DESC:TECHNICAL FIELD
[0001] The present invention relates to a synergistic combination of anthranilic diamide and pyrethroid insecticides for insect control in the field of agriculture. In particular, this invention pertains to an improved stable insecticidal composition comprising combination of chlorantraniliprole and fenpropathrin for insect control in the field of agriculture.

BACKGROUND
[0002] The background description includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.
[0003] This invention pertains to synergistic combination of anthranilic diamide and pyrethroid insecticides for protecting agricultural crops from infestation of insect pests. Chlorantraniliprole is a ryanoid receptor activator and belongs to a class of selective insecticides featuring a novel mode of action to control a range of pests belonging to the order Lepidoptera (moth) and some other Coleoptera (beetle), Diptera (fly) and Isoptera (termite) species. Pyrethroids, on the other hand, belong to a class of widely used chemicals, synthesized derivatives of natural insecticidal pyrethrins. These have been increasingly used in agriculture and household due to their outstanding potency against insect pests. Fenpropathrin, a pyrethroid, insecticide cum acaricide is used to control many species of insects. The diverse properties of both the insecticides were used to develop a synergistic combination viz., systemic efficacy of Chlorantraniliprole when combined with Fenpropathrin, a non-systemic and contact synthetic pyrethroid, works with twin actions. Chlorantraniliprole opens muscular calcium channels, in particular the ryanodine receptor, rapidly causing paralysis and death of insect pests. The mode of action of Fenpropathrin is similar to natural pyrethrum and synthetic pyrethroids, wherein it interferes with the kinetics of voltage gated sodium channels causing paralysis and death of the insects.
[0004] The two chemicals having different mode of actions / properties are combined in a particular ratio to show greater insecticidal activity coupled with better bioefficacy than that of their individual uses. The combination products based on either Chlorantraniliprole or Fenpropathrin are available in the market. Development of combination products has been in existence for long. However, choosing two active ingredients at the optimum strengths delivering better results than its individual components require a lot of precision, analytical ability and dedicated research & development efforts. After many years of research, the inventors of the present invention were able to develop a novel formulation of the composition comprising Chlorantraniliprole and Fenpropathrin. The formulation proved to be novel in many aspects: a) It was found to be effective against insect pests however, the same spectrum of efficacy was not achieved by its individual components. b) The formulation was found stable for two years. c) Both the individual molecules i.e. Chlorantraniliprole and Fenpropathrin belong to different chemical groups and have different mode of actions, which make them ideal combination partners for using in Integrated Pest Management (IPM) practices as well as resistance management strategies. d) This product has exhibited its bioefficacy against lepidopteran pests in paddy (grains), soybean (oilseed), brinjal (vegetable) and other crops grown in India. In view of above, the said formulation can be considered as novel and a boon to Indian Farmers reducing their crop losses.
[0005] Since chlorantraniliprole and fenpropathrin have different solubility profiles, the development of liquid water-based concentrate formulations is extremely difficult if the physical stability of the formulations is to be ensured. Attempts to prepare liquid water-based formulations of chlorantraniliprole and fenpropathrin are described in the patent document CN115281199A. This document focuses on developing an aqueous suspension concentrate (SC) of mixture of chlorantraniliprole and fenpropathrin. However, it has been found that liquid water-based formulations prepared with a combination of chlorantraniliprole and fenpropathrin, such as Suspension Concentrate (SC), have reduced product performance indexes, especially a low stability after shelf storage tests. Therefore, it is necessary to study and develop a new liquid water-based formulation to solve the technical problem of the long-term storage performance indexes of liquid formulations prepared from combination of chlorantraniliprole and fenpropathrin being reduced.
[0006] The present invention satisfies the existing needs, as well as others, and generally overcomes the deficiencies found in the prior art.
OBJECTS
[0007] An object of the present invention is to address the stability issues that occur when chlorantraniliprole and fenpropathrin are co-formulated in a single liquid water-based concentrate formulation.
