Description:FIELD OF INVENTION:
The present invention relates to a formulated synergistic insecticidal emulsifiable concentrate formulation with a green solvent comprising an effective amount of insecticides. More particularly the present invention relates to a formulated synergistic emulsifiable concentrates composition comprising a green solvent present in an amount of 40% to 70%w/w; bioactive amount of (A) Tolfenpyrad present in an amount of 5% to 25% w/w; and (B) an insecticide selected from abamectin, emamectin benzoate, fluxametamide, fipronil, profenofos, cyantraniliprole, chlorantraniliprole, azadirachtin, fenpyroximate, hexythiazox, fenazaquin present in an amount of 0.05% to 30% w/w; and (C) an one more insecticide present in an amount of 1% to 40% w/w and other formulation excipients.

BACKGROUND OF THE INVENTION:
Pesticides are widely used in agricultural areas to increase the yield and quality of crops. These days cultivation of crops and agriculture, in general, is cost-intensive. Receiving a high yield from the cultivated crops is key. Hence, to achieve a higher yield, protecting crops from pests and diseases is vital. Hence, the most effective way to control crop pests and disease is the application of pesticides following the appropriate management practices with proper formulation thereof.
Insecticides are agents of chemical or biological origin that control insects. Control may result from killing the insect or otherwise preventing it from engaging in behaviors deemed destructive. Insecticides may be natural or manmade and are applied to target pests in a myriad of formulations and delivery systems.
Emulsifiable concentrates (also referred to as emulsion concentrates or EC) are widely used formulations in crop protection. EC is typically based on hydrophobic solvents with high dissolution power. Due to their hydrophobicity, they typically result in stable emulsions when diluted with water.
EC (emulsifiable concentrates) are well known for active ingredients which are very soluble in non-polar solvents. They are formulated by dissolving surfactants in organic solvents.
The emulsifiable concentrates containing harmful organic solvents more particularly aromatic solvents such as benzene, toluene, xylene, etc. could pose potential risks to the ecological environment and human health due to their low flash points, easy volatility, and high toxicity. The usage of organic solvents in pesticide emulsifiable concentrate highlighted their potential hazards, and introduced the progress of organic solvents substitution by bio-based solvents, mineral-based solvents, and artificially synthetic solvents. These eco-friendly alternative green solvents with low toxicity showed good potential in the application of emulsifiable concentrates. However, the selection of alternative solvents through experiments was time-consuming and labor-intensive.
A solution of a pesticide with emulsifying agents in a water-insoluble organic solvent will form an emulsion when added to water. EC formulation should be storage stable without any visible cracking of emulsion.
There is however a need for improvement of these combinations. Single active combination used over a long period of time has resulted in resistance. With the onset of resistance to certain pests, there is a need in the art for a combination of actives that decrease the chances of resistance and improves the spectrum of insect pests control.
In general use, the pesticide actives are used in the form of a dilute aqueous composition because it can attain a good interaction with the target organism, such as plants, insect-pests and diseases. However, most active pesticide compounds that are used as pesticides are only sparingly or insoluble in water. The low solubility of such compounds present the challenges and difficulties to formulator in formulating pesticide compounds in stable formulations that can be easily stored for a long time and which can still have a high stability and effective activity until end use. This problem especially occurs and may get worsen if more than one active compound is present in the mixture.
CN102599169B patent discloses Tolfenpyrad-containing insecticidal composition. The Patent discloses a tolfenpyrad-containing insecticidal composition. The effective components include tolfenpyrad as a first active component, and chlorantraniliprole or dimethacarb as a second active component; the weight ratio of the first active component to the second active component is 1:70 to 70:1; the weight sum of the first active component and the second active component accounts for 1-70% of the total weight of an agricultural compound composition; and the tolfenpyrad-containing insecticidal composition can be prepared into a normal formulation such as suspension, water dispersible granules, wettable powders, microcapsule suspension, emulsifiable concentrate, water emulsion, microemulsion or the like. The composition is used for preventing and treating diseases caused by diamondback moth larvae in Lepidoptera, thrips in Thysanoptera, rice stem borers, leaf folders, cotton bollworms and the like. The composition has the advantages of high efficacy, long durability, reduced environment pollution and the like.
CN102630677A Patent discloses Tolfenpyrad-containing ultra-low volume liquid. This Patent discloses tolfenpyrad-containing ultra-low volume liquid. Tolfenpyrad or tolfenpyrad and an active component II are prepared into an active component, and auxiliaries and solvents are supplemented to 100% to obtain the ultra-low volume liquid, wherein the active component II is any one of lambda-cyhalothrin, bifenthrin, chlorantraniliprole, flubendiamide, phoxim, indoxacarb, diafenthiuron, hexaflumuron, clothianidin, buprofezin, abamectin, emamectin benzoate benzoate, diazinon and diflubenzuron. The ultra-low volume liquid disclosed by the invention is convenient to process, long in duration, high in working efficiency and less in environmental pollution, can be used for saving pesticides and water and improving the pesticide utilization rate; the target has less possibility of generating drug resistance; and through ultra-low volume spraying, low-volume spraying or ultra-low volume static spraying, various pests of lepidoptera, hemiptera, beetles, hymenoptera, diptera, thrips and mite can be controlled, and the effects of egg killing, eating inhibition, oviposition suppression and sterilization are also realized.
CN102132698A Patent discloses Green solvent for pesticide and application of green solvent. This Patent discloses relates to a green solvent for pesticide and an application of the green solvent. The green solvent for pesticide is a composition in which natural oils serve as the primary components and Gemini pyrrolidine serves as the cosolvent. The green solvent for pesticide has excellent dissolubility and application stability and is used for replacing the poisonous and harmful benzenes solvent in traditional pesticide preparation. The green solvent for pesticide is safe to human body, domestic animals and environment. The green solvent comprises the following components by weight percent: 70.0-99.0% of natural oils, 0.1-20.0% of cosolvent and 0-10.0% of anti-freezing agent. Such a green solvent is prepared by uniformly mixing the components according to a certain weight percent. The green solvent for pesticide has the advantages that the preparation process is simple, the solvent use is safe and convenient, the green solvent for pesticide meets the demand of replacing the benzenes solvent in pesticide preparation of national policy, and the green solvent for pesticide is suitable for being applied and popularized in large area.
Therefore, an object of the present invention is to provide a method and a composition for the Emulsifiable concentrates (EC) formulation with a green solvent comprising an effective amount of insecticides.
Another object of the present invention is to provide improved Emulsifiable concentrate (EC) formulation with a green solvent comprising combinations of (A) Tolfenpyrad; and (B) an insecticide selected from abamectin, emamectin benzoate, fluxametamide, fipronil, profenofos, cyantraniliprole, chlorantraniliprole, azadirachtin, fenpyroximate, hexythiazox, fenazaquin and (C) an insecticide; for the control of insect-pest. Another object of the present invention is to provide a method and a composition for controlling insect pests.
Embodiment of the present invention can ameliorate one or more of the above-mentioned problems.
The leads the inventor to prepare a insecticidal emulsifiable concentrate comprising in effective amount of (A) an insecticide Tolfenpyrad; and (B) an insecticide selected from abamectin, emamectin benzoate, fluxametamide, fipronil, profenofos, cyantraniliprole, chlorantraniliprole, azadirachtin, fenpyroximate, hexythiazox, fenazaquin; and (C) an insecticide. Widening the spectrum of action on the insects which can be controlled.
Surprisingly, Inventors of the present invention have surprisingly found that a formulated insecticidal emulsifiable concentrate composition with green solvent of present invention comprising an effective amount of Tolfenpyrad and an one insecticide selected from abamectin, emamectin benzoate, fluxametamide, fipronil, profenofos, cyantraniliprole, chlorantraniliprole, azadirachtin, fenpyroximate, hexythiazox, fenazaquin and an insecticide selected from class of an insecticide have enhanced efficacy and have widespread scope in end use.
Thus, the present invention has widen the spectrum of action on the insects with high efficiency on one hand and safety, environmental protection, and low toxicity on another hand.

SUMMARY OF INVENTION:
The present invention relates to a formulated synergistic emulsifiable concentrate formulation with a green solvent devoid of aromatic solvent comprising an effective amount of insecticides. More particularly the present invention relates to a formulated synergistic emulsifiable concentrate composition comprising a green solvent; a super wetting-spreading-penetrating agent with bioactive amount of insecticidal compounds and other formulation excipients.
The present invention more particularly relates to a formulated synergistic emulsifiable concentrate composition with a green solvent present in an amount of 40%-70%w/w along with bioactive amount of compound (A) Tolfenpyrad present in an amount of 5 to 25% w/w; (B) an insecticide selected from abamectin, emamectin benzoate, fluxametamide, fipronil, profenofos, cyantraniliprole, chlorantraniliprole, azadirachtin, fenpyroximate, hexythiazox, fenazaquin present in an amount of 0.05% to 30% w/w; and (C) an insecticide present in an amount of 1% to 40% w/w and other formulation excipients.
The present invention further relates to the selection of suitable formulation excipients, the process of preparation of the said emulsifiable concentrate formulation, and its application in the field of agriculture.
In further aspect of the invention the formulation excipients or inactive excipients are used in present emulsifiable concentrate formulation are selected from green solvent, emulsifier/surfactant, super wetting-spreading-penetrating agent.
Further essential aspect of the present invention green solvent for Emulsifiable concentrates (EC) formulation is selected from n-hexanol (1-hexanol), n-butanol (1-butanol), isobutanol (2-methyl-1-propanol), lactate esters, cyclopentylmethylethe, methyl tertbutyl ether, hexylene glycol, dipropyleneglycol, gamma butyrolactone, acetophenone, 1-methoxy-2-propanol, white mineral oil, g-valerolactone, 2-methyltetrahydrofuran, propylene carbonate, polyethylene glycol, oleic acid, fatty acid methyl ester, Tris (2-ethylhexyl) phosphate, mixture of octanoic acid, decanoic acid, N,N-dimethylamide, 2-ethylhexyl acetate, n-octyl-2-pyrrolidone, pentanol mixture of isomer, isobutanol, lactic acid dimethyl amide, 3-methoxy-N, N-dimethyl propionamide.
In a further aspect of the present invention emulsifier for Emulsifiable concentrates (EC) formulation selected more preferably from polysorbate 20 (polyoxyehtylene sorbitan monolaurate-Tween 20, polysorbate 60 (polyoxyethylene sorbitan monostearate-Tween 60), polysorbate 65 (polyoxyethylene sorbitan tristearate-Tween 65), polysorbate 80 (polyoxyethylene sorbitan monooleate-Tween 80).
In a further aspect of the present invention a super wetting-spreading-penetrating agent for Emulsifiable concentrates (EC) formulation is selected from Methylated seed oil, polyalkyleneoxide modified trisiloxane; Methylated seed oil, polyalkyleneoxide modified polydimethylsiloxane; Methylated seed oil, trisiloxane ethoxylate; Methylated seed oil, polyoxyethylene methyl polysiloxane; Methylated seed oil, polyether polymethyl siloxane copolymer; Methylated seed oil, polyether modified polysiloxane wherein seed oil is selected most preferably from sunflower oil, soybean oil, rapeseed oil cotton seed oil or their blend.
Further aspect of the present invention is to provide insecticidal Emulsifiable concentrates (EC) formulation comprising at least one active ingredient shows synergistic activity and stability over wide range of the conditions.
In an another aspect of the present invention, an insecticide as a component (C) is an insecticide compound may be selected from dimethoate, ethion, phenthoate, phosalone, profenofos, quinalphos, triazophos, ethiprole, fipronil, flufiprole, nicofluprole, pyrafluprole, pyriprole, broflanilide, cyproflanilide, fluxametamide, isocycloseram, afoxolaner, esafoxolaner, fluralaner, lotilaner, sarolaner, bifenthrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, deltamethrin, fenpropathrin, fenvalerate, permethrin, phenothrin, prallethrin, profluthrin, acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, flupyrimin, cycloxaprid, paichongding, guadipyr, cycloxylidin, sulfoxaflor, flupyradifurone, triflumezopyrim, dichloromezotiaz, fenmezoditiaz, spinosad, spinetoram, abamectin, emamectin benzoate, ivermectin, milbemectin, hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen, pymetrozine, pyrifluquinazon, afidopyropen, flonicamid, clofentezine, hexythiazox, diflovidazin, etoxazole, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron, buprofezin, cyromazine, chlorfenapyr, sulfluramid, methoxyfenozide, tebufenozide, halofenozide, fufenozide or chromafenozide, amitraz, diafenthiuron, azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon, fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, flufenerim, rotenone, fluacrypyrim, pyriminostrobin, cyenopyrafen, cyflumetofen, pyflubumide, hydramethylnon, acequinocyl, fluacrypyrim, bifenazate, flometoquin, indoxacarb, metaflumizone, spirodiclofen, spiromesifen, spirotetramat, spidoxamat, spiropidion, spirobudifen, chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole, tetrachlorantraniliprole, tyclopyrazoflor, cyhalodiamide, flubendiamide, fluchlordiniliprole, tiorantraniliprole, acynonapyr, azadirachtin, benzoximate, bromopropylate, benzpyrimoxan, chinomethionat, dicofol, pyridalyl, oxazosulfyl, dimpropyridaz, indazapyroxamet, fluhexafon, cyetpyrafen, flupentiofenox, acyonapyr, trifluenfuronate, cyclobutrifluram, fluazaindolizine, tioxazafen.
In a further aspect of the present invention, that active ingredient from compound (B) and compound (C) are not same.

