Description:FIELD OF INVENTION:
The present invention relates to a ternary agrochemical composition comprising a) compound A of Formula I known as 4-phenoxyphenyl (RS)-2(2-pyridyloxy) propyl ether or its agrochemically acceptable salts, esters and derivative; b) compound B of Formula II known as 4-[(5RS)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-1,2-oxazol-3-yl]-N-[(EZ) -(methoxyimino)methyl]-o-toluamide or its agrochemically acceptable salts, esters and derivative; c) compound C at least one insecticide is selected from neonicotinoids group; and d) one or more inactive excipients. The present invention also relates to process for preparing the said composition.

BACKGROUND OF THE INVENTION:
4-phenoxyphenyl (RS)-2(2-pyridyloxy) propyl ether is a pyridine derivative that is a synthetic insect growth regulator belonging to the chemical class of juvenile hormone analogs. It is a compound in which a pyridine ring is substituted with a phenyl group and a cyano group, with a 2-phenoxyphenyl group attached at the 1-position of the pyridine ring. The molecule also features an ester linkage between the phenoxyphenyl group and a 3-oxo-2-pyridinyl moiety, contributing to its biological activity as an insecticide.

4-phenoxyphenyl (RS)-2(2-pyridyloxy) propyl ether is a novel insect growth regulator that interferes with the normal development of insects. It acts on the insect's endocrine system by mimicking the action of the natural juvenile hormone, preventing the insect from completing its life cycle. This disruption results in the insect's failure to molt or mature, ultimately leading to its death. 4-phenoxyphenyl (RS)-2(2-pyridyloxy) propyl ether has a unique mechanism of action that makes it effective against a wide range of pests, including those resistant to other insecticides such as pyrethroids and organophosphates. It exhibits excellent residual activity, with effects lasting up to several weeks. 4-phenoxyphenyl (RS)-2(2-pyridyloxy) propyl ether is highly effective via contact, ingestion, and translaminar movement, ensuring thorough pest control. It is considered to have low toxicity to mammals, birds, and beneficial insects, including bees, and is regarded as environmentally compatible.

4-[(5RS)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-1,2-oxazol-3-yl]-N-[(EZ)- (methoxyimino)methyl]-o-toluamide is an novel isoxazoline insecticide based on chemical compounds derived from the active ingredient 4-[(5RS)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-1,2-oxazol-3-yl]-N-[(EZ)-(methoxyimino)methyl]-o-toluamide, which belongs to the pyrazole class of insecticides. Isoxazoline insecticide operates by inhibiting the activity of the ryanodine receptor in insect muscle cells, disrupting calcium ion regulation and leading to paralysis and death of the pests. It is characterized by its unique chemical structure, which includes a pyrazole ring attached to a phenyl group and a carboxylate ester functional group. Isoxazoline is moderately soluble in water and is designed to be highly effective against a broad spectrum of insect species while posing minimal risk to beneficial insects and the environment. It is typically formulated as a suspension concentrate for application in agricultural settings.

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. It has a role as a neonicotinoid insectide, an environmental contaminant and a xenobiotic. It is a monochloropyridine, a nitrile and a carboxamidine.

Imidacloprid is a systemic insecticide belonging to a class of chemicals called the neonicotinoids which act on the central nervous system of insects. Specifically, it causes a blockage of the nicotinergic neuronal pathway. By blocking nicotinic acetylcholine receptors, imidacloprid prevents acetylcholine from transmitting impulses between nerves, resulting in the insect's paralysis and eventual death. It is effective on contact and via stomach action.

Thiamethoxam is a nicotinoid compound with broad-spectrum insecticidal properties. It is registered for use on numerous crops in many countries against sucking and chewing insects in vegetables, ornamentals, field crops, deciduous fruits, citrus, cotton and rice. It possesses contact and stomach activity.

Clothianidin is an insecticide of the neonicotinoid class developed by Takeda chemical Industries and Bayer AG. Clothianidin and other neonicotinoids act on the central nervous system of insects as an agonist of nAChR, the same receptor as acetylcholine, the neurotransmitter that stimulates and activating post-synaptic acetylcholine receptors but not inhibiting AChE. Clothianidin and other neonicotinoids were developed to last longer than nicotine, which is more toxic and which breaks down too quickly in the environment.

Dinotefuran (MTI-446: (RS)-1-methyl-2-nitro-3-(tetrahydro-3-furylmethyl) guanidine) is a new neonicotinoid commercialized by Mitsui Chemicals. Research led to this novel neonicotinoid by the removal of the chloropyridine or chlorothiazole ring that had been considered as indispensable for neonicotinoides. It is a systemic insecticide belonging to the neonicotinoid class, which is commonly used for controlling a wide range of pests, including aphids, whiteflies, and other sap-feeding insects. As a broad-spectrum insecticide, it is used in agriculture, horticulture, and turf management.

Sulfoxaflor is a systemic insecticide that functions as a neurotoxin, affecting insects through contact or ingestion. As a member of the sulfoximine class of chemicals, it contains a pyridine and a trifluoromethyl group and targets sap-feeding insects. By binding to these receptors in place of acetylcholine, sulfoxaflor disrupts normal nerve signal transmission, leading to uncontrolled impulses, muscle tremors, paralysis, and eventual death. Other insecticides in the nAChR competitive modulator group, such as neonicotinoids, nicotine, and butenolides, interact differently with the receptor.

Thiacloprid is an insecticide belonging to the neonicotinoid class. Its mode of action is akin to that of other neonicotinoids, as it interferes with the insect's nervous system by activating nicotinic acetylcholine receptors. Developed by Bayer CropScience, thiacloprid is used on agricultural crops to control a range of sucking and chewing insects, particularly aphids and whiteflies.

Nitenpyram acts as an insect neurotoxin by irreversibly binding to the nicotinic acetylcholine receptor (nACHr), which disrupts neural signaling in the central nervous system. This binding halts the flow of ions in the postsynaptic membrane of neurons, leading to paralysis and death. It is highly selective for the variation of nACHr found in insects, making it effective in targeted pest control.

Indian Patent Application Number: 202011023685 (Indian Patent No. 372736) discloses synergistic pesticidal composition comprising of bioactive amounts of Diafenthiuron; Pyriproxyfen; and at least one agrochemically active insecticide selected from Thiamethoxam, Imidacloprid, Thiacloprid, Dinotefuran, Clothianidin, and Pymetrozine.

Indian Patent Application Number: 202011038682 disclose synergistic insecticidal composition comprising Acetamiprid, Flonicamid and Pyriproxyfen, process of preparation of composition and uses thereof.

Indian Patent Application Number: 202411045005 (Patent Number: 556883) discloses synergistic insecticidal composition of comprising of tolfenpyrad, pyriproxyfen and dinotefuran.

Indian Patent Application Number: 202411009947 (Patent Number: 559024) relates to a synergistic insecticidal composition comprising an isoxazoline insecticide and at least two insecticides. Particularly, the present invention provides a synergistic insecticidal composition comprising of Fluxametamide, Pyriproxyfen and Flonicamid, process of preparation of the composition and uses thereof.

The present invention overcomes the limitations associated with existing formulations available in the market. The use of insecticide combinations helps to expand the range of pest control, improve effectiveness through synergistic effects, and reduce the required dosage, thus minimizing environmental impact. These combinations are designed to target both chewing and sucking insects simultaneously, decrease the likelihood of resistance development, aid in resistance management, and extend residual control, which reduces the frequency of sprays needed for crop protection. As a result, this approach minimizes the overall pesticide load in the ecosystem. In some cases, the combination of insecticides can demonstrate additive or synergistic effects, leading to enhanced pest control.

SUMMARY OF THE INVENTION:
The main aspect of the present invention is to provide a ternary agrochemical composition comprising a) compound A of Formula I known as 4-phenoxyphenyl (RS)-2(2-pyridyloxy) propyl ether or its agrochemically acceptable salts, esters and derivative; b) compound B of Formula II known as 4-[(5RS)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-1,2-oxazol-3-yl]-N-[(EZ) -(methoxyimino)methyl]-o-toluamide or its agrochemically acceptable salts, esters and derivative; c) compound C at least one insecticide is selected from neonicotinoid group; and d) one or more inactive excipients.

