The present invention relates to a pesticidal composition, which comprises a combination of pesticidally active compounds, a method of controlling pests using the said composition, a process for the preparation of the composition, its use and plant propagation material treated with it, and the use of the compounds of the following formulae (A) and (B) for the preparation of the composition.

Certain mixtures of active compounds are proposed for pest control in the literature. How¬ ever, the biological properties of these known mixtures are not completely satisfactory in the field of pest control, and there is therefore the need to provide further mixtures, in particular for controlling insects and representatives of the order Acarina. This object is achieved ac¬ cording to the invention by providing the present composition.

The invention relates to a pesticidal composition which comprises a combination, which can be varied in terms of amounts, of the pesticidally active compound of the formula

(A, diafenthiuron),

in the free form or in the form of an agrochemically tolerated salt, and of the pesticidally active compound of the formula

(B, hexythiazox)

in the free form or in the form of an agrochemically tolerated salt, and at least one auxiliary.

The compound 1-tert-butyl-3-(2,6-diisopropyl-4-phenoxyphenyl)thiourea (diafenthiuron) of the formula (A) is known, for example, from The Pesticide Manual, 10 ^,h Ed. (1994), The Brit¬ ish Crop Protection Council, London, page 294.

The compound (4RS,5RS)-5-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxo-1 ,3-thiazolidine- 3-carboxamide (hexythiazox) of the formula (B) is known, for example, from The Pesticide Manual, 10 ^,h Ed. (1994), The British Crop Protection Council, London, page 567.

Agrochemically tolerated salts of the compounds of the formulae (A) and (B) are, for exam¬ ple, acid addition salts of inorganic or organic acids, in particular of hydrochloric acid, hy¬ drobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, malonic acid, toluenesulfonic acid or benzoic acid.

Compositions which comprise, as active ingredients, the compounds of the formulae (A) and (B) in the free form are preferred in the context of the present invention.

The combinations of active compounds according to the invention preferably comprise the active compound of the formula (A) and the active compound of the formula (B) in a mixing ratio (weight ratio, in the ratio of their molecular weights or the ratio of the LD _∞ values for a particular pest to be controlled) of 1 :50 to 50:1 , in particular in a ratio between 1 :20 and 20:1 , especially between 10:1 and 1 :10, also preferably between 50:1 and 3:1 , very par¬ ticulariy between 40:1 and 10:1 , also preferably between 2:1 and 1 :2, or in a ratio of 40:1 or 30:1 , or 20:1 , or 20:3, or 15:1 , or 10:1 , or 5:1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:3, or 3:1 , or 3:2, or 2:1 , or 1 : 20, or 1 :10, or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1:1.

Surprisingly, the composition according to the invention is outstandingly suitable for controlling curatively and, in some cases, also preventively a very advanta¬ geous spectrum of pests, even at low rates of application, while being well toler¬ ated by, for example, warm-blooded animals, fish and plants. The composition according to the invention is effective against all or individual development stages of normally sensitive and also resistant pests, such as insects or representatives of the order Acarina. The good pesticidal activity of the composition according to

the invention may manifest itself directly, that is to say in the death of the pests, which occurs immediately or only at a later date, or indirectly, for example in a re¬ duced oviposition and/or a reduced hatching rate of corresponding pests, the good activity corresponding, for example, to a mortality and/or a reduction in the oviposition and/or in the hatching rate of at least 50 to 60 %.

The pests, which can be controlled with the composition according to the inven¬ tion, include: from the order Lepidoptera, for example,

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseoia fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia am- biguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolo- mia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacosomaspp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.; from the order Coleoptera, for example,

Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Lepti- notarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Oryzaephilus spp., Otiorhyn- chus spp., Phlyctinus spp., Popilliaspp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.; from the order Orthoptera, for example,

Blatta spp., Blattelia spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.; from the order Isoptera, for example, Reticulitermes spp.; from the order Psocoptera, for example, Liposcelis spp.;

from the order Anoplura, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; from the order MaHophaga _r for example, Damaltaea spp. and Trichodectes spp.; from the order Thysanoptera, for example, Frankliniella spp., Hercinothrips spp., Taenio- thrips spp., Thrips palmi, Thrips tabaci and Scirtothrips aurantii; from the order Heteroptera, for example, Cimexspp., Distantiella theobroma, Dysdercus spp., Euchistus spp. Eurygaster spp. Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp.; from the order Homoptera, for example, Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma lanigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium comi, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudo- coccus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporari- orum, Trioza erytreae and Unaspis citri; from the order Hymenoptera, for example, Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium phar- aonis, Neodiprion spp., Solenopsis spp. and Vespa spp.; from the order Diptera, for example, Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyiaspp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hy- podeπna spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; from the order Siphonaptera, for example, Ceratophyllus spp. and Xenopsylla cheopis; from the order Thysanura, for example, Lepisma saccharina and from the order Acarina, for example, Acarus siro, Aceria sheldoni, Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyaiomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocop-

truta spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp..

