GB2532419A - A pesticidal composition - Google Patents

Abstract

The present invention relates to a pesticidal composition comprising spirobudiclofen and diafenthiuron. Also claimed is a method for treating pests at a locus comprising applying the composition to the locus, and the use of a combination of spirobudiclofen and diafenthiuron for preventing and/or controlling harmful organisms. The spirobudiclofen and diafenthiuron may be applied separately, sequentially or simultaneously. Preferably the composition may further comprise one or more surfactants and/or extenders. The pests are selected from the group of insects and mites, in particular the pests are selected from red mites and psyllids.

Description

A PESTICIDAL COMPOSITION

The present invention relates to a pesticidal composition and to a method of using the same, including a pesticidal method with rapid and long lasting effects.

Spirobudiclofen is the common chemical name of 3-(2,4-dichlorophenyI)-2-oxo-1-oxaspiro [4,5]-deca-3-ene-4-ylbutanoate and has the structural formula: Formula (I) Spirobudiclofen is a new tetronic acid pesticide, having a broad pesticidal spectrum and long lasting effect. Spirobudiclofen kills insect larvae by interfering with the biosynthesis of lipids in insects. No cross-resistance occurs between spirobudiclofen and conventional acaricides. Due to its unique mode of action, spirobudiclofen is effective in controlling harmful mites that are resistant to conventional acaricides. Spirobudiclofen has a good adaptability and is useful in controlling sucking pests, such as red spider mites, yellow spider mites, Polyphagotarsonemus latus, Tetranychus cinnabarinus, psyllids, Trialeurodes vaporariorum, and the like, in a range of crops, including in fruit trees, such as citrus, grapefruits, apples, pears, and the like, and Solanaceae plants, such as egg plants, capsicum, tomatoes, and the like. In particular, spirobudiclofen has good effectiveness in controlling Psylla pyrisuga and red spider mites which have strong propagation ability.

Diafenthiuron, also known as methamidophos, is the common chemical name of 1-tert-butyl-3-(2,6-di-isopropyl-4-phenyloxyphenyl)thiourea. The structural formula of diafenthiruon is as follows: 1-4 -k

S / CH3

r \ I: i 0 -? \----N ''' N C CH3 N:c,ii t i I --S, H H 1..H3 CH3-Ch i CH3 Formula (II) Diafenthiuron is a thiourea pesticide and is active as an acaricide. Diafenthiuron has systemic, contact and/or stomach action and fumigant action. Diafenthiuron exhibits insecticidal and acaricidal effects by interfering with the energy metabolism and destroying the basic function of the nervous system of the target, as well as inhibiting the synthesis of chitin. Diafenthiuron has a good controlling effect on mites (tetranychoidea, citrus rust mite), aphids, whitefly, leafhoppers, various moths, and the like, particularly resistant Psylla chinensis, resistant Pierisrapae Linne, resistant Adoxophyes honmai, and is useful in a range of crops, such as fruit trees (citrus, apples), cottons, vegetables, teas and ornamental plants.

There is a need to find an improved pesticidal composition. In particular, it would be advantageous to provide a pesticidal composition having reduced application rates of active ingredients and which can effectively control pests in target crops, while reducing or avoiding an adverse environmental impact or toxicological effects in the field. In addition, the pesticidal composition should preferably exhibit an effect that is rapid or long lasting, preferably both.

Moreover, experience with single active straight formulation pesticides worldwide indicates there is a high risk of the development of resistant insect subpopulations.

As a result, a preferred pesticidal composition would be one having a reduced application rate, a wide activity spectrum, a rapid effect, a long lasting effect and a delayed occurrence of resistance in the target species.

After extensive biological tests, it has now surprisingly been found that the combination of spirobudiclofen and diafenthiuron can effectively prevent and/or control harmful organisms. The activity of the combination in preventing and/or controlling harmful organisms is drastically higher than the sum of the activity of individual active ingredients. This unexpected effect is a synergistic effect rather than an additive effect.

Accordingly, in a first aspect the present invention provides a pesticidal composition comprising spirobudiclofen and diafenthiuron.

It has now surprisingly been found that the combination of spirobudiclofen and diafenthiuron not only broadens the control spectrum, but also shows a synergistic effect.

The term "synergistic effect" used herein means that the pesticidal effect achieved by the combination of spirobudiclofen and diafenthiuron is greater than the sum of individual active ingredients when applied separately from one another.

In another aspect of the present invention, therefore, a combination of spirobudiclofen and diafenthiuron with a significantly synergistic effect is provided, thereby reducing the required dosages of the two active ingredients.

The pesticidal composition of the present invention exhibits a good plant compatibility and favorable toxicity to warm-blooded animals and is suitable for preventing and/or controlling harmful organisms, particularly the class of Insecta and the class of Arachnida, in agriculture, forestry, stored products and materials as well as in the hygiene field. The pesticidal composition of the present invention is active against and useful in the control of species of pests, including all developmental stages, which are sensitive and/or exhibiting resistance to existing treatments.

