WO2015135420A1 - 一种杀虫组合物及控制有害生物的方法 - Google Patents

一种杀虫组合物及控制有害生物的方法 Download PDF

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Publication number
WO2015135420A1
WO2015135420A1 PCT/CN2015/073289 CN2015073289W WO2015135420A1 WO 2015135420 A1 WO2015135420 A1 WO 2015135420A1 CN 2015073289 W CN2015073289 W CN 2015073289W WO 2015135420 A1 WO2015135420 A1 WO 2015135420A1
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WIPO (PCT)
Prior art keywords
active ingredient
chlorpyrifos
pesticidal composition
flufenicol
pest
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PCT/CN2015/073289
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English (en)
French (fr)
Inventor
李成应
布里斯托詹姆斯.T
罗昌炎
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江苏龙灯化学有限公司
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Publication of WO2015135420A1 publication Critical patent/WO2015135420A1/zh

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals

Definitions

  • the present invention relates to a pesticidal composition comprising flupirizine and chlorpyrifos; in particular to a method of controlling pests.
  • aphids In agricultural production, aphids, scale insects, whiteflies, rice planthoppers, rice leaf roller, rice stem borer, rice gall midge, scorpion worm, Spodoptera litura, cabbage caterpillar, diamondback moth, yellow snapper, root Pests such as cockroaches and armyworms are common pests on crops such as rice, wheat, corn, cotton, vegetables, fruit trees, and tea. If the corresponding measures are not taken for the pests, it will affect the growth of the crops. Insecticides are mainly used to control agricultural pests and municipal hygiene pests.
  • Flumazepam is developed by the Japanese Pesticide Company and belongs to a class of new quinazoline (m-diazabenzene) insecticides. Flumazepam is generally applied as a water-dispersible granule. Its mechanism of action is to stop the pests from feeding and starvation, thereby preventing plant tissues from suffering more damage and limiting the spread of some important diseases. At present, it is mainly used to control whiteflies, mites and scale insects on vegetables, fruit trees and tea leaves.
  • Chlorpyrifos chemical name: O, O-diethyl-O-(3,5,6-trichloro-2-pyridyl) phosphorothioate, its molecular structure is:
  • Chlorpyrifos is an acetylcholinesterase inhibitor and is a phosphorothioate insecticide.
  • the mechanism of action is to inhibit the activity of acetylcholinesterase AChE or cholinesterase ChE in the nerves in the body and destroy the normal nerve impulse conduction, causing a series of symptoms of poisoning: abnormal excitement, paralysis, paralysis, and death. It has the triple effect of stomach poisoning, contact killing and fumigation. It has good control effect on various chewing and sucking mouthparts pests on rice, wheat, cotton, fruit trees, vegetables and tea trees, especially including rice planthopper, rice leaf roller, rice stem borer and rice gall midge.
  • the activity of the individual compounds is good; however, they are not always sufficient to meet the high requirements that must be met by insecticides, acaricides or nematicides when used at low application rates or for individual pests.
  • a typical need in the field of pest control is the need to reduce the dose rate of the active ingredient and to reduce or avoid adverse environmental or toxicological effects while still allowing effective pest control.
  • a pest control agent that combines knockdown activity and prolonged control time, ie, rapid action and long-acting action.
  • the object of the present invention is to solve the above problems and to provide an insecticidal composition and a method for controlling a pest, which composition has a gain in control effect by combining flubenzuron and chlorpyrifos.
  • the effect is to expand the insecticidal spectrum, improve the rapid action and long-term effect of pest control, and delay the emergence of drug resistance.
  • a pesticidal composition including
  • the first active ingredient flufenicol is flufenicol
  • the second active ingredient is chlorpyrifos
  • the first active ingredient flufenicol and the second active ingredient chlorpyrifos are in a weight ratio of 1:100-100:1.
  • the first active ingredient flufenicol and the second active ingredient chlorpyrifos are in a weight ratio of 1:50 to 50:1.
  • the first active ingredient flufenicol and the second active ingredient chlorpyrifos are 1:25-25:1 by weight.
  • the first active ingredient flufenicol and the second active ingredient chlorpyrifos are 1:10-10:1 by weight.
  • a pesticidal composition comprising a first active ingredient, flubenzuron, and a second active ingredient, chlorpyrifos, the weight of the first active ingredient flufenicol and the second active ingredient chlorpyrifos being a total of the composition by weight 5%-90%.
  • An insecticidal composition comprising a first active ingredient, fluprosin, and a second active ingredient, chlorpyrifos, wherein the first active ingredient flufenicol and the second active ingredient chlorpyrifos share a total of 10 by weight of the composition %-80%.
  • a pesticidal composition comprising a first active ingredient, flubenzuron, and a second active ingredient, chlorpyrifos, the first active ingredient flufenicol and a second active ingredient chlorpyrifos totaling 20% by weight of the composition %-60%.
  • the pesticidal composition according to the present invention further comprises a surfactant and/or a extender.
  • the pesticidal composition of the present invention can be formulated into any dosage form that is agriculturally acceptable.
  • the insecticidal composition is in the form of an emulsifiable concentrate, a suspending agent, a seed treatment agent, a water-dispersible granule, a wettable powder, a suspoemulsion, an aerosol, an aqueous emulsion, a microcapsule suspension, Microcapsule suspension-suspension, ultra-low volume liquid, microemulsion.
  • the invention also provides a use of the pesticidal composition of the invention for the prevention or control of pests.
  • the insecticidal composition is used for controlling aphids, scale insects, whiteflies, thrips, rice planthoppers, rice leaf roller, rice mites, rice gall midge, ticks, spodoptera, and cabbage caterpillars , Plutella xylostella, beet armyworm, yellow stripe, yellow leafhopper, root lice and armyworm.
  • the present invention provides a method for preventing or controlling a pest, which comprises applying the pesticidal composition of the present invention to a target useful plant, a target pest or an environment thereof, and a propagation material of the target useful plant.
  • the plant propagation material is seedlings, rhizomes, seedlings, cuttings or seeds.
  • a method for protecting crops from harmful organisms comprising cropping a crop with a chlorpyrifos containing a first active ingredient and a second active ingredient chlorpyrifos insecticidal composition with a target useful plant, a target pest or an environment thereof, a target useful plant
  • the breeding material is in contact.
  • a method for protecting crops against pest infestation comprises separately, sequentially or simultaneously administering a first active ingredient, fluprozin, and a second active ingredient, chlorpyrifos.
  • a method of preventing or controlling a pest wherein the first active ingredient flupirizine and the second active ingredient chlorpyrifos are each in the form of a formulated composition.
  • a method of protecting plant seeds comprising seeding an effective amount of the invention prior to sowing and/or after germination
  • the insecticidal composition is in contact.
  • a seed treated with the pesticidal composition of the present invention is
  • the present inventors have found that combining the first active ingredient flufenicol and the second active ingredient chlorpyrifos not only provides an additive effect on the insecticidal spectrum, but also achieves a surprising synergistic effect.
  • insecticidal effect means that the insecticidal effect of the active ingredient combination of the present invention is greater than the sum of the effects of the respective active ingredients, or that the effect is superadditive.
  • the present invention provides a pesticidal composition
  • a pesticidal composition comprising a first active ingredient, fipronil, and a second active ingredient, chlorpyrifos.
  • the present invention provides a pesticidal composition, wherein the weight ratio of the first active ingredient flufenicol and the second active ingredient chlorpyrifos is 1:100-100:1, preferably 1:50-50:1, and further preferably 1: 25-25:1, more preferably 1:10-10:1.
  • the total amount of active ingredient in the compositions of the invention can be selected based on the particular factors to achieve the desired effect.
  • the factors are, for example, a dosage form, a subject to be administered, an administration method, and the like.
  • the first active ingredient, flubenzuron and the second active ingredient, chlorpyrifos collectively comprise from 5% to 90%, preferably from 10% to 80%, more preferably from 20% to 60% by weight of the composition.
  • compositions of the present invention may optionally comprise an agronomically acceptable surfactant or extender.
  • the term "filler” refers to a natural or synthetic organic or inorganic compound which may be combined or combined with the active ingredient to make it easier to apply to a subject, such as a plant, crop or grass. Therefore, the filler is preferably inert and at least agriculturally acceptable.
  • the filler may be a solid or a liquid.
  • Suitable solid carriers are: for example, vegetable powders (eg soy flour, starch, cereal flour, wood flour, bark flour, sawdust, walnut shell flour, bran, cellulose powder, coconut shell, corn cob and tobacco stem) Granules, residues after extracting plant extracts, etc.), clays (such as kaolin, bentonite, acid china clay, etc.), talc.
  • Silica such as diatomaceous earth, silica sand, mica, hydrous silicic acid, calcium silicate), activated carbon, natural minerals (pumice, attapulgite and zeolite), fired diatomaceous earth, sand, plastic media, etc.
  • inorganic mineral powders such as potassium chloride, calcium carbonate, and calcium phosphate
  • chemical fertilizers such as ammonium sulfate, ammonium phosphate, urea, and green ammonium, and soil fertilizers.
  • the substances may be used singly or in combination of two or more.
  • Suitable liquid carriers can be selected from the group consisting of water, alcohols (eg methanol, ethanol, isopropanol, butanol, ethylene glycol, etc.), ketones (eg acetone, methyl ethyl ketone, diisobutyl) Ketones, cyclohexanone, etc.), ethers (such as diethyl ether, dioxane, methylcellulose, tetrahydrofuran, etc.), aliphatic hydrocarbons (such as kerosene, mineral oil, etc.), aromatic hydrocarbons (for example) Benzene, toluene, xylene, mineral spirits, alkylnaphthalenes, chlorinated aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorobenzene, etc.), halogenated hydrocarbons, amides, sulfones, dimethyl sulfoxide, minerals and vegetable oils, Animal oil, etc.
  • alcohols e
  • compositions of the present invention may also comprise additional additional components such as surfactants.
  • Suitable surfactants are emulsifiers, dispersants or wetting agents having ionic or nonionic properties, or mixtures of these surfactants.
  • Suitable of these surfactants are fatty alcohol polyoxyethylene ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene higher fatty acid esters, polyoxyethylene alcohol or phenol phosphates, fatty acid esters of polyhydric alcohols, and alkane Sodium aryl sulfonate, naphthalene sulfonate polymer, lignosulfonate, polymeric comb-shaped branched copolymer, butyl naphthalene sulfonate, alkyl aryl sulfonate, sodium alkyl sulfosuccinate , polyglycerides such as fats and oils, fatty alcohols and ethylene oxide condensates, alkyl taurate salts
  • Suitable oligosaccharides or polymers are for example based on the individual ethylene monomers, acrylic acid, polyoxyethylene or polyoxypropylene or their combination with, for example, (poly)alcohols or (poly)amines.
  • a surfactant When one of the active compounds and/or one of the inert carriers is insoluble in water and when applied in water, a surfactant must be present. The proportion of surfactant is from 5% to 40% by weight of the composition of the invention.
  • the active compound can be combined with any solid or liquid additive conventionally used for formulation purposes.
  • the preparation of the present invention may be mixed with the active ingredient in a known manner by at least one of a solvent or a diluent, an emulsifier, a dispersing agent, and/or a binder or a fixing agent, and wetting.