Another aspect of the present invention is to provide a ternary agrochemical composition comprising a) compound A of Formula I known as 4-phenoxyphenyl (RS)-2(2-pyridyloxy) propyl ether or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 25.0% w/w; b) compound B of Formula II known as 4-[(5RS)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-1,2-oxazol-3-yl]-N-[(EZ) -(methoxyimino)methyl]-o-toluamide or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 10.0% w/w; c) compound C at least one insecticide is selected from neonicotinoid group is in amount of 1.0 to 25.0% w/w.

Yet another aspect of the present invention is to provide neonicotinoid insecticide group is selected from acetamiprid, imidacloprid, thiamethoxam, clothianidin, dinotefuran, sulfoxaflor, thiacloprid or nitenpyram.

Yet another aspect of the present invention is to provide one or more inactive excipients is selected from 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.

Further another aspect of the present invention is to provide a ternary agrochemical composition is formulated as Water dispersible 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).

Further another aspect of the present invention is to provide a ternary agrochemical composition demonstrating high efficacy.

Further another aspect of the present invention is to provide a ternary agrochemical composition for controlling the harmful pests in plants and to provide complete protection to crop plants against insect-pests and mites.

Still another aspect of the present invention is to provide a ternary agrochemical composition which increases yield of treated plants.

Still another aspect of the present invention is to provide a ternary agrochemical composition to delay resistance development and effective control of hard to kill and resistant insect-pests and mites.

Still another aspect of the present invention is to provide residual control i.e. longer duration of control with immediate crop protection.

Further another aspect of the present invention is to provide a method of preparing a stable and non-phytotoxic formulation which improves overall health, yield and vigor of the treated plant.

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 provide 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 pesticidal activity or direct effect on the insect pests.

The present invention is to provide a ternary agrochemical composition comprising:
a) compound A of Formula I known as 4-phenoxyphenyl (RS)-2(2-pyridyloxy) propyl ether or its agrochemically acceptable salts, esters and derivative;
b) compound B of Formula II known as 4-[(5RS)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-1,2-oxazol-3-yl]-N-[(EZ) -(methoxyimino)methyl]-o-toluamide or its agrochemically acceptable salts, esters and derivative;
c) compound C at least one insecticide is selected from neonicotinoids group; and
d) one or more inactive excipients.

The present invention is to provide a ternary agrochemical composition comprising a) compound A of Formula I or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 25.0% w/w; b) compound B of Formula II or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 10.0% w/w; c) compound C at least one insecticide selected from neonicotinoids group is in amount of 1.0 to 25.0% w/w.

The present invention, where is neonicotinoid insecticide is selected from acetamiprid, imidacloprid, thiamethoxam, clothianidin, dinotefuran, sulfoxaflor, thiacloprid or nitenpyram.

The present composition is to provide one or more excipients are 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 a ternary agrochemical composition is formulated as Water dispersible 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 and mites belongs to the order Hemiptera, examples-aphid, jassid, leaf hopper, mango hopper, whitefly, mealybug, scale, rice brown plant hopper (BPH); order Lepidoptera, examples-fall army worm, rice stem borer, rice leaf folder, sugarcane early shoot borer, top borer, wheat pink stem borer, fruit borer, pod borer, Maruca, cut worm, diamond back moth (DBM), looper, semi looper, pink bollworm, brinjal fruit and shoot borer, Spodoptera spp. (litura, exigua, frugiperda), Helicoverpa; from the order Coleoptera, examples-white grub, wire worm, epilachna beetle, blue beetle, girdle beetle, flea beetle, rice water weevil; from the order Orthoptera, examples-locust; from the order Thysanoptera, examples-cotton thrips, chilly thrips, black thrips; from the order Isoptera, example-termite; from the order Diptera, examples-shoot fly, stem fly, fruit fly, leaf miner; from the order Acarina, examples-red mite, red spider mite, yellow mite, pink mite, purple mite.

The insects and mites may be controlled by contacting the target insect’s pest, its food supply, habitat, breeding ground or its locus with an agrochemical effective amount of present 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, potato, garlic, onion, groundnut, soybean, green gram, black gram, red gram, gram/chickpea, cucumber, melons, apple, mango, papaya, pomegranate, banana, grapes, tea, coffee, cumin, fennel, black pepper, flowers-rose, marigold etc.

The present an agrochemical composition to delay resistance development and effective control for hard to kill and resistant insect-pests and mites.

The present an agrochemical composition which increases plant vigor is tolerant against insect-pests and mites and is environmentally safe.

The synergistic a ternary agrochemical 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 Compound A Compound B Compound C
Examples 4-phenoxyphenyl (RS)-2(2-pyridyloxy) propyl ether
(Formula I) 4-[(5RS)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-
(trifluoromethyl)-1,2-oxazol-3-yl]-N-[(EZ)- (methoxyimino)methyl]-o-toluamide
(Formula II) At least insecticide selected from neonicotinoids group
% of active ingredients (w/w) 1.0% to 25.0% w/w 1.0% to 10.0% w/w 1.0% to 25.0% w/w

Further, a ternary agrochemical composition comprising a) compound A of Formula I known as (Pyriproxyfen) 4-phenoxyphenyl (RS)-2(2-pyridyloxy) propyl ether or its agrochemically acceptable salts, esters and derivative; b) compound B of Formula II known as (Fluxametamide) 4-[(5RS)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-1,2-oxazol-3-yl]-N-[(EZ) -(methoxyimino)methyl]-o-toluamide or its agrochemically acceptable salts, esters and derivative; c) compound C at least one insecticide is selected from neonicotinoids group; and d) one or more inactive excipients.

Further, a ternary agrochemical composition comprising a) compound A of Formula I known as 4-phenoxyphenyl (RS)-2(2-pyridyloxy) propyl ether or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 25.0% w/w; b) compound B of Formula II known as 4-[(5RS)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-1,2-oxazol-3-yl]-N-[(EZ) -(methoxyimino)methyl]-o-toluamide or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 10.0% w/w; c) compound C at least one insecticide selected from neonicotinoids group is in amount of 1.0 to 25.0% w/w.

In an embodiment of the present invention, neonicotinoid insecticide is selected from acetamiprid, imidacloprid, thiamethoxam, clothianidin, dinotefuran, sulfoxaflor, thiacloprid or nitenpyram.

Further, the present invention aspect is to provide a ternary agrochemical composition comprising a) compound A of Formula I known as 4-phenoxyphenyl (RS)-2(2-pyridyloxy) propyl ether or its agrochemically acceptable salts, esters and derivative 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 Formula II known as 4-[(5RS)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-1,2-oxazol-3-yl]-N-[(EZ) -(methoxyimino)methyl]-o-toluamide or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 10.0% w/w; more preferably in range of 2.0 to 8.0%w/w of the composition; c) compound C at least one insecticide selected from neonicotinoids group is in amount of 1.0 to 25.0% w/w; more preferably in range of 2.0 to 22.0%w/w of the composition.

The present invention wherein one or more inactive excipients is selected from 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, 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 of 1.0 to 30.0% w/w.

Dispersing agents 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, Poly(oxy-1,2-ethanediyl), .alpha.-sulfo-.omega.-[2,4,6-tris(1-phenylethyl)phenoxy]-, ammonium salt.One or more dispersing agents is used in the present composition in an amount of 1.0 to 30.0% w/w.

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 5.0% w/w.

An anti-freezing agent is generally added to the composition, to prevent the aqueous compositions from freezing. Suitable anti-freezing agents are water soluble alcohols (ethylene glycol, propylene glycol), glycerol, 1,3-butendiol, urea, magnesium sulfate heptahydrate, sodium chloride etc. The anti-freezing agent is present in an amount of 0.1 to 10.0% 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, 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 1.0% 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 5.0% 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), 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 of 1.0 to 50.0% w/w.

