Pesticidal mixture to control pests

Abstract

The present invention relates to a method of combating and / or controlling a pest selected from the Noctuidae family and the Pieridae 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 piperonyl butoxide as active ingredient B.

Description

[0001] PESTICIDAL MIXTURE TO CONTROL PESTS

[0002] The present invention relates to compositions of pesticidally active ingredients and to methods of using the compositions in the field of agriculture.

[0003] WO2011067272 discloses that certain isoxazoline compounds have insecticidal activity.

[0004] The present invention provides a method of combating and / or controlling a pest selected from the Noctuidae family and the Pieridae 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 piperonyl butoxide as active ingredient B.

[0005] It has now been found, surprisingly, that the pesticidal composition, or in other words the active ingredient mixture, according to the invention achieves a synergistic effect to treat a pest selected from the Noctuidae family and the Pieridae family, preferably selected from the Trichoplusia genus (such as more preferably Trichoplusia nil), the Artogeia genus (such as more preferably Artogeia rapae), and the Spodoptera genus (such as more preferably Spodoptera littoralis). The pesticidal composition achieves a high degree of pest control, especially within a short time.

[0006] Throughout this document, the expression “composition” stands for the various mixtures or combinations 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.

[0007] Isocycloseram is an insecticidal agrochemical with the following CAS number: 2061933-85-3, and has the following chemical formula:

[0008]

[0009] Isocycloseram can comprise the isomer (5S,4R) which is 4-[(5S)-5-(3,5-dichloro-4-fhroro-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 of the 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 the isomers (5S,4R), (5S,4S), (5R,4R) and (5R,4S).

[0010] 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).

[0011] 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 piperonyl butoxide (PBO) with the following CAS number: 51-03-6.

[0012] According to the present invention, the active ingredients (A) and (B) can be present in a synergistically effective amount in the pesticidal composition.

[0013] 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 1:30, preferably from 1:1 to 1:20, and more preferably from 1:1 to 1:15.

[0014] In another preferred embodimpent, the weight ratio (in grams of active ingredients ) of active ingredient A to active ingredient B can range from 100:1 to 1:1, preferably from 50:1 to 1:1, preferably from 40:1 to 1:1, preferably from 30:1 to 1:1, preferably from 20:1 to 1:1, and more preferably 10:1 to 1:1.

[0015] The active ingredient A according to the present invention can be used to prepare a suspension concentrate (SC), a flowable suspension (FS), a suspoemulsion (SE), a suspension concentratecapsule suspension blend (ZC), water soluble granules (SG), water dispersible granules (WG), water dispersible tablets (WT), a dispersible concentrate (DC), an emulsifiable concentrate (EC), or an oil dispersion (OD). The most preferred formulation type is a suspension concentrate, a dispersible concentrate, or a suspension concentrate-capsule suspension blend.

[0016] 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 or WO2023 / 232559.

[0017] For example, the pesticidal composition according to the present invention, especially for the preparation of the active ingredient A, can further comprise at least one of the components selected among a polyoxyalkylene copolymer, an acrylic graft copolymer, an oxygenated hydrocarbon, a lignin compound, a lactamide compound, and an ether type solvent, preferably at least two of said components, preferably at least three of said components, and more preferably preferably at least four of said components.

[0018] 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 the components selected among a polyoxyalkylene copolymer, an acrylic graft copolymer, and anoxygenated hydrocarbon, preferably at least two of said components, and more preferably said three components.

[0019] 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 the components selected among an acrylic graft copolymer, a lignin compound, a lactamide compound, and ether type solvent, preferably at least two of said components, preferably at least three of said components, and more preferably said four components.

[0020] 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.

[0021] The polyoxyalkylene copolymer can be more preferably a polyoxyalkylene block copolymer of the AB, ABA, BAB, or ABABA type.

[0022] 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.

[0023] In a preferred embodiment, the polyoxyalkylene copolymer can be an ethylene oxi de-propylene oxi de-ethylene oxide block copolymer (EO-PO-EO block copolymer), or in other words a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer or a poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) block copolymer.

[0024] 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.

