DESC:FIELD OF THE INVENTION
[001] The invention relates to a composition comprising a synergistic combination of insecticides. The invention specifically relates to an insecticidal composition comprising combination of three active ingredients and a process for preparation thereof.

BACKGROUND OF THE INVENTION
[002] In the present world, the agriculture industry follows a mix and match combination of fertilizers, pesticides, and genetically engineered crops for getting high yields for the world. High yielding variety of crops aids in preventing insect attacks in some cases, but at the same time pushes the crops to be more prone to such attacks as the new crops lose their natural defence mechanisms. Current farming practices are being greatly challenged with increasing labour shortage, water deficiency, demand of high and quality yields, leaching of fertilizers and pesticides and micronutrient deficiencies in the soil. The current agriculture practices are also heavily depended on the need to identify methods to ward off harmful pests and insects. There is also a need to arrive at a composition which is not toxic.
[003] Another problem faced by the farmers since the advent of agriculture is crops getting infested by pests resulting in a reduced crop yield, and on occasions, complete crop failure. Over the years, there has been an overuse of fertilizers, insecticides, pesticides, and other chemicals. Thus, there is greater need today to optimize farming practices by reducing the number of applications of various fertilizers and pesticides, reduce the burden on the environment by reducing the number of chemical adjuvants and excipient being added to the soil and the crops, without affecting crop yield.
[004] The main issue farmers face with the use of insecticides is that the repeated and exclusive application of an individual insecticidal compound leads, in many cases, to a natural or adapted resistance against the active compound. Inevitably the prerequisite for insecticidal products is that it has to be developed such that it prevents or overcomes resistance. Moreover, these insecticides, used to control different insects that requires high dosage rates to effectively control the disease. The contemporary manufacturing practices uses a variety of combination of active compounds, which range from fine-tuned ingredients for a special situation to broad spectrum insecticides. However, it should be kept in mind that the cost and focus need to develop such a mixture is significantly high.
[005] Due to these reasons, it is also common knowledge that the prevailing insecticides used in the market suffers from the problems of unfavourable environmental/toxicological effects. The needs of the agriculture sector have pushed scientists to develop insecticidal compositions containing more than one active ingredients in mixture to obtain the desired effect. However, all mixtures of ingredients do not guarantee efficiency as the chemical and physical stability of the product is an essential factor. It is also pertinent to note that the insecticide should not deter the effects of fertilizers and insecticides used alongside. This directly adds to the cost and research needed to develop new insecticides.
[006] Therefore, in view of the above shortcomings, there still exists a need for new and effective insecticidal compositions.

SUMMARY OF THE INVENTION
[007] In one aspect, the present invention is directed to a synergistic insecticidal composition comprising a diamide insecticide as a first active ingredient, an avermectin insecticide as a second active ingredient, an oxadiazine insecticide or organothiophosphate insecticide as a third active ingredient, and agrochemically acceptable excipients.
[008] In an embodiment, the diamide insecticide is selected from broflanilide, chlorantraniliprole, cyantraniliprole, cyhalodiamide, cyclaniliprole, flubendiamide, fluchlordiniliprole, tetrachlorantraniliprole, tetraniliprole, and tiorantraniliprole.
[009] In another embodiment, the avermectin insecticide is selected from abamectin, doramectin, emamectin, eprinomectin, ivermectin, selamectin, and emamectin benzoate.
[010] In yet another embodiment, the oxadiazine insecticide is Indoxacarb.
[011] In still another embodiment, the organothiophosphate insecticide is selected from azothoate, bromophos, bromophos-ethyl, chlorthiophos, cyanophos, cythioate, dicapthon, dichlofenthion, etaphos, famphur, fenchlorphos, fenitrothion, fensulfothion, fenthion, fenthion-ethyl, heterophos, jodfenphos, mesulfenfos, parathion, parathion-methyl, phosnichlor, profenofos, prothiofos, sulprofos, temephos, trichlormetaphos-3, trifenofos, and xiaochongliulin.
[012] In another embodiment, the agrochemically acceptable excipients are selected from wetting agent, dispersing agent (or dispersant), adjuvants / emulsifiers, polymeric surfactants, antifoam agents, rheology modifiers, antifreeze agent, preservatives, thickeners, binders, stabilizing agents, film forming agents, fillers, diluents, disintegrating agents, and combinations thereof.
[013] In a further embodiment, the insecticidal composition is formulated in a dosage form selected from the group consisting of suspension concentrate (SC) formulation, Wettable Powder (WP), Water Dispersible Granules (WG), Capsule Suspension (CS), Suspoemulsion (SE), Oil Dispersion (OD), Flowable suspension (FS), water dispersible powder for slurry treatment (WDP), powder for dry seed treatment (DS), Flowable for seed treatment (FS), Emulsiable Concentrate (EC), Emulsion in water (EW), Dual emulsion, Capsule suspension with suspension concentrate (ZC), Capsule suspension with emulsion (ZE), and Capsule suspension with emulsion in water (ZW).
[014] In a still further embodiment, the synergistic insecticidal composition comprises 0.1 wt.% to 60% wt.% of the first active ingredient comprising diamide insecticide; 0.1% to 30% wt.% of the second active ingredient comprising avermectin insecticide; 1% to 65% wt.% of the third active ingredient comprising oxadiazine insecticide or the organothiophosphate insecticide, and at least one agrochemically acceptable excipient. The wt.% is based on the total weight of the composition.
[015] In another aspect, the present invention is directed to a method for preparing the above synergistic insecticidal composition comprising mixing the following: diamide insecticide as the first active ingredient, avermectin insecticide as the second active ingredient, oxadiazine insecticide or organothiophosphate insecticide as the third active ingredient, and at least one agrochemically acceptable excipient.
[016] In an embodiment, the method comprises the following sub-steps:
A. mixing the agrochemically acceptable excipients to obtain an aqueous media,
B. mixing the first active ingredient, the second active ingredient, and the third active ingredient, with the aqueous media to obtain a pre-mix slurry, and
C. wet grinding the pre-mix slurry to obtain a particle size distribution Dv50 of less than 5 microns.
[017] In yet another aspect, the present invention is directed to a method of controlling and eliminating insects from a pre-determined area. The method comprises applying to a pest, to a locus of a pest or to a plant susceptible to attack by a pest, an effective amount of the above synergistic insecticidal composition.

