Title of Invention

AN IMPROVED PROCESS FOR THE MANUFACTURE OF THIOPHANATE-METHYL WATER DISPERSIBLE GRANULES

Abstract The present invention relates to an improved process for the manufacture of Thiophanate-methyl water dispersible granules. This process results in a dry-flowable form of superior water dispersible granules, which are manufactured through wet grinding the aqueous suspension, and subsequently subjecting the slurry to multiple steps of coating, drying and agglomeration. The final product has superior qualities of dispersion, suspensibility, and adhesion. The product has a smaller average particle size, but larger range of particles, leaves lesser residue in soil and is hence user friendly and environmentally friendly. The product also has better flowability, due to the granular nature of the product, and is practically dust-free. This prevents dermal and inhalation toxicity to the human being during manufacture and use. The necessary adjuvants such as the fillers, binders, wetting agents, dispersing agents, antifoaming agents, and the Thiophanate-methyl principle active, are blended in a tank to form an aqueous suspension, which is subjected to grinding, through at least one wet grinding equipment, to produce a slurry containing particles in the size range of 0.3 microns to 8 microns. The slurry is then atomized and dried to form granules, which are further dried or agglomerated and dried in a fluidized bed spray drier, to form granules, in the size range of 100 microns to 2.5 mm. These granules may be subjected to post-fluid bed drying, to remove any fines or remaining moisture, to give a final moisture content of less than 1%. To, The Controller of Patents The Patents Office Mumbai
Full Text FORM - 3 A
THE PATENTS ACT, 1970
COMPLETE SPECIFICATION
SECTION 10
TITLE : AN IMPROVED PROCESS FOR THE MANUFACTURE OF
THIOPHANATE-METHYL WATER D1SPERSIBLE GRANULES.
APPLICANT : 1) DEEPAK PRANJIVANDAS SHAH,
501/502 VANDANA APARTMENTS, JANKI KUTIR,
JUHU CHURCH ROAD, JUHU, MUMBAI : 400 049. MAHARASHTRA, INDIA. 2) VADAKKEKUTTUPUTHENPARAM THANKAPPAN BALCHANDRAN E-1/37/B-9SECTOR-B, PHASE- II, NERUL, NAVI MUMBAI - 400 706, MAHARASHTRA, INDIA
The following Specification particularly describes and ascertains the nature of this invention and the manner in which it is to be performed :-

