Title of Invention

AN IMPROVED PROCESS FOR THE MANUFACTURE OF DELTAMETHRIN WATER DISPERSIBLE GRANULES

Abstract The present invention relates to an improved process for the manufacture of Deltamethrin water dispersible granules. The said Deltamethrin water dispersible granules possess several advantages of coherence, superior characteristics of dispersion, blooming and suspension in water, resistance to attrition and abrasion upon handling and transportation, and reduced damage to the environment and the user. The present invention comprises blending the Deltamethrin active ingredient i)nd formulation adjuvants with water to form an aqueous suspension, which is then subjected to wet grinding to achieve a particle size distribution in the range of from 0.3 microns to 8 microns, followed by agglomeration and drying equipment, to form granules in the size range of from 100 microns to 2.5 mm. To: The Controller of Patents The Patents Office Mumbai
Full Text FORM 2
THE PATENTS ACT, 1970 (39 of 1970)
COMPLETE SPECIFICATION (See Section 10)
NOVEL PROCESS FOR THE MANUFACTURE OF A NOVEL INSECTICIDAL FORMULATION ;
DEEPAK PRANJIVANDA5 SHAH of 501/502 VANDANA APARTMENTS, JANKI KUTIR. CHURCH ROAD, JUHU, MUMBAI - 400 049, MAHARASHTRA, IndiJUHU a, Indian National AND VADAKKEKUTTUPUTHENPARAM THANKAPPAN BALCHANDRAN of E-1/37/B-9 SECTOR-B, PHASE-II, NERUL, NAVI MUMBAI - 400 706, MAHARASHTRA. India. Indian National

The following specification particularly describes the nature of the invention and the manner in which it is to be performed : -