[0025] In the present invention, the expression “a molecular weight” means an average molecular weight (i.e. a molecular weight approximately of). Molecular weight of a polymer, or in other words the molar mass, can be easily determined by method well-known in the art, such as gel permeation chromatography (GPC).

[0026] 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 polypropylene oxide) block of the EO-PO-EO block copolymer.

[0027] 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 polyethylene oxide) block in the EO-PO-EO block copolymer.

[0028] 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.

[0029] Examples include the GENAPOL® PF series (CLARIANT), the PLURONIC® series (BASF), the SYNPERONIC® PE series (CRODA), or the TOXIMUL® series (STEPAN).

[0030] The acrylic graft copolymer has typically a comb- or star-like structure, and preferably a comblike structure.

[0031] Graft copolymers are branched copolymers wherein the components forming the side chains are structurally different from the components forming the main chain.

[0032] Comb-like polymers comprise of a main chain (backbone) which contains branch points from each of which a linear side chain emanates.

[0033] Star-like polymers comprise of a multifunctional centre from which at least three polymer chains radiate.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] More preferably, the acrylic graft copolymer is a non-ionic polymer, and more particularly with a comb-like structure.

[0038] 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.

[0039] 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™ supplied by CRODA, or Tersperse 2500™ supplied by HUNTSMAN.

[0040] 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, the oxygenated hydrocarbon compound is preferably different from the polyoxyalkylene copolymer and from the acrylic graft copolymer.

[0041] 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 Cn, and more preferably with a chain length of C9 or C10. An example can be Rhodasurf DA / 630-E™ supplied by SOLVAY-RHODIA,

[0042] The sulfonated alkyl ester compound can be a sulfosuccinate ester or a salt of a sulfosuccinate ester. An example can be Aerosol™ OT-B, supplied by SOLVAY-RHODIA.

[0043] 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.

[0044] The lignin compound can be more particularly a kraft lignin and / or an unsulfonated lignin. In a preferred embodiment, the lignin compound can be an unsulfonated kraft lignin.

[0045] 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.

[0046] The lactamide compound can be of formula I: CH3CH(OH)C(=O)NRIR2 (I), wherein Ri and R2 are each independently hydrogen; or C1-6 alkyl, C2-6 alkenyl or C3-6 cycloalkyl, 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 Ri 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,Ri and R2 of the lactamide compound of formula I can be each independently hydrogen or Ci-6 alkyl, and more preferably hydrogen or C1-3 alkyl such as lactic acid dimethyl amide or lactic acid diethyl amide.

[0047] 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.

[0048] In the present invention, the composition may further comprise water.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] In a particular embodiment when the active ingredient A is prepared to form a formulation as cited above, and more particularly a suspension concentrate or a flowable suspension, the formulation may comprise:

[0053] - 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,

[0054] - a polyoxyalkylene copolymer, preferably from 0.0005% to 50.0% by weight of poly oxyalkylene copolymer, and more preferably from 0.002% to 25.0% by weight of polyoxyalkylene copolymer, over the total weight of the formulation,

[0055] - an acrylic graft copolymer, preferably from 0.0005% to 20.0% by weight of the acrylic graft polymer and more preferably from 0.001% to 10.0% by weight of the acrylic graft polymer, over the total weight of the formulation,

[0056] - an oxygenated hydrocarbon compound, preferably from 0.0001% to 10.0% by weight of the oxygenated 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

[0057] - optionally water.In a particular embodiment when the the active ingredient A is prepared to form a formulation as cited above, such as a dispersible concentrate, the formulation may comprise:

[0058] (a) from 0.01% to 70.0% by weight of the active ingredient A, and preferably from 0.1% to 50.0% by weight of the active ingredient A, over the total weight of the formulation,

[0059] (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,

[0060] (c) optionally acrylic graft copolymer, preferably from 0.01% to 30.0% by weight of the acrylic graft copolymer, and preferably from 0.1% to 20.0% by weight of the acrylic graft copolymer, over the total weight of the formulation,

[0061] (d) optionally a lactamide compound, preferably from 10.0% to 90.0% by weight of the lactamide compound, and preferably from 20% to 80% by weight of the lactamide compound, over the total weight of the composition, and

[0062] (e) optionally an ether type solvent, preferably from 1.0% to 70.0% by weight of the ether type solvent, and preferably from 1.0% to 60.0% by weight of the ether type solvent, over the total weight of the composition.