Thiophanate-methyl AN IMPROVED PROCESS FOR THE MANUFACTURE OF
The present invention relates to a novel process of manufacturing an agrochemical formulation. Furthermore, it relates to a process of manufacturing a superior, safe, improved, environmentally friendly, efficacious, less toxic agrochemical formulation.
BACKGROUND OF THE INVENTION
Agrochemicals, more known as pesticides, are a known art for years. Different pesticides such as insecticides, herbicides, fungicides, rodenticides, etc. find different applications. The present invention relates to a novel process for the manufacture of an improved agrochemical formulation. Agrochemical formulations are known to exist in several forms such as emulsifiable concentrates, wettable powders, suspension concentrates, microemulsions, dry-flowables such as water dispersible granules, etc. Dry flowables are beneficial due to their ease of use. improved shelf life, and dust-free nature.
Some of the most useful compounds in industry and agriculture are not water-soluble. This often inhibits their use. particularly when the application of the compound in solution is desired. One such compound is Thiophanate-methyl; (Dimethyl [(1,2-phenylene)bis-(iminocarbonothioyl)]bis[carbarnate]) . Not only is it insoluble in water, it is sparingly soluble in organic solvents. Thiophanate-methyl provides a broad spectrum of disease control in vegetables, fruits, turfs, almonds, celery, peanuts, soybeans, etc. Typical formulations of Thiophanate-methyl exist as wettable powder, dust, and granules.
The present invention relates to a novel process for the manufacture of an improved fungicidal formulation of water dispersible granules. More particularly, it relates to a novel process for the manufacture of an improved formulation of Thiophanate-methyl water dispersible granules.
Fungicides are used to protect crops from fungal diseases, such as powdery mildew, scab, leaf spot, downy mildew, etc. These fungicides comprise of the active, more commonly
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known as the technical, along with other adjuvants for imparting desired characteristics to the end user.
Fungicidal formulations are a known art for years. More so, Thiophanate-methyl (TPM) Wettable Powder (WP) and Thiophanate-methyl Water Dispersible Granules (WG), which contains Thiophanate-methyl technical along with blends of adjuvants such as wetting and suspending agents and fillers, are also a known art.
The conventional Thiophanate-methyl wettable powder is white or beige to tan in color, and exists as a fine powder. It contains normally 70% of Thiophanate-methyl technical, or principle active. The conventional wettable powder (W.P.) is made by blending the Thiophanate-methyl technical along with adjuvants like suspending, wetting, sticking agents etc., and suitable fillers like china clay or silica or both, in a ribbon blender or a suitable blender, after which, it is normally pulverized, either in a hammer or roller mill. In the recent years, the blended mixture is pulverized in an A.C.M. or air jet mill. The finely ground powder is again taken to the blender and is homogenized and packed and tested for its quality. The conventional Thiophanate-methyl wettable powder (W.P.) comprises a particle size in the range of 4 to 20 microns. The product has a bulk density range from 0.38 to 0.42. It is not free flowing and has a flow number in the range of 6 to 10. This formulation has a tendency to cake over a certain period of time. At the time of use, it creates a dust cloud and produces irritation in the eyes of the user, as well as inhalation and dermal toxicity. Since the particles are fine, they are dusty, and tend to fly away, causing a loss to the farmer, and potential damage to the environment. Another disadvantage of this formulation is that the product sticks to the bag, and cannot be fully emptied.
The conventional Thiophanate-methyl water dispersible granules are normally made through a pan granulation process or extrusion process. The Thiophanate-methyl technical is blended and pulverized with other adjuvants and fillers like china clay or silica or both, and is sprayed with a combination or individual sprays of bonding, binding, dispersing and wetting agents. The thick paste of the Thiophanate-methyl
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formulation mass containing moisture from 3% to 15% is extruded through either a basket extruder, twin-screw barrel extruder or any such (usually low pressure) extruder and is cut to sizes and dried to obtain extrudates of 0.5 mm to 3 mm in diameter and 1mm to 5 mm in length. The product comprises a particle size range of 4 to 12 microns. Since the product is a compacted, strongly bonded product, it does not disperse well when added to water. It takes a good long time for the complete product to disperse. This results in vigorous requirement of stirring, without which the product is not evenly distributed through the spray media resulting in uneven spraying and poor efficacy, as the product settles down quickly.
The conventional formulations of Thiophanate-methyl have problems of poor dispersion and suspensibility, phytotoxicity due to large residue in soil, inhalation and dermal toxicity to the user, wastage and damage to the environment.
PCT Specification WO 00/60942 claims agrochemical formulations manufactured by extrusion and subsequent drying in a fluid bed drier. US Patent 5,180, 420 claims water dispersible granules made by the process of pan granulation, or the extrusion process. US Patent 3,920,442 claims water dispersible pesticide aggregates, processed in fluid bed spray granulator. US Patent 5,628,800 claims a process for the manufacture of water dispersible granules, which are processed in a fluid bed spray granulator. Another prior art reference is the PCT specification, WO 93/14632 that claims water dispersible granules of low melting pesticides. The process consists of three stages; blending the active with the a portion of the filler, milling through an air-mill, hammer or pin disc mill, blending with the remaining portion of the filler and other adjuvants and final granulation by low pressure extrusion. Milling reduces the particle size to less than 50 microns. These prior art references suffer from the disadvantages of an undesirable product, which is dusty and does not possess desired levels of dispersion and suspension in water. The inventor seeks to solve these problems with the introduction of the improved Thiophanate-methyl water dispersible granules formulation.
