DESC:FORM 2
THE PATENTS ACT 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10 and rule 13)
1. TITLE OF THE INVENTION: “A pesticidal formulation of pyriproxyfen, tolfenpyrad and insecticide, and process for preparation thereof”
2. APPLICANT:
(a) Name : RAJDHANI PETROCHEMICALS PRIVATE LIMITED
(b) Nationality : INDIAN
(c) Address : 6, LALITA COMPLEX, RASALA ROAD, NAVRANGPURA, AHMEDABAD-380009 Gujarat, India
PROVISIONAL
The following specification describes the invention. þ COMPLETE
The following specification particularly describes the invention and the manner in which it is to be performed.

FIELD OF INVENTION
The present invention relates to a pesticidal formulation of pyriproxyfen, tolfenpyrad and insecticide, and process for preparation thereof. More specifically, the present invention relates to a pesticidal formulation comprising bioactive amounts of pyriproxyfen or its agrochemically acceptable salts thereof, tolfenpyrad or its agrochemically acceptable salts thereof, at least one insecticide selected from emamectin benzoate, abamectin; and agrochemically acceptable excipients; and a process for preparing said formulation which is environment-friendly and provides broad spectrum control of insect-pests and mites in one shot application.

BACKGROUND OF THE INVENTION
In the process of agricultural production, plant diseases and pests damage the roots, stems, leaves and other parts of plants, as well as fruit, seeds, tubers and other reproductive organs, resulting in reduced crop yield and a drastic drop in the quality. The protection of crops and its produce from insect pest damage is essential in agriculture produce enhancement. More than 40% of all food production is destroyed each year by insects, plant pathogens and weeds. The challenge of growing enough food to feed the world’s expanding population has driven the need to improve crop yield and quality through the control of a wide range of insect pests.
At present, in agricultural production, chemical control by the use of various chemicals and formulations is an important tool for the prevention and control of pests. However, with the continuous use of chemical pesticides to control pests year after year, the increase in the use of pesticides and the unscientific use of pesticides, etc., the resistance to pests has become increasingly serious, and the types of pests that have developed resistance have increased. Resistance denotes a formerly susceptible insect population that can no longer be controlled by a pesticide at normally recommended rates. Once resistance has developed, it tends to persist in the absence of the pesticide for varying amounts of time, depending on the type of resistance and the species of pest.
Furthermore, the high-intensity use of pesticides has led to other problems as well, such as excessive pesticide residues in agricultural products, environmental pollution, and increased costs for farmers to use drugs, which is not conducive to the sustainable development of agriculture.
Combination of insecticides are being used recently to broaden the spectrum of control of insects, to improve the pest control with synergistic effect, reduce dosage, thereby reducing environmental impact, decrease chances of resistance development and to enhance residual control so lesser the number of sprays for crop protections and minimizing the pesticidal load in ecosystem.
US 202110267207 Al relates to combinations of ryanodine receptor ligand inhibitor insecticides in combination with at least one nicotinic acetylcholine receptor agonist/antagonist and at least another insecticidal compound.
CN110199999A relates to a pesticide binary composition containing fluxametamide and tolfenpyrad in a weight ratio of fluxametamide to tolfenpyrad is 10:1 to 1:5, the composition comprises the active ingredients, and the balance of assistants.
CN112616845A relates to a pesticide composition containing pyrazolecarboxamide insecticide and application of pesticide composition. It discusses pesticide composition containing pyrazolyl amide insecticides, comprising dimpropyridaz, of chemical formula 1-(1,2 dimethylpropyl)-N- Ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide and at least an active compound selected from a group of compounds.
WO 20211067678 relates to an insecticidal composition comprising 2 wt.% to 50 wt.% of diamide insecticide active ingredient and a phosphate ester.
There is however a need for improvement of these combinations. There is a need in the art for a combination that decreases chances of resistance and improves the spectrum of disease and pest control.
The active ingredients known from the literature have certain disadvantages such as insufficient control efficacy, and the like. Therefore, there is a need to provide a pesticidal formulation which overcomes some of the existing problems and can be prepared easily without much complex manufacturing process. The present inventors have surprisingly developed an effective pesticidal combination which ameliorates the aforesaid shortcomings of the prior art.

OBJECT OF THE INVENTION
The principal object of the present invention is to provide a pesticidal formulation of pyriproxyfen, tolfenpyrad and insecticide, and process for preparation thereof.
Another object of the present invention is to provide a pesticidal formulation that gives broad spectrum control of insect-pests and mites in one shot application.
Further object of the present invention is to provide a pesticidal formulation that gives residual control i.e. longer duration of control.
Another object of the present invention is to provide a pesticidal formulation which prevents or causes delayed development of resistance to insects against insecticides with a specific site/ mode of action.
Further object of the present invention is to provide a pesticidal formulation that gives synergistic control; i.e. grams of active ingredients required are less to achieve desired level of control.
Another object of the present invention is to provide a pesticidal formulation that gives immediate protection to crops.
Further object of the present invention is to provide a pesticidal formulation that has improved rain-fastness properties.
Another object of the present invention is to provide a pesticidal formulation with environment-friendly formulations; i.e. formulations are without organic solvent as carrier.
Yet another object of the present invention is to provide a pesticidal formulation that is safe to the crops.
Still another object of the present invention is to provide a process for preparing a stable and non-phytotoxic formulation.

SUMMARY OF THE INVENTION
In light of the foregoing background, the following presents a simplified summary of the present disclosure in order to provide a basic understanding of some aspects of the disclosure. This summary is not an extensive overview of the disclosure. It is not intended to delineate the scope of the disclosure. The following summary merely presents some concepts of the disclosure in a simplified form as a prelude to the more detailed description provided below.
The present invention provides a pesticidal formulation comprising bioactive amounts of pyriproxyfen or its agrochemically acceptable salts thereof, tolfenpyrad or its agrochemically acceptable salts thereof, at least one insecticide selected from emamectin benzoate, abamectin; and agrochemically acceptable excipients; and a process for preparing said formulation. In practical application, the pesticidal formulation is prepared as suspo emulsion (SE) and oil dispersion (OD).
The process for preparing the present formulation can be modified accordingly by any person skilled in the art based on the knowledge of manufacturing the formulation. However, all such variations and modifications are still covered by the scope of present invention.
The present invention provides a pesticidal formulation which offers broad spectrum control of insect-pests and mites in one shot application, gives residual control i.e. longer duration of control, prevents or causes delayed development of resistance to insects against insecticides with a specific site/ mode of action, gives synergistic control i.e. grams of active ingredients required are less to achieve desired level of control, gives immediate protection to crops, has improved rain-fastness properties, is environment-friendly, and is safe to the crops.

DETAILED DESCRIPTION OF THE INVENTION
Before explaining the present invention in detail, it is to be understood that the invention is not limited in its application to the details of the parts illustrated. The invention is capable of other embodiments, as described above and of being practiced or carried out in a variety of ways. It is to be understood that the phraseology and terminology employed herein is for the purpose of description and not to limitation. The invention may have various embodiments and they may be performed as described in the following pages of the provisional specification.
The terms and words used in the following description are not limited to the bibliographical meanings, but, are merely used by the inventors to enable a clear and consistent understanding of the invention. Accordingly, it should be apparent to those skilled in the art that the following description of exemplary embodiments of the present invention are provided for illustration purpose only and not for the purpose of limiting the scope of the invention.
It is to be understood that the singular forms "a", "an", and "the" include plural reference unless the context clearly dictates otherwise.
Features that are described and/or illustrated with respect to one embodiment may be used in the same way or in a similar way in one or more other embodiments and/or in combination with or instead of the features of the other embodiments.
It should be emphasized that the term "comprises/comprising" when used in this specification is taken to specify the presence of stated features, steps or components but does not preclude the presence or addition of one or more other features, steps, components or groups thereof.
"Bioactive amounts” as mentioned herein means that amount which, when applied treatment of crops, is sufficient to effect such treatment.
As used herein, “weight percent”, “wt-%”, “percent by weight”, “% by weight”, and variations thereof refer to the concentration of a substance as the weight of that substance divided by the total weight of the formulation and multiplied by 100. It is understood that, as used here, “percent”, “%”, and the like are intended to be synonymous with “weight percent”, “wt-%”, etc.
The term "insects" as used herein, includes all organisms in the class "Insecta".
The term "animal pest" includes arthropods, gastropods, and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects. Insects, which are of particular relevance for crops, are typically referred to as crop insect pests.
The term "pesticidal" as used herein, refers to the ability of an insecticide to increase mortality or inhibit growth rate of insects.
To "control" or "controlling" pests means to inhibit, through a toxic effect, the ability of pests to survive, grow, feed, and/or reproduce, or to limit pest related damage or loss in crop plants. To "control" pests may or may not mean killing the pests, although it preferably means killing the pests.
The term 'plants' as used herein, refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage and fruits. The term "plant" is to be understood as including wild type plants and plants, which have been modified by either conventional breeding, or mutagenesis or genetic engineering, or by a combination thereof.
The term "crop" refers to both, growing and harvested crops.

The present invention provides a pesticidal formulation of pyriproxyfen, tolfenpyrad and insecticide, comprising 5% to 15% w/w pyriproxyfen or its agrochemically acceptable salts, 5% to 15% w/w tolfenpyrad or its agrochemically acceptable salts, 0.1% to 5% w/w at least one insecticide/s selected from emamectin benzoate, abamectin, and agrochemically acceptable excipients.

Pyriproxyfen, (2-[1-(4-phenoxyphenoxy) propan-2-yloxy]pyridine) is an insect growth regulator.

It mimics insect juvenile growth hormone and halts development during metamorphosis and larval development, thereby stopping young insects from maturing into adults. It can affect an insect if it is touched or eaten and mostly affects young insects and eggs. It is rarely toxic to adult insects. It may concentrate in female flea ovaries, causing non-viable eggs to be produced. It disturbs egg-laying and egg-hatch and keeps young insects from growing into adult forms. This prevents target insects from multiplying. It has been registered for use in pesticides by the Environmental Protection Agency (EPA) since 1995.

Tolfenpyrad, (4-chloro-5-ethyl-2-methyl-N-[[4-(4-methylphenoxy) phenyl] methyl] pyrazole-3-carboxamide) is a pyrazole insecticide, and was discovered by Mitsubishi Chemical Corporation in 1991. It is an aromatic amide obtained by formal condensation of the carboxyl group of 4-chloro-3-ethyl-1-methylpyrazole-5-carboxylic acid with the amino group of 1-[4-(4-methylphenoxy) phenyl] methylamine. Tolfenpyrad is a meti acaricide/insecticide with contact mode of action. The compound acts mainly through the inhibition of the mitochondrial electron transport system.

As a pesticide, tolfenpyrad has relatively broad activity against egg, larval, nymphal and adult stages of various arthropods (including Hemiptera, Coleoptera, Diptera, Lepidoptera, Thysanoptera and Acarina), and has been applied to various infested crops. Tolfenpyrad halts feeding damage immediately and oviposition within hours after application. It has an excellent know-down effect; pests are controlled usually within 24 to 48 hours. This chemical was developed in Japan and was first approved in 2002; it has been registered for commercial use in several countries.
At least one is selected from emamectin benzoate, abamectin.

The combination of the present invention is formulated in a manner which suits the specific application. The formulation is selected from capsule suspension (CS), emulsifiable concentrate (EC), emulsion, water in oil (EO), emulsion, oil in water (EW), jambo balls or bags (bags in water soluble pouch), micro-emulsion (ME), oil dispersion (OD), oil miscible flowable concentrate (oil miscible suspension (OF), oil miscible liquid (OL), suspension concentrate (SC), suspo-emulsion (SE), soluble concentrate (SL), wettable granule/water dispersible granule (WG/WDG), water soluble granule (SG), water soluble powder (SP), wettable powder (WP), a mixed formulation of CS and SC (ZC), a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW), granule (GR) / soil applied granules (SAG), controlled release granules (CR).

More particularly, the formulation is selected from oil dispersion (OD) and suspo-emulsion (SE).