DETAILED DESCRIPTION OF THE INVENTION:
The term “synergistic”, as used herein, refers to the combined action of two or more active agents blender and administered conjointly that is greater than the sum of their individual effects.
“Bioactive amounts” as mentioned herein means that amount which, when applied treatment of crops, is sufficiently to effect such treatment.
The emulsifiable concentrates containing harmful organic solvents such as benzene, toluene, xylene, etc. could pose potential risks to the ecological environment and human health due to their low flash points, easy volatility, and high toxicity. The usage of organic solvents in pesticide emulsifiable concentrate highlighted their potential hazards, and introduced the progress of organic solvents substitution by bio-based solvents, mineral-based solvents, and artificially synthetic solvents. These eco-friendly alternative green solvents with low toxicity showed good potential in the application of emulsifiable concentrates. However, the selection of alternative solvents through experiments was time-consuming and labor-intensive.
Therefore an aspect of the present invention provides a formulated synergistic insecticidal emulsifiable concentrate (EC) composition with green solvent and without aromatic solvent comprising bioactive amounts of along with bioactive amount of insecticides compounds along with formulation excipients.
One of the most common types of an agrochemical formulation is emulsifiable concentrate (EC) which is basically comprises an active ingredient (AI), a solvent or blend of solvents, surfactants, and small amounts of additives. The most common solvents present in these formulas contribute to volatile organic compound (VOC) emissions are flammable and classified as hazardous air pollutant (HAP) substances, these substances are toxic to users and farmers and can be phytotoxic for crops. The use of solvents that are more benign to human health and the environment is part of the “Green Chemistry” movement.
Important features of Green Chemistry defines for these new molecules were low volatility being derived from renewable feedstock and low toxicity and phytotoxicity. The green solvent had many desirable physical and chemical properties such as high boiling point, low volatility, and low freezing point. Due to their chemical characteristics, it is believed that they have low toxicity to humans and to the environment. A remarkable benefit of these products is that they do not cause eye irritation.
EC formulations usually contain active ingredients (pesticides), carrier solvents and adjuvants (surfactants). Surfactants are designed to perform specific functions including buffering, dispersing, emulsifying, spreading, sticking, and wetting properties. In the field, pesticide products (EC formulations) are mixed with water and directly used.
Conventional EC formulations use a large number of aromatic solvents, which are hazardous to human health. Nowadays, many studies have attempted to develop EC formulations using green carrier solvents such as vegetable oils, animal fats, or biodiesels. However, these solvents are highly viscous or may be in the solid-state at low temperatures. Therefore, it is necessary to explore environmentally friendly alternatives.
Emulsifiable concentrates (also referred to as emulsion concentrates or EC) are widely used formulations in crop protection.
Therefore an aspect of the present invention provides a formulated synergistic insecticidal emulsifiable concentrate (EC) composition with green solvent and without aromatic solvent comprising bioactive amounts of (A) Tolfenpyrad; and (B) an insecticide selected from abamectin, emamectin benzoate, fluxametamide, fipronil, profenofos, cyantraniliprole, chlorantraniliprole, azadirachtin, fenpyroximate, hexythiazox, fenazaquin; and (C) one more insecticide compound along with formulation excipients.
In an aspect of the present invention, formulation excipients are used in present emulsifiable concentrate formulation selected from green solvent, emulsifier/surfactant [surface-active emulsifying agent], an emulsifier, super-wetting-spreading-penetrating agent.
In another aspect of the present invention, an inactive/formulation excipient green solvent is selected from n-hexanol (1-hexanol), n-butanol (1-butanol), isobutanol (2-methyl-1-propanol), lactate esters, cyclopentylmethylethe, methyl tertbutyl ether, hexylene glycol, dipropyleneglycol, gamma butyrolactone, acetophenone, 1-methoxy-2-propanol, white mineral oil, g-valerolactone, 2-methyltetrahydrofuran, propylene carbonate, polyethylene glycol, oleic acid, fatty acid methyl ester, Tris (2-ethylhexyl) phosphate, mixture of octanoic acid, decanoic acid, N,N-dimethylamide, 2-ethylhexyl acetate, n-octyl-2-pyrrolidone, pentanol mixture of isomer, isobutanol, lactic acid dimethyl amide, 3-methoxy-N, N-dimethyl propionamide.
More preferred green solvent for the present formulated synergistic present emulsifiable concentrate composition is 1-hexanol, n-butanol, propylene carbonate, 1-methoxy-2-propanol, 3-methoxy-N, N-dimethyl propionamide.
Preferred range for the green solvent for the present formulated synergistic present emulsifiable concentrate composition is 40% to 70%w/w.
Most preferred range for the green solvent for the present formulated synergistic present emulsifiable concentrate composition is 44% to 69%w/w.
The present synergistic insecticidal emulsifiable concentrate formulation with a green solvent is found to be effective and broadens the spectrum of control. The present formulates composition shows wide control of the chewing type, piercing and sucking type of insects at a time, like control of chewing type lepidopteran (caterpillars, beetles), hemipteran (sucking type) and thysanopteran (piercing type) insects in crops.
The present formulated insecticidal composition delay or retard the resistance development in insects against a specific group or type of insecticides.
Further, the present invention achieve desirable bio-efficacy, duration of control. It reduce the doses of active ingredients and thereby reduce the loading of active ingredients into the environment. The present insecticidal emulsifiable concentrate formulation with a green solvent increase the yield of crops and plants and thereby achieve economical benefits and reduce the loading of harmful organic solvent as carrier of pesticides in to the crop ecosystem.
The present inventors believe that a formulated synergistic insecticidal emulsifiable concentrate (EC) composition with green solvent and without aromatic solvent of the present invention comprising bioactive amounts of (A) Tolfenpyrad; and (B) an insecticide selected from abamectin, emamectin benzoate, fluxametamide, fipronil, profenofos, cyantraniliprole, chlorantraniliprole, azadirachtin, fenpyroximate, hexythiazox, fenazaquin; and (C) one more insecticide compound along with formulation excipients shows:
• Excellent adhesion to the plant parts, improving the drift resistance and effectiveness of adjuvants and active ingredients.
• Uniform droplet size for even distribution on plant parts.
• Reduced evaporation loss, reduced drift in windy, rainy, and other weather seasons and enhance the absorption of active ingredients.
• Improved rain fast properties.
• Increase spreading properties on leaf surfaces, better wetting of waxy leaf surfaces.
• Increases leaf penetration of active ingredients.
• Enhanced synergistic activities between active ingredients.
• Enhanced residual control of insect pests and mites, and thereby reduced the number of applications.
• Increase penetration into the insect cuticles and insects with waxy cuticles like mealybug and scale insects.
• Due to its viscosity, low VOC and high flash point, it provides extended contact time.
• Biodegradable with low or no VOC content. Non-hazardous air pollutant or ozone depleting chemicals (ODC).
• Nontoxic, non-irritable, less hazardous and safer to use than hydrocarbon and petroleum based solvents.
In a further aspect of the present invention, an inactive or formulation excipients Super-Wetting-spreading-penetrating agent is blend of methylated seed oil-organo silicon compound.
The blend methylated seed oil-organo silicon compound comprises methylated seed oil present in an amount of 70% to 90% and organo-silicon surfactants are present in amount of 10% to 40% of the blend.
The preferred combination for the said blend of methylated seed oil and organo-silicon surfactants is selected from 84% Methylated seed oil, 16% polyalkyleneoxide modified trisiloxane; 90% Methylated seed oil, 10% polyalkyleneoxide modified polydimethylsiloxane; 80% Methylated seed oil, 20% trisiloxane ethoxylate; 70% Methylated seed oil, 30% polyoxyethylene methyl polysiloxane; 60% Methylated seed oil, 40% polyether polymethyl siloxane copolymer.
Methylated seed oil is a kind of fatty acid from seed oil esterified with methyl alcohol. For oil-based adjuvant, droplet spread on application surface for example leaf surfaces; and active agent penetration; are the two predominant factors regarding the mechanism of the enhancement in herbicide efficacy.
Organosilicon compounds have been found to be significantly useful as agricultural adjuvants because of their unique wetting properties. These surfactants provide surface tension values significantly lower than conventional nonionic surfactants and can provide highly efficient uptake of agricultural chemicals into the plant. The spreading of aqueous solutions due to the organosilicon compounds gives total wetting as measured by low contact angle on leaf surfaces while conventional surfactants provide for less spreading as indicated by higher contact angles. In addition, the organosilicon compounds have been shown to increase the speed and amount of uptake of agricultural active ingredients into plants, resulting in enhanced efficacy of the agricultural active ingredients, including in some cases, like rain fastness.
The present invention relates to blends of Methylated seed oil with organosilicon surfactants, which are useful as agricultural adjuvants for the present emulsifiable concentrate insecticidal composition.
In a further aspect of the present invention, an inactive or formulation excipients Super-Wetting-spreading-penetrating agent is blend of methylated seed oil-organic silicone compound may be selected from methylated seed oil-polyalkyleneoxide modified trisiloxane, methylated seed oil-polyalkyleneoxide modified polydimethylsiloxane, methylated seed oil-trisiloxane ethoxylate, methylated seed oil-polyoxyethylene methyl polysiloxane, methylated seed oil-polyether polymethyl siloxane copolymer, methylated seed oil-polyether modified polysiloxane.
The seed 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, 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 acid (Allium sativum), Ginger oil (Zingiber officinale), D-limonene, Citronella oil or Ceylon ironwood (Mesua ferrea) oil.
The preferred seed oils are sunflower oil, soybean oil, rapeseed oil, cotton seed oil or their blend.
In another aspect of the present invention, an inactive excipient emulsifier/surfactant [ surface-active emulsifying agent] may be selected from Sorbitan esters (sorbitan fatty acids esters SFAE) - their polyoxyethylene derivatives as polysorbates- polysorbate 20 (polyoxyethylene sorbitan monolaurate-Tween 20), polysorbate 60 (polyoxyethylene sorbitan monostearate-Tween 60), polysorbate 65 (polyoxyethylene sorbitan tristearate-Tween 65), polysorbate 80 (polyoxyethylene sorbitan monolaurate-Tween 80).
In further aspect of the present invention, an inactive excipient an emulsifier is a Glycerides-monoglycerides, diglycerides, triglycerides. Examples are monoglycerides (ACETEM), lactylated monoglycerides (LACTEM), diacetyl tartaric acid monoglycerides (DATEM) and citric acid esters of monoglycerides (CITREM), 1,2-diacylglycerols and 1,3-diacylglycerols, succinylated monoglyceride, ethoxylated monoglyceride, diacetyl tartaric acid esters of mono- and diglyceride, polyglyceryl-3 caprylate, polyglyceryl-3 acetyl ether; sucrose esters, sucrose stearate, propylene glycol esters, sodium stearoyl-2-lactylate, calcium stearoyl-2-lactylate, glycerol monolaurate.
In further aspect of the present composition active ingredients are selected from (A) Tolfenpyrad; and (B) an insecticide selected from abamectin, emamectin benzoate, fluxametamide, fipronil, profenofos, cyantraniliprole, chlorantraniliprole, azadirachtin, fenpyroximate, hexythiazox, fenazaquin; and (C) one more insecticide compound.
In an embodiment of the present invention, an insecticide compound (C) is selected from the dimethoate, ethion, phenthoate, phosalone, profenofos, quinalphos, triazophos, ethiprole, fipronil, flufiprole, nicofluprole, pyrafluprole, pyriprole, broflanilide, cyproflanilide, fluxametamide, isocycloseram, afoxolaner, esafoxolaner, fluralaner, lotilaner, sarolaner, bifenthrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, deltamethrin, fenpropathrin, fenvalerate, permethrin, phenothrin, prallethrin, profluthrin, acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, flupyrimin, cycloxaprid, paichongding, guadipyr, cycloxylidin, sulfoxaflor, flupyradifurone, triflumezopyrim, dichloromezotiaz, fenmezoditiaz, spinosad, spinetoram, abamectin, emamectin benzoate, ivermectin, milbemectin, hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen, pymetrozine, pyrifluquinazon, afidopyropen, flonicamid, clofentezine, hexythiazox, diflovidazin, etoxazole, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron, buprofezin, cyromazine, chlorfenapyr, sulfluramid, methoxyfenozide, tebufenozide, halofenozide, fufenozide or chromafenozide, amitraz, diafenthiuron, azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon, fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, flufenerim, rotenone, fluacrypyrim, pyriminostrobin, cyenopyrafen, cyflumetofen, pyflubumide, hydramethylnon, acequinocyl, fluacrypyrim, bifenazate, flometoquin, indoxacarb, metaflumizone, spirodiclofen, spiromesifen, spirotetramat, spidoxamat, spiropidion, spirobudifen, chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole, tetrachlorantraniliprole, tyclopyrazoflor, cyhalodiamide, flubendiamide, fluchlordiniliprole, tiorantraniliprole, acynonapyr, azadirachtin, benzoximate, bromopropylate, benzpyrimoxan, chinomethionat, dicofol, pyridalyl, oxazosulfyl, dimpropyridaz, indazapyroxamet, fluhexafon, cyetpyrafen, flupentiofenox, acyonapyr, trifluenfuronate, cyclobutrifluram, fluazaindolizine, tioxazafen.
For the present invention, compound (B) and compound (C) are not same.
In further aspect of the present invention combinations of active ingredients for the present invention are as depicted in following table.
Sr. No. Compound A Compound B Compound C
a. Tolfenpyrad Abamectin Fipronil
b. Tolfenpyrad Abamectin Fluxametamide
c. Tolfenpyrad Abamectin Lambda cyhalothrin
d. Tolfenpyrad Abamectin Fenpyroximate
e. Tolfenpyrad Abamectin Fenazaquin
f. Tolfenpyrad Abamectin Broflanilide
g. Tolfenpyrad Abamectin Hexythiazox
h. Tolfenpyrad Abamectin Azadirachtin
i. Tolfenpyrad Cyantraniliprole Abamectin
j. Tolfenpyrad Cyantraniliprole Fluxametamide
k. Tolfenpyrad Cyantraniliprole Fipronil
l. Tolfenpyrad Cyantraniliprole Fenpyroximate
m. Tolfenpyrad Cyantraniliprole Etoxazole
n. Tolfenpyrad Cyantraniliprole Azadirachtin
o. Tolfenpyrad Azadirachtin Fluxametamide
p. Tolfenpyrad Azadirachtin Spiropidion
q. Tolfenpyrad Azadirachtin Fipronil
r. Tolfenpyrad Azadirachtin Fenpyroximate
s. Tolfenpyrad Azadirachtin Hexythiazox
t. Tolfenpyrad Azadirachtin Chlorfenapyr
u. Tolfenpyrad Fipronil Lambda cyhalothrin
v. Tolfenpyrad Fipronil Fenpyroximate
w. Tolfenpyrad Fipronil Hexythiazox
x. Tolfenpyrad Fipronil Chlorfenapyr
y. Tolfenpyrad Fluxametamide Fenpropathrin
z. Tolfenpyrad Fluxametamide Fipronil
aa. Tolfenpyrad Fluxametamide Fenpyroximate
bb. Tolfenpyrad Fluxametamide Hexythiazox
cc. Tolfenpyrad Fluxametamide Lambda cyhalothrin
dd. Tolfenpyrad Fluxametamide Emamectin benzoate
ee. Tolfenpyrad Profenofos Lambda cyhalothrin
ff. Tolfenpyrad Profenofos Flonicamid
gg. Tolfenpyrad Profenofos Emamectin benzoate.