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Over the years, as man learnt of the hazard of using the pesticides and the risks associated with this to mankind, there is a growing need to make the same products which have been used for years in such an improved form so that it is more efficient, more efficacious and reduces the risk to the user and to the environment. With the use of the conventional formulations, the farmer constantly faces problems of larger quantities of harmful residues in the soil, low shelf life of the formulation, caking of the product over long period of time, poor dispersion and suspension qualities of the formulation after being dissolved in water, inhalation toxicity due to dusty nature of the formulation and irritation in the eyes and on the skin due to harmful dust of the product.
We, the inventors have carried out significant research in order to achieve an improved and novel formulation of Thiophanate-methyl, more particularly Thiophanate-methyl water dispersible granules. The developed formulation is coherent, dry-flowable formulation of Thiophanate-methyl water dispersible granules, with superior qualities of suspension and dispersion. Conventional wettable powder and conventional water dispersible granule formulations do not possess superior qualities of complete dispersion, excellent blooming and high suspension. When added to water, these conventional formulations are not uniformly distributed or dispersed, and tend to settle down. The said invention of the improved process of manufacture results in novel Thiophanate-methyl water dispersible granules possessing excellent dispersion and suspension properties. When added to water, the product displays an exceptional blooming capacity, and remains suspended in solution for a long period of time, and is uniformly distributed and dispersed. This is just one advantage of the alleged invention. The product also displays improved rainfastness; that is, the product tends to stick to the surface of the crop when sprayed, and adheres to the surface in spite of severe weather conditions such as a heavy rainfall, thus ensuring utmost protection from subsequent diseases. In addition to this, the alleged invention, results in a product that has an enhanced shelf life, which proves economical for the user. The product is practically dust-free, thus eliminating all the disadvantages of the conventional Thiophanate-methyl wettable powder and water dispersible granule formulations commercially available. Another advantage of the improved process is the elimination of dust during the process of manufacture. This is a
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common problem encountered during the conventional manufacture of several formulations, particularly Thiophanate-methyl. The alleged invention is a safe process for the manufacture of novel Thiophanate-methyl water dispersible granules, which prevent any dissipation of dust into the atmosphere, or any contact of the dust with the operators, and is therefore a preferred process.
Another problem encountered during the use of agrochemical formulations is the phytotoxicity caused due to residues left in the soil. Conventional formulations of Thiophanate-methyl leave residues, which can prove to be quite harmful for the environment, plant, animal and human life. Hence, there is the need to provide an improved formulation, which would reduce soil residues and enhance the crop yield and biological activity, while being affordable and economical to the user. The improved process delivers this most desired efficacious formulation of Thiophanate-methyl water dispersible granules, which displays enhanced biological activity, has a reduced dosage due to the novel formulation recipe and process, and then again is economical in use.
SUMMARY OF THE INVENTION
The alleged invention comprises a novel process for the manufacture of improved Thiophanate-methyl water dispersible granules, which are coherent, free-flowing, and display superior characteristics of dispersion and suspensibility. The novel process comprises the blending of the Thiophanate-methyl active ingredient along with formulation adjuvants and water to form an aqueous suspension, wet grinding the aqueous suspension to form a slurry comprising a particle size distribution in the range of from 0.3 microns to 8 microns, and then drying and granulating the slurry in a suitable spray drier or fluidized bed spray drier or fluid bed spray granulator. to form the said Thiophanate-methyl water dispersible granules in the range of from 100 microns to 2.5 mm.
OBJECT OF THE INVENTION
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The inventor has carried out continuous research to overcome the drawbacks of the prior art and processes. Not only is the process an improvement over prior art, but also the precise adjuvants for a superior formulation have resulted in an excellent product. The primary object of the invention is to provide an improved process of manufacturing fungicidal formulation of Thiophanate-methyl water dispersible granules, which provides enhanced biological activity.
Another object of the invention is to provide an improved process of manufacturing fungicidal formulation of Thiophanate-methyl. which has better dispersion properties.
Another object of the invention is to provide an improved process of manufacturing fungicidal formulation of Thiophanate-methyl, which gives better coverage, and thus reduces the amount of Thiophanate-methyl required.
Another object of the invention is to provide an improved process of manufacturing fungicidal formulation, which reduces the dust, due to larger granule size of the formulation, thus reducing inhalation toxicity to the user.
Another object of the invention is to provide an improved process of manufacturing fungicidal formulation of Thiophanate-methyl, which reduces eye irritation due to dust-free nature of the product.
Another object of the invention is to provide an improved process of manufacturing fungicidal formulation of Thiophanate-methyl, which has reduced dermal toxicity, due to the granular and dust-free nature of the product.
Another object of the invention is to provide an improved process of manufacturing fungicidal formulation of Thiophanate-methyl, which has better adhesion properties due to efficient formulation and particle size.
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Another object of the invention is to provide an imprPved Process of manufacturing fungicidal formulation of Thiophanate-methyl, which is having higher surface area giving better coverage while spraying and thus increasing bio-effieciancy
Another object of the invention is to provide an imprPved Process of manufacturing fungicidal formulation of Thiophanate-methyl, which has better flow Properties, which facilitates ease of use.