Especially representatives of the order Acarina can be controlled by the compositions ac¬ cording to the invention. These include, in particular:

Aculus spp., in particular A. schlechtendali; Brevipalpus spp., in particular B. califomicus and B. phoenicis; Phyllocoptruta spp., in particular P. oleivora; Eriophyes spp., in particular E. vitis; Panonychus spp., in particular P. uimi and P. citri; Eotetranychus spp., in particular E. carpini and E. orientalis; Polyphagotarsonemus spp., in particular P. latus; and Tetrany¬ chus spp., in particular T. urticae, T. cinnabarinus and T. kanzawai.

Pests of the type mentioned which occur on plants, in particular on useful plants and orna¬ mentals in agriculture, in horticulture and in forestry, or on parts, such as fruit, blossom, foli¬ age, stems, tubers or roots, of such plants can be controlled, i.e. checked or destroyed, in particular using the composition according to the invention, even parts of plants which grow later in some cases being protected against these pests.

The active composition according to the invention can advantageously be employed for pest control in cereals, such as maize or sorghum; in fruit, for example pome, stone and soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries and blackberries; in leguminous plants, such as beans, lentils, peas or soya; in oil crops, such as oilseed rape, mustard, poppy, olives, sunflowers, coco¬ nut, Ricinus, cocoa or groundnuts; in gourds, such as pumpkins, cucumbers or melons; in fibre plants, such as cotton, flax, hemp or jute; in citrus fruits, such as oranges, lemons, grapefruits or tangerines; in vegetables, such as spinach, lettuce, asparagus, cabbage spe¬ cies, carrots, onions, tomatoes, potatoes or capsicum; in laurel family plants, such as avo¬ cado, cinnamon or camphor, or in tobacco, nuts, coffee, aubergines, cane sugar, tea, pep¬ per, vines, hops, banana-family plants, natural rubber plants or ornamentals, in particular in maize, sorghum, pome and stone fruit, leguminous plants, gourds, cotton, citrus fruits, vegetables, aubergines, vines, hops or ornamentals, especially in maize, sorghum, apples, pears, plums, peaches, beans, peas, soya, olives, sunflowers, coconut, cocoa, groundnuts, cucumbers, pumpkins, citrus fruits, cabbage spe¬ cies, tomatoes, potatoes, vines or cotton,

preferably in vines, citrus fruit, apples, pears, tomatoes or cotton.

Other fields of use of the active composition according to the invention are the protection of stocks and stores and of material and in the hygiene sector, in particular the protection of domestic animals and productive livestock against pests of the type mentioned.

In particular, it has suφrisingly been found, that the pesticidal activity of the composition ac¬ cording to the invention, if compared with the combined pesticidal activities of the individual compounds (A) and (B) together forming the active ingredient of the instant composition, is not only additive, as can be expected in principle, but also shows a surprising synergistic effect. In this connection, the term "synergistic effect" is neither limited to the pure pesticidal activity against a certain pest species, nor is it necessary, that this term relates at all to the pure pesticidal activity, but this term can relate to any property of the instant composition, which is advantageous, if compared with the combined corresponding properties of the in¬ dividual compounds (A) and (B) together forming the active ingredients of the instant com¬ position. As examples of such advantageous properties of the instant composition there may be mentioned: a broadening in the spectrum of the pesticidal activity towards additional or different pests, for example towards a resistant pest species; a reduction in the rates of application of the compounds (A) and/or (B); a sufficient degree of pest control by means of the instant composition even in cases where the individual compounds (A) and (B) to¬ gether forming the active ingredient of the instant composition are totally ineffective due to their extremely low rates of application; an advantageous behaviour in the case of being formulated and/or applied, for example if being ground, sieved, compressed, emulsified, dissolved, dispersed or sprayed; an improved storage stability; a better light stability; a bet¬ ter heat stability; an advantageous behaviour in the case of being degraded; a better toxi¬ cology profile; an improved ecotoxicological behaviour; other advantages familiar to those skilled in the art.