The term "harmful organism(s)" used herein refers to any organism that causes damage to plants and includes the following: the order of Lepidoptera, for example, Chilo suppressalis, Tryporyza incertulas, Cnaphalocrocis medinalis Guenee, Hellulla undalis, Conogethes punctiferlis, Papilio xuthus, Pieris rapae crucivora, Parnara guttata, Malacosoma neustria testacea, Lymantria dispar, Hyphantria cunea, Euproctis subflava, Scopelodescontracus, Helicoverpa armigera, Pink bollworm, Trichoplusia ni, Mamestra brassicae, Spodoptera exigua, Spodoptera litura, Adoxophyes orana fasciata, Adoxophyes honmai, Archipsfuscocureanus, Homona magnanima, Plutella xylotella, Pectinophora gossypiella; the order of Coleoptera, for example, Sitophilus oryzae linne, Podagricomela nigricollis Che, S. zeamais, S. granarius, Cabbage leaf beetle, Daikon leaf beetle, Flea beetle, Altica Chalybea, Phyllotreta striolata, Epitrix cucumeris, Ehirtipennis, E. fuscula, Aulacophora indica (Gemlin), Phaedon cochleariae, etc; the order of Diptera, for example, Agromyza oryzae, Hydrellia griseola, Liriomyza trifolii, Chromatomyia horticola, Liriomyza bryoniae, Delia platura, Delia antiqua, Ceratitis capiata wiedgmann, Rhagoletis pomonella, R. cingulate; the order of Hemiptera, for example, Megacopta punctatissima, Eurydema rugosum, Eysarcoris lewis, Eysarcoris parvus, Nezara viridula, Plautia stali, Halymorphamista, Cletus punctiger, Leptocorisachinensis, Stephanotis pyrioides, Trigonotylus coelestialium; the order of Homoptera, for example, Nephotettix cincticeps, Laodelphax striatellus, Nilaparvata lugens, Sogatella furcifera, Psylla pyrisuga, Diaphorinatabaci, Bemisia tabaci, Homoptera, Eriosoma lanigerum; the order of Hymenoptera, for example, Athalia rosae ruficornis, Arge pagana, Formica japonica, Dryocosmus kuriphilus, etc; the order of Physanoptera, for example, Haplothrips chinensis Priesner; the class of Arachnida, for example, Panonychus citri, Tetranychus cinnabarinus, Panonychus ulmi, Tetranychus urticae, Tetranychus viennensis, Oligonychus ununguis, Eotetranychus kankitus, Brevipalpus phoenicis, Bryobia praetiosa, Aceria tulipae, Colomerus vitis, Calacarus carinatus, Polyphagotarsonemus latus, Rhizoglyphus rostochiensis, etc; the order of Anoplura (Phthiraptera), for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.; the order of lsopoda, for example, Oniscus asellus, Armadilliudium vulgare, Porcellio scaber; the class of Diplopoda, for example, Blaniulus guttulatus; the class of Chilopoda, for example, Geophilus carpophagus, Scutigera spp.; the class of Symphyla, for examples, Scutigerella immaculate; the order of Thysanura, for example, Lepisma saccharina; the order of Collembola, for example, Onychiurus armatus; the order of Orthoptera, for example, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria; the order of Blattaria, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica; the order of Dermaptera, for example, Forficula auricularia; the order of Isoptera, for example, Reticulitermes spp; the phylum of Nematoda, for example, Meloidogyne, Heterodera schachtii, Rhabditis strongyloides and Aphelenchoides fragariae, in particular nematodes from Heterodera, Golbodera rostochiensis, Meloidogyne incognita, etc.; the order of Dorylaimida, for example, Longidorus sp., etc. The pesticidal composition of the present invention exhibits an outstanding effect in preventing and/or controlling bollworms (Helicoverpa armigera), aphids, red spider mites, psyllids, moth or leafminers.

By combining two active ingredients, having different mode of actions, the combination has the effects of killing the target pests by a range of actions, for example by contact action, stomach toxicity, ovicidal action and reduction in egg-laying rate and hatchability rate.

The active ingredients spirobudiclofen and diafenthiuron may be present or employed together in a wide range of weight ratios. More particularly, the weight ratio of spirobudiclofen to diafenthiuron may be from about 100:1 to about 1:100, preferably from about 50:1 to about 1:50, more preferably from about 25:1 to about 1:25. More preferred ratios are from about 20:1 to about 1:20, more particularly from about 15:1 to about 1:15, still more preferably from about 10:1 to about 1:10, more preferably still from about 5:1 to about 1:5.