Another object of the invention is to provide an improved Process of manufacturing fungicidal formulation of Thiophanate-methyl, which increases the vield of the crop
Another object of the invention is to provide an improved Process of manufacturing fungicidal formulation of Thiophanate-methyl, which has a reduced volume, and therefore reduces the cost of packaging, making transportation econ°mical.
Another object of the invention is to provide an impfoved Process of manufacturing fungicidal formulation, such that no product remains in the contamer or pack, thus eliminating wastage and environmental hazard.
Another object of the invention is to provide an improved Process of manufacturing fungicidal formulation of Thiophanate-methyl, which has an improved shelf life.
Another object of the invention is to provide an improved Process of manufacturing fungicidal formulation of Thiophanate-methyl which has negligible electro-static forces of attraction between the particles or granules, which preVents caking of the product.
Another object of the invention is to provide an improved Process of manufacturing fungicidal formulation of Thiophanate-methyl, which has a suerior formulation.
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Another object of the invention is to provide an improved process of manufacturing fungicidal formulation of Thiophanate-methyl, which is easily dispersible in water in spite of bigger granule size.
Another object of the invention is to provide an improved process of manufacturing fungicidal formulation, which reduces the environmental damage, due to dust-free nature of the product.
Another object of the invention is to provide an improved process of manufacturing fungicidal formulation, by which there is no loss of the product to the environment, thus making it a safe and environmentally friendly process. The process uses clean atmospheric air, and again, sends out clean air, with practically no product content. The process is completely sealed, and thus eliminates any exposure of chemicals or the ingredients, to the workers, making it a safe and improved process.
In summation, the present invention comprises a novel and safe process for the manufacture of an improved formulation of Thiophanate-methyl water dispersible granules, which is more cost effective and beneficial due to lesser dosage and larger coverage on the crop, more efficacious due to better dispersion and suspension properties, and environmentally and user friendly due to lesser soil residue and less dust.
DESCRIPTION OF THE PROCESS AND PREFERRED EMBODIMENT (Refer to process flow diagram):
The present invention relates to an improved process for the manufacture of a novel formulation of Thiophanate-methyl water dispersible granules. The said Thiophanate-methyl water dispersible granules are coherent, free-flowing, with superior characteristics of uniformity, suspension and dispersion when added to water, shelf life and stability. The said formulation displays enhanced biological activity, with reduced phytotoxicity due to reduced soil residues and uniform coverage on the crop. In addition to improved biological activity, the said formulation is safe for the user and the environment. The dust-free nature eliminates the problems of contacting dust of the formulation to the
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user's eyes or skin, which are usually encountered during the use of finely ground powders, more particularly wettable powders, or granules with low resistance to attrition and abrasion, which do not withstand handling and shipping and turn to dust. Another problem associated with these powders is their tendency to cake over a period of time, resulting in poor dispersion and suspension properties. Also, the unintended but possible problem of dissipation of dust from the container, when open, into the environment is practically eliminated in the case of the said formulation of Thiophanate-methyl water dispersible granules due to the granular nature of the formulation. Errors occurring in measuring dosage, which commonly occur in the practical use of the conventional formulations, are also eliminated as a result of the novel formulation, obtained from the use of the improved process of manufacture.
The said formulation of Thiophanate-methyl water dispersible granules comprises Thiophanate-methyl active ingredient and formulation adjuvants such as dispersing agents, wetting agents, binding agents, and antifoaming agents or defoamers.
Dispersing agents enable the instant disintegration of the granules and dissolution of the active ingredient when added to water. Since the Thiophanate-methyl active ingredient is hydrophobic, the fine particles either tend to agglomerate or flocculate when added to water without the use of a dispersant. The use of a dispersant helps in promoting and stabilizing dispersions, suspensions of water insoluble pesticides, particularly Thiophanate-methyl, in this case. Various dispersing agents are commercially available for use in agrochemical formulations, such as those marketed by Rhone Poulenc, Witco. Westvaco, International Specialty Products, Croda Chemicals, Borregaard, etc. It is imperative that the dispersing agent does not react with the active ingredient in the formulation. Dispersing agents can be chosen from the group comprising condensates of phenol sulfonic acid and their salts, condensates of alkyl sulfonic acid and their salts, condensate of alkyl aryl sulfonic acid and their salts, sodium or potassium polycarboxylates, salts of sulfonated and carboxylated kraft lignin, ethoxylated tristyryJphenol phosphate, sodium salt of isodecylsulfosuccinic acid half ester, potassium salt of ethoxyalted tristyrylphenol phosphate, sodium salt of dioctyl sulfosuccinate, or a
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combination of these. Dispersing agents that can be preferably used in the formulation of Thiophanate-methyl water dispersible granules are chosen from the group comprising sodium salt of alkyl benzene sulfonic acid condensate, sodium or potassium polycarboxylate, or a combination of phenol sulfonic acid condensate and naphthalene sulfonic acid condensate.