Depending on the intended aims and given circumstances, the compositions according to the invention are emulsifiable concentrates, suspension concentrates, solutions which can be sprayed or diluted directly, spreadable pastes, dilute emulsions, wettable powders, solu¬ ble powders, dispersible powders, dusts, granules or capsules in polymeric substances, which comprise the active compounds of the formulae (A) and (B).

The active compounds are employed in these compositions together with at least one of the auxiliaries conventionally used in formulation technology, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).

Solvents can be, for example: non-hydrogenated or partially hydrogenated aromatic hydro¬ carbons, preferably fractions C ₈ to Cι ₂ of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols, such as ethanol, propanol or butanol, glycols and ethers and esters thereof, such as propylene glycol, dipropylene glycol ethers, ethylene glycol or ethylene glycol mono-methyl or -ethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methylpyrrolid-2-one, dimethyl sul¬ foxide or N.N-dimethylformamide, water, non-epoxidized or epoxidized vegetable oils, such as non-epoxidised or epoxidised rapeseed, castor, coconut or soya oil, and silicone oils.

Solid carriers which can be used, for example for dusts and dispersible powders, are as a rule natural rock powders, such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly disperse silicic acids or highly disperse absorbent polymers can also be added to improve the physical properties. Granular adsorptive granule carriers are porous types, such as pumice, crushed brick, sepiolite or bentonite, and non-absorbent carrier materials are calcite or sand. A large number of granulated materials of inorganic or organic nature, in particular dolomite or comminuted plant residues, can furthermore be used.

Surface-active compounds are, depending on the nature of the active compound to be for¬ mulated, nonionic, cationic and/or anionic surfactants or surfactant mixtures with good emulsifying, dispersing and wetting properties. The surfactants listed below are to be re¬ garded only as examples; many other surfactants which are conventionally used in the art of formulation and are suitable according to the invention are described in the relevant lit¬ erature.

Nonionic surfactants are, in particular, polyglycol ether derivatives of aliphatic or cy¬ cloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can con¬ tain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols. Water-soluble

polyethylene oxide adducts, containing 20 to 250 ethylene glycol ether and 10 to 100 pro¬ pylene glycol ether groups, on polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain are further¬ more suitable. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Examples are nonylphenolpolyethoxyethanols, castor oil polyglycol ether, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, poly¬ ethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene- sorbitan, such as polyoxyethylenesorbitan trioleate, are furthermore suitable.

The cationic surfactants are, in particular, quatemary ammonium salts which contain, as substituents, at least one alkyl radical having 8 to 22 C atoms and, as further substituents, lower, non-halogenated or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methyl-sulfates or ethyl-sulfates. Examples are stearyl-trimethyl-ammonium chloride and benzyl-di(2-chloroethyl)ethyl-ammonium bromide.

Suitable anionic surfactants can be either water-soluble soaps or water-soluble synthetic surface-active compounds. Suitable soaps are for instance the alkali metal, alkaline earth metal and substituted or unsubstituted ammonium salts of higher fatty acids (C10-C22), such as the sodium or potassium salts of oleic or stearic acid, or of naturally occurring fatty acid mixtures, which can be obtained, for example, from coconut oil or tall oil; they are also the fatty acid methyl-taurine salts. However, synthetic surfactants, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates, are more often used. The fatty sulfonates and sulfates are as a rule in the form of alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts and in general contain an alkyl radical having 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals; examples are the sodium or calcium salt of ligninsulfonic acid, of dodecylsulfuric acid ester or of a fatty alcohol sulfate mixture prepared from naturally occurring fatty acids. These also include the salts of the sulfuric acid esters and sulfonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid radical having about 8 to 22 C atoms. Alkylarylsulfonates are, for example, the sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid-formaldehyde condensation product. Corresponding phosphates, such as salts of the phosphoric acid

ester of a p-nonylphenol-(4-14)-ethylene oxide adduct or phospholipids, are furthermore also suitable.