The pesticidal composition of the present invention may comprise spirobudiclofen and diafenthiuron in a wide range of amounts. The amount of active ingredient may depend, for example on the type of formulation being employed. In many embodiments, the composition comprises spirobudiclofen and diafenthiuron in an amount of at least 5% by weight, preferably at least 10%, more preferably at least 15%, still more preferably at least 20%, more preferably still at least 25%. Compositions comprising at least 30% by weight, 35%, 40%, 45%, 50%, 60%, 65%, 70%, 75%, 80%, 85% or 90% by weight can also be formulated. The composition may comprise spirobudiclofen and diafenthiuron, in an amount of from about 5% to about 90% by weight of the composition, preferably from about 10% to about 80% by weight of the composition, more preferably from 15 to 60 %, more preferably still from about 20% to about 60% by weight of the composition.

The pesticidal composition may in addition to the above mentioned active compounds spirobudiclofen and diafenthiuron comprise one or more further active ingredients.

The pesticidal composition may be produced in conventional manner, for example by mixing the active ingredients with appropriate auxiliaries. Suitable auxiliaries which may be comprised in the composition according to the invention are all customary formulation adjuvants or components, such as extenders, carriers, solvents, surfactants, stabilizers, anti-foaming agents, anti-freezing agents, preservatives, antioxidants, colorants, thickeners, solid adherents, anti-aggregating agents and inert fillers. Such auxiliaries are known in the art and are commercially available. Formulations can be prepared by mixing the active ingredients with the appropriate extenders and/or surfactants suitable for agricultural chemical formulations in a known manner.

The pesticidal composition of the present invention can be formulated into a wide range of conventional formulations, such as suspension concentrates (SC), seed dressings, wettable powders (WP), water dispersible granules (WG), capsule suspensions (CS), coated granules, extruded granules, emulsifiable concentrate (EC), micro-emulsions (ME), emulsions, oil in water (EW), effervescent agents (PP), smoke candles (FK), ultra-low volume liquids (LDL), depending on the particular purpose and end use intended.

Each type of preparation should secure the uniform distribution of the compounds of the composition of the present invention. Techniques for formulating the composition in these manners are known in the art.

In accordance with the present invention, the term "extender(s)" means a natural or synthetic organic or inorganic compound that may be used in combination/conjunction with the active ingredient to make it easier for administration to a subject (such as plants, crops or grass and the like). Hence, the extenders are preferably inert and at least are agriculturally acceptable The extenders can be solid or liquid. Suitable solid extenders include vegetable powders (such as soybean flour, starch, cereal flour, wood dust, bark flour, sawdust, walnut shell powder, wheat bran, cellulose powder, coconut shells, maize cobs and tobacco stalks, residues after extraction of plant essence, etc.), paper, clays (such as kaolin, bentonite, acid clay, etc.), talc, silica (such as diatomaceous earth, silica sand, mica, hydrous silicic acid, calcium silicate), activated carbon, natural minerals (pumice, attapulgite and zeolite), the calcined diatomaceous earth, sand, plastic carriers, etc. (such as polyethylene, polypropylene), the inorganic mineral powders (such as potassium chloride, calcium carbonate, calcium phosphate, etc.), chemical fertilizers (such as ammonium sulfate, ammonium phosphate, urea, ammonium chloride, etc.), and soil fertilizers. These substances may be used alone or by combination of two or more.

Suitable liquid carriers can be selected from water, alcohols (for example, methanol, ethanol, isopropanol, butanol, ethylene glycol, etc.), ketones (for example, acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, etc.), ethers (for example, diethyl ether, dioxane, methylcellulose, tetrahydrofuran, etc.), aliphatic hydrocarbons (for example, kerosene, mineral oil), aromatic hydrocarbons (for example, benzene, toluene, xylene, solvent naphtha, alkylnaphthalene, chlorinated aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorobenzene, etc.), halogenated hydrocarbons, amides, sulfones, mineral oils, vegetable oils, animal oils, and the like.

To emulsify, disperse and/or wet the active ingredient, surfactants may be included in the formulations. The selection of one or more surfactants will depend, for example on the type of formulation being employed and the manner of the intended end use of the composition. Suitable surfactants are known in the art and include compounds such as polyoxethylene fatty alcohol ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene higher fatty acid esters, phosphoric esters of polyoxyethylene or phenols, fatty acid esters of polyhydric alcohols, alkyl aryl sulfonates, lignin sulfonate, branched polymer comb-shaped copolymers, butyl naphthalene sulfonate, alkyl aryl sulfonates, and alkyl sulfosuccinate.

To stabilize the dispersion of the active ingredient, stabilizers may be included in the formulation. Suitable stabilizers are known in the art and include xanthan gum, magnesium aluminum silicate, gelatin, starch, cellulose ether, polyvinyl alcohol, polyvinyl acetate, natural phospholipids (for example, cephalins and lecithin) and synthetic phospholipids, bentonite, and lignin sulfonate.

