WO2010007240A2 - Granule-appat procede de fabrication - Google Patents
Granule-appat procede de fabrication Download PDFInfo
- Publication number
- WO2010007240A2 WO2010007240A2 PCT/FR2009/000771 FR2009000771W WO2010007240A2 WO 2010007240 A2 WO2010007240 A2 WO 2010007240A2 FR 2009000771 W FR2009000771 W FR 2009000771W WO 2010007240 A2 WO2010007240 A2 WO 2010007240A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- bait
- seed
- pyrethrum
- granules
- soil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
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Classifications
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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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
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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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/002—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing a foodstuff as carrier or diluent, i.e. baits
- A01N25/006—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing a foodstuff as carrier or diluent, i.e. baits insecticidal
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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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
Definitions
- Granule bait and method of manufacture Granule bait and method of manufacture.
- the present invention relates to the field of agriculture, and more particularly to a novel insecticidal composition in the form of a bait, preferably based on pyrethrum.
- pesticide derived from the English word pest (“pests”), refers to substances or preparations used for the prevention, control or elimination of organisms considered to be undesirable, be they plants, animals or animals. , fungi or bacteria. In common parlance the term pesticide is generally associated with an agricultural use of these substances, but the generic term also includes domestic uses, urban, road ...
- pesticide means both the active substance, that is to say responsible for the intended action that the composition containing the active substance and sold to the user.
- plant protection products or phytosanitary products.
- herbicides to control weeds
- fungicides to control fungi
- insecticides to control insects
- Other products exist having an action on the rodents (rodonticides), on the snails and the slugs (molluscicides).
- the use of pesticides in agriculture dates back to antiquity. The use of sulfur seems to date back to 1000 years before J.
- arsenic was recommended by Pliny and arsenical products are known in China from the sixteenth century; it is also around this time that the insecticidal properties of tobacco and the roots of Derris and Lonchocarpus are reported. The more widespread use of pesticides has followed the progress of mineral chemistry. In the nineteenth century, fungicidal treatments are based on copper sulphate (the famous Bordeaux mixture) or mercury; insecticides such as copper arsenite, copper acetoarsenite and arsenate of lead are also emerging. Pyrethrum, a powder from flowers of the genus Chrysanthemum is introduced as an insecticide at this time.
- insecticides such as DDD and DDT were used in large quantities in preventive medicine to destroy the mosquito responsible for malaria and in agriculture for the elimination of the Colorado potato beetle.
- the use of these products has undergone a very strong development in past decades, making them almost indispensable for most agricultural practices, regardless of the level of economic development of the countries.
- pesticide consumption doubled every ten years.
- insecticides are active substances or preparations with the property of killing insects, their larvae and / or their eggs.
- the generic term insecticide also includes pesticides intended to control arthropods that are not insects (eg mites, spiders or ticks) as well as repellents.
- insecticides There are different chemical families of insecticides, which are related to their mode of action which may be based on disruption of the nervous system, cellular respiration, cuticle placement, or disruption of the moult. . These main families are organophosphorus, carbamate, pyrethroid, natural or synthetic, organochlorine and benzoyl urea.
- organophosphorus, carbamate, pyrethroid, natural or synthetic, organochlorine and benzoyl urea organophosphorus, carbamate, pyrethroid, natural or synthetic, organochlorine and benzoyl urea.
- the year 2006 marks the upsurge of the damage caused by underground pests, for example the gray fly, and the click beetles. The latter were strongly manifested in autumn 2005 everywhere and more particularly in the West of France. against these pests, only seed protection provides an effective response.
- Wireworms are a family of insects particularly harmful to these crops, and their harmfulness is all the more marked as the forms to wireworms can remain for very long periods in the soil, up to 5 years.
- Contamination by pesticides has been detected in all compartments of the environment: in the waters of rivers and groundwater, in the air and in rainwater. They are also found in fruits, vegetables, cereals and products of animal origin (eggs, milk, meat, fish ..) - They exist in their original form but they can also be degraded, it is called residues or metabolites
- microgranules granules obtained by the agglomeration of active material, filler and binding agents and dispersants, followed by drying.
- Microgranules are formulated for dry use and are ready for use. They are calibrated and have a uniform size to allow regular spreading of the active ingredient.
- the charge is a mineral charge; bait granules (GB): granules obtained by the agglomeration of active material, filler and binding agents and dispersants, followed by drying.
- the bait granules are formulated ready for use. They are calibrated and have a uniform size to allow regular spreading of the active ingredient.
- the load is a flour (wheat, durum wheat, etc ).
- the invention is very particularly intended for this type of formulation.
- soluble concentrates it is a solution of active ingredient to be diluted in water, added surfactants
- concentrated suspensions SC: the solid, water-insoluble active substances are kept in concentrated suspension in water, in the presence of wetting agents, dispersants, thickeners (xanthan gum, bentonite, silica) or agent anti-redeposition, antifreeze (ethylene glycol, urea) antifoam and sometimes bactericidal (1,2-Benzisothiazol-3 (2H) -one, methanal or formaldehyde).
- emulsifiable concentrates EC: the active ingredients are placed in concentrated solution in an organic solvent and added emulsifiers responsible for stabilizing the emulsions obtained at the time of use by dilution in water; concentrated emulsions (EW): the active ingredient is dissolved in an organic solvent.
- EW concentrated emulsions
- the added solution of emulsifying agents is dispersed in a large amount of water. This presentation is less toxic and less flammable than emulsifiable concentrates. It is diluted in water at the time of use.
- Pesticides can be sold as powders or concentrates to be diluted with water, aerosol, granules or bait.
- They are applied in different ways; they may be sprayed from an aircraft or a tractor-drawn spray, dissolved in irrigation water, buried in the ground, scattered in pellets or pellets on the ground near the plants, applied as a treatment of seeds, inserted into the collar of cattle or presented in the form of baits.