[0008] It is also an object of the present invention to provide a liquid water-based formulation of a composition comprising chlorantraniliprole and fenpropathrin that has advantageously improved storage stability, without significant reduction in product performance indexes after long-term storage.
[0009] Further object of the present invention is to provide an improved liquid concentrate co-formulation of chlorantraniliprole and fenpropathrin that is safe while being highly effective in controlling crop damaging insects.
[0010] Still further object of the present invention is to provide a method of preparing a stable liquid water-based concentrate formulation of mixture of chlorantraniliprole and fenpropathrin.

SUMMARY
[0011] The above and other objects are met by the present invention which, in one aspect, provides a suspoemulsion (SE) formulation of chlorantraniliprole and fenpropathrin. Surprisingly, it has now been found that when the combination of chlorantraniliprole and fenpropathrin is formulated in the form of suspoemulsion (SE), a more storage-stable and more effective liquid water-based coformulation of chlorantraniliprole and fenpropathrin can be achieved than could previously be achieved with formulation approaches known in the art. Notably, and as demonstrated in more detail below, the inventors have discovered that the SE formulation presented herein addresses the stability problems associated with the suspension concentrate (SC) formulations of said active ingredients.
[0012] Accordingly, one aspect of the present invention is directed to a SE formulation comprising:
(i) a continuous water phase, comprising:
chlorantraniliprole;
a dispersing agent; and
water having chlorantraniliprole suspended therein; and
(ii) an oil phase emulsified in the continuous water phase, the oil phase comprising:
fenpropathrin; and
a solvent having fenpropathrin dissolved therein.
[0013] In some embodiments, the continuous water phase further includes one or more wetting agents and other additives.
[0014] In some embodiments, the oil phase is an oil-in-water emulsion (EW) phase, comprising:
fenpropathrin;
a solvent having fenpropathrin dissolved therein;
an emulsifier; and
water.
[0015] According to embodiments of the present disclosure, the SE formulation disclosed herein can further include one or more of the following excipients: an anti-foaming agent, an antifreeze agent, a biocide, a thickener, a suspending agent, an antioxidant, and a colorant.
[0016] Another aspect of the present invention is directed to a process for preparing a SE formulation, which comprises the steps of mixing an oil-in-water emulsion phase with a continuous water phase,
wherein the oil-in-water emulsion phase is prepared by mixing fenpropathrin, a water-insoluble solvent that solubilizes fenpropathrin, an emulsifier and water; and
wherein the continuous water phase is prepared by mixing chlorantraniliprole, a dispersing agent, a wetting agent, water and optionally one or more further agrochemically acceptable excipients, wherein the SE formulation comprises particles in the size range of from 0.1 micron to 25 microns.
[0017] Another aspect of the present invention is directed to a method of controlling an insect, which comprises applying the suspoemulsion formulation as disclosed herein to an agricultural area in need thereof. In some embodiments, the agricultural area is a field of a crop.
[0018] Various objects, features, aspects and advantages of the inventive subject matter will become more apparent from the following detailed description of preferred embodiments.

DETAILED DESCRIPTION
[0019] Insecticides are those substance(s) or a combination of substances whose primary function when applied to plants, seeds or rhizosphere is to control various types of insect pests, which are either directly harmful to crops or indirectly interrupt crop growth. Such impact on crops deprive them from nutrient uptake, growth, yield, nutrition efficiency, crop quality, etc. Such insecticide formulation could be used / applied on agricultural crops as a part of Integrated Pest Management practices to protect them from insect pests and thereby enhancing yields.
[0020] Synergism is the cooperative action encountered in combinations of two insecticides in which the combined activity of two compounds exceeds the sum of the activities of the compounds when used alone. Keeping this in view, the preferred formulation of the present invention was kept Suspo-emulsion (SE) by combining two active ingredients with different properties into one formulation, broadening the spectrum of activity.