The compositions as a rule comprise 0.1 to 99%, in particular 0.1 to 95%, of a mixture of the active compound of the formula (A) with the active compound of the formula (B), and 1 to 99.9%, in particular 5 to 99,9%, of - at least - one solid or liquid auxiliary, and as a rule 0 to 25%, in particular 0.1 to 20%, of the composition can be surfactants (% is in each case percent by weight). While concentrated compositions tend to be preferred as commercial goods, the end user as a rule employs dilute compositions which have considerably lower active compound concentrations. Preferred compositions are composed, in particular, as follows (% = percent by weight):

Emulsifiable concentrates: Mixture of (A) and (B): 1 to 90%, preferably 5 to 20% Surfactant: 1 to 30%, preferably 10 to 20 % Solvent: 5 to 98%, preferably 70 to 85%

Dusts:

Mixture of (A) and (B): 0.1 to 10%, preferably 0.1 to 1%

Solid carrier 99.9 to 90%, preferably 99.9 to 99%

Suspension concentrates: Mixture of (A) and (B): 5 to 75%, preferably 10 to 50% Water: 94 to 24%, preferably 88 to 30% Surfactant: 1 to 40%, preferably 2 to 30%

Wettable powders: Mixture of (A) and (B): 0.5 to 90%, preferably 1 to 80% Surfactant: 0.5 to 20%, preferably 1 to 15% Solid carrier: 5 to 99%, preferably 15 to 98%

Granules:

Mixture of (A) and (B): 0.5 to 30%, preferably 3 to 15%

Solid carrier: 99.5 to 70%, preferably 97 to 85%

The compositions according to the invention can also comprise other solid or liquid auxilia¬ ries, such as stabilisers, for example non-epoxidized or epoxidized plant oils (for example epoxidised coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, pre¬ servatives, viscosity regulators, binders and/or tackifiers, as well as fertilizers or other active compounds for achieving specific effects, for example bactericides, fungicides, nematicides, moliuscicides or herbicides.

The compositions according to the invention are prepared in a known manner, for example by grinding, sieving and/or pressing an active compound or the composition, for example to a particular particle size, before mixing with the auxiliary or auxiliaries, and by intimate mix¬ ing and/or grinding of the composition with the auxiliary or auxiliaries. The invention there¬ fore also relates to the process for the preparation of the compositions.

The invention also relates to the methods of application of the compositions, i.e. the meth¬ ods for controlling pests of the type mentioned, such as - to be chosen according to the in¬ tended aims and given circumstances - spraying, wetting, atomising, dusting, brushing, dressing, scattering or pouring, and to the use of the compositions for controlling pests of the type mentioned. Typical rates of application are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active compound. The rate of application can vary within wide limits and depends on the nature of the soil, the type of application (foliar application; seed dressing; application in the seed furrow), the crop plant, the pest to be controlled, the par¬ ticular prevailing climatic circumstances and other factors determined by the type of appli¬ cation, the time of application and the target crop. The rates of application per hectare are in general 1 to 2000 g of active compound mixture per hectare, in particular 10 to 1000 g/ha, preferably 20 to 600 g/ha, particularly preferably 20 to 200 g/ha.

A preferred method of application in the field of plant protection is application to the foliage of the plants (foliar application), where the frequency of application and rate of application are appropriate to the risk of infestation by the particular pest. However, the active com¬ pounds can also enter the plants via the root system (systemic action), by soaking the loca-

tion of the plants with a liquid composition or introducing the active compounds into the lo¬ cation of the plants, for example into the soil, in solid form, for example in the form of gran¬ ules (soil application). In paddy rice crops, such granules can be metered into the flooded rice field.

The compositions according to the invention are also suitable for the protection of plant propagation material, for example, seed, such as fruit, tubers or grains, or plant seedlings, against animal pests. The propagation material can be treated with the composition before placement, for example seed can be dressed before sowing. The active compounds ac¬ cording to the invention can also be applied to seed grains (coating) by steeping the grains in a liquid composition or coating them with a solid composition. The composition can also be applied to the placement location during placement of the propagation material, for ex¬ ample during sowing in the seed furrow. The invention also relates to this treatment method for plant propagation material and to the plant propagation material treated in this way.

The following examples serve to illustrate the invention. They do not limit the invention.

Formulation examples (% = percent by weight, active compound ratios = weight ratios)

Example F1 : Emulsion concentrates a) b) c)

Active ingredients [ratio of the compound of the formula (A) to the compound of the 25 % 40 % 50 % formula (B) 1 :1]

Calcium dodecylbenzenesulfonate 5 % 8 % 6 %

Castor oil polyethylene glycol ether

(36 mol of EO) 5 % - -

Tributylphenol polyethylene glycol ether

(30 mol of EO) - 1 122 %% 4 4 %%

Cyclohexanone - 1 155 %% 2 200 %%

Xylene mixture 65 % 2 255 %% 2 200 %%

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.