  • the agent, the water repellent, and if necessary, may also contain a drier and a colorant, a stabilizer, a pigment, an antifoaming agent, a preservative, a thickener, water, and other processing aids.
  • compositions of the present invention may be used as such or may be used in the form of their formulations or in the form in which they are prepared, depending on their respective physical and/or chemical properties.
  • An example of a dosage form for a premix composition is:
  • WP wettable powder
  • EW emulsion, water emulsion
  • Examples of dosage forms suitable for tank mix compositions are solutions, diluted emulsions, suspensions or mixtures and powders thereof.
  • the tank mix composition is one or more premix compositions containing different pesticides, and optionally further auxiliaries, diluted with a solvent such as water.
  • compositions of the present invention include not only ready-to-use compositions that can be applied to plants or seeds by suitable means, but also commercially available concentrates that must be diluted with water prior to administration.
  • compositions of the present invention may also be administered in combination with other active ingredients such as fungicides, bactericides, attractants, insecticides, acaricides, nematicides, growth regulators, herbicides, Safety agents, fertilizers or chemical pheromones.
  • active ingredients such as fungicides, bactericides, attractants, insecticides, acaricides, nematicides, growth regulators, herbicides, Safety agents, fertilizers or chemical pheromones.
  • the insecticidal composition of the invention has good plant compatibility and favorable constant temperature animal toxicity, and is suitable for controlling pests encountered in agriculture, forestry, storage products and materials, and health fields, especially insects and aphids. . They are active against normally sensitive and resistant species and are active for all or a single developmental stage.
  • pest refers to any organism that can cause damage to the normal state of the plant. include:
  • Lepidopteran pests include, for example, chilosuppressalis (walker), Tryporyzaincertulas (walker), cnaphalocrocismedinalis Guenee, hellullaundalis, conogethespunctiferlis, mandarin Papilioxuthus, Pierisrapae crucivora, parnaraguttata, malacosoma Neustria testacea, lymantriadispar, hyphantriacunea, euproctissubflava, black Specimens motra (scopelodescontracus), cotton bollworm (helicoverplomigera), pink bollworm, trichoplusiani, mamestrabrassicae, spodopteraexigua, spodopteralitura , Tea leaf curler (adoxophyesoranafasciata), leaf roller moth (adoxophyeshonmai), apricot yellow moth (archips fuscocureanus), tea moth
  • Coleoptera pests include, for example, sitphilusoryzaelinne, Podagricomela nigricollis Che, S. zeamails, S. granarius, Cabbageleafbeetle, and small leafhoppers. (Daikon leaf beele), fleabeetle, Altica chalybea, phyllotretastriolata, Epitrixcucumeris, Ehirtipennis, E. fuscula, Aulacophoraindica (Gemlin), Phaedon cochleariae, etc.
  • Diptera pests include, for example, agromyzaoryzae, hydrelliagriseola, non- Liriomyzatrifolii, chromatomyiahorticola, liriomyzabryoniae, deliaplatura, deliaantiqua, ceratitiscapiatawiedgman, apple fruit fly (Rhagoletispomonella), cherry fruit fly (R. cingulata).
  • Hemipteran pests include, for example, megacoptapunctatissimum, eurydemarugosum, eysarcorislewisi, eysarcorisparvus, nezaraviridula, plautiastali, sylvestris Halymorphamista, cletuspunctiger, leptocorisachinensis, stephantispyrioides, and trigonotyluscoelestialium.
  • Homopteran pests include, for example, nephotettixcincticeps, laodelphaxstriatellus, nilaparvatalugens, sogatella furcifera, psyllapyrisuga, diaphorinatabaci, and tobacco powder Be (bemisiatabaci), locust (homoptera), apple aphid (eriosomalanigerum).
  • hymenoptera there are arachinasaefifinis, argepagana, formica japonica, and dryocsmuskuriphilus.
  • Thysanoptera pests such as Haplothrips Chinensis Priesner.
  • Arachnida pest For example, panonychus citri, Tetranychus cinnabarinus, panonychus ulmi, tetranychus urticae, tetranychus viennensis, and small needles Oligonychus ununguis) eotetranychus kankitus, brevipalus phoenicis, bryobia praetiosa, aceria tulipae, colomerus vitis, calacarus Carinatus), polyphagotarsonemus latus, rhizoglyphus rostochiensis, and the like.
  • Anoplura such as Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp. ).
  • Isopoda for example, Oniscus asellus, Armadilliudium vulgare, Porcellio scaber.
  • Diplopoda for example, Blaniulus guttulatus.
  • Chi lopoda for example, Geophilus carpophagus Scutigera spp.
  • Synphyla for example, Scutigerella immaculata.
  • Thysanura for example, Lepisma saccharina.
  • Collembola for example, the armed spiny worm (Onychiurus armatus).
  • Orthoptera for example, Acheta domesticus, Gryllotalpa spp., Locusta migratoriamigrator ioides, Melanoplus pp., Desert ⁇ (Schistocercagregaria) ).
  • Dermaptera for example, Forficula auricularia.
  • Isoptera (lsoptera), for example, Reticulitermes spp.
  • nematodes selected from root-knot nematodes, cyst-forming nematodes, stem nematodes, and leaf nematodes.
  • the following nematode soybeans, Heterodera, golbodera rostochiensis, melonogyne incognita, etc., in the dorylaimida, longidorus sp., and the like are preferred.
  • the insecticidal composition is used for controlling aphids, scale insects, whiteflies, thrips, rice planthoppers, rice leaf roller, rice mites, rice gall midge, ticks, spodoptera, and cabbage caterpillars , Plutella xylostella, beet armyworm, small green leafhopper, yellow stripe, root lice and armyworm.
  • the meaning of the plants herein is to be understood as meaning all plants and plant populations.
  • Plants are plants obtainable by conventional breeding and preferred methods or by biotechnological and genetic engineering methods or by a combination of these methods.
  • the plants include transgenic plants, as well as plant varieties that are protected or unprotected by plant breeders' rights.
  • the meaning of a plant part is understood to mean all parts and organs of the plant above and below the ground, such as branches, leaves, flowers and roots, examples of which may be leaves, needles, leaves, stems, stems, flowers, fruit bodies, fruits. And seeds, as well as roots, tubers and rhizomes.
  • the plant parts also include harvested material as well as vegetative and generative propagation material such as cuttings, tubers, rhizomes, young shoots and seeds.
  • Useful plants which can be used in the protection of the present invention, as well as the application of the pesticidal composition according to the invention, include: cereal plants such as wheat, oats, barley, triticale and rye, as well as corn, sorghum and chestnut, rice; beets, such as sugar Beet or fodder beet; fruit, such as apple fruit, stone fruit, tree nut or soft fruit such as apple, pear, plum, peach, banana, almond, walnut, pistachio, cherry or berry, such as strawberry, or blackberry; Crops such as kidney beans, peas or soybeans; oil crops such as canola, mustard, olive, sunflower, ramie, cocoa or peanut; cucurbits such as pumpkin, zucchini, cucumber or melon; fiber plants such as cotton, flax, marijuana Or jute; citrus fruits such as oranges, lemons, grapefruits or oranges; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, red peppers, potatoes or
  • the present invention provides a method for preventing or controlling a pest, which comprises applying the pesticidal composition of the present invention to a target useful plant, a target pest or an environment thereof, and a propagation material of the target useful plant.
  • compositions of the invention are carried out directly by conventional treatment or by acting on their environment, habitat or storage area, such as impregnation, watering, spraying, misting, spreading, Spraying, fogging, spreading, foaming, coating, coating, drip irrigation, etc. to the leaves of plants (foliar application), the frequency and amount of application can be adjusted to adapt to the extent of damage by the pests .
  • compositions of the invention are also suitable for protecting plant propagation material such as seeds, fruits, tubers or nucleoli or plant cuttings from pests, particularly insects and mites.
  • the propagation material can be treated with the composition prior to application, such as seed dressing prior to sowing.
  • the active ingredient can also be applied to the seed (coating) by soaking the nucleoli in the liquid composition or coating the nucleolus with a solid composition.
  • the composition can also be applied to the application site when the propagation material is applied, for example, within the seed ditch during sowing.
  • plant propagation material is understood to mean all parts of the plant capable of reproduction, such as seeds, as well as plant material such as cuttings or tubers (for example potatoes).
  • plant parts used herein include plant propagation material. Mention may be made, for example, of seeds (in the narrow sense), roots, fruits, tubers, bulbs, rhizomes and plant parts. Germinated plants and effective plants to be inhibited after germination from the soil or after emergence are also mentioned. Young plants can be protected by whole or partial treatment by dipping prior to transplantation.
  • Plant parts and subsequently grown plant organs are any part of a plant produced by plant propagation material such as seeds. Plant parts, plant organs and plants can also benefit from protecting plants from plant diseases by applying the compositions to plant propagation materials. Certain plant parts and certain subsequently grown plant organs can also be considered as plant propagation material, which can itself be applied (or treated) with the composition; thus plants produced from treated plant parts and treated plant organs, Other plant parts and other plant parts may also benefit from protecting the plant from plant pests by applying the composition to certain plant parts and certain plant organs.
  • the active ingredient can also be applied to the seed by successively impregnating the tubers or grains with a liquid preparation of the respective active ingredients, or by coating with a combined wet or dry preparation (coating) ).
  • compositions of the invention are applied to the seed in their own right or in a suitable dosage form.
  • the seed is treated in a steady state such that the treatment does not cause any damage.
  • the treatment of the seed can usually be carried out at any time between harvesting and sowing. It must generally be noted during seed treatment that the amount of the composition of the invention applied to the seed and/or the amount of other additives is selected so as not to affect the germination of the seed or to damage the resulting plant.
  • compositions of the present invention are particularly advantageous for treating plant propagation material, particularly seeds of rice, canola, cotton, wheat, barley, soybean, corn, peanuts.
  • a method of protecting a seed comprising contacting the seed with a synergistically effective amount of a pesticidal composition of the present invention prior to sowing and/or after germination.
  • a seed treated with the pesticidal composition of the present invention is
  • compositions of the invention can be applied to the environment, habitat or storage area in which the plants are grown.
  • the environment and habitat of plant growth refer to a support capable of rooting and growing crops, such as soil, water, etc.
  • Specific raw materials can be used, for example, sand, pumice, vermiculite, diatomaceous earth, agar, gelatin, High molecular substances, asbestos, wood chips, bark, etc. Soil is preferred.
  • a method of applying a medicament to the soil for example, diluting the liquid medicament in water or undiluting the root applied directly to the root of the plant or the method of growing the farm, and spreading the granule into the root of the plant or in the field of the nursery
  • powder, water-dispersible granules, etc. are sprayed into the soil and mixed with the soil as a whole.
  • the powder and the water-dispersible granules are diluted and sprayed in the planting hole and the seeding ditch. The method of sowing, etc.
  • the treatment of the present invention may also produce a super-additive effect of improving plant growth, increasing tolerance to high or low temperatures, increasing tolerance to drought or salinity to water or soil, and increasing flowering. Quality, ease of harvesting, accelerated maturity, improved harvesting yield, improved quality of harvested products and/or improved nutritional value, improved storage stability of harvested products and/or their processing properties.