The solvent and cosolvent 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.

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

Disintegrating agent is selected from Inert material 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.

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 10.0% w/w.

The binder is water soluble, water swellable or combinations of both. The binder is a 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 anti-caking properties to prevent clumping, making it crucial for consistent application of the pesticide when mixed with water for spraying on crops.

Capsule suspension (CS) or microcapsule technology that uses membrane forming wall material to embed the core materials that needs to be protected to form tiny particles, which can protect the core material from adverse environment and effectively plays its biological active functions. The wall forming material/ capsule making monomers may be selected from Tetramethylene diisocyanate, Penta methylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 4,4-diphenylmethene diisocyanate (MDI), polymethylene polyphenylene isocyanate, 2,4,4’-diphenyl ether tri-isocyanate, 3,3’-dimethyl-4,4’-diphenyl diisocyanate, 3,3’-dimethoxy-4,4’-diphenyl diisocyanate, 1,5-naphthylene diisocyanate and 4,4’4"-triphenylmethane tri-isocyanate, toluene diisocyanate or polymethylene polyphenylisocyanate, polyurethane comprising of polyfunctional iso cyanate and a polyamine in polarized form;, Diethylene triamine, Ammonia, hexamine, ethylenediamine, propylene-1,3-diamine, tetramethylenediamine, pentamethylenediamine, 1,6-hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetra ethylene pentaamine, pentaethylenehexamine, 4,9-dioxadodecane-1, 12-diamine, 1,3- phenylenediamine, 2,4- and 2,6-toluenediamine and 4,4’-diaminodiphenylmethane, 1,3-phenylenediamine, 2,4- and 2,6-toluenediamine, 4,4′-diaminodiphenylmethane, 1,5-diaminonaphthalene, 1,3,5-triaminobenzene, 2,4,6-triaminotoluene, 1,3,6-triaminonaphthalene, 2,4,4′-triaminodiphenyl ether, 3,4,5-triamino-1,2,4-triazole and 1,4,5,8-tetraminoanthraquinone. It presents in an amount in the range from 0.1 to 5.0% w/w.

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, Zinc EDTA), iron and its salt (ferrous sulphate, EDTA), copper and salts, sulphur, humic acid-salt, fulvic acid-salt, amino acid-soy protein, jasmonic acid-salt, carboxylic acid-salt, 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:

Example 1: Method of preparation Emulsifiable concentrate (EC) formulation.

Table 1: Formula I 8%+Formula II 4%+acetamiprid 4% EC
Ingredients Function Percent (w/w)
Formula I technical (on 100% purity basis) Active Ingredient 8.00
Formula II technical (on 100% purity basis) Active Ingredient 4.00
Acetamiprid technical (on 100% purity basis) Active Ingredient 4.00
Poly oxyethylene alkyl aryl ether Emulsifier 10.00
Sodium alkyl aryl sulfonate Emulsifier 2.00
N-Methyl-2-pyrrolidone Solvent 10.00
Aromatic solvent (solvent naphtha) Solvent 62.00
Total 100.00

Manufacturing process for 100 kg batch size of Formula I 8%+Formula II 4%+acetamiprid 4% EC
Step 1: Weighing the raw materials according to the batch size as follows:
Step 2: Add 62.0 kg of solvent naphtha, 10 kg of N-Methyl-2-pyrrolidone into the vessel.
Step 3: Slowly add 10 kg of Poly oxy ethylene alkyl aryl ether and 2 kg of sodium alkyl aryl sulfonate with slow stirring.
Step 4: Add 8 kg of Formula I technical, 4 kg of Formula II technical and 4 kg of acetamiprid technical and mix it properly for 30 to 45 minutes.
Step 5: Collect the sample for quality check and pack it in suitable container.

Storage stability study:
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- Formula I 8%+Formula II 4%+acetamiprid 4% EC
Parameters with specifications T0 T1 (AHS), for 14 days at 54 'C. T2- for three months at 40 'C
Formula I content (%) (-5% to +10% range) 8.64 8.62 8.62
Formula II content (%), (-5% to +10% range) 4.25 4.24 4.24
Acetamiprid content (%) (-5% to +10% range) 4.22 4.21 4.22
Emulsion stability (2 ml formulation in 98 ml 342 ppm hard water), maximum 2 ml creaming or sediment after 1 hour 0 ml 0.4 ml 0.4 ml
pH (5% in DM water, 6 to 8) 6.8 6.7 6.7
Cold test (at 10 ºC temperature) Any separation or creaming max. 2 ml after 1 hour pass pass pass
Flash point (above 24.5 0C) complies complies complies

The EC composition of Formula I 8%+Formula II 4%+acetamiprid 4% EC meets all the required storage stability criteria-active ingredient content, emulsion stability, pH, cold test and flash point.

EXAMPLE 2: Method of preparation Suspension Concentrate (SC) formulation.

Table 3: Formula I 8%+Formula II 4%+sulfoxaflor 7% SC
Ingredients Function Percent (w/w)
Formula I technical (on 100% purity basis) Active ingredient 8.00
Formula II technical (on 100% purity basis) Active ingredient 4.00
Sulfoxaflor technical (on 100% purity basis) Active ingredient 7.00
Acrylic Graft Copolymer (2-hydroxypropyl methacrylate) Dispersing agent 5.00
Alkyl naphthalene sulfonate formaldehyde condensate Dispersing agent 1.00
Tri siloxane ethoxylate Wetting agent 4.00
Aluminum magnesium silicate Suspending agent 0.50
Polydimethylsiloxane Anti-foaming agent 0.40
Propylene Glycol Anti-freezing agent 5.00
1,2-benzisothiazolin-3(2H)-one Preservative 0.20
Precipitate Silica Rheology modifier 0.40
Xanthan gum/Polysaccharide Thickener 0.20
Demineralized water Solvent 64.30
Total 100.00

Manufacturing process for 100 kg batch size of Formula I 8%+Formula II 4%+sulfoxaflor 7% 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 stir till completely dissolved to form a solution. This gum solution was made 12 to 18 hours prior to use.
Step 2: Take 54.30 kg of DM water and 5 kg of propylene glycol into designated vessel and mix thoroughly. Add 1 kg of Alkyl naphthalene sulfonate formaldehyde condensate, 5 kg of Acrylic Graft Copolymer (2-hydroxypropyl methacrylate) and 4 kg of tri siloxane ethoxylate into the vessel having water and homogenize the contents for 45 to 60 minutes using high shear homogenizer.
Step 3: Then 8 kg of Formula I technical, 4 kg of Formula II technical and 7 kg of sulfoxaflor technical and 0.5 kg of aluminum magnesium silicate were added and homogenized to get a 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 of the quantity of polydimethyl siloxane was added after the grinding process.
Step 5: Finally, add 0.4 kg of precipitated silica and 10 kg of remaining gum solution, 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 study:
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 4: Storage stability- Formula I 8%+Formula II 4%+sulfoxaflor 7% SC
Parameters T0 (initial) T1 (AHS),for 14 days at 0C T2- for three months at 40 0C
Formula I content (%) (-5% to +10% range) 8.64 8.63 8.63
Formula II content (%), (-5% to +10% range) 4.25 4.24 4.24
Sulfoxaflor content (%) (-5% to +10% range) 7.52 7.50 7.50
suspensibility (minimum 80%) 98.50 98.30 98.20
pH range (7 to 10, 1% aq. Suspension) 6.80 6.70 6.80
pourability (95% minimum) 98.00 97.80 97.80
Viscosity at spindle no. 62, 20 rpm (350 to 800 cps) 650 660 668
Particle size (D50<3, D90<10 micron) 2.2, 8.2 2.3, 8.3 2.2, 8.2

Formula I 8%+Formula II 4%+sulfoxaflor 7% SC meets all the required storage stability criteria-active ingredient content, suspensibility, pH range, pourability, viscosity and particle size.

EXAMPLE 3: Method of preparation Suspo Emulsion (SE) formulation.