- the pesticide active ingredient is generally not used pure: in the context of the present invention, it is associated with a bait product, the carrier, advantageously a flour such as, for example, wheat or corn flour, and more especially durum wheat flour.
- a flour such as, for example, wheat or corn flour, and more especially durum wheat flour.
- baits based on active course preferably pyrethrum, particularly those in the form of granules, are not known. Since pyrethrins are contact-acting compounds, and not vapor, they are usually used in liquid formulations. They are not used in bait or bait granule formulation, because applied conventionally, that is to say in the bottom of the seedling line or on the surface, their effect remains very localized and very limited.
- this formulation has many advantages, among which in particular, the active ingredient being integrated in the bait because of its method of preparation including an intimate mixing phase of the active ingredient and the support, its life is extended by in relation to a conventional granule wherein the active material is only adsorbed on the surface of said granule.
- the efficacy of the insecticide is then improved for an equivalent dose of active material, since its degradation is delayed because of the protection induced by the intimate mixture with the support.
- the Applicant to develop a new bait that may include an insecticidal active ingredient and a carrier, said bait is advantageously in the form of a granule (granule-bait). It is therefore an object of the present invention to provide a new insecticide bait, as well as its method of preparation and its method of application. Particularly according to the invention the bait may be in the form of a granule, this form being related to the particular mode of preparation that can be implemented to obtain the bait. Even more advantageously, the active ingredient of the bait according to the invention may be pyrethrum.
- pyrethrum refers to pyrethrum per se, pyrethrins and / or pyrethroids, whether natural or synthetic, and all their isomers or mixtures of isomers. But the invention as will be seen later relates to a bait whose active ingredient can be an insecticidal compound, preferably pyrethrum.
- Pyrethrum, or pyrethrum of Dalmatia is a perennial herb of the family Asteraceae (Compounds). It is a species native to southeastern Europe (Croatia, Montenegro, Bulgaria). It is a perennial plant 40 to 60 cm high, growing in tufts with many stems each carrying a terminal capitulum. It has been widely spread by culture, especially in Europe (Italy, Spain), Japan, North Africa, Kenya, Philippine. This plant is grown for its flowers from which an insecticidal powder is drawn.
- pyrethrum per se refers to the powder made of dried chrysanthemum flowers while the term “pyrethrin (s)” refers to the six insecticidal compounds naturally contained in this powder and well known to those skilled in the art. These six pyrethrins make up 0.9 to 1.3% of the dried flowers.
- pyrethrins Commercially, we generally try to purify pyrethrins. After a first extraction, refining to remove resins, waxes and allergens is performed. The extract is then used in the preparation of various insecticide products. This complex industrial process optimizes product efficiency. Additives can be added to increase the effectiveness of pyrethrum, or surfactants, or antioxidants.
- Pyrethroids are one of the few families of insecticidal compounds whose use is still allowed on the market, especially to protect seeds.
- Synthetic pyrethroids are so-called "third generation” insecticides, they are derived from natural pyrethrins, seeking to increase their toxicity and photostability. Endowed with a considerable toxicity and acting by contact, they almost instantaneously kill insects by neurotoxic shock effect, allowing to use them at very reduced doses (10 to 40 g of active ingredient per ha). They kill the insect by blocking the functioning of sodium channels essential for the transmission of nerve impulses.
- Examples of synthetic pyrethroids are: acrinathrin, bifenthrin, bioresmethrin, alphametrine, deltamethrin, depallethrin, etofenprox, fenpropathrin, cypermethrin, fenvalerate, esfenvalerate, cyfluthrin, betacyfluthrin , betacypermethrin, tralomethrin, fluvalinate, tau-fluvalinate, permethrin, lambda-cyhalothrin, flucythrinate, tefluthrin, zetacypermethrin.
- the invention relates to a solid insecticide in the form of bait comprising at least one active ingredient and a carrier.
- the bait may be in the form of granules. We can then speak of granule-bait.
- the active ingredient may be chosen from pyrethrum, neonicotinoids (for example thiamethoxam, clothianidin), chloronicotinils (for example acetamiprid, imidacloprid, thiacloprid), spinosoids (for example spinosad), pyridine-azomethrins (for example pyrimetrazine), pyridine-carboxamide (for example flonicamid), azadirectines, said compounds which may be natural or synthetic.
- the invention is also directed to all isomers or mixtures of isomers of said compounds.
- the active ingredient may be chosen from pyrethrum (Persian pyrethrum, pyrethrins and / or pyrethroids).
- the bait according to the invention may comprise as active ingredient, one of the above-mentioned compounds, alone, or any mixture thereof.
- the bait may also comprise, independently or simultaneously, pyrethrum per se and / or one or more pyrethrins and / or one or more pyrethroids.
- the bait may comprise, in addition to pyrethrum, one or more other pesticidal compounds.
- the synthetic pyrethroids may be chosen from acrinathrine, bifenthrin, bioresmethrin, alphametrine, deltamethrin, depallethrin, etofenprox, fenpropathrin, cypermethrin, fenvalerate, esfenvalerate, cyfluthrin, betacyfluthrin, betacypermethrin, tralomethrin, fluvalinate, tau-fluvalinate, permethrin, lambda-cyhalothrin, flucythrinate, tefluthrin, zetacypermethrin.
- the bait may advantageously comprise cypermethrin and / or natural pyrethrum.
- the support may be any support usually used for the preparation of baits (for example wheat flour, durum wheat flour, corn flour).
- the support may be wheat flour or bran flour or durum wheat flour or corn flour.
- the bait may comprise an active material in a proportion of between 2 to 12 grams of active ingredient per kilogram of composition, preferably between 6 and 10 g / kg, and very preferably between 7 and 9 g / kg.
- the bait may comprise a support in a proportion of between 800 and 998 g per kilogram of composition, preferably between 900 and 990 g / kg, and very preferably between 975 and 985 g / kg.