PROCESS FOR THE MANUFACTURE OF

The present invention relates to a novel process for the manufacture of novel insecticidat formulation. More particularly, the present invention relates to a novel process for the manufacture of a novel insecticiclal formulation, which is beneficial for (he user in terms of dosage and ease of usage.
BACKGROUND AND PRIOR ART
The present invention relates to an improved process for the manufacture of a novel insecticidal formulation. More particularly, the present invention relates to a novel process for the manufacture of novel formulation of Deltamethrin water dispersible granules. Deltamethrin, (S)-ot-cyano-3-phenoxybenzyl (1R, 3R)-3-(2,2-dibromovinyl)-2-2dimethylcyclopropane carboxylate or oc-cyano-m-phenoxybenzyl, (lR,3R)-3-(2,2-dibromovinyl)-2-2-dimethyl-cyclopropane carboxylate, is an insecticide and finds various uses. Deltamethrin is a pyrethroid insecticide that kills insects on contact and through digestion. It is used to control apple and pear suckers, plum fruit moth, caterpillars on brassicas, pea moth, aphids (applies, plum, hops), winter moth (apples and plums), codling and tortrix moths (apples). Control of aphids, mealy bugs, scale insects, and whitefly on glasshouse cucumbers, tomatoes, peppers, potted plants, and ornamentals is also achieved through the use of Deltamethrin. It is used in households, public health use for flying crawling insects, cotton market garden crops, fruit crops, field crops, grapevines, etc. for the treatment of Coleoptera, Homoptera, Lepidoptera, etc. Most commonly, the insecticide is available as an emulsion concentrate (EC), wettable powder (WP), and even micro-emulsions (ME).
Agrochemical formulations, also known as pesticides, have been known and used for years. Different agrochemical formulations such as insecticides, herbicides, fungicides, rodenticides, nematicides, etc. find several uses in agriculture and crop protection, etc. Agrochemical formulations carry at least one biologically active ingredient, along with
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other formulation adjuvants such as surfactants, binders, penetration promoters. adhesives. stabilizers, fillers or diluents, and antifoaming agents or defoamers, etc. These formulations, commonly available as dusting powders, emulsifiable concentrates, suspension concentrates, wettable powders, etc. pose several problems. Emulsifiable concentrates are undesirable due to the use of toxic solvents in these. The solvent also presents several problems of unpleasant odour, environmental hazard,, disposal constraints and degradation of the soil on prolonged use. Dustable and Wettable powders are dusty and unsafe for the user. In general practice, the process of making powders involves milling of the ingredients either separately and then blending, or blending the ingredients followed by milling or a combination of these- The resulting powder consists of fine particles, which may cause a series of problems during the use or handling of the agrochemicals, particularly Deltamethrin. The powder is dusty and has a tendency lo get suspended in the air during handling of open storage containers. Also, another threat posed by these powders is the possible damage to the environment, soil, water, plant and animal life, in the neighbouring areas where these powders are being charged to application equipment for use. Deltamethrin dusting and wettable powders, in particular. are a serious threat to the user, as they are known to produce burning sensation in the eyes, tiredness, heat in the face and upper shoulders in the eyes.
Other formulations of Deltamethrin, which are commercially available, are Ultra Low-Volume Liquids (ULV) and water dispersible tablets, such as Ezeetab™ by Avenlis. However, all these formulations possess disadvantages, which are not present in the alleged invention set forth. Liquids pose a problem, as they are not the most economical to transport, and are difficult to recover if spilled. The water dispersible tablet is large. with a diameter of about 2 cm. When added to water, it takes a long time for the tablet to disintegrate and disperse completely. The particles, which disintegrate from the tablet are too large and tend to settle down. As a result, the majority of the tablet tends to settle at the bottom of the container, not having a uniform suspension. Continuous mixing and stirring will be required for a very long period of time to obtain a stable and uniform suspension. It is also difficult to stir large volumes of formulation without the aid of modern devices such as motorized stirrers. This is definitely likely to be a problem in
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developing and under-developed countries where farmers do not have motorized stirrers to keep the formulation in suspension, and use bamboo sticks or similar devices to aid stirring.
In order to overcome the problems associated with the use of the conventional pesticides. researchers and organizations have conducted investigation in the field of formulation technology, which has engendered the concept of water dispersible granules. Water dispersible granules, also known as dry-flowable formulations, are superior due to their ease of flow, pouring properties and non-dusty granular nature. However, in spite of being a known art, water dispersible granules have different characteristics based on type of process used for manufacture, and on the formulation agents used. Various parameters such as suspensibility, spontaneity of dispersion, blooming capacity, wetting period, shelf life, etc. determine the quality and usefulness of the water dispersible granule formulations. Therefore, the kind of process, the process parameters, and the formulation agents, play a vital role in the quality and characteristics of the water dispersible granule formulation/ Water dispersible granules are expected to disperse and dissolve spontaneously upon contact with