[0021] The present invention relates to formulations having synergistically enhanced action and to a method of improving the health of plants by applying said formulations to the plants or the locus thereof. An important aspect of this invention is to primarily aim to protect crop from insect pests.
[0022] The results show the marked synergistic interaction of the compositions of the invention. A wide range of ratios of individual components were evaluated and it was found that the mortality of insect pests occurred due to synergistic effect of this composition (Chlorantraniliprole and Fenpropathrin) is unexpectedly greater than that to be expected from the added effects of the individual components. The synergistic compositions of this invention may be employed to control a variety of crop pests in Rice, Soybean and Brinjal. The formulation is prepared by incorporating suitable adjuvants, carriers and other ingredients in order to provide stability to the formulation for at least up to two years without impacting its bioefficacy parameters.
[0023] The term “insecticide” as used herein, refers to a compound that kills or materially inhibits the growth, proliferation, reproduction, or spread of insects.
[0024] The phrase “insecticidally effective amount” as used herein, refers to quantity of such a compound or combination of such compounds that is capable of killing or materially inhibiting the growth, proliferation, reproduction or spread of insects.
[0025] The term “plant” refers to all physical parts of a plant, including shoots, leaves, needles, stalks, stems, fruit bodies, fruits, seeds, roots, tubers and rhizomes.
[0026] As used herein, the term "locus" includes an area at which plant or plant part grows or is to be planted.
[0027] As used herein, the phrase "agrochemically acceptable excipients" means excipients which are known and accepted in the art for formation of formulations for agricultural or horticultural use.
[0028] The expression “controlling insects” as used herein, means killing insects, or preventing insects to develop or to grow, or preventing insects to infect or infest, or inhibiting the rate and extent of an insect attack, or delaying the onset of an insect attack.
[0029] As used herein, the term “insect” refers to any species injurious to plants or plant products.
[0030] The present invention provides a suspoemulsion (SE) formulation comprising combination of chlorantraniliprole and fenpropathrin. The inventors have surprisingly found that when the combination of chlorantraniliprole and fenpropathrin is formulated in the form of suspoemulsion (SE), a more storage-stable and more effective liquid water-based coformulation of chlorantraniliprole and fenpropathrin can be achieved than could previously be achieved with formulation approaches known in the prior art. As mentioned above, the prior art describes suspension concentrates (SC) of chlorantraniliprole and fenpropathrin which, however, suffer from shelf stability issues. In order to address the stability problems associated with suspension concentrates (SC), a suspoemulsion (SE) formulation has been developed which exhibits advantageously improved storage stability, without significant reduction in product performance indexes, such as physical stability and suspension/dispersion stability after long-term storage. Thus, the stability problems that occur when the combination of chlorantraniliprole and fenpropathrin is formulated in the form of suspension concentrates (SC) are substantially avoided.
[0031] The suspoemulsion (SE) formulation disclosed herein comprises a continuous water phase which contains emulsified oil droplets and solids in suspension. The oil droplets comprise the liquid active ingredient fenpropathrin that is essentially solubilized in a water-insoluble solvent. The solid active ingredient chlorantraniliprole is suspended in the continuous water phase due to its low solubility in water.
[0032] Accordingly, some embodiments of the present invention describe a SE formulation which comprises:
(i) a continuous water phase, comprising:
chlorantraniliprole;
a dispersing agent; and
water having chlorantraniliprole suspended therein; and
(ii) an oil phase emulsified in the continuous water phase, the oil phase comprising:
fenpropathrin; and
a solvent having fenpropathrin dissolved therein.
