Description:FIELD OF INVENTION:
The present invention relates to an agrochemical composition comprising a) compound A of Acetamiprid; b) compound B of Spinosad; c) compound C at least one insecticide selected from Diamide Insecticide group and d) one or more inactive excipients. The present invention also relates to process for preparing the said composition.

BACKGROUND OF THE INVENTION:
Acetamiprid is a carboxamidine that is acetamidine in which the amino hydrogens are substituted by a (6-chloropyridin-3-yl)methyl and a methyl group while the hydrogen attached to the imino nitrogen is replaced by a cyano group.

Acetamiprid is an organic compound with the chemical formula C10H11ClN4. It is an odorless neonicotinoid insecticide produced under the trade names Assail, and Chipco by Aventis Crop Sciences. It is systemic and intended to control sucking insects (Thysanoptera, Hemiptera, mainly aphids) on crops such as leafy vegetables, citrus fruits, pome fruits, grapes, cotton, cole crops, and ornamental plants. It is also a key pesticide in commercial cherry farming due to its effectiveness against the larvae of the cherry fruit fly.

The metabolism of acetamiprid has been primarily studied in plants and soil. However, a recent study (2005) focussed on the metabolism of acetamiprid in honey bees. The honey bees in this study were fed a sucrose solution that contained acetamiprid. Seven different metabolites were discovered, of which two could not be identified. The five most abundant of these metabolites were found in the abdomen of the bee. Within the first hour of ingestion, acetamiprid concentrations were highest in tissues with a high nicotinic acetylcholine receptor density such as the abdomen, thorax and head.

Acetamiprid was rapidly distributed throughout the bee's body, but also rapidly metabolised into the seven compounds. The substance is not just broken down in the gut, but in the entire body of the bee. This is mainly done by Type I enzymes such as mixed function oxidases. These enzymes use O2 to catalyze a reaction and convert acetamiprid into more polar metabolites. This makes it easier to excrete the compounds because the compounds become more hydrophilic. Phase I enzymes form the first step in metabolizing the compound. Phase I metabolites can be bioactive.

Spinosad is an insecticide based on chemical compounds found in the bacterial species Saccharopolyspora spinosa. The genus Saccharopolyspora was discovered in 1985 in isolates from crushed sugarcane. The bacteria produce yellowish-pink aerial hyphae, with bead-like chains of spores enclosed in a characteristic hairy sheath. This genus is defined as aerobic, Gram-positive, nonacid-fast actinomycetes with fragmenting substrate mycelium. S. spinosa was isolated from soil collected inside a nonoperational sugar mill rum still in the Virgin Islands. Spinosad is a mixture of chemical compounds in the spinosyn family that has a generalized structure consisting of a unique tetracyclic ring system attached to an amino sugar (D-forosamine) and a neutral sugar (tri-Ο-methyl-L-rhamnose). Spinosad is relatively nonpolar and not easily dissolved in water.

Spinosad is a novel mode-of-action insecticide derived from a family of natural products obtained by fermentation of S. spinosa. Spinosyns occur in over 20 natural forms, and over 200 synthetic forms (spinosoids) have been produced in the lab. Spinosad contains a mix of two spinosoids, spinosyn A, the major component, and spinosyn D (the minor component), in a roughly 17:3 ratio.

Spinosad is a new insecticide containing a structurally unique glycosylated macrolactone with selective activity against a wide variety of insect pest species. It is isolated from the fermentation broth of the aerobic, gram-positive soil bacterium Saccharopolyspora spinosa (Actinomycetes).

Spinosad is a novel mode-of-action insecticide derived from a family of natural products obtained by fermentation of S. spinosa. Spinosyns occur in over 20 natural forms, and over 200 synthetic forms (spinosoids) have been produced in the lab. Spinosad contains a mix of two spinosoids, spinosyn A, the major component, and spinosyn D (the minor component), in a roughly 17:3 ratio.

Spinosad is highly active, by both contact and ingestion, in numerous insect species. Its overall protective effect varies with insect species and life stage. It affects certain species only in the adult stage, but can affect other species at more than one life stage. The species subject to very high rates of mortality as larvae, but not as adults, may gradually be controlled through sustained larval mortality. The mode of action of spinosoid insecticides is by a neural mechanism. The spinosyns and spinosoids have a novel mode of action, primarily targeting binding sites on nicotinic acetylcholine receptors (nAChRs) of the insect nervous system that are distinct from those at which other insecticides have their activity. Spinosoid binding leads to disruption of acetylcholine neurotransmission. Spinosad also has secondary effects as a γ-amino-butyric acid (GABA) neurotransmitter agonist. It kills insects by hyperexcitation of the insect nervous system. Spinosad has proven not to cause cross-resistance to any other known insecticide.

Diamide insecticides are a class of insecticides, active mainly against lepidoptera (caterpillars), which act on the insect ryanodine receptor. They are diamides of either phthalic acid or anthranilic acid, with various appropriate further substitutions.

The following diamides have been given ISO common names. Flubendiamide and cyhalodiamide are phthalic diamides. Chlorantraniliprole, cyantraniliprole, cyclaniliprole, fluchlordiniliprole, pioxaniliprole, tetrachlorantraniliprole, tetraniliprole, and tiorantraniliprole are anthranilic diamides.

Chlorantraniliprole is an insecticide of the diamide class used for insects found on fruit and vegetable crops as well as ornamental plants. Chlorantraniliprole opens muscular calcium channels, in particular the ryanodine receptor, rapidly causing paralysis and ultimately death of sensitive species. The differential selectivity chlorantraniliprole has towards insect ryanodine receptors explains its low mammalian toxicity receptor. Chlorantraniliprole is active on chewing pest insects primarily by ingestion and secondarily by contact.

Cyantraniliprole is an insecticide of the diamide class (IRAC MoA group 28). It shows strong activity and lepidoptera (caterpillars), and since it shows systemic activity it is also active against sucking pests such as aphids and whitefly.

Cyclaniliprole is an insecticide belonging to the chemical class of diamide insecticides and pyrazole insecticides. Despite its structural similarity to some of the phenylpyrazole insecticides, this substance has a different mode of action, which it shares with other diamide insecticides. Diamides act at the ryanodine receptor, which is critical for muscle contraction. Cyclaniliprole is a racemic mixture (R and S enantiomers present in a 50:50 w/w ratio). The biological activity of the racemate is due to both enantiomers, which give equal insecticidal activity.

Tetraniliprole is a carboxamide. A wide variety of agricultural uses (>100 different crops) including including vegetables, tree fruits, grapes, other fruits, tree nuts, potatoes, soybean, corn and other crops. Landscape uses are limited to turfgrass. The only nursery use is for sod farms.

Flubendiamide works by activating the ryanodine receptor which regulates muscle and nerve activities by modifying levels of calcium in these cells. Ryanodine receptor activation results in rapid cessation of feeding followed by death and also exhibits residual larvicidal activity.

Many binary combinations of acetamiprid have been developed to broaden the spectrum of activities. In order to reduce the risk from increased number of resistant insect species, mixtures of different active compounds developed for controlling insects-pests. By combining different active compounds having different mode of action, it is possible to ensure successful control of insect-pests belongs to different orders over a relatively longer period of time and preventing development of resistance.

To address this problem, researches are trying to produce an extensive variety of active ingredients and active ingredients formulations for effective control of insects. Chemical insecticides of many types have been disclosed in the art and a large number are in commercial use. In crop protection, it is desirable in principle to increase specificity and reliability of action of insecticidal active ingredients.

Therefore, there still exists a need to develop insecticidal composition, which is stable, synergistic, more effective in control of wide spectrum of insect-pests in crop and environmentally safe.

Accordingly to the demonstration of synergism by combination of existing insecticide agents, permits use of individual agents of synergistic combination at lower rates than when used alone and in many instances ameliorates increasing resistance to insecticidal effectiveness.
The present invention overcomes the limitations associated with existing formulations available in the market. This novel formulation leverages plant-derived products with synergistic properties, thereby enhancing the overall pharmacological efficacy. The use of these synergistic plant components aims to achieve a significant therapeutic effect while minimizing adverse side effects and toxicity. This innovative approach represents advancement in formulation design, offering a safer and more effective option for cancer treatment.

SUMMARY OF THE INVENTION:
The main object of present invention is to provide an agrochemical composition comprising a) compound A of Acetamiprid; b) compound B of Spinosad; c) compound C at least one insecticide selected from diamide insecticide group; and d) one or more inactive excipients.