[0063] In said particular embodiment, the active ingredient A, the polyoxyalkylene copolymer, the acrylic graft copolymer, the oxygenated hydrocarbon, the lignin compound, the lactamide compound, and the ether type solvent are the compounds described in the present invention.

[0064] The active ingredient B according to the present invention can be used to prepare an emulsifiable concentrate, in using ingredients and techniques well-known in the art. An emulsifiable concentrate containing the active ingredient B can be the product EXPONENT commercialized by MGK.

[0065] In a preferred embodiment according to the present invention, the pesticidal composition can be a mixture of the active ingredient A and the active ingredient B, and more particularly a mixture of:

[0066] - a formulation containing the active ingredient A, such as 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, emulsifiable concentrate, or an oil dispersion, and preferably a suspension concentrate; and - a formulation containing the active ingredient B, such as an emulsifiable concentrate.

[0067] Said mixture can be diluted with water in a tank mix.The formulation containing the active ingredient A and the formulation containing the active ingredient B can be added to a farmer’s spray tank of water or it may be applied, once mixed, directly without further dilution.

[0068] In a further embodiment, the active ingredient A and the active ingredient B can respectively be applied in any desired sequence or simultaneously.

[0069] In a further embodiment, the formulation containing the active ingredient A and the formulation containing the active ingredient B can respectively be applied in any desired sequence or simultaneously.

[0070] 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.

[0071] In a particular embodiment, the composition of the present invention can further comprise an additional insecticide selected from abamectin, bifenthrin, broflanilide, chlorantraniliprole, cyantraniliprole, cypermethrin, deltametrin, emamectin benzoate, ethiprole, fluxametamide, gamma-cyhalothrin, lambda-cyhalothrin, lufenuron, methoxyfenozide, pymetrozine, spinetoram, spinosad, sulfoxaflor, tefluthrin, thiamethoxam, and any mixtures thereof.

[0072] In another paticular embodiment, the composition of the present invention can further comprise a biological selected from Bacillus species. Bacillus species are insecticidally and / or nematicidally active bacteria, and can include for example Bacillus firmus. Bacillus cercus. Bacillus sublilis. or Bacillus thuringiensis. The most preferred Bacillus species is Bacillus thuringiensis. and more particularly Bacillus thuringiensis var. kurstaki or Bacillus thuringiensis var. tenebrionis.

[0073] 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.

[0074] 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 Noctuidae family and from the Pieridae family, both families being from the Lepidoptera order.

[0075] More preferably, the Noctuidae family can be selected from:

[0076] - Agrotis genus, such as for example Agrotis gladiaria. Agrotis ipsilon, Agrotis orthogonia; - Autographa genus, such as for example Autographa gamma,

[0077] - Chloridea genus, such as for example Chloridea virescens;

[0078] - Chrysodeixis genus, such as for example Chrysodeixis includens;

[0079] - Diatraea genus, such as for example Diatraea saccharalis;

[0080] - Euxoa genus, such as for example Euxoa auxiliaris, Euxoa messoria, Euxoa ochrogaster; - Helicoverpa genus, such as for example Helicoverpa armigera, Helicoverpa zea;

[0081] - Lacinipolia genus, such as for example Lacinipolia renigera;

[0082] - Mythimna genus, such as for example Mythimna unipuncta;

[0083] - Nephelodes genus, such as for example Nephelodes minians;

[0084] - Peridroma genus, such as for example Peridroma saucia;

[0085] - Spodoptera genus, such as for example Spodoptera frugiperda, Spodoptera eridania, Spodoptera cosmioides, Spodoptera exigua, Spodoptera albula, Spodoptera littoralis, Spodoptera littura, Spodoptera ornithogalli, Spodoptera praefica;

[0086] - Striacosta genus, such as for example Striacosta albicosta;

[0087] - Rachiplusia genus, such as for example Rachiplusia nu:

[0088] - Trichoplusia such as for example Trichoplusia nr, and

[0089] - Xestia genus, such as for example Xestia c-nigrum.