[0033] As indicated above, the continuous water phase includes a dispersing agent in an amount sufficient to disperse the chlorantraniliprole in the continuous water phase. Non-limiting examples of the dispersing agent include methyl methacrylate graft copolymer with polyethylene glycol, alkoxylated polyarylphenol phosphate esters or salts or acid forms thereof, lignosulphonates, phenyl naphthalene sulphonates, ethoxylated alkyl phenols, ethoxylated fatty acids, alkoxylated linear alcohols, polyaromatic sulfonates, sodium alkyl aryl sulfonates, maleic anhydride copolymers, phosphate esters, condensation products of aryl/alkyl sulphonic acids and formaldehyde, addition products of ethylene oxide and fatty acid esters, sulfonates of condensed naphthalene, lignin derivatives, naphthalene formaldehyde condensates, polycarboxylates, sodium alkyl benzene sulfonates, salts of sulfonated naphthalene, ammonium salts of sulfonated naphthalene, salts of polyacrylic acids, salts of phenol sulfonic acids, and mixtures thereof. The dispersing agent is present in an amount of from about 0.1% to about 30% by weight, preferably from 0.5% to about 10% by weight, based on a total weight of the SE formulation.
[0034] In especially preferred embodiments, methyl methacrylate graft copolymer with polyethylene glycol is used as the dispersing agent.
[0035] According to embodiments of the present invention, the continuous water phase can further include one or more wetting agents and other additives. In some embodiments, the continuous water phase further comprises a wetting agent. Non-limiting examples of the wetting agent include alkyl phenol ethoxylate, fatty oil ethoxylate, fatty alcohol ethoxylate, phenyl naphthalene sulphonates, alkyl naphthalene sulfonates, sodium alkyl naphthalene sulfonate, sodium salt of sulfonated alkyl carboxylate, polyoxyalkylated ethyl phenols, polyoxyethoxylated fatty alcohols, polyoxyethoxylated fatty amines, lignin derivatives, alkane sulfonates, alkylbenzene sulfonates, salts of polycarboxylic acids, salts of esters of sulfosuccinic acid, alkylnaphthalenesulfonates, alkylbenzenesulfonates, alkylpolyglycol ether sulfonates, alkyl ether phosphates, alkyl ether sulfates and alkyl sulfosuccinic monoesters, and mixtures thereof. Wetting agent is present in an amount of from about 0.1% to about 25% by weight, preferably from 0.5% to about 10% by weight, based on a total weight of the SE formulation.
[0036] In especially preferred embodiments, fatty alcohol ethoxylate is used as the wetting agent.
[0037] In some embodiments, the continuous water phase comprises water in an amount of from about 5% to about 95% by weight, preferably from about 10% to about 70% by weight, more preferably from about 30% to about 60% by weight, based on a total weight of the SE formulation.
[0038] As indicated above, the oil phase includes a solvent, particularly a water-insoluble solvent, to dissolve fenpropathrin in the oil phase. Suitable solvents are aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, ketones, esters, ethers, mineral oils, vegetable oils, and mixtures thereof. Solvent can be used in amounts ranging from 2% to 40% by weight, preferably from 5% to 30% by weight, based on a total weight of the SE formulation.
[0039] In one embodiment, an aromatic hydrocarbon, such as Solvent C9, is used as the solvent to dissolve fenpropathrin.
[0040] In some embodiments, the oil phase comprises an emulsion wherein fenpropathrin is an emulsified component. In certain embodiments, the oil phase is an oil-in-water emulsion (EW) phase, comprising:
fenpropathrin;
a solvent having fenpropathrin dissolved therein;
an emulsifier; and
water.
[0041] Suitable emulsifiers for use in the oil-in-water emulsion (EW) phase include ionic and non-ionic emulsifiers, such as fatty acid esters, fatty alcohol esters, vegetable oil ethoxylates, ethers, alkyl sulphonates, aryl sulphonates and mixtures thereof. Emulsifier is usually present in an amount of from 0.1% to 20% by weight, preferably from 0.5% to about 15% by weight, based on a total weight of the SE formulation.
[0042] In especially preferred embodiments, castor oil ethoxylate is used as the emulsifier.