Another object of the present invention is to provide an agrochemical composition comprising a) compound A of Acetamiprid is in amount of 1.0 to 25.0% w/w; b) compound B of Spinosad is in amount of 4.0 to 35.0% w/w; c) compound C at least one insecticide selected from diamide insecticide is in amount of 1.0 to 25.0% w/w.

Yet another object of the present invention is to provide diamide insecticide group selected from chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole or flubendiamide.

Yet another object of the present invention is to provide one or more inactive excipients is selected from the group comprising of wetting agent, dispersing agent, antifoaming agent/defoamer, anti-freezing agent, biocide/preservative, thickener/suspending agent, disintegrating agent, emulsifier, solvent, pH stabilizer, anti-caking agent, humectant, binder, filler/carrier and wall forming materials or combination thereof. The composition may also contain if desired, one or more auxiliary customary for crop protection compositions.

Another object of the present invention is to provide an agrochemical composition of the present invention is formulated as Water dispersible granules/Wettable granules (WDG/WG), Water soluble granules (SG), Emulsifiable granule (EG), Wettable powder (WP), Water Dispersible Powder (WDP), Soluble powder (SP), Emulsifiable powder (EP), Oil dispersible powder (OP), Soluble Tablet (ST), Capsule suspension/Micro capsule (CS), Dispersible concentrate (DC), Emulsifiable concentrate (EC), Emulsion water-in-oil (EO), Emulsion oil-in-water (EW), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Suspension Concentrate (SC), Suspo Emulsion (SE), Soluble Liquid/Concentrate (SL), mixed formulation of CS and SC (ZC), mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW).

DETAILED DESCREPTION OF THE INVENTION:
In the following detailed description, reference is made to the accompanying drawings, which form a part hereof. In the drawings, similar symbols typically identify similar components, unless context dictates otherwise. The illustrative embodiments described in the detailed description, drawings, and claims are not meant to be limiting. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented here. The present technology is also illustrated by the examples herein, which should not be construed as limiting in any way.

As used herein, the terms below have the meanings indicated.

The singular forms "a," "an," and "the" may refer to plural articles unless specifically stated otherwise.

The term "about," as used herein, is intended to qualify the numerical values which it modifies, denoting such a value as variable within a margin of error. When no particular margin of error, such as a standard deviation to a mean value given in a chart or table of data, is recited, the term "about" should be understood to mean that range which would encompass the recited value and the range which would be included by rounding up or down to that figure as well, taking into account significant figures.

The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms “comprising,” “including,” “containing,” etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase “consisting essentially of” will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase “consisting of” excludes any element not specified.

As used herein, the term “excipient” refers to inert substances which are commonly used as diluent, to provide stability or to increase the activity profile of the composition or formulation without having any insecticidal activity or direct effect on the insect pests.

The present invention is to provide an agrochemical composition comprising a) compound A of Acetamiprid; b) compound B of Spinosad; c) compound C at least one insecticide selected from diamide insecticide group; and d) one or more inactive excipients.

The present invention is to provide diamide insecticide group selected from chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole or flubendiamide.

The composition of the present invention comprises excipients selected from the group comprising of wetting agent, dispersing agent, antifoaming agent/defoamer, anti-freezing agent, biocide/preservative, thickener/suspending agent, disintegrating agent, emulsifier, solvent, pH stabilizer, anti-caking agent, humectant, binder, filler/carrier and wall forming materials or combination thereof. The composition may also contain if desired, one or more auxiliary customary for crop protection compositions.

The present invention is to provide an agrochemical composition of the present invention is formulated as Water dispersible granules/Wettable granules (WDG/WG), Water soluble granules (SG), Emulsifiable granule (EG), Wettable powder (WP), Water Dispersible Powder (WDP), Soluble powder (SP), Emulsifiable powder (EP), Oil dispersible powder (OP), Soluble Tablet (ST), Capsule suspension/Micro capsule (CS), Dispersible concentrate (DC), Emulsifiable concentrate (EC), Emulsion water-in-oil (EO), Emulsion oil-in-water (EW), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Suspension Concentrate (SC), Suspo Emulsion (SE), Soluble Liquid/Concentrate (SL), mixed formulation of CS and SC (ZC), mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW).

The composition of the present invention is effective to control various insects-pests belongs to the order Hemiptera, for example, aphid, jassid, leaf hopper, mango hopper, whitefly, mealybug, scale, rice brown plant hopper (BPH), leaf hopper; order Lepidoptera, fall army worm, rice stem borer, rice leaf folder, sugarcane early shoot borer, top borer, wheat pink stem borer, fruit borer, pod borer, plume moth, maruca, cut worm, diamond back moth (DBM), looper, semi looper, pink bollworm, brinjal fruit and shoot borer, spodoptera spp. (litura, exigua, frugiperda), heliothis/helicoverpa; from the order Coleoptera, white grub, wire worm, epilachna beetle, blue beetle, girdle beetle, flea beetle, rice water weevil; from the order Orthoptera, for example, locust; from the order Thysanoptera, for example, cotton thrips, chilli thrips, black thrips; from the order Isoptera, example-termite; from the order Diptera, for example, shoot fly, stem fly, fruit fly, leaf miner; from the order Acarina, for example, red mite, red spider mite, pink mite, broad mite, purple mite.

The pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of inventive compositions.

The crops and plants treated by present compositions are comprises of genetically modified varieties or hybrid varieties or conventional varieties of paddy/rice, wheat, maize, sugarcane, cotton, okra, brinjal, chilly, tomato, cabbage, cauliflower, tomato, potato, garlic, onion, groundnut, soybean, green gram, black gram, red gram, chickpea, cucumber, melons, apple, mango, papaya, pomegranate, banana, grapes, tea, coffee, cumin, fennel, black pepper, flower crops like rose, marigold etc.

The synergistic insecticidal composition of specific active ingredient has the special advantage of being highly active against insect pests and mites. The present inventors believe that the combination of the present invention surprisingly results in a synergistic action. The combinations of the present invention allow for a broad spectrum of pest control. The broad spectrum of the present combination also provides a solution for preventing the development of resistance.

Active Ingredients Component A Component B Component C
Examples Acetamiprid Spinosad At least one insecticide from diamide group
% of active ingredients (w/w) 1.0% to 25.0% w/w 4.0% to 35.0% w/w 1.0% to 25.0% w/w

Further, agrochemical composition comprising a) compound A of Acetamiprid; b) compound B of Spinosad; c) compound C at least one insecticide selected from diamide insecticide group; and d) one or more inactive excipients.

The present invention is to provide an agrochemical composition comprising a) compound A of Acetamiprid is in amount of 1.0 to 25.0% w/w; b) compound B of Spinosad is in amount of 4.0 to 35.0% w/w; c) compound C at least one insecticide selected from diamide insecticide group is in amount of 1.0 to 25.0% w/w.

The present invention is to provide diamide insecticide group selected from chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole or flubendiamide.

The present invention is to provide an agrochemical composition comprising a) compound A of Acetamiprid is in amount of 1.0 to 25.0% w/w; more preferably in range of 4.0 to 22.0%w/w of the composition; b) compound B of Spinosad is in amount of 4.0 to 35.0% w/w; more preferably in range of 5.0 to 32.0%w/w of the composition; c) compound C at least one insecticide selected from diamide insecticide is in amount of 1.0 to 25.0% w/w; more preferably in range of 4.0 to 22.0%w/w of the composition.

The present invention is to provide one or more inactive excipients is selected from the group comprising of wetting agent, dispersing agent, antifoaming agent/defoamer, anti-freezing agent, biocide/preservative, thickener/suspending agent, disintegrating agent, emulsifier, solvent, pH stabilizer, anti-caking agent, humectant, binder, filler/carrier and wall forming materials or combination thereof. The composition may also contain if desired, one or more auxiliary customary for crop protection compositions.