Anti-freezing agents suitable for use are also known in the art and include ethylene glycol, propylene glycol, glycerin and sorbitol.

Anti-aggregating agents are known in the art and include naphthalene sulfonic acid polymers, polymeric phosphates, and the like.

Anti-foaming agents are also known in the art. A suitable group of anti-foaming agent are organic silicone defoamers.

Optionally, other additional components, such as protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilizers and masking agents can be included in the composition, as required.

The active ingredients, spirobudiclofen and diafenthiuron, of the present invention can also be applied in combination with other active ingredients to expand the active spectrum or prevent the development of resistance. Other active ingredients are, for example, fungicides, bactericides, attractants, insecticides, acaricides, nematocides, growth regulators, herbicides, security agents, fertilizers or chemical pheromones, etc. In another aspect, the present invention provides a method of preventing and/or controlling harmful organisms at a locus comprising applying to the locus a combination of spirobudiclofen and diafenthiuron.

In the method, spirobudiclofen and diafenthiuron may be applied to locus at the same time or at different times, that is separately, sequentially or simultaneously. In the event of separate application, the order of application generally does not affect the controlling effect.

Spirobudiclofen and diafenthiuron may be applied to the locus in the weight ratios discussed hereinbefore.

In one embodiment, the method comprises applying to the locus a composition comprising spirobudiclofen and diafenthiuron, such as the pesticidal composition hereinbefore described.

The locus may be a target plant or its surroundings, such as the surrounding soil or space, a target harmful organism or the habitat thereof, or a propagation material of the target plant.

The term 'propagation material(s) of plants' used herein means all grown parts including seeds, roots, fruits, tubers, corms, rhizomes, branches, seedlings and other plant parts. Seedlings and young plants transplanted after germination or emergence from the soil are also included. Propagation materials of plants can be treated with a plant protecting compound before planting or during or before transplantation.

A method of protecting crops from infestation of harmful organisms comprises contacting crops and/or their surroundings with a pesticidal composition comprising spirobudiclofen and diafenthiuron.

The pesticidal composition of the present invention is particularly important in preventing and/or controlling most of harmful organisms in various cultivated plants, such as cereals, fruits, vegetables and economic crops.

Plants that may be treated in accordance with the present invention include all genetically engineered plants or transgenic plants.

As noted above, the combination of spirobudiclofen and diafenthiuron, for example by way of a pesticidal composition, is useful in protecting the propagation material of plants and the grown plant organs subsequently.

In a further aspect, the present invention provides the use of spirobudiclofen and diafenthiuron in the control of pests at a locus.

The pesticidal composition and method of the present invention are useful in protecting all parts of the target plant from pests, for example by treating leaves and branches, and treating seeds and roots to avoid pests in the soil. As a result, the pesticidal composition and method of the present invention are suitable for seed treatment to protect seeds from infestation by insects and pests, particularly soil-borne insects and pests, and protect the grown plant roots and branches to avoid infestation by soil pests and insects on leaves.

Preferably, the propagation material of plants is seeds. The method of the seed treatment includes soaking seeds with a composition of the active ingredients, for example diluted liquids formulations or diluted solid formulations, or soaking seeds with undiluted liquid formulation; coating the surface of seeds with formulation by mixing a solid or a liquid formulation with the seeds; and spraying formulations of the active ingredients at the place of sowing the seeds.

In the practice of the method and use of the present invention, the active ingredients can be applied by techniques known in the art, including pouring, injection, spray, dusting, dispersal or fumigation. The application rates of the active ingredients can vary depending on such factors as the weather or the status of plants being treated.

For foliar treatments, the dosage rate of the active ingredients is generally from 0.1 to 10,000 g active ingredient per hectare (g A.I./ha), preferably from 10 to 1,000 g A.I./ha, and more preferably from 50 to 800 g A.I./ha. For seed treatments, the dosage is generally from 2 to 1,000 g A.I./100 kg of seeds, preferably from 3 to 300 g A.I./100 kg of seeds. For soil treatments, the dosage is generally from 0.1 to 10,000 g A.I./ha, and preferably from 1 to 5,000 g A.I./ha.

The above dosage rates are generally illustrative. The actual application rates can be adjusted by a person skilled in the art, depending on situations and needs, particularly depending on the properties of plants or crops to be treated and the severity of the pest infestation.

Controlling pest infestation should be carried out preferably at the initial onset of the pest infestation. However, in many cases, it is not possible to notice the pest infestation until severe damage to the crops or plants has been caused and becomes visible. By using the combination of spirobudiclofen and diafenthiuron according to the present invention, the combination has a rapid effect and the highest pest mortality may be achieved as soon as 12 hours after dosing. The effectiveness of the combination of active ingredients, once applied may last for 45 days.