[0043] In some embodiments, water is present in the oil-in-water emulsion (EW) phase in amounts ranging from about 5% to about 80% by weight, preferably from about 10% to about 70% by weight of the EW phase.
[0044] In some embodiments, the SE formulation disclosed herein is a combination of an oil-in-water emulsion (EW) of fenpropathrin and an aqueous suspension concentrate of chlorantraniliprole.
[0045] The active ingredients chlorantraniliprole and fenpropathrin may be present in the SE formulation in a wide range of amounts. In some preferred embodiments, the formulation comprises, by weight, from 0.1% to 50% of chlorantraniliprole and from 1% to 70% of fenpropathrin, based on the total weight of the SE formulation. Preferably, chlorantraniliprole is used in the range of 1% to 20% by weight and fenpropathrin is used in the range of 1% to 30% by weight of the SE formulation. In some embodiments, chlorantraniliprole is present in an amount of 4% by weight and fenpropathrin is present in an amount of 10% by weight, based on the total weight of the SE formulation. In some embodiments, chlorantraniliprole is present in an amount of 2% by weight and fenpropathrin is present in an amount of 8% by weight, based on the total weight of the SE formulation. In some embodiments, chlorantraniliprole is present in an amount of 5% by weight and fenpropathrin is present in an amount of 12.5% by weight, based on the total weight of the SE formulation.
[0046] According to embodiments of the present invention, the SE formulation disclosed herein can further include at least one excipient selected from an anti-foaming agent, an antifreeze agent, a biocide, a thickener, a suspending agent, an antioxidant, and a colorant.
[0047] Suitable anti-freezing agents for use in the SE formulation include organic solvents which are completely miscible with water, such as ethylene glycol, propylene glycol, other glycols, or glycerine. Anti-freezing agent is present in an amount of from about 0.1% to about 25% by weight, preferably from 0.5% to about 15% by weight, based on a total weight of the SE formulation. In especially preferred embodiments, glycerine (glycerol) is used as the anti-freezing agent.
[0048] Suitable anti-foaming agents for use in the SE formulation include all substances which can normally be used for this purpose in agrochemical compositions. Particularly preferred anti-foaming agents are silicone anti-foaming agents such as polydimethylsiloxane, and perfluroalkylphosphonic acids. Preferably, polydimethylsiloxane is used and is present in an amount of from about 0.01% to about 5% by weight based on a total weight of the SE formulation.
[0049] Suitable biocides include 1,2-benzisothiazolin-3-one, 5-chloro-2-methyl-2H-isothiazol-3-one, 1,2-benzisothiazol-3(2H)-one, 2-methyl-2H-isothiazol-3-one, formaldehyde, and mixtures thereof. Biocides may be present in an amount of from about 0.01% to about 5% by weight based on a total weight of the SE formulation.
[0050] The suspending agent can be selected from magnesium aluminium silicate, modified hydrophobic silica, colloidal silica, precipitated silica, hydrophobic silica powder and mixtures thereof. Preferably, the suspending agent is magnesium aluminium silicate. The suspending agent may preferably be used in an amount of from about 0.1% to about 10% by weight, preferably from 0.1% to about 6% by weight based on a total weight of the SE formulation.
[0051] Suitable thickeners for use in the formulation include all substances which can normally be used for this purpose in agrochemical compositions. Examples include xanthan gum, polyvinyl alcohol, cellulose and its derivatives, hydrated clay minerals, magnesium aluminium silicates and mixtures thereof. Preferably, thickener is present in an amount of from about 0.01% to about 10% by weight, more preferably from 0.05% to about 8% by weight, based on a total weight of the SE formulation. Preferably, xanthan gum is used as the thickener.
