suspension, in using ingredients and techniques well-known in the art. A suspension concentrate containing the active ingredient B can be the product CURBIX commercialized by BAYER. In a preferred embodiment according to the present invention, the pesticidal composition canbe a mixture of the active ingredient A and the active ingredient B, and more particularly amixture of:- a formulation containing the active ingredient A, such as a suspension concentrate, a flowablesuspension, a suspoemulsion, a suspension concentrate-capsule suspension blend, water soluble granules, water-dispersible granules, water-dispersible tablets, a dispersible concentrate,emulsifiable concentrate, or an oil dispersion, and preferably a suspension concentrate; and- a formulation containing the active ingredient B, such as a suspension concentrate or aflowable suspension, and preferably a suspension concentrate.Said mixture can be diluted with water in a tank mix. The formulation containing the active ingredient A and the formulation containing the activeingredient B can be added to a farmer’s spray tank of water or it may be applied, once mixed,directly without further dilution.In a further embodiment, the active ingredient A and the active ingredient B can respectivelybe applied in any desired sequence or simultaneously.In a further embodiment, the formulation containing the active ingredient A and the formulationcontaining the active ingredient B can respectively be applied in any desired sequence orsimultaneously. The pesticidal composition of the present invention may further comprise an additional agrochemical, or in other words a third agrochemical. The additional agrochemical can be an insecticide, a fungicide, an herbicide, a synergist, a plant growth regulator, a nematicide, a plant nutrient, a plant fertilizer, a biological, and a mixture thereof. In a particular embodiment, the composition of the present invention can further comprise anadditional insecticide selected from abamectin, bifenthrin, broflanilide, chlorantraniliprole,chlorfenapyr, cyantraniliprole, cypermethrin, deltametrin, emamectin benzoate,fluxametamide, gamma-cyhalothrin, lambda-cyhalothrin, lufenuron, methoxyfenozide,pymetrozine, spinetoram, spinosad, sulfoxaflor, tefluthrin, thiamethoxam, and any mixturesthereof. In another paticular embodiment, the composition of the present invention can further comprisea biological selected from Bacillus species. Bacillus species are insecticidally and / ornematicidally active bacteria, and can include for example Bacillus firmus, Bacillus cereus,Bacillus subtilis, or Bacillus thuringiensis. The most preferred Bacillus species is Bacillusthuringiensis, and more particularly Bacillus thuringiensis var. kurstaki or Bacillusthuringiensis var. tenebrionis.The weight ratio of isocycloseram to the additional insecticide can be from 1:100 to 100:1, preferably from 1:20 to 20:1, preferably from 1:10 to 10:1, preferably from 1:1 to 1:10, preferably from 1:1 to 1:6, and more preferably 1:2, 1:3, 1:4 or 1:5. The weight ratio of isocycloseram to the biological can be from 1:2000 to 1:2, preferably from 1:1000 to 1:100, preferably from 1:400 to 1:10, and more preferably from 1:200 to 1:100. The composition of the present invention may comprise a suitable amount of one or several of the above-mentioned ingredient(s) to obtain the respective properties, when appropriate.According to the present invention, the pest is selected from the Pentatomidae family (from theHemiptera order, and more particularly from the Heteroptera suborder).More preferably, the Pentatomidae family can be selected from Dichelops genus (such as forexample Dichelops melacanthus) and Euschistus genus (such as for example Euschistus heros).The preferred genus in the Pentatomidae family is Euschistus. The most preferred pestaccording to the present invention is Euschistus heros.Other pests can also be considered in the present invention such as for example species from other families of the Hemiptera order, the Lepidoptera order, the Coleoptera order, the Dipteraorder, the Thysanoptera order, the Acarida order, or the Blattodea order.The other families of the Hemiptera order can be selected from Cicadellidae family such as forexample Dalbulus maidis, Peregrinus maidis.The Lepidoptera order can be selected from:- Lyonetiidae family, such as for example Perileucoptera coffeella;- Noctuidae family, and more particularly the Autographa genus such as for exampleAutographa gamma; the Chrysodeixis genus such as for example Chrysodeixis includens; fromthe Diatraea genus, such as for example Diatraea saccharalis; from the Helicoverpa genussuch as for example Helicoverpa armigera;- Spodoptera genus, such as for example Spodoptera frugiperda, Spodoptera eridania,Spodoptera cosmioides, Spodoptera albula, Spodoptera littoralis;- Rachiplusia genus, such as for example Rachiplusia nu; and- Tuta genus, such as for example Tuta absoluta.The Coleoptera order can be selected from Chrysomelidae family (such as for exampleDiabrotica sp., Leptinotarsa sp., Phyllotreta sp., Chaetocnema sp.), Scarabidae family (such asfor example Phyllophaga sp., Cyclocephala sp., Popilia sp.), Curculionidae family (such as forexample Anthonomus sp., Sphenopherus sp., Otiorhynchus sp., Hypothenemus hampei), andNitidulidae