In another aspect, the occurrence of resistance in the target plants may be delayed by using the combination of active ingredients of the present invention.

Examples of the present invention will now be described, by way of illustration only. In the Examples, all percentages are by weight of the composition, unless otherwise indicated.

EXAMPLES

Preparation Examples

Example 1: 5% Spirobudiclofen + 10% Diafenthiuron (Oil suspension) An oil suspension formulation was prepared having the composition summarized in the following table.

Spirobudiclofen 5% Diafenthiuron 10% Nonylphenolpolyoxyethylene polyether 5% Bentonite 1% Glycerin 5% Corn oil Made up to 100% The components were mixed uniformly, ground and/or sheared at high speed to obtain a 5% Spirobudiclofen + 10% Diafenthiuron oil suspension.

Example 2: 30% spirobudiclofen + 60% diafenthiuron (WP) A wettable powder formulation was prepared having the composition summarized in the following table.

Spirobudiclofen 30% Diafenthiuron 60% Sodium lauryl sulfate 1% Sodium lignosulfonate 1% White carbon black 1% Kaolin Made up to 100% The components were mixed and milled in an ultrafine pulverizer to obtain 30% spirobudiclofen + 60% diafenthiuron wettable powder (WP).

Example 3: 20% spirobudiclofen + 60% Diafenthiuron (WP) A wettable powder formulation was prepared having the composition summarized in the following table.

Spirobudiclofen 20% Diafenthiuron 60% Sodium lauryl sulfate 1% Sodium lignosulfonate 1% Sucrose Made up to 100% The components were mixed and milled in an ultrafine pulverizer to obtain 20% spirobudiclofen + 60% Diafenthiuron wettable powder (WP).

Example 4: 10% Spirobudiclofen + 50% Diafenthiuron (WG) A water dispersible granule formulation was prepared having the composition summarized in the following table.

Spirobudiclofen 10% Diafenthiuron 50% Sodium lignosulfonate 3% Sodium lauryl sulfate 3% Urea 5% Sucrose Made up to 100% The components were mixed and then comminuted by jet milling to obtain a wettable powder. Water was added and mixed with the wettable powders to form a paste, which was then extruded and dried to obtain 10% Spirobudiclofen + 50% Diafenthiuron water dispersible granules (WG).

Example 5: 2% Spirobudiclofen + 3% Diafenthiuron (EC) An emulsion concentrate formulation was prepared having the composition summarized in the following table.

Spirobudiclofen 2% Diafenthiuron 3% Ethoxylated castor oil 3% Sodium lauryl sulfate 2% Dimethylsulfoxide Made up to 100% The components were stirred to obtain a homogeneous phase.

Example 6: 2% Spirobudiclofen + 20% Diafenthiuron (SD) A seed dressing formulation was prepared having the composition summarized in

the following table.

Spirobudiclofen 2% Diafenthiuron 20% Disodium alkyl polyoxyethylene sulfosuccinate 5% Ethoxylated castor oil 3% Bentonite 3% PVP-K30 1% Soybean oil Made up to 100% The components were mixed uniformly and then ground and/or sheared at high speed to obtain a seed dressing comprising 2% Spirobudiclofen + 20% Diafenthiuron.

Example 7: 10% Spirobudiclofen + 10% Diafenthiuron (WP) A wettable powder formulation was prepared having the composition summarized in the following table.

Spirobudiclofen 10% Diafenthiuron 10% Sodium lauryl sulfate 5% Sodium lignosulfonate 5% White carbon black 10% Kaolin Made up to 100% The components were mixed, milled and pulverized to obtain 10% Spirobudiclofen + 10% Diafenthiuron wettable powder (WP).

Example 8: 5% spirobudiclofen +35% diafenthiuron (WG) A water dispersible granule formulation was prepared having the composition summarized in the following table.

Spirobudiclofen 5% Diafenthiuron 35% Modified calcium lignosulfonate 5% Sodium lauryl sulfate 5% Urea 1% Kaolin Made up to 100% The components were mixed uniformly and then comminuted by jet milling to obtain a wettable powder. Thereafter, water was added with mixing, and the resulting mixture extruded and then dried to obtain 5% spirobudiclofen + 35% diafenthiuron water dispersible granules (WG).

Example 9: 5% spirobudiclofen + 10% diafenthiuron (SE) A suspoemulsion formulation was prepared having the composition summarized in the following table.