- the bait may have a diameter of between 0.5 and 3 mm, preferably between 1 and 2 mm, and very preferably a diameter of 1.6 mm.
- the apparent density of the baits is important because it conditions the good spreading of these.
- the baits may have an apparent density of between 0.40 and 1, preferably between 0.60 and 0.90.
- the bait according to the invention is small in comparison with products of the same type, which makes it possible to have a large number of grains per gram.
- the product is well distributed in the soil which increases its efficiency since the probability of contact between the granule and the pest is increased.
- the bait may have a number of grains per gram between 250 and 600, preferably between 300 and 450.
- the application rate of the baits can vary depending on the compound used.
- the bait can be used at a dose ranging from 2 to 20 kg / ha, preferably from 9 to 15 kg / ha, and very preferably from 12 kg / ha.
- the bait according to the invention may further comprise any other compound usually used in this industry (anti-mold agents, bittering agents, repellents, lubricating agents, palatability agents, etc.) . It is also possible to add to the bait according to the invention other adjuvants such as a bittering agent, for example denatonium benzoate or an olfactory repelling agent (in order to avoid ingestion of the granules by animals).
- a bittering agent for example denatonium benzoate or an olfactory repelling agent (in order to avoid ingestion of the granules by animals).
- the bait according to the invention may further comprise a dye that the skilled person will choose according to its constraints among the dyes usually used.
- the Hostaperm Blue B2G-KR from Clariant, which is a blue dye advantageously used because the birds do not distinguish very badly this color which makes it possible to avoid that they are too much attracted by the bait.
- the amounts of additional adjuvants added to the composition of the bait according to the invention are conventional in the field considered and the skilled person will have no trouble adjusting them according to the constraints he may encounter.
- Another object of the invention is the method of manufacturing the bait. Indeed to obtain the best possible results in terms of efficiency with the bait according to the invention, it is important that the granules are perfectly calibrated and therefore very uniform in size. When this criterion is satisfied, it facilitates the application of the bait to the ground (on the surface or at depth) and allows better control of the applied dose. However, the skilled person clearly understands that this criterion, important as it is, is not limiting.
- another subject of the invention is a process for manufacturing a bait comprising at least one active material and a support in which, in a first step, a premix of the active material is constituted with an absorption charge; in a second step, the extrudate comprising the active ingredient is prepared with the premix obtained in step 1; in a third step, said paste obtained in step 2 is extruded and cut to obtain the bait in the desired granule form; in a fourth step, the granules obtained in step 3 are dried.
- step 4 it is possible to provide a fifth step during which the dry granules obtained in step 4 are cooled.
- step 5 it is also possible to provide a sixth step during which the cooled granules obtained in step 5 are lubricated. Even more advantageously, it is also possible to provide a seventh step of sieving the granules.
- step 1 is intended to move the active ingredient from the physical state in which it is in the raw state, to the state of powder to facilitate its implementation during the steps following of the process.
- acties materials, especially pyrethrum are at room temperature in a resinoid or liquid state may be compatible with easy use.
- step 1 of the manufacturing method according to the invention a premix comprising active material in an amount in the pure state of between 25 and 75%, preferably between 45 and 55%, advantageously equal to 50% by weight, is obtained. weight of the total weight of the premix.
- step 2 of the process of manufacturing the bait is intended to obtain the most homogeneous powder possible.
- step 2 of the process may be subdivided into 3 sub-steps, namely a sub-step 2a) for preparing a solid mixture comprising the premix obtained in step 1 and the other ingredients entering in the final composition of the bait according to the invention, including in particular the support; a sub-step 2b) of moistening the solid mixture obtained in sub-step 2a); a sub-step 2c) of kneading of the product obtained in step 2b) to obtain the dough to be extruded in step 3 of the method of manufacturing the bait according to the invention.
- the solid mixture of sub-step 2a) can be made by any of the methods usually used.
- a L ⁇ dige® type mixer or, by extension, any coulter mixer so as to obtain a homogeneous powder.
- a ribbon mixer may also be used.
- step 2b) aims to prepare a paste having a consistency that will subsequently work by extrusion.
- This step requires the use of a fast mixer in which the powder obtained in sub-step 2a) is mixed and homogenized with a known and controlled flow of humidifying agent.
- said humidifying agent may be water or steam, advantageously water.
- the humidifying agent when the humidifying agent is steam, it can be introduced directly during step 3 of the process, during the transport of the paste to be extruded to the extrusion grid.
- the substeps of step 2 of the process are carried out at one time during step 3.
- the added humidifying agent may be heated from ambient temperature to 90 ° C., and preferably to a temperature of between 30 and 60 ° C.
- the amount of humidifying agent to be added to the mixture will have to be adjusted according to the water supplied by the raw materials (the flour in particular) and climatic conditions (a high humidity may have an impact on the kneading process ) so that the total amount of water contained in the extrusion paste obtained at the end of step 2 of the process for manufacturing the bait according to the invention varies between 25 and
- the residence time of the powder in the fast mixer must just allow to incorporate the water to the solid mixture obtained after the sub-step 2a) before moving to the sub-step 2c) of mixing. In this respect it must be short.
- the residence time of the powder in the mixer is short or very short. It can be between 30 seconds and 2 minutes, and preferably equal to 1 minute.
- certain low-content adjuvants such as the preservative or the bittering agent, may be incorporated into the dough after prior dilution with water. This helps to promote their homogeneous distribution in the dough.
- step 2c) is the most important of the process since it makes it possible to obtain a product that can be properly extruded.
- the water added in the form of the humidifying agent in the sub-step 2b) will be thoroughly mixed with the solid mixture obtained in the sub-step 2a) and thus be incorporated into the flour.
- the absorption charge may be silica, bentonites or kaolin, preferably silica.