family (such as for example Meligethes sp.).The Diptera order can be selected from Agromyzidae family such as for example Liriomyza huidobrensis. The Thysanoptera order or thrips can be selected from Thripidae family such as for example Frankliniella schultzei, Caliothrips phaseoli.The Acarida (Trombidiformes) order or mites can be from the Tetranychidae family such as forexample Tetranychus urticae.The Blattodea (Isoptera) order or termites can be selected from Rhinotermitidae family such asfor example Heterotermes sp.. The composition according to the present invention can be used for combating and / 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 protectedagainst these pests. Said composition can also be used for combating and / or controlling (i.e.containing or destroying) pests of the abovementioned type which occur in particular in soil and / or on plant propagation material.The term "plant" as used in the present description includes seedlings, bushes and trees. Suitabletarget crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize (e.g. field corn, popcorn, corn), millet or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya (soya beans); oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins,cucumbers, melons, watermelons or squashes; fibre plants, such as cotton, flax, hemp or jute;citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, broccolis, cauliflowers, carrots, onions, tomatoes, potatoes,eggplants, peppers or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; andalso tobacco, nuts, coffee, sugarcane, tea, grapevines, hops, the plantain family and latex plant.In a preferred embodiment, the plant can be selected from:- cereals, such as wheat, barley, rye, oats, rice, maize (e.g. field corn, popcorn, corn), millet orsorghum; and more preferably rice, maize (e.g. field corn, popcorn, corn), millet or sorghum;- leguminous crops, such as beans, lentils, peas or soya (soya beans); and more preferably soya(soya beans);- fibre plants, such as cotton, flax, hemp or jute; and more preferably cotton;- coffee; and- sugarcane.In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (GeneticallyModified Organisms), and parts thereof, can be treated by the pesticidal composition of theinvention. Particularly preferably, plants of the plant cultivars which are in each case commercially available or in use are treated according to the invention. Plant cultivars are understood as meaning plants having novel properties ("traits") which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can becultivars, bio- or genotypes.The genetic modified crops can be described in the following website https: / / www.isaaa.org / gmapprovaldatabase, incorporated by reference therein.For example, when considering soybean, the genetic modified crops can be selected from:Event Name and Code Trade NameSoybean - Glycine max L. : 46 Events N m MON87751 x MON87701 x MON87708 x MON89788t il blFor example, when considering maize, the genetic modified crops can be selected from:Event Name and Code Trade NameMaize - Zea mays L. : 193 Events xxCode: DP-ØØ4114-3 x SYN-IR6Ø4-5 x MON-ØØ6Ø3-6 Name: Bt11 x MIR162 x TC1507 x GA21 Agrisure™ Viptera 3220Code: SYN-BTØ11-1 x SYN-IR162-4 x DAS-Ø15Ø7-1 x MON- Name: TC1507 x 59122 x MON810 x NK603 Intrasect XTRA Name: TC1507 x 59122 x NK603 Herculex XTRA™ RRCode: DAS-Ø15Ø7-1 x DAS-59122-7 x MON-ØØ6Ø3-6 For example, when considering cotton, the genetic modified crops can be selected from:Event Name and Code Trade NameCotton - Gossypium hirsutum L. : 71 Events Name: 3006-210-23 x 281-24-236 x MON1445 WideStrike™ xCode: ACS-GHØØ1-3 x MON-15985-7II™ Name: T303-3t il bl In the present invention, 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. In the present invention, the term "plant propagation material" is understood to denote all the generative parts of the plant, such as seeds, which can be used for the multiplication of the latter including vegetative plant material such as cuttings. There may be mentioned, as plant propagation material, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, parts of plants. The plant propagation material can be treated with the composition of the invention before the material is sown or planted. Alternatively, the plant propagation material may be treated with the composition of the invention during sowing or planting. Additionally, the composition of the invention may be applied to the previously treated propagation material before or during its planting. The composition of the invention may be applied during the sowing of the seed. The composition may also be used to plant propagation material derived from plants grown in a green house and / or during transplantation.More preferably the plant propagation material is plant seeds. The seed treatment can occur toan unsown seed, and the term "unsown seed" is meant to include seed at any period between the harvest of the seed and the sowing of the seed in the ground for the purpose of germination and growth of the plant. Treatment to an unsown seed is not meant to include those practices inwhich the composition is applied to the soil but would include any application practice thatwould target the seed during the sowing / planting process. The treated plant propagation material of the present invention