Table 5: Formula I 7.5%+Formula II 3.5%+clothianidin 7.5% SE
Ingredients Function Percent (w/w)
Formula I content (%), on 100% purity basis Active ingredient 7.50
Formula II content (%), on 100% purity basis Active ingredient 3.50
Clothianidin content (%), on 100% purity basis Active ingredient 7.50
Polyarylphenyl anionic ether sulfate, ammonium salt Emulsifier 3.50
Aromatic solvent C-9 Solvent 20.00
Acrylic graft copolymer Dispersing agent 3.00
Butyl Polyalkylene Oxide block copolymer Dispersing agent 4.50
Aluminum magnesium silicate Suspending agent 0.50
Citric acid Buffering agent 0.10
Siloxane polyalkylene oxide Anti foaming agent 0.20
Polypropylene glycol Anti freezing agent 5.00
1,2-benzisothiazolin-3(2H)-one Preservative 0.20
Xanthan gum Thickener 0.20
Diluent water Solvent 44.30
Total 100.00

Manufacturing process for 100 kg batch size of Formula I 7.5%+Formula II 3.5%+clothianidin 7.5% SE
Step 1: Weighing the raw materials according to the batch size as follows:
Step 2: 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 stir till completely dissolved to form a solution. This gum solution was made 12 to 18 hours prior to use.
Step 3: Preparation of EC phase: Add 20 kg of aromatic solvent C-9, 3.5 kg of Polyarylphenyl anionic ether sulfate, ammonium salt into other vessel having slow stirring. Add 7.5 kg of Formula I technical and mix it properly for 30 to 45 minutes.
Step 4: Preparation of SC phase: Charge 34.3 kg of DM water and 5 kg of propylene glycol into designated vessel and mix thoroughly.
Step 5: Add 3 kg of acrylic graft copolymer, 4.5 kg of Butyl Polyalkylene Oxide block copolymer, 0.5 kg of Aluminum magnesium silicate and half quantity of siloxane polyalkylene oxide into the vessel and homogenize the mixture for 45 to 60 minutes using high shear homogenizer.
Step 6: Add 3.5 kg of Formula II technical and 7.5 kg of clothianidin technical to this premix slowly and homogenized to get uniform slurry ready for grinding.
Step 7: Before grinding, add half quantity of siloxane polyalkylene oxide, 0.1 kg of citric acid and do grinding process in Dyno mill till desired particle size achieved.
Step 8: Preparation of SE formulation: Now add EC phase slowly into this milled slurry using slow stirring and homogenize the mixture for 30 to 45 minutes.
Step 9: Finally add 10 kg of gum solution to this formulation.
Step 10: Collect the sample quality check and packing.

Storage stability study:
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 6: Storage Stability-Formula I 7.5%+Formula II 3.5%+clothianidin 7.5% SE
Parameters T0 (initial) T1 (AHS),for 14 days at 0C T2- for three months at 40 0C
Formula I content (%) (-5% to +10% range) 8.14 8.13 8.13
Formula II content (%), (-5% to +10% range) 3.77 3.75 3.76
Clothianidin content (%) (-5% to +10% range) 8.12 8.11 8.12
suspensibility (minimum 80%) 98.50 98.40 98.40
pH range (7 to 10, 1% aq. Suspension) 6.90 6.80 6.80
pourability (95% minimum) 97.80 97.60 97.60
Viscosity at spindle no. 62, 20 rpm (350 to 800 cps) 650 660 660
Particle size (D50<3, D90<10 micron) 2.1, 8.2 2.2, 8.3 2.2, 8.3

SE composition of Formula I 7.5%+Formula II 3.5%+clothianidin 7.5% meets all the required storage stability criteria- ingredient content, suspensibility, pH range, pourability, viscosity and particle size.

EXAMPLE 4: Method of preparation Oil Dispersion (OD) formulation.

Table 7: Formula I 10%+Formula II 4%+acetamiprid 4% OD
Ingredients Function Percent (w/w)
Formula I technical (on 100% purity basis) Active Ingredient 10.00
Formula II technical (on 100% purity basis) Active Ingredient 4.00
Acetamiprid content (%) (on 100% purity basis) Active Ingredient 4.00
Tristyrylphenol-polyglycolether-phosphate Dispersing agent 4.50
Octyl phenol ethoxylate Emulsifier 8.00
Sodium alkyl naphthalene sulfonate blend Wetting agent 5.00
Polydimethylsiloxane Anti-foaming agent 0.30
Propylene Glycol Anti-freezing agent 5.00
1,2-benzisothiazolin-3(2H)-one Preservative 0.20
Bentonite clay Stabilizer 2.00
Citric acid Buffering agent 0.20
Methyl soy ate Solvent 56.80
Total 100.00

Manufacturing process for 100 kg batch size of Formula I 10%+Formula II 4%+acetamiprid 4% OD
Step 1: Preparation of Bentonite clay solution: Add 2 kg of bentonite clay into 56.80 kg of methyl soy ate (oil phase), homogenized till it gets completely dissolved. It must be kept 12 to 18 hrs. prior to use.
Step 2: Charge 46.80 kg of solution into a designated vessel.
Step 3: Add 4.5 kg of Tristyrylphenol-polyglycolether-phosphate, 8 kg of octyl phenol ethoxylate, 5 kg of sodium alkyl naphthalene sulfonate blend, 0.3 kg of polydimethylsiloxane, 5 kg of propylene glycol, 0.2 kg of 1,2-benzisothiazolin-3(2H)-one and 0.2 kg of citric acid and homogenize the mixture for 45 to 60 minutes using high shear homogenizer.
Step 4: Add 10 kg of Formula I technical, 4 kg of Formula II technical and 4 kg of acetamiprid technical into this premix and again homogenized for 30 to 45 minutes until it gets uniform mixture.
Step 5: The uniform mixture should be milled at 25 °C and particle size is maintained at < 5μ.
Step 6: Now add remaining 10 kg of bentonite clay solution.
Step 7: Sending the sample to the quality analysis;
Step 8: Packing the formulated material in suitable packaging.

Storage stability study:
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 8: Storage stability- Formula I 10%+Formula II 4%+acetamiprid 4% OD
Parameters T0 (initial) T1 (AHS),for 14 days at 54 0C T2- for three months at 40 0C
Formula I content (%) (-5% to +5% range) 10.33 10.31 10.32
Formula II content (%), (-5% to +10% range) 4.25 4.24 4.24
Acetamiprid content (%) (-5% to +10% range) 4.23 4.22 4.21
Description/Appearance ivory color uniform dispersion ivory color uniform dispersion ivory color uniform dispersion
pH range (7 to 10, 1% aq. Suspension) 6.20 6.10 6.10
Dispersion stability-Sediments (24 hrs.) nil nil nil
Dispersion stability-Creaming (24 hrs.) nil nil nil
Stability stable 10% separation 10% separation
pourability (95% minimum) 98.00 97.80 97.80
Viscosity at spindle no. 62, 20 rpm 280 275 275
Persistent foam nil nil nil
Particle size distribution (microns) D10 0.28 1.08 1.08
Particle size distribution (microns) D50 0.92 2.54 2.54
Particle size distribution (microns) D90 2.17 5.41 5.51

The composition of Formula I 10%+Formula II 4%+acetamiprid 4% OD meets all the required storage stability criteria-active ingredient content, pourability, pH range, viscosity and particle size test.