  • the dose can even be reduced, in particular when applying an inert matrix When it is asbestos or pearl rock;
  • the pesticidal composition of the present invention comprises the separate, sequential or simultaneous administration of the first active ingredient flufenicol and the second active ingredient chlorpyrifos.
  • any of the technical features of any embodiment or embodiment of the present invention may be independently combined with any other embodiment of the present invention. That is, one or more of the technical features of any of the embodiments of the present invention can be recombined with any other technical features. Technical features formed by recombining such technical features are disclosed herein, as specifically recited herein.
  • the activity of the pesticidal composition exceeds the sum of the activities of the two active compounds when applied; this makes it possible to optimize the amount of active compound used;
  • the wettable powder of the present invention is obtained by mixing the active ingredients, various auxiliaries, fillers and the like in proportions of the formulation and pulverizing them by an ultrafine pulverizer.
  • the original drug, the solvent and the emulsifier are added together to dissolve into a uniform oil phase; the water-soluble component and water are mixed to prepare an aqueous phase; and the oil phase is mixed with the water phase under high-speed stirring to obtain the present invention.
  • Water emulsion Water emulsion.
  • the active ingredient, the dispersing agent, the wetting agent, the disintegrating agent and the filler are uniformly mixed according to the formulation ratio, and are pulverized into a wettable powder by a jet stream, and then added with a certain amount of water to be mixed and granulated.
  • the water-dispersible granules of the present invention are obtained by dry sieving.
  • microemulsion of the present invention is obtained by mixing and stirring the above components to a uniformly transparent liquid.
  • the wettable powder of the present invention is obtained by mixing the active ingredients, various auxiliaries, fillers and the like in proportions of the formulation and pulverizing them by an ultrafine pulverizer.
  • the second active ingredient chlorpyrifos is dissolved in SOLVESSO TM 200, and ethoxylated castor oil is added to obtain an emulsifiable concentrate; the first active ingredient flufenicol, a fatty alcohol polyoxyethylene ether sulfosuccinate monosodium disodium, is changed.
  • the above components of calcium lignosulfonate, xanthan gum, bentonite, glycerin, water, etc. are uniformly mixed in proportion and sand-milled to prepare a suspension.
  • the oil phase containing the first active ingredient flufenicol is added to a suspension containing the second active ingredient chlorpyrifos to obtain a suspoemulsion.
  • the above combinations are mixed in proportion, ground, and pulverized to prepare a wettable powder.
  • the milled active ingredient is uniformly applied to the carrier wetted with polyethylene glycol in a mixer. In this way, dust-free coated granules can be obtained.
  • the above components are mixed in proportion, ground and pulverized to prepare a wettable powder.
  • the active ingredient is mixed with the auxiliaries and ground and the mixture is moistened with water.
  • the mixture was extruded and then dried in a stream of air.
  • the second active ingredient chlorpyrifos is dissolved in SOLVESSO TM 200, ethoxylated castor oil is added to obtain emulsifiable concentrate; the second active ingredient is chlorpyrifos, fatty alcohol polyoxyethylene ether sulfosuccinate monosodium disodium, modified lignin
  • the above components of calcium sulfonate, xanthan gum, bentonite, glycerin, water, etc. are uniformly mixed in proportion and sand-milled to prepare a suspending agent.
  • the oil phase containing the second active ingredient chlorpyrifos is added to a suspension containing the first active ingredient flubenzuron to obtain a suspoemulsion.
  • the second active ingredient chlorpyrifos is dissolved in SOLVESSO TM 200, and ethoxylated castor oil is added to obtain a second active ingredient chlorpyrifos EC; the first active ingredient flufenicol, fatty alcohol polyoxyethylene ether sulfosuccinic acid
  • the monoester disodium, the modified lignosulfonate calcium, the xanthan gum, the bentonite, the glycerin, the water and the like are uniformly mixed in proportion and sand-milled to prepare a suspension.
  • the oil phase containing the second active ingredient chlorpyrifos is added to a suspension containing the first active ingredient flubenzuron to obtain a suspoemulsion.
  • Fluroxypyrazine 50% Second active ingredient chlorpyrifos 2% SOLVESSO TM 200 10% Ethoxylated castor oil 4% Fatty alcohol polyoxyethylene ether sulfosuccinate monosodium disodium 10% Modified calcium lignosulfonate 5% Xanthan gum 0.5% Bentonite 1% Glycerol 5% Defoamer 0.6% water make up to 100%
  • the second active ingredient chlorpyrifos is dissolved in SOLVESSO TM 200, and ethoxylated castor oil is added to obtain a second active ingredient chlorpyrifos EC; the first active ingredient flufenicol, fatty alcohol polyoxyethylene ether sulfosuccinic acid
  • the monoester disodium, the modified lignosulfonate calcium, the xanthan gum, the bentonite, the glycerin, the water and the like are uniformly mixed in proportion and sand-milled to prepare a suspension.
  • the oil phase containing the second active ingredient chlorpyrifos is added to a suspension containing the first active ingredient flufenicol to obtain a suspoemulsion.
  • the above components are mixed and stirred to a uniformly transparent liquid to obtain the emulsifiable concentrate of the present invention.
  • the plurality polymethylene polyphenyl polyisocyanate (the PAPI), and a second active ingredient chlorpyrifos SOLVESSO TM 200 oil was added an aqueous solution containing phase formed in ATLOX TM 4913, to form an emulsion.
  • the catalyst was then heated and kept warm at 50 ° C for 2 hours. After cooling, a microcapsule containing the second active ingredient chlorpyrifos is obtained.
  • ATLOX TM 4913 dispersant LFH, antifoaming agent, urea, the first active ingredient flufenicol and water are uniformly mixed in proportion and sanded to prepare a suspension.
  • microcapsule containing the second active ingredient chlorpyrifos is added to the aqueous suspension of the first active ingredient flufenicol, and stirred uniformly to obtain the microcapsule suspension-suspending agent of the present invention.
  • Fluroxypyrazine 5% Second active ingredient chlorpyrifos 50% SOLVESSO TM 200 20% Ethoxylated castor oil 5% Fatty alcohol polyoxyethylene ether sulfosuccinate monosodium disodium 10% Modified sodium lignosulfonate 5% Xanthan gum 0.5% Glycerol 5% Polyvinylpyrrolidone (PVP-K30) 1% Defoamer 0.6% water make up to 100%
  • the second active ingredient chlorpyrifos is dissolved in SOLVESSO TM 200, and ethoxylated castor oil is added to obtain emulsifiable concentrate containing the second active ingredient chlorpyrifos; the first active ingredient flufenicol, fatty alcohol polyoxyethylene ether sulfo amber
  • the acid monoester disodium, the modified lignosulfonate calcium, the xanthan gum, the glycerin, the polyvinylpyrrolidone, the water and the like are uniformly mixed in proportion and sand-milled to prepare a suspension.
  • the oil phase containing the second active ingredient chlorpyrifos is added to the suspension seed coating agent containing the first active ingredient flufenicol to obtain the suspension seed coating of the present invention.
  • the antifreeze propylene glycol, the diluent SOLVESSO TM 100 is mixed, and the first active ingredient flufenicol and the second active ingredient chlorpyrifos are added under stirring; the surfactant is added thereto, and the mixture is pulverized by a pulverizing equipment colloid mill under stirring.
  • the colloid milled suspension is passed through an ultrafine pulverizer. The cycle is repeated until the particle diameter of the solid particles is ⁇ 2 um.
  • the wettable powder of the present invention is obtained by mixing the active ingredients, various auxiliaries, fillers and the like in proportions of the formulation and pulverizing them by an ultrafine pulverizer.
  • the components of the active component, the dispersing agent and the wetting agent are uniformly mixed according to the formulation ratio, and after grinding and/or high-speed shearing, corn oil is added to obtain an oil suspensioning agent.
  • the first active ingredient flufenicol and the second active ingredient chlorpyrifos are uniformly mixed in proportion.
  • the ratio in the above embodiment is a weight ratio of one hundred.
  • the inventors conducted a large number of tests and effect analysis on the different ratios of flufenicol and chlorpyrifos through a large number of screening tests, and found that the new agricultural insecticidal compositions obtained have a gain effect within a certain ratio range. Rather than simply adding the two agents, the following embodiments are specifically described.
  • a combination of indoor virulence determination and insecticidal test is adopted, firstly, the indoor toxicity test is used to determine the co-toxicity coefficient (CTC) of the two agents after being compounded in a certain ratio, and CTC ⁇ 80 is resistant.
  • Test method the method of first immersing the leaves and then inoculation of the insects, so that the leaves of the same size that are not in contact with any medicament are soaked in the prepared liquid for 5s, then taken out, naturally dried, placed in the insect box, and then connected The larvae were tested and kept at 25 °C. Each treatment was repeated 3 times. The number of test insects used per replicate was 120. At the same time, a blank control was set. The number of dead insects was checked at 72 hours, and the mortality and corrected mortality were calculated to obtain virulence. Regression equations and calculate LC 50 values. If the control mortality is greater than 10%, it is considered an invalid test. Calculated as follows:
  • Mortality (%) (number of live insects before drug - number of live insects) / number of live insects before drug *100
  • the test insect corrected mortality rate was converted into probability value (y), the treatment concentration ( ⁇ g/ml) was converted into logarithmic value (x), and the virulence regression equation was obtained by least squares method, and thus each medicament was calculated. value.
  • the co-toxicity coefficient CTC was calculated. The calculation formula is as follows (with flufenicol as a standard drug, its virulence index is 100):
  • Measured virulence index (ATI) (standard drug LC 50 / test agent LC 50 ) ⁇ 100
  • Theoretical virulence index (TTI) A ATI ⁇ percentage of A in the mixture + B ATI ⁇ percentage of B in the mixture
  • CTC (mixture ATI / mixture TTI) ⁇ 100
  • Test 1 Determination of indoor virulence of citrus aphids
  • Test 2 Determination of indoor virulence of B. tabaci
  • the indoor virulence test results of rice planthopper, thrips and beet armyworm also showed that flufenicol and chlorpyrifos control rice planthopper, thrips, beet armyworm, When the ratio is 1:100-100:1, the co-toxicity coefficient is greater than 120, indicating that the mixing of the two in this range is a gain effect.
  • X is the kill rate when active compound A is used in an amount of m g/ha or at a concentration of m ppm, expressed as a percentage of the untreated control
  • Y is the kill rate when using the active compound B in an amount of n g/ha or a concentration of n ppm, expressed as a percentage of the untreated control
  • E is the killing rate when active ingredients A and B are used in amounts of m and n g/ha or at concentrations of m and n ppm, expressed as a percentage of the untreated control,
  • the lethal effect of the composition is superadditive, i.e., there is a synergistic effect.
  • the actually observed kill rate must exceed the value of the expected kill rate value (E) calculated using the above formula.