Spirobudiclofen 5% Diafenthiuron 10% Methyl oleate 10% Ethoxylated castor oil 4% Disodium 5% methylenebisnaphthalenesulphonate Modified calcium lignosulfonate 0.5% Xanthan gum 0.5% Bentonite 1% Glycerin 5% Anti-foaming agent 0.1% Water made up to 100% Spirobudiclofen was dissolved in methyl oleate and then ethoxylated castor oil was added to obtain a spirobudiclofen oil phase. Diafenthiuron, Disodium methylenebisnaphthalenesulphonate, modified calcium ligninsulfonate, xanthan gum, bentonite, glycerin and water were mixed uniformly and then milled to obtain a diafenthiuron suspension. The oil phase was added o the suspension and mixed to obtain 5% spirobudiclofen + 10% diafenthiuron suspoemulsion (SE).

Example 10: Coated granules of 2% spirobudiclofen + 8% diafenthiuron A coated granule formulation was prepared having the composition summarized in

the following table.

Spirobudiclofen 2% Diafenthiuron 8% Polyethylene glycol 3% Highly dispersed silicic acid 1% Calcium carbonate Made up to 100% In a mixer, the carriers wetted with polyethylene glycol were coated with finely ground active ingredients to obtain dust-free coated granules.

Example 11: Extruded granules of 20% spirobudiclofen + 40% diafenthiuron An extruded granule formulation was prepared having the composition summarized in the following table.

Spirobudiclofen 20% Diafenthiuron 40% Sodium lignosulfonate 5% Carboxymethyl cellulose 2% Kaolin Made up to 100% The active ingredients were mixed with auxiliaries, ground, wetted with water, extruded and then air dried to produce granules.

Example 12: 10% spirobudiclofen + 90% diafenthiuron A mixture formulation was prepared having the composition summarized in the following table.

Spirobudiclofen and diafenthiuron were mixed uniformly.

Biological Test Examples When combining different types of agricultural active ingredients, in general, three types of effect may be observed: additive effect, synergistic effect and antagonistic effect. The type of effect is generally unpredictable and may be known only by extensive tests. Tests were performed for different formulations of spirobudiclofen and diafenthiuron. It was found that the pesticidal compositions show a synergistic effect rather than additive or antagonistic effect.

The toxicity index of each of the tested formulations and the co-toxicity coefficient (CTC value) of the mixed formulation were determined by indoor toxicity test. When the CTC is found to be 580, the composition is considered to exhibit an antagonistic effect. When a value for the CTC of 80<CTC<120 is obtained, the composition is considered to exhibit an additive effect. When the CTC is found to be 120, the composition is considered to exhibit a synergistic effect.

Spirobudiclofen 10% Diafenthiuron 90% Test 1: The indoor toxicity test of Pylla tivrisuaa Test Method: Leaves from pear trees, having a similar size and which have had no contact with any pesticideal composition, were placed in a box and infested with larvae of Pylla pyrisuga.

Liquid formulations were prepared comprising spirobudiclofen and diafenthiuron in a range of ratios.

In each test, the leaves were soaked in the liquid formulation for 5 seconds. The leaves were dried naturally and then placed in a box. 20 larvae were fed at 25 °C in the box.

A control experiment was conducted under the same test conditions.

Each test was repeated 3 times.

After 72 hours, the number of dead insects was measured. The mortality (%), corrected mortality (%) and LC50 value were calculated and a toxicity regression equation was obtained, as follows: Mortality (%) = (number of live insects before dosing -number of live insects after dosing) / number of live insects before dosing x 100 Corrected mortality (%) = (mortality of the treated group -mortality of the control experiment) / (100 -mortality of the control experiment) x 100 The corrected mortality of the test insects are converted into probabilities (y), concentration (pg/ml) was converted into a logarithmic value (X) and a toxicity regression equation was obtained by the least squares method. The co-toxicity coefficient (CTC) was calculated according to the Sun Yunpei equation. The equation is shown below (Spirobudiclofen is used as the standard agent, the toxicity index is 100): Actual toxicity index (ATI) = (standard agent LC50/ test agent LC50) x 100 Theoretical toxicity index (TTI) = (ATI of Agent A) x (percentage of A in a mixture) + (ATI of Agent B) x (percentage of B in a mixture) Co-toxicity coefficient (CTC) = (ATI of Mixture / TTI of Mixture) x 100 If the mortality of the control experiment is greater than 10%, then the test was considered as invalid.

