Title of Invention

A COMPOSITION FOR THE CONTROL OF PESTS IN PLANTS

Abstract

2570/MAS/98 "A composition for the control of pests in plants" This invention relates to a composition for the control of insects and/or members of the order acarina which comprises a combination in variable proportions of emamectin (A), in free form or in the form of a salt, and one or more of the compounds selected from: azamethiphos; chlorfenvinphos; cypermethrin, cypermethrin high-cis; cyromazine; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; jodfenphos; kinoprene; lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon; profenofos; diofenolan; pymetrozine; bromopropylate; methoprene; disulfoton; quinalphos; tau-fluvalinate; thiocyclam; thiometon; propetamphos; formothion; dienochlor; or a product isolated from a strain of Bacillus thuringiensis; in free form or in the form of a salt, and at least one known adjuvant.

Full Text

The present invention relates to a composition comprising a pesticidal combination of active ingredients, to a metliod for controlling pests with this composition, to a method for preparing the composition, to its use and to plant propagation material treated with the composition, as well as to the use of emamectin and compounds of the following formulae (I) to (XXXIV) for preparing the composition. In the literature, certain mixtures of active ingredients are proposed for pest control. The biological properties of these mixtures of known compounds, however, are not fully satisfactory in the field of pest control, which is why there is a need to produce further mixtures with synergistic pesticidal properties, especially for the control of insects and members of the order acarina. This problem is solved according to the invention with the development of the present composition. The object of the invention is accordingly a composition for the control of insects and/or members of the order Acarina, which comprises a combination in variable proportions of emamectin (A), in free form or in the form of a salt, and one or more of the compounds: (I) azamethiphos; (XVI) lufenuron; (II) chlorfenvinphos; (XVII) methacriphos; (III) cypermethrin, cypermethrin high-cis; (XVIII) methidathion; (IV) cyromazine; (XIX) monocrotophos; (V) diafenthiuron; (XX) phosphamidon; (VI) diazinon; (XXI) profenofos; (VII) dichlon/os; (XXII) diofenolan; (VIII) dicrotophos; (XXIII) pymetrozine; (IX) dicyclanil; (XXIV) bromopropylate; (X) fenoxycarb; (XXV) methoprene; (XI) fluazuron; (XXVI) disulfoton; (XII) furathiocarb; (XXVII) quinalphos; (XIII) isazofos; (XXVIII) tau-fiuvalinate; (XIV) jodtenphos; (XXIX) thiocyclam; (XV) kinoprene; (XXX) thiometon; (XVI) propetamphos, (XXXIII) dienochlor; or (XVII) formothion, (XXXIV) a product which can be isolated from a strain of Bacillus thuringiensis] in each case in free form or in the form of a salt, and at least one adjuvant. Emamectin is a mixture of 4"-deoxy-4"-N-methylamino avermectin Bia/Bib and is described in US"P-4,4874,749 and as MK-244 in Journal of Organic Chemistry, Vol. 59 (1994), 7704-7708. Salts of emamectin which are of particular agrochemical value are described in US-P-5,288,710. (I) S-6-chloro-2,3-dihydro-2-oxo-1,3-oxazolo[4,5-b]pyridin-3-ylmethyl 0,0-dimethyl phosphorothioate (azamethiphos), The Pesticide Manual, 9*^Ed. (1991), is known from The British Crop Protection Council, London, page 44; (II) 2-chloro-1-(2,4-dichlorophenyl)vinyl diethyl phosphate (chlorfenvinphos), from The Pesticide Manual, 10*^ Ed. (1994), is from The British Crop Protection Council, London, page 174; (III) (RS)-a-cyano-3-phenoxybenzyl (1 RS)-cis-trans-3-(2,2-dichlorovinyl)-1,1-dimethylcyclo- propanecarboxylate (cypermethrin, cypermethrin high-cis), from The Pesticide Manual, 9*^ Ed. (1991), The British Crop Protection Council, London, page 208; (IV) N-cyclopropyl-1,3,5-triazine-2,4,6-triamine (cyromazine), from The Pesticide Manual, 9*^ Ed. (1991), The British Crop Protection Council, London, page 217; (V) 1-tert-butyl-3-(2,6-di-isopropyl-4-phenoxyphenyl)thiourea (diafenthiuron), from The Pesticide Manual, 10*^ Ed. (1994), The British Crop Protection