  • the test was carried out as follows: The test site was in Jiaxing, Zhejiang, and the time was in early March. The potted citrus test was carried out for 3 years. Before the spraying, 200 insects were inoculated with cotton aphid. Spray treatment 2 days after inoculation. According to the front and back of the wetted leaves, 3 citrus seedlings were treated each. Six days after the drug, 25 leaves were taken in the laboratory to investigate the number of adults on the leaves with binoculars, and the population reduction rate and control effect were calculated. The formula is as follows:
  • Test 4 Efficacy test for the control of Bemisia tabaci
  • the test was carried out as follows: The test site was in Jiaxing, Zhejiang, and the time was in early March. Potted cotton test was used. Before the spraying, each plant was inoculated with 200 adult worms. Spray treatment 2 days after inoculation. According to the front and back of the wetted blade, 3 cotton plants were treated each. Six days after the drug, 25 leaves were taken in the laboratory to investigate the number of adults on the leaves with binoculars, and the population reduction rate and control effect were calculated. The formula is as follows:
  • Sand 1 Rotating soil 1 Prepare experimental soil, 200 g of soil was placed in each 300 ml plastic container, and sprayed at a prescribed concentration of the drug. Each discharge vessel 10 striped flea beetle larvae in the dark at 25 O C temperature was allowed to stand at the desired time, spread the soil, counting the number of larvae mortality survival requirements.
  • Mortality (%) ⁇ 1 - (number of survival heads / number of insects) ⁇ X100
  • the theoretical value (%) of mortality is calculated by the "colby formula".
  • the test results show that the actual mortality rate (%) is higher than the theoretical value (%), indicating that the combination of flufenicol and chlorpyrifos is used for soil treatment and has synergistic effect on the prevention and treatment of yellow stripe.
  • Test 6 Effect of seed treatment on beet armyworm
  • the required amount of liquid formulation is added to the Erlenmeyer flask. Shake the flask to distribute the liquid to the entire bottom of the vessel. Immediately thereafter, the required amount of seeds is added to the bottle. The flask was shaken vigorously by hand for about 1 minute so that all the seeds were covered with liquid. The contents of the flask were poured onto a drying rack and dried in an oven.
  • each bottle was filled with a certain amount of solid preparation to obtain a desired amount of 0.3 mg of active ingredient per seed.
  • the flask was placed on a roller and spun at 80 rpm for 3 minutes. The flask was shaken by hand to cause the seed sticking to the wall of the flask to fall, and then the flask was rotated in the opposite direction for 3 minutes.
  • the agent and the single agent of Formulation Example 1-22 were subjected to seed treatment at a prescribed concentration according to Procedures F1 and F2.
  • the treated corn seeds are then sown. Twenty-six days after sowing, the 5-8 cm long portion of the topmost leaf of the plant was placed in a glass beaker and infested with 10 newly hatched beet armyworm first instar larvae. Cover the beaker with a lid and keep it at 25 ° C and Under 60% relative atmospheric humidity, 16 hours of light per day. Evaluation was performed after infestation 3-5. The mortality rate was recorded after recording the number of larvae that survived on the grown plants.
  • Mortality (%) ⁇ 1 - (number of survival heads / number of insects) ⁇ X100

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Abstract

本发明涉及一种杀虫组合物，包括氟虫吡喹和毒死蜱；尤其涉及一种控制有害生物的方法。一种杀虫组合物，包括氟虫吡喹和毒死蜱，所述氟虫吡喹和毒死蜱的重量配比为1:100到100:1。一种预防或控制有害生物的方法，将所述的杀虫组合物用于目标有用植物、目标有害生物或其环境、目标有用植物的繁殖材料。一种保护植物种子的方法，包括使种子在播种前和/或催芽之后与有效量的本发明的杀虫组合物接触。一种施用含有效量的本发明的杀虫组合物处理的种子。

Description

一种杀虫组合物及控制有害生物的方法 技术领域
本发明涉及一种杀虫组合物，包括氟虫吡喹和毒死蜱；尤其涉及一种控制有害生物的方法。
背景技术
在农业生产中，蚜虫、介壳虫、粉虱、稻飞虱、稻纵卷叶螟、三化螟、稻瘿蚊、蒂蛀虫、斜纹夜蛾、菜青虫、小菜蛾、黄曲跳甲、根蛆及粘虫等害虫为水稻、小麦、玉米、棉花、蔬菜、果树、茶叶等作物上常见的害虫。如果不对害虫进行相应的措施，那么必会影响农作物的生长。杀虫剂是主要用于防治农业害虫和城市卫生害虫的药品。
氟虫吡喹(Pyrifluquinazon)，化学名称为：(1-乙酰基-1,2,3,4-四氢-3-[(3-吡啶基甲基)氨基]-6-[1,2,2,2,-四氟-1-(三氟甲基)乙基]喹唑啉-2-酮；氟虫吡喹是已知的，并且描述于例如EP1097932.其分子结构式为：
Figure PCTCN2015073289-appb-000001
氟虫吡喹由日本农药公司开发，属于一种的新喹唑啉(间二氮杂苯)类杀虫剂。氟虫吡喹一般以水分散粒剂应用，其作用机理是使害虫停止取食进而饿死，从而防止植物组织遭受更多的损害，同时限制一些重要病害的传播。目前，主要用于防治蔬菜、果树和茶叶上的粉虱、蚜虫及介壳虫。
毒死蜱(Chlorpyrifos)，化学名称：O，O-二乙基-O-(3，5，6-三氯-2-吡啶基)硫代磷酸酯，其分子结构式为：
Figure PCTCN2015073289-appb-000002
毒死蜱是乙酰胆碱酯酶抑制剂，属硫代磷酸酯类杀虫剂。作用机理为抑制体内神经中的乙酰胆碱酯酶AChE或胆碱酯酶ChE的活性而破坏了正常的神经冲动传导，引起一系列中毒症状：异常兴奋、痉挛、麻痹、死亡。具有胃毒、触杀、熏蒸三重作用。对水稻、小麦、棉花、果树、蔬菜、茶树上多种咀嚼式和刺吸式口器害虫均具有较好防效，尤其包括稻飞虱、稻纵卷叶螟、三化螟、稻瘿蚊、介壳虫、棉蚜、蒂蛀虫、斜纹夜蛾、菜青虫、小菜蛾、黄曲跳甲、根蛆、蚜虫、粘虫等害虫。与常规农药相比毒性低，对天敌安全，是替代高毒有机磷农药的首选药剂。杀虫谱广，易于土壤中的有机质结合，对地下害虫特效，持效期长达30天以上。无内吸作用，保障农产品、消费者的安全，适用于无公害优质农产品的生产。