DETAILED DESCRIPTION OF THE INVENTION
[018] Before the compositions and formulations of the present invention are described, it is to be understood that this invention is not limited to particular compositions and formulations described, since such compositions and formulations may, of course, vary. It is also to be understood that the terminology used herein is not intended to be limiting since the scope of the present invention will be limited only by the appended claims.
[019] The terms “comprising”, “comprises” and “comprised of” as used herein are synonymous with “including”, “includes” or “containing”, “contains”, and are inclusive or open-ended and do not exclude additional, non-recited members, elements, or method steps. It will be appreciated that the terms “comprising”, “comprises” and “comprised of” as used herein comprise the terms “consisting of”, “consists” and “consists of”.
[020] Furthermore, the terms “first”, “second”, “third” or “(a)”, “(b)”, “(c)”, “(d)” etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein. In case the terms “first”, “second”, “third” or “(A)”, “(B)” and “(C)” or “(a)”, “(b)”, “(c)”, “(d)”, “i”, “ii” etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, that is, the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps unless otherwise indicated in the application as set forth herein above or below.
[021] In the following passages, different aspects of the present invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
[022] Reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, the appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment but may. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments. Furthermore, while some embodiments described herein include some, but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments, as would be understood by those in the art. For example, in the appended claims, any of the claimed embodiments can be used in any combination.
[023] Furthermore, the ranges defined throughout the specification include the end values as well, i.e., a range of 1 to 10 implies that both 1 and 10 are included in the range. For the avoidance of doubt, the applicant(s) shall be entitled to any equivalents according to applicable law.
[024] An aspect of the present invention relates to a synergistic insecticidal composition comprising: a diamide insecticide as a first active ingredient, an avermectin insecticide as a second active ingredient, an oxadiazine insecticide or organothiophosphate insecticide as a third active ingredient; and agrochemically acceptable excipients.
[025] In an embodiment, the composition includes the aforementioned ingredients in suitable amounts which render the composition effective as an insecticide. For instance, the composition comprises 0.1 wt.% to 60% wt.% of the diamide insecticide as the first active ingredient; 0.1 wt.% to 30% wt.% of the avermectin insecticide as the second active ingredient; and 1 wt.% to 65% wt.% of the oxadiazine insecticide or organothiophosphate insecticide as the third active ingredient. The agrochemically acceptable excipients are present in amounts to make the total weight of the composition as 100 wt.%. The wt.% of the ingredients in the composition should be considered to be based on the total weight of the composition, unless provided otherwise.
[026] In an embodiment, the diamide insecticide as the first active ingredient of the present invention is selected from broflanilide, chlorantraniliprole, cyantraniliprole, cyhalodiamide, cyclaniliprole, flubendiamide, fluchlordiniliprole, tetrachlorantraniliprole, tetraniliprole, and tiorantraniliprole. A preferred compound from this class is Chlorantranilipole.
[027] Chlorantraniliprole is a human-made insecticide belonging to the class of anthranilic diamide insecticides and resulting from the formal condensation of the carboxylic acid group of 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylic acid with the primary amino group of 2-amino-5-chloro-N,3-dimethylbenzamide. The diamide insecticide controls moth and butterfly caterpillars (larvae), as well as some beetles and "true" bugs like aphids and spittlebugs. Further, they also control some beetles and bugs like aphids and spittlebugs.
[028] The mechanism of diamide insecticide is such that it binds to a specific receptor in muscles called the ryanodine receptor. When these insecticide binds to this receptor, it causes muscle cells to leak calcium. The muscles stop working normally. The insect is paralyzed and dies. The ryanodine receptor is different in insects than in mammals. The diamide insecticide binds much more tightly to the receptor in insects. It is toxic to insects mainly if it is eaten. It is also toxic to insect eggs, larvae, and pupae on contact.
[029] Suitable amounts of the diamide insecticide may be added in the composition. In an embodiment, the diamide insecticide as the first active ingredient is present in an amount ranging between 0.1 wt.% to 60 wt.%. In another embodiment, the amount ranges between 0.1 wt.% to 50 wt.%, or 0.5 wt.% to 40 wt.%.
[030] In another embodiment, the avermectin insecticide as the second active ingredient in the composition belongs to a series of drugs and pesticides used to treat parasitic worms and insect pests. This class of pesticide has homologous semi-synthetic macrolides that are derived from the natural fermentation products of Streptomyces bacteria. The avermectin insecticide is selected from abamectin, doramectin, emamectin, eprinomectin, ivermectin, selamectin, and Emamectin Benzoate. A preferred compound from this class is Emamectin benzoate.
[031] Avermectin insecticide kills insects by disrupting neurotransmitters, causing irreversible paralysis. It is more effective when ingested, but it also is somewhat effective on direct contact. When sprayed to foliage, it penetrates the leaf tissue and forms reservoir within treated leaves, which provides residual activity against pests that ingest the substance when feeding. Avermectins such as Emamectin is approved by the EPA for use in prevention of emerald ash borer in ash trees. Emamectin also has promising applications in the eradication of fish lice and in fish farming. Emamectin benzoate is a potent insecticide that controls many pests such as thrips, leaf miners, and worms including alfalfa caterpillar, beet armyworm, cabbage looper, corn earworm, cutworms, diamondback moth, tobacco budworm, tomato fruit worm and tomato pinworm.
[032] Suitable amounts of avermectin insecticide may be added in the composition. In an embodiment, the avermectin insecticide as the second active ingredient is present in an amount ranging between 0.1 wt.% to 30% wt.%. In another embodiment, the amount ranges between 0.1 wt.% to 25 wt.%, or 0.1 wt.% to 20 wt.%.
[033] In yet another embodiment, the oxadiazine insecticide as the first active ingredient is Indoxacarb. Indoxacarb is a semicarbazone compound developed for use against Lepidopteran species. Indoxacarb is an organochlorine insecticide and a methyl ester. It has a role as a voltage-gated sodium channel blocker. Indoxacarb demonstrates effective control of lepidopteran insects including Cydia, Helicoverpa, Heliothis, Lobesia, Plutella and Spodoptera spp. Indoxacarb is used to control lepidopteran insect pests on edible fruits, vegetables, and fiber crops like cotton especially fruit borers and leaf folders on chillies, fruit borers on tomatoes, diamondback moths, and cabbage loopers. Indoxacarb blocks the sodium channel in insect neurons and is categorized as a reduced risk insecticide. The IUPAC name of Indoxacarb is Indeno[1,2-e] [1,3,4] oxadiazine-4a(3H)-carboxylic acid.
[034] In another embodiment, the composition includes organothiophosphate insecticide as an alternate to oxadiazine insecticide as the third active ingredient. The organothiophosphate, mechanism of action is via the inhibition of the acetylcholinesterase enzyme.
[035] In an embodiment, the organothiophosphate insecticide is selected from azothoate, bromophos, bromophos-ethyl, chlorthiophos, cyanophos, cythioate, dicapthon, dichlofenthion, etaphos, famphur, fenchlorphos, fenitrothion, fensulfothion, fenthion, fenthion-ethyl, heterophos, jodfenphos, mesulfenfos, parathion, parathion-methyl, phosnichlor, profenofos, prothiofos, sulprofos, temephos, trichlormetaphos-3, trifenofos, and xiaochongliulin. A preferred compound from this class is Profenofos.
[036] Suitable amounts of oxadiazine insecticide or the organothiophosphate insecticide as the third active ingredient may be added in the composition. In an embodiment, the oxadiazine insecticide or the organothiophosphate insecticide as the third active ingredient is present in an amount ranging between 1 wt.% to 65% wt.%. In another embodiment, the amount ranges between 5 wt.% to 55% wt.%, or 5 wt.% to 50% wt.%.
[037] In another embodiment, the synergistic insecticidal composition comprises: 0.1 wt.% to 60 wt.% of the diamide insecticide as the first active ingredient; 0.1 wt.% to 30 wt.% of the avermectin insecticide as the second active ingredient; 1 wt.% to 65 wt.% of the oxadiazine insecticide as the third active ingredient; and the agrochemically acceptable excipients, wherein the wt.% is based on the total weight of the composition.
[038] In another embodiment, the synergistic insecticidal composition comprises: 0.1 wt.% to 60 wt.% of the diamide insecticide as the first active ingredient; 0.1 wt.% to 30 wt.% of the avermectin insecticide as the second active ingredient; 1 wt.% to 65 wt.% of the organothiophosphate insecticide as the third active ingredient; and the agrochemically acceptable excipients, wherein the wt.% is based on the total weight of the composition.
[039] In another embodiment, the synergistic insecticidal composition comprises: 0.1 wt.% to 60 wt.% of Chlorantraniliprole as the first active ingredient; 0.1 wt.% to 30 wt.% of Emamectin benzoate as the second active ingredient; 1 wt.% to 65 wt.% of Indoxacarb or Profenofos as the third active ingredient; and the agrochemically acceptable excipients.
[040] In an embodiment, the composition includes more than one agrochemically acceptable excipient. A person skilled in the art is aware of the suitable agrochemically acceptable excipients that may be included in a typical insecticidal composition. In an embodiment, the agrochemically acceptable excipients can be selected from wetting agents, dispersing agents, adjuvants / emulsifiers, polymeric surfactants, antifoam agents, rheology modifiers, antifreeze agents, preservatives, thickeners, binders, stabilizing agents, film forming agents, fillers, diluents, disintegrating agents, and combinations thereof. The agrochemically acceptable excipients in a pre-determined ratio aid in improving the physical stability and also prevent the degradation of the composition, thereby leading to long term stability and spectrum activity.