Wetting agents are used for instantaneous dissolution of the active ingredient in the formulation, once added to water. They decrease the interfacial tension between the solid active ingredient (in this case, Thiophanate-methyl active ingredient) and water. The choice of a wetting agent has to be made taking into account the hydrophobic character of the active, as well as the type of dispersing agent used in the formulation. Wetting agents work in combination with some dispersing agents. Various wetting agents are commercially available for use in agrochemical formulations, such those marketed by Rhone Poulenc, Witco, International Specialty Products, BASF, Borregaard, etc. Wetting agents can be chosen from the group comprising condensates of alkyl aryl sulfonic acid, condensate of alkyl naphthalene sulfonate, condensate of aryl sulfonic acid, sodium or potassium polycarboxylates, ethoxylated tristyrylphenols phosphates and their salts. ethoxylated tristyrylphenols sulfates and their salts, or ammonium salt of polyoxyethylene, or a combination of these. Preferably, the wetting agent is chosen from the group comprising alkyl naphthalene aromatic sulfonic acid condensate, derivatives of polycarboxylate, ethoxylated tristyrylphenol sulfate, ammonium salt of polyoxyethylene or a combination of one or more derivatives of polycarboxylate and ammonium salt of polyoxyethylene.
Fillers or diluents, which are inert, are used to prevent sticking or caking of the finished or final formulation. Fillers commonly available to choose from are sub-bentonites, bentonites, attapulgites, kaolinites, montmorinonites, bauxite, hydrated or calcined aluminas, diatomaceous earths, prophyllites, talc, vermiculites, silicas, silicates, china clay, and the like. Amongst organic materials, which are also available as binding agents, are sugar, carbon, charcoal, wood flour, or ground corn cobs, and synthetic organic
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polymers. More preferably, the filler is selected from the group comprising kaolin, talc, china clay, bentonite, dolomite, or ppt Silica.
Binding agents are used to hold the active ingredient along with other adjuvants strongly in the granules in order to provide a coherent, non-dusty formulation, which can withstand handling and shipping. The binding agent helps to make the granules strong to resist crushing, abrasion or physical disintegration, which are likely during storage or even shipping and handling. Many choices of binding agents are available. The binding agent used in Thiophanate-methyl water dispersible granules is preferably chosen from the group comprising lignin derivatives or the group of derivatives of polycarboxylates.
Antifoaming agents to be used in the Thiophanate-methyl water dispersible granules preferably comprise water-based silicon antifoaming agents.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT: (REFER TO THE DIAGRAM)
The adjuvants(A). which are usually in a dry powder form, and the Thiophanate-methyl active ingredient (A), are added to water in a blending tank (1). equipped with a stirrer. Typically, a silverson type stirrer is used. Blending in the tank, gives an aqueous suspension (B), which is fairly homogenous in nature. Typically, the suspension comprises water, which may vary from 25% to 55% of the total suspension. The suspension is then transferred to a holding tank (3), through a pump (2) and then processed in a suitable wet grinding equipment (5), where the particle size is brought down to a range of from 0.3 microns to 8 microns. Wet grinding equipment comprises of sand mills, vertical or horizontal bead mills, Dyno mills, attritors, Pearl Mills, and the like. Grinding media used in these mills comprises beads. Various beads such as metallic stainless steel beads, silica, zirconium oxide beads, zirconium beads, sand, glass beads, ceramic beads, silica quartz, zirconium silicate beads and fused ceramic beads of high density high alumina micro beads or similar beads or a combination of these various beads can be used as grinding media. Beads with more than 0.4 mm in diameter and
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hardness greater than 3 Mohs can be used. The slurry formed after grinding, is then checked for the particle size distribution through a screen (6), if necessary, and then transferred to a holding tank (8). The slurry (E) from the holding tank (8) is then subjected to drying and agglomeration in suitable spray granulation equipment (9), comprising a Spray Drier or Fluidized Bed Spray Drier or Fluid Bed Spray Granulator. The slurry is first atomized, through a nozzle, which is either single-fluid, or two-fluid, at a pressure of from 10 to 50 bar, or through a rotary atomizer at 5000 RPM to 12000 RPM. The hot air enters at a temperature of from 70°C to 250°C. The atomized particles are simultaneously agglomerated in the integrated fluid bed, and dried, to form granules (G) containing moisture less than 10%. The granules are further processed through a post-fluid bed dryer (10), if required, to bring the final moisture content down to less than 1% (H). Dust (J) collected through the cyclone is recycled (M) whereas the remaining fines (N) are washed down by a scrubber (11) for further use in the slurry. This novel process developed by the inventor, allows each and every particle, regardless of its size, to be coated by adjuvants, i.e. the dispersing, wetting and binding agents, and when dried, the water content is lost, and the adjuvants are retained, covering the entire surface of each particle. Because of the coating, there is also no development of static charge, avoiding fusion of the particles.
The final formulation of Thiophanate-methyl water dispersible granules comprises granules in the size range of 100 microns to 2.5 mm, aggregated from particles in the size range of from 0.3 microns to 8 microns, wherein at least 50% of the said particles are in the size range of from 0.5 microns to 3 microns, comprising Thiophanate-methyl active ingredient in the range of 40% - 80%, at least one dispersing agent in the range of from 0.5% to 8%, a wetting agent in the range of from 0.5% to 7%, a binding agent in the range of from 1% to 8%, filler in the range of from 6% to 39%, and antifoaming agent in the range of from 0.02% to 1.4%, on a dry weight/weight basis. The said Thiophanate-methyl water dispersible granules have superior characteristics of suspensibility and dispersion when added to water. Suspensibility is defined as the amount of active ingredient suspended after a given time in a column of liquid, of stated height, expressed as a percentage of the amount of active ingredient in the original suspension.
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Another measure of quality of the water dispersible granule formulation is spontaneity of dispersion. This parameter measures the ease or rate of degree of dispersion or dissolution or disintegration. Storage Stability or Accelerated Storage, is a test conducted to accelerate the ageing of a product by heating, and provides a useful guide on the performance of the product after storage in hot or temperature climates.
DESCRIPTION