[0090] The preferred genus in the Noctuidae family is Trichoplusia. The most preferred pest according to the present invention is Trichoplusia ni.

[0091] More preferably, the Pieridae family can be selected from Artogeia (Pieris) genus, such as for example Artogeia (Pieris) rapae, Artogeia (Pieris) brassicae,' and Colias genus, such as for example Colias eury theme, Colias philodice.

[0092] The preferred genus in the Peridae family is Artogeia (Pieris). The most preferred pest according to the present invention is Artogeia (Pieris) rapae.

[0093] Other pests can also be considered in the present invention such as for example species from other families of the Lepidoptera order, the Coleoptera order, the Diptera order, the Hemiptera order, the Thysanoptera order, the Acarida order, or the Blattodea order.

[0094] The other family of the Lepidoptera order can be selected from Lyonetiidae family, such as for example Perileucopter a coffeella, from and Gelechiidae family, such as for example Tula absoluta, and from Crambidae family such as for example Scirpophaga incertulas.The Coleoptera order can be selected from Chrysomelidae family (such as for example Diabrotica sp., Leptinotarsa sp., Phyllotreta sp., Chaetocnema sp.), Scarabidae family (such as for example Phyllophaga sp., Cyclocephala sp., Popilia sp.), Curculionidae family (such as for example Anthonomus sp., Sphenopherus sp., Otiorhynchus sp., Hypothenemus hampei). and Nitidulidae family (such as for example Meligethes sp.).

[0095] The Diptera order can be selected from Agromyzidae family such as for example Liriomyza huidobrensis.

[0096] The Hemiptera order (Heteroptera suborder) can be selected from Pentatomidae family such as for example Dichelops melacanthus, Euschistus heros; from Cicadellidae family such as for example Dalbulus maidis, Peregrinus maidis, and Miridae family such as for example Lygus lineolaris, Lygus hesperus.

[0097] The Thysanoptera order or thrips can be selected from Thripidae family such as for example Frankliniella schnitzel. Frankliniella occidentalis, Caliothrips phaseoli, Thrips tabaci.

[0098] The Acarida (Trombidiformes) order or mites can be from Tetranychidae family such as for example Tetranychus urlicae from Eriophyidae family such as for example Phyllocoptruta oleivora and Tarsonemidae family such as for example Polyphagotarsonemus latus.

[0099] The Blattodea (Isoptera) order or termites can be selected from Rhinotermitidae family such as for example Heterotermes sp..

[0100] 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 protected against 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.

[0101] The term "plant" as used in the present description includes seedlings, bushes and trees. Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize (e.g. field corn, popcorn, com), 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, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas, peanuts 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 arugula, spinach, lettuce, asparagus, cabbages (including abyssinian cabbage, Chinese cabbage, seakale cabbage), broccolis (including Chinese broccoli), broccoli raab, brussels sprouts, cauliflowers, carrots, collards, cresses (including garden cress and upland cress), hanover salad, kale, maca, mizuna, mustard greens, onions, radish or radish leaves, rape greens, wild rocket, shepard’s purse, turnip greens, tomatoes, potatoes, eggplants, peppers or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts such as almonds, pistachios, walnuts; coffee, sugarcane, tea, grapevines, hops, the plantain family and latex plant; Moraceae, such as ficus.

[0102] In a preferred embodiment, the plant can be selected from vegetables, preferably from brassicales order, preferably from Brassicaceae family, preferably from Brassica genus, and more preferably Brassica oleracea.

[0103] In another preferred embodiment, the plant can be selected from vegetables, preferably from solanales order, preferably from Solanacae family, preferebly from Lycopersicon or Solanum genus, and more preferably Solanum lycopersicon.

[0104] In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof, can be treated by the pesticidal composition of the invention. 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 be cultivars, bio- or genotypes.

[0105] The genetic modified crops can be described in the following website https: / / www.isaaa.org / gmapprovaldatabase, incorporated by reference therein. For example, the genetic modified crops can be selected from cotton, maize or soybean crops.

[0106] 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.

[0107] 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 ofplants. 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.

[0108] More preferably the plant propagation material is plant seeds. The seed treatment can occur to an 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 in which the composition is applied to the soil but would include any application practice that would 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.

[0109] In a particular embodiment, the pesticidal composition according to the present invention can be applied to the pest, to a locus of the pest, or to a plant susceptible to attack by the pest, in spraying the pesticidal composition, for example dispensed from a spray container for foliar application.

[0110] 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 20 g to 80 g of the active ingredient A per hectare, and more preferably from 30 g to 60 g of the active ingredient A per hectare; and

[0111] - from 1 g to 800 g of the active ingredient B per hectare, preferably from 100 g to 600 g of the active ingredient B per hectare, preferably from 300 g to 500 g of the active ingredient B per hectare, preferably from 400 g to 500 g of the active ingredient B per hectare, and more preferably 450 g of the active ingredient B per hectare.

[0112] More particularly, the weight rate of the active ingredient A is inferior to the weight rate of the active ingredient B, preferably is at least 2 times lower than the weight rate of the active ingredient B, preferably is at least 5 times lower than the weight rate of the active ingredient B, preferably is at least 7 times lower than the weight rate of the active ingredient B, and more preferably from 7.5 to 15 times lower than the weight rate of the active ingredient B. This weight rate can be advantageously used for foliar application.The above-mentioned effective amount of the pesticidal composition (comprising active ingredients A and B) can be also applied against the other pests as described in the present invention.

[0113] In another object, the pesticidal composition as defined in the present invention can be used to combat and / or control the pests from the Noctuidae family and Pieridae family, preferably selected from the Trichoplusia genus (such as more preferably Trichoplusia ni) and the Artogeia genus (such as more preferably Artogeia rapae).

[0114] The pesticidal composition according to the present invention achieves a high degree of pest control, especially within a very short time such as for example at least 8 days after application.

[0115] Examples

[0116] The following non-limiting examples demonstrate the improved behaviour associated with a method according to the present invention.

[0117] 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):

[0118] ppm = milligrams of active ingredient (= a.i.) per liter of spray mixture

[0119] X = % action by active ingredient (A) using p ppm of active ingredient

[0120] Y = % action by active ingredient (B) using q ppm of active ingredient.

[0121] According to COLBY, the expected (additive) action of active ingredients (A)+(B) using p+q ppm of active ingredient is

[0122]

[0123] 100

[0124] 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 purely complementary addition of activities (expected activity), said difference (O-E) is zero. A negative value of said difference (O-E) signals a loss of activity compared to the expected activity.

[0125] The products used in the following examples are detailed below:- Isocy closeram: an SC200 formulation (suspension concentrate with 200 g of active ingredient per liter) comprising isocycloseram as active ingredient, this formulation being commercialized by SYNGENTA; and

[0126] - PBO: an EC200 formulation (suspension concentrate with 772 g of active ingredient per liter) comprising piperonyl butoxide as active ingredient, this formulation being commercialized by MGK, a company of SUMITOMO CHEMICAL, under the name EXPONENT.

[0127] In order to achieve adequate spray coverage on brassica species plants an adjuvant was added to each formulation (i.e. isocycloseram SC 200 formulation; PBO EC 200 formulation) and to each formulation mixture (i.e. mixture of isocycloseram SC 200 formulation and PBO EC 200 formulation), at the same amount (0.05 % by weight over the total weight of the formulation or the formulation mixture, respectively). A well-known in the art adjuvant can be used, such as for example a nonionic adjuvant based on polydimethylsiloxane. Said product can be for example the product KINETIC (a polyalkyleneoxide modified polydimethylsiloxane) commercialized by Helena.

[0128] Description of the experiments

[0129] Example 1 (Trichoplusia ni)

[0130] Cabbage variety ‘Primo Vantage’ was transplanted in to the field into double row beds on 40-inch centers. Plots were one bed wide by 30 feet long. Three replications of each treatment were arranged in a Randomized Complete Block Design. Treatments, rates, and insect data are provided in the Tables 1 and 2. One application was made with a carbon dioxide pressurized boom sprayer that delivered a broadcast application at 40 PSI and 40 gallons per acrethrough cone nozzles. The crop was in the late leaf development stage (BBCH scale 19: nine or more true leaves unfolded) when the application was initiated. The application occurred after the identification of Trichoplusia ni larvae hatching from eggs laid on the cabbage. Numbers of Trichoplusia ni larvae were counted on five random plants pulled from each plot. Counts were taken 14 days and 27 days after the application (DAA) occurred. The results are gathered in Tables 1 and 2.