Wetting is the first stage of dispersion, in which air surrounding the granular composition is substituted with water. Wetting of the composition with water cannot occur if the surface tension of the liquid is very high. Hence, it is recommended to add a wetting agent to the composition to facilitate the process of dispersion of the granules in the liquid. Non-limiting examples of wetting agents that can be used in the present invention include, but not limited to, tristyryl phenol ethoxylate non-ionic polymer, sodium iso propyl naphthalene sulphonate, alkyl phenyl ethoxylate, aryl phenyl ethoxylate, aryl phenyl ether phosphate, alkoxylated alcohol, ethoxylated fatty alcohol, ethylene oxide-propylene oxide (EO-PO) block copolymer, alkyl aryl sulphonate, alkyl olefin sulfonate, dioctyl succinate, sodium lauryl sulfate, alkyl polyglucoside, sodium alkyl aryl taurate, sorbitol esters, sorbitol oleate, poly aryl phenyl ether phosphate, polyalkoxylated butyl ether, ethoxylated fatty alcohol, sodium dioctyl sulfosuccinate, sodium dodecyl benzene sulfonate, alkyl diphenyl sulfonates, sodium isopropyl naphthalene sulfonate, sodium di-isopropyl naphthalene sulphonates, alkyl naphthalene sulfonate. Ethoxylated alcohol includes natural fatty alcohol, lauryl alcohol ethoxylate, lauryl alcohol alkoxylate, synthetic alcohol ethoxylate, tridecyl alcohol ethoxylate, 2-ethyl hexanol, 2-propylheptanol, isodecyl alcohol, trisiloxane ethoxylate, heptamethyl trisiloxane, modified form includes polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane, polyalkyleneoxide modified Tri siloxane, polyalkyleneoxide modified polydimethylsiloxane, may be liquid or powder form. One or more wetting agents may be used in the present composition. The wetting agent is present in an amount in the range from 1 to 10% w/w.

Dispersing agents /surfactants are added to prevent agglomeration of solid particles in a liquid and keep them suspended in fluid. Accordingly, the composition of the present invention contains the dispersing agent selected from the group comprising polyacrylate compound selected from a homopolymer, a block-copolymer or a random copolymer and the mixtures thereof. Polyacrylate compound selected from a group comprises poly(methyl acrylate), poly(ethyl acrylate), poly(propyl acrylate), poly(n-butyl acrylate), poly(isobutyl acrylate), poly(2-ethyl acrylate), poly(t-butyl acrylate), poly(ethylhexyl acrylate), poly(benzyl acrylate), poly(methyl methacrylate), poly(ethyl methacrylate), poly(n-butyl methacrylate), poly(isobutyl methacrylate), poly((ethylene glycol) methyl ether methacrylate), poly(methacrylate-coethylacrylate), poly(methacrylate-co-styrene), poly(methacrylate-co-butylmethacrylate), poly(n-butylmethacrylcate-co-methacrylate), poly((ethylene oxide)-co-poly(methyl acrylate)), polymethyl methacrylate-polyethylene glycol graft copolymer (Atlox 4913), nonionic comb-shaped polyacrylate (Dispersogen PSL 100), 2-Acrylamido-2-Methylpropane Sulfonic Acid, Sodium methallyl sulfonate, 3-sulfopropyl acrylate potassium salt, 3-sulfopropyl methacrylate potassium salt, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxymethyl methacrylate, Polyethylene-g-poly(n-butyl acrylate), and the mixtures thereof. Polyarylphenyl ether phosphate, Tri styryl phenol ethoxylate, ethoxylated tristryl phenol sulphate, acrylic polymer amine salt, naphthalene sulfonic acid-sodium salt condensate with formaldehyde, alkylated naphthalene sulfonate-sodium salt, ethoxylated oleylcetyl alcohol, poly alkelene glycol ether, ethoxylated fatty alcohol, alkyl sulfonate, styrene acrylic copolymer, alkyl phenol polyglycol ether, sodium lignosulfonate, calcium lignosulfonate, sodium polycarboxylate, EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propylene oxide- polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycol ether-phosphate, tristyrylphenole with 16 moles EO, oleyl-polyglycol ether with ethylene oxide, tallow fatty amine polyethylene oxide, nonylphenol polyglycol ether with 9-10 moles ethylene oxide. One or more dispersing agents is used in the present composition in an amount in the range from 1 to 25% w/w.

Defoamer/Antifoaming agent is generally added to the composition to prevent foam formation as the foam prevents the efficient filling of a container. Suitable defoamer used herein, but not limited to, siloxane polyalkylene oxide, polydimethyl siloxane, polysiloxane emulsion, vegetable oil-based antifoam, silicone oil emulsion, magnesium stearate or a combination thereof and present in an amount in range from 0.01 to 5% w/w.

An anti-freezing agent is generally added to the composition, to prevent the aqueous compositions from freezing. Suitable anti-freezing agents useful herein, but not limited to ethylene glycol, propane diols, glycerin or the urea, glycol, monoethylene glycol, diethylene glycol, polypropylene glycol, Propylene glycol, polyethylene glycol, glycerin, urea, magnesium sulfate heptahydrate, sodium chloride etc. The anti-freezing agent is present in an amount in the range from 0.1 to 15% w/w.

Preservative is added to the composition for its preservation against spoilage from bacteria, yeasts and fungi. Suitable biocides useful herein, but not limited to, include benzisothiazolin-3-one, formaldehyde, sodium benzoate, sodium o-phenyl phenate, potassium sorbate, 1,2-benzisothiazolin-3(2H)-one, 2-bromo-2-nitropropane-1,3-diol, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4-isothiazolin-3-one or a combination thereof, and is present in an amount in the range from 0.01 to 1% w/w.

Thickener and suspending agents are typically the same type of substance, usually a high molecular weight polymer, used to increase the viscosity of liquid formulation, preventing solid particles from settling out and ensuring stable suspension, allowing for even distribution when sprayed.

The synergistic composition comprises a thickener selected from the group comprising natural polymers (gelling agent): polysaccharides such as xanthan gum, guar gum, acacia gum, gelatin; cellulose derivatives: Carboxymethylcellulose (CMC), hydroxypropyl methylcellulose (HPMC), methylcellulose (MC), sodium carboxymethyl cellulose; clays & minerals: bentonite clay, attapulgite clay, sodium polyacrylate, aluminum magnesium silicate, or a combination thereof and is present in an amount in the range from 0.01 to 5% w/w.

An emulsifier helps to prevent the droplets of the dispersed phase of an emulsion from flocculating or coalescing in the emulsion. Suitable emulsifier is used herein, but not limited to castor oil ethoxylate 40 mole, Polyoxyethylenealkylphenyl ether alkyl aryl sulfonate, 3-methoxy N, N-dimethyl propionamide, Polyglyceryl-3 caprylate, Polysorbate 60, polyoxyethylene sorbitan monostearate-Tween 60, Calcium salts of dodecylbenzene sulphonate, solvents alkyl phenol, aryl phenol, alkyl phenol ethoxylate, fatty acid esters, fatty acid alkanol amides, alkoxylated fatty acid ester or a combination thereof. The emulsifier is present in an amount in the range from 1 to 50% w/w.

The solvent and co-solvent used in the present invention is selected from the group comprising of demineralized (DM) water, alcohols such as ethanol, propanol, n-octanol, isopropanol ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, acetophenone, glycerin, polyol ethers such as ethylene glycol monopropyl ether, diethylene glycol, monomethyl ether, Di propylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethers such as dipropyl ether, dioxane, tetrahydrofuran; aliphatic hydrocarbons such as normal paraffin, isoparaffin, kerosene, mineral oil; heavy aromatic hydrocarbons such as mixture of heavy aromatic naphtha hydrocarbon C-9 to C-16, xylene, toluene, naphthalene, solvent naphtha, solvent C9, solvent C10, solvent C12, solvesso 100, solvesso 150, solvesso 200; carboxamide; aliphatic or aromatic hydrocarbons such as chlorobenzene, chloroethylene, methylene chloride; esters such as ethyl acetate, Di isopropyl phthalate, dimethyl adipate, methyl oleate, methyl tallowate; lactones such as gamma-butyrolactone; alkyl amide, amides such as dimethylformamide, alkyl pyrrolidone, N-methyl-2-pyrrolidone, N-octyl pyrrolidone, N,N-dimethyldecanamide, N, N-dimethyloctanamide, N, N-dimethylamine, N,N-dimethylmethanamide; nitriles such as acetonitrile; organosulfur compound such as alkyl sulfoxide, dimethyl sulfoxide, propylene carbonate, mineral oil, methylated seed oil, methyl ester of palm oil/soybean oil/castor oil/cotton seed oil/blend of two or more seed oil.

The solvent may be used alone or in combination and is present in an amount quantity sufficient (QS) required to make 100% w/w formulation.

Castor oil ethoxylate 40 moles is non-ionic surfactant that is derived from castor oil. It has variety of uses such as emulsifier, wetting agent, dispersing agent, additive, antistatic agent and as a solvent.

Disintegrating agent or inert materials such as clays, bentonite, diatomaceous, colloidal silica, kaolin which swell by water absorption improve in dispersibility. Water soluble salts such as potassium phosphate, ammonium sulphate, sodium sulphate, sodium citrate or urea can be also used as disintegrating agent in an amount in the range from 1% to 25% w/w.