Further most preferred combination of the biological active compounds for the present formulated synergistic emulsifiable concentrate composition is compound (A) Tolfenpyrad and compound (B) Abamectin and compound (C) Fenpyroximate; compound (A) Tolfenpyrad and compound (B) Cyantraniliprole and compound (C) Fluxametamide; compound (A) Tolfenpyrad and compound (B) Fipronil and compound (C) Hexythiazox; compound (A) Tolfenpyrad and compound (B) Fluxametamide and compound (C) Emamectin benzoate.
More preferred range of the biological active compounds for the present formulated synergistic emulsifiable concentrate composition is compound (A) Tolfenpyrad present in an amount of 5 to 25% w/w; (B) an insecticide selected from abamectin, emamectin benzoate, fluxametamide, fipronil, profenofos, cyantraniliprole, chlorantraniliprole, azadirachtin, fenpyroximate, hexythiazox, fenazaquin present in an amount of 0.05% to 30% w/w; and (C) an insecticide present in an amount of 1% to 40% w/w.
Most preferred range of the biological active compounds for the present formulated synergistic emulsifiable concentrate composition is compound (A) Tolfenpyrad present in an amount of 7 to 12% w/w; (B) an insecticide selected from abamectin, emamectin benzoate, fluxametamide, fipronil, profenofos, cyantraniliprole, chlorantraniliprole, azadirachtin, fenpyroximate, hexythiazox, fenazaquin present in an amount of 1.0% to 5.0% w/w; and (C) an insecticide present in an amount of 1% to 40% w/w.
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 he existence of variations, combinations, and equivalents of the specific embodiment, method, and examples, but by all embodiments and methods within the scope and spirit of the invention. The invention shall now be described concerning 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 examples are provided merely as illustrations of the invention and are not intended to be construed as a limitation thereof.
EXAMPLE 1: Tolfenpyrad 12%+Abamectin 1%+Fenpyroximate 2.67% EC
Chemical composition TAF 1 (Tolfenpyrad 12%+Abamectin 1%+Fenpyroximate 2.67% EC) TAF 2 (Tolfenpyrad 12%+Abamectin 1%+Fenpyroximate 2.67% EC) TAF 3 (Tolfenpyrad 12%+Abamectin 1%+Fenpyroximate 2.67% EC)
Percent (w/w)
Tolfenpyrad a.i. 12.00 12.00 12.00
Abamectin a.i. 1.00 1.00 1.00
Fenpyroximate a.i. 2.67 2.67 2.67
Ethoxylated monoglyceride (emulsifier) 5.00 5.00 5.00
polysorbate 20 (polyoxyethylene sorbitan monolaurate-Tween 20) as an emulsifier 7.00 7.00 7.00
Methylated seed oil- polyalkyleneoxide modified trisiloxane as a super wetting-spreading-penetrating agent 5.00 7.50 10.00
1-hexanol (green solvent) 67.33 64.83 62.33
Total 100.00 100.00 100.00

The recipe TAF 1, TAF 2, and TAF 3 meets all the storage stability in house specifications (i.e. active ingredient content, pH (5% in DM water), emulsion stability (max. 2 ml creaming or sediment after 1 hour), cold test (any separation or creaming max. 2 ml after 1 hour), flash point (above 24.5 0C) for storage stability studies in the laboratory (at 54±2 C & At 0±2 C for 14 days) and room temperature (up to 12 months).
Procedure: Manufacturing process for Emulsifiable Concentrate formulation
Manufacturing process of 100 ltr batch mfg process for Tolfenpyrad 12%+Abamectin 1.0%+Fenpyroximate 2.67% EC.

Chemical composition Percent (w/w)
Tolfenpyrad a.i. 12.00
Abamectin a.i. 1.00
Fenpyroximate a.i. 2.67
Ethoxylated monoglyceride (emulsifier) 5.00
Polysorbate 20 (polyoxyehtylene sorbitan monolaurate-Tween 20) 7.00
Methylated seed oil, polyalkyleneoxide modified trisiloxane as a super wetting-spreading-penetrating agent 10.00
1-hexanol (green solvent) 62.33
Total 100.00

Manufacturing steps:
Step 1 Charge 1-hexanol (62.33 kg) into the vessel and then Tolfenpyrad technical (12 kg), Abamectin technical (1 kg) and Fenpyroximate technical (2.67 kg) slowly and mix thoroughly till it gets dissolved completely.
Step 2 Now add Ethoxylated monoglyceride (5 kg) and Polysorbate 20 (polyoxyethylene sorbitan monolaurate) (7 kg) into this premix slowly and homogenized to get a uniform solution.
Step 3 Finally add Methylated seed oil and, polyalkyleneoxide modified trisiloxane (10 kg) and mix thoroughly to get a uniform clear solution, and then send to QC for quality check.

EXAMPLE 2: Tolfenpyrad 10.67%+Azadirachtin 1.33%+Fluxametamide 4% EC (green solvent)

Chemical composition Percent (w/w)
Tolfenpyrad a.i. 10.67
Azadirachtin a.i. 1.33
Fluxametamide a.i. 4.00
Neem oil 20.00
Ethoxylated monoglyceride (emulsifier) 4.00
polysorbate 60 (polyoxyethylene sorbitan monostearate-Tween 60) as an emulsifier 7.50
Methylated seed oil-polyoxyethylene methyl polysiloxane 8.00
n-butanol (green solvent) 44.50
Total 100.00

EXAMPLE 3: Tolfenpyrad 10%+Cyantraniliprole 4.5%+Fluxametamide 3% EC (green solvent)

Chemical composition Percent (w/w)
Tolfenpyrad a.i. 10.00
Cyantraniliprole a.i. 4.50
Fluxametamide a.i. 3.00
diacetyl tartaric acid esters of mono- and diglyceride (emulsifier) 5.00
polysorbate 80 (polyoxyethylene sorbitan monooleate-Tween 80) as an emulsifier 7.00
Methylated seed oil- polyalkyleneoxide modified polydimethylsiloxane 10.00
propylene carbonate (green solvent) 60.50
Total 100.00

EXAMPLE 4: Tolfenpyrad 7.5%+Fluxametamide 3%+Emamectin benzoate 0.75% EC (green solvent)

Chemical composition Percent (w/w)
Tolfenpyrad a.i. 7.50
Fluxametamide a.i. 3.00
Emamectin benzoate a.i. 0.75
polyglyceryl-3 caprylate (emulsifier) 5.50
polysorbate 65 (polyoxyethylene sorbitan tristearate-Tween 65) as an emulsifier 8.50
Methylated seed oil- trisiloxane ethoxylate 6.00
1-methoxy-2-propanol (green solvent) 68.75
Total 100.00

EXAMPLE 5: Tolfenpyrad 8%+Fipronil 3%+Hexythiazox 1.6% EC (green solvent)

Chemical composition Percent (w/w)
Tolfenpyrad a.i. 8.00
Fipronil a.i. 3.00
Hexythiazox a.i. 1.60
sodium stearoyl-2-lactylate (emulsifier) 5.00
polysorbate 20polyoxyethylenene sorbitan monolaurate-Tween 20) 7.00
Methylated seed oil-polyether polymethyl siloxane copolymer 12.00
3-methoxy-N, N-dimethyl propionamide (green solvent) 63.40
Total 100.00

Marketed preparations available for active ingredients in present invention as an individual compound or in combination are Tolfenpyrad 15% EC, manufactured by Keefun by PI Industries; Fluxametamide 10% EC manufactured by Gracia by Godrej Agrovet Ltd.; Abamectin 1.9% EC manufactured by AgriMac by Syngenta India Ltd.; Profenofos 40%+Fenpyroximate 2.5% EC manufactured by ETNA by Sumitomo Chemical India Limited; Azadirachtin 1% EC manufactured by Econeem by P J Margo Biocontrols Pvt. Ltd. Composition for the marketed preparations are as below:
Marketed composition: Tolfenpyrad 15% EC (Keefun by PI Industries)
Chemical composition Percent (w/w)
Tolfenpyrad a.i. 15.00
Calcium dodecyl benzylsulfonate 3.00
Tristyryl phenol ethoxylate 7.00
Aromatic solvent (C9) 75.00
Total 100.00

Marketed composition: Fluxametamide 10% EC (Gracia by Godrej Agrovet Ltd.)
Chemical composition Percent (w/w)
Fluxametamide a.i. 10.00
3-methoxy-N, N-dimethyl propionamide 40.00
Polyoxyehtylene alkylphenyl ether alkylarylsulfonate 5.00
Aromatic solvent (C10-C13) 45.00
Total 100.00

Marketed composition: Abamectin 1.9% EC (AgriMac by Syngenta India Ltd.)
Chemical composition Percent (w/w)
Abamectin a.i. 1.90
Polyoxyethylene (30) castor oil (EL-620) 17.00
Fumaric acid 0.30
1-methyl-2-pyrrolidone 28.35
Polyoxyethylene (20) sorbitan mono-oleate (Tween 80) 17.00
Butylated hydroxy toluene 1.00
Paraffin oil sun spray 6 N 6.10
Hexanol 28.35
Total 100.00

Marketed composition: Azadirachtin 1% EC (Econeem by P J Margo Biocontrols Pvt. Ltd.)
Chemical composition Percent (w/w)
Azadirachtin a.i. 1.00
n-butanol (solvent) 23.00
butyl acetate 31.00
Neem oil 30.00
Poly oxyethylene (20) sorbitan mono oleate) (Emulsifier) 15.00
Total 100.00

Marketed composition: Profenofos 40%+Fenpyroximate 2.5% EC (ETNA by Sumitomo Chemical India Limited.)
Chemical composition Percent (w/w)
Profenofos a.i. 40.00
Fenpyroximate a.i. 2.50
Styrinated phenol ethoxylate (Emulsifier) 6.50
Calcium alkyl benzenesulfonate (Emulsifier) 3.50
Epoxidised soybean oil (stabilizer) 5.00
Aromatic solvent (C9) 42.50
Total 100.00

Biological Examples:
Field studies have been conducted to study the benefits of EC formulation (with green solvent) and synergism. The synergistic effect exists wherever the action of a combination of active ingredients 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 synergistic composition or combination is an amount that exhibits greater pesticide activity than the sum of the pesticide activities of the individual components.
The action expected for a given combination of two or three active components can be calculated as follows:

FIELD BIO-EFFICACY STUDIES:
The innovative EC (Emulsifiable Concentrate with green solvent) formulation of Tolfenpyrad+Insecticide+Insecticide has been developed in the laboratory and evaluated for its efficacy, and residual control in comparison with prior art formulations and tank mixes.