can be treated in the same manner as conventional plant propagation material. The treated propagation material can be stored, handled, sown and tilled in the same manner as any other pesticide treated material. In a particular embodiment, the pesticidal composition according to the present invention canbe applied to the pest, to a locus of the pest, or to a plant susceptible to attack by the pest, inspraying the pesticidal composition, for example dispensed from a spray container for foliarapplication. Said method can involve an effective amount of the pesticidal composition applied at a rate of:- from 1 g to 100 g of the active ingredient A per hectare, preferably from 5 g to 80 g of theactive ingredient A per hectare, preferably from 10 g to 40 g of the active ingredient A perhectare, and more preferably 20 g of the active ingredient A per hectare; and- from 1 g to 600 g of the active ingredient B per hectare, preferably from 5 g to 400 g of theactive ingredient B per hectare, preferably from 10 g to 200 g of the active ingredient B perhectare, preferably from 40 g to 100 g of the active ingredient B per hectare, and morepreferably 80 g of the active ingredient B per hectare.More particularly, the weight rate of the active ingredient A is inferior to the weight rate of theactive ingredient B, preferably is at least 2 times lower than the weight rate of the activeingredient B, preferably is at least 3 times lower than the weight rate of the active ingredient B,and more preferably is at least 4 times lower than the weight rate of the active ingredient B.This weight rate can be advantageously used for foliar application.In another object, the pesticidal composition as defined in the present invention can be used tocombat and / or control the pests from the Pentatomidae family, preferably selected from theEuschistus genus such as more preferably Euschistus heros.The pesticidal composition according to the present invention achieves a high degree of pestcontrol, especially within a very short time such as for example at least two days afterapplication. Examples The following non-limiting examples demonstrate the improved behaviour associated with a method according to the present invention. A synergistic effect exists whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components. The action to be expected E for a given active ingredient combination obeys the so-called COLBY formula and can be calculated as follows (COLBY, S.R. "Calculating synergistic and antagonistic responses of herbicide combination", Weeds, Vol.15, pages 20-22; 1967): ppm = milligrams of active ingredient (= a.i.) per liter of spray mixture X = % action by active ingredient (A) using p ppm of active ingredient Y = % action by active ingredient (B) using q ppm of active ingredient. According to COLBY, the expected (additive) action of active ingredients (A)+(B) using p+q ppm of active ingredient is X ^ Y E=X+Y - 100 If the action actually observed (O) is greater than the expected action (E), then the action of the combination is super-additive, i.e. there is a synergistic effect. In mathematical terms, synergism corresponds to a positive value for the difference of (O-E). In the case of purelycomplementary addition of activities (expected activity), said difference (O-E) is zero. Anegative value of said difference (O-E) signals a loss of activity compared to the expected activity.The products used in the following examples are detailed below:- Isocycloseram: an SC400 formulation (suspension concentrate with 400 g of active ingredientper liter) comprising isocycloseram as active ingredient, this formulation is commercialized bySYNGENTA under the name SPONTA SC400; and- Ethiprole: an SC200 formulation (suspension concentrate with 200 g of active ingredient perliter) comprising ethiprole as active ingredient, this formulation is commercialized by BAYERunder the name CURBIX SC200.Description of the experimentsExample 1 (Euschistus sp.)Each of the product SPONTA SC400 (Ex.1), the product CURBIX SC200 (Ex.2), and thepescitical composition (Ex.3) comprising the product SPONTA SC400 and the productCURBIX SC200 is diluted with the addition of water of 150 liter per hectare.The dose rate used for SPONTA SC400 and CURBIX SC200 are expressed in gram of activeingredients per hectare and gathered in the below table 1. Pots with soybean plants (4 plants per pot, 3 pots per treatment) were applied with a track-sprayer (150 l / ha) green nozzle (Lechler LU 120). After drying, leaves were sampled and placedin a petri dish (diameter: 14.5 cm) with 2 soybean seeds. Three replicates per treatment weredone. Leaves were infested with 10 Euschistus heros nymphs, at stage N2 (2nd larvae stage).Two and six days after application (DAA), mortality was assessed. The results are gathered inthe below table 1.Ex. Active ingredient(s)2DAA 6DAA (gram per hectare) (% mortality) (% mortality) Ex.1 Isocycloseram (1 g AI / ha) 27 87Ex.2 Ethiprole (2 g AI / ha) 7 57Ex.3 Isocycloseram (1 g AI / ha) + 60 100Ethiprole (2 g AI / ha) Expected efficacy 32 94Table 1 The tested active ingredients according to the invention, which are based on isocycloserammixed with ethiprole surprisingly guarantee a high degree of pest control against Euschistusgenus, and especially against Euschistus heros.