Rheology modifier is selected from China clay, bentonite, fuller’s earth, zeolite, quartz, precipitated silica, palygorskite, sepiolite, halloysite, and a combination thereof.

pH stabilizers may include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, potassium hydrogen phosphate salt solution, acetic acid & sodium acetate, ammonia & ammonium chlorides, citric acid, benzoic acid, salicylic acids, hydrochloric acid, phosphoric acid, sodium citrate, soda ash, carboxylic acids, 2,6-di-tert-butyl-p-cresol, butylhydroxyanisole (BHT), epoxidized soybean oil (ESBO), methyl oleate, potassium carbonate, potassium hydroxide, sodium hydroxide and sodium dihydrogen phosphate dihydrate or combination thereof. Optionally stabilizer present in an amount in the range from 0.05 to 2% w/w.

Common stabilizers used in dispersion concentrates include: polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), carboxymethyl cellulose sodium (NaCMC), sodium dodecyl sulfate (SDS), lecithin, polysorbates, and various types of gums like xanthan gum or guar gum; the specific choice depending on the desired properties and application of the dispersion concentrate.

Anti-caking agents are used to prevent caking, which is the formation of lumps. They also make packaging, transport, flowability, and consumption easier. The anticaking agent may be selected from silica/silicone dioxide, calcium silicate, sodium ferrocyanide, Calcium stearate. Optionally anti-caking agents are present in an amount in the range from 0.1 to 10% w/w.

The binder is water soluble, water swellable or combinations of both. The binder is water-
soluble binder selected from a group consisting of poly ethylene wax, poly vinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethylene oxide, polyethoxylated fatty acids, polyesters, polyamides, poly carbonates, poly urea, poly urethanes, styrene copolymer, butadiene copolymers, polyethoxylated alcohols, acrylate polymer such as polymethacrylate, poly ethyl methacrylate, poly methyl methacrylate, acrylate copolymers and styrene-acrylic copolymers or mixtures of thereof, a natural gum, lignosulphonate, and a combination thereof. The binder is a water swellable binder selected from a group consisting of China clay, bentonite, fuller’s earth, zeolite, quartz, precipitated silica, palygorskite, sepiolite, halloysite, and a combination thereof. Binder is present in an amount in the range from 0.1 to 10% w/w.

Precipitated silica acts as carrier material, absorbing and holding the active ingredient while maintaining a free flowing, easily dispersible powder form, enhancing wettability by improving water contact, and often providing Rheology modifier, anti-caking properties to prevent clumping, making it crucial for consistent application of the pesticide when mixed with water for spraying on crops.

A filler/carrier selected from the group comprising sand, silica, precipitated silica, bentonite, attapulgite, ceramic, montmorillonite, pumice, sepiolite, diatomaceous earth, clay, dolomite, calcite, silicon dioxide, china clay/kaolin clay, talc, starch, zinc and its salts (zinc sulphate, zinc oxide, zinc lactate gluconate, zinc polyflavonoid), iron and its salt (ferrous sulphate), copper and salts, sulphur, humic acid and salt, fulvic acid and salt, amino acids, sea weed extracts, chitosan or a combination thereof. It presents in an amount quantity sufficient (QS) required to make 100% w/w formulation.

The synergistic present composition provides the following advantages:
• Increased efficacy than their individual counterparts or their mixtures, thus allows a substantial reduction in the application rates of each of these active ingredients, while
maintaining good efficacy and thereby reducing costs and residue problems.
• The present compositions provide an improved and extended wide spectrum control of insect-pest & mite, reduced insecticide application rates and costs, less stringent use restrictions, and improved selectivity.
• Delays the emergence of resistant species/strains.
• Minimizes risk of development of resistance and achieves effective and
economical control of undesired insects.
• Economically beneficial to the farmers as it provides better yield of the crop
with reduction in the number of sprays.
• Reduced possibility of hazards to the farmers due to occupational exposure.
because of reduction in the number of sprays.
• Better storage stability.
• Non-phytotoxic and environment friendly.

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

While the foregoing written description of the invention enables one of ordinary skill to make and use what is considered presently to be the best mode thereof, those of ordinary skill will understand and appreciate the existence of variations, combinations, and equivalents of the specific embodiment, method, and examples herein. The invention should therefore not be limited by the above described embodiment, method, and examples, but by all embodiments and methods within the scope and spirit of the invention. The invention shall now be described with reference to the following specific examples. It should be noted that the example(s) appended below illustrate rather than limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the present invention.

These and other aspects of the invention may become more apparent from the examples set forth herein below. These examples are provided merely as illustrations of the invention and are not intended to be construed as a limitation thereof.

EXAMPLES:

WG formulation:
S. no. Ingredients Percent (w/w)
1 Acetamiprid 1 to 25
2 Spinosad 4 to 35
3 At least one insecticide selected from Diamide group 1 to 25
4 Wetting agent 2 to 8
5 Dispersing agent 8 to 20
6 Disintegrating agent 10 to 25
7 Antifoaming agent 0.1 to 2
8 Carrier cum filler qs

SC formulation:
S. No. Ingredients Percent (w/w)
1 Acetamiprid 1 to 25
2 Spinosad 4 to 35
3 At least one insecticide selected from Diamide group 1 to 25
4 Dispersing agents 2 to 10
6 Wetting agent 1 to 5
7 Anti-foaming agent 0.1 to 5
8 Anti-freezing agent 0.1 to 5
9 Rheology modifier 0.1 to 2
10 Thickener 0.1 to 5
11 Preservative 0.1 to 2
12 DM water q.s.

OD formulation:
S. No. Ingredients Percent (w/w)
1 Acetamiprid 1 to 25
2 Spinosad 4 to 35
3 At least one insecticide selected from Diamide group 1 to 25
4 Dispersing agents 2 to 10
5 Wetting agent 1 to 10
6 Anti-foaming agent 0.1 to 2
7 Anti-freezing agent 1 to 6
8 Emulsifier 2 to 10
9 Thickener 1 to 5
10 Solvent (Methylated seed oil) q.s.

Example 1: Method of Preparation of WDG formulation of acetamiprid 15%+spinosad 20%+chlorantraniliprole 15% WG

Table 1: acetamiprid 15%+spinosad 20%+chlorantraniliprole 15% WG
S.No. Ingredients Function Percent (w/w)
1 Acetamiprid technical (99.0% purity) Active ingredient 15.15
2 Spinosad technical (92% purity) Active ingredient 21.74
3 Chlorantraniliprole technical (93% purity) Active ingredient 16.13
4 sodium di-isopropyl naphthalene sulphonates Wetting agent 3.00
5 Sodium lignosulphonate Dispersing agent 10.00
6 Ammonium Sulphate Disintegrating agent 15.00
7 Polydimethylsiloxane Defoamer 0.50
8 China clay Carrier 18.48
Total 100.00

Manufacturing process-Acetamiprid 15%+Spinosad 20%+Chlorantraniliprole 15% WG (Water Dispersible Granule), 100 kg batch size.
Step 1- Charge the required quantity of 17.98 kg of China clay, 0.5 kg of polydimethylsiloxane, 15 kg of ammonium sulphate, 10 kg of sodium lignosulphonate, 3 kg of sodium di-isopropyl naphthalene sulphonates in premixing blender for homogenization for 30 minutes.
Step 2- Now add 15.15 kg of acetamiprid technical, 21.74 kg of spinosad technical and 16.13 kg of chlorantraniliprole technical and again homogenize for 30 more minutes.
Step 3- Pre-blended material is then grinded through Jet mill/ air classifier mills. Finely grinded material is blended in post blender till it becomes homogeneous. (for approx. 1.5 hr.)
Step 4- Finely grinded powder is mixed with required quantity of water to form extrudable dough.
Step 5- Dough is passed through extruder to get granules of required size.
Step 6- Wet granules are passed through Fluidized bed drier and further graded using vibrating screens.
Step 7- Final product is sent for QC approval.
Step 8- After approval material is packed in required pack sizes.

Storage stability:
The composition was evaluated for its stability. The composition was determined at T0, and under accelerated heat stability (AHS) conditions for 14 days at 54°C designated as T1. The stability was also evaluated after 3 months, at 40°C, designated as T2.