The result of the indoor toxicity tests are shown below in Table 1:

Table 1:

Test Agent Weight ratio LC50 Actual Theoretical Co-toxicity of active (mg/L) toxicity toxicity index coefficient ingredient index (TTI) (CTC) (ATI) Spirobudiclofen 2.412 100 / / Diafenthiuron 17.80 13.54 / / Spirobudiclofen: Diafenthiuron 100:1 1.55 155.56 99.14 156.9 Spirobudiclofen: Diafenthiuron 50:1 1.31 184.22 98.30 187.4 Spirobudiclofen: Diafenthiuron 25:1 1.26 190.74 96.67 197.3 Spirobudiclofen: Diafenthiuron 10:1 1.13 213.49 92.14 231.7 Spirobudiclofen: Diafenthiuron 5:1 1.11 217.48 85.59 254.1 Spirobudiclofen: Diafenthiuron 1:1 1.48 163.27 56.77 287.6 spirobudiclofen: diafenthiuron 1:5 2.96 81.50 27.95 291.6 spirobudiclofen: diafenthiuron 1:10 3.44 70.21 21.40 328.1 spirobudiclofen: diafenthiuron 1:25 5.03 47.91 16.87 284.1 spirobudiclofen: diafenthiuron 1:50 6.65 36.28 15.24 238.1 spirobudiclofen: diafenthiuron 1:100 9.40 25.65 14.40 178.2 From the results set out in Table 1 it is evident that the compositions comprising both spirobudiclofen and diafenthiuron exhibited a co-toxicity coefficient of greater than 120. The compositions thus exhibited a synergistic effect.

Test 2: The indoor toxicity test of Panonvchus citri Test Method: Leaves with stalks from citrus were cut and placed in an ampoule containing water. The leaves were infested with adult Panonychus citri mites. The adult mites were removed 24 hours after laying eggs.

Liquid formulations were prepared comprising spirobudiclofen and diafenthiuron in a range of ratios.

In each test, leaves carrying a sufficient number of eggs were immersed in liquid formulations for 10 seconds. Excess liquid formulation was absorbed using a paper. The leaves were replaced in the ampoule and dried naturally. The ampoule was 15 incubated.

Each test was repeated for 4 times.

Control experiments were conducted.

After the completion of hatching of nymphs in the control experiment, an investigation was performed into the condition of the eggs and any emerging nymphs in the tests. Nymphs which were unable to hatch and/or unable to crawl normally were considered to be dead.

The result of the indoor toxicity test is shown below in Table 2:

Table 2:

Test Agent Weight ratio of active ingredient LC50 (mg/L) Theoretical toxicity index (TTI) Actual toxicity index (ATI) Co-toxicity coefficient (CTC) Spirobudiclofen 0.921 100 / / Diafenthiuron 9.45 9.74 / / Spirobudiclofen: Diafenthiuron 100:1 0.62 148.16 99.11 149.5 Spirobudiclofen: Diafenthiuron 50:1 0.53 175.14 98.23 178.3 Spirobudiclofen: Diafenthiuron 25:1 0.51 179.83 96.53 186.3 Spirobudiclofen: Diafenthiuron 10:1 0.49 188.00 91.79 204.8 Spirobudiclofen: Diafenthiuron 5:1 0.50 185.89 84.96 218.8 Spirobudiclofen: Diafenthiuron 1:1 0.66 139.75 54.87 254.7 Spirobudiclofen: Diafenthiuron 1:5 1.33 69.22 24.78 279.3 Spirobudiclofen: Diafenthiuron 1:10 1.60 57.73 17.95 321.7 Spirobudiclofen: 1:25 2.43 37.97 13.21 287.4 Diafenthiuron Spirobudiclofen: 1:50 3.31 27.82 11.51 241.7 Diafenthiuron Spirobudiclofen: 1:100 4.48 20.54 10.63 193.2 Diafenthiuron From the results set out in Table 2 it is evident that the compositions of the present invention exhibited a co-toxicity coefficient of greater than 120, thus exhibiting a synergistic effect.

Field Test

A synergistic effect exists in a composition comprising two active ingredients when the activity of the composition is greater than the sum of the activities of the active ingredients applied individually. The expected activity for a given combination of two active ingredients can be calculated by the so-called Colby equation (see S.R. Colby, "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations'", Weeds 1967, 15, 20-22) as follows: If: X is the mortality (%) of the untreated control when active ingredient A is employed at an application rate of m g/ha or in a concentration of m ppm; Y is the mortality (%) of the untreated control when active ingredient B is employed at an application rate of n g/ha or in a concentration of n ppm; and E is the mortality (%) of the untreated control when active ingredients A and B are employed at an application rate of m g/ha and n g/ha or in a concentration of m and n ppm; Then

Y

E=X Hi-Y -1.00 If the actual mortality observed is greater than calculated, then the activity of the composition is superadditive. In other words, synergism is present.

Field Test for controlling Pylla pyrisuga

The test was carried out at the end of March. The test was performed at the hatching peak stage (hatch rate of greater than 60%) of PyHa pyrisuga. Formulations comprising spirobudiclofen and diafenthiuron in a range of ratios were sprayed on both sides of the leaves of pear trees. Three pear trees were treated in each test. The number of live insects on the leaves was determined with a binocular eyepiece in a laboratory at day 1, 7, 21, 45 after application.