Lists of agrochemically acceptable excipients used in the oil dispersion (OD) formulation:

The oil dispersion (OD) formulation of the present invention comprises agrochemically acceptable excipients including, but not limited to, wetting-spreading-penetrating agents, solvents, emulsifiers, dispersing agents, stabilizers, anti-foaming agent, anti-freezing agent, preservatives, buffering agent, and optionally polar cosolvents.
Wetting-spreading-penetrating agents is selected from, but not limited to, organic silicone, which includes trisiloxane ethoxylate, polydimethylsiloxane, polyoxyethylene methyl polysiloxane, polyoxyalkylene methyl polysiloxane, polyether polymethyl siloxane copolymer, trisiloxane heptamethyl, polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane, or mixture thereof. The organosilicone agents have super ability of spreading by drastically reducing the water surface tension. These enhance wetting and absorption of active ingredient through stomatal penetration. This will improve a spray application by modifying the wetting and spreading characteristics, the result being a more uniform spray deposit even at reduced spray volume. It also ensures thorough coverage without excessive runoff of the spray. They are safe to the human beings and environment. The most preferred super wetting-spreading-penetrating agent is polyalkyleneoxide modified heptamethyl trisiloxane (modified trisiloxane).
The solvent for the formulation of the present invention is selected from, but not limited to, blend of pongamia oil and palm oil; blend of pongamia oil and mahua oil; blend of pongamia oil and jojoba (Simmondsia chinensis); blend of pongamia oil and vegetable oil; blend of palm oil and mahua oil; blend of palm oil and jojoba oil; blend of palm oil and vegetable oil; blend of pongamia oil, palm oil and mahua oil; blend of pongamia oil, palm oil and jojoba oil; and blend of pongamia oil, palm oil and vegetable oil. The vegetable oil may be any one or mixture of two or more selected from soybean (Glycine max) oil, groundnut (Arachis hypogaea) oil, rapeseed (Brassica napus subspecies) oil, mustard (Brassica juncea) oil, sesame (Sesamum indicum) oil, corn (Zea mays) oil, rice (Oryza sativa) bran oil, castor (Ricinum communis) seed oil, cotton (Gossypium hirsutum) seed oil, linseed (Linum usitatissimum), coconut (Cocos nucifera) oil, sunflower (Helianthus annuus) oil, safflower (Carthamus tinctorius) seed oil, eucalyptus (Eucalyptus globulus) oil, olive (Olea europaea) oil, jatropha (Jatropha curcas) oil, kapok (Ceiba pentandra) oil, papaya (Carica papaya) seed oil, tea seed (Camellia oleifera) oil, garlic acid (Allium sativum), ginger oil (Zingiber officinale), d-limonene, citronella oil or ceylon ironwood (Mesua ferrea) oil. As solvent for the present formulation, the oil mixtures may be alkylated or ethoxylated or epoxylated or esterified. For example, methyl ester of pongamia oil and vegetable oil, methyl ester of palm oil and vegetable oil, methyl ester of pongamia oil and palm oil, methyl ester of pongamia oil+palm oil+vegetable oil.
Emulsifier is selected from, but not limited to, castor oil ethoxylates, alcohol ethoxylates, fatty acid ethoxylates, sorbitan ester ethoxylates, sulphosuccinate, calcium salts of dodecylbenzene sulphonate, alkylammonium salts of alkylbenzene sulphonate, alkylsulphosuccinate salts, ethylene oxide-propylene oxide block copolymers, ethoxylated alkylamines, octylphenol ethoxylate, ethoxylated alkyl phenols, ethoxylated sorbitol oleates, and polyoxyethylene sorbitan monolaurate.
Dispersing agents have the ability to adsorb strongly onto a particle surface and provide a charged or steric barrier for re-aggregation of particles. The dispersing agents used herein include, but not limited to, preparation of condensed naphthalene sulfonate, propoxylated ethoxylated copolymer monoalkylether (ethylhexanol), alkyl sulfonates, alkyl benzene sulfonates, alkyl aryl sulfonates, alkylphenolalkoxylates, tristyrylphenol ethoxylates, natural or synthetic fatty ethoxylate alcohols, natural or synthetic fatty acid alkoxylates, natural or synthetic fatty alcohols alkoxylates, alkoxylated alcohols (such as n-butyl alcohol poly glycol ether), block copolymers (such as ethylene oxide-propylene oxide block copolymers and ethylene oxide-butylene oxide block copolymers), fatty acid-polyalkylene glycol condensates, polyamine-fatty acid condensates, polyester condensates, salts of polyolefin condensates, sodium ligno sulfonate, sodium polycarboxylate, EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propyleneoxide-ethyleneoxide-copolymer, polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycolether-phosphate, tristyrylphenole with 16 moles EO, tristyrylphenol-polyglycolether-phosphate, oleyl-polyglycolether with ethylene oxide, tallow fattyamine polyethylene oxide, and nonylphenol polyglycolether with 9-10 moles ethylene oxide.
Stabilizer is selected from, but not limited to, hectorite clay, aluminium magnesium silicate, bentonite clay, silica, and attapulgite clay.
Antifoaming agent is selected from, but not limited to, silicone oil, silicone compound, C10~C20 saturated fat acid compounds or C8~C10 aliphatic alcohols compound, silicone antifoam emulsion, dimethylsiloxane, and polydimethyl siloxane.
Anti-freezing agent is selected from, but not limited to, ethylene glycol, propane diols, glycol (monoethylene glycol, diethylene glycol, polypropylene glycol, polyethylene glycol), glycerine, urea, magnesium sulfate heptahydrate, and sodium chloride.
Preservative is selected from, but not limited to, 1,2-benzisothiazolin-3(2H)-one, sodium salt, sodium benzoate, 2-bromo-2-nitropropane-1,3-diol, formaldehyde, sodium o-phenylphenate, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4-isothiazolin-3-one, and butyl hydroxyl toluene.
Buffering agent is selected from, but not limited to, citric acid, sodium carbonate, sodium bicarbonate, sulphuric acid, hydrochloric acid, sodium hydroxide, potassium hydroxide, acetic acid, and sorbic acid.
Polar cosolvent may be optionally present, and is selected from, but not limited to, cyclohexanone, acetophenone, butanol, n-octanol, n-propanol, 1-hexanol, propylene carbonate, and n-methyl-2-pyrrolidone.
However, those skilled in the art will appreciate that it is possible to utilize additional agrochemically acceptable excipients without departing from the scope of the present invention. Such agrochemically acceptable excipients can be in the range from 1% to 99% of the total weight of the formulation.

More particularly, the present invention also refers to the method for preparation of oil dispersion (OD) formulation as describing the following steps:

Manufacturing process for oil dispersion (OD) formulation:
Part A-Preparation of the liquid premix
(i) The oil (methyl ester of pongamia oil and vegetable oil; or methyl ester of palm oil and vegetable oil; or methyl ester of pongamia oil and palm oil; or methyl ester of pongamia oil, palm oil and vegetable oil) is charged as a solvent, with or without co-solvent into a vessel with an anchor stirrer.
(ii) The emulsifier/super wetting-spreading-penetrating agent (polyalkyleneoxide modified heptamethyl trisiloxane) and dispersing agents are added under stirring condition until all ingredients get completely dissolved.
Part B-Preparation of the slurry
(iii) The liquid premix is charged into a second vessel, equipped with a cooling, heating device and a high shear stirrer.
(iv) The active ingredient(s) are added and homogenized thoroughly. This mixture is pre-milled using a bead mill/sand mill/attritor and finally milled to achieve a particle size distribution as required by the specification.
Part C-Preparation of the Thickener gel
(v) The remaining oil is charged to the vessel, equipped with a high shear stirrer.
(vi) The thickening agent is gradually added by throughout maintaining and mixing high-shear and the stirring is continued until thoroughly mixed.
(vii) The thickener is added under stirring condition by allowing the gel to swell whilst maintaining mixing.
Part D-Preparation of the final formulation
(viii) The thickener gel solution is added into milled slurry and the mixture is dispersed by using a high shear stirrer.
(ix) The finished formulation is ready.
The process for preparing the present pesticidal formulation can be modified accordingly by any person skilled in the art based on the knowledge of manufacturing the formulation. However, all such variation and modification is still covered by the scope of present invention.