Appearance: The product is white / beige to tan in color and in a granular, dry flowable form. Also known as Water Dispersible Granules, DF, WG or WDG. The international accepted nomenclature is WG.
Properties: Specification of Thiophanate-methyl water dispersible granules
70%
80%
Maximum 60 seconds
Less than 0.015
90%
Oto 1
Below 7 microns
Maximum 0.5%
l0ml(CIPAC)
More than two years
Thiophanate-methyl content
Suspensibility
Wetting time
Acidity less than
Granules above 200 micron
Flow point
99.5% of particle size range
Moisture
Foam
Shelf Life
BENEFITS:
1) Better bioefficacy
2) More surface area is available
3) Less quantity of product is required, that is, less dosage
4) Better flowability
5) Practically dust - free
6) Reduced inhalation toxicity
7) Higher bulk density than a conventional WP reducing packing cost per kg of product
8) Reduces Thiophanate-methyl residue to the environment
9) Less injurious to human being due to lesser inhalation toxicity
10) Better particle size range
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11) Better adhesion property
12) Product is adapted to use practices by farmers
13) Because of better flowability (normally 0), no product remains in the bag/packet
14) Better shelf life because almost all micron particles are coated. Hence there is almost not electro-static attraction
15) No eye irritation due to dust - free nature of formulation
16) Reduced cost of formulation
USES
As a fungicide, bactericide for better biological activity and to control variety of fungal diseases.
BIOEFFICACY
It was observed, in preliminary trials that the product performs better, in various aspects. The superior performance is attributed to formulation properties, adjuvants, process and parameters, leading to an improved, and most cost effective formulation recipe. Improved properties have enabled the uniform distribution of the formulation, when sprayed on crops.
It has also been observed, while conducting trials, that the dosage has been effectively reduced by about 20% to 40% as compared to conventional formulations. Other trials have shown a further decrease in dosage.
RESULTS OF FORMULATION TRIALS OF THIOPHANATE-METHYL 70
The following examples are illustrative of the present invention, and are not intended to limit the scope of the invention as set forth in the appended claims.
Examples of Thiophanate-methyl 70 WG: Example-Set'A'
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The following ingredients are combined and/or mixed together to form a substantially homogenous slurry. (The ingredients are added to water which may be varying from 20% to 70% water). 1.
(a) Thiophan ate -methyl Technical of 98% purity : 750.00
(b) Sodium salt of Alkyl Naphthalene Sulphonate: 10-00
(c) Salt of Sulphonic Acid Cond. : 60-00
(d) Lignin Derivative of wood pulp: 60.00
(e) China clay: 120-00
The resulting slurry is then milled to produce an average particle size of approximately 1 to 2 microns. The slurry is dried on our special dryer equipment having an inlet temperature of 120°C to 140°C and outlet temperature of approximately 68°C. This formula was the most successful of different temperatures and tms exact rat^° °f ingredients of above category yields the best results.
The following ingredients are combined and/or mixed together to form a substantially homogenous slurry. (The ingredients are added to water which may be varying from 20% to 70%) 2.
(a) Thiophanate-methyl technical of 98% purity: 750.00
(b) Condensate of Alkyl Naphthalene/Phenol Sul. Atfid: 30-00
(c) Naphthalene Sulphonate Derivative: 10.00
(d) Lignin Derivative of wood pulp: 60.00
(e) China clay: 150-00
The resulting slurry is then milled to produce an average particle size of approximately 1 to 3 microns. The slurry is dried on our special dryer equiPment having inlet temperature of 125°C to 140°C and outlet of 69°C approximately.This formula was the most successful of different temperatures and this exact ratio 0f ingredients of above category did not yield the favourable results.
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The following ingredients are combined and/or mixed to form a substantially
homogenous slurry. (The ingredients are added to water, which may be varying from
20% to 70%).
j.
(a) Thiophanate-methyl technical of 98% purity: 750.00
(b) Synthetic polymer like Polycarboxylate: 60.00
(c) Napthalene Sulphonate Derivative: 10.00
(d) Lignin Derivative of Wood Pulp: 60.00
(e) China Clay: 120.00
The resulting slurry is then milled to produce an average particle size of approximately 2 to 3 microns. The slurry is dried on out special dryer equipment having inlet temperature of 130°C to 140°C and outlet temperature of 70°C approximately. This formula was the most successful of different temperatures and this exact ratio of ingredients of above category yields the best result.
The following ingredients are combined and/or mixed together to form a substantially homogenous slurry. (The ingredients are added to water, which may be varying from 20% to 70%).
4.
(a) Thiophanate-methyl technical of 98% purity: 750.00
(b) Synthetic Polymer like Polycarboxylate: 30.00
(c) Naphthalene Sulphonate Derivate: 5.00
(d) Lignin Derivative of wood pulp: 65.00
(e) China clay: 150.00
The resulting slurry is then milled to produce an average particle size of approximately 1.5 to 2.5 microns. The slurry is dried on our special dryer equipment having inlet temperature of 120°C to 135°C and outlet of 69°C approximately. This formula was the
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most successful of different temperatures and this exact ratio of ingredients of above category yields the best results.
The following ingredients are combined and/or mixed together to form substantially homogenous slurry. (The ingredients are added to water, which may be varying from 20% to 70%.)
5.
(a) Thiophanate-methyl technical of 98% purity: 750.00
(b) Condensate of. Alkyl Naphthalene / Phenol Sulphonic Acid: 10.00
(c) Synthetic Polymer like Polycarboxylate: 30.00
(d) Lignin Derivative of wood pulp: 60.00
(e) China Clay: 150.00
The resulting slurry is then milled to produce an average particle size of approximately 2 to 3 microns. The slurry is dried on our special dryer equipment having inlet temperature of 120°C to 140°C and outlet of 67°C approximately. This formula was the most successful of different temperatures and this exact ratio of ingredients of above category yields the best results.
COMPARATIVE TESTS:
Tests were conducted to obtain a comparative analysis between the Thiophanate-methyl
wettable powder and the alleged invention, Thiophanate-methyl water dispersible
granules.
Suspensibility Test:
Conventional Thiophanate-methyl wettable powder: 80.36% Invention, Thiophanate-methyl water dispersible granules: 80.58%