[041] In an embodiment, the agrochemically acceptable excipients are present in an amount ranging between 1 wt.% to 80 wt.%. In another embodiment, the amount ranges between 10 wt.% to 80 wt.%, or 20 wt.% to 80 wt.%, or 30 wt.% to 80 wt.%, or 40 wt.% to 80 wt.%, or 50 wt.% to 80 wt.%.
[042] In one embodiment, the antifoam/defoamer is selected from silicon emulsions, poly dimethyl siloxane powder or liquid, and silicon base antifoam.
[043] In another embodiment, the wetting agent is selected from non-ionic surfactant blend, Polyalkylene oxide block copolymer, Salts of Di-octyl sulfosuccinate, Alcohol alkoxylate diester, Sodium N-methyl oleoyl taurate, Sodium cocoyl sarcosinate, sodium lauryl sulphate, Sodium dioctyl sulfosuccinate, alkyl polyglucoside, Naphthalenesulfonic acids, and branched or linear Butyl derivatives sodium salts.
[044] In yet another embodiment, the disintegrating agent is selected from sodium chloride, sodium sulphate, ammonium sulphate, sodium carbonate, sodium bicarbonate, and sodium tripolyphosphate (STPP).
[045] In another embodiment, the buffering agent is selected from sodium acetate, potassium acetate; ammonium carbonate, calcium carbonate, sodium carbonate, acidic buffers such as mono carboxylic, dicarboxylic acid, succinic acid, citric acid, fumaric acid, glycine, phosphate-based buffers, potassium phosphate, glacial acetic acid, boric acid, hydroxy carboxylic functionality base, and sulphonic base.
[046] In another embodiment, the dispersing agent is selected from Napthalene sulphonate formaldehyde condensate, Amine alkyl benzenesulfonate, Sodium Ligno Sulphonate, Blend of Naphthalene sulphonate, Blend of Lignin sulphonates, Ethoxylated Lignin sulphonates, Linear alkyl benzene sulphonate, tristyrylphenol phenol ethoxylates, acrylic copolymer solution, Modified styrene acrylic polymer, Ammonium distyrylphenyl ether sulphate, and salts of polystyrene sulphonic acids.
[047] In another embodiment, the adjuvants / emulsifiers are selected from Polyoxyethylene alkylamine, Polyoxyethylene linear alkyl ether, Ethoxylated Castor Oil, Epoxidized soyabean oil, Polyoxyethyene alkylamine quaternary, Polyoxyethyene tallow ethylmonium ethosulfate, Glycerol monostearate, Glycerol monooleate, ethoxylated monostearate / distearate / tri stearate ethoxylated monooleate / trioleate, Polyoxyethylene branched tridecyl Phosphate, Polyoxyethylene branched tridecyl phosphate neutralised, Polyoxyethylene alkyl ether phosphate, and ethoxylated propoxylated sorbitan mono esters or Tallow amine ethoxylate.
[048] In still another embodiment, the polymeric surfactants are selected from Alkoxylated ethylene diamine, Butyl block copolymer, Alkoxylated polyol ester, Butyl Polyalkylene Oxide Block Copolymers, Polyacrylate copolymer, and polycarboxylates.
[049] In one embodiment, the antifreeze agent is selected from Propylene glycol, 1-methoxyl-2-propoanol, and Butyl cellosolve.
[050] In another embodiment, the preservatives are selected from 1-2-benziisothiazolin-3-one, 5-Chloro-2-methyl-4-isothiazolin-3-one, and 2-methyl-4-isothiazolin-3-one.
[051] In still further embodiment, the rheology modifier is selected from polyester block co-polymer, poly saccharides, polyamide, clay, xanthum gum, carboxymethyl cellulose, and silicates.
[052] In yet another embodiment, the binder / film-forming agent is selected from polyvinyl alcohol, hydrophilic polymers, hydrobhobic polymers, Poly(vinylpyrrolidone), vinypyrrolidone-vinylacetate, Starch, and Dextrin.
[053] In another embodiment, the stabilizing agent is selected from phosphoric acid monoesters, phosphoric acid diesters, phosphoric acid mono- and di- ester mixture, sodium phosphates, butylated hydroxytoluene, castor oil ethoxylate, ethoxylated hydrogenated castor oil, vegetable oil, and epoxidized soyabean oil.
[054] In a further embodiment, the filler and/or diluent is selected from starches and their derivatives, sugars and sugar alcohols, silicates, calcium phosphates, calcium sulfate, dextrates, kaolin clay, bentonite clay, attapulgite, diatomaceous earth, magnesium carbonate, talc, and salts.
[055] In the present context, water is used as a diluent to dilute the active ingredient to a desired concentration. Water used is purified water and includes deionized water and/or distilled water.
[056] In an embodiment, the composition is formulated in a dosage form selected from the group consisting of suspension concentrate (SC) formulation, Wettable Powder (WP), Water Dispersible Granules (WG), Capsule Suspension (CS), Suspoemulsion (SE), Oil Dispersion (OD), Flowable suspension (FS), water dispersible powder for slurry treatment (WDP), powder for dry seed treatment (DS), Flowable for seed treatment (FS), Emulsiable Concentrate (EC), Emulsion in water (EW), Dual emulsion, Capsule suspension with suspension concentrate (ZC), Capsule suspension with emulsion (ZE), and Capsule suspension with emulsion in water (ZW).
[057] The person skilled in the art is well aware of suitable techniques for making these dosage forms.
[058] Another aspect of the present invention relates to a method for preparing the synergistic insecticidal composition, as above. Accordingly, the embodiments pertaining to the synergistic insecticidal composition are applicable here as well.
[059] In an embodiment, the method comprises at least the step of mixing the following ingredients: first active ingredient comprising diamide insecticide, second active ingredient comprising avermectin insecticide, third active ingredient comprising oxadiazine insecticide or organothiophosphate insecticide, and the agrochemically acceptable excipients.
[060] In another embodiment, the aforementioned ingredients may be used in suitable and/or predetermined amounts which is capable of imparting enhanced insecticidal and synergistic effect to the overall composition.
[061] In a further embodiment, the method comprises the following sub-steps:
(A) mixing the agrochemically acceptable excipients to obtain an aqueous media,
(B) mixing the first active ingredient, the second active ingredient, and the third active ingredient, with the aqueous media to obtain a pre-mix slurry, and
(C) wet grinding the pre-mix slurry to obtain a particle size distribution Dv50 of less than 5 microns.
[062] Herein, "grinding" refers to a mechanical process involving the reduction of particle size of the ingredients of the composition. This reduction in particle size may enhance the dispersibility, solubility, or efficacy of the insecticidal agents within the composition. Grinding in this context can encompass various techniques such as milling, pulverizing, or comminution, typically performed using equipment such as mills, crushers, or grinders. The person skilled in the art is well aware of suitable grinding techniques that may be employed for this purpose.
[063] In a further embodiment, the method comprises the following sub-steps:
(A) mixing the anti-freezing agents, wetting agents, dispersants, and polymeric dispersants into de-ionised water to prepare the aqueous media;
(B) mixing the rheology modifier, anti-freezing agents, and a small amount of water in a separate vessel to allow the rheology modifier to hydrate and swell;
(C) mixing the preservative, anti-foaming agents and the active ingredients into the aqueous media with low shear mixing followed by high shear mixing to produce a homogenous pre-mix slurry;
(D) wet grinding the pre-mix slurry in a bead mill to achieve required particle size of Dv50 of less than 5 µm and forming a concentrated mill base; and
(E) High shear mixing of the rheology modifier and half quantity of the anti-freeze to the concentrated mill base produces the final homogenous solution.
[064] The aforementioned method steps result in suspension concentrate (SC) dosage form of the composition. Herein, the particle size Dv50 is determined in accordance with CIPAC MT 187.
[065] Still another aspect of the present invention relates to a method of controlling and eliminating insects from a pre-determined area.
[066] In an embodiment, the method comprises applying to a pest, to a locus of a pest or to a plant susceptible to attack by a pest, an effective amount of the synergistic insecticidal composition, as described above. Accordingly, the embodiments pertaining to the composition are applicable here as well.
[067] Effective application rates of the present invention cannot generally be defined, as it varies depending upon various conditions such as the type of pesticide, target pest, weather conditions, nature of the soil, and the type of crop. The application rates can be varied within a relatively wide range, depending on the kind of application.
[068] In an embodiment of the present invention, the synergistic composition may be used for foliar application, ground application or application to plant propagation materials. These application rates are merely by way of example and are not limiting for the purposes of the invention.
[069] In yet another embodiment, the methods of the present invention may be applied to any crop plants, including but not limited to paddy, chilli, tomato, potato, soybean, vegetables Cole crops, maize and Pulses Black gram, green gram, beans.
[070] In another embodiment, of the present invention can be used in the agricultural sector and related fields of use for preventing and/or treating, controlling large spectrum of insects for example, but not limited to hemiptera, diptera, lepidoptera, coleoptera, hymenoptera, isopteran and is also effective against controlling soil pest, gram pod borer, stem borer, fruit borer, leaf roller, leaf folder, leaf miner, looper, hoppers, thrips, jassids, aphid and mites.
[071] The present invention herein may be applied to a desired locus by any suitable methods including coating, spraying, dipping, soaking, injection, and irrigation. The means such as airplane spray tanks, knapsack spray tanks, cattle dipping vats, farm equipment used in ground spraying (e.g., boom sprayers, hand sprayers), and the like. The desired locus may be soil, plants, and the like.
[072] Advantageously, the present invention provides a synergistic composition containing three active ingredients – diamide insecticide, avermectin insecticide, and oxadiazine insecticide or organothiophosphate insecticide, having several benefits, such as but not limited to, improved efficacy in combination to achieve synergistic effect. The enhancements of insecticidal agents and compositions have been achieved to improve control of insect pests and application practice to target crops as single or mixed pesticides. Having an insecticidal composition with a high synergistic action with no cross resistance to existing insecticide agents and with a low environmental impact is achieved with the composition of the present invention. The present composition further provides a dependable, safe, and efficient composition for controlling insect and insect-borne diseases in agricultural settings, contributing to enhanced productivity, sustainability, and profitability.