Lists of agrochemically acceptable excipients used in the suspo-emulsion (SE) formulation:
The suspo-emulsion (SE) formulation of the present invention comprises agrochemically acceptable excipients including, but not limited to, super wetting cum spreading agent cum penetrant cum co-solvent, green solvent cum emulsifier, wetting agent cum penetrant, dispersing agent, suspending agent, anti-freezing agent, antifoaming agent, preservatives, thickeners, stabilizer, and buffering agent.
Super wetting cum spreading agent cum penetrant cum co-solvent is selected from, but not limited to, blend of methylated or ethylated seed oil, organo-silicone surfactant and emulsifier cum surfactant. The methylated or ethylated seed oil includes any one or blend of two or more seed oil. The seed oil may be selected from but not limited to soybean (Glycine max) oil, groundnut (Arachis hypogaea) oil, rapeseed (Brassica napus subspecies) oil, mustard (Brassica juncea) oil, sesame (Sesamum indicum) oil, corn (Zea mays) oil, rice (Oryza sativa) bran oil, castor (Ricinum communis) seed oil, cotton (Gossypium hirsutum) seed oil, linseed (Linum usitatissimum), coconut (Cocos nucifera) oil, kapok (Ceiba pentandra) oil, papaya (Carica papaya) seed oil, tea seed (Camellia oleifera) oil, sunflower (Helianthus annuus) oil, safflower (Carthamus tinctorius) seed oil, eucalyptus (Eucalyptus globulus) oil, olive (Olea europaea) oil, jatropha (Jatropha curcas) oil, garlic (Allium sativum) oil, ginger (Zingiber officinale) oil, d-limonene, citronella oil or ceylon ironwood (Mesua ferrea) oil, mahua (Madhuca longifolia) oil. The content of methylated or ethylated seed oil varies from 60 to 80% w/w. The organosilicone surfactant includes trisiloxane ethoxylate, polyalkyleneoxide modified trisiloxane, polydimethylsiloxane, polyoxyethylene methyl polysiloxane, polyoxyalkylene methyl polysiloxane, polyether polymethyl siloxane copolymer, heptamethyl trisiloxane, polyalkyleneoxide modified heptamethyl trisiloxane, and polyether modified polysiloxane. It may be liquid or powder form. The content of organo silicone surfactant varies from 20 to 35% w/w. Emulsifier cum surfactant such as ethoxylated fatty alcohol, sodium dioctyl sulfosuccinate, sodium lauryl sulphate, sodium dodecyl benzene sulfonate, alkyl diphenyl sulfonates, sodium isopropyl naphthalene sulfonate, alkyl naphthalene sulfonate, and alkyl phenol ethoxylate, (1 to 5% w/w) added to bridge the vegetable seed oil and organosilicon surfactant. Example of super wetting cum spreading agent cum penetrant cum co-solvent include, but not limited to, blend of methylated seed oil (75% w/w) and polyalkyleneoxide modified trisiloxane (20% w/w) and ethoxylated fatty alcohol (5% w/w), blend of methylated seed oil (73% w/w) and polyalkyleneoxide modified heptamethyl trisiloxane (23% w/w) and sodium dioctyl sulfosuccinate (4% w/w), blend of methylated rapeseed oil (72% w/w) and polyether modified polysiloxane (25% w/w) and sodium lauryl sulphate (3% w/w).
The green solvent cum emulsifier is selected from, but not limited to, N,N decanamide chemistry (Armid series), propylene carbonate (Jeffsol series) or 2 ethylhexyl lactate base solvent (purasolve series). The examples of N,N decanamide chemistry (Armid series) are N,N-Dimethyloctanamide, N,N-Dimethylethylamine, N,N-Dimethylethanamide, and N,N-Dimethylmethanamide Dimethylformamide.
The wetting agent cum penetrant is selected from, but not limited to, polyoxyethylene, polyhydric alcohol. The polyoxyethylene surfactant may, for example, be a polyoxyethylene alkyl phenyl ether, a polyoxyethylene fatty acid ester, formalin condensate of a polyoxyethylene alkyl phenyl ether, a polyoxyethylene alkyl ether, a polyoxyethylene aryl ether, polyoxyethylene (mono-, di- or tri-)phenyl phenyl ether, polyoxyethylene (mono-, di- or tri-)benzyl phenyl ether, polyoxypropylene (mono-, di- or tri-)benzyl phenyl ether, polyoxyethylene (mono-, di- or tri-)styryl phenyl ether, polyoxypropylene (mono-, di- or tri-)styryl phenyl ether, a polymer of polyoxyethylene (mono-, di- or tri-)styryl phenyl ether, a polyoxyethylene/polyoxypropylene block polymer, an alkylpolyoxyethylene/polyoxypropylene block polymer ether, an alkylphenylpolyoxyethylene/polyoxypropylene block polymer ether, a polyoxyethylene bisphenyl ether, a polyoxyethylene resinate, a polyoxyethylene fatty acid amide, an alkylphenoxy polyethoxy ethanol, polyoxyethylene nonylphenoxy ether, a polyoxyethylene alkylamine or a polyoxyethylene rosin ester. Specific examples of the polyoxyethylene alkyl phenyl ether include polyoxyethylene nonyl phenyl ether, polyoxyethylene nonyl phenoxy ether, 4-nonylphenyl-polyethylene glycol, octylphenoxypolyethoxyethanol, polyoxyethylene nonyl pheno, polyoxyethylene octyl phenyl ether, polyoxyethylene styryl phenyl ether and polyoxyethylene alkyl phenyl ether. Specific examples of the polyoxyethylene fatty acid ester include a lanolin fatty acid polyethylene glycol ester, a polyoxyethylene C16-C18 fatty acid ester, a polyoxyethylene resinate and a polyoxyethylene fatty acid ester. Specific examples of the polyoxyethylene alkylamine include polyoxyethylene oleylamine. Specific examples of the polyoxyethylene alkyl ether include polyoxyethylene tridecyl ether, an alkyl aryl polyoxyalkene ether, and N,N-bis2-omega-hydroxypolyoxyethylene alkylamine. The polyhydric alcohol surfactant may, for example, the polyhydric alcohol surfactant include a polyoxyethylenehexitan fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a sorbitan fatty acid ester, mixture with a polyoxyethylene fatty acid ester and dialkyldimethylammonium polynaphthylmethanesulfonate, polyethylene glycol isotridecyl ester, polyethylene glycol monooleate, polyethylene glycol monostearate and a mixture of a polyhydric alcohol fatty acid ester and a polyhydric alcohol polyethylene oxide fatty acid ester. The preferred wetting agent cum penetrants are a polymer of polyoxyethylene (mono-, di- or tri-)styryl phenyl ether, a polyoxyethylene/polyoxypropylene block polymer, polyoxyethylene nonyl phenyl ether, a polyoxyethylenehexitan fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a sorbitan fatty acid ester, mixture with a polyoxyethylene fatty acid ester and a dialkyldimethylammonium polynaphthylmethanesulfonate, polyethylene glycol isotridecyl ester.
Dispersing agent is selected from, but not limited to, polyesters, polyamides, polycarbonates, polyurea and polyurethanes, acrylic polymers and copolymers, styrene copolymers, butadiene copolymers, polysaccharides such as starch and cellulose derivatives, vinylalcohol, vinylacetate and vinylpyrrolidone polymers and copolymers, polyethers, epoxy, phenolic and melamine resins, polyolefins and define copolymers and mixtures thereof. Examples of preferred polymers are acrylate polymers such as poly(methacrylate), poly(ethyl methacrylate), poly(methylmethacrylate), acrylate copoylmers and styrene-acrylic copolymers as defined herein below, poly(styrene-co maleic anhydride), cellulosic polymers such as ethyl cellulose, cellulose acetate, cellulose acetatebutyrate, acetylated mono, di, and triglycerides, poly(vinylpyrrolidone), vinyl acetate polymers and copolymers, poly(alkylene glycol), styrene butadiene copolymers, poly(orthoesters), polyarylphenyl ether sulphate ammonium salt, alkyl resins, and mixtures of two or more of these. Polymers that are biodegradable are also useful in the present invention. As used herein, a polymer is biodegradable if is not water soluble, but is degraded over a period of several weeks when placed in an application environment. Examples of biodegradable polymers that are useful in the present invention include biodegradable polyesters, starch, polylactic acid starch blends, polylactic acid, poly(lactic acid-glycolic acid) copolymers, polydioxanone, cellulose esters, ethyl cellulose, cellulose acetate butyrate, starch esters, starch ester-aliphatic polyester blends, modified corn starch, polycaprolactone, poly(namylmethacrylate), wood rosin, polyanhydrides, polyvinylalcohol, polyhydroxybutyratevalerate, biodegradable aliphatic polyesters, and polyhydroxybutyrate or mixtures thereof. The examples of dispersing agents are alkylated naphthalene sulfonate, sodium salt, sodium salt of naphthalene sulfonate condensate, sodium ligno sulfonate, sodium polycarboxylate, EO/PO block copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propyleneoxide-ethyleneoxide-copolymer, polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycolether-phosphate, tristyrylphenole with 16 moles EO, tristyrylphenol-polyglycol ether-phosphate, oleyl-polyglycol ether with ethylene oxide, tallow fatty amine polyethylene oxide, and nonylphenol polyglycol ether with 9-10 moles ethylene oxide.
Suspending agent is selected from, but not limited to, aluminum magnesium silicate, bentonite clay, silica, silicone dioxide, and attapulgite clay.
Anti-freezing agent is selected from, but not limited to, glycol (monoethylene glycol, diethylene glycol, polypropylene glycol, and polyethylene glycol), propane diols, glycerin, urea, magnesium sulfate heptahydrate, and sodium chloride.
Antifoaming agent is selected from, but not limited to, silicone oil, silicone compound, C10~C20 saturated fat acid compounds or C8~C10 aliphatic alcohols compound, silicone emulsion, vegetable oil based antifoam, and tallow based fatty acids.
Preservative is selected from, but not limited to, 1,2-benzisothiazol-3(2H)-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2- methyl-4-isothiazolin-3-one, propionic acid and its sodium salt, sorbic acid and its sodium or potassium salt, benzoic acid and its sodium salt, p-hydroxy benzoic acid sodium salt; methyl p-hydroxy benzoate; and biocide such as sodium benzoate, potassium sorbate, para hydroxy benzoates or mixtures thereof.
Thickening, gelling, and anti-settling agents generally fall into two categories, namely water-insoluble particulates and water-soluble polymers. It is possible to produce suspension concentrate formulations using clay and silica. Examples of these types of materials include, but not limited to, montmorillonite, e.g. bentonite; magnesium aluminum silicate; and attapulgite. Water-soluble polysaccharides have been used as thickening-gelling agents for many years. The types of polysaccharides most commonly used are natural extracts of seeds and seaweeds, synthetic derivatives of cellulose or mixtures thereof. Examples of these types of materials include, but not limited to, guar gum, locust bean gum, carrageenan, xanthan gum, alginates, methyl cellulose, sodium carboxymethyl cellulose (SCMC), hydroxyethyl cellulose (HEC) or mixtures thereof. Other types of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide or mixtures.
Stabilizer is selected from, but not limited to, butylated hydroxytoluene (BHT), epoxidized soybean oil (ESBO), and epichlorohydrin.
Buffering agent is selected from, but not limited to, calcium hydroxyapatite, potassium dihydrogen phosphate, sodium hydroxide, carbonated apatite, calcium carbonate, sodium bicarbonate, tricalcium phosphate, calcium phosphates, carbonated calcium phosphates, amine monomers, lactate dehydrogenase and magnesium hydroxide.
However, those skilled in the art will appreciate that it is possible to utilize additional agrochemically acceptable excipients without departing from the scope of the present invention. Such agrochemically acceptable excipients can be in the range from 1% to 99% of the total weight of the formulation.
More particularly, the present invention also refers to the method for preparation of suspo-emulsion (SE) formulation as describing the following steps:
Manufacturing process for suspo-emulsion (SE) formulation:
Step 1: Gel Solution preparation
The thickening agent is added in to DM water followed by preservative and homogenized till it gets completely dissolved and kept for 12-18 hours prior to use.
Step 2: Preparation of emulsifying (EC) phase
The green solvent cum emulsifier and wetting/spreading/co-solvent are charged into a vessel and the required quantity of technical (active ingredient 1) is added and mixed till it gets homogenized completely.
Step 3: Preparation of suspension (SC) phase
The required quantity of DM water is charged into a designated vessel for suspension concentrate production.
The dispersing agent(s), wetting cum penetrating agent and anti freezing agent are added and the contents are homogenized for 45 – 60 minutes by using high shear homogeniser.
The required quantity of technical (active ingredient 2) and suspending agent(s) are added into this premix and homogenized for 30-45 minutes.
The required quantity of antifoaming agent is added and then the material was grinded in dyno mill till desired particle size is achieved.
The remaining quantity of antifoaming agent is added after milling to avoid foaming.
Step 4: Preparation of suspo emulsion formulation
The SC premix is charged into other vessel followed by EC premix into SC and slowly homogenized to avoid phase change. The gel solution is added and the final product is ready.

The process for preparing the present pesticidal formulation can be modified accordingly by any person skilled in the art based on the knowledge of manufacturing the formulation. However, all such variation and modification is still covered by the scope of present invention.

EXAMPLES

The present invention has been described with reference to specific embodiment which is merely illustrative and not intended to limit the scope of the invention as defined in the present complete specification.

Biological Examples:

The pesticidal action of the inventive mixtures can be demonstrated by the experiments below. A synergistic effect exists wherever the action of a combination (ready-mix) or tank mix of active ingredient is greater than the sum of the action of each of the components alone. Therefore, a synergistically effective amount or an effective amount of a pesticidal composition or combination is an amount that exhibits greater pesticide activity than the sum of the pesticide activities of the individual components.

In the field of agriculture, it is often understood that the term “synergy” is as defined by Colby S.R. in an article entitled “ Calculation of the synergistic and antagonistic responses of herbicide combinations” published in the journal Weeds, 1967, 15, p.20-22, incorporated herein by reference in its entirety. The action expected for a given combination of two or three active components can be calculated as follows:

The objective of the present studies is to study the synergism, residual control, spectrum of activity and benefits of compositions comprising of pyriproxyfen, tolfenpyrad and at least one insecticide selected from group of diamide.

Example 1: Control of insect-pests in Okra crop.
Crop : Okra
Location : Durg, Chhattishgarh
No. of Treatments : 13
Crop age : 77 days after sowing.
Spray water volume : 480 liter per hectare
Method of Application: Foliar spray with battery operated knapsack sprayer fitted with hollow cone nozzle.

Observation Methods:
Jassid (Amrasca biguttula biguttula) control (%): Count the number of live jassid (nymphs and adults) per leaf, record the observations from 3 leaves per plant and 10 plants per plot. Record the observations on 3, 7, 10 and 14 days after application (DA A).

Fruit borer (Helicoverpa armigera) larval control (%): Count the number of live larvae per plant. Record observations from 10 plants per plot on 3, 7, 10 and 14th days after application (DAA).

T1 of Ex:1: Composition of Pyriproxyfen 8% + Tolfenpyrad 14% + Emamectin benzoate 1.6% SE (Suspo emulsion)

T1 of Ex:1: Storage stability-Pyriproxyfen 8%+Tolfenpyrad 14%+Emamectin benzoate 1.6% SE (Suspo emulsion)
Laboratory storage stability for 14 days
Parameters (in-house) Specifications Initial at 54±2 0C at 0±2 0C
Pyriproxyfen tech. 7.60 to 8.80 8.25 8.10 8.24
Tolfenpyrad tech. 13.30 to 14.70 14.50 14.25 14.48
Emamectin benzoate tech. 1.52 to 1.76 1.69 1.62 1.69
Pyriproxyfen suspensibility (%) 80 98.90 97.50 98.50
Tolfenpyrad suspensibility (%) 80 99.00 97.90 98.60
Emamectin benzoate suspensibility (%) 80 98.50 97.60 98.30
pH range (1% aq. Suspension) 5.5 to 8.5 7.50 7.50 7.55
Pourability (%) 95 98.20 98.20 97.80
Specific gravity 1.00-1.10 1.05 1.05 1.05
Viscosity at spindle no.62,20 rpm 350-800 cps 550 555 560
Particle size (micron) D50<3, D90<10 2.1,8.2 2.2,8.5 2.1,8.2
Persistent foam ml (after 1 minute) max. 60 nil nil nil

T1 of Ex:1: Room temperature storage stability
Parameters (in-house) Specification Initial 3 month 6 month
Pyriproxyfen tech. 7.60 to 8.80 8.25 8.25 8.24
Tolfenpyrad tech. 13.30 to 14.70 14.50 14.50 14.48
Emamectin benzoate tech. 1.52 to 1.76 1.69 1.69 1.68
Pyriproxyfen suspensibility (%) 80 98.90 98.90 98.50
Tolfenpyrad suspensibility (%) 80 99.00 99.00 98.60
Emamectin benzoate suspensibility (%) 80 98.50 98.50 98.30
pH range (1% aq. Suspension) 5.5 to 8.5 7.50 7.50 7.55
Pourability (%) 95 98.20 98.20 97.80
Specific gravity 1.00-1.10 1.05 1.05 1.05
Viscosity at spindle no.62,20 rpm 350-800 cps 550 550 560
Particle size (micron) D50<3, D90<10 2.1,8.2 2.1,8.2 2.1,8.2
Persistent foam ml (after 1 minute) max. 60 nil nil nil

The composition of Pyriproxyfen 8%+Tolfenpyrad 14%+Emamectin benzoate 1.6% SE (Suspo emulsion) meets the all inhouse specifications for storage stability studies in laboratory (at 54±2 °C & At 0±2 °C for 14 days) and room temperature (for 6 months).