所述单独化合物的活性良好；然而，在低施用率或针对单独的害虫使用时它们不是总能满足杀昆虫剂、杀螨剂或杀线虫剂所必须满足的高要求。
在害虫防治领域出现的一个典型的需求是需要降低防治活性成分的剂量率以及降低或避免不利的环境或毒理学影响，同时仍允许有效的害虫防治。还需要结合了击倒活性和延长防治时间，即快速作用和长效作用的害虫防治剂。
使用杀虫剂的另一个难处在于重复和唯一地使用单一杀虫化合物在许多情况下导致对所述活性化合物产生天然或适应抗药性的害虫的快速选择。因此，需要有助于防止或克服抗药性的害虫防治剂。
发明内容
本发明目的是为了解决上述技术问题，提供了一种杀虫组合物及控制有害生物的方法，该组合物通过将氟虫吡喹和毒死蜱进行组合，使得得到的组合物在防治效果上具有增益效果，并且拓展了杀虫谱，提高了害虫防治的快速作用和长效作用，延缓了抗药性的产生。
因此，本发明的一个目的是提供解决了所述问题中的至少一个，如降低剂量率、扩大活性谱或结合击倒活性和延长防治时间或抗药性管理的杀虫组合物，延缓抗性。
本发明解决其技术问题所采用的技术方案为：
一种杀虫组合物，包括
第一活性成分氟虫吡喹：
第二活性成分毒死蜱，
所述第一活性成分氟虫吡喹和第二活性成分毒死蜱按重量配比为1:100-100:1。
作为本发明的进一步改进，所述第一活性成分氟虫吡喹和第二活性成分毒死蜱按重量配比是1:50-50:1。
作为本发明的进一步改进，所述第一活性成分氟虫吡喹和第二活性成分毒死蜱按重量配比是1:25-25:1。
作为本发明的进一步改进，所述第一活性成分氟虫吡喹和第二活性成分毒死蜱按重量配比是1:10-10:1。
一种杀虫组合物，包括第一活性成分氟虫吡喹和第二活性成分毒死蜱，所述第一活性成分氟虫吡喹和第二活性成分毒死蜱的重量总共占所述组合物以重量计的5％-90％。
一种杀虫组合物，包括第一活性成分氟虫吡喹和第二活性成分毒死蜱，所述第一活性成分氟虫吡喹和第二活性成分毒死蜱共占所述组合物以重量计的10％-80％。
一种杀虫组合物，包括第一活性成分氟虫吡喹和第二活性成分毒死蜱，所述第一活性成分氟虫吡喹和第二活性成分毒死蜱总共占所述组合物以重量计的20％-60％。
根据本发明的杀虫组合物，还包含表面活性剂和/或增充剂。
根据本发明的杀虫组合物，所述杀虫组合物可配制成农业上允许的任意剂型。
根据本发明的杀虫组合物，所述杀虫组合物的剂型为乳油、悬浮剂、种子处理剂、水分散粒剂、可湿性粉剂、悬乳剂、烟雾剂、水乳剂、微囊悬浮剂、微囊悬浮-悬浮剂、超低容量液剂、微乳剂。
另一方面，本发明还提供了一种将本发明的杀虫组合物用于预防或控制有害生物的用途。
优选的，所述杀虫组合物用于防治蚜虫、介壳虫、粉虱、蓟马、稻飞虱、稻纵卷叶螟、三化螟、稻瘿蚊、蒂蛀虫、斜纹夜蛾、菜青虫、小菜蛾、甜菜夜蛾、黄条跳甲、小绿叶蝉、根蛆及粘虫。
另一方面，本发明还提供了一种预防或控制有害生物的方法，将本发明的杀虫组合物作用于目标有用植物、目标有害生物或其环境、目标有用植物的繁殖材料。所述植物繁殖材料是籽苗、根茎、圃苗、插条或种子。
一种保护作物以防有害生物侵袭的方法，包括使作物与含第一活性成分氟虫吡喹和第二活性成分毒死蜱杀虫组合物与目标有用植物、目标有害生物或其环境、目标有用植物的繁殖材料接触。
一种保护作物以防有害生物侵袭的方法，包括分开、依次或同时施用第一活性成分氟虫吡喹、第二活性成分毒死蜱。
一种预防或控制有害生物的方法，其中第一活性成分氟虫吡喹和第二活性成分毒死蜱各自是经配制组合物的形式。
一种保护植物种子的方法，其包括使种子在播种前和/或催芽之后与有效量的本发明 的杀虫组合物接触。
一种施用本发明的杀虫组合物处理的种子。
具体实施方法
本发明发现：将第一活性成分氟虫吡喹和第二活性成分毒死蜱组合不仅可带来对于杀虫谱的加和性提高，而且还实现令人惊喜的协同作用。
本文中使用的术语“协同作用”指本发明活性成分组合杀虫效果大于各活性成分效果之和，或者说，其作用是超加和性的。
本发明提供了一种包含第一活性成分氟虫吡喹和第二活性成分毒死蜱的杀虫组合物。
本发明提供了一种杀虫组合物，其中第一活性成分氟虫吡喹和第二活性成分毒死蜱重量比为1:100-100:1，优选1:50-50:1，再优选1:25-25:1，更优选1:10-10:1。
本发明组合物中活性成分的总量可根据具体因素而进行选择，以实现所期望的作用。所述因素例如，剂型、待施用对象、施用方法等。第一活性成分氟虫吡喹和第二活性成分毒死蜱总共占所述组合物以重量计的5％到90％，优选10％到80％，更优选20％到60％。
本发明的组合物可任选地包含农学上可接受的表面活性剂或增充剂。
根据本发明，术语“填充剂”指可与活性成分相组合或联合以使其更易于施用给对象(例如植物、作物或草类)的天然或合成的有机或无机化合物。因此，所述填充剂优选为惰性的，至少应为农业可接受的。所述填充剂可以为固体或液体。
适用的固体载体为：例如植物质粉末类(例如大豆粉、淀粉、谷物粉、木粉、树皮粉、锯末、核桃壳粉、麸皮、纤维素粉末、椰壳、玉米穗轴和烟草茎的颗粒，提取植物精华后的残渣等)、黏土类(例如高岭土、皂土、酸性瓷土等)、滑石粉类。硅石类(例如硅藻土、硅砂、云母、含水硅酸，硅酸钙)、活性炭、天然矿物质类(浮石、绿坡缕石及沸石等)、烧制硅藻土、砂、塑料媒介等(例如聚乙烯、聚丙烯、聚偏二氯乙烯等)、氯化钾、碳酸钙、磷酸钙等的无机矿物性粉末、硫酸铵、磷酸铵、尿素、绿化铵等的化学肥料、土肥，这些物质可以单独使用或者2种以上混用。
适用的液体载体可以在下列材料中选择，例如水，酒精类(例如甲醇、乙醇、异丙醇、丁醇、乙二醇等)、酮类(例如丙酮、甲基乙基酮、二异丁基甲酮、环己酮等)、醚类(例如乙醚、二恶烷、甲基纤维素、四氢呋喃等)、脂肪族碳氢化合物类(例如煤油、矿物油等)、芳香族碳氢化合物类(例如苯、甲苯、二甲苯、溶剂油、烷基萘、氯代芳烃、氯代脂肪烃、氯苯等)、卤化碳氢化合物类、酰胺类、砜类、二甲基亚砜、矿物和植物油、动物油等。
本发明的组合物还可包含附加的其他组分，例如表面活性剂。适用的表面活性剂有具有离子或非离子性质的乳化剂、分散剂或润湿剂，或这些表面活性剂的混合物。这些表面活性剂的适合的有脂肪醇聚氧乙烯醚、聚氧乙烯烷基芳基醚、聚氧乙烯高级脂肪酸酯、聚氧乙烯醇或酚的磷酸酯、多元醇的脂肪酸酯、烷芳基磺酸钠、萘磺酸聚合物、木质素磺酸盐、高分子梳形的支装共聚物、丁基萘磺酸盐、烷基芳基磺酸盐、烷基磺基琥珀酸钠、油脂、脂肪醇与环氧乙烷缩合物、烷基牛磺酸盐等聚丙烯酸盐、蛋白质水解物。合适的低聚糖物或聚合物，例如基于单独的乙烯单体、丙烯酸、聚氧乙烯或聚氧丙烯或者其与例如(多元)醇或(多元)胺的结合。当活性化合物中的一种和/或惰性载体中的一种不溶于水且当在水中施用时，必须存在表面活性剂。表面活性剂的比例为本发明的组合物的5％至40％重量。
如果合适，也可以存在其他添加组分，例如保护胶体、粘合剂、胶粘剂、增稠剂、触变剂、渗透剂、稳定剂、掩蔽剂、多价螯合剂、络合物形成剂。通常，所述的活性化合物可以与常规用于制剂目的的任何固体或液体添加剂结合。
本发明的所述制剂可通过已知方式将所述活性成分与以下物质中的至少一种进行混合：溶剂或稀释剂、乳化剂、分散剂、和/或粘合剂或固定剂、润湿剂、防水剂，如果需要，还可以包含催干剂和着色剂、稳定剂、颜料、消泡剂、防腐剂、增稠剂、水以及其它加工助剂。
本发明的杀虫组合物可以其本身使用，或者可根据其各自的物理和/或化学性质以其制剂形式或由其制备的使用形式使用。预混组合物的剂型实例是：
GR：颗粒剂
WP：可湿性粉剂
SP：可溶性粉剂
WG：水可分散粒剂
SG：可溶粒剂
SL：可溶液剂
EC：乳油
EW：乳剂、水乳剂
ME：微乳剂
SC：悬浮剂
CS：微囊悬浮剂
OD：油基悬浮剂
SE：悬乳剂
FS：种衣剂
适合桶混组合物的剂型实例是溶液、稀释乳剂、悬浮剂或其混合和粉剂。通常，桶混组合物是用溶剂(如水)稀释而成的含不同农药，和任选地进一步助剂的一种或多种预混组合物。
本发明的组合物不仅包括可用合适的装置施用于植物或种子的即用组合物，而且包括在施用之前必须用水稀释的市售浓缩液。
本发明的组合物还可以与其它活性成分联合施用，所述其它活性成分例如杀真菌剂、杀细菌剂、引诱剂、杀昆虫剂、杀螨剂、杀线虫剂、生长调节剂、除草剂、安全剂、肥料或化学信息素等。
本发明的杀虫组合物，具有良好的植物相容性和有利的恒温动物毒性，适于防治在农业、林业、保护储藏产品和材料以及卫生领域中遇到的有害生物，尤其是昆虫和螨虫。它们对于通常敏感和抗性的物种具有活性，并且对于所有或单个发育阶段均具有活性。
本文中使用术语“有害生物”意指可对植物的正常状态造成损失的任何有机体。包括：
鳞翅目害虫包括例如：二化螟(chilosuppressalis(walker)、三化螟(Tryporyzaincertulas(walker))、稻纵卷叶螟(cnaphalocrocismedinalisGuenee)、菜心螟(hellullaundalis)、桃蛀螟(conogethespunctiferlis)、柑桔凤蝶(papilioxuthus)、白粉蝶(pierisrapaecrucivora)、直纹稻弄蝶(parnaraguttata)、天幕毛虫(malacosoma Neustria testacea)、舞毒蛾(lymantriadispar)、美国白蛾(hyphantriacunea)、东方毒蛾(euproctissubflava)、黑纹刺蛾(scopelodescontracus)、棉铃虫(helicoverpaarmigera)、红铃麦蛾(Pink bollworm)、粉纹夜蛾(trichoplusiani)、甘蓝夜蛾(mamestrabrassicae)、甜菜夜蛾(spodopteraexigua)、斜纹夜蛾(spodopteralitura)、茶小卷叶蛾(adoxophyesoranafasciata)、卷叶蛾(adoxophyeshonmai)、杏黄卷蛾(archipsfuscocureanus)、茶长卷蛾(homonamagnanima)、小菜蛾(plutellaxylotella)、棉红铃虫(pectinophoragossypiella)。
鞘翅目害虫包括例如：米象(sitophilusoryzaelinne)、柑橘潜叶甲(Podagricomela nigricollis Che)、玉米象(S.zeamails)、谷象(S.granarius)、大猿叶虫(Cabbageleafbeetle)、小猿叶虫(Daikon leaf beele)，跳甲(fleabeetle)、葡萄跳甲(Alticachalybea)、曲条跳甲(phyllotretastriolata)、黄瓜跳甲(Epitrixcucumeris)、烟草跳甲(Ehirtipennis)、茄跳甲(E.fuscula)、黄守瓜(Aulacophoraindica(Gemlin)、芥菜叶甲(Phaedon cochleariae)等。