[0052] According to an embodiment, the SE formulation comprises particles in the size range of 0.1 micron to 25 microns. According to an embodiment, the SE formulation comprises particles in the size range of 0.1 micron to 20 microns. According to an embodiment, the SE formulation comprises particles in the size range of 0.1 micron to 15 microns. According to an embodiment, the SE formulation comprises particles in the size range of 0.1 micron to 10 microns.
[0053] The SE formulation according to the present invention is typically a liquid that has a viscosity of from 10 cps to 3000 cps. According to an embodiment, viscosity of the SE formulation is determined as per CIPAC MT-192. A sample is transferred to a standard measuring system. The measurement is carried out under different shear conditions and the apparent viscosities are determined. During the test, the temperature of the liquid is kept constant.
[0054] According to an embodiment, the SE formulation has a viscosity at 25° C. of about 10 cps to about 3000 cps. According to an embodiment, the SE formulation has a viscosity at 25° C. of about 10 cps to about 2500 cps. According to an embodiment, the SE formulation has a viscosity at 25° C. of about 10 cps to about 2000 cps. According to an embodiment, the SE formulation has a viscosity at 25° C. of about 10 cps to about 1500 cps. According to an embodiment, the SE formulation has a viscosity at 25° C. of about 10 cps to about 1200 cps. According to an embodiment, the SE formulation has viscosity at 25° C. of about 10 cps to about 500 cps. According to an embodiment, the SE formulation has a viscosity at 25° C. of about less than 500 cps. According to an embodiment, the SE formulation has viscosity at 25° C. of about 10 cps to about 400 cps. According to an embodiment, the SE formulation has viscosity at 25° C. of about 10 cps to about 300 cps.
[0055] According to an embodiment, the liquid SE formulation of the present invention is easily pourable. The pourability is the measure of percent of residue.
[0056] In some embodiments, the SE formulation disclosed herein comprises, based on a total weight of the SE formulation:
(i) a continuous water phase, comprising:
chlorantraniliprole;
a dispersing agent;
a wetting agent; and
water having chlorantraniliprole suspended therein; and
(ii) an oil-in-water emulsion (EW) phase emulsified in the continuous water phase, the EW phase comprising:
fenpropathrin;
a solvent having fenpropathrin dissolved therein;
an emulsifier; and
water.
[0057] In some embodiments, the SE formulation disclosed herein comprises, based on a total weight of the SE formulation:
(i) a continuous water phase, comprising:
chlorantraniliprole;
a dispersing agent;
a wetting agent;
an antifreeze agent;
an antifoam agent;
a suspending agent; and
water having chlorantraniliprole suspended therein; and
(ii) an oil-in-water emulsion (EW) phase emulsified in the continuous water phase, the EW phase comprising:
fenpropathrin;
a solvent having fenpropathrin dissolved therein;
an emulsifier; and
water.
[0058] The present invention also provides a process for preparing a suspoemulsion (SE) formulation which comprises the step of mixing an oil-in-water emulsion phase with a continuous water phase,
wherein the oil-in-water emulsion phase is prepared by mixing fenpropathrin, a water-insoluble solvent that solubilizes fenpropathrin, an emulsifier and water; and
wherein the continuous water phase is prepared by mixing chlorantraniliprole, a dispersing agent, a wetting agent, water and optionally one or more further agrochemically acceptable excipients, wherein the SE formulation comprises particles in the size range of from 0.1 micron to 25 microns.
[0059] Some embodiments of the present invention describe a process for preparing a suspoemulsion (SE) formulation which comprises the steps of mixing an oil-in-water emulsion phase with a continuous water phase to obtain a mixture, and mixing a quantity of an aqueous thickener solution into the mixture under continuous agitation,
wherein the oil-in-water emulsion phase is prepared by mixing fenpropathrin, a water-insoluble solvent that solubilizes fenpropathrin, an emulsifier and water; and
wherein the continuous water phase is prepared by mixing chlorantraniliprole, a dispersing agent, a wetting agent, water and optionally one or more further agrochemically acceptable excipients, wherein the SE formulation comprises particles in the size range of from 0.1 micron to 25 microns.