water. Water dispersible granules, known so far, are made from various processes. The size of the granules made by conventional pesticide granulation techniques such as those of pan granulation and extrusion, is too large. These granules also tend to contain too low an active ingredient concentration, not allowing a low-volume application with uniform coverage over the crop, and do not present good dispersion properties. A PCT patent WO 93/14632 claims water dispersible granules of low melting pesticides, which are prepared by milling the pesticides with a first portion of finely divided filler and blending the milled mixture with a second portion of finely divided filler, wetting the blend with water and then forming granules from the wetted blend through the process of extrusion. The particle size of the mixture after the milling stage is less than 50 microns. Milling is carried out in fluid energy mills using air or inert gas, and mechanical mills such hammer or pin disc mills. However, since the milling is dry, the particle size distribution is not optimum, as at least 50% of the particles are usually above about 7 microns.
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US patent 3,920,442 reveals water dispersible granules of bromacil, diruon or a combination.of bromacil and diuron, aggregated in a fluidized bed, to a size in the range of US 10 mesh to US 140 mesh. The process comprises fluidizing the pesticide with the binder-dispersant while spraying water onto the fluidized solids to effect agglomeration, followed by drying. Another US patent 5,628,800 claims the same process, with controlled parameters of airflow rate and feed rate of the dispersion solution at the onset of the process. Granules obtained from these processes however still have disadvantages of dustiness, insufficient dispersion, and coverage over the crop.
Another US patent 5,602,177 reveals water-emulsifiable granules of Deltamethrin. These granules comprise an organic solvent, and therefore, possess disadvantages not present in the alleged invention set forth.
We, the inventors have carried out significant research in order to achieve an improved and novel formulation of Deltamethrin water dispersible granules. Surprisingly, we have determined, that the novel process of manufacture yields a far superior and novel formulation of Deltamethrin water dispersible granules. The developed formulation is coherent, dry-flowable formulation, with superior qualities of suspension and dispersion. Conventional wettable powders and conventional granules of Deltamethrin do not possess superior qualities of complete dispersion and high suspension. When added to water, these conventional formulations are not distributed uniformly distributed or dispersed, and tend to settle down. The said invention of Deltamethrin water dispersible granules possesses exceptional qualities of complete and instantaneous dispersion and disintegration on addition to water. 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 an advantage of the alleged granules compared to commercially available water dispersible tablets. However, this is just one advantage of the alleged invention. In addition to this, the alleged invention has an enhanced shelf life, which proves economical to the user. The product is practically dust-free, thus eliminating all the disadvantages of the conventional Deltamethrin wettable powder and granule formulations commercially available. Also, the alleged
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granules possess resistance to crushing and abrasion upon handling, shipping and transportation. The product also does not cake over a long period of time, and as a result. preserves its suspension properties. At the same time, the said Deltamethrin formulation is economically available to the user.
SUMMARY OF THE INVENTION
The alleged invention comprises a novel process for the manufacture of improved Deltamethrin water dispersible granules, which are coherent, free-flowing, and display superior characteristics of dispersion and suspensibility. The novel process comprises the blending of the Deitamethrin 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 the slurry in a suitable spray drier or fluidized bed spray drier or fluid bed spray granulator, to form the said Deltamethrin water dispersible granules in the range of from 100 microns to 2.5 mm.
OBJECT OF THE INVENTION
The primary object of the invention is to provide a novel process to manufacture a novel and improved formulation of Deltamethrin water dispersible granules such that, when the said improved formulation is added to water, the formulation is stable, superior, and is yet safe and convenient to use. The formulation when added to water and sprayed. delivers a uniform coverage on the crop.
Another object of the invention is to provide a novel process of manufacturing an improved insecticidal formulation, which has better disintegration and dispersion properties. It is important that the product remains in suspension and does not settle down, is uniformly dispersed and suspended in the solution, and this is what the alleged invention most satisfies. Also, another problem of elimination of dust is overcome by the use of this invention. The process of manufacture is completely dust-free and prevents
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any emission of dust to the atmosphere. The air used in the process, is sent'back clean to the atmosphere, thus making a conducive environment for the labourers. It is another aim of the invention to prevent toxicity caused due to the dust produced by conventional formulations. The novel formulation is practically dust-free, and hence eliminates problems of toxicity to the user, in the eyes, throat, and the skin. Along with this. anolhc:' aim is to provide a safe formulation, which is safe for the plant and animal life.