- This step can be carried out in a kneader, advantageously in a kneader having two stirring arms such as those of the brand Clextral (formerly AFREM).
- the mechanical energy added to the heat generated by the shear and the added water allow to gelatinize the starch and the proteins contained in the wheat flour and to obtain the point of paste.
- the mixing time is an important fact of the process: if it is too short, the dough point can not be reached, and it will then quickly plug the extrusion grid; if it is too long, the dough will be too plastic, creating preferential passages through the extrusion grid, which will have the effect of generating heterogeneous granules in size.
- the rotational speed of the stirring shafts may be between 50 and 70 rpm (rotations per minute), preferably equal to 60 rpm.
- the residence time can be between 10 and 60 minutes, preferably between 15 and 45 minutes.
- step 3 the plastic paste obtained in step 2 is transported via an endless screw, called the compression screw, to the extrusion head, at the exit of which is the extrusion grid through which the dough is pushed.
- the compression screw is housed in a futon.
- the rise in pressure is necessary to complete the passage in the viscoelastic phase.
- said barrel may be cooled to a temperature between 20 and 30 c C preferably at 25 ° C;
- the core of the screw which has a variable diameter, allows an increase in pressure as the dough progresses, this due to the decrease in volume between the turns of the screw.
- the extrusion pressure is all the more important as it will define the structure of the granule, and therefore its physical and ballistic properties.
- the extrusion pressure may be between 20 and 120 bar, preferably between 40 and 70 bar.
- the extrusion can be carried out by means of any extruder usually known provided that it allows to vary the previously described elements. In this respect we can mention the extruder range Clextral (formerly AFREM).
- a drawing may be used at the screw outlet to allow a better distribution of the paste at the extrusion head inlet.
- This tréfilette can be for example a system of blades that cut the dough to homogenize its distribution.
- the extrusion head may comprise an empty space at the outlet of the screw before the extrusion grid.
- the extrusion head may have a double envelope. It can also be heated to promote the drawing of the dough, that is to say the passage of the dough through the holes of the extrusion grid.
- the extrusion head may be preheated to a temperature between 30 and 40 0 C, preferably at 35 ° C. In fact the extrusion head must be hotter than it was.
- the extrusion grid (or mold) consists of holes (or dies) of diameter that can vary from 0.5 to 3 mm, preferably from 1 to 2 mm, and very preferably equal to 1, 6 mm. The diameter of the holes defines the diameter of the granules.
- the extrusion grid may be any material usually used for this type of device.
- it may be bronze, but may also be equipped with Teflon® or Arnite® inserts.
- the internal surface of the holes may be made of Teflon® or Arnite® to promote the passage of the paste through the holes (tréfilation) and promote the cohesion of the granules, which will have the effect of limiting the generation dust later, during the particular drying step. By this step the granules are smoothed. The friction induced by the passage of the dough through the mold will allow heating of the mold to reach the desired working temperature.
- the extrusion grid may also be equipped with a pressure distribution plate which will provide a homogeneous profile of drawing. Indeed, the speed of drawing is usually lower on the edges of the mold because of the friction, which gives a heterogeneous profile of tréfilation.
- Said pressure distribution plate can be defined according to the diameter of the mold, the flow rate and the nature of the product.
- a coarse filter can also be positioned above the distribution plate in order to stop the agglomerates and to avoid clogging of the dies.
- the extruded paste which leaves in the form of long vermicelli can then be cut by blades using for example a multi-blade knife, which may for example comprise from 2 to 8 blades. Said knife may be placed at the gate exit, advantageously flush with the gate.
- the desired length of the granules can be obtained by adjusting the speed of rotation of the knives.
- the length of the granules may be between 0.5 and 3 mm, preferably between 1 and 2 mm.
- the granules obtained in step 3 can be dried.
- This step is also essential in the preparation of the granules. Indeed, the kinetics of drying must be defined so as to obtain granules: sufficiently hard on the surface to prevent them from disintegrating in the rain; sufficiently soft in depth so that they remain appetizing for pests, and easy to ingest.
- the wet granules pass through a first dryer whose role is surface drying in order to avoid agglomeration of the wet granules with each other.
- the granules thus "crusted” then pass through a second dryer whose action is in the viscoelastic phase (existence of a glass transition temperature of the starch “crosslinked” in the protein network of the flour).
- the granules are close to the glass transition they will cross in a third dryer where the kinetics of water extraction is slowed down.
- Each dryer has eight different zones in which temperature, humidity and residence time are adjusted and controlled to manage the drying kinetics.
- Dryer 1 temperature between 40 and 80 0 C - time between 3 and 5 min;
- Dryer 2 temperature between 40 and 80 0 C - time between
- the final moisture of the granules is an important parameter.
- the pellets will be more friable and may break more easily during transport or application.
- the humidity of the granules has an impact on their density, and therefore on the application rate per hectare (a wetter granule will be heavier, therefore at equal density a smaller number of granules will be applied, ie a lower dose of active ingredient per hectare). It is therefore important that it is well controlled.
- the moisture of the granules may be between 8 and 15%, preferably between 10 and 15%, and very preferably between 12.5 and 14%.
- Humidity because of its impact on the actual density of the granules, also has an impact on their ballistic properties and thus on the homogeneity of the application.
- the overall method of implementation also ensures the integrity of the granules over a long period: the extrusion and drying thus implemented give them good cohesion and better resistance to moisture.
- the cooling temperature may be the ambient temperature and the residence time in the cooler may be between 3 and 5 minutes.
- lubricant can be any oil that has no impact on the attractiveness of the granules.
- paraffin oil or diethyl phthalate may be mentioned by way of example. This precaution offers users a better user experience and greater security.
- the granules can also be lubricated. It is then a question of spraying paraffin oil on the granules.
- Other lubricating products may be used such as diethyl phthalate or any other oil that has no impact on the attractiveness of the granules.