The mortality of insects and the controlling effect of each composition were calculated by the equation below: Mortality of insects (%) = (number of live insects before dosing -number of live insects after dosing)/number of live insects before dosing x 100 Controlling effect (%) = (mortality of the treated group -mortality of the control experiment)/(100-destruction rate of the control experiment) x 100 The results of the field test are set out in Table 3 below:

Table 3

Treatment Dose Observed controlling effect (%) Expected contro ling effect (%) g/ha Day 1 Day 7 Day 21 Day 45 Day Day 7 Day Day 1 21 45 Spirobudiclofen 33.3 14.29 48.35 96.73 81.32 Diafenthiuron 333 71.62 89.46 33.17 12.16 Spirobudiclofen + Diafenthiuron 33.3+ 84.81 97.67 100 92.31 75.68 94.56 97.81 83.59 From the results set out in Table 3, the observed controlling effect of the composition comprising spirobudiclofen and diafenthiuron can be seen to have been much higher than the expected controlling effect. The composition comprising spirobudiclofen and diafenthiuron showed a significant synergistic effect. It was noted that the effects were rapid and long lasting.

Claims (21)

1. CLAIMS1. A pesticidal composition comprising a compound of formula (I),CI cH,- Formula (0; and a compound of formula (II), C1-1;* i CH3-CH S ti CH3 cT 0 i, .2'--N NI C -CH3 0..H H CHCH3-CH 1 C1-13 Formula (II).
2. 2. The pesticidal composition according to claim 1, wherein the weight ratio of the active ingredient of the formula (I) to the active ingredient of the formula (II) is from about 100:1 to about 1:100.
3. 3. The pesticidal composition according to claim 2, wherein the weight ratio of the active ingredient of the formula (I) to the active ingredient of the formula (II) is from about 50:1 to about 1:50.
4. 4. The pesticidal composition according to claim 3, wherein the weight ratio of the active ingredient of the formula (I) to the active ingredient of the formula (II) is from about 25:1 to about 1:25.
5. 5. The pesticidal composition according to claim 4, wherein the weight ratio of the active ingredient of the formula (I) to the active ingredient of the formula (II) is from about 10:1 to about 1:10.
6. 6. The pesticidal composition according to claim 5, wherein the weight ratio of the active ingredient of the formula (I) to the active ingredient of the formula (II) is from about 5:1 to about 1:5.
7. 7. The pesticidal composition according to any preceding claim, wherein the active ingredient of the formula (I) and the active ingredient of the formula (II) together comprise from about 5% to about 90% by weight of the composition.
8. 8. The pesticidal composition according to claim 7, wherein the active ingredient of the formula (I) and the active ingredient of the formula (II) together comprise from about 10% to about 80% by weight of the composition.
9. 9. The pesticidal composition according to claim 8, wherein the active ingredient of the formula (I) and the active ingredient of the formula (II) together comprise from about 20% to about 60% by weight of the composition.
10. 10. The pesticidal composition according to any preceding claim, further comprising one or more surfactants and/or extenders.
11. 11. The pesticidal composition according to any preceding claim, wherein the pesticidal composition is formulated as an emulsifiable concentrate (EC), a suspension concentrate (SC), a seed dressing, water dispersible granules (WG), a wettable powder (WP), a suspoemulsion (SE), a smoke candle (FK), an emulsion (oil in water) (EW) or an ultra-low volume liquid (LDL).
12. 12. A method for treating pests at a locus comprising applying to the locus a compound of formula (I), H'3 Formula (0; and a compound of formula (II), CH3 (14.3 C CE3 (.7H 3-H A 0--es s] r'i C El 2 Formula (II).
13. 13. The method according to claim 12, wherein the compounds of formula (I) and formula (II) are applied to plants, target harmful organisms or the habitats thereof, or propagation materials of plants.
14. 14. The method according to claim 13, wherein the propagation material of plants is seedlings, roots, garden seedlings, cuttings or seeds.
15. 15. The method according to either of claims 12 or 13, wherein the pests are selected from the group of insects and mites.
16. 16. The method according to claim 15, wherein the pests are selected from red mites and psyllids.
17. 17. The method according to any of claims 12 to 16, wherein the active ingredient of the formula (I) and the active ingredient of the formula (II) are applied separately, sequentially or simultaneously.
18. 18. The method according to any of claims 12 to 17, wherein the method comprising applying to the locus a composition according to any of claims 1 to 11.
19. 19. The use of a combination of a compound of formula (I),CI Cl H3Formula (0; and a compound of formula (II), 043 i-CH -, S CH3r - %'' cc I :::--..-, G-C1,.. ,% ,, N * -NI-C.---CH3 \ H H CH3CH -CH -,CH_. Formula (II) for preventing and/or controlling harmful organisms.
20. 20. A pesticidal composition substantially as hereinbefore described.
21. 21. A method for controlling pests at a locus substantially as hereinbefore 10 described.