Table 2: storage stability-acetamiprid 15%+spinosad 20%+chlorantraniliprole 15% WG
Test parameters T0 (initial) T1 (AHS),for 14 days at 54 0C T2- for three months at 40 0C
acetamiprid content (% w/w, -5% to +5%) 15.78 15.75 15.74
spinosad content (% w/w, -5% to +5%) 22.18 22.17 22.16
chlorantraniliprole content (% w/w, -5% to +5%) 16.56 16.55 16.55
wettability (60 second, maximum) 12.00 10.00 10.00
suspensibility (minimum 70%) 96.20 95.40 95.20
pH range (5 to 8, 1% aq. Suspension) 7.20 7.10 7.00

The formulation Acetamiprid 15%+Spinosad 20%+Chlorantraniliprole 15% WG meets required storage stability criteria-active ingredient content, wettability, suspensibility and pH range.

Example 2: Method of Preparation of WDG formulation of Acetamiprid, Spinosad and Flubendiamide

Table 3: Acetamiprid 15%+Spinosad 15%+Flubendiamide 15% WG
S. no. Compositions Function Percent (w/w)
1 Acetamiprid technical (99.0% purity) Active ingredient 15.15
2 Spinosad technical (85% purity) Active ingredient 17.65
3 Flubendiamide technical (95% purity) Active ingredient 15.79
4 Castor oil 40 mole ethoxylate Wetting agent 1.00
5 Sodium lauryl sulphate Wetting agent 3.50
6 Sodium lignosulfonate Dispersing agent 15.00
7 Calcium lignosulfonate Dispersing agent 4.00
8 Ammonium sulphate Disintegrating agent 12.00
9 Polydimethylsiloxane Defoamer 1.00
10 Kaolin Carrier 14.91
Total 100.00

Storage stability:
WG formulation of acetamiprid 15%+spinosad 20%+flubendiamide 15% meets required storage stability criteria-active ingredient content, wettability, suspensibility and pH range.

Example 3: Preparation of composition of Acetamiprid, Spinosad and Cyantraniliprole in Suspension Concentrate (SC) form.

Table 4: acetamiprid 5%+spinosad 8%+cyantraniliprole 8% SC
S.No. Ingredients Function Percent (w/w)
1 Acetamiprid technical (99.0% purity) Active ingredient 5.05
2 Spinosad technical (92% purity) Active ingredient 8.70
3 Cyantraniliprole technical (93% purity) Active ingredient 8.60
4 Acrylic Graft Copolymer (2-hydroxypropyl methacrylate) Dispersing agent 5.00
5 Naphthalene sulfonic acid, with sodium salt condensate with formaldehyde Dispersing agent 0.50
6 Trisiloxane ethoxylate Wetting agent 4.00
7 Polydimethylsiloxane Anti-foaming agent 0.50
8 Propylene Glycol Anti-freezing agent 5.00
9 Precipitate Silica Rheology modifier 0.20
10 Polysaccharide Thickener 0.20
11 1,2-benzisothiazolin-3(2H)-one Preservative 0.20
12 Dimeneralized water Solvent 62.05
Total 100.00

Manufacturing process-Acetamiprid 5%+Spinosad 8%+Cyantraniliprole 8% SC
Weighing the raw materials according to the batch size as follows:
Step 1: Preparation of gum solution: Dissolve 2 kg of 1,2-benzisothiazolin-3(2H)-one into 96 kg of Demineralized (DM) water. Now add 2 kg of Polysaccharide slowly and stirred till completely dissolved to form a solution. This gum solution was made 12 to 18 hours prior to use.
Step 2: Take 52.05 kg of DM water and 5 kg of propylene glycol into designated vessel and mix thoroughly. Add 0.5 kg of Naphthalene sulfonic acid-sodium salt condensate with formaldehyde and 2 kg of Ethylene-propylene oxide block copolymer and 5 kg of (2-hydroxypropyl methacrylate) into the vessel having water and homogenize the contents for 45 to 60 minutes using high shear homogenizer.
Step 3: Then 5.05 kg of acetamiprid tech., 8.70 kg of spinosad tech. and 8.60 kg of cyantraniliprole and 0.2 kg of precipitated silica were added and homogenized to get uniform slurry for grinding.
Step 4: Then half of the quantity of polydimethyl siloxane was added to the slurry and then the slurry was subjected to three cycles of grinding in a bead mill till desired particle size achieved. Remaining half quantity of polydimethyl siloxane and 4 kg of trisiloxane ethoxylate were added after the grinding process.
Step 5: Finally, 10 kg of remaining gum solution added and homogenize it to obtain the title formulation.
Step 6: Sending the sample to the quality analysis;
Step 7: Packing the formulated material in suitable packaging.

Storage stability:
The composition was evaluated for its stability. The composition was determined at T0, and under accelerated heat stability (AHS) conditions for 14 days at 54°C designated as T1. The stability was also evaluated after 3 months, at 40°C, designated as T2.

Table 5: storage stability-acetamiprid 5%+spinosad 8%+cyantraniliprole 8% SC
Parameters T0 T1 (AHS),for 14 days at 54 'C T2- for three months at 40 'C
acetamiprid content (%) (-5% to +10% range) 5.45 5.43 5.44
spinosad content (%), (-5% to +10% range) 9.33 9.32 9.31
cyantraniliprole content (%) (-5% to +10% range) 9.20 9.19 9.19
suspensibility (minimum 80%) 98.40 98.30 98.30
pH range (5 to 7, 1% aq. Suspension) 6.80 6.70 6.80
pourability (95% minimum) 98.50 98.20 98.00
Viscosity at spindle no. 62, 20 rpm (350 to 800 cps) 640 650 660

The formulation Acetamiprid 5%+Spinosad 8%+Cyantraniliprole 8% SC meets required storage stability criteria-active ingredient content, suspensibility, pH range, pourability and viscosity.

Example 4: Preparation of composition of Acetamiprid, Spinosad and Cyclaniliprole in Oil Dispersion (OD) form.

Table 6: Acetamiprid 7.5%+Spinosad 7.5%+Cyclaniliprole 7.5% OD
S.no. Ingredients Function Percent (w/w)
1 Acetamiprid technical (99.0% purity) Active ingredient 7.58
2 Spinosad technical (92% purity) Active ingredient 8.15
3 Cyclaniliprole technical (95% purity) Active ingredient 7.89
4 Tristyrylphenol-polyglycol ether-phosphate Dispersing agent 4.50
5 Trisiloxane ethoxylate Wetting agent 5.00
6 Polydimethyl siloxane Anti-foaming agent 0.30
7 Polypropylene glycol Anti-freezing agent 5.00
8 Calcium salts of dodecylbenzene sulphonate Emulsifier 8.00
9 Attapulgite clay Thickener 2.00
10 Methylated seed oil Solvent 51.58
Total 100.00

Preparation of 100 kg composition of Acetamiprid 7.5%+Spinosad 7.5%+Cyclaniliprole 7.5% OD
Step 1: Charge 51.58 kg of methylated seed oil into a vessel for OD production.
Step 2: Add 4.5 kg of tristyrylphenol polyglycol ether phosphate, 8 kg of calcium salts of dodecylbenzene sulphonate, 5 kg of polypropylene glycol and 0.3 kg of polydimethyl siloxane and homogenize the contents for 60 minutes using high shear homogenizer.
Step 3: Add 7.58 kg of acetamiprid technical, 8.15 kg of spinosad technical and 7.89 kg of cyclaniliprole technical into above premix and homogenized for 45 minutes.
Step 4: Mill the above prepared slurry using a suitable colloidal mill or using dyno mill till the required particle size is achieved.
Step 5: After achieving the required particle size discharge the material into final vessel and add attapulgite clay (2.00 kg), 5 kg of Tri siloxane ethoxylate and mix till homogeneous.
Step 6: Do the quality check of this final formulation and pack it in suitable container.
Storage stability:
The composition was evaluated for its stability. The composition was determined at T0, and under accelerated heat stability (AHS) conditions for 14 days at 54°C designated as T1. The stability was also evaluated after 3 months, at 40°C, designated as T2.

Table 7: storage stability- Acetamiprid 7.5%+Spinosad 7.5%+Cyclaniliprole 7.5% OD
Parameters T0 T1 (AHS),for 14 days at 54 'C. T2- for three months at 40 'C
acetamiprid content (%) (-5% to +10% range) 8.22 8.21 8.21
spinosad content (%), (-5% to +10% range) 8.75 8.74 8.73
cyclaniliprole content (%) (-5% to +10% range) 8.45 8.42 8.41
suspensibility (minimum 80%) 96.20 96.00 96.00
pH range (5.5 to 7, 1% aq. Suspension) 6.80 6.70 6.70
pourability (95% minimum) 97.20 97.00 97.00
Viscosity at spindle no. 62, 20 rpm (350 to 800 cps) 590 580 580

The formulation Acetamiprid 7.5%+Spinosad 7.5%+Cyclaniliprole 7.5% OD meets required storage stability criteria-active ingredient content, suspensibility, pH range, pourability and viscosity.