EXAMPLES
[073] The present invention is more particularly described in the following examples that are intended as illustration only, since numerous modifications and variations within the scope of the present invention will be apparent to those skilled in the art. Unless otherwise noted, all parts, percentages and ratios reported in the following examples are on a weight basis, and all ingredients used in the examples were obtained or are available from the chemical suppliers.
[074] The following examples illustrate the basic methodology and versatility of the present invention.
[075] General synthesis of the composition
[076] Suitable amounts of the anti-freezing agent, wetting agent, dispersant, and polymeric dispersant were dissolved in deionised water to obtain an aqueous media. Subsequently, suitable amounts of the rheology modifier, anti-freezing agent, and a small amount of water was mixed in a separate vessel to allow the rheology modifier to hydrate and swell. In the aqueous media, suitable amounts of the preservative, anti-foam, and all the active ingredients were added with low shear mixing followed by high shear mixing to produce a homogenous pre-mix slurry. The pre-mix slurry was then wet ground in a bead mill to a required particle size (Dv50) of less than 5 µm to obtain a concentrated mill base.
[077] High shear mixing of the rheology modifier and half quantity of the anti-freeze to the concentrated mill base produces the final homogenous solution. Several compositions were prepared with varying amounts of the ingredients. The details are summarized in Table 1 below.
[078] Example 1: Chlorantraniliprole 10%+ Emamectin Benzoate 4% + Indoxacarb 10% SC
[079] Example 2: Chlorantraniliprole 30% + Emamectin Benzoate 1% + Indoxacarb 3% SC
[080] Example 3: Chlorantraniliprole 0.5% + Emamectin Benzoate 10% + Indoxacarb 16% SC
[081] Table 1: SC formulations
Description Example 1
(in wt.%) Example 2
(in wt.%) Example 3
(in wt.%)
Chlorantraniliprole Technical 10.7 32.0 0.6
Emamectin Benzoate Technical 4.4 1.1 10.8
Indoxacarb Technical 20.0 6.2 31.5
Acrylic Copolymer (dispersant) 1.0 2.0 1.0
Non-ionic surfactant blend (wetting agent) 1.0 1.0 1.0
Tristyrylphenol ethoxylate (dispersant) 5.0 5.0 3.0
Sodium lignosulphonate (dispersant) 2.0 2.0 1.0
Propane-1,2-diol (anti-freezing agent) 5.0 3.0 3.0
1-2 benzisothiazolin 3- one (preservative) 0.1 0.1 0.1
Polydimethylsiloxane (defoamer) 0.5 0.5 0.5
Carboxymethyl Cellulose (2%) (rheology modifier) 5.0 5.0 5.0
D I Water (diluent) 45.2 42.1 42.5
Total 100 100 100

[082] Physical characteristics of examples 1 -3 have been summarized in Table 2 below:
[083] Table 2: Physical parameter evaluation of SC formulations
Description Example 1 Example 2 Example 3
Analytical output: RT HT RT HT RT HT
Chlorantraniliprole A. I 10.4 10.28 30.1 30.04 0.53 0.5
Emamectin Benzoate A. I 4.16 4 1.01 1 10.2 10.2
Indoxacarb A. I 10.38 10.23 3.3 3.1 16.4 16.27
Suspensibility by Gravity % 92.72 80.16 87.65 77.63 89.48 82.35
Persistent foam (ml) 4 6 4 6 6 6
pH (1% aq. solution) 6.14 6.14 6.5 6.7 6.2 6.3
Specific gravity 1.162 1.15 1.19 1.18 1.12 1.11
Wet sieve Test (Retention on 45 µ) 0.06 0.08 0.08 0.1 0.06 0.07

[084] From Table 2 it may be observed that Examples 1-3 are stable and there is no appreciable drop in suspensibility parameter even after accelerated storage study. That there was no significant decrease in the amount of the actives after the storage period, thus indicating that the pesticidal composition prepared of the present disclosure were stable.
[085] Example 4: Chlorantraniliprole 2% + Emamectin Benzoate 0.8% + Profenofos 20% WG
[086] Example 5: Chlorantraniliprole 5% + Emamectin Benzoate 2% + Profenofos 50% WG
Description Example 4
(in wt.%) Example 5
(in wt.%)
Chlorantraniliprole Technical 2.1 5.3
Emamectin Benzoate Technical 0.85 2.11
Profenofos Technical 21.1 52.6
Sodium isopropyl naphthalene sulfonate (wetting agent) 5.0 5.0
Alkyl naphthalene formaldehyde sulfonate sodium salt (dispersing agent) 3.0 3.0
Silicon dioxide (thickening agent) 20.0 20.0
Dextrose (filler) 5.0 5.0
Clay (rheology modifier) 42.5 6.5
Polydimethylsiloxane emulsion (defoamer) 0.5 0.5
Total 100 100

[087] Bioefficacy and phytotoxicity data
[088] The present invention composition was evaluated for bioefficacy and phytotoxicity for pest complex (Thrips, Spodopetra spp) in Chilli. The findings of the evaluation are summarized below.
[089] Bioefficacy: A ready mix of three-way combinations, Example 1: Chlorantraniliprole 10%, Emamectin Benzoate 4% and Indoxacarb 10% SC were tested at specified concentrations against the pest complex (Thrips, Spodoptera spp.) in Chilli.
[090] Possible tank mix combinations: Chlorantraniliprole 18.50 % SC, Emamectin Benzoate 5% SG, Indoxacarb 15.80% EC, Solo individual insecticides Chlorantraniliprole 18.50 % SC, Emamectin Benzoate 5% SG, Indoxacarb 15.80% EC, and untreated control were tested. All the insecticides were applied as foliar spray using a Knapsack Sprayer fitted with a hollow cone nozzle. The spraying schedule was initiated at the onset of individual pest infestations in the field and applications were done at 10-day intervals.
[091] Pest infestations for the individual pests (Thrips, and Spodoptera spp.) were recorded on randomly tagged 20 plants in each treatment at specified intervals as per the protocol. The appearance of pest infestation was recorded before the 1st spray and then at 3, 5 and 10 days after subsequent sprays. The Bioefficacy treatment details are listed below in Table 3.
[092] Table 3: Bio-efficacy Treatment Details
Tr. No Treatment Details Dose
(g a.i./ha) Dose
(ml or g/ha)

T1 Chlorantraniliprole 10%+ Emamectin Benzoate 4% + Indoxacarb 10% SC (Example 1) 25+ 10+25 250
T2 Chlorantraniliprole 18.50 % SC + Emamectin Benzoate 5% SG (Tank Mixture of market std) 27.7+ 11 150+ 220
T3 Chlorantraniliprole 18.50 % SC + Indoxacarb 15.80% EC (Tank Mixture) 27.7+ 31.6 150+ 200
T4 Emamectin Benzoate 5% SG + Indoxacarb 15.80% EC (Tank Mixture) 11+ 31.6 220+200
T5 Chlorantraniliprole 18.50 % SC + Emamectin Benzoate 5% SG + Indoxacarb 15.80% EC (Tank Mixture) 27.7+ 11+ 31.6 150+ 220+ 200
T6 Chlorantraniliprole 18.50 % SC (market standard) 27.7 150
T7 Emamectin Benzoate 5% SG (market standard) 11 220
T8 Indoxacarb 15.80% EC 31.6 200
T9 Untreated

[093] Table 4: Bio-efficacy of different Insecticide treatments against Thrips
S.No. Product Dose/ha No of Thrips/plant (Average of 20 plants)
(g a.i.) Formulation Before Spray 3 DAA1
1st spray 5 DAA1
1st Spray 10 DAA1
1st Spray 3 DAA2
2nd Spray 5 DAA2
2nd Spray 10 DAA2
2nd Spray
(g or ml)
T1 Chlorantraniliprole 10%+ Emamectin Benzoate 4% + Indoxacarb 10% SC (Example 1) 25+ 10+25 250 6.5 3.5 2.9 2.2 2.4 2.1 2.9
T2 Chlorantraniliprole 18.50 % SC + Emamectin Benzoate 5% SG (Tank Mixture of market std) 27.7+ 11 150+ 220 6.7 3.6 3.1 3.1 2.5 2.6 3.6
T3 Chlorantraniliprole 18.50 % SC + Indoxacarb 15.80% EC (Tank Mixture) 27.7+ 31.6 150+ 200 6.2 7.3 8.3 12.2 11.0 12.3 13.4
T4 Emamectin Benzoate 5% SG + Indoxacarb 15.80% EC (Tank Mixture) 11+ 31.6 220+200 6.3 3.7 3.3 3.4 3.3 3.2 3.4
T5 Chlorantraniliprole 18.50 % SC + Emamectin Benzoate 5% SG + Indoxacarb 15.80% EC (Tank Mixture) 27.7+ 11+ 31.6 150+ 220+ 200 6.0 3.8 3.1 2.4 3.2 3.1 3.5
T6 Chlorantraniliprole 18.50 % SC (market standard) 27.7 150 6.4 7.5 8.2 12.3 10.3 11.5 12.2
T7 Emamectin Benzoate 5% SG (market standard) 11 220 6.5 3.8 3.3 3.2 3.4 3.2 3.4
T8 Indoxacarb 15.80% EC 31.6 200 6.2 6.9 9.1 12.4 11.3 12.6 13.3
T9 Untreated 6.1 7.1 10.3 13.0 13.8 14.3 15.5
CD at 0.05% NS 0.54 0.63 0.8 0.63 0.64 0.35

[094] The results presented in Table 4 indicate uniformity of trial plot across all the treatments as uniform pest infestation was observed during trial initiation. 10 days after 1st application, the highest incidence of thrips was recorded in control (13 Thrips/plant). All the insecticide treatments except T3, T6 and T8 reduced the pest incidence than untreated control, but the significant lowest pest incidence was observed in T1 (2.2 thrips/plant) superior to all other treatments.
[095] 10 days after second application also, similar trend was observed with T1 having minimum thrips incidence (2.9 thrips/plant), which was significantly superior to all other treatments. Untreated plot had maximum population (15.5 Thrips/plant).