T1 of Ex:1: Manufacturing process for 100 kg batch of Pyriproxyfen 8%+Tolfenpyrad 14%+Emamectin benzoate 1.6% SE (Suspo emulsion)
Step 1: 2% Gum solution: 2 kg xanthan gum and 2 kg 1,2-benzisothiazoline-3-one were charged into 96 kg water and was homogenized. The above mentioned mixture was prepared 12-18 hours prior to use.

Step 2: EC premix- 15.0 kg of N,N-Dimethylethylamine, 5.0 kg blend of methylated seed oil (75% w/w), polyalkyleneoxide modified trisiloxane (20% w/w) and ethoxylated fatty alcohol (5% w/w) were added into other vessel having slow stirring. Further, 8.0 kg of pyripoxyfen technical (melted) and 3.0 kg of polyoxyethylene octyl phenyl ether were added and mixed properly for 30-45 minutes.

Step 3: 32.9 kg of DM water and 5 kg of 1,2-propylene glycol were charged into designated vessel and mixed thoroughly.

Step 4: 0.5 kg of aluminum magnesium silicate, 4.50 kg of sodium salt of polycarboxylate and 0.10 kg of polydimethylsiloxane were added into the vessel having water and the contents were homogenized for 45 – 60 minutes using high shear homogeniser.

Step 5: 14.0 kg of tolfenpyrad technical and 1.6 kg of emamectin benzoate technical were added slowly to this premix and homogenised to achieve uniform slurry ready for grinding.
Step 6: Half of the quantity of antifoam was added prior grinding and then the material was subjected to grind in dyno mill till desired particle size was achieved.

Step 7: The remaining 0.10 kg of polydimethyl siloxane antifoam was added after the completion of grinding process and prior the sampling for in process analysis.

Step 8: The EC premix was mixed to this milled slurry under slow stirring and homogenized for 30-45 minutes.

Step 9: 10.0 kg of 2% gum solution was added to this formulation and sent to QC for quality check.

T2: of Ex: 1: Composition of Pyriproxyfen 5%+Tolfenpyrad 10%+Emamectin benzoate 0.56% SE

Ingredient Function Percent (w/w)
Pyriproxyfen tech. active ingredient 1 5.00
Tolfenpyrad tech. active ingredient 2 10.00
Emamectin benzoate tech. active ingredient 3 0.56
N,N-Dimethylethylamine solvent 12.00
polyoxyethylene octyl phenyl ether wetting agent 3.00
Blend of methylated seed oil (75% w/w) and polyalkyleneoxide modified trisiloxane (20% w/w) and ethoxylated fatty alcohol (5% w/w) wetting-spreading penetrating agent 5.00
Sodium salt of polycarboxylate dispersing agent 4.00
Aluminum magnesium silicate suspending agent 0.50
Polydimethylsiloxane anti foaming agent 0.20
1,2-benzisothiazolin-3(2H)-one preservative 0.20
Polypropylene glycol anti freezing agent 5.00
Xanthan gum thickner 0.20
Diluent water carrier 54.34
Total 100.00
technicals/active ingredients on 100% purity basis

T2: of Ex: 1: Storage stability-Pyriproxyfen 5%+Tolfenpyrad 10%+Emamectin benzoate 0.56% SE (Suspo emulsion)
Laboratory storage stability for 14 days
Parameters (in-house) Specifications Initial at 54±2 0C at 0±2 0C
Pyriproxyfen tech. 4.75 to 5.50 5.30 5.18 5.28
Tolfenpyrad tech. 9.50 to 10.50 10.50 10.3 10.50
Emamectin benzoate tech. 0.532 to 0.616 0.58 0.57 0.58
Pyriproxyfen suspensibility (%) 80 97.90 97.50 98.50
Tolfenpyrad suspensibility (%) 80 98.00 97.80 98.60
Emamectin benzoate suspensibility (%) 80 98.50 97.65 98.30
pH range (1% aq. Suspension) 5.5 to 8.0 7.30 7.50 7.55
Pourability (%) 95 98.20 98.25 97.80
Specific gravity 1.00-1.10 1.05 1.05 1.05
Viscosity at spindle no.62,20 rpm 350-800 cps 550 555 565
Particle size (micron) D50<3, D90<10 2.2,8.2 2.2,8.5 2.1,8.25
Persistent foam ml (after 1 minute) max. 60 nil nil nil

T2: of Ex: 1: Room temperature storage stability
Parameters (in-house) Specification Initial 3 month 6 month
Pyriproxyfen tech. 4.75 to 5.50 5.30 5.30 5.28
Tolfenpyrad tech. 9.50 to 10.50 10.50 10.50 10.45
Emamectin benzoate tech. 0.532 to 0.616 0.58 0.58 0.58
Pyriproxyfen suspensibility (%) 80 98.90 97.50 98.50
Tolfenpyrad suspensibility (%) 80 99.00 97.90 98.60
Emamectin benzoate suspensibility (%) 80 98.50 97.60 98.30
pH range (1% aq. Suspension) 5.5 to 8.5 7.50 7.50 7.55
Pourability (%) 95 98.20 98.20 97.80
Specific gravity 1.00-1.10 1.05 1.05 1.05
Viscosity at spindle no.62,20 rpm 350-800 cps 550 555 560
Particle size (micron) D50<3, D90<10 2.1,8.2 2.2,8.5 2.1,8.2
Persistent foam ml (after 1 minute) max. 60 nil nil nil
The composition of Pyriproxyfen 5%+Tolfenpyrad 10%+Emamectin benzoate 0.56% SE (Suspo emulsion) meets the all inhouse specifications for storage stability studies in laboratory (at 54±2 °C & At 0±2 °C for 14 days) and room temperature (for 6 months).

T2: of Ex: 1: Manufacturing process for 100 kg batch of Pyriproxyfen 5%+Tolfenpyrad 10%+Emamectin benzoate 0.56% SE (Suspo emulsion)
Step 1: 2% Gum solution: 2 kg Xanthan gum and 2 kg 1,2-benzisothiazoline-3-one were charged into 96 kg water and homogenized. The above mentioned mixture was made 12-18 hours prior to use.
Step 2: EC premix: 12.0 kg of N,N-Dimethylethylamine and 5.0 kg blend of methylated seed oil (75% w/w), polyalkyleneoxide modified trisiloxane (20% w/w) and ethoxylated fatty alcohol (5% w/w) were added into another vessel having slow stirring. Further, 5.0 kg of pyripoxyfen technical (melted) and 3.0 kg of polyoxyethylene octyl phenyl ether were added and mixed properly for 30-45 minutes.
Step 3: 44.34 kg of DM water and 5 kg of 1,2-propylene glycol were charged into designated vessel and mixed thoroughly.
Step 4: 0.5 kg of aluminum magnesium silicate, 4.00 kg of sodium salt of polycarboxylate, 3.0 kg of polyoxyethylene octyl phenyl ether and 0.10 kg of polydimethylsiloxane were added into the vessel having water and the contents were homogenized for 45 – 60 minutes using high shear homogeniser.
Step 5: 10.0 kg of tolfenpyrad technical and 0.56 kg of emamectin Benzoate technical were added slowly to this premix and homogenized to achieve uniform slurry ready for grinding.
Step 6: Prior grinding half of the quantity of antifoam was added and then the material was subjected to grind in dyno mill till desired particle size was achieved.
Step 7: The remaining 0.10 kg of polydimethyl siloxane antifoam was added before sampling for in process analysis and on the completion of grinding process.
Step 8: EC premix was mixed to this milled slurry under slow stirring and homogenized for 30-45 minutes.
Step 9: 10.0 kg of 2% gum solution was added to this formulation and sent to QC for quality check.

T3: of Ex: 1: Composition Pyriproxyfen 6%+Tolfenpyrad 7.2%+Emamectin benzoate 0.64% SE

Ingredient Function Percent (w/w)
Pyriproxyfen tech. active ingredient 1 6.00
Tolfenpyrad tech. active ingredient 2 7.20
Emamectin benzoate tech. active ingredient 3 0.64
N,N-Dimethylethylamine solvent 18.00
polyoxyethylene octyl phenyl ether wetting agent 3.00
Blend of methylated seed oil (75% w/w) and polyalkyleneoxide modified trisiloxane (20% w/w) and ethoxylated fatty alcohol (5% w/w) wetting-spreading penetrating agent 5.00
Sodium salt of polycarboxylate dispersing agent 4.00
Aluminum magnesium silicate suspending agent 0.50
Polydimethylsiloxane anti foaming agent 0.20
1,2-benzisothiazolin-3(2H)-one preservative 0.20
Polypropylene glycol anti freezing agent 5.00
Xanthan gum thickner 0.20
Diluent water carrier 50.06
Total 100.00
technicals/active ingredients on 100% purity basis

T3: of Ex: 1: Storage stability-Pyriproxyfen 6%+Tolfenpyrad 7.2%+Emamectin benzoate 0.64% SE (Suspo emulsion)
Laboratory storage stability for 14 days
Parameters (in-house) Specifications Initial at 54±2 0C at 0±2 0C
Pyriproxyfen tech. 5.70 to 6.60 6.25 6.10 6.25
Tolfenpyrad tech. 6.84 to 7.92 7.50 7.35 7.49
Emamectin benzoate tech. 0.608 to 0.702 0.67 0.65 0.67
Pyriproxyfen suspensibility (%) 80 98.95 97.55 98.50
Tolfenpyrad suspensibility (%) 80 98.50 97.95 98.60
Emamectin benzoate suspensibility (%) 80 98.55 97.60 98.30
pH range (1% aq. Suspension) 5.5 to 8.5 7.50 7.50 7.55
Pourability (%) 95 98.20 98.20 97.80
Specific gravity 1.00-1.10 1.05 1.05 1.05
Viscosity at spindle no.62,20 rpm 350-800 cps 550 555 560
Particle size (micron) D50<3, D90<10 2.1,8.2 2.2,8.5 2.1,8.2
Persistent foam ml (after 1 minute) max. 60 nil nil nil

T3: of Ex: 1: Room temperature storage stability
Parameters (in-house) Specification Initial 3 month 6 month
Pyriproxyfen tech. 5.70 to 6.60 6.25 6.25 6.23
Tolfenpyrad tech. 6.84 to 7.92 7.50 7.5 7.49
Emamectin benzoate tech. 0.608 to 0.702 0.67 0.67 0.665
Pyriproxyfen suspensibility (%) 80 98.90 97.50 98.50
Tolfenpyrad suspensibility (%) 80 99.00 97.90 98.60
Emamectin benzoate suspensibility (%) 80 98.50 97.60 98.30
pH range (1% aq. Suspension) 5.5 to 8.5 7.50 7.50 7.55
Pourability (%) 95 98.20 98.20 97.80
Specific gravity 1.00-1.10 1.05 1.05 1.05
Viscosity at spindle no.62,20 rpm 350-800 cps 550 555 560
Particle size (micron) D50<3, D90<10 2.1,8.2 2.2,8.5 2.1,8.2
Persistent foam ml (after 1 minute) max. 60 nil nil nil
The composition ofPyriproxyfen 6%+Tolfenpyrad 7.2%+Emamectin benzoate 0.64% SE (Suspo emulsion) meets the all inhouse specifications for storage stability studies in laboratory (at 54±2 °C & At 0±2 °C for 14 days) and room temperature (for 6 months).