Council, London, page 294; (VI) 0,0-Diethyl 0-2-lsopropyl-6-methylpyrimidin-4-yl-phosphorothioate (diazinon), from The Pesticide Manual, 9^^ Ed. (1991), The British Crop Protection Council, London, page 243; (VII) 2,2-dichlorovinyl dimethyl phosphate (dichlorvos), from The Pesticide Manual, 9*'^Ed. (1991), The British Crop Protection Council, London, page 259; (VIII) (E)-2-dimethylcarbamoyl-1-methylvinyl dimethyl phosphate (dicrotophos), from The Pesticide Manual, 10*^ Ed. (1994), The British Crop Protection Council, London, page 322; (IX) 5-cyano-2-cyclopropylamino-4,6-diaminopyrimidine (dicyclanil), known from EP-A- 244360; (X) ethyl 2-(4-phenoxyphenoxy)ethylcarbamate (fenoxycarb), from The Pesticide Manual, 9*^ Ed. (1991), The British Crop Protection Council, London, page 375; (XI) 1-[4-chloro-3-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl]-3-(2,6-difluorobenzoyl)urea (fluazuron), from The Pesticide Manual, 10*^ Ed. (1994), The British Crop Protection Council, London, page 475; (XII) butyl 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N,N'-dimethyl-N,N'-thiodicarbamate (furathiocarb), from The Pesticide Manual, 9*^ Ed. (1991), The British Crop Protection Council, London, page 448; (XIII) 0-5-chloro-1-isopropyl-1H-1,2,4-triazol-3-yl 0,0-diethylphosphorothioate (isazofos), aus The Pesticide Manual, 9*^ Ed. (1991), The British Crop Protection Council, London, page 502; (XIV) 0-2,5-dichloro-4-iodophenyl 0,0-dimethylphosphorothioate (jodfenphos), from The Pesticide Manual, 10*^ Ed. (1994), The British Crop Protection Council, London, page 1102; (XV) prop-2-ynyl (±) (E,E)-3,7,11"trimethyldodeca-2,4-dienoate (kinoprene) from The Pesticide Manual, 10*^ Ed. (1994), The British Crop Protection Council, London, page 1102; (XVI)(R,S)-1-[2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-3-(2,6- difluorobenzoyl)urea (lufenuron), from The Pesticide Manual, 10*^ Ed. (1994), The British Crop Protection Council, London, page 628; (XVII) methyl (E)-3-(dimethoxyphosphinothioyloxy)-2-methylacrylate (methacriphos) from The Pesticide Manual, 9^^ Ed. (1991), The British Crop Protection Council, London, page 562; (XVIII) S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl 0,0-dimethyl phosphorodithioate (methidathion), from The Pesticide Manual, 10*^ Ed. (1994), The British Crop Protection Council, London, page 674; (XIX) dimethyl (E)-1-methyl-2-(methylcarbamoyl)vinyl phosphate (monocrotophos), from The Pesticide Manual, 9*^ Ed. (1991), The British Crop Protection Council, London, page 597; (XX) 2-chloro-2-diethylcarbamoyl-1-methylvinyl dimethyl phosphate (phosphamidon), known from The Pesticide Manual, 9*^ Ed. (1991), The British Crop Protection Council, London, page 679; (XXI) 0-4-bromo-2-chlorophenyl 0-ethyl S-propyl phosphorothioate (profenofos), from The Pesticide Manual, 9**^ Ed. (1991), The British Crop Protection Council, London, page 705; (XXII) a mixture of 50 to 80% (2RS,4SR)-4"(2-ethyl-1,3-dioxolan-4-ylmethoxy)phenyl phenyl ether and 50 to 20% (2RS,4RS)-4-(2-ethyl-1,3-dioxoian-4-ylmethoxy)phenyl phenyl ether (diofenolan), from The Pesticide Manual, 10*^ Ed. (1994), The British Crop Protection Council, London, page 363; (XXIII) 2,3,4,5-tetrahydro-3-oxo-4-[(pyridin-3-yl)methyleneamino]-6-methyM,2,4-triazine (pymetrozine), from The Pesticide Manual, 10*^ Ed. (1994), The British Crop Protection Council, London, page 868; and (XXIV) isopropyl 4,4'-dibromobenzilate (bromopropylate), from The Pesticide Manual, 9^^ Ed. (1991), The British Crop Protection Council, London, page 99, (XXV) Isopropyl (E,E)-(R,S)-11-methoxy-3,7,11-trimethyl-dodeca-2,4-dienoat (Methoprene), aus The Pesticide Manual, 10*^ Ed. (1994), The British Crop Protection Council, London, Seite 680;isopropyl (E,E)-(R,S)-11-methoxy-3,7,11-trimethyl-dodeca-2,4-dienoate (methoprene) from The Pesticide Manual, 10*^ Ed. (1994), The British Crop Protection Council, London, page 680; (XXVI) 0,0-diethyl S-2-ethylthioethyl phosphorodithioate (disulfoton), from The Pesticide Manual, 10*^Ed. (1994), The British Crop Protection Council, London, page 372; (XXVII) 0,0-diethyl O-quinoxalin-2-yl phosphorothioate (quinalphos), from The Pesticide Manual, 10*^Ed. (1994), The British Crop Protection Council, London, page 890, and (XXVIII) (RS)-a-cyano-3-phenoxybenzyl N-(2-ChlorO"a,a,a-trifluoro-p-tolyl)-D-valinate (tau- fluvalinate), known from The Pesticide Manual, 9^^Ed. (1991), The British Crop Protection Council, London, page 428; (XXIX) N,N-dimethyl-1,2,3-trithian-5-yl"amine (thiocyclam) from The Pesticide Manual, 9**'Ed. (1991), The British Crop Protection Council, London, page 816; (XXX) S-2-ethylthioethyl 0,0-dimethyl phosphorodithioate (thiometon) from The Pesticide Manual, 9*^Ed. (1991), The British Crop Protection Council, London, page 819, and (XXXI) propetamphos from The Pesticide Manual, 10*^Ed. (1994), from The British Crop Protection Council, London, page 852; (XXXII) formothion from The Pesticide Manual, 10*^Ed. (1994), from The British Crop Protection Council, London, page 527; (XXXIII) dienochlorfrom The Pesticide Manual, lO^^Ed. (1994), The British Crop Protection Council, London, page 523, and (XXXIV) products obtainable from a strain of Bacillus thuringiensis, known from The Pesticide Manual, lO^^Ed. (1994), The British Crop Protection Council, London, page 62; Compounds (1) to (XXXIV) showing at least one basic centre may form acid addition salts. These are formed for example with strong inorganic acids, such as mineral acids, e.g. sulfuric acid, perchloric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrogen halide acid, with strong organic carbonic acids, typically CrC4alkanecarbonic acids substituted where appropriate for example by halogen, e.g. acetic acid, such as dicarbonic acids that are unsaturated where appropriate, e.g. oxalic, malonic, succinic, maleic, fumaric or phthalic acid, typically hydroxycarbonic acids, e.g. ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or with organic sulfonic acids, typically CrC4alkanesulfonic or arylsulfonic acids substituted where appropriate for example by halogen, e.g. methanesulfonic or p-toluenesulfonic acid. In a broader sense, compounds of formula (I) to (XXXIV) with at least one acid group can form salts with bases. Suitable salts with bases are for example metal salts, typically alkali or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. ethyl, diethyl, triethyl or dimethylpropylamine, or a mono-, di- or trihydroxy-lower alkylamine, e.g. mono-, di- or triethanolamine. Corresponding internal salts where appropriate may also be formed. Preferred compounds within the scope of this invention are agrochemically useful salts. The term compounds (I) to (XXXIV) in free form used hereinbefore and hereinafter refers also to the corresponding salts, and the term salts is taken to refers by the same token also to the free compounds (I) to (XXXIV). The same applies also to tautomers of compounds (I) to (XXXIV) and their salts. In each case, the free form is generally preferred. Thiocyclam is preferred as a hydrogen oxalate salt. Preferred within the scope of the present invention is a composition comprising emamectin as agrochemically acceptable salt, especially as benzoate, substituted benzoate, benzenesulfonate, citrate, phosphate, tartrate or maleate; preferably as benzoate or benzenesulfonate; especially benzoate. Also preferred are mixtures comprising emamectin (MK-244) in a ratio of Bia > 80 wt-%, Bib 90 wt-%, Bib A composition is preferred which comprises in addition to emamectin only one further pesticidally active compound (I) to (XXXIV). Further preferred compositions are those comprising in addition to emamectin also azamethiphos, orfenoxycarb, or cypermethrin high-cis, or profenofos, or lufenuron, or pymetrozine. Likewise preferred are compositions comprising a compound which is obtainable from a strain of Bacillus thuringlensis. Especially preferred are the following insecticidally active compounds or strains from which these compounds are obtainable: SAN 4151, San 2391, SAN 4011, H7 (B401), HI 4, EG2348 (Condor OF®), EG2349 (Bollgard®), EG2371 (Cutlass®). EG2424 (Foil®, Jackpot®); H3a,3b (Javelin®, Steward®. Thuricide®, Vault®); CGA237218 (M200. Able®), HI4. GC91 (Agree®, Turex®), DSM3435, known from US-P-4,996,156; DSM3440, known from US-P-4,996,156; HD541, HD571 and HD73; particularly H7 (B401), H14, H3a,3b, CGA237218 (M200), H14, GC91, DSM3435; DSM3440, HD541, HD571 and HD73; especially GC91; H3a,3b; and M200; most especially GC91. The combination of active ingredients according to the invention comprises active ingredient (A) and one of the active ingredients (I) to (XXXIV) preferably in a ratio of 100:1 to 1:6000, especially 1:50 to 50:1, in particular in a ratio of between 1:20 and 20:1, especially between 10:1 and 1:10, very especially between 5:1 and 1:5, especially preferably between 2:1 and 1:2, also preferably between 4:1 and 2:1, very particularly in the ratio 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or, 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. These ratios refer both to weight ratios and to molar ratios. It has now been surprisingly found that the combination of emamectin or one of its salts with one of the active ingredients (I) to (XXXIV) not only has an additive effect with regard to the spectrum of activity against the pests to be controlled, which in principle was to be expected, but also exerts a synergistic effect, extending the spectrum of activity of each composition in two respects: Firstly, the concentrations of emamectin and the individual compounds (I) to (XXXIV) are reduced, while efficacy remains unchanged. Secondly, the combined mixture also achieves a high degree of pest control where the two individual substances have become completely ineffective when applied at unduly low concentrations. This allows a considerable widening of the spectrum of pests which can be controlled and increased safety of use. In addition to the actual synergistic effect with regard to the pesticidal activity, however, the composition of the invention also shows further surprising advantages, which can likewise be described as synergistic in a broader sense: for example, they allow the control of pests which are not sufficiently, or not at all, susceptible to treatment with emamectin or a compound (I) to (XXXIV) when applied separately, and the compositions of the invention are better tolerated by plants, i.e. they are less phytotoxic, for example, than emamectin and (I) to (XXXIV). The insects can also be controlled in their different development stages, which is not always the case with emamectin or the individual compounds (1) to (XXXIV), because these compounds for example can be used only as adulticides or only as larvicides against very specific instars. In addition, combinations of emamectin with certain compounds (I) to (XXXIV) show more favourable behaviour during grinding, mixing, storage, and also spraying. The compositions of the invention are of preventive and/or curative merit for use in pest control among warm-blooded animals, fish, and plants even at low concentrations and show a very favourable spectrum of biocidal activity. The active ingredients according to the invention are active against all or individual development stages of animal pests showing normal sensitivity, and also of those showing resistance, for example insects or members of the order acarina. The insecticidal or acaricidal effect of the compositions of the invention can manifest itself directly, i.e. killing the pests either immediately or after some time has elapsed, for example when moulting occurs, or indirectly, e.g. reducing the number of eggs laid and/or the hatching rate, good efficacy corresponding to a destruction rate (mortality) of at least 50 to 60%. The said animal pests include, for example, those which are mentioned in the European Patent application EP-A-736'252 . The pests mentioned in EP-A-736'252 are thus included by reference in the object of the present invention. Pests of said type which occur on plants, especially on crops and ornamentals in agriculture, horticulture and forestry, or on parts of such plants, such as fruits, blooms, leaves, stems, tubers or roots, can be controlled, i.e. kept in check or eradicated, using the active ingredient mixtures of the invention, this protection remaining for parts of some plants whose growth does not occur until later. The pesticide mixture according to the invention can be used to advantage for pest control especially in cereals, such as corn or sorghum; in fruit, e.g. pomes, drupes and soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, e.g. strawberries, raspberries or blackberries; in leguminous plants, such as beans, lentils, peas or soybean; in oil crops, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans or groundnuts; in cucumber plants, such as pumpkins, cucumbers or melons; in fibrous plants, such as cotton, flax, hemp or jute; in citrus fruits, such as oranges, lemons, grapefruit or mandarins; in vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or paprika; in lauraceae, such as avocado, cinnamon or camphor; and in tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, grapevines, hops, banana plants, natural rubber plants and ornamentals, most especially in corn, sorghum, pomes and drupes, leguminous plants, cucumber plants, cotton, citrus fruits, vegetables, aubergines, vines, hops, or ornamentals, especially in corn, sorghum, apples, pears, plums, peaches, beans, peas, soybeans, olives, sunflowers, coconut, cocoa, peanuts, cucumbers, pumpkins, citrus fruits, cabbages, tomatoes, potatoes, vines, or cotton, with special preference in vines, citrus fruits, apples, pears, tomatoes and cotton. Other indication areas for the active ingredient mixtures of the invention are the protection of stored products and stores and of material and, in the hygiene sector, in particular the protection of domestic animals and livestock against pests of said type. The pesticides of the invention are, depending on the intended objectives and prevailing circumstances, emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, coatable pastes, dilute emulsions, spray powders, soluble powders, dispersible powders, wettable powders, dusts, granulates or encapsulations in polymeric substances, comprising emamectin and one of the other active ingredients (I) to (XXXIV) according to the invention. In these compositions, the active ingredients are employed in pure form, the solid active ingredients in a specific particle size, or preferably together with - at least - one of the adjuvants conventionally used in the art of formulation, such as extenders, e.g. solvents or solid carriers, or surface-active compounds (surfactants). The adjuvants which can be used for formulation are, for example, solid carriers, solvents, stabilizers, "slow-release" agents, dyes, and where appropriate surfactants. Carriers and adjuvants can be any substance conventionally used in crop protection agents. Adjuvants such as solvents, solid carriers, surface-active compounds, non-ionic surfactants, cationic surfactants, anionic surfactants, and other adjuvants in the compositions of the invention can, for example, be the same as those described in EP-A-736'252 . As a rule, the compositions comprise 0.01 to 99.99%, in particular 0.1 to 95%, of a mixture of active ingredient (A) with one of the active ingredients (I) to (XXXIV), and 1 to 99.9%, in particular 5 to 99.9%, of - at least - one solid or liquid adjuvant, it being possible as a rule for 0 to 25%, in particular 0.1 to 20%, of the compositions to be surfactants (% in each case meaning percent by weight). Whereas concentrated compositions tend to be preferred for commercial goods, the end consumer as a rule uses dilute compositions which have substantially lower concentrations of active ingredient. Preferred compositions are composed in particular as mentiond in EP-A-736'252. The compositions of the invention can also comprise other solid or liquid adjuvants, such as stabilizers, e.g. vegetable oils, epoxidized where appropriate (e.g. epoxidized coconut oil, rapeseed oil or soya oil), antifoams, e.g. silicone oil, preservatives, viscosity modulators, binders and/or tackifiers, and also fertilizers or other active ingredients to achieve specific effects, e.g. acaricides, bactericides, fungicides, nematocides, molluscicides or selective herbicides. The compositions of the invention are prepared in a known manner, e.g. in the absence of adjuvants by grinding, sieving, and/or compressing a solid active ingredient or active ingredient mixture, e.g. to a specific particle size, and in the presence of at least one adjuvant, e.g. by intimately mixing and/or grinding the active ingredient or the mixture of active ingredients with the adjuvant(s). The method for preparing the compositions is therefore a further object of the invention. The mixtures of emamectin with one or more of the compounds (I) to (XXXIV) are preferably employed with the adjuvants conventionally used in the art of formulation and are therefore processed in a known manner to give, for example, emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, fiiiRtR nranules or microencaosulations in for example polymeric substances. As with the type of compositions, the methods of application, such as spraying, atomizing, dusting, wetting, scattering or pouring, are selected in accordance with the intended objectives and the prevailing circumstances. The methods of application for the compositions, i.e. the methods of controlling pests of said type, such as spraying, atomizing, dusting, coating, dressing, scattering or pouring (chosen in accordance with the intended objectives and prevailing circumstances), and the use of the compositions for controlling pests of said type are further objects of the invention. Typical concentrations of active ingredient are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. The rate of application can vary within wide limits and depends on the nature of the soil, the type of application (leaf application, seed dressing, application to the seed furrow), the cultivated plant, the pest to be controlled, the prevailing climatic conditions, and on other factors governed by the type and time of application and the target crop. The rates of application are generally 1 to 2000 g of active ingredient (a.i.) per hectare, especially 10 to 1000 g a.i./ha, and preferably 20 to 600 g a.i./ha. A preferred method of application for crop protection is to apply the active ingredient to the foliage of the plants (leaf application), the number of applications and the rate of application depending on the intensity of infestation by the pest in question. However, the active ingredients can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plants with a liquid composition, or by applying the compounds in solid form to the locus of the plants, e.g. to the soil, for example in granular form (soil application). With paddy rice cultures, granules may be metered into the flooded paddy field. The compositions of the invention are also suitable for protecting plant propagation material, e.g. seeds, such as fruits, tubers or grains, or plant seedlings, from animal pests. The propagation material can be treated with the composition before the start of cultivation, seeds for example being dressed before they are sown. The active ingredients of the invention can also be applied to seeds (coating) by either soaking the seeds in a liquid composition or coating them with a solid composition. The composition can also be given when the propagation material is introduced to the place of cultivation, e.g. when the seeds are sown in the seed furrow. The treatment procedures for plant propagation material and the propagation material thus treated are further objects of the invention. The invention is illustrated by the following examples. They do not impose any limitation on the invention. Formulation examples (% = percent by weight, ratios of active ingredients = weight ratios) Example F1: Emulsion concentrates a) b) c) Active ingredient mixture [emamectin benzoate: compound (I) to (XXXIV) = 1 : 30] 25 % 40 % 50 % Calcium dodecylbenzenesulfonate 5 % 8 % 6 % Castor oil polyethylene glycol ether (36 mol EO) 5 % Tributyl phenol polyethylene glycol ether (30 mol EO) 12 % 4 % Cyclohexanone 15 % 20 % Xylene mixture 65 % 25 % 20 % EO means the degree of ethoxylation of castor oil or tributyl phenol. Emulsions of any desired concentration can be prepared from such concentrates by dilution with water. Example F2: Solutions a) b) c) d) Active ingredient mixture [emamectin benzoate: compound (I) to (XXXIV) = 1:10] 80 % 10 % 5 % 95 % Ethylene glycol monomethyl ether 20 % Polyethylene glycol MW 400 - 70 % N-Methyl-2-pyrrolidone 20 % Epoxidized coconut oil 1 % 5 % Petroleum ether (boiling limits 160-190°C) 94 % The solutions are suitable for use in the form of microdrops. Example F3: Granulates a) b) c) d) Active ingredient mixture [emamectin benzoate: compound (I) to (XXXIV) = 1:5] 5 % 10 % 8 % 21 % Kaolin 94 % 79 % 54 % Highly dispersed silicic acid 1 % 13 % 7 % Attapulgite 90% 18% The active ingredients are dissolved in dichloromethane, the solution sprayed onto the carrier, and the solvent subsequently evaporated in vacuo. It is often more convenient to formulate the active ingredient of formula (A) and one of the compounds (I) to (XXXIV) separately and not to combine them until shortly before application in the applicator in the desired mixing ratio in the form of a 'lank mix" in water. Biological examples (% = percent by weight, unless othenA^ise indicated) A synergistic effect is present whenever the action Ae of the combination of an active ingredient of formula (A) with one of the compounds (I) to (XXXIV) is greater than the sum of the actionss of the active ingredients applied individually: >4e > X + Y (B) The expected pesticidal action Ae for a given combination of two pesticides can be calculated as follows (q.v. COLBY, S.R.."Calculating synergistic and antagonistic response of herbicide combinations". Weeds 15, pages 20-22, 1967): 100 In this formula: X = percent mortality after treatment with emamectin at a rate of application of p kg / hectare (ha = approximately 2.471 acres) versus untreated controls (= 0 %). Y = percent mortality after treatment with compound (I) to (XXXIV) at a rate of application of q kg / ha versus untreated controls. Ae = expected pesticidal action (percent mortality versus the untreated controls) after treatment with emamectin and a compound (I) to (XXXIV) at a rate of application of p + q kg / ha. If the effect actually obsen/ed is greater than the expected Ae value, then synergism is present. Example B1: Effect on Bemisia tabaci Dwarf bean plants are placed into gauze cages and populated with adults of Bemisia tabaci. Following oviposition, all adults are removed. Ten days later, the plants and the nymphs thereon are sprayed with an aqueous suspension spray mixture comprising 50 ppm of the mixture of active ingredients. After a further 14 days, the percentage hatching rate of the eggs is compared with that for untreated controls. In this experiment, the combinations of emamectin with one of the compounds (I) to (XXXIV) show a synergistic effect. In particular, a suspension spray mixture comprising 40 ppm emamectin and 10 ppm of compound (II) is very effective. Example B2: Effect on Spodoptera //'tforafe caterpillars Young soya plants are sprayed with an aqueous emulsion spray mixture comprising 360 ppm of the mixture of active ingredients. After the spray deposit has dried, the soya plants are populated with 10 third-instar caterpillars of Spodoptera littoralis and placed in a plastic container. Three days later they are evaluated. The percentage reduction of the population and percentage reduction in feeding damage (% response) is determined by comparing the number of dead caterpillars and the extent of feeding damage on the treated plants with those on the untreated plants. In this experiment, the combinations of emamectin with one of the compounds (I) to (XXXIV) show a synergistic effect. In particular, a suspension spray mixture comprising 20 ppm emamectin and 160 ppm of compound (II) and a suspension spray mixture comprising 180 ppm emamectin and 180 ppm of compound (XV) are very effective. Example B3: Ovicidal effect on Lobesia botrana Eggs of Lobesia botrana deposited on filter paper are immersed briefly in a test solution comprising 400 ppm of the mixture of active ingredients to be tested in acetone / water. After the test solution has dried, the eggs are incubated in Petri dishes. After 6 days, the percentage hatching rate of the eggs is compared with that for untreated controls (% reduction in hatching rate). In this experiment, the combinations of emamectin with one of the compounds (I) to (XXXIV) show a synergistic effect. In particular, a suspension spray mixture comprising 300 ppm emamectin and 100 ppm of compound (III) and a suspension spray mixture comprising 200 ppm emamectin and 200 ppm of compound (XVI) are very effective. Example B4: Ovicidal effect on Heliothis virescens Eggs of Heliothis virescens deposited on filter paper are immersed briefly in a test solution comprising 400 ppm of the mixture of active ingredients to be tested in acetone / water. After the test solution has dried, the eggs are incubated in Petri dishes. After 6 days, the percentage hatching rate of the eggs is compared with that for untreated controls (% reduction in hatching rate). In this experiment, the combinations of emamectin with one of the compounds (I) to (XXXIV) show a synergistic effect. In particular, a suspension spray mixture comprising 240 ppm emamectin and 160 ppm of compound (XII) and a suspension spray mixture comprising 300 ppm emamectin and 100 ppm of compound (V) are very effective. Example B5: Effect on Plutella xvlostella caterpillars Young cabbage plants are sprayed with an aqueous emulsion spray mixture comprising the mixture of active ingredients. After the spray deposit has dried, the cabbage plants are populated with 10 third-instar caterpillars of Plutella xylostella and placed in a plastic container. Three days later they are evaluated. The percentage reduction of the population and percentage reduction in feeding damage (% response) is determined by comparing the number of dead caterpillars and the extent of feeding damage on the treated plants with those on the untreated plants. In this study, the combinations of emamectin with one of the compounds (1) to (XXXIV) show a synergistic effect. In particular, a suspension spray mixture comprising 400 ppm emamectin and 40 ppm of compound (VII) and a suspension spray mixture comprising 220 ppm emamectin and 220 ppm of compound (IV) are very effective. WE CLAIM: A composition for the control of insects and/or members of the order acarina which comprises a combination in variable proportions of emamectin (A), in free form or in the form of a salt, and one or more of the compounds selected from: (I) azamethiphos; (XVIII) methidathion; (II) chlorfenvinphos (XIX) monocrotophos; (III) cypermethrin, cypermethrin high-cis; (XX) phosphamidon; (IV) cyromazine; (XXI) profenofos; (V) diafenthiuron; (XXII) diofenolan; (VI) diazinon; (XXIII) pymetrozine; (VII) dichlorvos; (XXIV) bromopropylate; (VIII) dicrotophos; (XXV) methoprene; (IX) dicyclanil; (XXVI) disulfoton; (X) fenoxycarb; (XXVII) quinalphos; (XI) fluazuron; (XXVIII) tau-fluvalinate; (XII) furathiocarb; (XXIX) thiocyclam; (XIII) isazofos; (XXX) thiometon; (XIV) jodfenphos; (XXXI) propetamphos; (XV) kinoprene; (XXXII) formothion; (XVI) lufenuron; (XXXIII) dienochlor; or (XVII) methacriphos; (XXXIV) a product isolated from a strain of Bacillus thuringiensis; in free form or in the form of a salt, and at least one known adjuvant. The composition as claimed in claim 1, comprising azamethiphos. 3. The composition as claimed in claim 1, comprising cyperethrin high-cis. 4. The composition as claimed in claim 1, comprising fenoxycarb. 5. A method for the control of pests in plants/plant propagation material comprising applying the composition as claimed in any of the claims 1 to 4, to pest or their habitat. 6. The method as claimed in claim 5 for protecting plant propagation material, comprising treatment of said propagation material or of the locus for cultivation of said propagation material. 7. The method for preparing a composition as claimed in claims 1 to 4, comprising the intimate mixing of the active ingredients with the adjuvant(s).

Documents:

2570-mas-1998-abstract.pdf

2570-mas-1998-claims duplicate.pdf

2570-mas-1998-claims original.pdf

2570-mas-1998-correspondence others.pdf

2570-mas-1998-correspondence po.pdf

2570-mas-1998-description complete duplicate.pdf

2570-mas-1998-description complete.pdf

2570-mas-1998-form 1.pdf

2570-mas-1998-form 26.pdf

2570-mas-1998-form 3.pdf

2570-mas-1998-other documents.pdf