双翅目害虫包括例如：稻潜蝇(agromyzaoryzae)、大麦水蝇(hydrelliagriseola)、非 洲菊斑潜蝇(liriomyzatrifolii)、豌豆叶潜蝇(chromatomyiahorticola)、番茄斑潜蝇(liriomyzabryoniae)、灰地种蝇(deliaplatura)、葱地种蝇(deliaantiqua)地中海实蝇(ceratitiscapiatawiedgman)、苹果实蝇(Rhagoletispomonella)、樱桃实蝇(R.cingulata)。
半翅目害虫包括例如：臭蝽(megacoptapunctatissimum)、菜蝽(eurydemarugosum)、大刺白星蝽(eysarcorislewisi)、白星蝽(eysarcorisparvus)、稻绿蝽(nezaraviridula)、斯氏珀蝽(plautiastali)、臭梧桐蝽(halymorphamista)、稻棘缘蝽(cletuspunctiger)、中华稻缘蝽(leptocorisachinensis)、杜鹃网蝽(stephantispyrioides)、赤须盲蝽(trigonotyluscoelestialium)。
同翅目害虫包括例如黑尾叶蝉(nephotettixcincticeps)、灰飞虱(laodelphaxstriatellus)、稻褐飞虱(nilaparvatalugens)、白背飞虱(sogatellafurcifera)、梨木虱(psyllapyrisuga)、柑橘木虱(diaphorinatabaci)、烟粉虱(bemisiatabaci)、蚜虫(homoptera)、苹果棉蚜(eriosomalanigerum)。
膜翅目(hymenoptera)中有，黄翅菜叶蜂(athaliarosaeruficornis)、蔷薇叶蜂(argepagana)、黑山蚁(formica japonica)、栗瘿蜂(dryocsmuskuriphilus)等。
缨翅目害虫，例如蓟马(HaplothripsChinensisPriesner)。
蛛形纲(Arachnida)的害虫。例如柑橘全爪螨(panonychus citri)、朱砂叶螨(Tetranychus cinnabarinus)、苹果全爪螨(panonychus ulmi)、二点叶螨(tetranychus urticae)、山楂叶螨(tetranychus viennensis)、针叶小爪螨(oligonychus ununguis)柑橘始叶螨(eotetranychus kankitus)、紫红短须螨(brevipalpus phoenicis)、苜蓿苔螨(bryobiapraetiosa)、小麦卷叶螨(aceria tulipae)、葡萄瘿螨(colomerus vitis)、茶叶瘿螨(calacarus carinatus)、茶黄螨(polyphagotarsonemus latus)、长毛根螨(rhizoglyphus rostochiensis)等。
虱目(Anoplura,Phthiraptera)，例如畜虱属(Damalinia spp.)、血虱属(Haematopinus spp.)、毛虱属(Linognathus spp.)、虱属(Pediculus spp.)、嚼虱属(Trichodectes spp.)。
等足目(Isopoda)，例如，栀水虱(Oniscus asellus)、鼠妇(Armadilliudium vulgare)、球鼠妇(Porcellio scaber)。
倍足目(Diplopoda)，例如，Blaniulus guttulatus。
唇足目(Chi lopoda)，例如，地蜈蚣属(Geophilus carpophagusScutigera spp.)。
综合目(Symphyla)，例如，白松虫(Scutigerella immaculata)。
缨尾目(Thysanura)，例如，衣鱼(Lepisma saccharina)。
弹尾目(Collembola)，例如，武装棘跳虫(Onychiurus armatus)。
直翅目(Orthoptera)，例如，家蟋(Acheta domesticus)、喽蛄属属种(Gryllotalpa spp.)、亚洲飞蝗(Locusta migratoriamigrator ioides)、黑蝗属种(Melanopluss pp.)、沙漠蝗(Schistocercagregaria)。
蜚蠊目(Blattaria)，例如，东方蜚蠊(Blattaorientalis)、美洲大蠊(Periplaneta americana)、马德拉蜚蠊(Leucophaea maderae)、德国小蠊(Blattella germanica)。
革翅目(Dermaptera)，例如，欧洲球螋(Forficula auricularia)。
等翅目(lsoptera)，例如，散白蚁属种(Reticulitermes spp.)。
线虫纲((Nematoda))的代表性生物有选自根结线虫、胞囊形成线虫、秆线虫和叶线虫的线虫。优选下列线虫的大豆胞囊线虫(Heterodera),马铃薯金线虫(golbodera rostochiensis)、南方根结线虫(meloidogyne incognita)等、矛线目(dorylaimida)中有，长针线虫属(longidorus sp.)等。
优选的，所述杀虫组合物用于防治蚜虫、介壳虫、粉虱、蓟马、稻飞虱、稻纵卷叶螟、三化螟、稻瘿蚊、蒂蛀虫、斜纹夜蛾、菜青虫、小菜蛾、甜菜夜蛾、小绿叶蝉、黄条跳甲、根蛆及粘虫。
本文中的植物的含义应理解为所有植物和植物群体。植物为可通过常规育种和优选方法或可通过生物技术和遗传工程方法或可通过这些方法的组合获得的植物。所述植物包括转基因植物，也包括可受植物育种者权(plant breeders'rights)保护或不受其保护的植物品种。植物部位的含义应理解为所述植物全部地上和地下的部分和器官，如枝条、叶、花和根，可提及的实例为叶、针、叶、茎、干、花、子实体、果实和种子，以及根、块茎和根茎。所述植物部位也包括采收物以及无性与有性繁殖物，如插枝、块茎、根茎、幼枝和种子。
可以用于本发明保护的，以及根据本发明施用杀虫组合物的有用植物包括：谷类植物如小麦、燕麦、大麦、黑小麦和黑麦，以及玉米、高梁和栗、稻；甜菜，如糖用甜菜或饲料甜菜；水果，例如苹果类水果、核果、树坚果或软水果，如苹果、梨、李子、桃子、香蕉、杏仁、核桃、开心果、樱桃或浆果，如草莓、或黑莓；豆科作物如菜豆、豌豆或大豆；油作物，如油菜、芥菜、橄榄、向日葵、蓖麻、可可树或花生；葫芦科植物，如南瓜、西葫芦、黄瓜或甜瓜；纤维植物，如棉花、亚麻、大麻或黄麻；柑橘类水果，如橘子、柠檬、葡萄柚或橘子；蔬菜如菠菜、莴苣、芦笋、卷心菜、胡萝卜、洋葱、番茄、红椒、马铃薯或灯笼椒；樟科，如鳄梨、肉桂或樟脑；以及烟草、坚果、咖啡、茄子、甘蔗、茶叶、胡椒、葡萄藤、啤酒花、车前草科、产胶植物、草坪、草坪、饲料草，以及观赏植物，如矮牵牛属、三色堇及凤仙花；以及灌木、阔叶树以及常绿植物，如针叶树。
本发明提供了一种预防或控制有害生物的方法，将本发明的杀虫组合物作用于目标有用植物、目标有害生物或其环境、目标有用植物的繁殖材料。
用本发明组合物对植物及植物部分的处理以常规处理方法直接进行或通过作用于其环境、生境或贮存区域而进行，所述常规处理方法例如浸渍、进行浇灌、喷雾、弥雾、撒播、喷粉，成雾、撒播、发泡、涂覆、涂布、滴灌等方式向植物的叶片施用(叶面施用)，可以调节施用的频率和用量，使其适应被所述有害生物侵害的程度。
本发明的组合物也适合于保护植物的繁殖材料例如种子、果实、块茎或核仁或者植物插条不受有害生物特别是昆虫和螨虫的侵害。可在施用前用组合物处理该繁殖材料，例如在播种前拌种。也可通过在液体组合物中浸泡核仁或用固体组合物包被核仁，将活性成分施加到种仁上(包被)。当在播种过程中将繁殖材料施加到例如种子播沟内时，也可将该组合物施加到应用地点。这些对植物繁殖材料的处理方法和如此处理的植物繁殖材料都是本发明进一步的主题。
术语“植物繁殖材料”应理解为指所有有繁殖能力的植物部分，例如种子，以及植物性材料例如扦插条或块茎(例如马铃薯)。因此，本文中所使用的植物部分包括植物繁殖材料。可以提及的是例如种子(狭义上)，根，果实，块茎，鳞茎，根茎和植物部分。待从土壤中发芽后或出苗后抑制的发芽植株和有效植株也是可以提及的。幼小植株可以在移植前通过浸渍进行全部或局部处理来进行保护。
植物部分和随后长出的植物器官是由植物繁殖材料例如种子产生的植物的任何部分。植物部分、植物器官和植物也可以受益于通过将组合物施用于植物繁殖材料保护植物免于植物病害。某些植物部分和某些随后长出的植物器官也可以看成植物繁殖材料，其自身可以用组合物施用(或处理)；从而由经处理的植物部分和经处理的植物器官产生的植物、其它的植物部分和其它的植物器官也可以受益于通过将组合物施用于某些植物部分和某些植物器官保护植物免于植物虫害。
为了处理植物繁殖材料特别是种子，还可通过用各活性成分的液体制剂接连浸渍块茎或谷粒，或通过用已组合的湿或干制剂涂覆，从而将活性成分施用到种子上(涂覆)。
本发明的组合物以其本身或合适的剂型施用于种子。优选，种子在稳定状态下被处理，从而使得处理不造成任何损害。对种子的处理通常可在采收和播种之间的任何时间进行。通常在种子处理期间必须注意，施用于种子的本发明组合物的量和/或其它添加剂的量选择为不会影响种子的发芽或不会损害所得植物。
本发明的组合物对于处理植物繁殖材料，特别是水稻、油菜、棉花、小麦、大麦、大豆、玉米、花生的种子是特别有利的。
一种保护种子的方法，其包括使种子在播种前和/或催芽之后与协同有效量的本发明的杀虫组合物接触。
一种施用本发明的杀虫组合物处理的种子。
可将本发明组合物施用于植物生长的环境、生境或贮存区域。植物生长的环境、生境是指能够使农作物生根、生长的支撑体，例如：土壤，水等，具体的原材料可以使用例如砂子、浮石、蛭石、硅藻土、琼胶、凝胶状物、高分子物质、石棉、木屑、树皮等。优选土壤。
向土壤中施用药剂的方法，例如将液体药剂稀释于水中或不稀释直接施用于植物体的根部或育秧用的秧田中等方法，将颗粒剂散播到植物体的根部或者育秧的秧田中的方法有在播种前将粉剂、水分散粒剂等喷洒于土壤中并与土壤整体混合的方法，播种前或栽种植物体前将粉剂、水分散粒剂稀释后喷洒于种植孔、播种沟中，在进行播种的方法等。
另一方面，本发明的处理还可产生如下的超加和效应：改善植物生长、提高对高温或低温的耐受性、提高对干旱或者对水或土壤含盐量的耐受性、提高开花品质、使采收更简便、加快成熟、提高采收产率、改善采收产品的质量和/或提高其营养价值、改善采收产品的贮存稳定性和/或其加工性能。
本发明的杀虫组合物通常以以下剂量施用是常见的和有利的：
-对于叶部处理：0.1-10000g/ha，优选10-1000g/ha，更优选20-300g/ha；对于浸渍或滴注施用而言，所述剂量甚至还可以降低，特别是当施用惰性基质如石棉或珍珠岩石时；