- the bait according to the invention can be applied to crops by any means and in any form of spreading known to those skilled in the art.
- the inventors have demonstrated that by applying the baits according to the invention, particularly pyrethrum baits in burial, they significantly increased the effectiveness of these for the protection of seeds.
- the use of baits according to the invention in landfill provides a barrier around the seed preventing pests from reaching it.
- the active ingredient is in the best conditions because it is close to the seed and can prevent its biochemical target from reaching the seed. For this purpose we increase their chances of contact with the target pest through the formation of this barrier.
- the Applicant has indeed found that the effect of a bait according to the invention, particularly a pyrethrum bait, was greatly increased when it is applied to burial over the entire width of the seed line in which the seed is placed, be it a furrow culture or a ridge crop.
- the baits are a barrier to soil insects, which can less easily attack and denature the seed, as well as the buried part of the plant, once the seed has germinated and the seedling has begun to grow.
- a higher effect of the active ingredient used, particularly pyrethrum derivatives is thus obtained by this mode of use, in comparison with a conventional means of application, particularly when the insecticides are applied in liquid form.
- baits because they are not captured by soil colloids (such as clay), presents less environmental risks. Indeed, the products used in liquid form for example, they can be captured by these colloids soil. Then there is a risk of runoff in heavy rain that takes the colloids and therefore the product to the rivers. In addition, their sequestration makes them less bio-available (contact between the product and the pest obstructed by the layers of the colloid). Which is not the case of baits.
- soil colloids such as clay
- bait pyrethrum over the entire width of the line of the seedling is advantageous because the product, present in the soil all around the seed, can have an effect all around the seed.
- the effectiveness of the products is increased compared to liquid formulations.
- Another advantage is that it can thus reduce the doses of the product applied, and consequently reduce their toxicity, both for the environment and for the person who applies the product.
- the inventors propose the use in burying in the ground of a bait comprising at least one active ingredient, advantageously pyrethrum and a support, said bait being able to be in the form of granules.
- the invention also relates to the use in the ground of a bait comprising at least one active material, preferably pyrethrum, and a suppport.
- the invention relates to the aforementioned use, in a method of protecting a furrow culture against soil insects which comprises the following steps: a) furrowing into the soil; b) the seed is placed in the soil in the bottom of the seedling line formed by the furrow; (c) the bait is then spread over the entire width of the seed line in which the seed has been placed; and d) closing the furrow with the soil prepared in step c).
- the second and third steps of the process may be reversed.
- the second and third steps can be simultaneous.
- the bait is first deposited, then the seed.
- an excavation in the form of a half cylinder is formed in the ground.
- Application of the bait on the entire surface of the excavation, before or after or at the time of removal of the seed allows, when closing the furrow, to create an insecticidal barrier all around the seed, that - it is embedded in a network of insecticide, which protects it from soil insects that can not reach it.
- the invention is also applicable in billon crops.
- the bait according to the invention advantageously a bait based on pyrethrum is applied to a surface of the soil greater than the surface occupied by the seed, before or after or at the time of removal of the seed, and when the ridge is formed, the seed is enclosed in soil mixed with insecticide bait all around it, which effectively protects it against soil pests.
- the seed is thus completely surrounded by the formulation comprising the active ingredient.
- the invention also relates to a method for protecting a billon crop against soil insects which comprises the following steps: a) placing the seed on the ground, b) then depositing the bait comprising at least one active ingredient , advantageously pyrethrum, on a surface equivalent to the largest circumference occupied by the seed, c) forming a ridge by covering the seed placed in a) with the earth prepared in the previous step.
- the first and second steps of the logging process may be reversed.
- the first and the second step of the cultivation method in billon can be simultaneous.
- the bait is first deposited, then the seed.
- the baits are well distributed in the seedling line over the entire profile of the furrow. Thus during the closing of the furrow or the creation of the ridge, the active compound is distributed all around the seed. The seed is thus protected against insects from the soil. These are more difficult to reach the seed.
- the use of baits according to the invention burial according to the invention is more effective closer to the seed, without being on the seed.
- the method according to the invention therefore optimizes the protection of the seed without having the disadvantages of the coated seeds.
- the insecticide barrier it kills a significant amount of soil insects wanting to reach the seed. Due to this increased efficacy of the insecticide compared to the usual modes of application, the method is particularly advantageous in that it allows the use of lower doses of active product.
- the process according to the invention protects the seed, but also the parts buried in the soil of the plant resulting from the germination of the seed, - A yield gain is thus obtained for the farmer because fewer seeds are damaged.
- the method according to the invention is, moreover, easy and quick to implement.
- the insecticide dispersion is also limited in the environment.
- the method of application of the insecticide does not cause any propagation or pollution on the soil surface, which avoids contaminating animals other than animals living in the soil.
- the process according to the invention can be used for any agricultural crop (cereals, market garden plants, horticultural plants, etc.). It is understood that the seeds and then the plant resulting from the seed, are protected by the process according to the invention.
- the use is for corn, rapeseed, sorghum, sunflower, potato, beet, carrot, cereal, cabbage, bean, melon and tomato crops. ornamental crops or tobacco. Even more preferably, the invention applies to corn.
- furrow we mean a trench dug in the ground.
- the characteristics of the furrow are those usually used in agriculture, and vary according to the seeds used, which the farmer will be able to adapt.
- the insecticides regularly to a depth of at least greater than 1.5 cm, preferably greater than 2 cm.
- the width of the spreading surface of the baits according to the invention, advantageously pyrethrum-based baits in the furrow or in the ridge must be at least greater than the largest circumference occupied by the seed.
- the method according to the invention can be used against any insect or soil parasites as long as it is sensitive to the active ingredient used for the preparation of the bait.
- any insect or soil parasites for example: wireworms, cutworms, cutworms, moths, scutigérelles, cranes, grapevines, flies such as seedling maggots and onion maggots, corn rootworm.