Claims

CLAIMS1. A method of combating and / or controlling a pest selected from the Pentatomidae family,which comprises applying to said pest, to a locus of said pest, to a plant susceptible to attack bysaid pest, or to a plant propagation material susceptible to attack by said pest, a pesticidalcomposition comprising isocycloseram as active ingredient A, and ethiprole as activeingredient B.

2. A method according to claim 1, characterized in that the pest is selected from theEuschistus genus.

3. A method according to any one of the preceding claims, characterized in that the pest isEuschistus heros.

4. A method according to any one of the preceding claims, characterized in that the weightratio of active ingredient A to active ingredient B ranges from 1:1 to 1:100, preferably from 1:1to 1:50, preferably from 1:1 to 1:20, preferably from 1:1 to 1:10, and more preferably from 1:1 to 1:

5.

5. A method according to any one of the preceding claims, characterized in that aneffective amount of the pesticidal composition is applied at a rate of from 1 g to 100 g of theactive ingredient A per hectare, preferably from 5 g to 80 g of the active ingredient A perhectare, preferably from 10 g to 40 g of the active ingredient A per hectare, and more preferably20 g of the active ingredient A per hectare.

6. A method according to any one of the preceding claims, characterized in that an effective amount of the pesticidal composition is applied at a rate of from 1 g to 600 g of theactive ingredient B per hectare, preferably from 5 g to 400 g of the active ingredient B perhectare, preferably from 10 g to 200 g of the active ingredient B per hectare, preferably from40 g to 100 g of the active ingredient B per hectare, and more preferably 80 g of the activeingredient B per hectare.

7. A method according to any one of the preceding claims, characterized in that the active ingredient A is used to prepare a suspension concentrate, a flowable suspension, a suspoemulsion, a suspension concentrate-capsule suspension blend, water soluble granules,water-dispersible granules, water-dispersible tablets, a dispersible concentrate, emulsifiableconcentrate, or an oil dispersion.

8. A method according to any one of the preceding claims, characterized in that the activeingredient B is used to prepare a suspension concentrate, or a flowable suspension.

9. A method according to any one of the preceding claims, characterized in that thepesticidal composition further comprises at least one of the components selected among apolyoxyalkylene copolymer, an acrylic graft copolymer, an oxygenated hydrocarbon, a lignin compound, a lactamide compound, and an ether type solvent.

10. A method according to any one of the preceding claims, characterized in that the activeingredients A and B are applied in mixing a formulation containing the active ingredient A anda formulation containing the active ingredient B.

11. A method according to any one of the preceding claims, characterized in that the methodis applied in spraying the pesticidal composition.

12. A method according to any one of the preceding claims, characterized in that the plantis selected from cereals, leguminous crops, fiber plants, and sugarcane.

13. A method according to any one of the preceding claims, characterized in that the plantis selected from rice, maize, millet, sorghum, soya, cotton, and sugarcane.

14. Use of the pesticidal composition as defined in any one of claims 1 to 13, to combatand / or control the pests from the Pentatomidae family.

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