T3: of Ex: 1: Manufacturing process for 100 kg batch of Pyriproxyfen 6%+Tolfenpyrad 7.2%+Emamectin benzoate 0.64% SE (Suspo emulsion)
Step 1: 2% Gum solution: 2 kg xanthan gum and 2 kg 1,2-benzisothiazoline-3-one were charged into 96 kg water and homogenized. The above mentioned mixture was made 12-18 hours prior to use.
Step 2: EC premix: 18.0 kg of N,N-Dimethylethylamine, 6.0 kg of pyriproxifen technical and 5.0 kg of blend of methylated seed oil (75% w/w), polyalkyleneoxide modified trisiloxane (20% w/w) and ethoxylated fatty alcohol (5% w/w) were added into another vessel having slow stirring. Further, 6.0 kg of pyripoxyfen technical (melted) and 3.0 kg of polyoxyethylene octyl phenyl ether were added and mixed properly for 30-45 minutes.
Step 3: 40.06 kg of DM water and 5 kg of 1,2-propylene glycol were charged into designated vessel and mixed thoroughly.
Step 4: 0.5 kg of aluminum magnesium silicate, 4.00 kg of sodium salt of polycarboxylate , 3.0 kg of polyoxyethylene octyl phenyl ether and 0.10 kg of polydimethylsiloxane were added into the vessel having water and the contents were homogenized for 45 – 60 minutes using high shear homogeniser.
Step 5: 7.2 kg of tolfenpyrad technical and 0.64 kg of emamectin benzoate technical were slowly added to this premix and homogenized to achieve uniform slurry ready for grinding.
Step 6: Prior grinding half of the quantity of antifoam was added and then the material was subjected to grind in dyno mill till desired particle size was achieved.
Step 7: The remaining 0.10 kg of polydimethyl siloxane antifoam was added before sampling for in process analysis on completion of grinding process.
Step 8: EC premix was mixed to this milled slurry under slow stirring and homogenized for 30-45 minutes.
Step 9: 10.0 kg of 2% gum solution was added to this formulation and sent to QC for quality check.

Table 1: Treatment details [Example 1]
Treatment number Treatment details gram active ingredient per hectare
T1 Pyriproxyfen 8%+Tolfenpyrad 14%+Emamectin benzoate 1.6% SE 50+87.5+10
T2 Pyriproxyfen 5%+Tolfenpyrad 10%+Emamectin benzoate 0.56% SE 62.5+125+7
T3 Pyriproxyfen 6%+Tolfenpyrad 7.2%+Emamectin benzoate 0.64% SE 75+90+8
T4 Pyriproxyfen 10% EC 50
T5 Pyriproxyfen 10% EC 62.5
T6 Pyriproxyfen 10% EC 75
T7 Tolfenpyrad 15% EC 87.5
T8 Tolfenpyrad 15% EC 90
T9 Tolfenpyrad 15% EC 125
T10 Emamectin benzoate 1.9% EC 7
T11 Emamectin benzoate 1.9% EC 8
T12 Emamectin benzoate 1.9% EC 10
T13 UTC (Untreated Control) -

T1 to T3- present compositions, T4 to T12-market available products.

Table 2: Jassid and fruit borer larval control in okra crop [Example 1]

Treatment number Jassid control (%) on Fruit borer larval control (%)
3rd DAA 7th DAA 10th DAA 14th DAA 3 DAA 7th DAA 10th DAA 14th DAA
Observed Expected Colby's ratio Observed Expected Colby's ratio
T1 100.0 94.12 1.06 98.2 90.2 82.4 100.0 97.51 1.03 100 97.2 94.6
T2 100.0 95.51 1.05 99.2 95.4 86.8 100.0 97.67 1.02 100 96.4 91.8
T3 100.0 95.10 1.05 98.6 93.6 85.2 100.0 97.68 1.02 100 98.6 95.2
T4 57.4 48.6 35.2 20.8 50.8 30.8 44.4 30.8 10.2
T5 63.2 56.4 43.6 30.6 55.4 36.2 50.2 36.2 22.4
T6 67.2 60.2 50.8 43.6 62.2 45.6 58.8 45.6 34.6
T7 66.8 57.8 49.4 41.2 62.8 43.6 57.6 43.6 25.8
T8 68.6 61.4 52.2 44.8 68.4 48.4 60.2 48.4 33.6
T9 75.8 70.2 65.8 58.4 78.6 60.4 70.4 60.4 50.6
T10 49.6 48.8 29.8 19.6 75.6 56.2 69.2 56.2 41.8
T11 52.4 45.6 36.4 24.6 80.6 66.2 75.6 66.2 52.6
T12 58.4 53.8 45.2 34.8 86.4 74.4 82.4 74.4 65.2
T13 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0

All the present compositions (T1 to T3) provide synergistic control of key sucking pests, i.e., jassid and fruit borer larval in okra crop on 3rd DAA and provides residual control up to 14 DAA.

Ex:1: Conclusion: Among the various compositions as shown in Table 1 treatment number T1-T3 are considered to be present compositions which showed excellent synergism and effectiveness against jassid control and fruit borer larval control on okra crop. In Table 2 the jassid control observed at 3 DAA (days after application) for T1 to T3 were 100%. Further, at 7 DAA T2 showed (99.2%) followed by T3 (98.6%) and T1 (98.2%) of jassid control. Similarly on 10 DAA T2 showed (95.4%) followed by T3 (93.6%) and T1 (90.2%) of jassid control. At last on 14 DAA T2 showed (86.8%) followed by T3 (85.2%) and T1 (82.4%) control on jassid when compared with market available products.

In addition to that in Table 2 the fruit borer larval control of T1-T3 was 100%. On 3 DAA and 7 DAA. Further, at 10 DAA T3 showed (98.6%) followed by T1 (97.2%) and T2 (96.4%) fruit borer larval control. Similarly, at 14 DAA T3 showed (95.2%) followed by T1 (94.6%) and T2 (91.8%) fruit borer larval control when compared with market available products. At last but not least the Colby’s ratio was found to be >1 which shows stronger synergism of the present compositions to control jassid and fruit borer larval.

Example 2: Control of insect-pests in chilli crop.
Crop : Chilli
Location : Gondal, Gujarat
No. of Treatments : 10
Crop age : 85 days after transplanting.
Spray water volume : 500 liter per hectare
Method of Application: Foliar spray with battery operated knapsack sprayer fitted with hollow cone nozzle.

Observation Methods:
Thrips (Scirtothrips dorsalis): Count the number of live thrips by shaking the twigs on black piece of paper. Record the observations from 3 twigs per plant and 10 plants per plot on 3, 7, 10 and 14 DAA (days after application). Calculate thrips control (%) as observed control and apply colby’s formula to calculate synergism.

Chilli Flowers and Fruit counts: count the number of flowers and healthy fruits per plant, record the observations from 10 plants per plot on 14th DAA.

T1 of Ex.2: Composition of Pyriproxyfen 6%+Tolfenpyrad 7.2%+Abamectin 0.8% SE (Suspo emulsion)

Ingredient Function Percent (w/w)
Pyriproxyfen tech. active ingredient 1 6.00
Tolfenpyrad tech. active ingredient 2 7.20
Abamectin tech. active ingredient 3 0.80
2 ethylhexyl lactate base solvent solvent 15.00
Blend of methylated 5 rapeseed oil (72% w/w) and polyether modified polysiloxane (25% w/w) and sodium lauryl sulphate (3% w/w) wetting-spreading penetrating agent 5.00
acrylate copoylmers and styrene-acrylic
copolymers dispersing agent 4.00
polyoxyethylene/polyoxypropylene block polymer wetting agent 3.00
Bentonite clay suspending agent 1.00
Polydimethylsiloxane anti foaming agent 0.20
1,2-benzisothiazolin-3(2H)-one preservative 0.20
Polypropylene glycol anti freezing agent 5.00
Xanthan gum thickner 0.20
Diluent water carrier 52.40
Total 100.00
technicals/active ingredients on 100% purity basis

T1 of Ex.2: Storage stability-Pyriproxyfen 6%+Tolfenpyrad 7.2%+Abamectin 0.8% SE (Suspo emulsion)
Laboratory storage stability for 14 days
Parameters (in-house) Specifications Initial at 54±2 0C at 0±2 0C
Pyriproxyfen tech. 5.70 to 6.60 6.30 6.15 6.3
Tolfenpyrad tech. 6.84 to 7.92 7.55 7.35 7.52
Abamectin tech. 0.76 to 0.88 0.85 0.81 0.85
Pyriproxyfen suspensibility (%) 80 98.90 97.55 98.50
Tolfenpyrad suspensibility (%) 80 99.50 97.90 98.60
Abamectin suspensibility (%) 80 98.50 97.60 98.35
pH range (1% aq. Suspension) 5.5 to 8.5 7.52 7.50 7.55
Pourability (%) 95 98.20 98.25 97.80
Specific gravity 1.00-1.10 1.03 1.03 1.03
Viscosity at spindle no.62,20 rpm 350-800 cps 550 560 560
Particle size (micron) D50<3, D90<10 2.1,8.2 2.2,8.5 2.1,8.2
Persistent foam ml (after 1 minute) max. 60 nil nil nil

T1 of Ex.2: Room temperature storage stability
Parameters (in-house) Specification Initial 3 month 6 month
Pyriproxyfen tech. 5.70 to 6.60 6.30 6.30 6.28
Tolfenpyrad tech. 6.84 to 7.92 7.55 7.55 7.54
Abamectin tech. 0.76 to 0.88 0.85 0.85 0.84
Pyriproxyfen suspensibility (%) 80 98.90 98.90 98.50
Tolfenpyrad suspensibility (%) 80 99.50 99.45 98.60
Abamectin suspensibility (%) 80 98.50 98.48 98.35
pH range (1% aq. Suspension) 5.5 to 8.5 7.52 7.52 7.53
Pourability (%) 95 98.20 98.25 98.15
Specific gravity 1.00-1.10 1.03 1.03 1.03
Viscosity at spindle no.62,20 rpm 350-800 cps 550 550 560
Particle size (micron) D50<3, D90<10 2.1,8.2 2.2,8.5 2.1,8.2
Persistent foam ml (after 1 minute) max. 60 nil nil nil
The composition of Pyriproxyfen 6%+Tolfenpyrad 7.2%+Abamectin 0.8% SE (Suspo emulsion) meets the all inhouse specifications for storage stability studies in laboratory (at 54±2 °C & At 0±2 °C for 14 days) and room temperature (for 6 months).

T1 of Ex.2: Manufacturing process for 100 kg batch of Pyriproxyfen 6%+Tolfenpyrad 7.2%+Abamectin 0.8% SE (Suspo emulsion)

Step 1: 2% Gum solution: 2 kg xanthan gum and 2 kg 1,2-benzisothiazoline-3-one were charged into 96 kg water and homogenized. The above mentioned solution was made 12-18 hours prior its use.

Step 2: EC premix: 15.0 kg of 2 ethylhexyl lactate base solvent, 5.0 kg of blend of methylated 5 rapeseed oil (72% w/w), polyether modified polysiloxane (25% w/w) and sodium lauryl sulphate (3% w/w) were added into other vessel having slow stirring. Now 6.0 kg of pyripoxyfen technical (melted) and 3.0 kg of polyoxyethylene octyl phenyl ether were added and mixed properly for 30-45 minutes.

Step 3: 42.5 kg of DM water and 5 kg of 1,2-propylene glycol were charged into designated vessel and mixed thoroughly.

Step 4: 1.0 kg of bentonite clay, 3.0 kg of polyoxyethylene/polyoxypropylene block polymer, 4.0 kg of acrylate copoylmers, styrene-acrylic copolymer and 0.10 kg of polydimethylsiloxane were added into the vessel containing water and the contents were homogenized for 45–60 minutes using high shear homogeniser.

Step 5: 7.20 kg of tolfenpyrad technical and 0.8 kg of abamectin technical were added slowly to this premix and homogenized to achieve uniform slurry ready for grinding.

Step 6: Half of the quantity of antifoam was added prior grinding and then the material was subjected to grind in Dyno mill until the desired particle size was achieved.

Step 7: Remaining 0.10 kg of polydimethyl siloxane antifoam was added after the completion of grinding process and prior the sampling for in process analysis.

Step 8: The EC premix was mixed to this milled slurry under slow stirring and homogenized for 30-45 minutes.

Step 9: 10.0 kg of 2% gum solution was added to this formulation and sent to QC for quality check.