[096] Table 5: Bio-efficacy of Insecticide treatments against Spodoptera spp.
S.No. Product Dose/ha Count of larva/plant (Average of 20 plants)
(g a.i.) Formulation Before Spray 3 DAA1
1st spray 5 DAA1
1st Spray 10 DAA1
1st Spray 3 DAA2
2nd Spray 5 DAA2
2nd Spray 10 DAA2
2nd Spray
(g or ml)
T1 Chlorantraniliprole 10%+ Emamectin Benzoate 4% + Indoxacarb 10% SC (Example 1) 25+ 10+25 250 2.4 2.1 2.9 3.2 1.9 1.9 1.9
T2 Chlorantraniliprole 18.50 % SC + Emamectin Benzoate 5% SG (Tank Mixture of market std) 27.7+ 11 150+ 220 2.5 2.4 3.5 3.8 2.0 2.4 2.4
T3 Chlorantraniliprole 18.50 % SC + Indoxacarb 15.80% EC (Tank Mixture) 27.7+ 31.6 150+ 200 2.6 2.3 3.2 3.7 2.0 2.4 2.5
T4 Emamectin Benzoate 5% SG + Indoxacarb 15.80% EC (Tank Mixture) 11+ 31.6 220+200 2.0 2.2 3.6 3.9 2.0 2.5 2.3
T5 Chlorantraniliprole 18.50 % SC + Emamectin Benzoate 5% SG + Indoxacarb 15.80% EC (Tank Mixture) 27.7+ 11+ 31.6 150+ 220+ 200 2.5 2.2 3.0 3.3 1.9 2.4 2.5
T6 Chlorantraniliprole 18.50 % SC (market standard) 27.7 150 2.4 2.4 3.2 3.5 1.8 2.3 2.6
T7 Emamectin Benzoate 5% SG (market standard) 11 220 2.1 3.1 3.5 3.8 1.9 2.4 2.7
T8 Indoxacarb 15.80% EC 31.6 200 2.3 3.2 3.8 4.0 2.0 2.4 2.6
T9 Untreated 2.2 4.6 6.3 8.8 9.5 11.3 11.8
CD at 0.05% NS 0.23 0.52 0.46 0.12 0.44 0.24

[097] The results presented in Table 5 show that before trial initiation all the treatments had almost equal level of Spodoptera pest infestation. 10 days after the 1st application, the highest larval count was recorded in untreated plot (8.8 larvae/plant) which was significantly higher than rest all the treatments. Treatment T1, having the least infestation (3.2 larva/plant) was superior to all other treatments. 10 days after the second application also had the similar trend with T1 being the most superior treatment (1.9 larva)). The untreated plot had serious infestation level (11.8 larvae/plant).
[098] Phytotoxicity
[099] Observations were taken on damage caused to plant (if any) by the application of different treatments taking into the account phytotoxic symptoms viz. leaf injury on tips and leaf surface, wilting, vein clearing, necrosis, epinasty and hyponasty on ten plants per plot. The observations were recorded before spray and 1, 3, 5, 7, 10 and 15th day after applications. For Phytotoxicity study on leaf injury on tips and leaf surface, the Scale (0-10) used is given below.
[0100] Table 6: Phytotoxicity Rating Scale (PRS)
Crop response/ Crop injury Rating
0-00 0
1-10% 1
11-20% 2
21-30% 3
31-40% 4
41-50% 5
51-60% 6
61-70% 7
71-80% 8
81-90% 9
91-100% 10

[0101] Analysis of variance was calculated by using OPSTAT Computer Software Program.
[0102] Table 7: Phytotoxicity Treatment Details
S.No. Product Dose/ha
(g a.i.) Formulation
(g or ml)
T1 Chlorantraniliprole 10%+ Emamectin Benzoate 4% + Indoxacarb 10% SC (Example 1) 25+ 10+25 250
T2 Chlorantraniliprole 10%+ Emamectin Benzoate 4% + Indoxacarb 10% SC 50+ 20+50 500
T3 Chlorantraniliprole 18.50 % SC + Emamectin Benzoate 5% SG + Indoxacarb 15.80% EC (Tank Mixture) 27.7+ 11+ 31.6 150+ 220+ 200
T4 Chlorantraniliprole 18.50 % SC + Emamectin Benzoate 5% SG + Indoxacarb 15.80% EC (Tank Mixture) 55.4+ 22+ 63.2 300+ 440+ 400
T5 Untreated - -

[0103] Table 8: Phyto-toxicity effect of different Insecticide treatments on Chilli
Tr. No. Treatment Details
Dose *Phytotoxicity (Based on 0-10 Phytotoxicity Rating Scale)
g a.i./ha ml or g/ha Before Spray Days after application (DAA)
1 3 5 7 10 15
T1 Chlorantraniliprole 10%+ Emamectin Benzoate 4% + Indoxacarb 10% SC (Example 1) 25+ 10+25 250 0 0 0 0 0 0 0
T2 Chlorantraniliprole 10%+ Emamectin Benzoate 4% + Indoxacarb 10% SC 50+ 20+50 500 0 0 0 0 0 0 0
T3 Chlorantraniliprole 18.50 % SC + Emamectin Benzoate 5% SG + Indoxacarb 15.80% EC (Tank Mixture) 27.7+ 11+ 31.6 150+ 220+ 200 0 0 0 0 0 0 0
T4 Chlorantraniliprole 18.50 % SC + Emamectin Benzoate 5% SG + Indoxacarb 15.80% EC (Tank Mixture) 55.4+ 22+ 63.2 300+ 440+ 400 0 0 0 0 0 0 0
T5 Untreated - - 0 0 0 0 0 0 0
*For phytotoxic symptoms- Leaf injury on tips and Leaf surface, Wilting, Vein Clearing, Necrosis, Epinasty and Hyponasty

[0104] (Table 8) The three-way ready-mix combination was sprayed at doses of X (250 ml/ha) and 2X (500 ml/ha) to check the phytotoxic effects like leaf injury on tips/surface, vein clearing, wilting, necrosis, hyponasty and epinasty on the Potato crop. The observations on these phytotoxicity parameters were observed on before spray and at 1, 3, 5, 7, 10 and 15 days after application. But there was no phytotoxicity observed on Chilli crop after spraying. There was even no adverse effect noticed on the crop in the field applied with tank mix insecticide combinations at highest dose of 300+440+400 ml/ha.
[0105] Crop yield was assessed by combining the fruit harvest obtained at different pickings for whole plots for each replication. The yield was expressed as Q/Ha in below table.
[0106] Table 9: Yield
S.No. Product Dose/ha
(g a.i) Formulation
(g or ml) Yield
(Q/ha)
T1 Chlorantraniliprole 10%+ Emamectin Benzoate 4% + Indoxacarb 10% SC (Example 1) 25+ 10+25 250 4.5
T2 Chlorantraniliprole 18.50 % SC + Emamectin Benzoate 5% SG (Tank Mixture of market std) 27.7+ 11 150+ 220 4.0
T3 Chlorantraniliprole 18.50 % SC + Indoxacarb 15.80% EC (Tank Mixture) 27.7+ 31.6 150+ 200 4.0
T4 Emamectin Benzoate 5% SG + Indoxacarb 15.80% EC (Tank Mixture) 11+ 31.6 220+200 4.0
T5 Chlorantraniliprole 18.50 % SC + Emamectin Benzoate 5% SG + Indoxacarb 15.80% EC (Tank Mixture) 27.7+ 11+ 31.6 150+ 220+ 200 4.2
T6 Chlorantraniliprole 18.50 % SC (market standard) 27.7 150 3.9
T7 Emamectin Benzoate 5% SG (market standard) 11 220 3.6
T8 Indoxacarb 15.80% EC 31.6 200 3.2
T9 Untreated 2.9
CD at 0.05% 0.23