Wetting:
Conventional Thiophanate-methyl wettable powder: 40 seconds Invention, Thiophenate-methyl water dispersible granules: 5 seconds
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The alleged invention has a faster wetting, compared to the conventional wettable powder formulation. A lower wetting time, indicates a faster rate of dispersion, and ease of mixing, when dissolved in water.
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WE CLAIM:
1. An improved process for the manufacture of Thiophanate-methyl water
dispersible granules, comprising of the following steps:
a) Blending the adjuvants with the active ingredient, Thiophanate-methyl, in 'desired proportions, to give an aqueous suspension, wherein the said adjuvants comprise, at least one dispersing agent, with or without wetting agents, binding agents, fillers, and one antifoaming agent. Grinding the said aqueous suspension, in at least one wet grinding equipment, to produce a slurry, having particles in the size range of 0.3 microns to 8 microns.
b) Atomizing the said slurry through a rotary atomizer or a nozzle, or through a combination of a rotary atomizer in the top, and a nozzle in the lower part, in the spray chamber of the fluidized bed spray drier, or a fluid bed spray granulator. or a spray drier.
c) Drying the atomized spray to give yet moist micro-granules, which are further dried or agglomerated and dried through the air from the hot-air inlet, with or without the air from the integrated fluid bed drier, to form larger granules, in the size range of 75 microns to 2.5 mm.
d) Post drying the said granules, if required, to remove any fine dust, if any, and moisture, if any, to obtain practically dust-free granules with moisture content less than 1 %.
2. An improved process for the manufacture of Thiophanate-methyl water
dispersible granules, in accordance with claims 1, wherein the said water
dispersible granules, comprise of 40% to 80% Thiophanate-methyl technical,
0.5% to 7% of a wetting agent, 0.5% to 8% of the dispersing agent, 1% to 8% of
binding agent 6% to 39% of fillers and 0.2% to 1.4% of Anti-foaming agents,
provided that the total number of percentage parts of the ingredients does not
exceed 100, on a dry weight/weight (w/w) basis.
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3. An improved process tor the manufacture of 1 mophanate-methyl water
dispersible granules, in accordance with claims land 2, wherein the said dispersing agent is selected from the group comprising condensates of phenol sulfonic acid and their salts, condensates of alkyl sulfonic acid and their salts, condensates of alkyl aryl sulfonic aci and their salts, sodium or potassium polycarboxylates, salts of sulfonated and carboxylated kraft lignin, ethoxylated tristyrylphenol phosphate, sodium salt of isodecylsulfosuccinic acid half ester, potassium salt of ethoxylated tristyrylphenol phosphate, sodium salt of dioctyl sulfosuccinate, or a combination of these.
4. An improved process for the manufacture of Thiophanate-methyl water dispersible granules, in accordance with claims 1 and 2, wherein the said wetting agent is selected from the group comprising condensates of alkyl aryl sulfonic acid, condensates of aryl sulfonic acid, condensates of alkyl sulfonic acids, potassium or sodium polycarboxylates, ethoxylated tristyrylphenol phosphates and their salts, ethoxylated tristyrylphenol sulfates and their salts, or ammonium salt of polyoxyethylene, or a combination of these.
5. An improved process for the manufacture of Thiophanate-methyl water dispersible granules, in accordance with claim 1, wherein the said binding agent is selected from the group comprising lignin derivatives or the group of derivatives of polycarboxylates.
6. An improved process for the manufacture of Thiophanate-methyl water dispersible granules, in accordance with claims 1 and 2, wherein the said filler is selected from the group comprising kaolin, china clay, talc, bentonite, dolomite or ppt Silica.
7. An improved process for the manufacture of Thiophanate-methyl water dispersible granules, in accordance with claims 1 and 2, wherein the said antifoaming agent comprises water based silicon antifoaming agent.
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8. An improved process for the manufacture of Thiophanate-methyl water dispersible granules, in accordance with claim 1.wherein the said wet grinding equipment comprises a sand mill, a vertical or horizontal bead mill, turbo mill, dyno mill, attritor, pearl mill or a series of combination of these.
9. An improved process for the manufacture of Thiophanate-methyl water dispersible granules, in accordance with claim 8, wherein the grinding media used in the said wet grinding equipment comprises stainless steel beads, silica beads, zirconium oxide beads, zirconium beads, sand, glass beads, ceramic beads, silica quartz, zirconium silicate, fused ceramic beads of high density, high alumina micro beads or similar beads or a combination of these.
10. An improved process for the manufacture of Thiophanate-methyl water dispersible granules, in accordance with claim 9, wherein the said grinding beads comprise a size range of from 0.4 mm to 20 mm.
11. An improved process for the manufacture of Thiophanate-methyl water dispersible granules, in accordance with claim 1, wherein wet grinding is maintained from 5°C to 50°C, with the aid of a cooling jacket.
12. An improved process for the manufacture of Thiophanate-methyl water dispersible granules, in accordance with claim 1, wherein the pH of the said aqueous suspension and the said slurry is maintained between 5 to 8.
13. An improved process for the manufacture of Thiophanate-methyl water dispersible granules, in accordance with claim 1, wherein the said slurry has a particle size distribution such that at least 50% of the particles are less than 2 microns and at least 90% of the particles are less than 8 microns.
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14. An improved process for the manufacture of Thiophanate-methyl water dispersible granules, in accordance with claim 1, wherein the temperature of the said slurry, before drying is maintained at a temperature of from 20°C to 65°C.
15. An improved process for the manufacture of Thiophanate-methyl water dispersible granules, in accordance with claims 1, wherein the said hot. air from the said hot-air inlet, is in the temperature range of from 70°C to 250°C.
16. An improved process for the manufacture of Thiophanate-methyl water dispersible granules, wherein the outlet air or saturated air is in the temperature range of from 40°C to 100°C.
Dated, this 9lh day of April, 2001