Experiment 1: Synergistic control of thrips and mites in Chilli
Crop : Chilli, Pikador variety
Location : Umreth, Gujarat
Treatments : 19
Plot size : 24 sq.m.
Crop age : 70 days
Spray water volume : 500 liter per hectare
Method of Application: Foliar spray with battery-operated knapsack sprayer fitted with hollow cone nozzle.
Agronomic Practices : All agronomic practices have been followed as per the crop requirement.
Observation Methods:
Thrips (Scirtothrips dorsalis & Thrips parvispinus) control (%):
Count the number of live thrips per twig by shaking it gently over a piece of paper. Record the observations from 4 twigs per plant and 10 plants per plot. Calculate thrips control (%) as;

Mite (Polyphagotarsonemus latus) control (%):
Record the number of motile stages of mite per spot, 4 spots per plant and 10 plants per plot. Calculate mite control (%) as;

Thrips and Mite control (%) data were used (as observed value) to check the synergism by applying Colby’s formula.
Fruit count: Count the number of healthy fruits per plant. Record the observations from 10 plants per plot.
Fruits & Flower count: Count the number of healthy fruits and flowers per plant. Record the observations from 10 plants per plot.
Table 1: Treatment details:
Treatment Number Treatment details with application Rate (ml or g per Hectare) gram active per hectare
(A+B+C) Total
T1 Tolfenpyrad 16%+Abamectin 0.8%+Fluxametamide 2.67% EC, 750 ml 120+6+20 146
T2 Tolfenpyrad 12%+Abamectin 1%+Fluxametamide 3.33% EC, 750 ml 90+7.5+25 122.5
T3 Tolfenpyrad 12%+Abamectin 1%+Fluxametamide 4% EC, 750 ml 90+7.5+30 127.5
T4 Tolfenpyrad 10%+Abamectin 1.2%+Fluxametamide 4.67% EC, 750 ml 75+9+35 119
T5 Tolfenpyrad 8%+Abamectin 1.4%+Fluxametamide 5.33% EC, 750 ml 60+10.5+40 110.5
T6 Tolfenpyrad 15% EC, 800 ml 120 120
T7 Tolfenpyrad 15% EC, 600 ml 90 90
T8 Tolfenpyrad 15% EC, 500 ml 75 75
T9 Tolfenpyrad 15% EC, 400 ml 60 60
T10 Abamectin 1.9% EC, 315.8 ml 6 6
T11 Abamectin 1.9% EC, 394.8 ml 7.5 7.5
T12 Abamectin 1.9% EC, 473.7 ml 9 9
T13 Abamectin 1.9% EC, 552.6 ml 10.5 10.5
T14 Fluxametamide 10% EC, 200 ml 20 20
T15 Fluxametamide 10% EC, 250 ml 25 25
T16 Fluxametamide 10% EC, 300 ml 30 30
T17 Fluxametamide 10% EC, 350 ml 35 35
T18 Fluxametamide 10% EC, 400 ml 40 40
T19 Untreated Check (UTC) -
T1 to T5 were ready mix EC (emulsifiable concentrate with green solvent) formulation.
T6 to T18 were market available products.

Table 2: Control of thrips and mites
Treatment Number Thrips control (%) at 5 DAA Mites control (%) at 5 DAA
Observed control Expected control Colby's ratio Observed control Expected control Colby's ratio Synergism (Y/N)
T1 96.2 94.67 1.02 93.8 89.05 1.05 Yes
T2 100.0 92.49 1.08 99.2 93.11 1.07 Yes
T3 100.0 94.27 1.06 99.8 94.32 1.06 Yes
T4 99.0 96.22 1.03 98.8 96.46 1.02 Yes
T5 98.6 98.00 1.01 98.0 97.29 1.01 Yes
T6 85.2 64.2
T7 70.4 54.4
T8 55.6 35.6
T9 41.6 22.2
T10 46.4 60.8
T11 56.4 76.4
T12 70.2 86.2
T13 83.2 89.2
T14 32.8 22.0
T15 41.8 36.0
T16 55.6 47.2
T17 71.4 60.2
T18 79.6 67.8
T19 0.0 0.0
DAA-days after application.
Table 2a. Fruits and Flowers count in chilli
Treatment Number At 10 DAA
Number of flowers/plant Increase (%) over UTC Number of fruits/plant Increase (%) over UTC
T1 28.5 99.30 57.3 99.65
T2 27.9 95.10 54.8 90.94
T3 28.3 97.90 54.1 88.50
T4 27.7 93.71 57.0 98.61
T5 28.2 97.20 56.3 96.17
T6 20.5 43.36 43.6 51.92
T7 18.3 27.97 40.4 40.77
T8 17.6 23.08 37.6 31.01
T9 15.7 9.79 31.5 9.76
T10 15.2 6.29 33.2 15.68
T11 15.8 10.49 35.9 25.09
T12 16.7 16.78 37.5 30.66
T13 18.3 27.97 40.7 41.81
T14 16.3 13.99 32.5 13.24
T15 17.4 21.68 34.6 20.56
T16 18.5 29.37 40.2 40.07
T17 20.3 41.96 44.3 54.36
T18 21.9 53.15 45.7 59.23
T19 14.3 0.00 28.7 0.00

The field trial results show synergism between tolfenpyrad+abamectin+fluxametamide in terms of thrips and mite control. All the ready mix EC (green solvent) formulation of tolfenpyrad+abamectin+fluxametamide (T1 to T5) produces a higher number of flowers and fruits per plant.

Experiment 2: Residual control of thrips in Chilli (comparison of different recipes of EC (green solvent) vs conventional formulations)
Crop : Chilli, Nisha variety
Location : Umreth, Gujarat
Treatments : 8
Plot size : 35 sq.m.
Crop age : 81 days
Spray water volume : 480 liter per hectare
Method of Application: Foliar spray with battery-operated knapsack sprayer fitted with hollow cone nozzle.
Agronomic Practices : All agronomic practices have been followed as per the crop requirement.
Observation Methods: same as given in Experiment 1.
Table 3: T4: Tolfenpyrad 12%+Abamectin 1%+Fenpyroximate 2.67%EC (conventional)
Chemical composition Percent (w/w)
Tolfenpyrad a.i. 12.00
Abamectin a.i. 1.00
Fenpyroximate a.i. 2.67
Calcium dodecyl benzylsulfonate 3.00
Tristyryl phenol ethoxylate 7.00
Aromatic solvent (C9) 74.33
Total 100.00

Table 4: T5: Tolfenpyrad 12%+Abamectin 1%+Fenpyroximate 2.67% SC (conventional)
Chemical composition Percent (w/w)
Tolfenpyrad a.i. 12.00
Abamectin a.i. 1.00
Fenpyroximate a.i. 2.67
Ethylene-propylene oxide block copolymer (dispersing agent I) 4.50
Sodium salt of polycarboxylate (dispersing agent II) 2.50
Aluminum magnesium silicate (suspending agent) 1.50
Polydimethylsiloxane (antifoaming agent) 0.30
1,2-benzisothiazolin-3(2H)-one (preservative) 0.20
Polypropylene glycol (antifreezing agent) 5.00
Xanthum gum (thickener) 0.20
water (diluent) 70.13
Total 100.00

Table 5: Residual control of chili thrips
Treatment details with application Rate (ml or g per Hectare) Thrips control (%) at Increase in control over T6 on 14 DAA Increase in control over T7 on 14 DAA
3 DAA 7 DAA 10 DAA 14 DAA
T1-TAF 1 (Tolfenpyrad 12%+Abamectin 1%+Fenpyroximate 2.67% EC), 750 ml 99.6 92.40 86.20 78.2 60.25 8.91
T2-TAF 2 (Tolfenpyrad 12%+Abamectin 1%+Fenpyroximate 2.67% EC), 750 ml 99.4 91.80 85.40 77.2 58.20 7.52
T3-TAF 3 (Tolfenpyrad 12%+Abamectin 1%+Fenpyroximate 2.67% EC), 750 ml 99.4 92.60 86.00 77.8 59.43 8.36
T4-Tolfenpyrad 12%+Abamectin 1%+Fenpyroximate 2.67% EC (conventional), 750 ml 96.2 85.40 74.20 61.4 25.82
T5-Tolfenpyrad 12%+Abamectin 1%+Fenpyroximate 2.67% SC (conventional), 750 ml 95.8 86.00 73.60 59.8 22.54
T6-Tolfenpyrad 15% EC,600 ml+Abamectin 1.9% EC,394.7 ml+Fenpyroximate 5% EC,400 ml (tank mix) 93.6 82.60 68.60 48.8 0.00
T7-Tolfenpyrad 15% EC,750 ml+Abamectin 1.9% EC,500 ml+Fenpyroximate 5% EC,500 ml (tank mix) 99.4 92.60 80.20 71.8 47.13
T8-Untreated Check (UTC) 0.00 0.00 0.00 0.00 0.00

T1, T2, and T3-were different recipes EC (green solvent) formulation [TAF1, TAF2, TAF3] of Tolfenpyrad+Abamectin+Fenpyroximate. (As per Example 1).

T4-conventional EC formulation (As per table 3), T5-conventional SC (suspension concentrate) formulation (As per table 4), T6-on farm tank mixing of market available products, T7-on farm tank mixing of market available products with 25% higher dosages (like farmers practices).

All the innovative recipes of EC formulations of Tolfenpyrad+Abamectin+Fenpyroximate (T1,T2,T3) provides residual control of thrips up to 14 days, which was much higher than conventional EC (T4), SC (T5), tank mix (T6) and tank mix with 25% higher dose (T7). We can say that with innovative recipes of EC formulation, we can reduce (up to 25%) the loading of active ingredients to achieve desire insect control.

Experiment 3: Comparison of EC (green solvent) vs tank mixes and their effect on residual control
Crop : Marigold, Orange shade lemon variety
Location : Ode, Anand, Gujarat
Treatments : 21
Plot size : 20 sq.m.
Crop age : 62 days
Spray water volume : 400 liter per hectare
Method of Application: Foliar spray with battery operated knapsack sprayer fitted with hollow cone nozzle.
Agronomic Practices : All agronomic practices has been followed as per the crop requirement.
Observation Methods:
Thrips control (%): Count the number of live thrips per compound leaf, 4 leaves per plant and 10 plants per plot. Calculate thrips control (%).
Table 6: Treatment details
Treatment Number Treatment details formulation (ml per hectare)

T1 Tolfenpyrad 12%+Abamectin 1.2%+Fipronil 5% EC 750
T2 Tolfenpyrad 12%+Abamectin 1.2%+Fenazaquin 10% EC 750
T3 Tolfenpyrad 12%+Abamectin 1.2%+Lambda cyhalothrin 3.33% EC 750
T4 Tolfenpyrad 12%+Abamectin 1.2%+Broflanilide 1.2% EC 750
T5 Tolfenpyrad 12%+Abamectin 1.2%+Hexythiazox 3% EC 750
T6 Tolfenpyrad 12%+Abamectin 1.2%+Azadirachtin 1.33% EC 750
T7 Tolfenpyrad 15% EC+Abamectin 1.9% EC+Fipronil 5% SC 600+473.7+750 (1823.7)
T8 Tolfenpyrad 15% EC+Abamectin 1.9% EC+Fenazaquin 10% EC 600+473.7+750 (1823.7)
T9 Tolfenpyrad 15% EC+Abamectin 1.9% EC+Lambda cyhalothrin 5% EC 600+473.7+500 (1573.7)
T10 Tolfenpyrad 15% EC+Abamectin 1.9% EC+Broflanilide 10% SC 600+473.7+90 (1163.7)
T11 Tolfenpyrad 15% EC+Abamectin 1.9% EC+Hexythiazox 5.45% EC 600+473.7+450 (1523.7)
T12 Tolfenpyrad 15% EC+Abamectin 1.9% EC+Azadirachtin 1% EC 600+473.7+1000 (2073.7)
T13 Tolfenpyrad 15% EC 600
T14 Abamectin 1.9% EC 473.7
T15 Fipronil 5% SC 750
T16 Fenazaquin 10% EC 750
T17 Lambda cyhalothrin 5% EC 500
T18 Broflanilide 10% SC 90
T19 Hexythiazox 5.45% EC 450
T20 Azadirachtin 1% EC 1000
T21 Untreated Check (UTC) -

T1 to T6- EC (green solvent) formulation of tolfenpyrad+abamectin+insecticide.
T7 to T12-tank mix of market available products. T13 to T20-market available product (solo).