[0107] Table 9 depicts the yield that was found in the respective treatments after collating the different pickings in Chili. It was found that T1 had maximum Yield (4.5Q/Ha). These treatments were superior to other treatments. The untreated plot had the minimum Yield (2.9 Q/Ha).
[0108] The three-way ready-mix combination of insecticides (Chlorantraniliprole 10%+ Emamectin Benzoate 4% + Indoxacarb 10% SC) effectively controls the pest complexes in Chilli. The efficacy of the tested insecticides was far superior to market standards, Chlorantraniliprole 18.50 % SC, Emamectin Benzoate 5% SG, and Indoxacarb 15.80% EC.
[0109] Advantageously, the tested insecticides significantly increased the yield of Chilli crop without exhibiting any phytotoxic effects on chilli, even at double the recommended dosage. Overall, the three-way combination test insecticides demonstrated synergistic effect for controlling the pests. To mitigate resistance issues and minimize crop losses, the tested insecticides can be utilized safely and effectively compared to using solo insecticides or their three-way or two-way tank mix combinations alone.
[0110] The foregoing description of the invention has been set merely to illustrate the invention and is not intended to be limiting. While the present invention has been described with respect to certain embodiments, it will be apparent to those skilled in the art that various changes and modification may be made without departing from the scope of the invention as defined in the following claims. ,CLAIMS:WE CLAIM:
1. A synergistic insecticidal composition comprising:
a) a diamide insecticide as a first active ingredient;
b) an avermectin insecticide as a second active ingredient;
c) an oxadiazine insecticide or an organothiophosphate insecticide as a third active ingredient; and
d) agrochemically acceptable excipients.

2. The insecticidal composition as claimed in claim 1, wherein the diamide insecticide is selected from broflanilide, chlorantraniliprole, cyantraniliprole, cyhalodiamide, cyclaniliprole, flubendiamide, fluchlordiniliprole, tetrachlorantraniliprole, tetraniliprole, and tiorantraniliprole.

3. The insecticidal composition as claimed in claim 1, wherein the avermectin insecticide is selected from abamectin, doramectin, emamectin, eprinomectin, ivermectin, selamectin, and emamectin benzoate.

4. The insecticidal composition as claimed in claim 1, wherein the oxadiazine insecticide is Indoxacarb.

5. The insecticidal composition as claimed in claim 1, wherein the organothiophosphate insecticide is selected from azothoate, bromophos, bromophos-ethyl, chlorthiophos, cyanophos, cythioate, dicapthon, dichlofenthion, etaphos, famphur, fenchlorphos, fenitrothion, fensulfothion, fenthion, fenthion-ethyl, heterophos, jodfenphos, mesulfenfos, parathion, parathion-methyl, phosnichlor, profenofos, prothiofos, sulprofos, temephos, trichlormetaphos-3, trifenofos, and xiaochongliulin.

6. The insecticidal composition as claimed in claim 1, wherein the agrochemically acceptable excipients are selected from wetting agent, dispersing agent, adjuvants / emulsifiers, polymeric surfactants, antifoam agents, rheology modifiers, antifreeze agent, preservatives, thickeners, binders, stabilizing agents, film forming agents, fillers, diluents, disintegrating agents, and combinations thereof.

7. The insecticidal composition as claimed in claim 1, wherein the insecticidal composition is formulated in a dosage form selected from suspension concentrate (SC) formulation, Wettable Powder (WP), Water Dispersible Granules (WG), Capsule Suspension (CS), Suspoemulsion (SE), Oil Dispersion (OD), Flowable suspension (FS), water dispersible powder for slurry treatment (WDP), powder for dry seed treatment (DS), Flowable for seed treatment (FS), Emulsiable Concentrate (EC), Emulsion in water (EW), Dual emulsion, Capsule suspension with suspension concentrate (ZC), Capsule suspension with emulsion (ZE), and Capsule suspension with emulsion in water (ZW).

8. The insecticidal composition as claimed in claim 1, wherein the said composition comprises:
a) 0.1% to 60% wt.% of the diamide insecticide as the first active ingredient;
b) 0.1% to 30% wt.% of the avermectin insecticide as the second active ingredient;
c) 1% to 65% wt.% of the oxadiazine insecticide or the organothiophosphate insecticide as the third active ingredient; and
d) agrochemically acceptable excipients,
wherein the wt.% is based on the total weight of the composition.

9. A method for preparing the synergistic insecticidal composition as claimed in claims 1 to 8 comprising mixing the following: diamide insecticide as the first active ingredient, avermectin insecticide as the second active ingredient, oxadiazine insecticide or organothiophosphate insecticide as the third active ingredient, and agrochemically acceptable excipients.

10. The method as claimed in claim 9, wherein the method comprises the following sub-steps:
a) mixing the agrochemically acceptable excipients to obtain an aqueous media,
b) mixing the first active ingredient, the second active ingredient, and the third active ingredient, with the aqueous media to obtain a pre-mix slurry, and
c) wet grinding the pre-mix slurry to obtain a particle size distribution Dv50 of less than 5 microns.

11. A method of controlling and eliminating insects from a pre-determined area, said method comprising applying to a pest, to a locus of a pest or to a plant susceptible to attack by a pest, an effective amount of the synergistic insecticidal composition as claimed in claims 1 to 8.

Dated this 2nd day of June 2023.
Indofil Industries Limited India
By their Agent & Attorney

(Nisha Austine)
of Khaitan & Co
Reg. No. IN/PA-1390