Another object of the invention is to provide a novel process for the manufacture of an improved insecticidal formulation with an improved shelf life. Considering the needs of the farmer, it is important to provide an economical product to the farmer. With the use of the alleged formulation, the farmer can obtain the necessary protection, having a more stable product lasting for a longer time, with superior coverage and properties, and reduction in use, thus proving to be economical and beneficial.
Yet another object of the invention is to provide an improved process for the manufacture of the Deltamethrin formulation, which has better suspensibility when added to water, is more resistant to crushing, abrasion, and disintegration upon storage, handling and transportation.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a novel process for the manufacture of an improved formulation of Deltamethrin water dispersible granules. The said Deltamethrin 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 uniform coverage on the crop. In addition to uniform coverage. 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 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
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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 Deltamethrin 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 alleged novel formulation.
The said formulation of Deltamethrin water dispersible granules comprises Deltamethrin active ingredient and formulation adjuvants such as dispersing agents, wetting agents. binding agents, fillers 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 Deltamethrin 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 Deltamethrin, in this case. Various dispersing agents are commercially available for use in agrochemical formulations, such as those marketed by Rhone Poulenc. Wiico. Westvaco. International Specialty Products, Croda Chemicals, Borregaard. etc. [t 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 ary] sulfonic acid 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 ethoxyalted tristyrylphenol phosphate, sodium salt of dioctyl sulfosuccinate, or a combination of these. Dispersing agents that can be preferably used in the formulation of Deltamethrin water dispersible granules are chosen from the group comprising sodium salt of alkyl benzene sulfonic acid condensate, sodium or potassium polycarboxylate,
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ethoxylated tristyrylphenol phosphate amine salt, 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, Deltamethrin 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. Wilco, International Specialty Products, Borregaard, BASF, etc. Welling 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, combination of phenol sulfonic acid condensate and naphthalene sulfonic acid condensate.
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 Deltamethrin water dispersible granules is preferably chosen from the group comprising lignin derivatives or the group of derivatives of polycarboxylates.
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
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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 polymers. More preferably, the filler is selected from the group comprising kaolin, talc. china clay, bentonite, dolomite or ppt Silica.
^ntifoaming agents to be used in the Deltamethrin water dispersible granules preferably comprise water-based silicon antifoaming agents.
DESCRIPTION OF THE PREFERRED EMBODIMENT: (refer to the diagram)
The adjuvants, which are usually in a dry powder form, and the Deltamethrin 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 30% to 60% of the total suspension. The suspension is then transferred to a holding tank (2) via pump (1) 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 hardness greater than 3 Mohs can be used. The slurry (D) formed after grinding is then screened (6) for any over¬size particles, if required, and transferred to a holding tank (8). The slurry (E) from the holding tank 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 3 nozzle, which is either single-fluid, or two-fluid, at a pressure of from 10 bars to 50 bars, or through a rotary atomizer
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at 5000 rpm to 12000 rpm. The hot air (F) enters at a temperature of from 80°C to 200°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, if required, to bring the final moisture content down to less than 1% (H). This novel process developed by the inventor, allows each and every particle, regardless of its size, to be coated by some adjuvants, i.e. the d;spersing, wetting and binding agents, and when dried, the water content is lost, and the adjuvants are retained, covering the entire surface of the particles. Because of the coating, there is no development of static charge, avoiding fusion of the particles.
The fine dust particles (J) from the spray granulation equipment are sent to a cyclone (13) where some are recycled (M), and the others (N) are sent to a scrubber (14), where water (K) washes down the fines to give a solution (L), re-used in the slurry.
The final formulation of Deltamethrin 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 Deltamethrin active ingredient in the range of 5% to 85%, at least one dispersing agent in the range of from 3% to 15%, a wetting agent in the range of from 1% to 13%, a binding agent in the range of from 1% to 10%. at least one filler in the range of from 8% to 82%, and antifoaming agent in the range of from 0.02% to 1.4%, on a dry weight/weight basis. The said Deltamethrin water dispersible granules have superior characteristics of suspensibiJity 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.
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
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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 beige to tan in colour 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 Deltamelhrin water dispersible granules:

Deltamethrin content: 10% 25%
Suspensibility: 85% Min. 85% Min.
Wetting time: 60 - 90 sec 60 - 90 sec
Acidity less than: Less than 0.1 Less than 0.1
Granules above 200 microns: 90% 90%
Flow Point: 0to 1 0 to 1
50% of particles below: 3 microns 3 microns
.90% of particle size range: 8 microns 8 microns
Moisture: 0.5% Max. 0.5% Max.
Foam: 10 ml Max. 10 ml Max.
Shelf Life: More than 2 yrs More than 2 yrs
BENEFITS OF THE PRODUCT:
1. Better Bioeftlcacy
2. Better coverage is achieved
3. Better flowabiiity
4. Practically dust-free
5. Reduced inhalation toxicity
6. Higher bulk density than a conventional WP reducing packing cost per kg of product
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7. Reduces Mancozeb residue to the environment
8. Less injurious to human being due to lesser inhalation toxicity
9. Better particle size range
10. Better adhesion property
11. Product is adapted to use practices by farmer
12. Because of better flowability, no product remains in the bag/packet.
13. Better shelf life because almost all micron particles are coated. Hence there is almost no electrostatic attraction
14. Cost effective formulation
Uses:
As an insecticide, in households, and in crops, for protection against Coleoptera, Homoptera. Lepidoptera. etc.
BIOEFFICACY, TESTS AND STUDIES
The following tests were conducted to understand certain attributes of the invention. The tests are illustrative of the laboratory and pilot plant studies conducted, and are noi intended to limit the scope of the alleged invention as set forth in the appended claims.
Methods of Testing:
Test for Suspensibility:
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.
A suspension of known concentration in standard water or distilled water is prepared, placed in a prescribed measuring cylinder at a constant temperature, and allowed to remain undisturbed for the specified time. The top 9/10th'are drawn off and the content of
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active ingredient in the bottom l/10th determined, so allowing the content of the top 9/10th to be calculated.
Test for Spontaneity of Dispersion;
A known amount of a water dispersible granule (WG) is added to a defined volume of water and mixed by stirring to form a suspension. After standing for a short period, the top nine-tenths are drawn off and the remaining tenth dried and determined gravimetrically. The method is virtually a shortened test of suspensibility and is appropriate for establishing the ease with which a WG is dispersed uniformly in water.
Accelerated Storage Procedure: (OPAC. Volume F. Pg. 148)
For Wettable Powders: Put the sample (20 g) into the beaker and spread it. without using any pressure, in a smooth even layer of constant thickness. Place the disc on the surface of the powder in the beaker, and put in the oven. After the specified time remove the beaker, take out the disc, and allow the beaker to cool in the dessicator. Carry out the appropriate tests for suspensibility of wettable powders, within 24 hours of cooling.
For Water Dispersible Pastes: Put 20 grams of the sample in a bottle, hermetically seal it, and keep in an oven at the specified temperature (±2°C) for the given time. Remove the bottle from the oven and allow the paste to reach room temperature naturally, then carry out the appropriate tests of suspensibility within 24 hours of cooling.
For Emulsifiable concentrates: Place the emulsifiable concentrate (about 50 ml) in a bottle, fit the polyethylene inserts, and put the uncapped bottle and contents in the oven. After the bottle has been in the oven for 0.5 hours, cap the bottle, and allow the bottle to remain in the oven for the specified time. At the end of this time, remove the bottle from the oven, remove the cap, and allow the bottle and contents to cool naturally to room temperature,-replacing the cap when cool. Carry out the appropriate tests specified in the general methods of analysis of emulsifiable concentrates within 24 hours of cooling.
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LIST OF ADJUVANTS:
A: Combination of sodium salt of phenol sulfonic acid condensate and naphthalene
sulfonic acid condensate.
B: Sodium salt of Polycarboxylate
C: Ethoxylated tristyrylphenol sulfate
D: Potassium salt of Polycarboxylate
E: China Clay
F: Ethoxylated tristyrylphenol phosphate amine salt
G: Sodium Salt of Polycarboxylate
F: Silica
COMPARATIVE TEST: 1
Tests were conducted to observe the formulation characteristics of various Dehamethrin formulations, based on suspensibility, dispersion, stability, etc. The results are documented as follows:

Spec.
Number Specification / Test Dehamethri nWP Dehamethrin WG
1. Date of Manufacture 18-Nov-2000 25-Nov-2000
2. Batch "Number DP-1 D-2
Active ingredient % 10% 10%
4. Type of Grinding Dry Wet
5. Suspensibility 84.30% 89.20%
6. Spontaneity of dispersion - 93.60%
7. Flowability 7 times 0 times
8. Storage Stability at 54°C 80.43% 87.60%
9. Wetting time 40 seconds 5 seconds
These tests indicate that the water dispersible granule is a far superior formulation. considering tests and also because it does not require a solvent.
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Comparative Test 2: Comparison between developed Deltamethrin water dispersible granule formulations:
Purity of the Deltamethrin active ingredient in all the samples is 98%.
Sample 1
Batch No.:D-102344
Water was added to the following formulation composition (given on a dry basis).
Usually, water is added to form an aqueous suspension, wherein the water content is in
the range of 25% to 55%) of the aqueous suspension.
Formulation Composition:
Deltamethrin active ingredient: 10.5
Adjuvant "G": 2.0
Adjuvant "B": 3.0
Adjuvant "F": 4.0
Adjuvant "D": 4.0
Adjuvant "E": 76.5
The resulting aqueous suspension is then milled in wet grinding equipment, achieving particle size in the range of 1 to 2 microns. The slurry is then dried and agglomerated in our special lab spray agglomeration and drying equipment. This formulation gave excellent results of dispersion and suspensibility (90.30%)-
Sample 2 ■
Batch No.: D-2
Water was added to the following formulation composition (given on a dry basis).
Usually, water is added to form an aqueous suspension, wherein the water content is in
the range of 25% to 55% of the aqueous suspension.
Formulation Composition:
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Deltamethrin active ingredient; 10.5
Adjuvant "B": 3.0
Adjuvant "C": 4.0
Adjuvant "D": 2.0
Adjuvant "E": 80.5
The resulting aqueous suspension was then milled in wet grinding equipment, achieving particle size in the range of 0.5 to 2 microns. The slurry was then dried and agglomerated in our special lab spray agglomeration and drying equipment. The formulation gave excellent results of dispersion and suspensibility (89.2%).
Sample 3:
Batch No. :D-3
Water is added to the following formulation composition (based on a dry weight/weight
% basis). Usually, water is added to form an aqueous suspension, such that the water
content is in the range of 25% to 55% of the aqueous suspension.
Formulation Composition:
Deltamethrin active ingredient: 10.5
Adjuvant "F": 5.0
Adjuvant "C": 4.0
Adjuvant "E": 80,5
The resulting aqueous suspension was then milled in wet grinding equipment, achieving a particle size in the range of 1 to 2.5 microns. The slurry was then dried and agglomerated to give granules in the size ranee of 150 microns to 2 mm. The formulation gave excellent results of dispersion and suspensibility (91.3%).
Sample 4:
Batch No.: D-243
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Water is added to the following formulation composition (based on a dry weight/weight % basis). Usually, water is added to form an aqueous suspension, such that the water content is in the range of from 25% to 55% of the aqueous suspension. Formulation Composition:
Deltamethrin active ingredient: 81.6
Adjuvant "B": 2.0
Adjuvant "D": 4.0
Adjuvant "F": 3.0
Adjuvant "E": 10.0
The resulting aqueous suspension was then milled in the lab. achieving a particle size in the range of from 1 to 3 microns. The slurry was then dried and agglomerated in our lab equipment to give granules. The formulation gave excellent results of dispersion and suspensibility (85.3%).
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WE CLAIM: -
1. An improved process for the manufacture of coherent, free-flowing, non-dusty
Deltamethrin water dispersible granules, comprising the following steps:
(a) Blending water, the Deltamethrin active ingredient, at least one dispersing
agent, at least one filler, with or without wetting agents, binding agents.
and antifoaming agent, to form an aqueous suspension, wherein the water
. content in the said aqueous suspension is in the range of from 25% to 55%
(b) Grinding the said aqueous suspension in at least one wet grinding equipment, to form a slurry comprising a particJe size distribution in the range of from 0.3 microns to 8 microns
(c) Atomizing the said slurry through a nozzle or a rotary atomizer, or a combination of a rotary atomizer at the top and a nozzle near the bottom, in a spray drier or fluidized bed spray drier or fluid bed spray gra:'.ulator
(d) Drying the atomized slurry by means of hot air, with or without further drying and agglomeration in an integrated fluid bed, to form granules in the size range of from 100 microns to 2.5 mm
(e) Post drying the said granules in a post fluid bed drier, if required, to remove any fine dust and moisture, if any, to obtain the said, practicaliy dust-free, Deltamethrin water dispersible granules in the size range of from 100 microns to 2.5 mm,
2. An improved process for the manufacture of Deltamethrin water dispersible
granules, in accordance with claim 1, wherein the said granules comprise
dispersing agent is present in the range of from 3% to 15%, the said wetting agenl
is in the range of from 1% to 13%, the said binding agent is in the range of from
1% to 10%, the said filler is in the range of from 8% to 82%, the antifoaming
agent is in the range of from 0.02% to 1.4%. the Deltamethrin active ingredient in
the range of from 5% to 85%, such that the percentage parts of the said dispersing
agent, wetting agent, binding agent, filler, antifoaming agent and Deltamethrin
active ingredient does not exceed 100 on a dry weight/weight basis.
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An improved process for the manufacture of Deltamethrin water dispersible granules, in accordance with claim 1, wherein the said dispersing agent comprises 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 krrft lignin, ethoxylated tristyrylphenol phosphate, sodium salt of isodecylsuffosuccinic acid half ester, potassium salt of ethoxyalted tristyrylphenol phosphate, sodium sail of dioctyl sulfosuccinate, or a combination of these.
An improved process for the manufacture of Deltamethrin water dispersible granules, in accordance with claim 3, wherein the said dispersing agent preferably comprises sodium salt of alkyl benzene sulfonic acid condensate, sodium or potassium poly car boxy late, ethoxylated tristyrylphenol phosphate amine salt, or a combination of phenol sulfonic acid condensate and naphthalene sulfonic acid condensate.
An improved process for the manufacture of Deltamethrin water dispersible granules, in accordance with claim 1. wherein the said wetting agent comprises 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.
An improved process for the manufacture of Deltamethrin water dispersible granules, in accordance with claim 5, wherein the said wetting agent preferably comprises alkyl naphthalene aromatic sulfonic acid condensate, derivatives of polycarboxylates, ethoxylated tristyrylphenol sulfate, combination of phenol sulfonic acid condensate and naphthalene sulfonic acid condensate.
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7. An improved process for the manufacture of Deltamethrin water dispersible granules, in accordance with claim 1, wherein the said binding agent comprises a group of lignin derivatives or group of derivatives of polycarboxylates.
8. An improved process for the manufacture of Deltamethrin water dispersible granules, in accordance with claim 1. wherein the said filler comprises talc, china clay, bentonite, dolomite, ppt Silica, or the like, or a combination of these.
9. An improved process for the manufacture of Deltamethrin water dispersible granules, in accordance with claim 1, wherein the said antifoaming agent comprises water-based silicone antifoaming agents.
10. An improved process for the manufacture of Deltamethrin 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,
11. An improved process for the manufacture of Deltamethrin water dispersible granules, in accordance with claim 10, 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.
12. An improved process for the manufacture of Deltamethrin water dispersible granules, in accordance with claim 11. wherein the said grinding beads comprise a size range of from 0.4 mm to 20 mm.
13. An improved process for the manufacture of Deltamethrin water dispersible granules, in accordance with claim 1. wherein wet grindine is maintained from 5°C to 50°C, with the aid of a cooling jacket.
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14. -An improved process for the manufacture of Deltamethrin water dispersible
granules, in accordance with claim 1. wherein the pH of the said aqueous suspension and the said slurry is maintained between 5 and 8.
15. An improved process for the manufacture of Deltamethrin 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 3 microns and ai least 90% of the particles are less than 8 microns.
16. An improved process for the manufacture of Deltamethrin 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.
17. An improved process for the manufacture of Deltamethrin water dispersible granules, in accordance with claim 1. wherein the said hot air is in the temperature range of from 75°C to 160°C.
18. - An improved process for the manufacture of Deltamethrin water dispersible
granules, wherein the outlet air or saturated air temperature is in the range of from 60°Cto 120°C.
Dated this 4th day of April 2001

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Documents:

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

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

387-mum-2001-cancelled pages(25-9-2001).pdf

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

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

387-mum-2001-correspondence 1(26-4-2001).pdf

387-mum-2001-correspondence 2(25-9-2001).pdf

387-mum-2001-correspondence(ipo)-(11-2-2002).pdf

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

387-mum-2001-form 1(25-9-2001).pdf

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

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

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

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

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

387-mum-2001-general power of authority(26-4-2001).pdf

387-mum-2001-specification(amended)-(25-9-2001).pdf


Patent Number 248160
Indian Patent Application Number 387/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 DEEPAK PRANJIVANDAS SHAH
Applicant Address 501/502 VANDANA APARTMENTS, JANKI KUTIR, JUHU CHURCH ROAD, JUHU, MUMBAI 400 049.
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 A01N25/12
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA