AU2011250709A1 - Pesticidal composition and method for controlling pests - Google Patents

Abstract

A pesticidal composition comprising the ester compound represented by formula (I): F F H3C CH 3 H3COH 2C /CH=CC 2 (I) and the ester compound represented by formula (II): N ONC H =C B r2 ( 11) 0* as active ingredients, which has an excellent controlling effect on pests.

Description

Australian Patents Act 1990- Regulation 3.2 ORIGINAL COMPLETE SPECIFICATION STANDARD PATENT Invention Title Pesticidal composition and method for controlling pests The following statement is a full description of this invention, including the best method of performing it known to me/us: P/00/0 II C 1 /\l la DESCRIPTION 5 TECHNICAL FIELD [0001] The present application is filed claiming the priority of the Japanese Patent Application No. 2010-266206 (filed on November 30, 2010), the entire contents of which are 10 herein incorporated by the reference. The present invention relates to a pesticidal composition and a method for controlling pests. BACKGROUND ART 15 [0002] The ester compound represented by formula (I): F F H 3 C CH 3

H

3

COH

2 C /CH=CCl 2 (I) F F is known as an active ingredient of pesticidal agents (for example, EP0054360A2 and CN101306997A). 20 [0003] EP0054360A2 discloses the compounds of formula I: 0 Fn R-- C=CH--CH-H-C--0 -- CH 2 12 /c R 2 N (1) CK 2XR 3 wherein R1 and R 2 are methyl, halomethyl or halo, X is 0, S, 2 S(O), SO 2 or NR 4 where R 4 is H, lower alkyl or lower carboxylic acyl, R 3 is lower alkyl, lower alkenyl, phenyl or benzyl, and additionally R 3 may be H when X is NR 4 ; and n is 1 to 4, and compositions comprising them, useful as 5 insecticides. [0004] CN101306997A discloses a pyrethroid compound with a structure as a formula A: R 2 1 P F (A) 10 In the formula A, the compound is a dextrogyrous single optical isomer, wherein, R 1 and R 2 are respectively the same halogen or different halogens. [0005] The ester compound represented by formula (II): /& O H 3 C CH 3 - CN CN CH=CBr 2 G I) 15 O is also known as an active ingredient of pesticidal agents (for example, US5004822). [0006] US5004822 discloses insecticides of formula: 3

R

3

(

2 )C=C-CH-CH-COOR C CH3

CH

3 wherein R1 represents hydrogen or a methyl group; R2 represents hydrogen or a halogeno or lower alkyl group; R 3 represents hydrogen or a halogen, lower alkyl (which is 5 difference to R2 when R2 represents a lower alkyl group) or carboloweralkoxy group which contains at least 2 carbon atoms in the lower alkoxy residue when R 2 represents methyl or R2 and R 3 together with the carbon atom to which they are attached represent a cycloalkylene ring having at least 10 one endocyclic carbon to carbon double bond; with the proviso that (a) R 2 and R 3 each represent hydrogen only when Ri represents methyl and (b) R 3 contains at least 2 carbon atoms when R' and R 2 each represent hydrogen; and R represents a group which form insecticidal esters with 15 chrysanthemic acid e.g. 5-benzyl-3-furylmethyl, 3 phenoxybenzyl, c'-cyano-3-phenoxybenzyl. [0007] However, there is a need to provide pesticidal agents having a larger controlling effect in some cases, depending 20 on their use situation and pests to be controlled by them. SUMMARY OF INVENTION [0008] An object of the present invention is to provide a 25 pesticidal composition having an excellent controlling 4 effect on pests and a method for controlling pests. [0009] The present inventor has intensively studied and found that an excellent control effect on pests is obtained by 5 concomitantly using an ester compound represented by formula (I) and an ester compound represented by formula (II). As a result, the present invention was completed. [0010] The present invention relates to the followings: 10 [1] A pesticidal composition comprising an ester compound represented by formula (I): F F H 3 C CH 3

H

3

COH

2 C

CH=CC

2 (I) F F (hereinafter referred to as "ester compound A") and an ester compound represented by formula (II): O H 3 C CH 3 / CN CH=CBr 2 (II) - 0 15 O (hereinafter referred to as "ester compound B") as active ingredients (hereinafter referred to as "the present pesticidal composition"). [2] The composition according to the above [1], wherein the 20 weight ratio of the ester compound A to the ester compound B is from 50:1 to 1:50. [3] A method for controlling a pest comprising applying an effective amount in total of the ester compound A and the ester compound B to a pest or a habitat where the pest 5 inhabits. [4] Use of a combination of the ester compound A and the ester compound B, for controlling a pest. 5 EFFECT OF THE INVENTION [0011] The pesticidal composition has an excellent controlling effect on pests. 10 MODE FOR CARRYING OUT THE INVENTION [0012] The pesticidal composition is characterized by containing the ester compound A and the ester compound B. The ester compound A can be produced by, for example, 15 the process described in EP0054360A2. [0013] The ester compound B can be produced by, for example, the process described in US5004822. [0014] 20 The ester compound A and the ester compound B can form isomers because these compounds respectively have two asymmetric carbon atoms on the cyclopropane ring. In the present invention, a compound containing such active isomers in any ratio may be used as the ester compound A or 25 the ester compound B. [0015] The pest, which the pesticidal composition has an effect on, includes harmful anthropods such as harmful insects and harmful acarina. Specific examples thereof are 30 as follows: 6 [0016] Lepidoptera: Pyralidae such as Chilo suppressalis, Cnaphalocrosis medinalis and Plodia interpunctella; Noctuidae such as Spodoptera litura, Pseudaletia separata, 5 and Mamestra brassicae; Pieridae such as Pieris rapae crucivora; Tortricidae such as Adoxophyes spp.; Carposinidae; Lyonetiidae; Lymantriidae; Antographa; Agrotis spp. such as Agrotis segetum and Agrotis ipsilon; Helicoverpa spp.; Heliothis spp.; Plutella xylostella; 10 Parnara guttata; Tinea pellionella; Tineola bisselliella, etc. Diptera: Culex spp. such as Culex pipiens pallens, Culex tritaeniorhynchus and Culex quinquefasciatus; Aedes spp. such as Aedes aegypti and Aedes albopictus; Anopheles spp. 15 such as Anopheles sinensis; Chironomidae; Muscidae such as Musca domestica, Musca corvina, Muscina stabulans and Fannia canicularis; Calliphoridae; Sarcophagidae; Anthomyiidae such as Delia platura and Delia antiqua; Sepsidae; Tephritidae; Agromyzidae; Drosophilidae such as 20 Drosophia melanogaster; Psychodidae; Phoridae such as Megaselia spiracularis; Simuliidae; Tabanidae; Stomoxyidae; Ceratopogonidae, etc. Blattaria: Blattella germanica, Periplaneta fuliginosa, Periplaneta americana, Periplaneta brunnea, Blatta 25 orientalis, etc. Hymenoptera: Formicidae, Vespidae, Bethylidae, Tenthredinidae such as Athalia rosae ruficornis, etc. Siphonaptera: Ctenocephalides canis, Ctenocephalides felis, Pulex irritants, etc. 30 Anoplura: Pediculus humanus, Pthirus pubis, Pediculus 7 humanus capitis, Pediculus humanus corporis, etc. Isoptera: Reticulitermes speratus, Coptotermes formosanus, etc. Hemiptera: Delphacidae such as Laodelphax striatellus, 5 Nilaparvata lugens and Sogatella furcifera; Deltocephalidae such as Nephotettix cincticeps and Nephotettix virescens; Aphididae; Pentatomidae; Aleyrodidae; Coccoidae; Cimicidae such as Cinex lectularius; Tingidae; Psyllidae, etc. Coleoptera: Attagenus unicolor; Anthrenus verbasci; corn 10 rootworms such as Diabrotica virgifera and Diabrotica undecimpunctaca howardi; Scarabaeidae such as Anomala cuprea and Anomala rufocuprea; Curculionidae such as Sitophilus zeamais, Lissorhoptrus oryzophilus, Anthonomus grandis grandis and Callosobruchus chinensis; Tenebrionidae 15 such as Tenebrio molitor and Tribolium castaneum; Chrysomelidae such as Oulema oryzae, Phyllotreta striolata and Aulacophora femoralis; Anobiidae; Epilachna spp. such as Henosepilachna vigintioctopunctata; Lyctidae; Bostrychidae; Cerambycidae; Paederus fuscipes; etc. 20 Thysanoptera: Thrips palmi, Frankliniella occidentalis, Thrips hawaiiensis, etc. Orthoptera: Gryllotalpidae, Acrididae, etc. Acarina: Pyroglyphidae such as Dermatophagoides farinae and Dermatophagoides pteronyssinus; Acaridae such as Tyrophagus 25 putrescentiae and Aleuroglyphus ovatus; Glycyphagidae such as Glycyphagus privatus, Glycyphagus domesticus and Glycyphagus destructor; Cheyletidae such as Cheyletus malaccensis and Cheyletus moorei; Tarsonemidae; Chortoglyphidae; Oribatei; Tetranychidae such as 30 Tetranychus urticae, Tetranychus kanzawai, Panonychus citri 8 and Panonychus ulmi; Ixodidae such as Haemaphysalis longicornis; Dermanyssidae such as Ornithonyssus sylvairum and. Dermanyssus galinae; etc. [0017] 5 The present pesticidal composition has an excellent controlling effect particularly on Diptera. [0018] The weight ratio of the ester compound A to the ester compound B contained in the present pesticidal composition 10 is usually from 50:1 to 1:50, preferably from 10:1 to 1:10. [0019] As the present pesticidal composition, while a simple mixture of the ester compound A and the ester compound B may be used as it is, it is applied usually after having 15 been formulated into any of the following formulations. The formulation includes oil formulations, emulsifiable concentrates, wettable powders, flowable concentrates (e.g. aqueous suspension concentrates and aqueous emulsion concentrates), microcapsules, dusts, granules, tablets, 20 aerosols, carbon dioxide formulations, volatile formulations by heating (e.g. insecticidal coils, insecticidal mats for electric heating, and volatile formulations by heating with absorbent wick), Piezo-type insecticidal formulations, heating fumigants (e.g. self 25 burning-type fumigants, chemical-reaction-type fumigants, and porous ceramic plate fumigants), non-heating volatile formulations (e.g. resin volatile formulations, paper volatile formulations, nonwoven fabric volatile formulations, braided textile volatile formulations, and 30 sublimable tablets), smoking formulations (e.g. foggings), 9 direct contact formulations (e.g. sheet-like contact formulations, tape-like contact formulations and net-like contact formulations), ULV formulations, and poisonous baits. 5 [0020] As a method for the formulation, the following methods can be exemplified. (1) A method in which the ester compound A and the ester compound B are mixed with a solid carrier, liquid carrier, 10 gaseous carrier, bait or the like, and if necessary, a surfactant and/or other auxiliaries for formulation are added thereto, followed by processing. (2) A method in which a base material is impregnated with the ester compound A and the ester compound B. 15 (3) A method in which the ester compound A, the ester compound B and a base material are mixed and then molded or shaped. Such a formulation contains the ester compound A and the ester compound B in the total amount of usually 0.001 20 to 98% by weight, although the total amount is dependent on the type of the formulation. [0021] The solid carrier used for formulation includes fine powders and granules of clays (e.g. kaolin clay, 25 diatomaceous earth, bentonite, fubasami clay and acid clay), synthetic hydrated silicon dioxide, talcs, ceramics, other inorganic minerals (e.g. sericite, quartz, sulfur, activated carbon, calcium carbonate and hydrated silica) and chemical fertilizers (e.g. ammonium sulfate, ammonium 30 phosphate, ammonium nitrate, ammonium chloride and urea); 10 substances which are solid at ordinary temperatures (e.g. 2,4,6-triisopropyl-1,3,5-trioxane, naphthalene, p dichlorobenzene, camphor and adamantane); and felt, fiber, cloth, knitted goods, sheets, paper, yarn, foams, porous 5 materials and multifilaments of one or more of the following materials: wool, silk, cotton, flax, pulp, synthetic resins (e.g. polyethylene resins such as low density polyethylenes, linear low-density polyethylenes and high-density polyethylenes; ethylene-vinyl ester copolymers 10 such as ethylene-vinyl acetate copolymers; ethylene methacrylic ester copolymers such as ethylene-methyl methacrylate copolymers and ethylene-ethyl