- the invention is directed to the control of wireworms.
- solid formulation applicators or powder applicators can be used.
- applicator of solid formulations can be used granule spreaders or small granule dispersing equipments handled by hand as push rotary spreaders to treat smaller areas.
- powder applicator is meant, for example, manual dusting devices or tractor dusting machines.
- an application with a diffuser will be carried out, the diffuser being able to be installed at the end of the output tubes of a microgranulator.
- said diffuser will be the QUEUE-DE-CARPE DXP TM diffuser of the Applicant.
- Said diffuser can be adapted to the end of the microgranulator outlet tubes, particularly on disk seed drills, also on coulter seed drills with the aid of an installation kit, characterized in that it comprises a cylindrical body or frustoconical, hollow, open at both ends, one of said ends for fixing said diffuser to said output tubes of the microgranulator, and the other end being open on an inclined plane, of any shape, preferably of circular or oval shape, integral with said diffuser and having with said diffuser an angle of between 35 ° and 55 °, preferably between 40 ° and 50 °.
- said diffuser may further comprise a means of attachment to the output tube of the microgranulator.
- said fixing means may be a screw positioned perpendicularly to the central axis of the cylinder or truncated cone forming said diffuser and passing through the wall of said cylinder or truncated cone.
- a diffuser can allow precise positioning of granules 7 or granules of insecticide over the entire width of the seed line.
- the burying uses of baits according to the invention in the soil may be carried out with this diffuser, preferably a CARP DXP TM QUEUE Diffuser.
- the subject of the invention is also a method for treating crops at the time of sowing, characterized in that a bait comprising at least one active material, advantageously pyrethrum, is advantageously used in the ground, preferably in one of the uses according to the invention.
- the invention also relates to the use of a diffuser as described above for burying solid insecticide baits according to the invention.
- the subject of the invention is also a method for treating crops at the time of sowing, characterized in that a bait according to the invention is used in the soil in the landfill, preferably according to one of the uses described above.
- the mixture is first made of 53.76% of technical Cypermethrin (Bayer Bilag (India)) (guaranteed minimum content of 930 g / kg) and 46.24% of precipitated amorphous silica (Tixosil 38® (RHODIA)) .
- Example 2 Control of Wireworms with Cypermethrin Bait The objective of this study is to evaluate the effectiveness of cypermethrin-based bait against wireworms.
- the trial was set up in LARREULE (64), a site characterized by a strong presence of wireworms (almost exclusive species Agriotes sordidus).
- Seeding was carried out on 10/201707 at a conventional depth (3-4 cm). Targeted seeding density is 78000 plants / ha; the variety used is RIXXER® (R.A.G.T. Seeds).
- the soil is loam-clay (touyas type) with a high level of organic matter (greater than 4%).
- the site is not irrigated.
- the meteorological conditions are particularly favorable for the surface activity of wireworms: temperatures are regularly above seasonal norms and regular, heavy rains during the first three months of the corn cycle promote the maintenance of moisture at the soil surface. Factors studied and modes of application Seven modalities were put to the test. Compared to a microgranular reference carbamate (CURATER®), to a microgranular reference pyrethroid
- Control E2 CURATER® (50g active substance / kg) at 12 kg PC / ha (seed line
- E3 FORCE 1.5 G® (15g active substance / kg) at 11.7 kg PF / ha (RDS);
- E4 Cypermethrin bait (composition of Example 1 at 200 gr / g) at 12 kg
- Cypermethrin bait 2 composition of Example 1 at 420 gr / g) at 12 kg PF / ha (RDS) without diffuser;
- Cypermethrin baits contain 8g of active substance per kg of bait.
- Seeding is carried out with a NODET drill with 3 rows spaced 0.80 m apart.
- the elementary parcel comprises 3 rows over 20 m.
- the experiment implements a block device with 4 repetitions.
- the distribution of parcels is done, within each block, randomly using the SILENA software.
- the central row of 20 m is the subject of observations.
- the weeding and fertilization of the plot are done by the farmer in his usual working conditions (pre-emergence weed control and nitrogen supply in localized inter-row at the 5-6 leaf stage).
- Table n ° 2 Influence of the attacks on the rate of plants with ears and on the yield.
- the granular insecticide baits at the dose of 12 kg PF / ha located by means of a diffuser show an interesting protection potential.
- Seeding was carried out on 10/01/07 at a conventional depth (3-4 cm). The seeding density retained is 78000 vines / ha; the variety used is RIXXER®. The soil is loam-clay (touyas type) with a high level of organic matter (greater than 4%).
- the plot is not irrigated.
- the meteorological conditions are particularly favorable for the surface activity of wireworms: temperatures are regularly above seasonal norms and regular, heavy rains during the first three months of the maize cycle favor the maintenance of moisture at the soil surface.
- T4 cypermethrin bait 1 (200 gr / g) at 6 kg PF / ha (RDS) with T5 diffuser: cypermethrin bait 1 (200 gr / g) at 9 kg PF / ha (RDS) with T6 diffuser: cypermethrin bait 1 ( 200 gr / g) at 12 kg PF / ha (RDS) with diffuser
- T7 cypermethrin bait 2 (420 gr / g) at 6 kg PF / ha (RDS) with T8 diffuser: cypermethrin bait 2 (420 gr / g) at 9 kg PF / ha (RDS) with T9 diffuser: cypermethrin bait 2 ( 420 gr / g) at 12 kg PF / ha (RDS) with diffuser
- Cypermethrin baits contain 8g of active substance / kg.
- Seeding is carried out with a NODET drill with 3 rows spaced 0.80 m apart.
- the elementary parcel includes 3 rows over 20m.
- the experiment uses a block device with 4 repetitions.
- the distribution of parcels is done, within each block, randomly using the SILENA software.