EXAMPLE 5: Method of preparation Wettable Granule (WG) formulation.
Table 9: Formula I 20%+Formula II 10%+Thiamethoxam 20% WG
Ingredients Function Percent (w/w)
Formula I technical (on 100% purity basis) Active ingredient 20.00
Formula II technical (on 100% purity basis) Active ingredient 10.00
Thiamethoxam content (%) (on 100% purity basis) Active ingredient 20.00
Sodium salt of naphthalene sulfonate condensate Dispersing agent 5.00
Potassium laurate Dispersing agent 1.00
Sodium lauryl sulphate Wetting agent/stabilizer 2.00
Ammonium sulphate Disintegrating agent 5.00
Polydimethylsiloxane Antifoaming Agent 0.50
Corn starch Filler 10.00
Lactose Binder 0.50
China clay Carrier 26.00
Total 100.00

Example for manufacturing of 100 kg batch of Formula I 20%+Formula II 10%+Thiamethoxam 20% WG
Step 1: Charge 26 kg of China clay, 0.5 kg of lactose, 10 kg of corn starch, 0.5 kg of polydimethyl siloxane, 5 kg of ammonium sulphate, 2 kg of sodium lauryl sulphate, 1 kg of potassium laurate, 5 kg of sodium salt of naphthalene sulfonate condensate in premixing blender for homogenization for 30 minutes.
Step 2: Now add 20 kg of formula I technical, 10 kg of formula II technical and 20 kg of thiamethoxam technical and again homogenize for 30 more minutes.
Step 3: Pre-blended material is then grinded through Jet mill until a mean particle size of below 10 microns obtained. Finely grinded material is blended in post blender till it becomes homogeneous.
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 having a particle size in the range of 0.5 mm to 2 mm.
Step 6: Wet granules are passed through fluid bed dryer 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 study:
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 10: Storage Stability-Formula I 20%+Formula II 10%+Thiamethoxam 20% WG
Parameters T0 (initial) T1 (AHS),for 14 days at 0C T2- for three months at 40 0C
Formula I content (%) (-5% to +5% range) 20.86 20.84 20.85
Formula II content (%), (-5% to +5% range) 10.36 10.35 10.35
Thiamethoxam content (%) (-5% to +5% range) 20.72 20.70 20.70
wettability (60 second, maximum) 12 13 13
suspensibility (minimum 70%) 91.50 91.30 91.30
pH range (5.5 to 7.5, 1% aq. Suspension) 7.0 6.9 6.9

WG formulation of Formula I 20%+Formula II 10%+Thiamethoxam 20% is dry and free flowing granules and meets all the storage stability criteria-active ingredient content, wettability, suspensibility, pH 1% solution.

EXAMPLE 6: Micro Emulsion (ME) formulation.

Table 11: Formula I 8%+Formula II 4%+acetamiprid 6% ME (Micro Emulsion)
Ingredients Function Percent (w/w)
Formula I technical (on 100% purity basis) Active Ingredient 8.00
Formula II technical (on 100% purity basis) Active Ingredient 4.00
Acetamiprid technical (on 100% purity basis) Active Ingredient 6.00
Polyoxyethylene ether of triglyceride ester Emulsifier 4.00
Poly(oxy-1,2-ethanediyl) alpha-(tris(1-phenylethyl)phenyl-omega-hydroxy Emulsifier 4.00
N,N-dimethyldecanamide Solvent 10.00
Aromatic solvent (C-9) Solvent 64.00
Total 100.00

Example for manufacturing of 100 kg batch of Formula I 8%+Formula II 4%+Acetamiprid 6% ME
Step 1: Weighing the raw materials according to the batch size as follows:
Step 2: Add 64 kg of solvent naphtha, 10 kg of N,N-dimethyldecanamide into the vessel.
Step 3: Slowly add 4 kg of Polyoxyethylene ether of triglyceride ester, 4 kg of poly(oxy-1,2-ethanediyl) alpha-(tris(1-phenylethyl)phenyl-omega-hydroxy with slow stirring.
Step 4: Add 8 kg of Formula I technical, 4 kg of Formula II technical and 6 kg of acetamiprid technical and mix it properly for 30 to 45 minutes.
Step 5: The solution passed through a filtration apparatus to obtain the clean ME products.
Step 6: Collect the sample for quality check and pack it in suitable container.

The composition of Formula I 8%+Formula II 4%+acetamiprid 6% ME meets all the required storage stability criteria-active ingredient content, persistent foam, emulsion stability, density and pH.

Example 7
BIOLOGICAL EXAMPLES:
Evaluation of synergistic effect of agrochemical composition of the present invention:
The synergism between two or three agrochemical compounds can be evaluated as per the method providen 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: Control of insect-pests in brinjal crop.
Crop: Brinjal
Plot size: 6 m x 5 m.
Pests: Jassid (Amrasca devastans), Whitefly (Bemisia tabaci),
Crop stage: 75 days after transplanting.
Application method: Foliar spray with battery operated backpack sprayer.
Spray volume: 500 liters per hectare.
Methodology: Whitefly (nymph & adults) and Jassid (nymph & adults) are sucking insects, mostly present on lower surface of leaf and suck the cell sap. Observations recorded by counting the number of live insects per leaf, three leaves each one from upper, middle and lower canopy of plant, ten plants per plot. Insect control (as an observed value) calculated by providen formula.

Observations were recorded on 5th, 10th and 15th days after application to judge residual control by present compositions. Based on the insect control observed, expected control calculated by Colby’s formula.

Table 12: Treatment details
S.No. Treatment details Dose per hectare
active ingredients (g) formulation (g)
T1 Control-Untreated -
T2 Formula I 10% EC 75 750.0
T3 Formula I 10% EC 60 600.0
T4 Formula I 10% EC 45 450.0
T5 Formula II 10% EC 37.5 375.0
T6 Formula II 10% EC 30 300.0
T7 Formula II 10% EC 22.5 225.0
T8 Dinotefuran 20% SG 30 150.0
T9 Dinotefuran 20% SG 45 225.00
T10 Dinotefuran 20% SG 60 300.00
T11 Formula I 8%+Formula II 4% SE (prior art) 60+30 750
T12 Formula I 8%+dinotefuran 6% SE (prior art) 60+45 750
T13 Formula II 4%+dinotefuran 6% SE (prior art) 30+45 750
T14 pyriproxyfen 8%+diafenthiuron 18%+dinotefuran 5% SC (prior art) 80+180+50 1000
T15 pyriproxyfen 8%+tolfenpyrad 15%+dinotefuran 7% SE (prior art) 66+123.75+57.75 825
T16 pyriproxyfen 9.5%+fluxametamide 4.5%+flonicamid 13% SE (prior art) 71.25+33.75+97.5 750
T17 Formula I 10%+Formula II 5%+dinotefuran 4% SE 75+37.5+30 750
T18 Formula I 8%+Formula II 4%+dinotefuran 6% SE 60+30+45 750
T19 Formula I 6%+Formula II 3%+dinotefuran 8% SE 45+22.5+60 750
T17 to T19-present compositions, T14 to T16-prior art ternary compositions, T11 to T13-prior art binary compositions

Table 13: Synergistic control of jassid and whitefly infesting brinjal crop
S.No. Jassid control (%) Whitefly control (%)
5th day 10th day 15th day 5th day 10th day 15th day
OV CV Ratio OV CV Ratio
T1 0.0 - - 0.00 0.00 0.0 - - 0.0 0.0
T2 56.8 - - 46.7 32.7 78.4 - - 70.4 58.6
T3 45.3 - - 34.2 21.2 70.4 - - 59.8 44.2
T4 35.4 - - 25.4 8.4 56.5 - - 40.2 24.2
T5 86.4 - - 81.3 65.3 40.7 - - 30.6 15.2
T6 78.4 - - 69.7 52.2 30.5 - - 18.4 6.4
T7 62.2 - - 50.5 32.9 16.4 - - 7.6 1.3
T8 55.9 - - 42.4 24.0 36.6 - - 20.8 4.8
T9 66.4 - - 57.4 40.1 51.4 - - 35.6 20.6
T10 75.3 - - 64.6 49.3 62.8 - - 50.8 32.6
T11 88.8 88.18 1.01 70.2 53.7 79.2 79.43 1.00 64.6 40.6
T12 82.3 81.61 1.01 72.5 60.9 86.2 85.61 1.01 71.4 48.2
T13 93.4 92.75 1.01 84.6 71.2 67.5 66.22 1.02 44.8 20.8
T14 90.2 - - 80.5 67.8 92.8 - - 86.2 75.6
T15 93.5 - - 88.4 80.4 88.2 - - 80.6 68.2
T16 96.2 - - 91.6 85.6 90.6 - - 82.3 71.7
T17 100.0 97.40 1.03 100.0 98.7 99.8 91.88 1.09 97.4 94.8
T18 100.0 96.03 1.04 99.2 96.8 97.5 90.00 1.08 94.6 90.3
T19 98.4 93.96 1.05 95.2 90.2 94.8 86.47 1.10 90.2 84.8
OV-observed value (observed control), CV-calculated value (expected control as per colby formula).