[0060] In some embodiments, the continuous water phase (aqueous suspension concentrate) is prepared by mixing chlorantraniliprole, a dispersing agent, a wetting agent, an antifreeze agent, an antifoam agent, a suspending agent and water under continuous agitation until the mixture is a homogeneous suspension. Subsequently, the suspension obtained is passed through a wet mill to obtain a desired particle size in the range of 0.1 to 25 microns. However, those skilled in the art will appreciate that it is possible to modify or alter or change the process or process parameters to obtain an aqueous suspension concentrate without departing from the scope of the present invention.
[0061] In addition to the stability of the SE formulation, the inventors surprisingly found that the SE formulation comprising chlorantraniliprole and fenpropathrin provides excellent control of insects and improves crop yield when the particles in the composition are present in the size range of 0.1 micron to 25 microns. The SE formulation comprising particles in the size range of 0.1 micron to 25 microns also enhances the physical nature of the formulation by providing improved suspensibility, dispersibility, improved viscosity, instant dispersion of actives on application via soil or foliar route which provides effective control of crop damaging insects.
[0062] The present invention also provides a method for controlling an insect, which comprises applying the suspoemulsion formulation as disclosed herein to an agricultural area in need thereof. In some embodiments, the agricultural area is a field of a crop. Crops in which the SE formulation according to the present invention can be used include soybeans, rice, wheat, cereals, oilseed rape, sugar beet, sugarcane, cotton, maize, corn, and vegetables in general. The SE formulation may be applied directly in the field or it may be applied as a fine spray after being added to tank water. The application rates of the co-formulation can vary over a wide range. The optimal application rates will depend on the crop to be treated, the stage of growth of the crop and of the insect, and the manner in which application is made, i.e., whether by spraying, irrigation, or other means. The total application rate of chlorantraniliprole and fenpropathrin can vary within a wide range, for example from 1 to 1000g per hectare (g/ha). Preferably, the application rate ranges from 2 to 650 g/ha, more preferably from 100 to 650 g/ha.
[0063] In some embodiments, the SE formulation according to the present invention is effective in controlling Lepidoptera – Yellow rice stem borer in Rice (Scirpophaga incertulas; Scirpophaga spp.), Lepidoptera - Leaf folder in Rice (Cnaphalocrocis medinalis Guenée; Cnaphalocrocis spp.), Lepidoptera – Fruit & Shoot borer in Brinjal (Leucinodes orbonalis; Leucinodes spp.) and Lepidoptera – Tobacco caterpillar in Soybean (Spodoptera litura; Spodoptera spp.).
[0064] The following list of embodiments forms part of the description.
[0065] Embodiment 1: A synergistic insecticidal composition comprising:
a. Chlorantraniliprole in the range of 0.1% to 50%;
b. Fenpropathrin in the range of 1% to 70%; and
c. at least one excipient in the range of 0.05% to 80%.
[0066] Embodiment 2: The synergistic insecticidal composition of one or more of Embodiments 1-8, wherein Chlorantraniliprole is 4.00 % w/w, and Fenpropathrin is 10.0 % w/w.
[0067] Embodiment 3: The synergistic insecticidal composition of one or more of Embodiments 1-8, wherein excipients are selected from the group consisting of wetting agent, thickener, sticking agent, anti-freezing agent, dispersant, anti-foam agent/defoamer, suspension aid, anti-microbial/anti-fungal/anti-bacterial agent, binders / stickers, buffering agent, and surfactant, etc.
[0068] Embodiment 4: The synergistic insecticidal composition of one or more of Embodiments 1-8, wherein the composition a suspoemulsion.
[0069] Embodiment 5: The synergistic insecticidal composition of one or more of Embodiments 1-8, wherein the said composition controls insect pests in paddy (rice), soybean and brinjal crops.