Example 5

BIOLOGICAL EXAMPLES:

Evaluation of synergistic effect of insecticidal composition of the present invention:
The synergism between two or three pesticidal compounds can be evaluated as per the method given by S R Colby. Calculating Synergistic and Antagonistic Responses of Herbicide Combinations, published online by Cambridge University Press: 12 June 2017, pp. 20-22 (Weeds, Journal of The Weed society of America, Volume 15, January 1967, Issue 1, Page 20-22).

Experiment 1: Synergistic control insect-pests in chilly crop.
Crop: Chilly
Plot size: 8 m x 5 m.
Pests: Fruit borer larva (Heliothis armigera), Thrips (Scirtothrips dorsalis)
Spray volume: 460 liters per hectare.
Methodology: Heliothis armigera larvae is foliage feeding insect including green chilly fruits. Live larval count recorded per plant; observation recorded from 10 plants per treatment. The foliar sprays of respective treatment done with backpack sprayer (water volume-460 liter/ha) with hollow cone nozzle. Proper coverage was done while spraying. The follow up observations on larval count were done at 7 DAA (days after application). The larval control was calculated by given formula.

Thrips (Scirtothrips dorsalis) control (%): Count the number of live thrips per twig, 3 twigs per plant and 10 plants per plot. Observations recorded by shaking the twigs over black color piece of paper as thrips is very minute and delicate insect.

Table 8: Synergistic control of fruit borer and thrips in chilly crop
S.No. Treatments with (GAI/H) Heliothis larval control (%) Thrips control (%)
acetamiprid spinosad chlorantraniliprole Observed Expected Colby ratio Observed Expected Colby ratio
T1 16 - - 8.46 - - 20.18 - -
T2 24 - - 12.58 - - 44.28 - -
T3 32 - - 19.87 - - 56.72 - -
T4 - 16 - 34.15 - - 28.94 - -
T5 - 32 - 60.48 - - 51.15 - -
T6 - 48 - 75.92 - - 63.76 - -
T7 - - 16 47.58 - - 4.38 - -
T8 - - 24 71.83 - - 8.92 - -
T9 - - 32 80.42 - - 12.48 - -
T10 32 48 - 82.67 80.70 1.02 86.25 84.32 1.02
T11 32 - 32 86.85 84.31 1.03 63.47 62.12 1.02
T12 - 48 32 96.87 95.29 1.02 69.27 68.28 1.01
T13 16 48 16 98.98 88.45 1.12 97.95 72.34 1.35
T14 24 32 24 100.00 90.27 1.11 99.37 75.21 1.32
T15 32 16 32 99.83 89.67 1.11 98.78 73.08 1.35
GAI/H-gram active ingredients per hectare

Field trial result shows innovative combinations of acetamiprid+spinosad+chlorantraniliprole (T13, T14 and T15) gives synergistic control of chilly fruit borer larvae and thrips. The maximum control was obtained with T14 treatment.

Experiment 2: Insect pests control in tomato crop.
Crop: Tomato
Plot size: 7 m x 4 m.
Pests: Leaf miner (Liriomyza trifolii), Fruit borer larva (Heliothis armigera).
Spray volume: 420 liters per hectare.
Methodology: As per experiment 1.

Table 9: Treatment details
S.No. Treatments Dose (GAI/H)
T1 control -
T2 acetamiprid 20% SP 30
T3 spinosad 45% SC 60
T4 spinosad 45% SC 48
T5 cyantraniliprole 10% OD 36
T6 cyantraniliprole 10% OD 48
T7 acetamiprid 15%+ spinosad 30% WG 30+60
T8 acetamiprid 15%+ cyantraniliprole 24% WG 30+48
T9 spinosad 15%+ cyantraniliprole 12% WG 60+48
T10 acetamiprid 5%+spinosad 10%+cyantraniliprole 6% SC 30+60+36
T11 acetamiprid 5%+spinosad 8%+cyantraniliprole 8% SC 30+48+48
T10 & T11-present compositions; T7 to T9-known binary mixtures; T2 to T6-market products

Table 10: Synergistic control of insect-pests in tomato
S.No. leaf miner control (%)
at 7 days at 14 days
observed expected colby ratio Synergism (Y/N) observed Synergism (Y/N)
T1 0.00 - - - 0.00 -
T2 52.64 - - - 38.67 -
T3 50.82 - - - 34.62 -
T4 42.48 - - - 25.46 -
T5 52.45 - - - 40.17 -
T6 65.92 - - - 56.36 -
T7 77.26 76.71 1.01 Y 58.87 N
T8 84.16 83.86 1.00 Y 72.36 N
T9 83.86 83.24 1.01 Y 70.43 N
T10 96.85 88.92 1.09 Y 90.85 Y
T11 98.48 92.06 1.07 Y 93.46 Y
Both the present compositions (T10 & T11) provide synergistic and residual control of leaf miner on 14th day.

Table 11: Fruit borer larval control
S.No. fruit borer larval control (%)
at 7 days at 14 days
observed expected colby ratio Synergism (Y/N) observed Synergism (Y/N)
T1 0.00 - - - 0.00 -
T2 15.82 - - - 4.74 -
T3 74.18 - - - 61.32 -
T4 61.32 - - - 46.83 -
T5 53.26 - - - -14.00 -
T6 66.85 - - - 51.65 -
T7 79.53 78.26 1.02 Y 62.47 N
T8 73.25 72.09 1.02 Y 51.82 N
T9 92.88 91.44 1.02 Y 80.38 N
T10 100.00 89.84 1.11 Y 95.28 Y
T11 100.00 92.79 1.08 Y 98.89 Y
Both the present compositions (T10 & T11) provide synergistic and residual control of tomato fruit borer larvae on 14th day.

Experiment 3: Residual control provided by innovative composition.
Crop: Chickpea
Plot size: 10 m x 5 m.
Pests: Pod borer, Heliothis armigera.
Spray volume: 400 liters per hectare.
Methodology: Count the number of live larvae from 50 cm x 50 cm (0.25 sq.m.) spot, 10 spots per plot and calculate larval control. Record observations as precount, 3, 7, 10 and 14 DAA (days after application). Calculate % control as observed value.
Healthy pod count: count the number of healthy pods per plant, record observations from 10 plants per plot. Present the data as average number of healthy pods per plant.

Table 12: Treatment details
S.No. Treatments Dose (GAI/H)
T1 Control -
T2 Acetamiprid 20% SP 24
T3 Acetamiprid 20% SP 30
T4 Spinosad 45% SC 32
T5 Spinosad 45% SC 40
T6 Chlorantraniliprole 35% WG 24
T7 Chlorantraniliprole 35% WG 30
T8 spinosad 20%+chlorantraniliprole 15% WG 40+30
T9 acetamiprid 15%+spinosad 20% WG 30+40
T10 acetamiprid 20%+chlorantraniliprole 20% WG 30+30
T11 acetamiprid 15%+spinosad 20%+chlorantraniliprole 15% WG 24+32+24
T12 acetamiprid 4%+spinosad 5.33%+chlorantraniliprole 4% SC 24+32+24
GAI/H-gram active ingredients per hectare and T11 & T12-present compositions; T8 to T10-known binary combinations; T2 to T7-market products.

Table 13: Residual control of pod borer larvae in chickpea crop
S.No. Pod borer larval control (%) Healthy pods per plant Increase (%) in healthy pods over T1
3 DAA 7 DAA 10 DAA 14 DAA
T1 0.00 0.00 0.00 0.00 40.3 0.00
T2 13.28 8.56 2.14 0.48 45.4 12.66
T3 15.73 10.84 6.84 1.65 49.6 23.08
T4 71.28 52.58 34.54 20.10 57.5 42.68
T5 80.72 68.96 52.59 38.53 61.9 53.60
T6 56.43 45.72 34.24 18.54 57.4 42.43
T7 68.75 60.56 49.76 31.76 59.3 47.15
T8 96.58 90.63 75.47 57.87 72.8 80.65
T9 88.64 73.15 53.87 35.87 65.3 62.03
T10 78.68 65.42 52.27 30.64 63.6 57.82
T11 100.00 98.62 92.42 86.58 81.7 102.73
T12 100.00 99.54 95.26 89.67 82.3 104.22

This experiment was conducted to compare the efficacy and duration of control provided by present compositions (T11 & T12) with their binary mixtures (T8 to T10) at higher doses. For example, innovative composition T11: Acetamiprid 15%+Spinosad 20%+Chlorantraniliprole 15% WG tested at 24+32+24 gai/hectare, whereas their binary combinations T8: Spinosad 20%+Chlorantraniliprole 15% WG tested at 40+30 g.a.i/hectare, T9: Acetamiprid 15%+Spinosad 20% WG at 30+40 g.a.i./hectare and T10: Acetamiprid 20%+Chlorantraniliprole 20% WG at 30+30 gai/ha.