- the central row of 20 m is the subject of observations.
- the weeding and fertilization of the plot are done by the farmer in his usual working conditions (pre-emergence weed control and nitrogen supply in localized inter-row at the 5-6 leaf stage).
- Bait 1 and 2 have very similar responses for the same dose.
- the 6 kg doses (T4, T7) have attack rates of 23.7% and 17.9% respectively for baits 1 and 2.
- results indicate: correct results with insecticides-baits 1 and 2 in granular form applied with diffuser at doses of 9 and 12 kg PF / ha. inferior results with both baits at 6 kg PF / ha even if statistically these doses are in the same group as the 2 previous doses.
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Insects & Arthropods (AREA)
- Food Science & Technology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Catching Or Destruction (AREA)
Abstract
Description
Claims
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09784229A EP2291083A2 (fr) | 2008-06-25 | 2009-06-24 | Granule-appat procede de fabrication |
| AU2009272604A AU2009272604A1 (en) | 2008-06-25 | 2009-06-24 | Bait granule production method |
| CA2728177A CA2728177A1 (fr) | 2008-06-25 | 2009-06-24 | Granule-appat et procede de fabrication |
| BRPI0914643-1A BRPI0914643A2 (pt) | 2008-06-25 | 2009-06-24 | Isca inseticida sólida sob a forma de granulados, processo de fabricação de uma isca e utilização de uma isca |
| US13/001,518 US20110239917A1 (en) | 2008-06-25 | 2009-06-24 | Bait granule production method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0803577A FR2932954B1 (fr) | 2008-06-25 | 2008-06-25 | Procede de lutte contre les insectes du sol |
| FR08/03577 | 2008-06-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2010007240A2 true WO2010007240A2 (fr) | 2010-01-21 |
| WO2010007240A3 WO2010007240A3 (fr) | 2011-07-21 |
Family
ID=40290719
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FR2009/000770 Ceased WO2010007239A2 (fr) | 2008-06-25 | 2009-06-24 | Procédé de lutte contre les insectes du sol |
| PCT/FR2009/000771 Ceased WO2010007240A2 (fr) | 2008-06-25 | 2009-06-24 | Granule-appat procede de fabrication |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FR2009/000770 Ceased WO2010007239A2 (fr) | 2008-06-25 | 2009-06-24 | Procédé de lutte contre les insectes du sol |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US20110239917A1 (fr) |
| EP (2) | EP2291082A2 (fr) |
| AU (2) | AU2009272603A1 (fr) |
| BR (2) | BRPI0914642A2 (fr) |
| CA (2) | CA2728174A1 (fr) |
| FR (1) | FR2932954B1 (fr) |
| WO (2) | WO2010007239A2 (fr) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2979186A1 (fr) * | 2011-08-25 | 2013-03-01 | Sbm Dev | Procede de lutte contre les insectes du sol |
| FR2979187A1 (fr) * | 2011-08-25 | 2013-03-01 | Sbm Dev | Microgranule insecticide a base de pyrethre et d'au moins un autre compose actif et utilisations |
| FR2979185A1 (fr) * | 2011-08-25 | 2013-03-01 | Sbm Dev | Procede de lutte contre les insectes du sol |
| WO2017129496A1 (fr) | 2016-01-29 | 2017-08-03 | S.I.P.C.A.M.Societa' Italiana Prodotti Chimici E Per L'agricoltura Milano S.P.A. | Compositions granulaires ayant une activité insecticide |
| KR102577637B1 (ko) * | 2023-03-28 | 2023-09-13 | (주)국보싸이언스 | 수중 발포 분산형 살충 조성물 |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102228052B (zh) * | 2011-04-11 | 2013-10-02 | 贵州省生物技术研究所 | 一种马铃薯微型薯种衣剂及制备方法 |
| FR2979184B1 (fr) | 2011-08-25 | 2015-04-10 | Sbm Dev | Procede de lutte contre les insectes du sol |
| HUP1300436A2 (en) | 2012-07-20 | 2014-02-28 | Sumitomo Chemical Co | Method for reducing damage by harmful organisms in corn cultivation |
| JP2014141454A (ja) | 2012-12-27 | 2014-08-07 | Sumitomo Chemical Co Ltd | トウモロコシ栽培における有害生物の被害軽減方法 |
| EP2893795B1 (fr) | 2014-01-14 | 2018-11-21 | Livio Sut | Distributeuer pour matériaux granulaires ou microgranulaires sur terre |
| WO2016018155A1 (fr) * | 2014-08-01 | 2016-02-04 | Vadaflor B.V. | Billes de carbonate de calcium comme support d'agents phytoprotecteurs et/ou produits nutritionnels |
| CN106719636B (zh) * | 2017-01-13 | 2022-03-18 | 北京林业大学 | 一种新型农药牛血清白蛋白-噻虫啉纳米粒子的制备方法 |
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| US363606A (en) * | 1887-05-24 | Drill-tube | ||
| US1934490A (en) * | 1930-04-23 | 1933-11-07 | Dempster Mill Mfg Company | Combination seed scattering and shovel back device |
| DE2840992A1 (de) * | 1978-09-21 | 1980-05-29 | Bayer Ag | Mittel gegen bodeninsekten |
| CA1091101A (fr) * | 1978-10-25 | 1980-12-09 | Philippe F. Denis | Dispositif d'ensemencement a deflecteur d'air, fixe par boulonnage |
| US4370346A (en) * | 1979-12-21 | 1983-01-25 | Imperial Chemical Industries Plc | Halogenated esters |