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Documents:

393-mum-2001-abstract(26-4-2001).doc

393-mum-2001-abstract(26-4-2001).pdf

393-mum-2001-claims(26-4-2001).doc

393-mum-2001-claims(26-4-2001).pdf

393-mum-2001-correspondence (ipo)-(26-4-2002).pdf

393-mum-2001-correspondence 1(23-10-2002).pdf

393-mum-2001-correspondence 2(26-4-2001).pdf

393-MUM-2001-CORRESPONDENCE(18-9-2012).pdf

393-mum-2001-description(complete)-(26-4-2001).pdf

393-mum-2001-form 1(26-4-2001).pdf

393-mum-2001-form 2(26-4-2001).doc

393-mum-2001-form 2(26-4-2001).pdf

393-mum-2001-form 2(title page)-(26-4-2001).pdf

393-mum-2001-form 3(26-4-2001).pdf

393-mum-2001-general power of attorney(26-4-2001).pdf

393-mum-2001-patent document(26-4-2001).pdf


Patent Number 248161
Indian Patent Application Number 393/MUM/2001
PG Journal Number 26/2011
Publication Date 01-Jul-2011
Grant Date 23-Jun-2011
Date of Filing 26-Apr-2001
Name of Patentee VADAKKEKUTTUPUTHENPARAM THANKAPPAN BALCHANDRAN
Applicant Address E-1/37/B-9 SECTOR-B, PHASE-II, NERUL, NAVI MUMBAI 400 706.
Inventors:
# Inventor's Name Inventor's Address
1 DEEPAK PRANJIVANDAS SHAH 501/502 VANDANA APARTMENTS, JANKI KUTIR, JUHU CHURCH ROAD, JUHU, MUMBAI 400 049.
2 VADAKKEKUTTUPUTHENPARAM THANKAPPAN BALCHANDRAN E-1/37/B-9 SECTOR-B, PHASE-II, NERUL, NAVI MUMBAI 400 706.
PCT International Classification Number A01N25/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA