Title of Invention	NOVEL COATED GRANULES CONTAINING INSECTICIDE
Abstract	A novel insecticidal formulation in the form of coated granules containing 1 - (6-chloro-3-pyridinylmethyl)-N-nitroimidazolidin-2-ylideneamine as active ingredient and a process for preparation thereof has been described.

Full Text

FORM 2 THE PATENTS ACT 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION (See section 10; rule 13) 1. TITLE OF THE INVENTION: NOVEL COATED GRANULES CONTAINING INSECTICIDE 2. APPLICANT(S): (a) Name: Excel Crop Care Limited (b) Nationality: An Indian Company (c) Address: 184-87 S.V. Road, Jogeshwari (West), Mumbai 400 102, Maharashtra, India. 3. PREAMBLE TO THE DESCRIPTION The following complete specification particularly describes the invention and the manner in which it is to be performed. FIELD OF INVENTION This invention relates to a novel insecticidal formulation in the form of coated granules containing 1 - (6-chloro-3-pyridinylmethyl)-N-nitroimidazolidin-2-ylideneamine as active ingredient and a process for preparation thereof. The product of invention is non-dusty, free flowing, directly usable and with enhanced shelf-life. BACKGROUND AND PRIOR-ART l-(6-chloro-3-pyridin-3ylmethyl)-N-nitroimidazolidin-2-yldenamine, is powerful insecticide for control of sucking insects such as aphides, rice hoppers, termites, white flies, thrips, turf insects and some bettle species such as Colorado and potato beetle. It is widely used on soil, seed or foliar treatment of cereal, cotton, fruit, maize, potatos, rice, vegetables etc. Various formulations containing the said insecticide have been reported in the prior art. JP7242502 describes a composition prepared by melting or tableting a mixture of an agrochernical technical product, a substance such as paraffin wax and a water-insoluble mineral oil, and granulating. JP5221803 discloses an emulsifiable composition containing the active ingredient and sparingly water-soluble organic solvent along with other components. A gel-formulation for seed dressing has been disclosed in DE4417555. Formulation in form of a tablet or capsule for controlling insects of paddy field has been described in JP4279503, containing active ingredient, a surfactant, a foaming agent and a binder. US5783203 discloses a mixture of the said insecticide with a fertilizer and an adhesive. A composition of the said insecticide in form of a paste has been disclosed in DE19506095. The paste contains a pesticide or fungicide, an adjuvant, one or more excipients and water. A formulation in form of water surface floating granules containing the insecticide active ingredient, foamed perlite, foamed silas and cork, a water surface spreader like an acetylene-based surfactant, a silicone-based surfactant or a fluorine-based surfactant has been reported in JP8099803. Poisonous baits for controlling soil-inhabiting pests containing the said insecticide as active component has been claimed in EP648412 comprising active compounds for controlling soil-inhabiting pests and, as excipient, an artificial culture medium for mushrooms or the medium obtained after the culture thereof. A formulation in form of a tablet or capsule is described in JP5070304 which contains insecticidal component, a surfactant composed of anionic surfactant, nonionic surfactant or their mixture, a foaming agent and a binder such as CMC, dextrin, polyvinyl alcohol or lignin sulfonic acid salt. An insecticidal composition for use in paddy-field, comprising a solid carrier, insecticidal active ingredient, and a water-immiscible oil has been disclosed in EP0415568. JP2003252702 describes a method for producing granules containing the active ingredient wherein the agrochemical granule is produced through a mixing step, a kneading step and an extruding step. Use is made of a thermoplastic material and an inorganic diluting carrier in the preparation of the said granules. Wettable granules for agriculture comprising in addition to active ingredient, a surfactant composed of a combination of sodium lignosulfonate, a sodium polycarboxylate, a sodium polystyrenesulfonate and a sodium dialkylsulfosuccinate has been reported in JP2003292403. The formulation disintegrates under water and forms a suspension. A granular composition of the insecticide coated with a water-insoluble film material such as a silicon-based polymer wax has been reported in JP2003055106. US2003013612 discloses a method of producing lignin-based matrix microparticles for the controlled release of an agricultural active includes forming an emulsion of an organic solution in an aqueous solution, wherein the organic solution contains a lignin derivative and an agricultural active in a volatile organic solvent and the aqueous solution contains an emulsifier, and removing the organic solvent, thereby producing microparticles having a matrix comprising the lignin derivative within which the agricultural active is distributed. An emulsion containing active ingredient and two or more kinds of organic solvents and a surfactant, a combination of organic solvents having water absorption properties to be packed into the water-permeable plastic container is selected as described in JP2002370901. DE19601430 describes an adhesive layer for sustained release of the active ingredient to plants. One adhesive matrix layer containing the active substance is painted onto the plant at the application site in a desired pattern and consists of a brush-on adhesive polymer-based composition containing the active substance. A backing layer is then painted or sprayed onto the first layer. DE19624819 discloses rods or sticks for treating plants, consisting of an erodable structural substance produced from one or more matrix formers, agrochemical active ingredient, one or more penetration-enhancing substances, one or more abrasive solids and additives. A flowable composition is described in W09742815 comprising active compound, one or more signal substances selected from the group consisting of pheromones, kairomones and attractants, a UV absorber or a UV absorber mixture and one or more additives selected from the group consisting of viscosity-regulating thickeners, fillers, solvents and other formulation auxiliaries. A foaming agrochemical aerosol containing the active ingredient has been described in JP 9,295,902. JP9295903 discloses a granular agrochemical composition containing the active ingredient on a water-floating hollow carrier along with other adjuvants. JP9,291,002 describes a composition of the active ingredient and a vinyl acetate-based polymer such as a vinyl acetate resin. The composition is applied to a pruned cut surface or injected into a grafting treated part of a plant. DEI9622355 describes shaped bodies which release active substance for treating woody plants. The active substances are introduced into a cavity previously formed in the woody plant, their volume filling the volume of the cavity by between 10 and 95 %. The shaped bodies contain agrochemical active substances, water-insoluble polymers which can be treated thermoplastically, water-soluble polymers and optionally further auxiliary substances. A formulation comprising the pesticide compounded with biodegradable thermoplastic aliphatic polyester resin for controlled release has been given in EP0843963. A sustained release composition has been disclosed in WO03061383, which includes an absorbing carrier having 0.0005 PRG unit by weight of the biologically active substance adsorbed in 1000 unit by weight of a porous carrier, and a sustained release layer having a mixture of 0.05 PRG unit by weight of polysaccharide, 0.3 PRG unit by weight of inorganic alkali, and 0.25 PRG unit by weight of one or more release regulators made of either organic or inorganic acid selected from the group consisting of phosphorous acid, phosphoric acid, acetic acid and hydrochloric acid, the mixture coated on the surface of the adsorbing carrier. The invention described in WO03056921 relates to powder formulations, which consist of at least one agrochemical active ingredient, at least one biodegradable polyester containing hydroxyl groups, optionally blended with one or more additional biodegradable polymer(s), in addition to optional additives. Said formulations have a particle diameter of less than 125 mu m. The invention in WO03051116 provides a microencapsulated insecticide which is prepared by oil-in-water interfacial polymerization. An agrochemical granular formulation comprising hollow microballoons having a wall film of a thermoplastic polymer as a component of the granular formulation has been disclosed in JP10245303. W09819532 and W09819531 disclose an invention concerning the active-substance-containing moulded bodies which can be used as insecticides on outdoor or indoor plants,.based on thermoplastically processable biodegradable polymers, preferably polyesters, polyester amides, polyester urethanes and polyester urethane ureas. A composition comprising imidacloprid, synergist, penetrant, stabilizer, emulsifier and solvent has been disclosed in CN1212838. An invention disclosed in CNl196179 describes an imidacloprid smoking agent as insecticide for vegetable pests such as powdery hopper, aphid, thrips, etc. prepared from l-(hexachloro-3-pyridylmethyl)-N-nitro imidazolane-2-amine, 0,0-dimethyl-0-(2,2-dichloro) vinyl phosphate, oxidant, fuel and flame-retarding agent. Insecticide containing said active ingredient and light diesel oil for plant protection has been reported in CNl, 192,855. Agrochemical granules containing the active ingredient, a sodium ligninsulfonate, a polyoxyethylene-polyoxypropylene block copolymer-styryl- phenyl ether sodium sulfate, a carboxymethylcellulose sodium, and a carrier such as a mixture of bentonite and clay has been disclosed in JP2000143403. Formulation in pearl polymers consisting of a continuos solid polymeric phase, a liquid oil phase, at least one agrochemical active substance, at least one oil-soluble dispersant and optionally additives has been reported in WO0062611, wherein the content of agrochemical active substances ranges between 5 and 75 percent by weight. Microemulsion containing 1-15% of imidacloprid, 4-35% of emulsifying agent, 0.1-0.2% of synergistic agent, 5-30% of cosolvent and water has been claimed in CN1245644. 3% Imidacloprid emulsifiable solution made up by using imidaclorprid as main ingredient, and adding hypertonic agent, composite adjuvant and organic solvent in the tank through the processes of stirring and mixing has been reported in CN1242940. Wettable powder prepared from raw imidacloprid powder (1-15%), filler (60-90%), stabilizer (0.1-2%) and adjuvants (6-30%) has been reported in CN1246280. EP1063215 describes controlled release pesticide and fertilizer briquettes containing the active ingredient. DEI9947147 covers microcapsules comprising a polymer shell enclosing a mixture of a continuous solid polymer, a liquid oil phase 1-75 wt.% (based on the microcapsule weight) of agrochemical, oil-soluble dispersant(s); and optionally adjuvants. Microemulsion formulation is disclosed in CN1,299,594. Microencapsulation with polyurethanes and/or poly ureas is described in DE 10,117,784. Sustained release composition containing the active ingredient has been claimed in WO 02 49,430. A water dispersible composition of the active ingredient has been described in WO01 13,721. WO0168234 discloses a microcapsule suspension containing the active ingredient. A polymeric pest control sheet containing the active ingredient is disclosed in WO02 35,930. Microemulsifiable hydrophobic agrochemical concentrate is reported in WO 02 45,507. A formulation with organo-silicon additive for seed treatment is described in WO 02 58,454. A polymeric coating containing the active ingredient is also disclosed in EP 1,247,436. Wettable granular powder characterized by including agrochemical active ingredients, a ligninsulfonic acid salt, a polyoxyethylene alkyl ether sulfate and a water-soluble inorganic salt is disclosed in JP2002179506. WO 2003105584 describes a formulation wherein acrylonitrile-styrene copolymer was melted at 190°, kneaded with imidacloprid and, after cooling, the resin was pulverized to a particle diam, of -0.2-50 mm to obtain a controlled-release powder formulation. Slow-release pesticide granules containing active ingredient have been reported in JP 2004043370. A pesticide, hydrofobic substances (e.g. carnauba wax), a substance absorbing oil (e.g. starch, cellulose, etc.), and a carrier are mixed, kneaded, and extruded at temp, higher the coagulation temp, but less than the m.p. Pesticide capsules containing the active ingredient and their application method has been disclosed in JP 2004143081 wherein the capsules (outside diam. 0.7-10 mm, film thickness 0.005- to 0.1-fold the outside diam.) comprising biodegradable polymers, can be directly applied to the soil, and show delayed release of pesticide components after the spraying. The abovementioned formulations are complicated or pose several problems to the user and environment. Emulsifiable concentrates are undesirable due to use of solvents which may be flammable, pose odour nuisance and disposal constraints. Wettable powders are dusty and not safe to the user. The present invention relates to a novel, less hazardous insecticidal formulation in form of coated granules containing an insecticidally effective amount of 1 - (6-chloro-3-pyridinylmethyl)-N-nitroimidazolidin-2-ylideneamine(imidacloprid), which are non-dusty, free-flowing, easy to use directly and comparatively safer. The said granules contain one or more wetting agents, one or more binders, film forming agent from the group of vinyl polymers and carriers such as silica or sand. OBJECTS OF INVENTION The main object of present invention is to provide an insecticidal formulation containing effective amount of l-(6-chloro-3- pyridinylmethyl)-N-nitroimidazolidin-2-ylideneamine, which is comparatively safer than the formulations of prior-art. A further object of the invention is to provide a formulation of the abovementioned insecticide which is directly usable for field application without dilution aid. Another object of the invention is to provide an insecticidal formulation which is dust free. Yet another object of the present invention is to provide a formulation with improved shelf-life. Another object of this invention is to provide a formulation which is easy to store, handle and use. Still another object of the invention is to provide a formulation of the said insecticide which does not stick to the container or application device and thus ensures easy cleaning thereof. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the novel formulation of l-(6-chloro-3-pyridin-3ylmethyl)-N-nitroimidazolidin-2-yldenamine coated granules, which is coherent and free flowing, which can be directly applied to the field without diluting aid. The product of the present invention has several advantages such as ease of handling and use, and improved shelf life. In addition to its efficacy, the invented formulation is also preferred due to its flowability and non dusty granular nature resistant to crushing and attrition. The present formulation of the l-(6-chloro-3-pyridin-3ylmethyl)-N-nitroimidazolidin-2-yldenamine coated granules comprises the active ingredient along with necessary formulation adjuvants such as wetting agents, binding agents, plasticizing agents, carriers and film forming agents. The product of present invention can be prepared by a method comprising blending the l-(6-chloro-3-pyridin-3ylmethyl)-N- nitroimidazolidin-2-yldenamine active ingredient with formulation adjuvants in stipulated quantities and to form an aqueous sprayable mixture, spraying the above mentioned mixture on silica or sand for uniform coating, drying the said granules by drying means, again spraying the film forming solution on the dried granules prepared as mentioned above, again drying the coated granules to get the desired formulation. Active ingredient content of the product was determined by BIS method. Wetting agents are used for instant wetting of the active ingredient in the formulation once added to water. They decrease the interfacial tension between the solid ingredient [in this case l-(6-chloro-3-pyridin-3ylmethyl)-N-nitroimidazolidin-2-yldenamine active ingredient] and water. Wetting agents can be chosen from the group comprising of condensates of alkyl aryl sulfonic acid, condensate of alkyl naphthalene sulfonate, condensate of aryl sulfonic acid, sodium or potassium polycarboxylates, ethoxylated tristeryl phenol phosphates and their salts, or ammonium salt of polyoxyethylene or a combination of these and castor oil ethoxylates. Preferably, the wetting agent in the present invention is chosen from the group comprising of castor oil ethoxylates, hereinafter referred to as Adjuvant A. Binding agents or adhesives are used to hold the active ingredients along with other adjuvants strongly in the granules, so that they withstand handling and transportation. Binding agents are used in the formulation to make the granules strong to resist abrasion or physical disintegration. Various classes of binding agents can be chosen from the group consisting of polymers and copolymers of poly vinyl acetate, methyl cellulose, polyvinyl alcohol, vinylidine chloride, cellulose, polyvinyl pyrrolidone and poly saccharide. Preferable binder for the present invention is vinyl alcohol polymer (Polyvinyl alcohol), hereinafter referred to as Adjuvant B. Plasticizers are typically used in the insecticidal solution to make the film that is formed by the insecticidal coating layer more flexible, improve adhesion and spreadability. Various plasticizers may be used such as polyethylene glycol, Tri hydroxy alcohol (Glycerol), Butyl benzyl phthalate, Glycol benzoates and related compounds. Preferred plasticizer for the present invention is Glycerol, herein referred to as Adjuvant C. Film forming agents form a temporary protective coating layer on the desired material. Film over coating can be applied to the insecticide coated granules of the present invention. The film overcoats protect the insecticide granules from mechanical damage during transportation, storage and handling. Moreover, it also makes the formulation safe to handle and use during application. Various film forming agents including but not limited to methyl cellulose, hydroxyl propyl methyl cellulose, dextrin, gums, waxes, vegetable oils or paraffin oils, synthetic polymers such as polyethylene oxide, polyvinyl alcohol, Polyvinyl pyrrolidone and their copolymers and related polymers and mixtures of these are suitable. Preferred film forming agent used in the present invention is vinyl alcohol polymer (polyvinyl alcohol) which is adjuvant B. Preferred carrier material used in the present invention is silica or sand having particle size preferably between 16-40 mesh herein referred to as adjuvant D. Optionally, a coloring agent may also be added to the formulation. Preferred coloring agent used in the present invention Malachite Green herein referred to as Adjuvant E. EXAMPLE 1 l-(6-chloro-3-pyridin-3ylmethyl)-N-nitroimidazolidin-2-yldenamine