Table 7: Residual control of thrips (EC vs tank mixes):
Treatment Number Thrips control (%) at 5 DAA Thrips control (%) at 10 DAA
Observed control Expected control Colby's ratio Observed control Expected control Colby's ratio Synergism (Y/N)
T1 100.0 96.68 1.03 93.2 90.38 1.03 Yes
T2 99.2 96.43 1.03 92.0 89.56 1.03 Yes
T3 98.4 96.03 1.02 91.6 88.47 1.04 Yes
T4 100.0 95.54 1.05 90.6 87.42 1.04 Yes
T5 100.0 96.41 1.04 93.0 89.17 1.04 Yes
T6 99.4 96.68 1.03 92.6 88.86 1.04 Yes
T7 98.4 96.68 1.02 77.8 79.35 0.98 No
T8 97.6 96.43 1.01 75.6 77.60 0.97 No
T9 97.4 96.03 1.01 73.4 75.25 0.98 No
T10 96.8 95.54 1.01 71.6 73.00 0.98 No
T11 98.2 96.41 1.02 74.4 76.76 0.97 No
T12 97.4 96.68 1.01 73.8 76.09 0.97 No
T13 72.8 58.2
T14 69.2 53.4
T15 60.4 50.6
T16 57.4 46.4
T17 52.6 40.8
T18 46.8 35.4
T19 57.2 44.4
T20 60.4 42.8
T21 0.0 0.0

The EC (green solvent) formulation of tolfenpyrad+abamectin+insecticide (T1 to T6) provides synergistic residual control (10 DAA) of marigold thrips, as compared to their tank mixes (T7 to T12). All the conventional tank-mix treatments (T7 to T12) are bulky and contain aromatic solvents.

Experiment 4: Synergistic control of thrips and fruit borer in Chilli
Crop : Chilli, Capsicum (Shimla) type variety
Location : Umreth, Gujarat
Treatments : 28
Plot size : 20 sq.m.
Crop age : 77 days
Spray water volume : 520 liter per hectare
Method of Application: Foliar spray with battery-operated knapsack sprayer fitted with hollow cone nozzle.
Agronomic Practices : All agronomic practices like fertilizer application and weed control have been followed as per the crop requirement.
Observation Methods:
Thrips control (%): As given in Experiment 1.
Fruit borer (Helicoverpa armigera): Count the number of live larve per plant. Record the observations from 5 plants per plot. Calculate larval control (%) by formula as given below.

Table 8: Treatment details
Treatment Number Treatment details with application Rate (ml or g per Hectare) gram active per hectare
T1 Tolfenpyrad 10%+Cyantraniliprole 4.5%+Abamectin 1% EC 100+45+10
T2 Tolfenpyrad 10%+Cyantraniliprole 4.5%+Fluxametamide 3% EC 100+45+30
T3 Tolfenpyrad 10%+Cyantraniliprole 4.5%+Fipronil 5% EC 100+45+50
T4 Tolfenpyrad 10%+Cyantraniliprole 4.5%+Fenpyroximate 2% EC 100+45+20
T5 Tolfenpyrad 10%+Cyantraniliprole 4.5%+Etoxazole 3% EC 100+45+30
T6 Tolfenpyrad 10%+Cyantraniliprole 4.5%+Azadirachtin 1% EC 100+45+10
T7 Tolfenpyrad 15%+Abamectin 1.5% EC 100+10
T8 Tolfenpyrad 15%+Fluxametamide 4.5% EC 100+30
T9 Tolfenpyrad 10%+Fipronil 5% EC 100+50
T10 Tolfenpyrad 15%+Fenpyroximate 3% EC 100+20
T11 Tolfenpyrad 15%+Etoxazole 4.5% SC 100+30
T12 Tolfenpyrad 15%+Azadirachtin 1.5% EC 100+10
T13 Cyantraniliprole 9%+Abamectin 2% SC 45+10
T14 Cyantraniliprole 10.26% OD+Fluxametamide 10% EC 45+30
T15 Cyantraniliprole 10.26% OD+Fipronil 2.92% EC 45+50
T16 Cyantraniliprole 10.26% OD+Fenpyroximate 5% EC 45+20
T17 Cyantraniliprole 10.26% OD+Etoxazole 10% SC 45+30
T18 Cyantraniliprole 10.26% OD+Azadirachtin 1% EC 45+10
T19 Tolfenpyrad 15% EC+Cyantraniliprole 10.26% OD 100+45
T20 Tolfenpyrad 15% EC (Keefun)* 100
T21 Cyantraniliprole 10.26% OD (Benevia)* 45
T22 Abamectin 1.9% EC (AgriMac)* 10
T23 Fluxametamide 10% EC (Gracia)* 30
T24 Fipronil 2.92% EC (Agenda)* 50
T25 Fenpyroximate 5% EC (Mitigate)* 20
T26 Etoxazole 10% SC (Borneo)* 30
T27 Azadirachtin 1% EC (Econeem)* 10
T28 Untreated Check (UTC) -

*Brand name, T1 to T6- EC (green solvent) formulation, T7 to T12-conventional ready mix EC formulation, T13-conventional ready mix SC formulation, T14 to T19-on-farm tank mixes of market available products.

Table 9: Synergistic control of Chilli thrips and fruit borer larvae
Treatment Number Thrips control (%) at 7 DAA Helicoverpa larval control (%) at 7 DAA
Observed control Expected control Colby's ratio Synergism (Y/N) Observed control Expected control Colby's ratio Synergism (Y/N)
T1 100.0 95.46 1.05 Yes 100.0 95.61 1.05 Yes
T2 100.0 94.78 1.06 Yes 100.0 97.09 1.03 Yes
T3 100.0 95.36 1.05 Yes 100.0 96.29 1.04 Yes
T4 97.2 93.61 1.04 Yes 100.0 95.33 1.05 Yes
T5 97.6 93.21 1.05 Yes 100.0 93.94 1.06 Yes
T6 99.2 95.18 1.04 Yes 100.0 95.41 1.05 Yes
T7 85.6 87.92 0.97 No 82.4 86.95 0.95 No
T8 84.2 86.12 0.98 No 89.6 91.33 0.98 No
T9 83.4 87.65 0.95 No 85.2 88.96 0.96 No
T10 80.2 83.00 0.97 No 82.4 86.09 0.96 No
T11 78.8 81.94 0.96 No 77.8 81.96 0.95 No
T12 84.8 87.18 0.97 No 82.4 86.34 0.95 No
T13 82.2 86.31 0.95 No 80.6 82.60 0.98 No
T14 80.8 84.28 0.96 No 83.2 88.44 0.94 No
T15 82.4 86.01 0.96 No 81.2 85.28 0.95 No
T16 77.4 80.75 0.96 No 78.8 81.45 0.97 No
T17 74.6 79.55 0.94 No 72.4 75.94 0.95 No
T18 81.2 85.49 0.95 No 78.6 81.79 0.96 No
T19 82.0 87.52 0.94 No 91.0 91.53 0.99 No
T20 66.8 74.8
T21 62.4 66.4
T22 63.6 48.2
T23 58.2 65.6
T24 62.8 56.2
T25 48.8 44.8
T26 45.6 28.4
T27 61.4 45.8
T28 0.0 0.0

The EC (green solvent) formulations of Tolfenpyrad+Cyantraniliprole+Insecticide (T1 to T6) provides synergistic control of chili thrips and fruit borer larvae on 7th days after application as compared to all conventional treatments (T7 to T27).

Experiment 5: Synergistic control of sucking insects in okra crop
Crop & Variety : Okra
Location : Borsad, Anand, Gujarat
Treatments : 28
Plot size : 25 sq.m.
Crop age : 64 days after sowing
Spray water volume : 470 liter per hectare
Method of Application: Foliar spray with battery-operated knapsack sprayer fitted with hollow cone nozzle.
Agronomic Practices : All agronomic practices followed as per the crop requirement.
Observation Methods:
Thrips (Thrips tabaci) control (%): Count the number of live insects per leaf. Record observations from 3 leaves per plant and 10 plants per plot.
Jassid (Amrasca biguttula biguttual) control (%):
Count the number of live insects (nymph and adults) per leaf. Record the observation from 3 leaves per plant and 10 plants per plot. Record the observations on 5th day after application (DAA). Jassid control (%) as the observed value was used to check the synergism by applying Colby’s formula.
Fruits count: Count the number of healthy and marketable fruits per plant. Record the observations from 10 plants per plot 10 days after application.
Table 10: Treatment details
Treatment Number Treatment details Application Rate (ml per hectare)
T1 Tolfenpyrad 10.67%+Azadirachtin 1.33%+Fluxametamide 4% EC 750 ml
T2 Tolfenpyrad 10.67%+Azadirachtin 1.33%+Spiropidion 6.67% EC 750 ml
T3 Tolfenpyrad 10.67%+Azadirachtin 1.33%+Fipronil 5% EC 750 ml
T4 Tolfenpyrad 10.67%+Azadirachtin 1.33%+Fenpyroximate 3% EC 750 ml
T5 Tolfenpyrad 10.67%+Azadirachtin 1.33%+Hexythiazox 3% EC 750 ml
T6 Tolfenpyrad 10.67%+Azadirachtin 1.33%+chlorfenapyr 8% EC 750 ml
T7 Tolfenpyrad 15% EC+Fluxametamide 10% EC 533.33+300 (833.33 ml)
T8 Tolfenpyrad 15% EC+Spiropidion 20% SC 533.33+250 (783.33 ml)
T9 Tolfenpyrad 15% EC+Fipronil 5% SC 533.33+750 (1283.33 ml)
T10 Tolfenpyrad 15% EC+Fenpyroximate 5% EC 533.33+450 (983.33 ml)
T11 Tolfenpyrad 15% EC+Hexythiazox 5.45% EC 533.33+450 (983.33 ml)
T12 Tolfenpyrad 15% EC+Chlorfenapyr 10% SC 533.33+600 (1133.33 ml)
T13 Azadirachtin 1% EC+Fluxametamide 10% EC 1000+300 (1300 ml)
T14 Azadirachtin 1% EC+Spiropidion 20% SC 1000+250 (1250 ml)
T15 Azadirachtin 1% EC+Fipronil 5% SC 1000+750 (1750 ml)
T16 Azadirachtin 1% EC+Fenpyroximate 5% EC 1000+450 (1450 ml)
T17 Azadirachtin 1% EC+Hexythiazox 5.45% EC 1000+450 (1450 ml)
T18 Azadirachtin 1% EC+Chlorfenapyr 10% SC 1000+600 (1600 ml)
T19 Tolfenpyrad 15% EC+Azadirachtin 1% EC 1000+533.33 (1533.33 ml)
T20 Tolfenpyrad 15% EC 533.33 ml
T21 Azadirachtin 1% EC 10000 ml
T22 Fluxametamide 10% EC 300 ml
T23 Spiropidion 20% SC 250 ml
T24 Fipronil 5% SC 750 ml
T25 Fenpyroximate 5% EC 450 ml
T26 Hexythiazox 5.45% EC 450 ml
T27 Chlorfenapyr 10% SC 600 ml
T28 Untreated Check (UTC) -

T1 to T6 were EC (green solvent) formulations. T7 to T19 were on farm tank mix combinations of market available products.