-对于种子处理：2-200g/100kg种子，优选3-150g/100kg种子；
-对于土壤处理：0.1-10000g/ha，优选1-5000g/ha。
上述剂量仅是一般性的示例性剂量，实际施用时本领域的技术人员会根据实际情况和需要，尤其是根据待处理的植物或作物的性质以及虫害情况来调整施用率。
本发明的杀虫组合物包括分开、依次或同时施用第一活性成分氟虫吡喹和第二活性成分毒死蜱。
应当指出，本发明的任何实施方案或实施方案的任何技术特征都可以独立地与本发明的任何其它实施方案彼此组合。也就是说，本发明的任何实施方案的一个或多个技术特征都可与任何其它技术特征重新组合。由此技术特征重新组合而形成的技术特征公开在本文中，如其特别记载在本文中一样。
本发明通过两者复配的益处有以下几点：
A、所述杀虫组合物的活性超过所述两种活性化合物各自施用时的活性之和；这使得优化所用活性化合物的量成为可能；
B、两者混用，解决了持效期与速效性的问题，从而减少用药次数，降低了人工成本；
C、延缓了抗性的产生：两者作用机理和作用方式完全不同，组合之后具有触杀、胃毒、杀卵及降低产卵率和孵化率的作用，从而使害虫更易被杀灭，从而延缓了抗性的产生。
具体实施方式
以下将结合实施例对本发明作进一步的阐述。
制剂实施例
实施例1 乳油
第一活性成分氟虫吡喹 2％
第二活性成分毒死蜱 3％
N-甲基吡咯烷酮 20％
乙氧基化蓖麻油 4％
脂肪醇聚氧乙烯醚磺基琥珀酸单酯二钠 10
SOLVESSOTM200 补足至100％
将上述组分混合搅拌至均一透明的液体，即得到本发明的乳油制剂。
实施例2 可湿性粉剂
第一活性成分氟虫吡喹 10％
第二活性成分毒死蜱 10％
十二烷基硫酸钠 2％
木质素磺酸钠 10％
白炭黑 10％
高岭土 补足至100％
将活性成分、各种助剂及填料等按配方的比例成分混合，经超细粉碎机粉碎后，即得到本发明的可湿性粉剂。
实施例3 水乳剂
第一活性成分氟虫吡喹 10％
第二活性成分毒死蜱 2％
N-甲基吡咯烷酮 15％
十二烷基苯磺酸钠 5％
苯乙基苯酚聚氧乙烯醚 5％
水 补足至100％
将原药、溶剂、乳化剂加在一起，使溶解成均匀油相；将水溶性组分和水混合制得水相；在高速搅拌下，将油相与水相混合，制得本发明的水乳剂。
实施例4 水分散粒剂
第一活性成分氟虫吡喹 50％
第二活性成分毒死蜱 10％
木质素磺酸钠 5％
十二烷基硫酸钠 2％
尿素 10％
高岭土 补足至100％
将活性成分、分散剂、润湿剂、崩解剂和填料按配方的比例混合均匀，经过气流粉碎成可湿性粉剂，再加入一定量的水混合挤压造粒。经干燥筛分后得到本发明的水分散粒剂。
实施例5 微乳剂
第一活性成分氟虫吡喹 10％
第二活性成分毒死蜱 50％
N-甲基吡咯烷酮 20％
乙氧基化蓖麻油 5％
脂肪醇聚氧乙烯醚磺基琥珀酸单酯二钠 5％
水 补足至100％
将上述组分混合搅拌至均一透明的液体，即得到本发明的微乳剂。
实施例6 可湿性粉剂
第一活性成分氟虫吡喹 50％
第二活性成分毒死蜱 1％
十二烷基硫酸钠 10％
木质素磺酸钠 15％
白炭黑 10％
高岭土 补足至100％
将活性成分、各种助剂及填料等按配方的比例成分混合，经超细粉碎机粉碎后，即得到本发明的可湿性粉剂。
实施例7 悬乳剂
Figure PCTCN2015073289-appb-000003
将第二活性成分毒死蜱溶解在SOLVESSOTM200中，加入乙氧基化蓖麻油，得到乳油；将第一活性成分氟虫吡喹，脂肪醇聚氧乙烯醚磺基琥珀酸单酯二钠，改性木质素磺酸钙，黄原胶，膨润土，丙三醇，水等上述各组分按比例混合均匀，并经砂磨，制备成悬浮剂。将含第一活性成分氟虫吡喹的油相加入到含第二活性成分毒死蜱的悬浮剂中，得到悬乳剂。
实施例8 水乳剂
油相：
第一活性成分氟虫吡喹 1％
第二活性成分毒死蜱 10％
油酸甲酯 10％
聚苯乙烯 3.7％
水相：
黄原胶 0.07％
磺化的萘磺酸-甲醛缩合产物的钠盐 1％
杀菌剂 0.2％
水 补足至100％
将第一活性成分氟虫吡喹和第二活性成分毒死蜱溶解在油酸甲酯中，加入聚苯乙烯得到油相；按照配方中的组分混合均匀得到水相；在搅拌下将油相加入水相得到水乳剂。
实施例9 可湿性粉剂
第一活性成分氟虫吡喹 70％
第二活性成分毒死蜱 20％
木质素磺酸钠 7％
月桂基硫酸钠 2％
高岭土 补足至100％
将上述组合按比例混合，并研磨，粉碎，制备成可湿性粉剂。
实施例10 包衣颗粒剂
第一活性成分氟虫吡喹 30％
第二活性成分毒死蜱 50％
聚乙二醇 3％
高度分散的硅酸 1％
碳酸钙 补足至100％
在混合器中，将磨细的活性成分均匀涂布到被聚乙二醇润湿的载体上。以此方式可获得无尘包衣颗粒剂。
实施例11 可湿性粉剂
第一活性成分氟虫吡喹 5％
第二活性成分毒死蜱 25％
木质素磺酸钠 10％
十二烷基磺酸钠 3％
白炭黑 5％
高岭土 补足至100％
将上述组分按比例混合，并研磨、粉碎，制备成可湿性粉剂。
实施例12 挤出颗粒剂
第一活性成分氟虫吡喹 1％
第二活性成分毒死蜱 50％
木质素磺酸钠 4％
羧甲基纤维素 2％
白炭黑 5％
高岭土 补足至100％
将活性组分与助剂混合并研磨，混合物用水湿润。将该混合物挤出，然后在空气流中干燥。
实施例13 悬乳剂
第一活性成分氟虫吡喹 20％
第二活性成分毒死蜱 2％
SOLVESSO TM200 10％
乙氧基化蓖麻油 4％
脂肪醇聚氧乙烯醚磺基琥珀酸单酯二钠 10％
改性木质素磺酸钙 5％
黄原胶 0.5％
膨润土 1％
丙三醇 5％
消泡剂 0.6％
水 补足至100％
将第二活性成分毒死蜱溶解在SOLVESSOTM200中，加入乙氧基化蓖麻油，得到乳油；将第二活性成分毒死蜱，脂肪醇聚氧乙烯醚磺基琥珀酸单酯二钠，改性木质素磺酸钙，黄原胶，膨润土，丙三醇，水等上述各组分按比例混合均匀，并经砂磨，制备成悬浮剂。将含第二活性成分毒死蜱的油相加入到含第一活性成分氟虫吡喹的悬浮剂中，得到悬乳剂。
实施例14 悬乳剂
第一活性成分氟虫吡喹 25％
第二活性成分毒死蜱 25％
SOLVESSO TM200 10％
乙氧基化蓖麻油 4％
脂肪醇聚氧乙烯醚磺基琥珀酸单酯二钠 10％
改性木质素磺酸钙 5％
黄原胶 0.5％
膨润土 1％
丙三醇 5％
消泡剂 0.6％
水 补足至100％
将第二活性成分毒死蜱溶解在SOLVESSOTM200中，加入乙氧基化蓖麻油，得到含第二活 性成分毒死蜱乳油；将第一活性成分氟虫吡喹，脂肪醇聚氧乙烯醚磺基琥珀酸单酯二钠，改性木质素磺酸钙，黄原胶，膨润土，丙三醇，水等上述各组分按比例混合均匀，并经砂磨，制备成悬浮剂。将含第二活性成分毒死蜱的油相加入到含第一活性成分氟虫吡喹的悬浮剂中，得到悬乳剂。
实施例15 悬乳剂
第一活性成分氟虫吡喹 50％
第二活性成分毒死蜱 2％
SOLVESSOTM200 10％
乙氧基化蓖麻油 4％
脂肪醇聚氧乙烯醚磺基琥珀酸单酯二钠 10％
改性木质素磺酸钙 5％
黄原胶 0.5％
膨润土 1％
丙三醇 5％
消泡剂 0.6％
水 补足至100％
将第二活性成分毒死蜱溶解在SOLVESSOTM200中，加入乙氧基化蓖麻油，得到含第二活性成分毒死蜱乳油；将第一活性成分氟虫吡喹，脂肪醇聚氧乙烯醚磺基琥珀酸单酯二钠，改性木质素磺酸钙，黄原胶，膨润土，丙三醇，水等上述各组分按比例混合均匀，并经砂磨，制备成悬浮剂。
将含第二活性成分毒死蜱的油相加入到含第一活性成分氟虫吡喹的悬浮剂中，得到悬浮乳剂。
实施例16 乳油
第一活性成分氟虫吡喹 5％
第二活性成分毒死蜱 15％
N-甲基吡咯烷酮 20％
乙氧基化蓖麻油 4％
脂肪醇聚氧乙烯醚磺基琥珀酸单酯二钠 10
SOLVESSOTM200 补足至100％
将上述组分混合搅拌至均一透明的液体，即得到本发明的乳油。
实施例17 微囊悬浮-悬浮剂
ATLOXTM4913 4％
柠檬酸 0.05％
催化剂 0.1％
水 13％
第二活性成分毒死蜱 5％
PAPI 1.35％
SOLVESSOTM200 10％
ATLOXTM4913 16％
分散剂LFH 0.3％
消泡剂 0.16％
尿素 8.4％
第一活性成分氟虫吡喹 25％
水 补足至100％
将多亚甲基多苯基多异氰酸酯(PAPI)，第二活性成分毒死蜱和SOLVESSOTM200形成的油相加入含ATLOXTM4913的水溶液中，形成乳状液。然后加热并保温在50℃下加入催化剂反应2小时。冷却后得到含第二活性成分毒死蜱的微囊剂。
ATLOXTM 4913,分散剂LFH,消泡剂，尿素，第一活性成分氟虫吡喹和水按比例混合均匀，并经砂磨，制备成悬浮剂。
将得到的含第二活性成分毒死蜱的微囊剂加入第一活性成分氟虫吡喹的水悬浮剂中，搅拌均匀得到本发明的微囊悬浮-悬浮剂。
实施例18 悬浮种衣剂
第一活性成分氟虫吡喹 5％
第二活性成分毒死蜱 50％
SOLVESSOTM200 20％
乙氧基化蓖麻油 5％
脂肪醇聚氧乙烯醚磺基琥珀酸单酯二钠 10％
改性木质素磺酸钠 5％
黄原胶 0.5％
丙三醇 5％
聚乙烯吡咯烷酮(PVP-K30) 1％
消泡剂 0.6％
水 补足至100％
将第二活性成分毒死蜱溶解在SOLVESSOTM200中，加入乙氧基化蓖麻油，得到含第二活性成分毒死蜱的乳油；将第一活性成分氟虫吡喹，脂肪醇聚氧乙烯醚磺基琥珀酸单酯二钠，改性木质素磺酸钙，黄原胶，丙三醇，聚乙烯吡咯烷酮，水等上述各组分按比例混合均匀，并经砂磨，制备成悬浮剂。
将含第二活性成分毒死蜱的油相加入到含第一活性成分氟虫吡喹的悬浮种衣剂中，得到本发明的悬浮种衣剂。
实施例19 烟雾剂
第一活性成分氟虫吡喹 5％
第二活性成分毒死蜱 5％
丙二醇 5％
磷酸酯类 3.5％
乙氧基化的蓖麻油 2.0％
SOLVESSOTM 100 补足至100％
首先将防冻剂丙二醇，稀释剂SOLVESSOTM 100混合，搅拌下加入第一活性成分氟虫吡喹和第二活性成分毒死蜱；将表面活性剂加入其中，在搅拌下通过一个粉碎设备胶体磨进行粉碎，将通过胶体磨后的悬浮液，再经过一个超微粉碎机。循环往复至固体粒子的粒径≤2um为止。
实施例20 可湿性粉剂
第一活性成分氟虫吡喹 50％
第二活性成分毒死蜱 5％
十二烷基硫酸钠 1％
木质素磺酸钠 1％
白炭黑 1％
高岭土 补足至100％
将活性成分、各种助剂及填料等按配方的比例成分混合，经超细粉碎机粉碎后，即得到本发明的可湿性粉剂。
实施例21：油悬浮剂
Figure PCTCN2015073289-appb-000004
将活性组分、分散剂、润湿剂各组分按照配方的比例混合均匀，经研磨和/或高速剪切后，加入玉米油，得到油悬浮剂。
实施例22 活性成分结合物
第一活性成分氟虫吡喹 10％
第二活性成分毒死蜱 90％
将第一活性成分氟虫吡喹和第二活性成分毒死蜱按比例混合均匀。
以上实施例中的配比为重量百分配比。
生物测试例
将不同农药的有效成分组合制成农药，是目前开发和研制新农药以及防治农业上抗性害虫的一种有效和快捷的方式。不同品种的农药混合后，通常表现出三种作用类型：相加作用、增效作用和拮抗作用。但具体为何种作用，无法预测，只有通过大量实验才能知道。复配增效很好的配方，由于明显提高了实际防治效果，降低了农药的使用量，从而大大地延缓了害虫抗药性的产生速度，是综合防治病害的重要手段。
发明人通过大量的筛选试验，对氟虫吡喹和毒死蜱的不同配比进行了大量试验以及效果性分析，发现在一定的配比范围内，所得到的新型农用杀虫组合物具有增益效果，而不仅仅是两种药剂的简单相加，具体用以下实施方式进行说明。
在本发明实施方式中采用室内毒力测定和杀虫试验相结合的方式，首先通过室内毒力测定，明确两种药剂按一定比例复配后的共毒系数(CTC)，CTC<80为抗拮作用，80≤CTC≤120为相加作用，CTC＞120为增效作用，在此基础上再进行杀虫试验。
试验方法：采用先浸叶后接虫的方法，将未接触任何药剂的大小一致的叶片在配置好的药液中浸泡5s后取出、自然晾干，放入养虫盒中，然后接上供试幼虫，在25℃条件下饲养，每处理3次重复，每重复所用试虫数为120头，同时设空白对照，于72h检查死虫数，计算死亡率和校正死亡率，求得毒力回归方程并计算LC50值。若对照死亡率大于10％，则视为无效试验。计算公式如下：
死亡率(％)＝(药前活虫数-药后活虫数)/药前活虫数*100
校正死亡率(％)＝(处理组死亡率-对照组死亡率)/(100-对照组死亡率)*100
将供试昆虫校正死亡率换算成机率值(y)，处理浓度(μg/ml)转换成对数值(x)，以最小二乘法得出毒力回归方程，并由此计算出每种药剂的值。按照孙云沛公式法计算出共毒系数CTC。计算公式如下(以氟虫吡喹为标准药剂，其毒力指数为100)：
实测毒力指数(ATI)＝(标准药剂LC50/供试药剂LC50)×100
理论毒力指数(TTI)＝A药剂ATI×混剂中A的百分含量+B药剂ATI×混剂中B的百分含量
共毒系数(CTC)＝(混剂ATI/混剂TTI)×100
试验一：对柑橘蚜虫的室内毒力测定
表1
Figure PCTCN2015073289-appb-000005
从表1可知，氟虫吡喹与毒死蜱在防治柑橘蚜虫，在配比1:100-100:1的范围里时，共毒系数均大于120，说明两者在这个范围内的混配均表现为增益效果，尤其是当两者的比例在1:10时，增益效果尤为突出。
试验二：对烟粉虱的室内毒力测定结果
表2
Figure PCTCN2015073289-appb-000006
从表2可知，氟虫吡喹与毒死蜱在防治烟粉虱，在配比1:100-100:1的范围里时，共毒系数均大于120，说明两者在这个范围内的混配均表现为增益效果，尤其是当两者的比例在1:10时，增益效果尤为突出。
另外按照以上的毒力测定的方法，对稻飞虱，蓟马、甜菜夜蛾的室内毒力测定结果也表明，氟虫吡喹与毒死蜱防治稻飞虱、蓟马、甜菜夜蛾，在配比1:100-100:1的范围里时，共毒系数均大于120，说明两者在这个范围内的混配均表现为增益效果。
防效试验
当活性化合物组合物的作用超过当各活性化合物单独施用时的作用的总和时，存在协同的杀虫和杀螨作用。两种活性化合物的特定组合的预期作用可使用所谓的"Colby公式"(参见S.R.Colby,"Calculating Synergistic and Antagonistic Responses of Herbicide Combinations“,Weeds 1967,15,20-22)如下计算:如果
X是当使用用量为m g/ha或浓度为m ppm的活性化合物A时的杀死率，表示为占未处理对照的百分率，
Y是当使用用量为n g/ha或浓度为nppm的活性化合物B时的杀死率，表示为占未处理对照的百分率，
E是当使用用量为m和n g/ha或浓度为m和n ppm的活性化合物A和B时的杀死率，表示为占未处理对照的百分率，
那么
Figure PCTCN2015073289-appb-000007
如果实际的杀虫致死率超过计算值，则组合物的致死作用是超加和的，即存在协同作用。在这种情况下，实际观察到的杀死率必须超过使用上述公式计算的预期杀死率值(E)的值。
试验三：防治柑橘棉蚜的药效试验
试验如下进行：试验地点为浙江嘉兴，时间为3月初。采用盆栽柑橘试验，苗龄为3年。喷药前每株接种棉蚜成虫200头。接种后2天喷药处理。以喷湿叶片正反面为准，每个处理3株柑橘苗。于药后6天，采25张叶片于实验室内用双目镜调查叶片上的成虫数，计算虫口减退率和防治效果，公式如下：
具体试验方法及数据如下：
虫口减退率(％)＝(处理区药前活虫数－处理区药后活虫数)/处理区药前活虫数*100防治效果(％)＝(处理区虫口减退率±对照区虫口减退率)/(100±对照区虫口减退率)*100
表3：
Figure PCTCN2015073289-appb-000008
从表3的试验结果看，氟虫吡喹和毒死蜱的复配后观察到的防效明显高于计算防效，显示出明显的增效作用。
试验四：防治烟粉虱的药效试验
试验如下进行：试验地点为浙江嘉兴，时间为3月初。采用盆栽棉花试验。喷药前每株接种烟粉虱成虫200头。接种后2天喷药处理。以喷湿叶片正反面为准，每个处理3株棉株。于药后6天，采25张叶片于实验室内用双目镜调查叶片上的成虫数，计算虫口减退率和防治效果，公式如下：
具体试验方法及数据如下：
虫口减退率(％)＝(处理区药前活虫数－处理区药后活虫数)/处理区药前活虫数*100防治效果(％)＝(处理区虫口减退率±对照区虫口减退率)/(100±对照区虫口减退率)*100
表4：
Figure PCTCN2015073289-appb-000009
从表4的试验结果看，氟虫吡喹和毒死蜱的复配后观察到的防效明显高于计算防效，显示出明显的增效作用。
试验五土壤处理对黄条跳甲的防效
混合土壤2：砂1：腐食土1制备实验土壤，每个300ml塑料制容器中装入200g土壤，以规定的药剂浓度喷药处理。每个容器中放10个黄条跳甲的幼虫，黑暗下在25OC恒温静置后，在所需的时间后，分散开土壤，计数生存的幼虫数后求死亡率。
死亡率(％)＝{1-(生存头数/放虫头数)}X100
通过“colby公式”计算死亡率的理论值(％)。试验结果表明，实际死亡率(％)比理论值(％)高，说明氟虫吡喹和毒死蜱复配，用于土壤处理对于防治黄条跳甲具有增效作用。
试验六：种子处理对甜菜夜蛾的防效
液体拌种的一般方法F1:
将所需量的液体制剂加入锥形瓶中。摇动烧瓶使液体分布到容器的整个底部。之后立即向瓶中加入所需量的种子。用手剧烈摇动烧瓶约1分钟以便所有种子都被液体覆盖。将烧瓶的内容物倒在干燥架上并在烘箱内干燥。
干拌种的一般方法F2:
向每个给广口瓶中装入同样数目的种仁，并且在每只瓶中装入一定量的固体制剂，以获得所需量的0.3mg有效成分/种仁。将烧瓶放在辊上以80转/分钟的速度旋转3分钟。用手摇动烧瓶，使粘在烧瓶壁上的种仁掉下来，然后将烧瓶反方向旋转3分钟。
按照程序F1和F2对制剂实施例1-22的药剂和单剂按照规定的浓度进行种子处理。接着将处理过的玉米种子播种。播种后26天，取植株最顶端叶片的5-8cm长的部分放在玻璃烧杯中并用10只刚孵化的甜菜夜蛾一龄幼虫侵染。用盖子盖住烧杯并保持在25℃及 60％相对大气湿度下，每天光照16小时。侵染3-5后进行评估。记录长成的植株上存活的幼虫数目后求死亡率。
死亡率(％)＝{1-(生存头数/放虫头数)}X100
通过“colby公式”计算死亡率的理论值(％)。试验结果表明，实际死亡率(％)比理论值(％)高，说明氟虫吡喹和毒死蜱复配，用于种子处理，对防治甜菜夜蛾有增效作用。
另外，通过上述实验方法对水稻、小麦、玉米、棉花、蔬菜、果树及茶叶上的稻纵卷叶螟、三化螟、稻瘿蚊、蒂蛀虫、斜纹夜蛾、菜青虫、小菜蛾、黄条跳甲、根蛆、小绿叶蝉及粘虫等害虫进行防效试验，氟虫吡喹与毒死蜱复配后显示出良好的增效作用，具有较好的持效性和速效性，降低了有效成份的用药量。

Claims (19)

  1. 一种杀虫组合物，其特征在于包含第一活性成分氟虫吡喹
    Figure PCTCN2015073289-appb-100001
    和第二活性成分毒死蜱，
    Figure PCTCN2015073289-appb-100002
    所述第一活性成分氟虫吡喹和第二活性成分毒死蜱的重量比为1:100到100:1。
  2. 根据权利要求1的杀虫组合物，其特征在于：第一活性成分氟虫吡喹和第二活性成分毒死蜱的重量配比为1:50到50:1。
  3. 根据权利要求1所述的杀虫组合物，其特征在于：所述第一活性成分氟虫吡喹和第二活性成分毒死蜱的重量配比为1:25到25:1。
  4. 根据权利要求1所述的杀虫组合物，其特征在于：所述第一活性成分氟虫吡喹和第二活性成分毒死蜱的重量配比为1:10到10:1。
  5. 根据权利要求1所述的杀虫组合物，其特征在于：所述第一活性成分氟虫吡喹和第二活性成分毒死蜱总共占所述组合物以重量计的5％-90％。
  6. 根据权利要求1所述的杀虫组合物，其特征在于：所述第一活性成分氟虫吡喹和第二活性成分毒死蜱总共占所述组合物以重量计的10％-80％。
  7. 根据权利要求1所述的杀虫组合物，其特征在于：所述第一活性成分氟虫吡喹和第二活性成分毒死蜱总共占所述组合物以重量计的20％-60％。
  8. 根据权利要求1所述的杀虫组合物，其特征在于：还包含表面活性剂和/或增充剂。
  9. 根据权利要求1所述的杀虫组合物，其特征在于所述剂型为乳油、悬浮剂、种衣剂、水分散粒剂、可湿性粉剂、悬乳剂、挤出颗粒剂、包衣颗粒剂、烟雾剂、水乳剂、微囊悬浮剂、超低容量液剂、微囊悬浮-悬浮剂。
  10. 根据权利要求1所述的杀虫组合物用于预防或控制有害生物的用途。
  11. 一种预防或控制有害生物的方法，其特征在于：将权利要求1的杀虫组合物用于目标有用植物、目标有害生物或其环境、目标有用植物的繁殖材料。
  12. 根据权利要求11所述的一种预防或控制有害生物的方法，其特征在于：所述植物繁殖材料是籽苗、根茎、圃苗、插条或种子。
  13. 根据权利要求11所述的一种预防或控制有害生物的方法，其特征在于：所述有害生物选自昆虫、螨虫。
  14. 根据权利要求11所述的一种预防或控制有害生物的方法，其特征在于：所述有害生物选自蚜虫、介壳虫、粉虱、蓟马、稻飞虱、稻纵卷叶螟、三化螟、稻瘿蚊、蒂蛀虫、斜纹夜蛾、甜菜夜蛾、菜青虫、小菜蛾、黄条跳甲、小绿叶蝉、根蛆及粘虫。
  15. 根据权利要求11所述的一种预防或控制有害生物的方法，其特征在于：包括分开、依次或同时施用第一活性成分氟虫吡喹、第二活性成分毒死蜱。
  16. 根据权利要求11所述的一种预防或控制有害生物的方法，其特征在于：其中第一活性成分氟虫吡喹和第二活性成分毒死蜱各自是经配制组合物的形式。
  17. 一种保护作物以防有害生物侵袭的方法，其特征在于：包括使目标有用植物、目标有害生物或其环境、目标有用植物的繁殖材料与含第一活性成分氟虫吡喹和第二活性成分毒死蜱的杀虫组合物接触。
  18. 一种保护植物种子的方法，其特征在于：包括使种子在播种前和/或催芽之后与有效量的根据权利要求1所述的杀虫组合物接触。
  19. 一种施用根据权利要求1所述的杀虫组合物处理的种子。
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