| US4373455A (en) * | 1981-06-08 | 1983-02-15 | Friggstad Manufacturing Ltd. | Seed boot assembly |
| DE3270859D1 (en) * | 1981-08-31 | 1986-06-05 | Shell Int Research | Protection of crops against soil pests employing an alkylbenzyl cyclopropane carboxylate, novel cyclopropane carboxylates, and compositions containing them |
| US4778822A (en) * | 1982-05-21 | 1988-10-18 | Imperial Chemical Industries Plc | Insecticidally active ester |
| HU190421B (en) * | 1982-10-27 | 1986-09-29 | Chinoin Gyogyszer Es Vegyeszeti Termekek Gyara Rt,Hu | Composition against nematodes and soil insect pests, and process for producing the composition |
| US4624070A (en) * | 1983-02-01 | 1986-11-25 | Query Grady W | Method and composition for pest control using anesthetic and insecticide |
| US4686914A (en) * | 1983-09-09 | 1987-08-18 | Versatile Corporation | Seed planter |
| US4758590A (en) * | 1984-03-14 | 1988-07-19 | Fmc Corporation | Method for control of soil-borne insects |
| US5277905A (en) * | 1991-01-16 | 1994-01-11 | Mycogen Corporation | Coleopteran-active bacillus thuringiensis isolate |
| US5271343A (en) * | 1992-04-06 | 1993-12-21 | House John L | Planter insecticide tube alignment bracket |
| ATE138243T1 (de) * | 1992-06-23 | 1996-06-15 | Rhone Poulenc Agrochimie | Granulierte pestizide zusammensetzungen und verfahren zur deren herstellung |
| CA2152808C (fr) * | 1993-01-04 | 2004-07-13 | Kang-Chi Lin | Compositions pesticides granulaires |
| JPH06239712A (ja) * | 1993-02-19 | 1994-08-30 | Sumitomo Chem Co Ltd | 土壌害虫防除剤 |
| US6082275A (en) * | 1995-10-30 | 2000-07-04 | Schaffert; Paul E. | Extension for reducing seed bounce and associated attachment brackets |
| US6289829B1 (en) * | 1998-09-18 | 2001-09-18 | Aventis Cropscience S.A. | Planting apparatus with improved liquid pesticide delivery device and related method for delivering liquid pesticide |
| ATE271314T1 (de) * | 1998-12-22 | 2004-08-15 | Bayer Cropscience Sa | Verfahren zur schädlingsbekämpfung |
| FR2798042B1 (fr) * | 1999-09-07 | 2003-04-25 | Aventis Cropscience Sa | Compositions insecticides dont la matiere active est de type phenyl-pyrazole et procede de lutte contre les insectes du sol |
| AUPR709901A0 (en) * | 2001-08-17 | 2001-09-06 | Grotech Australia Pty Ltd | Edible pesticidal formulations |
| EP1816907A4 (fr) * | 2004-12-01 | 2008-06-11 | Fmc Corp | Procede de lutte contre les parasites du sol s'attaquant aux cultures transplantees |
-
2008
- 2008-06-25 FR FR0803577A patent/FR2932954B1/fr active Active
-
2009
- 2009-06-24 AU AU2009272603A patent/AU2009272603A1/en not_active Abandoned
- 2009-06-24 CA CA2728174A patent/CA2728174A1/fr not_active Abandoned
- 2009-06-24 WO PCT/FR2009/000770 patent/WO2010007239A2/fr not_active Ceased
- 2009-06-24 US US13/001,518 patent/US20110239917A1/en not_active Abandoned
- 2009-06-24 AU AU2009272604A patent/AU2009272604A1/en not_active Abandoned
- 2009-06-24 BR BRPI0914642-3A patent/BRPI0914642A2/pt not_active IP Right Cessation
- 2009-06-24 US US13/001,526 patent/US20110174898A1/en not_active Abandoned
- 2009-06-24 EP EP09784228A patent/EP2291082A2/fr not_active Withdrawn
- 2009-06-24 BR BRPI0914643-1A patent/BRPI0914643A2/pt not_active IP Right Cessation
- 2009-06-24 EP EP09784229A patent/EP2291083A2/fr not_active Withdrawn
- 2009-06-24 CA CA2728177A patent/CA2728177A1/fr not_active Abandoned
- 2009-06-24 WO PCT/FR2009/000771 patent/WO2010007240A2/fr not_active Ceased
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2979186A1 (fr) * | 2011-08-25 | 2013-03-01 | Sbm Dev | Procede de lutte contre les insectes du sol |
| FR2979187A1 (fr) * | 2011-08-25 | 2013-03-01 | Sbm Dev | Microgranule insecticide a base de pyrethre et d'au moins un autre compose actif et utilisations |
| FR2979185A1 (fr) * | 2011-08-25 | 2013-03-01 | Sbm Dev | Procede de lutte contre les insectes du sol |
| WO2017129496A1 (fr) | 2016-01-29 | 2017-08-03 | S.I.P.C.A.M.Societa' Italiana Prodotti Chimici E Per L'agricoltura Milano S.P.A. | Compositions granulaires ayant une activité insecticide |
| KR102577637B1 (ko) * | 2023-03-28 | 2023-09-13 | (주)국보싸이언스 | 수중 발포 분산형 살충 조성물 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20110174898A1 (en) | 2011-07-21 |
| BRPI0914642A2 (pt) | 2015-08-04 |
| CA2728177A1 (fr) | 2010-01-21 |
| EP2291082A2 (fr) | 2011-03-09 |
| BRPI0914643A2 (pt) | 2015-08-04 |
| CA2728174A1 (fr) | 2010-01-21 |
| AU2009272604A1 (en) | 2010-01-21 |
| WO2010007240A3 (fr) | 2011-07-21 |
| US20110239917A1 (en) | 2011-10-06 |
| AU2009272603A1 (en) | 2010-01-21 |
| EP2291083A2 (fr) | 2011-03-09 |
| FR2932954A1 (fr) | 2010-01-01 |
| FR2932954B1 (fr) | 2010-11-05 |
| WO2010007239A2 (fr) | 2010-01-21 |
| WO2010007239A3 (fr) | 2011-07-21 |
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