The experiment data presented in Table 3 clearly shows present compositions (T11 & T12) provides higher percent larval control and for longer duration (>14 days) in comparison with their binary combinations (T8, T9 and T10) at higher doses. The present compositions (T11 & T12) also yielded highest number of healthy pods per plant.

Experiment 4: Synergistic control of pod borer complex in Red gram crop.
Crop: Red gram
Pests: Pod borer (mixed infestation of Heliothis and Plume moth)
Plot size: 8m x 8m.
Spray volume: 500 liters per hectare.
Methodology: As given in Experiment 2.

Table 14: Treatment details
S.No. Treatments Dose (GAI/H)
T1 control -
T2 acetamiprid 20% SP 37.5
T3 spinosad 45% SC 37.5
T4 tetraniliprole 20% SC 37.5
T5 flubendiamide 20% WG 37.5
T6 cyantraniliprole 10% OD 37.5
T7 acetamiprid 25%+tetraniliprole 25% WG 37.5+37.5
T8 acetamiprid 25%+flubendiamide 25% WG 37.5+37.5
T9 acetamiprid 25%+cyantraniliprole 25% WG 37.5+37.5
T10 spinosad 25%+tetraniliprole 25% WG 37.5+37.5
T11 spinosad 25%+flubendiamide 25% WG 37.5+37.5
T12 spinosad 25%+cyantraniliprole 25% WG 37.5+37.5
T13 acetamiprid 25%+spinosad 25% WG 37.5+37.5
T14 acetamiprid 15%+spinosad 15%+tetraniliprole 15% WG 37.5+37.5+37.5
T15 acetamiprid 15%+spinosad 15%+flubendiamide 15% WG 37.5+37.5+37.6
T16 acetamiprid 7.5%+spinosad 7.5%+cyclaniliprole 7.5% OD 37.5+37.5+37.7
T14 to T16-present compositions; T2 to T6-market products, T7 to T13-known binary mixtures

Table 15: Synergistic control of pod borer larval complex
S.No. Pod borer larval complex control (%) number of healthy pods per plant increase in healthy pods over control (T1)
at 7 days at 14 days
observed expected colby ratio Synergism (Y/N) observed Synergism (Y/N)
T1 0.00 - - - 0.00 - 31.5 0.0
T2 17.48 - - - 3.76 - 38.6 22.5
T3 53.94 - - - 39.75 - 47.6 51.1
T4 47.13 - - - 32.36 - 47.1 49.5
T5 45.75 - - - 30.17 - 46.2 46.7
T6 48.32 - - - 33.43 - 46.9 48.9
T7 57.12 56.37 1.01 Y 32.57 N 56.1 78.1
T8 56.29 55.23 1.02 Y 30.97 N 55.7 76.8
T9 58.74 57.35 1.02 Y 34.17 N 56.3 78.7
T10 76.24 75.65 1.01 Y 57.64 N 62.3 97.8
T11 76.22 75.01 1.02 Y 55.38 N 61.9 96.5
T12 77.48 76.20 1.02 Y 57.92 N 62.8 99.4
T13 62.32 61.99 1.01 Y 40.88 N 54.8 74.0
T14 98.87 79.90 1.24 Y 90.86 Y 68.4 117.1
T15 97.54 79.38 1.23 Y 90.12 Y 67.7 114.9
T16 98.25 80.36 1.22 Y 91.13 Y 68.9 118.7

The field trial results shows that present compositions (T14, T15 and T16) are highly synergistic in terms of pod borer larval complex control, whereas all the binary mixtures (T7 to T13) provide only additive effect on 7th day; and does not provides satisfactory control on 14th day. The present compositions also yielded higher number of healthy pods per plant (i.e. >114% increase over T1).
, C , Claims:Claims:
I/we claim,
1. An agrochemical composition comprising:
a. compound A of acetamiprid;
b. compound B of spinosad;
c. compound C at least one insecticide selected from diamide insecticide group; and
d. one or more inactive excipients.

2. The agrochemical composition as claimed in claim 1, wherein a) compound A of acetamiprid is in amount of 1.0 to 25.0% w/w; b) compound B of spinosad is in amount of 4.0 to 35.0% w/w; c) compound C at least one insecticide selected from diamide insecticide group is in amount of 1.0 to 25.0% w/w.

3. The agrochemical composition as claimed in claim 1, wherein diamide insecticide group is selected from chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole or flubendiamide.

4. The agrochemical composition as claimed in claim 1, wherein one or more inactive excipients is selected from the group comprising of wetting agent, dispersing agent, antifoaming agent/defoamer, anti-freezing agent, biocide/preservative, thickener/suspending agent, disintegrating agent, emulsifier, solvent, pH stabilizer, anti-caking agent, humectant, binder, filler/carrier and wall forming materials or combination thereof.

5. The agrochemical composition as claimed in claim 1, wherein the formulation for the said composition is selected from Water dispersible granules/Wettable granules (WDG/WG), Water soluble granules (SG), Emulsifiable granule (EG), Wettable powder (WP), Water Dispersible Powder (WDP), Soluble powder (SP), Emulsifiable powder (EP), Oil dispersible powder (OP), Soluble Tablet (ST), Capsule suspension/Micro capsule (CS), Dispersible concentrate (DC), Emulsifiable concentrate (EC), Emulsion water-in-oil (EO), Emulsion oil-in-water (EW), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Suspension Concentrate (SC), Suspo Emulsion (SE), Soluble Liquid/Concentrate (SL), mixed formulation of CS and SC (ZC), mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW).

6. The agrochemical composition as claimed in claim 5, wherein the Water dispersible granules/Wettable granules (WDG/WG) formulation comprises:
a. compound A of acetamiprid is in amount of 1.0 to 25.0% w/w;
b. compound B of spinosad is in amount of 4.0 to 35.0% w/w;
c. compound C at least one insecticide selected from diamide insecticide group is in amount of 1.0 to 25.0% w/w; and
d. wetting agent is in amount of 2.0 to 8.0% w/w;
e. dispersing agent is in amount of 8.0 to 20.0% w/w;
f. disintegrating agent is in amount of 10.0 to 25.0% w/w;
g. defoamer is in amount of 0.1 to 2.0% w/w; and
h. carrier in amount of quantity sufficient.

7. The agrochemical composition as claimed in claim 5, wherein the suspension concentrate (SC) formulation comprises:
a. compound A of acetamiprid is in amount of 1.0 to 25.0% w/w;
b. compound B of spinosad is in amount of 4.0 to 35.0% w/w;
c. compound C at least one insecticide selected from diamide insecticide group is in amount of 1.0 to 25.0% w/w; and
d. dispersing agent is in amount of 2.0 to 10.0% w/w;
e. wetting agent is in amount of 1.0 to 5.0% w/w;
f. anti-foaming is in amount of 0.1 to 5.0% w/w;
g. anti-freezing agent is in amount of 0.1 to 5.0% w/w;
h. rheology modifier is in amount of 0.1 to 2.0% w/w;
i. thickener is in amount of 0.1 to 5.0% w/w;
j. preservative is in amount of 0.1 to 2.0% w/w; and
k. solvent in amount of quantity sufficient.

8. The agrochemical composition as claimed in claim 5, wherein the Oil-dispersion (OD) formulation comprises:
a. compound A of acetamiprid is in amount of 1.0 to 25.0% w/w;
b. compound B of spinosad is in amount of 4.0 to 35.0% w/w;
c. compound C at least one insecticide selected from diamide insecticide group is in amount of 1.0 to 25.0% w/w; and
d. dispersing agent is in amount of 2.0 to 10.0% w/w;
e. wetting agent is in amount of 1.0 to 10.0% w/w;
f. anti-foaming is in amount of 0.1 to 2.0% w/w;
g. anti-freezing agent is in amount of 1.0 to 6.0% w/w;
h. emulsifier is in amount of 2.0 to10.0% w/w;
i. thickener is in amount of 1.0 to 5.0% w/w; and
j. solvent in amount of quantity sufficient.