methacrylate copolymers; ethylene-acrylic ester copolymers such as ethylene-methyl acrylate copolymers and ethylene-ethyl 15 acrylate copolymers; ethylene-vinylcarboxylic acid copolymers such as ethylene-acrylic acid copolymers; ethylene-tetracyclododecene copolymers; polypropylene resins such as propylene homopolymers and propylene ethylene copolymers; poly-4-methylpentene-1, polybutene-1, 20 polybutadienes and polystyrenes; acrylonitrile-styrene resins; styrene-based elastomers such as acrylonitrile butadiene-styrene resins, styrene-conjugated diene block copolymers and styrene-conjugated diene block copolymer hydrogenation products; fluororesins; acrylic resins such 25 as poly(methyl methacrylate)s; polyamide resins such as nylon 6 and nylon 66; polyester resins such as poly(ethylene terephthalate)s, polyethylene naphthalate)s, poly (butylene terephthalate) s, and poly(cyclohexylenedimethylene terephthalate)s; and porous 30 resins such as polycarbonates, polyacetals, polyacryl 11 sulfones, polyarylates, hydroxybenzoic acid polyesters, polyether imides, polyester carbonates, polyphenylene ether resins, poly (vinyl chloride) s, poly (vinylidene chloride) s, polyurethanes, expanded polyurethanes, expanded 5 polypropylenes and expanded polyethylene), glass, metals, ceramics and the like. [0022] The liquid carrier includes aromatic or aliphatic hydrocarbons (e.g. xylene, toluene, alkylnaphthalene, 10 phenylxylylethane, kerosene, light oil, hexane and cyclohexane), halogenated hydrocarbons (e.g. chlorobenzene, dichloromethane, dichloroethane and trichloroethane), alcohols (e.g. methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol and ethylene glycol), 15 ethers (e.g. diethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, tetrahydrofuran and dioxane), esters (e.g. ethyl acetate and butyl acetate), ketones (e.g. acetone, methyl ethyl 20 ketone, methyl isobutyl ketone and cyclohexanone), nitriles (e.g. acetonitrile and isobutyronitrile), sulfoxides (e.g. dimethyl sulfoxide), acid amides (e.g. N,N dimethylformamide, N,N-dimethylacetamide and N methylpyrrolidone), alkylidene carbonates (e.g. propylene 25 carbonate), vegetable oils (e.g. soybean oil and cotton seed oil), vegetable essential oils (e.g. orange oil, hyssop oil and lemon oil), and water. [0023] The gaseous carrier includes butane gas, CFC gas, 30 liquefied petroleum gas (LPG), dimethyl ether and carbon 12 dioxide. [0024] The surfactant includes alkyl sulfates, alkylsulfonates, alkylarylsulfonates, alkyl aryl ethers and 5 their polyoxyethylenated products, polyethylene glycol ethers, polyhydric alcohol esters and sugar alcohol derivatives. [0025] The other auxiliary for formulation includes adhesive 10 agents, dispersants and stabilizers. Specific examples thereof are casein, gelatin, polysaccharides (e.g. starch, gum arabic, cellulose derivatives and alginic acid), lignin derivatives, bentonite, saccharides, synthetic water soluble polymers [e.g. poly(vinyl alcohol)s, 15 poly(vinylpyrrolidone)s and poly(acrylic acid)s], BHT (2,6 di-tert-butyl-4-methylphenol), BHA (a mixture of 2-tert butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), etc. [0026] 20 The base material for the insecticidal coil includes mixtures of raw plant powders (e.g. wood powder and Pyrethrum marc) and binders (e.g. Tabu powder, starch and gluten). The base material for the insecticidal mat for 25 electric heating includes plates of compacted fibrils of cotton linters, and plates of compacted fibrils of a mixture of cotton linters and pulp. The base material for the self-burning-type fumigant includes combustible and exothermic agents (e.g. nitrates, 30 nitrites, guanidine salts, potassium chlorate, 13 nitrocellulose, ethylcellulose and wood powder), pyrolysis promoting agents (e.g. alkali metal salts, alkaline earth metal salts, dichromates and chromates), oxygen-supplying agents (e.g. potassium nitrate), combustion-supporting 5 agents (e.g. melamine and wheat starch), extending agents (e.g. diatomaceous earth) and binders (e.g. synthetic pastes). [0027] The base material for the chemical-reaction-type 10 fumigant includes exothermic agents (e.g. sulfides, polysulfides and hydrosulfides of alkali metals, and calcium oxide), catalysts (e.g. carbonaceous substances, iron carbide and activated clay), organic foaming agents (e.g. azodicarbonamide, benzenesulfonylhydrazide, 15 dinitropentamethylenetetramine, polystyrenes and polyurethanes) and fillers (e.g. natural fiber pieces and synthetic fiber pieces). [0028] The resin used as a base material for the resin 20 volatile formulations and the like includes polyethylene resins such as low-density polyethylenes, linear low density polyethylenes and high-density polyethylenes; ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymers; ethylene-methacrylic ester copolymers 25 such as ethylene-methyl methacrylate copolymers and ethylene-ethyl methacrylate copolymers; ethylene-acrylic ester copolymers such as ethylene-methyl acrylate copolymers and ethylene-ethyl acrylate copolymers; ethylene-vinylcarboxylic acid copolymers such as ethylene 30 acrylic acid copolymers; ethylene-tetracyclododecene 14 copolymers; polypropylene resins such as propylene homopolymers and propylene-ethylene copolymers; poly-4 methylpentene-1, polybutene-1, polybutadienes, polystyrenes and acrylonitrile-styrene resins; styrene-based elastomers 5 such as acrylonitrile-butadiene-styrene resins, styrene conjugated diene copolymers and styrene-conjugated diene block copolymer hydrogenation products; fluororesins; acrylic resins such as poly(methyl methacrylate)s; polyamide resins such as nylon 6 and nylon 66; polyester 10 resins such as poly(ethylene terephthalate)s, poly(ethylene naphthalate)s, poly(butylene phthalate)s, and poly(cyclohexylenedimethylene terephthalate)s; and polycarbonates, polyacetals, polyacryl sulfones, polyacrylates, hydroxybenzoic acid polyesters, polyether 15 imides, polyester carbonates, polyphenylene ether resins, poly(vinyl chloride)s, poly(vinylidene chloride)s and polyurethanes. These base materials may be used singly or as a mixture thereof. If necessary, these base materials may contain plasticizers such as phthalic acid esters (e.g. 20 dimethyl phthalate and dioctyl phthalate), adipic acid esters and stearic acid. The resin volatile formulation can be obtained by kneading the ester compound A and the ester compound B with the above-exemplified base material and then molding or shaping the kneaded product by injection 25 molding, extrusion, pressing or the like. If necessary, the resin formulation obtained can be processed into a plate, film, tape, net, string or the like through steps such as molding or shaping, cutting and the like. Such a resin formulation is processed into, for example, any of collars 30 for animal, ear tags for animal, sheet formulations, 15 attracting strings and horticultural stays. [0029] The base material for the poisonous bait includes bait components (e.g. cereal flour, vegetable oils, saccharides 5 and crystalline cellulose), antioxidants (e.g. dibutylhydroxytoluene and nordihydroguaiaretic acid), preservatives (e.g. dehydroacetic acid), agents for preventing consumption by children or pets (e.g. red pepper powder) and insect-pest-attracting perfumes (e.g. cheese 10 perfume, onion perfume and peanut oil). [0030] In the method of the present invention, a pest is controlled by applying the present pesticidal composition to the pest or a habitat where the pest inhabits (plants, 15 soil, inside of house, animals, etc.). In addition, a pest is controlled by applying an effective amount in total of the ester compound A and the ester compound B separately to the pest or a habitat where the pest inhabits. Herein, the "effective amount in total" means the 20 total amount of the ester compound A and the ester compound B in which amount the application of both compounds can make a pest controlled. Specific examples of method for applying the present pesticidal composition are the following methods. The 25 application method may be properly chosen depending on the form of the present pesticidal composition, application site, etc. (1) A method in which the present pesticidal composition itself is applied to a pest or a habitat where the pest 30 inhabits.

16 (2) A method in which the present pesticidal composition is diluted with a solvent such as water and then applied to a pest or a habitat where the pest inhabits. In the method (2), the present pesticidal composition 5 formulated into an emulsifiable concentrate, wettable powder, flowable concentrate, microcapsules or the like is usually diluted so that the total concentration of the ester compound A and the ester compound B may be 0.01 to 1,000 ppm. 10 (3) A method in which the present pesticidal composition is heated in a habitat where a pest inhabits, to vaporize the active ingredients. In the method (3), both the applying dosages and applying concentrations of the ester compound A and the 15 ester compound B can be properly determined depending on the form of the present pesticidal composition, when, where and how the pesticidal composition is applied, degree of damage, etc. [0031] 20 When the present pesticidal composition is used for preventing epidemics, its applying dosage is usually 0.0001 to 1,000 mg/m 3 in terms of the total amount of the ester compound A and the ester compound B in the case of application in a space, and is usually 0.0001 to 1,000 25 mg/m 2 in terms of the total amount of the ester compound A and the ester compound B in the case of application on a plane. The volatile formulations by heating such as insecticidal coils and insecticidal mats for electric heating are used with vaporizing the active ingredients by 30 heating, depending on the type of such formulations. The 17 non-heating volatile formulations such as resin volatile formulations, paper volatile formulations, nonwoven fabric volatile formulations, braided textile volatile formulations and sublimable tablets can be used, for 5 example, by allowing them to stand in a space where they are applied, or by blowing air against them. A space where the present pesticidal composition is applied for preventing epidemics includes closets, wall cupboards, chests of drawers, sideboards, toilets, baths, 10 lumber rooms, living rooms, dining rooms, warehouses and the inside of a car. In addition, the present pesticidal composition can be used also in outdoor open spaces. [0032] When the present pesticidal composition is used for 15 controlling ectoparasites on livestock such as cattle, horse, pig, sheep, goat, chicken, etc. and small animals such as dog, cat, rat, mouse, etc., it can be applied to the animals by a method well known in veterinary medicine. Specifically, a method for using the present pesticidal 20 composition is as follows. For systemic control, the pesticidal composition is administered in the form of, for example, tablets, a mixture with feed, a suppository, or an injection (e.g. an intramuscular, subcutaneous, intravenous or intraperitoneal injection) . For non-systemic control, 25 the pesticidal composition is used by a method such as spraying with an oil formulation or an aqueous liquid formulation, pour-on or spot-on treatment with the oil formulation or aqueous liquid formulation, washing of the animal with a shampoo formulation, or attachment of a resin 30 volatile formulation in the form of a collar or an ear tag 18 to the animal. When the present pesticidal composition is administered to the animal, the total amount of the ester compound A and the ester compound B ranges usually from 0.01 to 1,000 mg per kg of the body weight of the animal. 5 [0033] Further, in the present pesticidal composition, other pesticidal agents such as insecticides and acaricides, repellents, synergists, pigments, etc. may be mixed or concomitantly used with the ester compound A and the ester 10 compound B. EXAMPLES [0034] The present invention is illustrated in further detail 15 with the following formulation examples and test example, which should not be construed as limiting the scope of the invention. Firstly, formulation of the present pesticidal composition is exemplified. In the formulation examples and 20 test example, parts are all by mass unless otherwise specified. [00351 Formulation Example 1 An emulsifiable concentrate is obtained by dissolving 25 9 parts of the ester compound A and 0.9 part of the ester compound B in a mixture of 37.5 parts of xylene and 37.5 parts of N,N-dimethylformamide, adding thereto 9.1 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate, and thoroughly stirring and mixing 30 the resultant mixture.

19 [0036) Formulation Example 2 A wettable powder is obtained by thoroughly mixing 20 parts of the ester compound A, 20 parts of the ester 5 compound B and 5 parts of Sorpol 5060 (a registered trade name, Toho Chemical Co., Ltd.), adding thereto 32 parts of Carplex #80 (a registered trade name, Shionogi & Co., Ltd.; fine powder of synthetic hydrated silicon dioxide) and 23 parts of 300-mesh diatomaceous earth, and mixing the 10 resultant mixture in a juice mixer. [0037] Formulation Example 3 Five (5) parts of fine powder of synthetic hydrated silicon dioxide, 5 parts of sodium dodecylbenzenesulfonate, 15 30 parts of bentonite and 56.7 parts of clay are added to a mixture of 3 parts of the ester compound A and 0.3 part of the ester compound B, and the resultant mixture is thoroughly stirred and mixed. Thereafter, an appropriate quantity of water is added to the resulting mixture and 20 further stirred. The thus stirred mixture is subjected to particle size regulation with a granulator and then through-flow drying, to obtain granules. [0038] Formulation Example 4 25 Five (5) parts of the ester compound A, 0.5 part of the ester compound B, 1 part of fine powder of synthetic hydrated silicon dioxide, 1 part of Driless B (mfd. by Sankyo Co., Ltd.) as flocculant and 7 parts of clay are thoroughly mixed in a mortar and then stirred and mixed in 30 a juice mixer. To the resultant mixture is added 85.5 parts 20 of cut clay, and the resulting mixture is thoroughly stirred and mixed to obtain a dust. [00391 Formulation Example 5 5 A dust is obtained by mixing 10 parts of the ester compound A, 1 part of the ester compound B, 35 parts of white carbon containing 50% of polyoxyethylene alkyl ether sulfate ammonium salt, and 54 parts of water, and finely grinding the resultant mixture by a wet grinding method. 10 [0040] Formulation Example 6 An oil formulation is obtained by dissolving 0.05 part of the ester compound A and 0.1 part of the ester compound B in 10 parts of dichloromethane and mixing the resulting 15 solution with 89.85 parts of an isoparaffin solvent (Isopar M, a registered trade name, Exxon Chemical Co.). [0041] Formulation Example 7 An oil-based aerosol is obtained by placing 0.1 part 20 of the ester compound A, 0.05 part of the ester compound B and 49.85 parts of Neochiozol (Chuokasei Co., Ltd.) in an aerosol can, attaching an aerosol valve to the can, charging 25 parts of dimethyl ether and 25 parts of LPG into the can, shaking the can, and then attaching an 25 actuator to the can. [00421 Formulation Example 8 A water-based aerosol is obtained by charging a mixture of 0.5 part of the ester compound A, 0.05 part of 30 the ester compound B, 0.01 part of BHT, 5 parts of xylene, 21 3.44 parts of deodorized kerosene and 1 part of an emulsifier {Atmos 300 (a registered trade name, Atlas Chemical Corp.)} and 50 parts of distilled water into an aerosol container, attaching a valve part to the container, 5 and then compressing 40 parts of a propellant (LPG) into the container under pressure through the valve. [0043] Formulation Example 9 A substantially columnar carrier with a diameter of 10 5.5 cm and a height of 0.2 cm is produced by rolling up a piece of paperwork (0.5 cm thick, 69 cm long and 0.2 cm wide) having a honeycomb structure, from one end. An appropriate quantity of a solution of 5 parts of the ester compound A and 0.5 part of the ester compound B in 94.5 15 parts of acetone is uniformly applied on the above mentioned carrier and then air-dried to remove the acetone, to obtain a paper volatile formulation. [0044] Formulation Example 10 20 Three-dimensional knitting fabric (trade name: Fusion, model number: AKE69440, selling agency: Asahi Kasei Fibers Corp., thickness: 4.3 mm,- basis weight: 321 g/m 2 ; made of polyamide) is cut into a substantially circular piece with a diameter of 5 cm. An appropriate quantity of a solution 25 of 5 parts of the ester compound A and 0.5 part of the ester compound B in 94.5 parts of acetone is uniformly applied on the above-mentioned piece of the three dimensional knitting fabric and then air-dried to remove the acetone, to obtain a braided textile volatile 30 formulation.

22 [0045] Formulation Example 11 A resin volatile formulation is obtained by melt kneading 97.8 parts by weight of an ethylene-methyl 5 methacrylate copolymer (methyl methacrylate content: 10% by weight, MFR=2 [g/10 min]), 2 parts of the ester compound A and 0.2 part of the ester compound B at 130*C with a 45-mmp same-direction twin-screw extruder, further melt-kneading them at 150*C with a 40-mmp extruder, extruding the kneaded 10 product into a sheet through a T-die, and then cooling the sheet with a cooling roll. [0046] Formulation Example 12 A resin volatile formulation is obtained by melt 15 kneading 97.8 parts by weight of an ethylene-vinyl acetate copolymer (vinyl acetate content: 10% by weight, MFR=2 [g/10 min]), 2 parts of the ester compound A and 0.2 part of the ester compound B at 130*C with a 45-mmp same direction twin-screw extruder, further melt-kneading them 20 at 150 0 C with a 40-mmp extruder, extruding the kneaded product into a sheet through a T-die, and then cooling the sheet with a cooling roll. [0047] Formulation Example 13 25 Five (5) parts of the ester compound A and 0.5 part of the ester compound B are dissolved in 94.5 parts of acetone. An appropriate quantity of the resultant solution is applied on paper (2000 cm 2 ) having a foldable structure and is air-dried to remove the acetone, to obtain a paper 30 volatile formulation.

23 [0048] Formulation Example 14 Three (3) parts of the ester compound A and 0.3 part of the ester compound B are dissolved in 14.6 parts of 5 acetone to obtain a solution. 0.2 Part of zinc oxide, 1.0 part of pregelatinized starch and 42.8 parts of azodicarbonamide are added to the solution, followed by adding thereto 38.1 parts of water. The resultant mixture is kneaded, shaped into granules with an extruder, and then 10 dried. The granules containing the above-mentioned compounds according to the present invention are accommodated in the upper space in a container divided at the center by an aluminum partition, and 50 g of calcium oxide is accommodated in the lower space in the container. 15 Thus, a fumigant is obtained. [0049] Formulation Example 15 0.5 Part of zinc oxide, 2 parts of pregelatinized starch and 97.5 parts of azodicarbonamide are mixed and the 20 resultant mixture is kneaded with water. The kneaded product is shaped into granules with an extruder and dried. Two (2) grams of the granules are uniformly impregnated with an acetone solution containing 0.58 g of the ester compound A and 0.058 g of the ester compound B, and then 25 are dried. The granules thus obtained are accommodated in the upper space in a container divided at the center by an aluminum partition, and 50 g of calcium oxide is accommodated in the lower space in the container. Thus, a fumigant is obtained. 30 [0050) 24 Formulation Example 16 An insecticidal coil is obtained by dissolving 0.5 g of the ester compound A and 0.05 g of the ester compound B in 20 ml of acetone, adding the resultant solution to a 5 mixture of 99.4 g of a carrier for mosquito coil (a mixture of Tabu powder, Pyrethrum marc and wood powder in a weight ratio of 4:3:3) and 0.3 g of a green pigment, uniformly stirring and mixing the resultant mixture, adding thereto 120 ml of water, thoroughly kneading the resulting mixture, 10 and then molding and drying the kneaded mixture. [0051] Formulation Example 17 An insecticidal mat for electric heating is obtained by uniformly impregnating a base material for electric mat 15 (a plate obtained by coagulating fibrils of a mixture of cotton linter and pulp) having an area of 3.4 cm x 2.1 cm and a thickness of 0.22 cm with a solution obtained by mixing 10 parts of the ester compound A, 1 part of the ester compound B, 39.5 parts of acetyltributyl citrate, 20 39.5 parts of isononyl adipate, 5 parts of a blue pigment and 5 parts of a flavoring material. [0052] Formulation Example 18 A part of the formulation to be volatilized by heating 25 with absorbent wick is obtained by dissolving 0.1 part of the ester compound A and 0.01 part of the ester compound B in 99.89 parts of deodorized kerosene, placing the resultant solution in a container made of vinyl chloride, and inserting one end of an absorbent wick (obtained by 30 coagulating inorganic powder with a binder and baking the 25 coagulated powder) into the container so that the other end of the wick can be heated with a heater. [0053] Formulation Example 19 5 An aerosol is obtained by placing 0.2 part of the ester compound A, 0.02 part of the ester compound B and 49.78 parts of Neochiozol (Chuokasei Co., Ltd.) in an aerosol can, attaching an aerosol valve to the can, charging 25 parts of dimethyl ether and 25 parts of LPG 10 into the can, shaking the can, and then attaching an actuator for whole-jetting type aerosol to the can. [00543 Formulation Example 20 A formulation for spot-on treatment for controlling 15 ectoparasites on animals is obtained by adding 99.78 parts of diethylene glycol monoethyl ether to a mixture of 0.2 part of the ester compound A and 0.02 part of the ester compound B, and thoroughly stirring and mixing the resultant mixture. 20 [0055] Formulation Example 21 Tablets are obtained by uniformly applying 1 mL of a solution consisting of 3 parts of the ester compound A, 0.3 part of the ester compound B and 96.7 parts of acetone on 25 discoid solid substances (diameter: 3 cm, thickness: 3 mm) obtained by molding 4,000 mg of 2,4,6-triisopropyl-1,3,5 trioxane under pressure (4 t/cm 2 ), and then drying the solid substances. [0056] 30 Formulation Example 22 26 Tablets are obtained by molding a homogeneous mixture of 0.2 g of the ester compound A, 0.02 g of the ester compound B and 4 g of 2,4,6-triisopropyl-1,3,5-trioxane into discs (diameter: 3 cm, thickness: 3 mm) under pressure 5 (4 t/cm 2 ) [0057] Formulation Example 23 Tablets are obtained by placing 0.2 g of the ester compound A, 0.02 g of the ester compound B and 4 g of 10 2,4,6-triisopropyl-1,3,5-trioxane in a 50-mL screw tube, melting them with heating, and then cooling them to room temperature. [0058] The following test example demonstrates the excellent 15 controlling effect of the present pesticidal composition on pests. [0059] In the following test example, [2,3,5,6-tetrafluoro-4 (methoxymethyl)phenyl]methyl=(lR)-trans-3-(2,2 20 dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate was used as the ester compound A. In addition, (S)-a-cyano-3-phenoxybenzyl=(lR)-cis-3 (2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate was used as the ester compound B. 25 [0060] Test Example 1 oil formulations having the concentrations as shown in Table 1 were prepared by dissolving certain amounts of the ester compound B in an isoparaffin solvent (Isopar M, a 30 registered trade name, Exxon Chemical Co.). These oil 27 formulations are hereinafter referred to as comparative compositions (1) to (3). Similarly, oil formulations having the concentrations as shown in Table 1 were prepared by dissolving certain amounts of the ester compound A in an 5 isoparaffin solvent (Isopar M, a registered trade name, Exxon Chemical Co.). These oil formulations are hereinafter referred to as comparative compositions (4) to (6). As the pesticidal compositions of the present 10 invention, oil formulations containing active ingredients in the concentrations as shown in Table 1 were prepared by dissolving certain amounts of the ester compound A and the ester compound B in an isoparaffin solvent (Isopar M, a registered trade name, Exxon Chemical Co.). These oil 15 formulations are hereinafter referred to as the present compositions (1) to (6). [0061] Ten mosquitos (Culex pipiens pallens) (10 females) were released in a cubic chamber having each side of 70 cm. 20 With a spray gun, 0.7 ml of the present composition (1) was sprayed (spray pressure: 0.9 kg/cm 2 ) from a small window at the inlet of the chamber. Seven (7) minutes after spraying, the knocked-down insects were counted, and the knocking down (KD) rate was calculated. 25 The same tests as above were carried out except for using each of the present compositions (2) to (6) and the comparative compositions (1) to (6) in place of the present composition (1), and the knocking-down rate at 7 minutes after spraying was calculated. For the test there were 2 30 replicates.

28 The results are shown in Table 1 [0062] Table 1 Content Content KD rate (%) (w/v %) of (w/v %) of after 7 Ester Ester minutes compound A compound B cPstion (1) 0.015 0.00313 95 Present 0.015 0.00156 90 composition (2) Present 0.00313 0.015 90 composition (3) Pstion (4) 0.00313 0.00313 80 Present 0.00313 0.00156 70 composition (5) Present 0.00156 0.015 85 composition (6) Comparative copsto-1 0.015 30 Comparative composition (1) 0053 Comparative -0.00313 10 composition (2) Comparative 0.155 composition (3) 0.00156 5 Comparative composition (4) 0.015 50 Comparative 00332 composition (5) 0.00313 20 potio (6) 0.00156 10 5 INDUSTRIAL APPLICABILITY [0063] According to the present invention, a pesticidal composition having an excellent controlling effect on pests and a method for controlling pests are provided.

29 Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as an acknowledgment or admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates.

Claims (4)

1. A pesticidal composition comprising an ester compound represented by formula (I): F F H 3 C CH 3 H3COH

2 C CH=CCl 2 (I) 5 F F and an ester compound represented by formula (II): / \H

3 C CH 3 / CN CH=CBr 2 (ID 0 as active ingredients. 10 2. The composition according to claim 1, wherein the weight ratio of the ester compound represented by formula (I) to the ester compound represented by formula (II) is from 50:1 to 1:50. 15 3. A method for controlling a pest comprising applying an effective amount in total of an ester compound represented by formula (I): F F H 3 C CH 3 H 3 COH 2 C /CH=CC 2 () F F and an ester compound represented by formula (II): 31 / \H 3 C CH 3 /N CH=CBr 2 0 to a pest or a habitat where the pest inhabits.

4. Use of a combination of an ester compound 5 represented by formula (I): F F H 3 C CH 3 H 3 COH 2 C CH=CCl 2 (1) F F and an ester compound represented by formula (II) O H 3 C CH 3 /N\ CH=CBr 2 (I f0 for controlling a pest.