T2: of Ex: 2: Composition of Pyriproxyfen 7.5%+Tolfenpyrad 12%+Abamectin 0.8% OD
Ingredients Function Percent (w/w)
Pyriproxyfen tech. active ingredient 1 7.50
Tolfenpyrad tech. active ingredient 2 12.00
Abamectin tech. active ingredient 3 0.80
Calcium alkyl benzene sulfoante oil emulsifier 9.00
ethoxylated alkyl phenols co-emulsifier 7.50
alkyl aryl sulfonates non-aqueous dispersant 4.00
polyalkyleneoxide modified heptamethyl trisiloxane wetting-spreading penetrating agent 3.00
sodium polycarboxylate aqueous dispersant 1.50
Silicon antifoam antifoam 0.30
Bentonite clay rheology modifier 1.50
methyl ester of palm oil and vegetable oil carrier 52.90
Total 100.00
technicals/active ingredients on 100% purity basis

T2: of Ex: 2: Storage Stability-Pyriproxyfen 7.5%+Tolfenpyrad 12%+Abamectin 0.8% OD
Laboratory storage stability for 14 days
Parameters (in-house) Specification Initial at 54±2 0C at 0±2 0C
Pyriproxyfen tech. 7.125 to 8.25 7.80 7.6 7.78
Tolfenpyrad tech. 11.40 to 12.60 12.50 12.3 12.5
Abamectin tech. 0.76 to 0.88 0.85 0.83 0.85
Pyriproxyfen suspensibility (%) 80 98.70 98.70 98.64
Tolfenpyrad suspensibility (%) 80 98.90 98.96 98.75
Abamectin suspensibility (%) 80 98.97 98.90 98.85
pH range (1% aq. Suspension) 4.0 to 6.0 5.52 5.53 5.50
Pourability (%) 95 98.00 98.00 98.00
Specific gravity 1.00-1.10 1.05 1.05 1.05
Viscosity at spindle no.62,20 rpm 350-800 cps 680 690 690
Particle size (micron) D50<3, D90<10 2.0,7.8 2.0,7.8 2.0,7.9
Persistent foam ml (after 1 minute) max. 60 nil nil nil

T2: of Ex: 2: Room temperature storage stability
Parameters (in-house) Specification Initial 3 month 6 month
Pyriproxyfen tech. 7.125 to 8.25 7.80 7.80 7.78
Tolfenpyrad tech. 11.40 to 12.60 12.50 12.50 12.48
Abamectin tech. 0.76 to 0.88 0.85 0.85 0.848
Pyriproxyfen suspensibility (%) 80 98.70 98.70 98.60
Tolfenpyrad suspensibility (%) 80 98.90 98.95 98.75
Abamectin suspensibility (%) 80 98.95 98.90 98.80
pH range (1% aq. Suspension) 4.0 to 6.0 5.52 5.53 5.50
Pourability (%) 95 98.00 98.00 98.00
Specific gravity 1.00-1.10 1.05 1.05 1.05
Viscosity at spindle no.62,20 rpm 350-800 cps 680 690 690
Particle size (micron) D50<3, D90<10 2.0,7.8 2.0,7.8 2.0,7.9
Persistent foam ml (after 1 minute) max. 60 nil nil nil
The composition of Pyriproxyfen 7.5%+Tolfenpyrad 12%+Abamectin 0.8% OD meets the all inhouse specifications for storage stability studies in laboratory (at 54±2 °C & At 0±2 °C for 14 days) and room temperature (for 6 months).

T2: of Ex: 2: Manufacturing Process for 100 kg batch of Pyriproxyfen 7.5%+Tolfenpyrad 12%+Abamectin 0.8% OD

Step 1: 15% Bentonite clay solution preparation: 15 kg of bentonite was added into 85 kg of methyl ester of pongamia oil and vegetable oil and was homogenized till it gets completely dissolved. The above mentioned mixture was kept for 12-18 hours prior to use.

Step 2: OD Premix: 43.40 kg of methyl ester of pongamia oil and vegetable oil were charged into a designated vessel for OD production.
Step 3: 9.0 kg of calcium alkyl benzene sulfoante, 1.50 kg of sodium polycarboxylate, 7.50 kg of ethoxylated alkyl phenols ,4.00 kg of alkyl aryl sulfonates and 0.15 kg of polydimethyl siloxane were added and the contents were homogenized for 45 – 60 minutes using high shear homogeniser.

Step 4: 7.5 kg of pyriproxifen technical, 12.0 kg of tolfenpyrad and 0.8 kg of abamectin technical were added into this premix and homogenized for 30-45 minutes.

Step 5: The remaining 0.15 kg of silicon antifoam, 3.0 kg of polyalkyleneoxide modified heptamethyl trisiloxane and 10 kg of 15% bentonite solution were added after milling to avoid foaming.
Step 6: The final formulation was sent to QC for quality check.

Table 3: Treatment details [Example 2]
Treatment number Treatment details gram active ingredient per hectare
T1 Pyriproxyfen 6%+Tolfenpyrad 7.2%+Abamectin 0.8% SE 75+90+10
T2 Pyriproxyfen 7.5%+Tolfenpyrad 12%+Abamectin 0.8% OD 75+120+8
T3 Pyriproxyfen 10% EC+Tolfenpyrad 15% EC+Abamectin 1.9% EC (tank mixes) 75+90+10
T4 Pyriproxyfen 10% EC+Tolfenpyrad 15% EC+Abamectin 1.9% EC (tank mixes) 75+120+8
T5 Pyriproxyfen 10% EC 75
T6 Tolfenpyrad 15% EC 90
T7 Tolfenpyrad 15% EC 120
T8 Abamectin 1.9% EC 8
T9 Abamectin 1.9% EC 10
T10 UTC (Untreated Control) -

T1 and T2 present compositions, T3 and T4-tank mixes of market available products, T5 to T9-market available products.

Table 4: Control of chilli thrips [Example 2]
Treatment number Thrips control (%) on cottonchilli crop avg. number of flowers per plant avg. number of green fruits per plant
3rd DAA 7th DAA 10th DAA 14th DAA
Observed Expected Colby's ratio
T1 98.6 95.20 1.04 96.4 86.4 75.8 43.1 56.3
T2 99.2 96.25 1.03 98.2 90.2 80.2 43.5 57.1
T3 94.6 95.20 0.99 84.6 75.4 60.2 38.5 50.7
T4 95.8 96.25 1.00 87.8 80.6 67.6 38.7 52.3
T5 58.4 45.6 30.6 18.8 22.5 34.8
T6 67.8 57.4 46.2 36.2 28.7 40.2
T7 78.2 70.2 58.8 47.8 30.6 44.3
T8 58.6 48.4 39.6 30.4 26.8 37.6
T9 64.2 56.2 45.2 38.2 27.3 41.7
T10 0.0 0.0 0.0 0.0 18.3 23.3

Both the present compositions (T1, T2) synergistic control as well as residual control up to 14 days as compared to the tank mixes (T3, T4) and market products (T5 to T9). Both the present compositions (T1, T2) also yielded higher number of flowers and green chilli fruits per plant.

Ex: 2: Conclusion: Among the various compositions as shown in Table 3 treatment numbers T1-T2 are considered to be present compositions which showed excellent synergism and effectiveness against chilli thrips control in chilli crop. Further, in Table 4 the control of chilli thrips showed maximum of 99.2% (T2) on 3 DAA (days after application) followed by 98.6% (T1). Further, on 7 DAA T2 showed (98.2%) and T1 showed (96.4%) control of thrips. Similarly, on 10 DAA T2 showed (90.2%) and T1 showed (86.4%) control of thrips. Moreover, on 14 DAA T2 showed (80.2%) and T1 showed (75.8%) control of chilli thrips on chilli crop as compared to tank mixes of market available products and market available products.

In addition to that the average number of flowers per plant were found to be 43.5 (T2) followed by 43.1 (T1) when compared with tank mixes of market available products and market available products. Moreover, the average number of green fruits per plant were found to be 57.1 (T2) followed by 56.3 (T1) as compared to tank mixes of market available products and market available products. At last the Colby’s ratio found for T1 and T2 (present compositions) were = 1 which shows effectiveness and synergism of the present compositions as compared to tank mixes of market available products and market available products.

Example 3: Control of Insect-pests in brinjal crop.
Crop : Brijal
Location : Kanthariya, Anand, Gujarat
No. of Treatments : 9
Crop age : 66 days after sowing.
Spray water volume : 500 liter per hectare
Method of Application: Foliar spray with battery operated knapsack sprayer fitted with hollow cone nozzle.

Observation Methods:
Brinjal shoot & fruit borer (Leucinoides orbonalis) control: Brinjal shoot and fruit borer adult lays eggs on flowers, tender shoots and young fruits. The larvae after hatching from eggs, bores into tender shoots and fruits, remains insides shoots and fruits and causing damage to shoots and fruits. The observations on shoots damage recorded by counting number of healthy (non infested) and damage (infested) shoots per plant, 10 plants per plot. The infested shoots and fruits were removed from the plants after observations at before spray. The observations were recorded at before spray and 15 days after spray.

Whitefly count: count the number of live whitefly adults per leaf, record the observations from 3 leaves per plant and 10 plants per plot. Observations were recorded at before spray and 15 days after spray.

T1 of Ex.3: Composition of Pyriproxyfen 7.5%+Tolfenpyrad 12%+Emamectin benzoate 0.8% OD (Oil Dispersion)

Ingredients Function Percent (w/w)
Pyriproxyfen tech. active ingredient 1 7.50
Tolfenpyrad tech. active ingredient 2 12.00
Emamectin benzoate tech. active ingredient 3 0.80
Polyoxyethylene sorbitol hexaoleate oil emulsifier 10.00
Ethoxylated sorbitan ester co-emulsifier 8.50
polyalkyleneoxide modified heptamethyl trisiloxane wetting-spreading penetrating agent 3.00
Salts of polyolefin condensates non-aqueous dispersant 2.50
Styrene acrylic polymeer aqueous dispersant 1.50
Silicon antifoam antifoam 0.30
Bentonite clay rheology modifier 1.50
methyl ester of pongamia oil and vegetable oil carrier 52.40
Total 100.00
technicals/active ingredients on 100% purity basis

T1 of Ex.3: Storage Stability-Pyriproxyfen 7.5%+Tolfenpyrad 12%+Emamectin benzoate 0.8% OD
Laboratory storage stability for 14 days
Parameters (in-house) Specification Initial at 54±2 0C at 0±2 0C
Pyriproxyfen tech. 7.125 to 8.25 7.80 7.55 7.78
Tolfenpyrad tech. 11.40 to 12.60 12.50 12.35 12.49
Emamectin benzoate tech. 0.76 to 0.88 0.85 0.81 0.84
Pyriproxyfen suspensibility (%) 80 98.70 98.10 98.60
Tolfenpyrad suspensibility (%) 80 98.90 98.50 98.70
Emamectin benzoate suspensibility (%) 80 98.90 98.40 98.80
pH range (1% aq. Suspension) 4.0 to 6.0 5.50 5.45 5.50
Pourability (%) 95 98.00 98.10 98.00
Specific gravity 1.00-1.10 1.03 1.03 1.03
Viscosity at spindle no.62,20 rpm 350-800 cps 650 675 655
Particle size (micron) D50<3, D90<10 2.0,7.8 2.1,8.0 2.0,7.9
Persistent foam ml (after 1 minute) max. 60 nil nil nil

T1 of Ex.3: Room temperature storage stability
Parameters (in-house) Specification Initial 3 month 6 month
Pyriproxyfen tech. 7.125 to 8.25 7.80 7.80 7.78
Tolfenpyrad tech. 11.40 to 12.60 12.50 12.50 12.48
Emamectin benzoate tech. 0.76 to 0.88 0.85 0.85 0.84
Pyriproxyfen suspensibility (%) 80 98.70 98.70 98.60
Tolfenpyrad suspensibility (%) 80 98.90 98.90 98.70
Emamectin benzoate suspensibility (%) 80 98.90 98.90 98.80
pH range (1% aq. Suspension) 4.0 to 6.0 5.50 5.50 5.50
Pourability (%) 95 98.00 98.00 98.00
Specific gravity 1.00-1.10 1.03 1.03 1.03
Viscosity at spindle no.62,20 rpm 350-800 cps 650 650 655
Particle size (micron) D50<3, D90<10 2.0,7.8 2.0,7.8 2.0,7.9
Persistent foam ml (after 1 minute) max. 60 nil nil nil
The composition of Pyriproxyfen 7.5%+Tolfenpyrad 12%+Emamectin benzoate 0.8% OD meets the all inhouse specifications for storage stability studies in laboratory (at 54±2 °C & At 0±2 °C for 14 days) and room temperature (for 6 months).

T1 of Ex.3: Manufacturing Process for 100 kg batch of Pyriproxyfen 7.5%+Tolfenpyrad 12%+Emamectin benzoate 0.8% OD
Step 1: 15% Bentonite clay solution preparation: 15 kg of bentonite clay was added in to 85 kg of methyl ester of pongamia oil and vegetable oil and homogenized till it gets completely dissolved. The above mentioned solution was kept 12-18 hours prior its use.

Step 2: OD premix: 42.40 kg of methyl ester of pongamia oil and vegetable oil were charged into a designated vessel for OD production.
Step 3: 10.0 kg of polyoxyethylene sorbitol hexaoleate, 1.50 kg of styrene acrylic polymer, 8.50 kg of ethoxylated sorbitan ester, 2.50 kg of salts of polyolefin condensates and 0.15 kg of polydimethyl siloxane were added and homogenized for 45 – 60 minutes using high shear homogeniser.

Step 4: 7.50 kg of pyriproxifen technical, 0.8 kg of emamectin benzoate technical and 12.0 kg of tolfenpyrad technical were added into the above mentioned premix and homogenized for 30-45 minutes.

Step 5: The remaining 0.15 kg of silicon antifoam, 3.0 kg of polyalkyleneoxide modified heptamethyl trisiloxane and 10 kg of 15% bentonite caly solution were added after milling to avoid foaming.

Step 6: The final formulation was sent to QC for quality check

Table 5: Treatment details [Example 3]

Treatment number Treatment details gram active ingredient per hectare
T1 Pyriproxyfen 7.5%+Tolfenpyrad 12%+Emamectin benzoate 0.8% OD 75+120+8
T2 Pyriproxyfen 10% EC+Tolfenpyrad 15% EC+Emamectin benzoate 1.9% EC (tank mixes) 75+120+8
T3 Pyriproxyfen 7.5%+Tolfenpyrad 12% SC 75+120
T4 Pyriproxyfen 7.5%+Emamectin benzoate 0.8% SC 75+8
T5 Tolfenpyrad 12%+Emamectin benzoate 0.8% SC 120+8
T6 Pyriproxyfen 10% EC 75
T7 Tolfenpyrad 15% EC 120
T8 Emamectin benzoate 1.9% EC 8
T9 Untreated control (without spray) -

T1- present composition, T2-tank mix of market available products, T3 to T5-conventional ready- mix formulations, T6 to T8-market available products.

Table 6: Bioefficacy against brinjal shoot and fruit borers and fruits yield [Example 3]
Treatment number Brinjal shoot & fruit borer damage Number of whitefly per leaf Average umber of healthy fruits per plant Increase (%) in healthy fruits over T9
Shoot damage (%) Fruit damage (%)
Before 1st spray 15 days after 1st spray Before 1st spray 15 days after 1st spray Before 1st spray 15 days after 1st spray
T1 2.17 0.00 1.15 0.00 12.67 1.22 22.4 187.18
T2 2.53 1.32 1.12 0.72 13.25 2.65 18.4 135.90
T3 1.98 3.96 1.56 1.23 14.92 2.96 15.6 100.00
T4 2.33 3.74 1.43 1.17 11.47 3.12 16.1 106.41
T5 2.61 3.23 1.39 1.12 13.62 3.86 16.8 115.38
T6 1.96 6.84 1.15 2.85 12.57 2.26 11.2 43.59
T7 2.14 5.78 1.72 1.88 13.82 3.16 13.9 78.21
T8 2.64 4.62 1.57 1.72 12.48 6.75 14.5 85.90
T9 2.2 11.26 1.38 8.7 13.8 26.42 7.8 0.00

The present composition T1 (Pyriproxyfen 7.5%+Tolfenpyrad 12%+Emamectin benzoate 0.8% OD) provides superior control and complete protections against brinjal shoot and fruit borer as compared to all other treatments (T2 to T8).
Ex:3: Conclusion: Among the various compositions as shown in Table 5 treatment number T1 is considered to be present composition which showed excellent synergism and effectiveness against brinjal shoot and fruit borers and number of whitefly per leaf in brinjal crop. Further, in Table 6 the control of shoot damage after 15 days of first spray was (T1) 0.00%. Similarly, for fruit damage after 15 days of first spray was (T1) 0.00%. Moreover, the number of whitefly per leaf after 15 days of first spray was 1.22 (T1) as compared to tank mix of market available products, conventional ready mix formulations and market available products.

In addition to that the average number of healthy fruits per plant was maximum of T1 i.e. 22.4. Similarly, increase in healthy fruits over T9 i.e. untreated control (without spray) was 187.18% (T1) when compared with tank mix of market available products, conventional ready mix formulations and market available products.

The amount of the present formulation to be applied will depend on various factors such as, the subject of the treatment, for example, plants, soil or seeds; the type of treatment, for example, spraying, dusting or seed dressing; the purpose of the treatment, for example, prophylactic or therapeutic control; in case of insect control, the type of insects or mites to be controlled or the application time. This amount of the formulation of the present invention to be applied can be readily deduced by a skilled agronomist.
Suitable application methods include foliar application. Foliar application means pesticidally active formulation further diluted with water before spraying over the plant canopy.
The rates of application vary within wide limits and depend on the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
The lists of crops on which the pesticidal formulation of the present invention is used, include, but not limited to, GMO (Genetically Modified Organism) and non GMO traits, hybrids and conventional varieties of cotton (Gossypium spp.), paddy (Oryza sativa), wheat (Triticum aestavum), barley (Hordeum vulgare), maize (Zea mays), sorghum (Sorghum bicolor), oat (Avena sativa), pearl millet (Pennisetum glaucum), sugarcane (Saccharum officinarum), sugarbeet (Beta vulgaris), soybean (Glycin max), groundnut/peanut (Arachis hypogaea), sunflower (Helianthus annuus), mustard (Brassica juncea), rape seed (Brassica napus), sesame (Sesamum indicum), green gram (Vigna radiata), black gram (Vigna mungo), chickpea (Cicer aritinum), cowpea (Vigna unguiculata), red gram (Cajanus cajan), french bean (Phaseolus vulgaris), Indian bean (Lablab purpureus), horse gram (Macrotyloma uniflorum), field pea (Pisum sativum), cluster bean (Cyamopsis tetragonoloba), lentils (Lens culinaris), brinjal (Solanum melongena), cabbage (Brassica oleracea var. capitata), cauliflower (Brassica oleracea var. botrytis), okra (Abelmoschus esculentus), onion (Allium cepa L.), tomato (Solanum lycopersicun), potato (Solanum tuberosum), sweet potato (Ipomoea batatas), chilly (Capsicum annum), bell pepper (Capsicum annum), garlic (Allium sativum), cucumber (Cucumis sativus), muskmelon (Cucumis melo), watermelon (Citrullus lanatus), bottle gourd (Lagenaria siceraria), bitter gourd (Momordica charantia), radish (Raphanus sativus), carrot (Dacus carota subsp. sativus), turnip (Brassica rapa rapa), apple (Melus domestica), banana (Musa spp.), citrus groups (Citrus spp.), grape (Vitis vinifera), guava (Psidium guajava), mango (Mangifera indica), papaya (Carica papaya), pineapple (Ananas comosus), pomegranate (Punica granatum), sapota (Manilkara zapota), tea (Camellia sinensis), coffea (Coffea Arabica), turmeric (Curcuma longa), ginger (Zingiber officinale), cumin (Cuminum cyminum), black pepper (Piper nigrum), mentha (Mentha spp.), rose (Rosa spp.), jasmine (Jasminum spp.), marigold (Tagetes spp.), common daisy (Bellis perennis), dahlia (Dahlia hortnesis), gerbera (Gerbera jamesonii), and carnation (Dianthus caryophyllus).
Crops are also to be understood as including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.
Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins or transgenic plants able to synthesize such toxins, are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants comprising one or more genes that code for insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops or seed material thereof can be resistant to herbicides, and at the same time, be resistant to insect feeding (“stacked” transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.
Crops are also to be understood to include those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
Other useful plants include turf grass in golf-courses, lawns, parks and roadsides or grown commercially for sod, and ornamental plants such as flowers or bushes.
The pesticidal formulation of the present invention is used to control insects-pests and mites. The major insects-pests belong to the order Hemiptera for example, but not limited to, rice leafhopper/green leaf hopper (GLH) (Nephotettix nigropictus), rice brown plant hopper (BPH) (Nilaparvata lugen), rice backed plant hopper (WBPH) (Sogatella furcifera), apple mealy bug (Phenococcus aceris), bean aphid (Aphis fabae), black citrus aphid (Toxoptera aurantii), citrus black scale (Saissetia oleae), cabbage aphid (Brevicoryne brassicae), (Lipaphis erysimi), citrus red scale (Aonidiella aurantii), yellow scale (Aonidiella citrine), citrus mealybug (Planococcus citri), corn leaf aphid (Rhopalosiphum maidis), aphid (Aphis gossypii), jassid (Amrasca biguttula biguttla), mealy bug (Planococcus spp. and Pseudococcus spp.), cotton stainer (Dysdercus suturellus), whitefly (Bemisia tabaci), cowpea aphid (Aphis crassivora), grain aphid (Sitobion avenae), golden glow aphid (Uroleucon spp.), grape mealybug (Pseudococcus maritimus), green peach aphid (Myzus persicae), greenhouse whitefly (Trialeurodes vaporariorum), papaya mealy bug (Pracoccus marginatus), pea aphid (Acyrthosiphon pisum), sugarcane mealybug (Saccharicoccus sacchari), potato aphid (Myzus persicae), potato leaf hopper (Empoasca fabae), cotton whitefly (Bemisia tabaci), tarnished plant bug (Lygus lineolaris), wooly apple aphid (Eriosoma lanigerum), and mango hopper (Amritodus atkinsoni, Idioscopus spp.); to the order Lepidoptera for example, but not limited to, army worm (Mythimna unipuncta), asiatic rice borer (Chilo suppressalis), bean pod borer (Maruca vitrata), beet armyworm (Spodoptera exigua), black cutworm (Agrotis ipsilon), bollworm (Helicoverpa armigera), cabbage looper (Trichoplusia ni), codling moth (Cydia pomonella), croton caterpillar (Achea janata), diamond backmoth (Plutella xylostella), cabbage worm (Pieris rapae), pink bollworm (Pectinophora gossypiella), sugarcane borer (Diatraea saccharalis), sugarcane early shoot borer (Chilo infuscatellus), tobacco budworm (Heliothis virescens), tomato fruitworm (Helicoverpa zea), velvet bean caterpillar (Anticarsia gemmatalis), yellow stem borer (Scirpophaga incertulas), spotted bollworm (Earias vittella), rice leaf-folder (Cnaphalocrocis medinalis), tobacco leaf-eating caterpillar (Spodoptera litura); brinjal fruit and shoot borer (Leucinodes orbonalis), bean pod borer (Maruca vitrata, Maruca testulalis), armyworm (Mythimna separata), citrus leaf-miner (Phyllocnistis citrella), cabbage butterfly (Pieris brassicae), paddy stem borer (Scirpophaga excerptallis, Scirpophaga incertulas, Scirpophaga innotata), wheat stem borer (Sesamia inferens, Sitotroga cerealella, Spilosoma obliqua), and fall armyworm (Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Tryporyza nivella, Tryporyza incertulas, Tuta absoluta); to the order Coleoptera for example, but not limited to, apple twig borer (Amphicerus spp.), corn root worm (Diabrotica virgifera), cucumber beetle (diabrotica balteata), boll weevil (Anthonomus grandis), grape flea beetle (Altica chalybea), grape root worm (Fidia viticola), grape trunk borer (Clytoleptus albofasciatus), radish flea beetle (Phyllotreta armoraciae), maize weevil (Sitophilus zeamais), northern corn rootworm (Diabrotica barberi), rice water weevil (Lissorhoptrus oryzophilus, Anthonomus grandis, Bruchus lentis, Diabrotica semipunctata, Diabrotica virgifera, Dicladispa armigera, Epilachna varivestis), and various species of white grubs (Holotrichia bicolor, Holotrichia consanguinea, Holotrichia serrata, Leptinotarsa decemlineata, Phyllotreta chrysocephala, Popillia japonica); to the order Orthoptera for example, but not limited to, Gryllotalpa spp., Locusta spp., and Schistocerca spp.; to the order Thysanoptera for example, but not limited to, Frankliniella spp., Thrips palmi, Thrips parvispinus, Thrips tabaci and Scirtothrips dorsalis; to the order Heteroptera for example, but not limited to, Dysdercus spp., and Leptocorisa spp., to the order Hymenoptera for example, but not limited to, Solenopsis spp.; to the order Diptera for example, but not limited to, Antherigona soccata, Dacus spp., Liriomyza spp., and Melanagromyza spp., to the order Acarina or arachnida for example, but not limited to, Aceria mangiferae, Brevipalpus spp., Eriophyes spp., Oligonychus mangiferus, Oligonychus punicae, Panonychus citri, Panonychus ulmi, Polyphagotarsonemus latus, Tarsonemus spp., Tetranychus urticae, and Tetranychus cinnabarinus.
The formulation of present invention provides a number of benefits such as, broad spectrum of control i.e. controls sucking insects, foliage feeder, internal borers in one shot application - sucking insects belong to hemiptera, homoptera, thysanoptera; foliage feeder and internal borers belong to lepidoptera; mites belongs to arachnida class; residual control i.e. longer duration of control; delayed or prevents development of resistance in insects against insecticides with a specific site/mode of action; synergistic control i.e. gram of active ingredients required are less to achieve desired level of control; immediate protection to crops; rain-fastness; environment-friendly formulations i.e. formulations without organic solvent as carrier; and is safe to the crops.
The present invention has been described with reference to specific embodiment which is merely illustrative and not intended to limit the scope of the invention as defined in the present complete specification.
,CLAIMS:We Claim:

1. A pesticidal formulation of 5% to 15% w/w pyriproxyfen, 5% to 15% w/w tolfenpyrad, 0.1% to 5% w/w at least one insecticide/s selected from emamectin benzoate and/or abamectin and agrochemically acceptable excipients.

2. The pesticidal formulation as claimed in claim 1, wherein the agrochemically acceptable excipients are selected from the group consisting of wetting-spreading-penetrating agent(s), solvent(s), emulsifier(s), dispersing agent(s), stabilizer(s), anti-foaming agent(s), anti-freezing agent(s), preservative(s), buffering agent(s), thickening, gelling and anti-settling agent(s), suspending agent(s), thickener(s) and optionally polar cosolvent(s).

3. The pesticidal formulation as claimed in claim 1, wherein the agrochemically acceptable excipients are present in the range from 1% to 99% of the total weight of the composition.

4. The pesticidal formulation as claimed in claim 1, wherein the composition is in the form of oil dispersion (OD) and suspo-emulsion (SE).

5. The pesticidal formulation as claimed in claim 2, wherein the wetting-spreading-penetrating agent(s) for oil dispersion (OD) is selected from organic silicone, trisiloxane ethoxylate, polydimethylsiloxane, polyoxyethylene methyl polysiloxane, polyoxyalkylene methyl polysiloxane, polyether polymethyl siloxane copolymer, trisiloxane heptamethyl, polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane and mixture thereof.

6. The pesticidal formulation as claimed in claim 2, wherein the solvent(s) for oil dispersion (OD) is selected from blend of pongamia oil and palm oil; blend of pongamia oil and mahua oil; blend of pongamia oil and jojoba (Simmondsia chinensis); blend of pongamia oil and vegetable oil; blend of palm oil and mahua oil; blend of palm oil and jojoba oil; blend of palm oil and vegetable oil; blend of pongamia oil, palm oil and mahua oil; blend of pongamia oil, palm oil and jojoba oil; and blend of pongamia oil, palm oil and vegetable oil and mixture thereof.

7. The pesticidal formulation as claimed in claim 2, wherein the emulsifier(s) for oil dispersion (OD) is selected from castor oil ethoxylates, alcohol ethoxylates, fatty acid ethoxylates, sorbitan ester ethoxylates, sulphosuccinate, calcium salts of dodecylbenzene sulphonate, alkylammonium salts of alkylbenzene sulphonate, alkylsulphosuccinate salts, ethylene oxide-propylene oxide block copolymers, ethoxylated alkylamines, octylphenol ethoxylate, ethoxylated alkyl phenols, ethoxylated sorbitol oleates, polyoxyethylene sorbitan monolaurate and mixture thereof.

8. The pesticidal formulation as claimed in claim 2, wherein the dispersing agent(s) for oil dispersion (OD) is selected from condensed naphthalene sulfonate, propoxylated ethoxylated copolymer monoalkylether (ethylhexanol), alkyl sulfonates, alkyl benzene sulfonates, alkyl aryl sulfonates, alkylphenolalkoxylates, tristyrylphenol ethoxylates, natural or synthetic fatty ethoxylate alcohols, natural or synthetic fatty acid alkoxylates, natural or synthetic fatty alcohols alkoxylates, alkoxylated alcohols, n-butyl alcohol poly glycol ether, block copolymers, ethylene oxide-propylene oxide block copolymers, ethylene oxide-butylene oxide block copolymers, fatty acid-polyalkylene glycol condensates, polyamine-fatty acid condensates, polyester condensates, salts of polyolefin condensates, sodium ligno sulfonate, sodium polycarboxylate, EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propyleneoxide-ethyleneoxide-copolymer, polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycolether-phosphate, tristyrylphenole with 16 moles EO, tristyrylphenol-polyglycolether-phosphate, oleyl-polyglycolether with ethylene oxide, tallow fattyamine polyethylene oxide, nonylphenol polyglycolether with 9-10 moles ethylene oxide and mixture thereof.

9. The pesticidal formulation as claimed in claim 2, wherein the stabilizer(s) for oil dispersion (OD) is selected from hectorite clay, aluminium magnesium silicate, bentonite clay, silica, attapulgite clay and mixture thereof.

10. The pesticidal formulation as claimed in claim 2, wherein the antifoaming agent(s) for oil dispersion (OD) is selected from silicone oil, silicone compound, C10~C20 saturated fat acid compounds or C8~C10 aliphatic alcohols compound, silicone antifoam emulsion, dimethylsiloxane, polydimethyl siloxane and mixture thereof.

11. The pesticidal formulation as claimed in claim 2, wherein the anti-freezing agent(s) for oil dispersion (OD) is selected from ethylene glycol, propane diols, glycol, monoethylene glycol, diethylene glycol, polypropylene glycol, polyethylene glycol, glycerine, urea, magnesium sulfate heptahydrate, sodium chloride and mixture thereof.

12. The pesticidal formulation as claimed in claim 2, wherein the preservative(s) for oil dispersion (OD) is selected from 1,2-benzisothiazolin-3(2H)-one, sodium salt, sodium benzoate, 2-bromo-2-nitropropane-1,3-diol, formaldehyde, sodium o-phenylphenate, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4-isothiazolin-3-one, butyl hydroxyl toluene and mixture thereof.

13. The pesticidal formulation as claimed in claim 2, wherein the buffering agent(s) for oil dispersion (OD) is selected from citric acid, sodium carbonate, sodium bicarbonate, sulphuric acid, hydrochloric acid, sodium hydroxide, potassium hydroxide, acetic acid, sorbic acid and mixture thereof.

14. The pesticidal formulation as claimed in claim 2, wherein the polar cosolvent(s) for oil dispersion (OD) is selected from cyclohexanone, acetophenone, butanol, n-octanol, n-propanol, 1-hexanol, propylene carbonate, n-methyl-2-pyrrolidone and mixture thereof.

15. The pesticidal formulation as claimed in claim 2, wherein the wetting-spreading-penetrating agent(s) for suspo-emulsion (SE) is selected from trisiloxane ethoxylate, polyalkyleneoxide modified trisiloxane, polydimethylsiloxane, polyoxyethylene methyl polysiloxane, polyoxyalkylene methyl polysiloxane, polyether polymethyl siloxane copolymer, heptamethyl trisiloxane, polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane, polyethylene glycol isotridecyl ester, polyethylene glycol monooleate, polyethylene glycol monostearate, polyhydric alcohol fatty acid ester, polyhydric alcohol polyethylene oxide fatty acid ester, polymer of polyoxyethylene (mono-, di- or tri-) styryl phenyl ether, polyoxyethylene/polyoxypropylene block polymer, polyoxyethylene nonyl phenyl ether, polyoxyethylenehexitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene fatty acid ester, dialkyldimethylammonium polynaphthylmethanesulfonate, polyethylene glycol isotridecyl ester and mixture thereof.
16. The pesticidal formulation as claimed in claim 2, wherein the solvent(s) for suspo-emulsion (SE) is selected from N,N-Dimethyloctanamide, N,N-Dimethylethylamine, N,N-Dimethylethanamide, N,N-Dimethylmethanamide, acetophenone, g-valerolactone, 2-methyltetrahydrofuran, cyclopentylmethylether propylene carbonate, 2 ethylhexyl lactate base solvent and mixture thereof.

17. The pesticidal formulation as claimed in claim 2, wherein the dispersing agent(s) for suspo-emulsion (SE) is selected from polyesters, polyamides, polycarbonates, polyurea, polyurethanes, acrylic polymers and copolymers, styrene copolymers, butadiene copolymers, polysaccharides, starch and cellulose derivatives, vinylalcohol, vinylacetate, vinylpyrrolidone polymers and copolymers, polyethers, epoxy, phenolic and melamine resins, polyolefins and copolymers, acrylate polymers, poly(methacrylate), poly(ethyl methacrylate), poly(methylmethacrylate), acrylate copoylmers, styrene-acrylic copolymers, poly(styrene-co maleic anhydride), cellulosic polymers, ethyl cellulose, cellulose acetate, cellulose acetatebutyrate, acetylated mono, di, and triglycerides, poly(vinylpyrrolidone), vinyl acetate polymers and copolymers, poly(alkylene glycol), styrene butadiene copolymers, poly(orthoesters), polyarylphenyl ether sulphate ammonium salt, alkyl resins, biodegradable polyesters, starch, polylactic acid starch blends, polylactic acid, poly(lactic acid-glycolic acid) copolymers, polydioxanone, cellulose esters, ethyl cellulose, cellulose acetate butyrate, starch esters, starch ester-aliphatic polyester blends, modified corn starch, polycaprolactone, poly(namylmethacrylate), wood rosin, polyanhydrides, polyvinylalcohol, polyhydroxybutyratevalerate, biodegradable aliphatic polyesters, polyhydroxybutyrate, alkylated naphthalene sulfonate, sodium salt, sodium salt of naphthalene sulfonate condensate, sodium ligno sulfonate, sodium polycarboxylate, EO/PO block copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propyleneoxide-ethyleneoxide-copolymer, polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycolether-phosphate, tristyrylphenole with 16 moles EO, tristyrylphenol-polyglycol ether-phosphate, oleyl-polyglycol ether with ethylene oxide, tallow fatty amine polyethylene oxide, nonylphenol polyglycol ether with 9-10 moles ethylene oxide and mixture thereof.

18. The pesticidal formulation as claimed in claim 2, wherein the stabilizer(s) for suspo-emulsion (SE) is selected from butylated hydroxytoluene (BHT), epoxidized soybean oil (ESBO), epichlorohydrin and mixture thereof.

19. The pesticidal formulation as claimed in claim 2, wherein the antifoaming agent(s) for suspo-emulsion (SE) is selected from silicone oil, silicone compound, C10~C20 saturated fat acid compounds, C8~C10 aliphatic alcohols compound, silicone emulsion, vegetable oil based antifoam, tallow based fatty acids and mixture thereof.

20. The pesticidal formulation as claimed in claim 2, wherein the anti-freezing agent(s) for suspo-emulsion (SE) is selected from glycol, monoethylene glycol, diethylene glycol, polypropylene glycol, polyethylene glycol, propane diols, glycerin, urea, magnesium sulfate heptahydrate, sodium chloride and mixture thereof.

21. The pesticidal formulation as claimed in claim 2, wherein the preservative(s) for suspo-emulsion (SE) is selected from 1,2-benzisothiazol-3(2H)-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2- methyl-4-isothiazolin-3-one, propionic acid and its sodium salt, sorbic acid and its sodium or potassium salt, benzoic acid and its sodium salt, p-hydroxy benzoic acid sodium salt; methyl p-hydroxy benzoate; and biocide, sodium benzoate, potassium sorbate, para hydroxy benzoates and mixture thereof.

22. The pesticidal formulation as claimed in claim 2, wherein the buffering agent(s) for suspo-emulsion (SE) is selected from calcium hydroxyapatite, potassium dihydrogen phosphate, sodium hydroxide, carbonated apatite, calcium carbonate, sodium bicarbonate, tricalcium phosphate, calcium phosphates, carbonated calcium phosphates, amine monomers, lactate dehydrogenase, magnesium hydroxide and mixture thereof.
23. The pesticidal formulation as claimed in claim 2, wherein the thickening, gelling, and anti-settling agent(s) for suspo-emulsion (SE) is selected from montmorillonite, bentonite, magnesium aluminum silicate, attapulgite, guar gum, locust bean gum, carrageenan, xanthan gum, alginates, methyl cellulose, sodium carboxymethyl cellulose (SCMC), hydroxyethyl cellulose (HEC), modified starches, polyacrylates, polyvinyl alcohol, polyethylene oxide and mixture thereof.

24. The pesticidal formulation as claimed in claim 2, wherein the suspending agent(s) for suspo-emulsion (SE) is selected from aluminum magnesium silicate, bentonite clay, silica, silicone dioxide, attapulgite clay and mixture thereof.

Dated this on 30th September, 2023