Example F2: Solutions a) b) c) d)

Active ingredients (20 : 1) 80% 10% 5% 95%

Ethylene glycol monomethyl ether 20% - - -

Polyethylene glycol MW 400 - 70% - -

N-Methyl-2-pyrrolidone - 20% - -

Epoxidized coconut oil - - 1% 5%

Benzene (boiling limits

160-190°C) - - 94% -

The solutions are suitable for use in the form of very fine drops.

Example F3: Granules a) b) c) d)

Active compound mixture (20 : 3) 5 % 10% 8% 21 %

Kaolin 94 % - 79% 54%

Highly disperse silicic acid 1 % - 13% 7% Attapulgite 90% _ 18%

The active compounds are dissolved together in dichloromethane, the solution is sprayed onto the carrier and the solvent is then evaporated off in vacuo.

Example F4: Dusts a) b)

Active ingredients (5:1) 2% 5%

Highly disperse silicic acid 1 % 5%

Talc 97% -

Kaolin . 90%

Ready-to-use dusts are obtained by intimate mixing of the carriers with the active com¬ pounds.

Example F5: Wettable powders a) b) c)

Active ingredients (30:1) 25% 50% 75%

Sodium lignin sulfonate 5% 5% -

Sodium lauryl sulfate 3 % - 5 %

Sodium diisobutylnaphthalene- sulfonate - 6 % 10 %

Octylphenol polyethylene glycol ether (7-8 mol of EO) - 2 %

Highly disperse silicic acid 5 % 10 % 10 %

Kaolin 62 % 27 %

The active compounds are mixed with the additives and the mixture is ground thoroughly in a suitable mill. Wettable powders which can be diluted with water to give suspensions of any desired concentration are obtained.

Example F6: Emulsion concentrate

Active ingredients (40 : 1) 10 %

Octylphenol polyethylene glycol ether

(4-5 mol of EO) 3 %

Calcium dodecylbenzenesulfonate 3 %

Castor oil polyglycol ether

(36 mol of EO) 4 %

Cyclohexanone 30 %

Xylene mixture 50 %

Emulsions of any desired concentration can be prepared from this concentrate by dilution with water.

Example F7: Dusts a) b)

Active compound mixture (3 : 1) 5 % 8 %

Talc 95 % -

Kaolin . 92 °/<

Ready-to-use dusts are obtained by mixing the active compounds with the carrier and grinding the mixture on a suitable mill.

Example F8: Extruded granules

Active compound mixture (10 : 1) 10 %

Sodium ligninsulfonate 2 %

Carboxymethylcellulose 1 %

Kaolin 87 %

The active compounds are mixed with the additives and the mixture is ground and mois¬ tened with water. This mixture is extruded and granulated and the granules are then dried in a stream of air.

Example F9: Coated granules

Active ingredients (20 : 3) 3 %

Polyethylene glycol (MW 200) 3 %

Kaolin 94 %

The finely ground active compounds are applied uniformly, in a mixer, to the kaolin mois¬ tened with polyethylene glycol. Dust-free coated granules are obtained in this manner.

Example F10: Suspension concentrate

Active compound mixture (15 : 1) 40 %

Ethylene glycol 10 %

Nonylphenol polyethylene glycol ether

(15 mol of EO) 6 %

Sodium ligninsulfonate 10 %

Carboxymethylcellulose 1 %

37% aqueous formaldehyde solution 0.2 %

Silicone oil in the form of a 75 % aqueous emulsion 0.8 %

Water 32 %

The finely ground active compounds are intimately mixed with additives. A suspension con¬ centrate from which suspensions of any desired concentration can be prepared by dilution with water is obtained in this way.

It is often more practical to formulate the active compound of the formula (A) and the mixing partner (B) individually and then to bring them together in the applicator in the desired mix¬ ing ratio as a "tank mix" in water only shortly before application.

Biological examples (% = per cent by weight, unless stated otherwise)

A pesticidally synergistic effect is always present if the action of the combination of the ac¬ tive compound of the formula (A) with the active compound of the formula (B) is greater than the sum of the actions of the active compounds applied individually.