active ingredient (50% aqueous suspension) 0.6 wt%, adjuvant A 0.5 wt%, adjuvant B 0.1 wt%, adjuvant C 0.5 wt% and adjuvant E 0.08 wt% were mixed to form a homogenous mixture in water. It was sprayed uniformly on adjuvant D 98.12 wt% to obtain insecticide coated granules which were dried at about 70°C. Again 0.1 wt% aqueous solution of adjuvant B was uniformly sprayed on the insecticide coated granules prepared as above and dried at about 70°C to obtain final granular product. The active content in the obtained granules was about 0.3%. EXAMPLE 2 l-(6-chloro-3-pyridin-3ylmethyl)-N-nitroimidazolidin-2-yldenamine active ingredient (50% aqueous suspension) 6.0 wt%, adjuvant A 0.5 wt%, adjuvant B 0.1 wt%, adjuvant C 0.5 wt% and adjuvant E 0.08 wt% were mixed to form a homogenous mixture in water. It was sprayed uniformly on adjuvant D about 92 wt% to obtain insecticide coated granules which were dried at about 70°C. Again 0.1 wt% aqueous solution of adjuvant B was uniformly sprayed on the insecticide coated granules prepared as above and dried at about 70°C to obtain final granular product. The active content in the obtained granules was about 3 %. WE CLAIM: 1. A coated granular insecticidal formulation comprising 0.03 - 3.0 wt% l-(6-chloro-3-pyridin-3ylmethyl)-N-nitroimidazolidin-2-yldenamine as active ingredient, 0.1 - 5.0 wt% of one or more binding agent(s), 0.1-5 wt% of one or more plasticizer(s), 0.1 - 5 wt % one or more wetting agent(s), 0.05 - 5 wt% of one or more film forming or coating agent(s), 91 - 99% carrier material, and optionally containing 0.01 - 1.0 wt% coloring agent(s). 2. A formulation as claimed in claim 1, wherein the binding agent is selected from the group of polymer(s) and/or copolymer(s) of vinyl acetate, methyl cellulose, vinyl alcohol, vinylidine chloride, cellulose, vinyl pyrrolidone and saccharide. 3. A formulation as claimed in claim 1, wherein the wetting agent may be selected from condensates of alkyl aryl sulfonic acid, condensate of alkyl naphthalene sulfonate, condensate of aryl sulfonic acid, sodium or potassium polycarboxylates, ethoxylated tristeryl phenol phosphates and their salts, ammonium salt of polyoxyethylene and castor oil ethoxylates, either individually or a combination of these. 4. A formulation as claimed in claim 1, wherein the plasticizer(s) may be selected from polyethylene glycol, trihydroxy alcohol (glycerol), butyl benzyl phthalate, glycol benzoates and derivatives thereof. 5. A formulation as claimed in claim 1, wherein the film forming or coating agent(s) is selected from methyl cellulose, hydroxyl propyl methyl cellulose, dextrin, gums, waxes, vegetable oils or paraffin oils, polyethylene oxide, polyvinyl alcohol, polyvinyl pyrrolidone and their copolymers or related polymers or mixture thereof. 6. A formulation as claimed in claim 1, wherein the said carrier material is preferably silica or sand 7. A formulation as claimed in claim 1 & 6, wherein the particle size of said carrier material is preferably between 12-50 mesh, more preferably between 16 - 40 mesh. 8. A formulation as claimed in claim 1, wherein the said coloring agent is Malachite Green. 9. A process for preparing granular insecticidal formulation claimed as in claims 1-8 comprising the steps of (a) mixing the active ingredient, wetting agent(s), binding agent(s), plasticizer(s), optionally a coloring agent and water (b) spraying the mixture as prepared in step (a) above on the carrier material to obtain insecticide coated granules (c) drying the insecticide coated granules as obtained in step (b) above (d) spraying the solution of film forming or coating agent on the granules as obtained in step (c) above (e) drying the granules as obtained in step (d) above 10. A formulation comprising 0.25-0.35 wt% l-(6-chloro-3-pyridin- 3ylmethyl)-N-nitroimidazolidin-2-yldenamine active ingredient; 0.25 - 0.75 wt% wetting agent(s), preferable wetting agent being castor oil ethoxylate; 0.05-0.2 wt% binding agent(s), preferable binding agent being polyvinyl alcohol; 0.25 - 0.75 wt% plasticizer(s), preferable plasticizer being glycerol; optionally added about 0.08 wt% coloring agent, preferable coloring agent being Malachite Green; about 98 wt% carrier or filler material, preferable carrier or filler material being silica or sand with particle size preferably between 16 - 40 mesh; 0.05 - 2.0 wt% film forming agent, preferable film forming agent being polyvinyl alcohol. 11. A formulation as claimed in claim 1 or claim 10, and prepared as per the process claimed in claim 9. ABSTRACT A novel insecticidal formulation in the form of coated granules containing 1 - (6-chloro-3-pyridinylmethyl)-N-nitroimidazolidin-2-ylideneamine as active ingredient and a process for preparation thereof has been described.

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1337-MUM-2005-CANCELLED PAGES 18-6-2008.pdf

1337-mum-2005-cancelled pages(25-10-2005).pdf

1337-MUM-2005-CLAIMS(AMENDED)-(13-8-2008).pdf

1337-mum-2005-claims(granted)-(25-10-2008).pdf

1337-mum-2005-claims.doc

1337-mum-2005-claims.pdf

1337-MUM-2005-CORRESPONDENCE 18-6-2008.pdf

1337-mum-2005-correspondence(12-08-2008).pdf

1337-MUM-2005-CORRESPONDENCE(13-8-2008).pdf

1337-mum-2005-correspondence(ipo)-(05-01-2009).pdf

1337-mum-2005-description (complete).pdf

1337-MUM-2005-EXAMINATION REPORT 18-6-2008.pdf

1337-MUM-2005-FORM 1 18-6-2008.pdf

1337-mum-2005-form 1(25-10-2005).pdf

1337-mum-2005-form 13(13-08-2008).pdf

1337-mum-2005-form 13(13-8-2008).pdf

1337-mum-2005-form 13(29-01-2009).pdf

1337-mum-2005-form 18(06-01-2006).pdf

1337-mum-2005-form 2(granted)-(25-10-2005).pdf

1337-MUM-2005-FORM 2(TITLE PAGE) 18-6-2008.pdf

1337-mum-2005-form 3(25-10-2005).pdf

1337-mum-2005-form 9(25-10-2005).pdf

1337-mum-2005-form-1.pdf

1337-mum-2005-form-2.doc

1337-mum-2005-form-2.pdf

1337-mum-2005-form-3.pdf

1337-mum-2005-form-9.pdf