[0131]

[0132]

[0133] Table 1

[0134]

[0135] Table 2

[0136] The tested active ingredients according to the invention, which are based on isocycloseram mixed with piperonyl butoxide surprisingly guarantee a high degree of pest control against Trichoplusia genus, and especially against Trichoplusia ni.

[0137] Example 2 (Artogeia rapae)

[0138] Data gathered for Artogeia rapae occurred in the same field and under the same conditions as Example 1 described above for Trichoplusia ni. Treatments, rates, and insect data are provided in the Tables 3 and 4. Numbers of Artogeia rapae larvae and percentage control were countedon five random plants pulled from each plot. Counts were taken 8 days and 21 days after the application (DAA) occurred. The results are gathered in Tables 3 and 4.

[0139]

[0140] Table 3

[0141]

[0142] Table 4The tested active ingredients according to the invention, which are based on isocycloseram mixed with piperonyl butoxide surprisingly guarantee a high degree of pest control against Artogeia genus, and especially against Artogeia rapae.

[0143] Example 3 (Spodoptera littoralis)

[0144] Cotton leaf discs were placed onto agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10’000 ppm DMSO (Dimethyl sulfoxide) stock solutions. After drying the leaf discs were infested with LI larvae. The samples were assessed for mortality 3 days after infestation. The results are gathered in the below table 5.

[0145]

[0146]

[0147] Table 5

[0148] The tested active ingredients according to the invention, which are based on isocycloseram mixed with piperonyl butoxide surprisingly guarantee a high degree of pest control against Spodoptera genus, and especially against Spodoptera littoralis.

Claims

CLAIMS1. A method of combating and / or controlling a pest selected from the Noctuidae family and the Pieridae 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 piperonyl butoxide as active ingredient B.

2. A method according to claim 1, characterized in that the pest is selected from the Trichoplusia genus, Artogeia genus, and Spodoptera genus.

3. A method according to any one of the preceding claims, characterized in that the pest is Trichoplusia ni or Artogeia rapae, or Spodoptera littoralis.

4. A method according to any one of the preceding claims, characterized in that the weight ratio of active ingredient A to active ingredient B ranges from 1 : 1 to 1 : 100, preferably from 1 : 1 to 1:50, preferably from 1:1 to 1:30, preferably from 1:1 to 1:20, and more preferably from 1:1 to 1:15.

5. A method according to any one of the preceding claims, characterized in that the weight ratio of active ingredient A to active ingredient B ranges from 100:1 to 1:1, preferably from 50:1 to 1:1, preferably from 40:1 to 1:1, preferably from 30:1 to 1:1, preferably from 20:1 to 1:1, and more preferably 10:1 to 1:1.

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 100 g of the active ingredient A per hectare, preferably from 20 g to 80 g of the active ingredient A per hectare, and more preferably from 30 g to 60 g of the active ingredient A per hectare.

7. 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 800 g of the active ingredient B per hectare, preferably from 100 g to 600 g of the active ingredient B per hectare, preferably from 300 g to 500 g of the active ingredient B per hectare, and more preferably from 400 g to 500 g of the active ingredient B per hectare.

8. 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, emulsifiable concentrate, or an oil dispersion.

9. A method according to any one of the preceding claims, characterized in that the active ingredient B is used to prepare an emulsifiable concentrate.

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

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

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

13. A method according to any one of the preceding claims, characterized in that the plant is selected from vegetables, preferably from brassicales order, preferably from Brassicaceae family, preferably from Brassica genus, and more preferably Brassica oleracea.

14. A method according to any one of the preceding claims, characterized in that the plant is selected from vegetables, preferably from solanales order, preferably from Solanacae family, preferebly from Lycopersicon or Solanum genus, and more preferably Solanum lycopersicon.

15. Use of the pesticidal composition as defined in any one of claims 1 to 14, to combat and / or control the pests from the Noctuidae family and the Pieridae family.

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