9. The agrochemical composition as claimed in claim 6, claim 7 & claim 8, wherein wetting agent is selected from tristyryl phenol ethoxylate non-ionic polymer, sodium iso propyl naphthalene sulphonate, alkyl phenyl ethoxylate, aryl phenyl ethoxylate, aryl phenyl ether phosphate, alkoxylated alcohol, ethoxylated fatty alcohol, ethylene oxide-propylene oxide (EO-PO) block copolymer, alkyl aryl sulphonate, alkyl olefin sulfonate, dioctyl succinate, sodium lauryl sulfate, alkyl polyglucoside, sodium alkyl aryl taurate, sorbitol esters, sorbitol oleate, poly aryl phenyl ether phosphate, polyalkoxylated butyl ether, ethoxylated fatty alcohol, sodium dioctyl sulfosuccinate, sodium dodecyl benzene sulfonate, alkyl diphenyl sulfonates, sodium isopropyl naphthalene sulfonate, sodium di-isopropyl naphthalene sulphonates, alkyl naphthalene sulfonate. Ethoxylated alcohol includes natural fatty alcohol, lauryl alcohol ethoxylate, lauryl alcohol alkoxylate, synthetic alcohol ethoxylate, tridecyl alcohol ethoxylate, 2-ethyl hexanol, 2-propylheptanol, isodecyl alcohol, trisiloxane ethoxylate, heptamethyl trisiloxane, modified form includes polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane, polyalkyleneoxide modified Tri siloxane, polyalkyleneoxide modified polydimethylsiloxane, may be liquid or powder form or combination thereof.

10. The agrochemical composition as claimed in claim 6, claim 7 & claim 8, wherein dispersing agent is selected from Polyacrylate compound, poly(methyl acrylate), poly(ethyl acrylate), poly(propyl acrylate), poly(n-butyl acrylate), poly(isobutyl acrylate), poly(2-ethyl acrylate), poly(t-butyl acrylate), poly(ethylhexyl acrylate), poly(benzyl acrylate), poly(methyl methacrylate), poly(ethyl methacrylate), poly(n-butyl methacrylate), poly(isobutyl methacrylate), poly((ethylene glycol) methyl ether methacrylate), poly(methacrylate-coethylacrylate), poly(methacrylate-co-styrene), poly(methacrylate-co-butylmethacrylate), poly(n-butylmethacrylcate-co-methacrylate), poly((ethylene oxide)-co-poly(methyl acrylate)), polymethyl methacrylate-polyethylene glycol graft copolymer (Atlox 4913), nonionic comb-shaped polyacrylate (Dispersogen PSL 100), 2-Acrylamido-2-Methylpropane Sulfonic Acid, Sodium methallyl sulfonate, 3-sulfopropyl acrylate potassium salt, 3-sulfopropyl methacrylate potassium salt, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxymethyl methacrylate, Polyethylene-g-poly(n-butyl acrylate), and the mixtures thereof. Polyarylphenyl ether phosphate, Tri styryl phenol ethoxylate, ethoxylated tristryl phenol sulphate, acrylic polymer amine salt, naphthalene sulfonic acid-sodium salt condensate with formaldehyde, alkylated naphthalene sulfonate-sodium salt, ethoxylated oleylcetyl alcohol, poly alkelene glycol ether, ethoxylated fatty alcohol, alkyl sulfonate, styrene acrylic copolymer, alkyl phenol polyglycol ether, sodium lignosulfonate, calcium lignosulfonate, sodium polycarboxylate, EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propylene oxide- polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycol ether-phosphate, tristyrylphenole with 16 moles EO, oleyl-polyglycol ether with ethylene oxide, tallow fatty amine polyethylene oxide, nonylphenol polyglycol ether with 9-10 moles ethylene oxide or combination thereof.

11. The agrochemical composition as claimed in claim 6, wherein disintegrating agent is selected from clays, bentonite, diatomaceous, colloidal silica, kaolin, Water soluble salts such as potassium phosphate, ammonium sulphate, sodium sulphate, sodium citrate or urea or combination thereof.

12. The agrochemical composition as claimed in claim 6, claim 7 & claim 8, wherein defoamer/antifoaming agent is selected from siloxane polyalkylene oxide, polydimethyl siloxane, polysiloxane emulsion, vegetable oil-based antifoam, silicone oil emulsion, magnesium stearate or a combination thereof.

13. The agrochemical composition as claimed in claim 6, wherein carrier cum filler is selected from sand, silica, precipitated silica, bentonite, attapulgite, ceramic, montmorillonite, pumice, sepiolite, diatomaceous earth, clay, dolomite, calcite, silicon dioxide, china clay/kaolin clay, talc, starch, zinc and its salts (zinc sulphate, zinc oxide, zinc lactate gluconate, zinc polyflavonoid), iron and its salt (ferrous sulphate), copper and salts, sulphur, humic acid and salt, fulvic acid and salt, amino acids, sea weed extracts, chitosan or a combination thereof.

14. The agrochemical composition as claimed in claim 7 & claim 8, wherein anti-freezing agent is selected from ethylene glycol, propane diols, glycerin or the urea, glycol, monoethylene glycol, diethylene glycol, polypropylene glycol, Propylene glycol, polyethylene glycol, glycerin, urea, magnesium sulfate heptahydrate, sodium chloride or combination thereof.

15. The agrochemical composition as claimed in claim 7, wherein rheology modifier is selected from China clay, bentonite, fuller’s earth, zeolite, quartz, precipitated silica, palygorskite, sepiolite, halloysite, and a combination thereof.

16. The agrochemical composition as claimed in claim 7 & claim 8, wherein thickener is selected from natural polymers (gelling agent), polysaccharides such as xanthan gum, guar gum, acacia gum, gelatin; cellulose derivatives, Carboxymethylcellulose (CMC), hydroxypropyl methylcellulose (HPMC), methylcellulose (MC), sodium carboxymethyl cellulose; clays & minerals, bentonite clay, attapulgite clay, sodium polyacrylate, aluminum magnesium silicate, or a combination thereof.

17. The agrochemical composition as claimed in claim 7, wherein preservative is selected from benzisothiazolin-3-one, formaldehyde, sodium benzoate, sodium o-phenyl phenate, potassium sorbate, 1,2-benzisothiazolin-3(2H)-one, 2-bromo-2-nitropropane-1,3-diol, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4-isothiazolin-3-one or a combination thereof.

18. The agrochemical composition as claimed in claim 8, wherein emulsifier is selected from castor oil ethoxylate 40 mole, Polyoxyethylenealkylphenyl ether alkyl aryl sulfonate, 3-methoxy N, N-dimethyl propionamide, Polyglyceryl-3 caprylate, Polysorbate 60, polyoxyethylene sorbitan monostearate-Tween 60, Calcium salts of dodecylbenzene sulphonate, solvents alkyl phenol, aryl phenol, alkyl phenol ethoxylate, fatty acid esters, fatty acid alkanol amides, alkoxylated fatty acid ester or a combination thereof.

19. The agrochemical composition as claimed in claim 7 & claim 8, wherein solvent is selected from demineralized (DM) water, alcohols such as ethanol, propanol, n-octanol, isopropanol ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, acetophenone, glycerin, polyol ethers such as ethylene glycol monopropyl ether, diethylene glycol, monomethyl ether, Di propylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethers such as dipropyl ether, dioxane, tetrahydrofuran; aliphatic hydrocarbons such as normal paraffin, isoparaffin, kerosene, mineral oil; heavy aromatic hydrocarbons such as mixture of heavy aromatic naphtha hydrocarbon C-9 to C-16, xylene, toluene, naphthalene, solvent naphtha, solvent C9, solvent C10, solvent C12, solvesso 100, solvesso 150, solvesso 200; carboxamide; aliphatic or aromatic hydrocarbons such as chlorobenzene, chloroethylene, methylene chloride; esters such as ethyl acetate, Di isopropyl phthalate, dimethyl adipate, methyl oleate, methyl tallowate; lactones such as gamma-butyrolactone; alkyl amide, amides such as dimethylformamide, alkyl pyrrolidone, N-methyl-2-pyrrolidone, N-octyl pyrrolidone, N,N-dimethyldecanamide, N, N-dimethyloctanamide, N, N-dimethylamine, N,N-dimethylmethanamide; nitriles such as acetonitrile; organosulfur compound such as alkyl sulfoxide, dimethyl sulfoxide, propylene carbonate, mineral oil, methylated seed oil, methyl ester of palm oil/soybean oil/castor oil/cotton seed oil/blend of two or more seed oil or combination thereof.

Dated this 18th day of February, 2025.