Table 10a: Synergistic control of sucking pests in okra crop
Treatment Number Thrips control (%) at 5 DAA Jassid control (%) at 5 DAA
Observed control Expected control Colby's ratio Observed control Expected control Colby's ratio Synergism (Y/N)
T1 100.0 94.43 1.06 100.0 96.30 1.04 Yes
T2 100.0 94.96 1.05 100.0 96.19 1.04 Yes
T3 100.0 94.40 1.06 99.0 94.08 1.05 Yes
T4 99.2 93.30 1.06 97.2 93.63 1.04 Yes
T5 98.8 93.58 1.06 98.6 93.34 1.06 Yes
T6 97.2 93.13 1.04 98.2 93.19 1.05 Yes
T7 84.8 86.85 0.98 88.8 90.17 0.98 No
T8 85.6 88.11 0.97 87.2 89.88 0.97 No
T9 83.4 86.79 0.96 82.2 84.25 0.98 No
T10 81.2 84.20 0.96 81.4 83.07 0.98 No
T11 82.4 84.86 0.97 80.8 82.30 0.98 No
T12 80.8 83.80 0.96 78.4 81.88 0.96 No
T13 80.2 83.21 0.96 82.4 87.52 0.94 No
T14 81.6 84.82 0.96 85.6 87.14 0.98 No
T15 80.2 83.12 0.96 77.4 80.00 0.97 No
T16 75.8 79.82 0.95 75.6 78.49 0.96 No
T17 77.6 80.67 0.96 74.2 77.52 0.96 No
T18 74.4 79.31 0.94 74.0 76.99 0.96 No
T19 80.2 85.92 0.93 85.0 88.87 0.96 No
T20 66.8 70.4
T21 57.6 62.4
T22 60.4 66.8
T23 64.2 65.8
T24 60.2 46.8
T25 52.4 42.8
T26 54.4 40.2
T27 51.2 38.8
T28 0.0 0.0

Table 10b: Fruit yield in okra crop
Treatment Number At 10 DAA
Number of healthy and marketable fruits/10 plants Increase (%) over UTC (T28)
T1 41.3 145.83
T2 39.3 133.93
T3 40.5 141.07
T4 40.1 138.69
T5 38.8 130.95
T6 39.7 136.31
T7 35.3 110.12
T8 33.7 100.60
T9 33.2 97.62
T10 33.1 97.02
T11 32.7 94.64
T12 32.5 93.45
T13 34.5 105.36
T14 31.8 89.29
T15 31.5 87.50
T16 30.6 82.14
T17 31.2 85.71
T18 30.0 78.57
T19 34.2 103.57
T20 26.7 58.93
T21 25.6 52.38
T22 27.1 61.31
T23 22.5 33.93
T24 23.7 41.07
T25 23.2 38.10
T26 24.2 44.05
T27 24.3 44.64
T28 16.8 0.00

The EC (green solvent) formulations of Tolfenpyrad+Azadirachtin+Insecticide (T1 to T6) provides synergistic control of jassid and thrips on 5th days after application as compared to all conventional treatments. All treatments of EC (green solvent) formulation of Tolfenpyrad+Azadirachtin+Insecticide (T1 to T6) also produce a significantly higher number of healthy and marketable fruits per plant as compared to all conventional treatments (T7 to T27).

Experiment 6: Sucking insects control in brinjal crop
Crop : Brinjal, Dolly variety
Location: Dehgam, Gujarat
Treatments : 15
Plot size : 40 sq.m.
Crop age : 110 days
Spray water volume : 570 liter per hectare
Method of Application: Foliar spray with battery operated knapsack sprayer fitted with hollow cone nozzle.
Agronomic Practices : All agronomic practices has been followed as per the crop requirement.
Observation Methods:
Sucking insects control (%): The main sucking insects observed were jassid and whitefly. The observations were recorded as given in Experiment 5.
Table 11: Treatment details
Treatment Number Treatment details Formulation per hectare
T1 Tolfenpyrad 8%+Fipronil 3%+Lambda cyhalothrin 2% EC 1250 ml
T2 Tolfenpyrad 8%+Fipronil 3%+Fenpyroximate 1.6% EC 1250 ml
T3 Tolfenpyrad 8%+Fipronil 3%+Hexythiazox 1.6% EC 1250 ml
T4 Tolfenpyrad 8%+Fipronil 3%+Chlorfenapyr 4.8% EC 1250 ml
T5 Tolfenpyrad 8%+Fipronil 3%+Lambda cyhalothrin 2% SE 1250 ml
T6 Tolfenpyrad 8%+Fipronil 3%+Fenpyroximate 1.6% SE 1250 ml
T7 Tolfenpyrad 8%+Fipronil 3%+Hexythiazox 1.6% SC 1250 ml
T8 Tolfenpyrad 8%+Fipronil 3%+Chlorfenapyr 4.8% SC 1250 ml
T9 Tolfenpyrad 15% EC 666.67 ml
T10 Fipronil 18.87% w/w SC 187.5 ml
T11 Lambda cyhalothrin 5% EC 500 ml
T12 Fenpyroximate 5% EC 400 ml
T13 Hexythiazox 5.45% EC 400 ml
T14 Chlorfenapyr 10% SC 600 ml
T15 Untreated Check (UTC) -

T1 to T4- EC formulation with green solvent. T5 to T6-conventional SE (suspo emulsion) formulation, T7 & T8-conventional SC (suspension concentrate) formulation.

Table 12: Residual control of sucking insects
Treatment Number Sucking insects control (%)
3 DAA 7 DAA 10 DAA 14 DAA
Observed control Expected control Colby's ratio Synergism (Y/N)
T1 100.0 97.6 89.2 76.2 74.10 1.03 Yes
T2 99.8 98.2 88.6 74.4 72.13 1.03 Yes
T3 99.2 96.8 87.4 72.8 71.29 1.02 Yes
T4 98.8 96.0 87.2 71.2 70.87 1.00 Yes
T5 96.2 90.2 74.2 56.4 60.40 0.93 No
T6 97.4 89.8 73.6 51.2 57.39 0.89 No
T7 96.6 90.6 72.2 50.8 56.10 0.91 No
T8 94.8 87.4 71.0 49.6 55.45 0.89 No
T9 83.6 75.8 60.2 46.2
T10 66.2 60.6 48.6 34.6
T11 61.2 52.4 40.2 26.4
T12 60.4 51.8 38.8 20.8
T13 58.6 47.6 35.4 18.4
T14 55.6 45.4 33.2 17.2
T15 0.0 0.0 0.0 0.0

The EC (green solvent) formulations of Tolfenpyrad+Fipronil+Insecticide (T1 to T4) provides excellent synergistic residual control (up to 14 days) of sucking insects (jassid and whitefly) as compared to all conventional treatments.

Experiment 7: Synergistic control of Diamond back moth (DBM) and aphid (Lipaphi erysimi) in cauliflower
Crop & Variety : Cauliflower
Insect-Pests : Diamond back moth (DBM, Plutella xylostella)
Location : Padra, Gujarat
Treatments : 21
Plot size : 20 sq.m.
Crop age : 66 days after transplanting.
Spray water volume : 480 liter per hectare
Method of Application: Foliar spray with battery-operated knapsack sprayer fitted with hollow cone nozzle.
Agronomic Practices : All agronomic practices followed as per the crop requirement.
Observations method:
Count the number of live larvae per plant. Record the observations from 10 plants per plot on 0, 3, 7, 10 and 14 days after application. Calculate larval control (%) as observed control and apply Colby’s formula to calculate synergism.

Table 13: Treatment details
Treatment Number Treatment details Formulation per hectare
T1 Tolfenpyrad 7.5%+Fluxametamide 3%+Fenpropathrin 4% EC 1000 ml
T2 Tolfenpyrad 7.5%+Fluxametamide 3%+Fipronil 3% EC 1000 ml
T3 Tolfenpyrad 7.5%+Fluxametamide 3%+Fenpyroximate 2% EC 1000 ml
T4 Tolfenpyrad 7.5%+Fluxametamide 3%+Hexythiazox 2% EC 1000 ml
T5 Tolfenpyrad 7.5%+Fluxametamide 3%+Lambda cyhalothrin 2% EC 1000 ml
T6 Tolfenpyrad 7.5%+Fluxametamide 3%+Emamectin benzoate 0.75% EC 1000 ml
T7 Tolfenpyrad 15% EC+Fluxametamide 10% EC+Fenpropathrin 10% EC 500+300+400=1200 ml
T8 Tolfenpyrad 15% EC+Fluxametamide 10% EC+Fipronil 5% SC 500+300+600=1400 ml
T9 Tolfenpyrad 15% EC+Fluxametamide 10% EC+Fenpyroximate 5% EC 500+300+400=1200 ml
T10 Tolfenpyrad 15% EC+Fluxametamide 10% EC+Hexythiazox 5.45% EC 500+300+400=1200 ml
T11 Tolfenpyrad 15% EC+Fluxametamide 10% EC+Lambda cyhalothrin 5% EC 500+300+400=1200 ml
T12 Tolfenpyrad 15% EC+Fluxametamide 10% EC+Emamectin benzoate 1.9% EC 500+300+394.74=1194.74 ml
T13 Tolfenpyrad 15% EC 500 ml
T14 Fluxametamide 10% EC 300 ml
T15 Fenpropathrin 10% EC 400 ml
T16 Fipronil 5% SC 600 ml
T17 Fenpyroximate 5% EC 400 ml
T18 Hexythiazox 5.45% EC 400 ml
T19 Lambda cyhalothrin 5% EC 400 ml
T20 Emamectin benzoate 1.9% EC 394.74 ml
T21 Untreated Check (UTC) -

T1 to T6 were EC (green solvent) formulations. T7 to T12 were tank mixes of market available products.

Table 14: Synergistic larval control of DBM in cauliflower
Treatment Number DBM larval control (%) on
3 DAA 7 DAA 10 DAA 14 DAA
Observed control Expected control Colby's ratio
T1 98.8 96.4 90.4 80.2 72.16 1.11
T2 99.6 97.0 89.6 81.2 74.83 1.09
T3 98.6 95.6 88.4 78.4 71.33 1.10
T4 97.4 95.2 88.0 77.6 69.89 1.11
T5 99.8 96.4 89.2 77.2 72.64 1.06
T6 100.0 98.2 90.6 80.8 78.94 1.02
T7 98.0 91.4 82.4 70.2 72.16 0.97
T8 98.6 90.6 80.4 71.4 74.83 0.95
T9 97.2 89.8 79.8 68.8 71.33 0.96
T10 96.6 90.2 80.2 66.4 69.89 0.95
T11 98.4 91.8 81.2 69.2 72.64 0.95
T12 100.0 92.4 82.8 73.6 78.94 0.93
T13 56.8 52.4 41.2 33.8
T14 70.6 66.4 58.8 48.2
T15 58.4 48.4 31.2 18.8
T16 62.2 51.8 40.8 26.6
T17 64.2 50.8 36.4 16.4
T18 58.8 40.2 26.6 12.2
T19 60.2 48.6 34.6 20.2
T20 68.2 60.4 50.4 38.6
T21 0.0 0.0 0.0 0.0

The EC (green solvent) formulations of Tolfenpyrad+Fluxametamide+Insecticide (T1 to T6) provides synergistic larval control of DBM (Diamond back moth) up to 14 DAA (days after application).

Experiment 8: Comparison of recipes (EC with green solvent vs aromatic solvent)
Crop & Variety : Chilli
Insect-Pests : Thrips (Scirtothrips dorsalis)
Location : Bochasan, Anand, Gujarat
Treatments : 7
Plot size : 60 sq.m.
Crop age : 88 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.
Agronomic Practices : All agronomic practices followed as per the crop requirement.
Observations method:
Phytotoxicity: Visual symptoms of phytotoxicity (0 to 100% basis) was recorded in comparison with UTC (untreated plot).

Table 15: Treatment details
Treatment Number Treatment details Formulation per hectare
T1 Tolfenpyrad 9%+Fluxametamide 2.5%+Abamectin 0.75% EC (green solvent) 1000 ml
T2 Tolfenpyrad 9%+Fluxametamide 2.5%+Hexythiazox 2% EC (green solvent) 1000 ml
T3 Tolfenpyrad 9%+Fluxametamide 2.5%+Abamectin 0.75% EC (aromatic solvent) 1000 ml
T4 Tolfenpyrad 9%+Fluxametamide 2.5%+Hexythiazox 2% EC (aromatic solvent) 1000 ml
T5 Tolfenpyrad 15% EC+Fluxametamide 10% EC+Abamectin 1.9% EC (tank mixes of market sample) 600+250+394.7=1244.7 ml
T6 Tolfenpyrad 15% EC+Fluxametamide 10% EC+Hexythiazox 5.45% EC (tank mixes of market sample) 600+250+200=1050 ml
T7 Untreated Check (UTC) -

T1 & T2- EC formulation with green solvent, T3 & T4- EC formulation with aromatic solvent (as conventional EC formulation), T5 & T6- on farm tank mixes of market available products.

Table 15a: Thrips control
Treatment Number Thrips control (%) at
1 DAA 5 DAA 10 DAA 15 DAA
T1 100.0 99.2 95.2 92.2
T2 100.0 99.4 95.8 90.8
T3 97.4 92.6 84.8 78.4
T4 98.2 92.6 84.2 77.6
T5 93.8 87.4 80.6 67.4
T6 94.6 88.2 81.2 66.2
T7 0.0 0.0 0.0 0.0

Table 15b: Phytotoxicity symptoms
Treatment Number Leaf scorching symptoms (%) Average number of flowers/plant Increase(%) over T7 Average number of fruits/plant Increase(%) over T7
5 DAA 10 DAA 15 DAA
T1 0 0 0 27.5 152.29 36.2 109.25
T2 0 0 0 27.3 150.46 37.1 114.45
T3 15 10 5 22.3 104.59 31.7 83.24
T4 15 10 5 21.6 98.17 31.5 82.08
T5 5 5 0 19.7 80.73 26.7 54.34
T6 5 5 0 19.4 77.98 26.4 52.60
T7 0 0 0 10.9 0.00 17.3 0.00

The EC (green solvent) formulation (T1 & T2) provides excellent, residual control of thrips up to 15 DAA, does not cause any kind of phytotoxic symptoms, and also produces a higher number of flowers and fruits. The conventional treatments, EC (aromatic solvent) formulation (T3 &T4) and their tank mixes of market available products (T5 & T6) shows leaf scorching symptoms.

Comparison of Tolfenpyrad 9%+Fluxametamide 2.5%+Abamectin 0.75% recipes between EC with Green solvent and EC with Aromatic solvent.

Table 16.1 Tolfenpyrad 9%+Fluxametamide 2.5%+Abamectin 0.75% EC with Green Solvent

Chemical composition Percent (w/w)
Tolfenpyrad a.i. 9.00
Fluxametamide a.i. 2.50
Abamectin a.i. 0.75
polyglyceryl-3 caprylate (emulsifier) 5.00
polysorbate 60 (polyoxyethylene sorbitan monostearate-Tween 60) as an emulsifier 8.00
Methylated seed oil-polyether-modified polysiloxane as a super wetting-spreading-penetrating agent 8.00
acetophenone (green solvent) 66.75
Total 100.00

Storage stability-Tolfenpyrad 9%+Fluxametamide 2.5%+Abamectin 0.75% EC with Green solvent
Laboratory storage stability for 14 days
Parameters Specification (in the house) Initial at 54±2 0C at 0±2 0C
Tolfenpyrad a.i. 8.55 to 9.90 9.15 9.09 9.14
Fluxametamide a.i. 2.38 to 2.75 2.55 2.53 2.55
Abamectin a.i. 0.71 to 0.83 0.77 0.76 0.76
pH (5% in DM water) 6.0 - 8.0 7.00 7.10 7.00
Emulsion stability Max. 2ml creaming or sediment after 1 hour 0.00 0.10 0.00
Cold test Any separation or creaming max. 2 ml after 1 hour Pass Pass Pass
Flash point Above 24.5 0C 85 85 85
Room temperature storage stability up to 12 months
Parameters Specification (in house) Initial 6 month 12 month
Tolfenpyrad a.i. 8.55 to 9.90 9.15 9.15 9.14
Fluxametamide a.i. 2.38 to 2.75 2.55 2.55 2.55
Abamectin a.i. 0.71 to 0.83 0.77 0.77 0.76
pH (5% in DM water) 6.0 - 8.0 7.00 7.00 7.05
Emulsion stability Max. 2ml creaming or sediment after 1 hour 0.00 0.00 0.00
Cold test Any separation or creaming max. 2 ml after 1 hour Pass Pass Pass
Flash point Above 24.5 0C 85 85 85

The storage stability study of Tolfenpyrad 9%+Fluxametamide 2.5%+Abamectin 0.75% EC with green solvent meets the all in house specifications like active ingredient content, pH, emulsion stability, cold test and flash point criteria of laboratory storage and room temperature storage (up to 12 months).
Table 16.2 Tolfenpyrad 9%+Fluxametamide 2.5%+Abamectin 0.75% EC with Aromatic Solvent

Chemical composition Percent (w/w)
Tolfenpyrad a.i.(active ingredient) 9.00
Fluxametamide a.i. 2.50
Abamectin a.i. 0.75
Styrinated phenol ethoxylate (Emulsifier) 6.50
Calcium alkyl benzenesulfonate (Emulsifier) 3.50
Aromatic solvent (C9) 77.75
Total 100.00

Storage stability-Tolfenpyrad 9%+Fluxametamide 2.5%+Abamectin 0.75% EC with Aromatic solvent
Laboratory storage stability for 14 days
Parameters Specification (in house) Initial at 54±2 0C at 0±2 0C
Tolfenpyrad a.i. 8.55 to 9.90 9.15 9.01 9.1
Fluxametamide a.i. 2.38 to 2.75 2.55 2.51 2.55
Abamectin a.i. 0.71 to 0.83 0.77 0.75 0.76
pH (5% in DM water) 6.0 - 8.0 7.10 7.50 7.00
Emulsion stability Max. 2ml creaming or sediment after 1 hour 0.80 3.20 2.20
Cold test Any separation or creaming max. 2 ml after 1 hour Pass crystal formation observed minor crystal formation observed
Flash point Above 24.5 0C 45 45 45
Room temperature storage stability up to 12 months
Parameters Specification (in house) Initial 6 month 12 month
Tolfenpyrad a.i. 8.55 to 9.90 9.15 9.13 9.09
Fluxametamide a.i. 2.38 to 2.75 2.55 2.54 2.53
Abamectin a.i. 0.71 to 0.83 0.77 0.76 0.75
pH (5% in DM water) 6.0 - 8.0 7.00 7.10 7.30
Emulsion stability Max. 2ml creaming or sediment after 1 hour 0.80 1.60 3.30
Cold test Any separation or creaming max. 2 ml after 1 hour Pass Pass crystal formation observed
Flash point Above 24.5 0C 45 45 45

The storage stability study of Tolfenpyrad 9%+Fluxametamide 2.5%+Abamectin 0.75% EC with Aromatic solvent does not meets the in-house specifications like emulsion stability and cold test (shows minor crystal formation) criteria of laboratory storage and room temperature storage (up to 12 months).

Comparison of Tolfenpyrad 9%+Fluxametamide 2.5%+Hexythiazox 2% recipes between EC with Green solvent and EC with Aromatic solvent.

Table 16.3 Tolfenpyrad 9%+Fluxametamide 2.5%+Hexythiazox 2% EC with Green Solvent

Chemical composition Percent (w/w)
Tolfenpyrad a.i. 9.00
Fluxametamide a.i. 2.50
Hexythiazox a.i. 2.00
sodium stearoyl-2-lactylate (emulsifier) 3.00
polysorbate 65 (polyoxyethylene sorbitan tristearate-Tween 65) 10.00
Methylated seed oil-trisiloxane ethoxylate as a super wetting-spreading-penetrating agent 10.00
1-hexanol (green solvent) 63.50
Total 100.00

Storage stability-Tolfenpyrad 9%+Fluxametamide 2.5%+Hexythiazox 2% EC with Green solvent

Laboratory storage stability for 14 days
Parameters Specification (in the house) Initial at 54±2 0C at 0±2 0C
Tolfenpyrad a.i. 8.55 to 9.90 9.15 9.12 9.14
Fluxametamide a.i. 2.38 to 2.75 2.55 2.52 2.55
Hexythiazox a.i. 1.90 to 2.20 2.25 2.22 2.25
pH (5% in DM water) 6.0 - 8.0 7.00 7.15 7.00
Emulsion stability Max. 2ml creaming or sediment after 1 hour 0.00 0.10 0.00
Cold test Any separation or creaming max. 2 ml after 1 hour Pass Pass Pass
Flashpoint Above 24.5 0C 85 85 85
Room temperature storage stability for up to 12 months
Parameters Specification (in house) Initial 6 month 12 month
Tolfenpyrad a.i. 8.55 to 9.90 9.15 91.50 9.14
Fluxametamide a.i. 2.38 to 2.75 2.55 2.55 2.55
Hexythiazox a.i. 1.90 to 2.20 2.25 2.25 2.24
pH (5% in DM water) 6.0 - 8.0 7.00 7.00 7.09
Emulsion stability Max. 2ml creaming or sediment after 1 hour 0.00 0.00 0.00
Cold test Any separation or creaming max. 2 ml after 1 hour Pass Pass Pass
Flash point Above 24.5 0C 85 85 85

The storage stability study of Tolfenpyrad 9%+Fluxametamide 2.5%+Hexythiazox 2% EC with green solvent meets the all in house specifications like active ingredient content, pH, emulsion stability, cold test and flash point criteria of laboratory storage and room temperature storage (up to 12 months).

Table 16.4 Tolfenpyrad 9%+Fluxametamide 2.5%+Hexythiazox 2% EC with Aromatic solvent

Chemical composition Percent (w/w)
Tolfenpyrad a.i.(active ingredeint) 9.00
Fluxametamide a.i. 2.50
Hexythiazox a.i. 2.00
Styrinated phenol ethoxylate (Emulsifier) 7.50
Calcium alkyl benzenesulfonate (Emulsifier) 4.50
Aromatic solvent (C9) 74.50
Total 100.00

Storage stability-Tolfenpyrad 9%+Fluxametamide 2.5%+Hexythiazox 2% EC with Aromatic solvent

Laboratory storage stability for 14 days
Parameters Specification (in house) Initial at 54±2 0C at 0±2 0C
Tolfenpyrad a.i. 8.55 to 9.90 9.15 9.01 9.14
Fluxametamide a.i. 2.38 to 2.75 2.55 2.50 2.53
Hexythiazox a.i. 1.90 to 2.20 2.25 2.05 2.21
pH (5% in DM water) 6.0 - 8.0 7.20 7.60 7.00
Emulsion stability Max. 2ml creaming or sediment after 1 hour 0.75 2.80 2.10
Cold test Any separation or creaming max. 2 ml after 1 hour Pass minor crystal observed Pass
Flash point Above 24.5 0C 45 45 45
Room temperature storage stability up to 12 months
Parameters Specification (in house) Initial 6 month 12 month
Tolfenpyrad a.i. 8.55 to 9.90 9.15 9.12 9.10
Fluxametamide a.i. 2.38 to 2.75 2.55 2.53 2.51
Hexythiazox a.i. 1.90 to 2.20 2.25 2.20 2.15
pH (5% in DM water) 6.0 - 8.0 7.20 7.25 7.30
Emulsion stability Max. 2ml creaming or sediment after 1 hour 0.75 1.80 3.00
Cold test Any separation or creaming max. 2 ml after 1 hour Pass Pass crystal observed
Flash point Above 24.5 0C 45 45 45

The storage stability study of Tolfenpyrad 9%+Fluxametamide 2.5%+Hexythiazox 2% EC with Aromatic solvent does not meets the in-house specifications like emulsion stability and cold test (shows minor crystal formation) criteria of laboratory storage and room temperature storage (up to 12 months).

Experiment 9: Spreading properties study:
The required samples were prepared and stored at room temperature. The samples were collected after 1 month, 6 months and 12 months of storage to study the spreading properties.
Method: Spreading properties test conducted by preparing 1% solution (1ml formulation in 100 ml water). Drop the solution on leaf surface (Cauliflower leaf) and measure the spreading diameter (mm) after 30 seconds. Spreading diameter measured by graph paper.
Table 17a: TCF 1 (Tolfenpyrad 10%+Cyantraniliprole 4.5%+Fluxametamide 3% EC)
Chemical composition Percent (w/w)
Tolfenpyrad a.i. 10.00
Cyantraniliprole a.i. 4.50
Fluxametamide a.i. 3.00
Ethoxylated monoglyceride (emulsifier) 5.00
polysorbate 65 (polyoxyethylene sorbitan tristearate-Tween 65) as an emulsifier 7.00
Methylated seed oil-polyether modified polysiloxane (wetting-spreading-penetrating agent) 10.00
acetophenone (green solvent) 60.50
Total 100.00

Table 17b: TCF 2 (Tolfenpyrad 10%+Cyantraniliprole 4.5%+Fluxametamide 3% EC)
Chemical composition Percent (w/w)
Tolfenpyrad a.i. 10.00
Cyantraniliprole a.i. 4.50
Fluxametamide a.i. 3.00
Ethoxylated monoglyceride (emulsifier) 5.00
polysorbate 65 (polyoxyethylene sorbitan tristearate-Tween 65) as emulsifier 7.00
acetophenone (green solvent) 70.50
Total 100.00

Table 18: Spreading properties study of different recipes of Tolfenpyrad + Cyantraniliprole + Fluxametamide
Recipes Room temperature storage
1 month 6 months 12 months
(Spreading diameter in mm)
TCF 1 (Tolfenpyrad 10%+Cyantraniliprole 4.5%+Fluxametamide 3% EC) 19 18 17
TCF 2 Tolfenpyrad 10%+Cyantraniliprole 4.5%+Fluxametamide 3% EC) 10 8 6

The recipe TCF 1 (Methylated seed oil-polyether modified polysiloxane) shows excellent spreading action in comparison with recipe TCF 2 (without methylated seed oil-polyether modifier polysiloxane). This will improve the bio-efficacy under field condition, ensures quick control and residual control of target insect pests, and improves the rain-fast properties during rainy days.
Overall summary of field trials:
The field trials results show many benefits/advantages of innovative EC formulations (green solvent) as compared to their conventional tank mixes and conventional EC (aromatic solvent), SC, and SE formulations.
• Innovative EC formulation (green solvent) provides strong synergism in comparison with their conventional tank mixes and conventional EC, SC, and SE formulation
• Residual control. The longer residual control experienced with innovative EC formulation (with green solvent) due to improved spreading properties of spray solution over leaf surface, increase in penetration into the leaf surface.
• Protection against multiple insect pests (chewing, sucking, and piercing type insects) i.e. thrips, mites, jassid, aphid, and lepidopteran insects (fruit borer and DBM) at a time (one-shot control).
• Reduce the doses of active ingredients to get desirable insect control and thereby minimize the pesticide load into the environment.
• Innovative EC (green solvent) formulations meet all the in-house parameters of storage stability studies.
• Innovative EC (green solvent) safe to the crops (nonphytotoxic).
, C , Claims:CLAIMS
We claim;
1. A synergistic insecticidal emulsifiable concentrate composition comprising:
a. compound (A) tolfenpyrad;
b. compound (B) selected from abamectin, emamectin benzoate, fluxametamide, fipronil, profenofos, cyantraniliprole, chlorantraniliprole, azadirachtin, fenpyroximate, hexythiazox, fenazaquin;
c. compound (C) one more insecticide;
d. a super wetting-spreading-penetrating agent;
e. green solvent; and
one or more formulation excipients.

2. The synergistic emulsifiable concentrate insecticidal composition as claimed in claim 1, wherein green solvent for the said composition is selected from n-hexanol (1-hexanol), n-butanol (1-butanol), isobutanol (2-methyl-1-propanol), lactate esters, cyclopentylmethylethe, methyl tertbutyl ether, hexylene glycol, dipropyleneglycol, gamma butyrolactone, acetophenone, 1-methoxy-2-propanol, white mineral oil, g-valerolactone, 2-methyltetrahydrofuran, propylene carbonate, polyethylene glycol, oleic acid, fatty acid methyl ester, Tris (2-ethylhexyl) phosphate, mixture of octanoic acid, decanoic acid, N,N-dimethylamide, 2-ethylhexyl acetate, n-octyl-2-pyrrolidone, pentanol mixture of isomer, isobutanol, lactic acid dimethyl amide, 3-methoxy-N, N-dimethyl propionamide.

3. The synergistic emulsifiable concentrate insecticidal composition as claimed in claim 1, wherein most preferred green solvent for the said composition is selected from 1-hexanol, n-butanol, propylene carbonate, 1-methoxy-2-propanol, 3-methoxy-N, N-dimethyl propionamide.

4. The synergistic emulsifiable concentrate insecticidal composition as claimed in claim 1, wherein green solvent present in an amount of 40%w/w to 70%w/w.

5. The synergistic emulsifiable concentrate insecticidal composition as claimed in claim 1, wherein most preferred range for green solvent present in an amount of 44%w/w to 69%w/w.

6. The synergistic emulsifiable concentrate insecticidal composition as claimed in claim 1, wherein tolfenpyrad present in an amount of 5% to 25% w/w.

7. The synergistic emulsifiable concentrate insecticidal composition as claimed in claim 1, wherein compound (B) is present in an amount of 0.05% to 30% w/w.

8. The synergistic emulsifiable concentrate insecticidal composition as claimed in claim 1, wherein compound (C) is selected from the dimethoate, ethion, phenthoate, phosalone, profenofos, quinalphos, triazophos, ethiprole, fipronil, flufiprole, nicofluprole, pyrafluprole, pyriprole, broflanilide, cyproflanilide, fluxametamide, isocycloseram, afoxolaner, esafoxolaner, fluralaner, lotilaner, sarolaner, bifenthrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, deltamethrin, fenpropathrin, fenvalerate, permethrin, phenothrin, prallethrin, profluthrin, acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, flupyrimin, cycloxaprid, paichongding, guadipyr, cycloxylidin, sulfoxaflor, flupyradifurone, triflumezopyrim, dichloromezotiaz, fenmezoditiaz, spinosad, spinetoram, abamectin, emamectin benzoate, ivermectin, milbemectin, hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen, pymetrozine, pyrifluquinazon, afidopyropen, flonicamid, clofentezine, hexythiazox, diflovidazin, etoxazole, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron, buprofezin, cyromazine, chlorfenapyr, sulfluramid, methoxyfenozide, tebufenozide, halofenozide, fufenozide or chromafenozide, amitraz, diafenthiuron, azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon, fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, flufenerim, rotenone, fluacrypyrim, pyriminostrobin, cyenopyrafen, cyflumetofen, pyflubumide, hydramethylnon, acequinocyl, fluacrypyrim, bifenazate, flometoquin, indoxacarb, metaflumizone, spirodiclofen, spiromesifen, spirotetramat, spidoxamat, spiropidion, spirobudifen, chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole, tetrachlorantraniliprole, tyclopyrazoflor, cyhalodiamide, flubendiamide, fluchlordiniliprole, tiorantraniliprole, acynonapyr, azadirachtin, benzoximate, bromopropylate, benzpyrimoxan, chinomethionat, dicofol, pyridalyl, oxazosulfyl, dimpropyridaz, indazapyroxamet, fluhexafon, cyetpyrafen, flupentiofenox, acyonapyr, trifluenfuronate, cyclobutrifluram, fluazaindolizine, tioxazafen.

9. The synergistic emulsifiable concentrate insecticidal composition as claimed in claim 1, wherein compound (C) is present in an amount of 1% to 40% w/w.

10. The synergistic emulsifiable concentrate insecticidal composition as claimed in claim 1 and claim 8, wherein preferred combinations of active ingredients for the said composition is selected from
a. Tolfenpyrad+Abamectin+Fipronil;
b. Tolfenpyrad+Abamectin+Fluxametamide;
c. Tolfenpyrad+Abamectin+Lambda cyhalothrin;
d. Tolfenpyrad+Abamectin+Fenpyroximate;
e. Tolfenpyrad+Abamectin+Fenazaquin;
f. Tolfenpyrad+Abamectin+Broflanilide;
g. Tolfenpyrad+Abamectin+Hexythiazox;
h. Tolfenpyrad+Abamectin+Azadirachtin;
i. Tolfenpyrad+Cyantraniliprole+Abamectin;
j. Tolfenpyrad+Cyantraniliprole+Fluxametamide;
k. Tolfenpyrad+Cyantraniliprole+Fipronil;
l. Tolfenpyrad+Cyantraniliprole+Fenpyroximate;
m. Tolfenpyrad+Cyantraniliprole+Etoxazol;
n. Tolfenpyrad+Cyantraniliprole+Azadirachtin;
o. Tolfenpyrad+Azadirachtin+Fluxametamide;
p. Tolfenpyrad+Azadirachtin+Spiropidion;
q. Tolfenpyrad+Azadirachtin+Fipronil;
r. Tolfenpyrad+Azadirachtin+Fenpyroximate;
s. Tolfenpyrad+Azadirachtin+Hexythiazox;
t. Tolfenpyrad+Azadirachtin+Chlorfenapyr;
u. Tolfenpyrad+Fipronil+Lambda cyhalothrin;
v. Tolfenpyrad+Fipronil+Fenpyroximate;
w. Tolfenpyrad+Fipronil+Hexythiazox;
x. Tolfenpyrad+Fipronil+Chlorfenapyr;
y. Tolfenpyrad+Fluxametamide+Fenpropathrin;
z. Tolfenpyrad+Fluxametamide+Fipronil;
aa. Tolfenpyrad+Fluxametamide+Fenpyroximate;
bb. Tolfenpyrad+Fluxametamide+Hexythiazox;
cc. Tolfenpyrad+Fluxametamide+Lambda cyhalothrin;
dd. Tolfenpyrad+Fluxametamide+Emamectin benzoate;
ee. Tolfenpyrad+Profenofos+Lambda cyhalothrin;
ff. Tolfenpyrad+Profenofos+Flonicamid;
gg. Tolfenpyrad+Profenofos+Emamectin benzoate.

11. The synergistic emulsifiable concentrate insecticidal composition as claimed in claim 11, wherein most preferred combinations of active ingredients for the said composition is selected from
a. Tolfenpyrad+Abamectin+Fenpyroximate;
b. Tolfenpyrad+Cyantraniliprole+Fluxametamide;
c. Tolfenpyrad+Fipronil+Hexythiazox;
d. Tolfenpyrad+Fluxametamide+Emamectin benzoate.

12. The synergistic emulsifiable concentrate insecticidal composition as claimed in claim 1, a super wetting-spreading-penetrating agent is present in an amount of 5.0% w/w to 12.0% w/w.

13. The synergistic emulsifiable concentrate insecticidal composition as claimed in claim 1, a super wetting-spreading-penetrating agent is a blend of methylated seed oil and organosilicon compound.

14. The synergistic emulsifiable concentrate insecticidal composition as claimed 13, wherein a blend comprises of methylated seed oil present in an amount of 70% to 90% and organo-silicon surfactants are present in amount of 10% to 40% of the blend.

15. The synergistic emulsifiable concentrate insecticidal composition as claimed in claim 14, wherein preferred combination for blend of methylated seed oil and organo-silicon surfactant is selected from 84% Methylated seed oil and 15% polyalkyleneoxide modified trisiloxane; 90% Methylated seed oil and 10% polyalkyleneoxide modified polydimethylsiloxane; 80% Methylated seed oil and 20% trisiloxane ethoxylate; 70% Methylated seed oil and 30% polyoxyethylene methyl polysiloxane; 60% Methylated seed oil and 40% polyether polymethyl siloxane copolymer.

16. The synergistic emulsifiable concentrate insecticidal composition as claimed 15, wherein seed oil is 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, 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 acid (Allium sativum), Ginger oil (Zingiber officinale), D-limonene, Citronella oil, Ceylon ironwood (Mesua ferrea) oil or mixture thereof.

17. The synergistic emulsifiable concentrate insecticidal composition as claimed 17, wherein the preferred seed oil for the said composition is selected from sunflower oil, soybean oil, rapeseed oil, cotton seed oil or blend thereof.

18. The synergistic emulsifiable concentrate insecticidal composition as claimed 1, wherein formulation excipients are selected from an emulsifier, surface-active emulsifying agent.

19. The synergistic emulsifiable concentrate insecticidal composition as claimed 18, wherein surface-active emulsifying agent is polyoxyethylene derivatives of sorbitan esters selected from polysorbate 20 (polyoxyethylene sorbitan monolaurate-Tween 20), polysorbate 60 (polyoxyethylene sorbitan monostearate-Tween 60), polysorbate 65 (polyoxyethylene sorbitan tristearate-Tween 65), polysorbate 80 (polyoxyethylene sorbitan monooleate-Tween 80).

20. The synergistic emulsifiable concentrate insecticidal composition as claimed 18, wherein an emulsifier is glyceride compound selected from lactylated monoglycerides (LACTEM), diacetyl tartaric acid monoglycerides (DATEM) and citric acid esters of monoglycerides (CITREM), 1,2-diacylglycerols and 1,3-diacylglycerols, succinylated monoglyceride, ethoxylated monoglyceride, diacetyl tartaric acid esters of mono- and diglyceride, polyglyceryl-3 caprylate, polyglyceryl-3 acetyl ether; sucrose esters, sucrose stearate, propylene glycol esters, sodium stearoyl-2-lactylate, calcium stearoyl-2-lactylate, glycerol monolaurate.

21. The synergistic emulsifiable concentrate insecticidal composition as claimed 18, wherein an emulsifier is present in an amount of 4.0% to 8.0% w/w.

Dated this 30th day of May, 2022