For example, the pesticidal action to be expected Ae for a given combination of two pesti¬ cides can be calculated as follows (cf. COLBY, S.R., "Calculating synergistic and antago¬ nistic response of herbicide combinations", Weeds 15, pages 20-22, 1967):

Y ( 100 -X )

Ae = X +

100 where:

X = Per cent mortality under treatment with the compound of the formula (A) at a rate of application of p kg per hectare compared with the untreated control (= 0 %).

Y = Per cent mortality under treatment with the compound of the formula (B) at a rate of application of q kg per hectare compared with the untreated control.

Ae = Expected pesticidal action (percent mortality compared with the untreated control) af¬ ter treatment with the compound of the formula (A) and the compound of the formula (B) at a rate of application of p + q kg of active compound per hectare.

If the action actually observed is greater than the action Ae to be expected, synergism exists.

The synergistic effect of the combinations of the active compound of the formula (A) with the active compound of the formula (B) is demonstrated in the following examples.

Example B1 : Action against Bemisia tabaci

Dwarf bean plants are placed in gauze cages and populated with adults of Bemisia tabaci. After oviposition has taken place, all the adults are removed. 10 days later, the plants with the nymphs on them are sprayed with an aqueous suspension spray mixture which com¬ prises a total amount of 50 ppm of the active ingredients. After a further 14 days, the per¬ cent hatching of the eggs is evaluated in comparison with the untreated control set-ups.

In this experiment, the combinations of the active compound of the formula (A) with the ac¬ tive compound of the formula (B) show a synergistic effect. In particular, the combinations of the active compounds of the formulae (A) ands (B) in the ratios of 20:1 and 20:3 show a very good effect.

Example B2: Action against Spodoptera littoralis caterpillars

Young soya plants are sprayed with an aqueous emulsion spray mixture which comprises 400 ppm of the active ingredients. After the spray coating has dried on, the soya plants are populated with 10 caterpillars of the third stage of Spodoptera littoralis and placed in a plas¬ tic container. The evaluation is carried out 3 days later. The percentage reduction in the population or the percentage reduction in feeding damage (% action) is determined by comparison of the number of dead caterpillars and the feeding damage on the treated plants to those on untreated plants.

In this experiment, the combinations of the active compound of the formula (A) with the ac¬ tive compound of the formula (B) show a synergistic effect. In particular, the combinations of the active ingredient of the formula (A) with the active ingredient of the formula (B) in the ratios of 10:1 and 40:1 show a very good effect.

Example B3: Ovicidal action on Lobesia botrana

Lobesia botrana eggs deposited on filter paper are immersed for a short time in an acetone- water test solution which comprises 400 ppm of the active compound mixture to be tested. After the test solution has dried, the eggs are incubated in Petri dishes. After 6 days, the percentage hatching of the eggs is evaluated in comparison with untreated control set-ups (% hatching reduction).

ln this experiment, the combinations of the active compound of the formula (A) with the ac¬ tive compound of the formula (B) show a synergistic effect. In particular, the combinations of the active compounds of the formulae (A) and (B) in the ratio of 20:1 and in the ratio of 20:3 show a very good effect.

Example B4: Action against Panonychus ulmi (OP and carb-resistant. Apple seedlings are populated with adult females of Panonychus ulmi. After 7 days, the in¬ fected plants are sprayed to drip point with an aqueous emulsion spray mixture comprising 400 ppm of the active ingredients to be tested, and are grown in a greenhouse. The evaluation is carried out after 14 days. The percentage reduction in the population (% ac¬ tion) is determined by comparison of the number of dead spider mites on the treated plants to those on untreated plants.

In this experiment, the combinations of the active compound of the formula (A) with the ac¬ tive compound of the formula (B) show a synergistic effect. In particular, the combinations of the active compounds of the formulae (A) and (B) in the ratios of 5:1 , 15:1 and 30:1 show a very good effect.

Example B5: Action against Tetranychus urticae

Young bean plants are populated with a mixed population of Tetranychus urticae, and are sprayed one day later with an aqueous emulsion spray mixture which comprises 400 ppm of the active ingredients. The plants are then incubated for 11 days at 24°C and thereafter evaluated. The percentage reduction in the population (% action) is determined by compari¬ son of the number of dead eggs, larvae and adults on the treated plants to those on un¬ treated plants.

In this experiment, the combinations of the active ingredients of the formula (A) with the ac¬ tive compound of the formula (B) show a synergistic effect. In particular, the combinations of the active compounds of the formulae (A) and (B) in the ratios of 10:1 , 15:1 and 20:1 show a very good effect.