The trial results show present compositions at various doses (T17 to T19) are highly synergistic in terms of efficacy and residual control against jassid and whitefly on 5th, 10th and 15th day after application. They also provide higher percentage of control as compared with T14 to T16-prior art ternary compositions (T14 to T16) and prior art binary compositions (T11 to T13).

Table 14: Fruit count
S.No. number of healthy fruits/plant increase (%) in healthy fruits over T1


T1 15.6 0.0
T2 23.8 52.6
T3 22.9 46.8
T4 21.2 35.9
T5 24.8 59.0
T6 24.3 55.8
T7 21.5 37.8
T8 19.8 26.9
T9 21.4 37.2
T10 21.8 39.7
T11 28.1 80.1
T12 27.6 76.9
T13 27.3 75.0
T14 28.3 81.4
T15 27.7 77.6
T16 29.2 87.2
T17 33.5 114.7
T18 33.2 112.8
T19 32.7 109.6

All the doses of present composition (T17 to T19) also yielded higher number of fruits per plant. The fruits per plant were observed in T17 (33.5 fruits/plant) followed by T18 (33.3 fruits/plant) and T19 (32.7 fruits/plant). All the doses of present composition (T17 to T19) yielded higher number of fruits/plant as compared to all the ternary prior art composition (T14 to T16) and binary prior art composition (T11 to T13).

Experiment 2: Residual control of citrus scale and psylla.
Crop: Citrus
Plot size: 1 tree per treatment.
Pests: Citrus scale, Citrus Psylla
Crop stage: 5 yrs old tree
Application method: Foliar spray with battery operated backpack sprayer.
Spray volume: 5 liters per tree.
Observation method: Count the number of live scale and psylla insects per 20 cm long twigs, 5 twigs per tree. Calculate % control observe as per the formula providen in Experiment 1.
Table 15: Treatment details
S.No. Treatment details Dose per hectare
active ingredients (g) formulation (g or ml)
T1 Control-Untreated - -
T2 Formula I 10% EC 100 1000.0
T3 Formula I 10% EC 75 750.0
T4 Formula I 10% EC 50 500.0
T5 Formula II 10% EC 50 500.0
T6 Formula II 10% EC 35 350.0
T7 Formula II 10% EC 20 200.0
T8 clothianidin 50% WG 50 100.0
T9 clothianidin 50% WG 75 150.0
T10 clothianidin 50% WG 100 200.0
T11 Formula I 7.5%+Formula II 3.5% SE (prior art) 75+35 1000
T12 Formula II 3.5%+clothianidin 7.5% SE (prior art) 30+45 750
T13 pyriproxyfen 8%+clothianidin 3.5% SE (prior art) 52.5+120 1500
T14 pyriproxyfen 9.5%+fluxametamide 4.5%+flonicamid 13% SE (prior art) 71.25+33.75+97.5 750
T15 Formula I 10%+Formula II 5%+clothianidin 5% SE 100+50+50 1000
T16 Formula I 7.5%+Formula II 3.5%+clothianidin 7.5% SE 75+35+75 1000
T17 Formula I 5%+Formula II 2%+clothianidin 10% SE 50+20+100 1000
T15 to T17-present compositions, T14-prior art ternary composition, T11 to T13-prior art binary compositions

Table 16: Residual control of citrus scale and psylla
S.No. Scale insect control (%) Citrus Psylla control (%)
7th day 14th day 7th day 14th day
OV CV Ratio OV CV Ratio
T1 0.0 - - 0.00 0.0 - - 0.0
T2 75.8 - - 64.3 64.6 - - 56.4
T3 67.4 - - 55.6 55.2 - - 42.6
T4 56.7 - - 42.8 41.8 - - 22.8
T5 62.6 - - 53.6 70.2 - - 64.8
T6 50.4 - - 39.2 60.5 - - 49.4
T7 35.5 - - 22.4 45.8 - - 23.2
T8 55.5 - - 40.7 55.4 - - 41.2
T9 65.8 - - 56.9 69.3 - - 60.8
T10 72.5 - - 63.2 78.6 - - 72.4
T11 84.9 83.83 1.01 71.5 82.8 82.30 1.01 67.3
T12 83.7 83.04 1.01 72.3 88.6 87.87 1.01 78.6
T13 85.8 - - 75.6 92.6 - - 88.5
T14 82.6 - - 70.4 84.6 - - 72.8
T15 99.4 95.97 1.04 98.4 98.6 95.30 1.03 95.7
T16 98.8 94.47 1.05 97.6 100.0 94.57 1.06 99.3
T17 96.3 92.32 1.04 94.8 100.0 93.25 1.07 100.0

The experiment data presented in Table 16 clearly shows present compositions (T15 to T17) provide synergistic control of citrus scale and psylla for longer duration (>14 days) in comparison with known binary combinations (T11 to T13) and known ternary composition (T14). The present compositions will helps the farmers to protect their crop for longer duration and thereby reducing crop protection cost and lowering the active ingredients loading into the environment.

Experiment 3: Sucking pests control in Okra crop
Crop : Okra
Plot size: 6 m x 5 m.
Pests: Thrips (Thrips tabaci), Whitefly (Bemisia tabaci),
Crop stage: 67 days after sowing.
Application method: Foliar spray with battery operated backpack sprayer.
Spray volume: 440 liters per hectare.
Methodology: as per experiment 1.

Table 17: Treatment doses
S.No. Treatment details Dose per hectare
active ingredients (g) formulation (g)
T1 Control-Untreated -
T2 Formula I 10% EC 75 750
T3 Formula I 10% EC 60 600
T4 Formula I 10% EC 45 450
T5 Formula II 10% EC 45 450
T6 Formula II 10% EC 30 300
T7 Formula II 10% EC 15 150
T8 Acetamiprid 20% SP 15 75
T9 Acetamiprid 20% SP 30 150
T10 Acetamiprid 20% SP 45 225
T11 Formula I 8%+Formula II 4% SE (prior art) 60+30 750
T12 Formula I 8%+acetamiprid 4% EC (prior art) 60+30 750
T13 Formula II 4%+acetamiprid 4% EC (prior art) 30+30 750
T14 pyriproxyfen 12%+flonicamid 15%+acetamiprid 2% OD (prior art) 60+75+10 500
T15 pyriproxyfen 9.5%+fluxametamide 4.5%+flonicamid 13% SE (prior art) 71.25+33.75+97.5 750
T16 Formula I 10%+Formula II 6%+acetamiprid 2% EC 75+45+15 750
T17 Formula I 8%+Formula II 4%+acetamiprid 4% EC 60+30+30 750
T18 Formula I 6%+Formula II 2%+acetamiprid 6% EC 45+15+45 750
T16 to T18-present compositions, T14 & T15-prior art ternary compositions, T11 to T13-prior art binary compositions

Table 18: Synergistic and residual control of sucking pests in Okra crop
S.No. Thrips control (%) Whitefly control (%)
5th day 10th day 15th day 5th day 10th day 15th day
OV CV Ratio OV CV Ratio
T1 0.0 - - 0.00 0.0 0.0 - - 0.0 0.0
T2 67.2 - - 58.4 40.6 78.6 - - 69.8 58.2
T3 55.5 - - 46.4 27.4 70.2 - - 59.2 43.9
T4 41.4 - - 30.2 14.6 55.8 - - 39.6 23.8
T5 86.5 - - 80.2 67.4 50.7 - - 37.6 18.6
T6 75.8 - - 66.4 50.3 30.2 - - 17.9 6.2
T7 60.2 - - 41.6 21.7 11.5 - - 4.8 1.2
T8 38.8 - - 22.1 5.8 31.5 - - 17.3 2.5
T9 51.8 - - 37.5 20.3 50.2 - - 36.2 20.4
T10 64.8 - - 55.4 40.2 62.7 - - 50.6 35.8
T11 89.8 89.23 1.01 80.2 60.8 80.4 79.20 1.02 65.8 45.8
T12 79.2 78.55 1.01 64.6 37.8 86.4 85.16 1.01 72.8 53.6
T13 89.1 88.34 1.01 77.6 57.3 66.5 65.24 1.02 47.4 23.9
T14 81.4 - - 70.5 54.3 88.5 - - 78.7 66.3
T15 91.8 - - 85.2 73.6 90.8 - - 86.2 72.8
T16 100.0 97.29 1.03 99.3 96.2 98.5 92.77 1.06 94.2 91.8
T17 99.8 94.81 1.05 98.2 94.8 97.2 89.64 1.08 93.6 90.6
T18 98.6 91.79 1.07 95.5 90.2 94.6 85.41 1.11 90.2 87.4

Field trial results data presented in Table 18 shows all the present composition (T16 to T18) provide synergistic and residual control (>15 days) of thrips and whitefly infesting okra and gave higher percentage of control in comparison with known binary compositions (T11 to T13) and ternary compositions (T14 & T15).

Experiment 4: Sucking pests control in cotton crop.
Crop : Okra
Plot size: 6 m x 5 m.
Pests: Jassid and Whitefly
Crop stage: 80 days after sowing.
Application method: Foliar spray with battery operated backpack sprayer.
Spray volume: 520 liters per hectare.
Methodology: as per experiment 1.

Table 19: Treatments details
S.No. Treatment details Dose per hectare
active ingredients (g) formulation (g)
T1 Control-Untreated -
T2 Formula I 10% EC 60 600
T3 Formula II 10% EC 30 300
T4 sulfoxaflor 24% SC 52.5 218.8
T5 Formula I 8%+Formula II 4% SC (prior art) 60+30 750
T6 Formula I 8%+sulfoxaflor 7% SC (prior art) 60+52.5 750
T7 Formula II 4%+sulfoxaflor 7% SC (prior art) 30+52.5 750
T8 Formula I 8%+Formula II 4%+sulfoxaflor 7% SC 60+30+52.5 750
T8-present composition, T5 to T7-prior art binary compositions

Table 20: Sucking pests control in cotton crop
S.No. Jassid control (%) Whitefly control (%)
5th day 10th day 15th day 5th day 10th day 15th day
OV CV Ratio OV CV Ratio
T1 0.0 - - 0.00 0.00 0.0 - - 0.0 0.0
T2 44.8 - - 33.9 20.8 71.8 - - 60.2 45.5
T3 79.3 - - 70.5 53.6 29.7 - - 17.6 5.6
T4 68.6 - - 59.3 41.4 58.4 - - 47.1 31.7
T5 89.2 88.57 1.01 78.8 58.6 79.6 80.18 0.99 66.7 45.8
T6 83.4 82.67 1.01 71.3 50.3 87.5 88.27 0.99 77.2 60.5
T7 94.8 93.50 1.01 87.8 70.7 71.3 70.76 1.01 54.8 33.4
T8 100.0 96.41 1.04 98.8 95.6 96.4 91.75 1.05 93.4 90.1

The present composition (T8) provides synergistic and residual control of jassid and whitefly infesting cotton crop.

Experiment 5: Aphid (Lipaphis erysimi) control in mustard crop.

Table 21: Aphid control
Treatments rate (g.a.i./ha) control (%)
Observed Expected Colby Ratio
T1-Control Untreated - 0.0 - -
T2-Formula I 10% EC 75 35.8 - -
T3-Formula II 10% EC 30 28.4 - -
T4-acetamiprid 20% SP 30 56.3 - -
T5-Formula I 10%+Formula II 4%+acetamiprid 4% OD 75+30+30 97.8 79.91 1.22
g.a.i/ha-gram active ingredients per hectare

Formula I 10%+Formula II 4%+acetamiprid 4% OD (T5) provides synergistic control of aphid infesting mustard crop on 7th day.

Experiment 6: Whitefly (Aleyrodes spp.) control in cabbage crop.

Table 22: Whitefly control
Treatments rate (g.a.i./ha) control (%)
Observed Expected Colby Ratio
T1-Control Untreated - 0.0 - -
T2-Formula I 10% EC 60 65.7 - -
T3-Formula II 10% EC 30 30.5 - -
T4-acetamiprid 20% SP 45 58.4 - -
T5-Formula I 8%+Formula II 4%+acetamiprid 6% ME 60+30+45 96.3 90.08 1.07

Formula I 8%+Formula II 4%+acetamiprid 6% ME provides synergistic control of whitefly infesting cabbage crop.

Experiment 7: Flea beetle (Phytotreta Cruciferae) control in cauliflower crop.

Table 23: Flea beetle control
Treatments rate (g.a.i./ha) control (%)
Observed Expected Colby Ratio
T1-Control Untreated - 0.0 - -
T2-Formula I 10% EC 60 26.4 - -
T3-Formula II 10% EC 30 45.2 - -
T4-thiamethoxam 25% WG 60 65.2 - -
T5-Formula I 20%+Formula II 10%+thiamethoxam 20% WG 60+30+60 94.8 85.96 1.10

Formula I 20%+Formula II 10%+thiamethoxam 20% WG provides synergistic control of flea beetles in cauliflower crop.

Experiment 8: Jassid (Emposca spp.) control in potato crop.

Table 24: Jassid control
Treatments rate (g.a.i./ha) control (%)
Observed Expected Colby Ratio
T1-Control Untreated - 0.0 - -
T2-Formula I 10% EC 60 34.6 - -
T3-Formula II 10% EC 30 76.3 - -
T4-Nitenpyradm 20% SG 40 60.3 - -
T5-Formula I 7.5%+Formula II 3.75%+nitenpyram 5% DC 60+30+40 98.2 93.85 1.05

Formula I 7.5%+Formula II 3.75%+nitenpyram 5% DC provides synergistic control of jassid infesting potato crop.

Experiment 9: Epilachna beetle control in watermelon.

Table 25: Epilachna beetle control
Treatments rate (g.a.i./ha) control (%)
Observed Expected Colby Ratio
T1-Control Untreated - 0.0 - -
T2-Formula I 10% EC 60 24.8 - -
T3-Formula II 10% EC 30 43.5 - -
T4-Imidacloprid 20% SL 40 52.4 - -
T5-Formula I 12%+Formula II 6%+nitenpyram 6% EW 60+30+40 88.7 79.78 1.11

Formula I 12%+Formula II 6%+nitenpyram 6% EW provides synergistic control of epilachna beetle control in watermelon.
, C , C , Claims:We Claims:
1. A ternary agrochemical composition comprising:
a) compound A of Formula I known as 4-phenoxyphenyl (RS)-2(2-pyridyloxy) propyl ether or its agrochemically acceptable salts, esters and derivative;
b) compound B of Formula II known as 4-[(5RS)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-1,2-oxazol-3-yl]-N-[(EZ)-(methoxyimino)methyl] -o-toluamide or its agrochemically acceptable salts, esters and derivative;
c) compound C at least one insecticide selected from neonicotinoids group; and
d) one or more inactive excipients.

2. The ternary agrochemical composition as claimed in claim 1, wherein a) compound A of Formula I known as 4-phenoxyphenyl (RS)-2(2-pyridyloxy) propyl ether or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 25.0% w/w; b) compound B of Formula II known as 4-[(5RS)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-1,2-oxazol-3-yl]-N-[(EZ)-(methoxyimino)methyl]-o-toluamide or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 10.0% w/w; c) compound C at least one insecticide selected from neonicotinoids group is in amount of 1.0 to 25.0% w/w.

3. The ternary agrochemical composition as claimed in claim 1, wherein neonicotinoids group is selected from acetamiprid, imidacloprid, thiamethoxam, clothianidin, dinotefuran, sulfoxaflor, thiacloprid or nitenpyram.

4. The ternary 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 ternary agrochemical composition as claimed in claim 1, wherein the formulation for the said composition is selected from Water dispersible 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 ternary agrochemical composition as claimed in claim 5, wherein the Emulsifiable concentrate (EC) formulation comprises:
a. compound A of Formula I or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 25.0% w/w;
b. compound B of Formula II or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 10.0% w/w;
c. compound C at least one insecticide selected from neonicotinoids group is in amount of 1.0 to 25.0% w/w;
d. emulsifier is in amount of 1.0 to 50.0 w/w; and
e. solvent in amount of quantity sufficient.

7. The ternary agrochemical composition as claimed in claim 5, wherein the Suspension Concentrate (SC) formulation comprises:
a. compound A of Formula I or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 25.0% w/w;
b. compound B of Formula II or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 10.0% w/w;
c. compound C at least one insecticide selected from neonicotinoids group is in amount of 1.0 to 25.0% w/w;
d. dispersing agent is in amount of 1.0 to 30.0% w/w;
e. wetting agent is in amount of 1.0 to 30.0% w/w;
f. suspending agent is in amount of 0.01 to 5.0% w/w;
g. anti-foaming agent is in amount of 0.01 to 5.0% w/w;
h. anti-freezing agent is in amount of 0.1 to 10.0% w/w;
i. preservative is in amount of 0.01 to 1.0% w/w;
j. rheology modifier is in amount of 0.05 to 2.0% w/w;
k. thickener is in amount of 0.01 to 5.0% w/w; and
l. solvent in amount of quantity sufficient.

8. The ternary agrochemical composition as claimed in claim 5, wherein the Suspo Emulsion (SE) formulation comprises:
a. compound A of Formula I or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 25.0% w/w;
b. compound B of Formula II or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 10.0% w/w;
c. compound C at least one insecticide selected from neonicotinoids group is in amount of 1.0 to 25.0% w/w;
d. emulsifier is in amount of 1.0 to 50.0% w/w;
e. dispersing agent is in amount of 1.0 to 30.0% w/w;
f. suspending agent is in amount of 0.01 to 5.0% w/w;
g. buffering agent is in amount of 0.01 to 3.0% w/w;
h. anti-foaming is in amount of 0.1 to 5.0% w/w;
i. anti-freezing agent is in amount of 1.0 to 10.0% w/w;
j. preservative is in amount of 0.01 to 1.0% w/w;
k. thickener is in amount of 0.01 to 5.0% w/w; and
l. solvent in amount of quantity sufficient.

9. The ternary agrochemical composition as claimed in claim 5, wherein the Oil Dispersion (OD) formulation comprises:
a. compound A of Formula I or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 25.0% w/w;
b. compound B of Formula II or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 10.0% w/w;
c. compound C at least one insecticide selected from neonicotinoids group is in amount of 1.0 to 25.0% w/w;
d. dispersing agent is in amount of 1.0 to 30.0% w/w;
e. emulsifier is in amount of 1.0 to 50.0% w/w;
f. wetting agent is in amount of 1.0 to 30.0 w/w;
g. anti-foaming agent is in amount of 0.01 to 5.0% w/w;
h. anti-freezing agent is in amount of 0.1 to 10.0% w/w;
i. preservative is in amount of 0.01 to1.0% w/w;
j. stabilizer is in amount of 0.05 to 2.0% w/w;
k. buffering agent is in amount of 0.05 to 2.0% w/w; and
l. solvent in amount of quantity sufficient.

10. The ternary agrochemical composition as claimed in claim 5, wherein the Wettable Granule (WG) formulation comprises:
a. compound A of Formula I or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 25.0% w/w;
b. compound B of Formula II or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 10.0% w/w;
c. compound C at least one insecticide selected from neonicotinoids group is in amount of 1.0 to 25.0% w/w;
d. dispersing agent is in amount of 1.0 to 30.0% w/w;
e. wetting agent is in amount of 1.0 to 30.0% w/w;
f. disintegrating agent is in amount of 1.0 to 25.0% w/w;
g. antifoaming agent is in amount of 0.01 to 5.0% w/w;
h. binder is in amount of 0.1 to 10.0% w/w; and
i. filler/carrier amount of quantity sufficient.

11. The ternary agrochemical composition as claimed in claim 5, wherein the Micro Emulsion (ME) formulation comprises:
a. compound A of Formula I or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 25.0% w/w;
b. compound B of Formula II or its agrochemically acceptable salts, esters and derivative is in amount of 1.0 to 10.0% w/w;
c. compound C at least one insecticide selected from neonicotinoids group is in amount of 1.0 to 25.0% w/w;
d. emulsifier is in amount of 1.0 to 50.0% w/w; and
e. solvent in amount of quantity sufficient.

12. The ternary agrochemical composition as claimed in claim 7, claim 9 & claim 10, 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, 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.

13. The ternary agrochemical composition as claimed in claim 7, claim 8, claim 9 & claim 10, wherein dispersing agent is selected from 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, Poly(oxy-1,2-ethanediyl), .alpha.-sulfo-.omega.-[2,4,6-tris(1-phenylethyl)phenoxy]-, ammonium salt or combination thereof.

14. The ternary agrochemical composition as claimed in claim 10, wherein disintegrating agent is selected from 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 or a combination thereof.

15. The ternary agrochemical composition as claimed in claim 6, claim 8, claim 9 & claim 11, wherein emulsifier is selected from castor oil ethoxylate 40 mole, Polyoxyethylene alkyl aryl ether, Polyarylphenyl anionic ether sulfonate, 3-methoxy N, N-dimethyl propionamide, Polyglyceryl-3 caprylate, Polyoxyethylene ether of triglyceride ester, Polysorbate 60, Poly(oxy-1,2-ethanediyl) alpha-(tris(1-phenylethyl)phenyl-omega-hydroxy, polyoxyethylene sorbitan monostearate-Tween 60, Sodium alkyl aryl sulfonate, ammonium salt, alkyl phenol ethoxylate, fatty acid esters, fatty acid alkanol amides, alkoxylated fatty acid ester or a combination thereof.

16. The ternary agrochemical composition as claimed in claim 7, claim 8, claim 9 and claim 10, wherein 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.

17. The ternary agrochemical composition as claimed in claim 7, claim 8 & claim 9, wherein anti-freezing agent is selected from water soluble alcohols, ethylene glycol, propylene glycol, glycerol, 1,3-butendiol, urea, magnesium sulfate heptahydrate, sodium chloride or a combination thereof.

18. The ternary 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.

19. The ternary agrochemical composition as claimed in claim 7 & claim 8, wherein thickener/suspending agent is selected from 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.

20. The ternary agrochemical composition as claimed in claim 7, claim 8 & claim 9, wherein preservative is selected from benzisothiazolin-3-one, formaldehyde, sodium benzoate, sodium o-phenyl phenate, potassium sorbate, 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.

21. The ternary agrochemical composition as claimed in claim 8 & claim 9, wherein buffering agent is selected from sodium hydroxide, 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, calcium carbonate, 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.

22. The ternary agrochemical composition as claimed in claim 10, wherein filler/carrier 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, Zinc EDTA), iron and its salt (ferrous sulphate, EDTA), copper and salts, sulphur, humic acid-salt, fulvic acid-salt, amino acid-soy protein, jasmonic acid-salt, carboxylic acid-salt, sea weed extracts, chitosan or a combination thereof.

23. The ternary agrochemical composition as claimed in claim 9, wherein stabilizer is selected from silica, bentonite clay, attapulgite, ceramic, montmorillonite, pumice, sepiolite, diatomaceous earth, clay, dolomite, calcite or combination thereof.

24. The ternary agrochemical composition as claimed in claim 10, wherein binder is selected from 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, China clay, bentonite, fuller’s earth, zeolite, quartz, precipitated silica, palygorskite, sepiolite, halloysite or a combination thereof.

25. The ternary agrochemical composition as claimed in claim 6, claim 7, claim 8, claim 9 & claim 11, 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