[0070] Embodiment 6: The synergistic insecticidal composition of one or more of Embodiments 1-8, wherein the said composition is used to control insect and/or pests in conventional, hybrid, and genetically modified varieties of crops like Rice, Soybean and Brinjal.
[0071] Embodiment 7: The synergistic insecticidal composition of one or more of Embodiments 1-8, wherein the said composition controls insects and/or pests from order including, Lepidoptera – Yellow rice stem borer in Rice (Scirpophaga incertulas; Scirpophaga spp.), Lepidoptera - Leaf folder in Rice (Cnaphalocrocis medinalis Guenée; Cnaphalocrocis spp.), Lepidoptera – Fruit & Shoot borer in Brinjal (Leucinodes orbonalis; Leucinodes spp.) and Lepidoptera – Tobacco caterpillar in Soybean (Spodoptera litura; Spodoptera spp.).
[0072] The foregoing description of the invention has been set merely to illustrate the invention and is not intended to be limiting. Since modifications of the disclosed embodiments incorporating the substance of the invention may occur to persons skilled in the art, the invention should be construed to include everything within the scope of the disclosure.
EXAMPLES
[0073] The present disclosure is further explained in the form of following examples. However, it is to be understood that the foregoing examples are merely illustrative and are not to be taken as limitations upon the scope of the invention. Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the scope of the invention.
Examples 1 to 3 - Preparation of Suspoemulsions (SE)
[0074] Suspoemulsion (SE) formulations were prepared according to the components and amounts shown in Table-1.
Table-1
Ingredients
Function Example 1
(% w/w) Example 2
(% w/w) Example 3
(% w/w)
Chlorantraniliprole Active ingredient 4.0 2.0 5.0
Fenpropathrin Active ingredient 10.0 8.0 12.5
Castor oil ethoxylate 40 EO Emulsifier 3.0 3.0 3.0
Solvent C9 Solvent 20.0 20.0 20.0
Methyl methacrylate graft copolymer with polyethylene glycol Dispersing agent 2.5 2.5 2.5
Fatty alcohol ethoxylate Wetting agent 2.5 2.5 2.5
Propylene glycol Antifreeze 4.0 4.0 4.0
Magnesium aluminium silicate Suspending agent 2.0 2.0 2.0
Polydimethylsiloxane Antifoam 0.5 0.5 0.5
1,2-benzisothiazol-3(2H)-one Biocide 0.1 0.1 0.1
Xanthan gum Thickener 0.2 0.2 0.2
Water Carrier QS to 100 QS to 100 QS to 100

Manufacturing Process
Step 1: Thickener solution preparation
Water, biocide and thickener were combined and mixed in a mixing vessel to form a thickener solution.
Step 2: Oil-in-water emulsion (EW) phase preparation
Fenpropathrin was dissolved in Solvent C9 and the resulting solution was added with the emulsifier. To this water was added and mixed with a high shear mixer to obtain the EW phase.
Step 3: Suspension concentrate (SC) phase preparation
Chlorantraniliprole, dispersing agent, wetting agent, antifreeze agent, antifoam agent, suspending agent and a required amount of water were combined and mixed in a mixing vessel to form a SC premix. This SC premix was then wet milled in a horizontal bead mill until the average particle size was under 3 microns to obtain the SC phase.
Step 4: Preparation of suspoemulsion (SE)
The EW phase was added to the SC phase under a continuous agitation for an optimum amount of time at room temperature. Then suitable quantity of thickener solution was added to the above mixture and continuously agitated until a homogeneous suspoemulsion was obtained.
Stability Study
[0075] The suspoemulsion (SE) formulations prepared in Examples 1 to 3 were subjected to storage stability study and the results are presented in Table 2.

Table 2
Parameter Example 1 Example 2
Initial At 54±2?C
(14 days) At 0±2?C
(7 days) Initial At 54±2?C
(14 days) At 0±2?C
(7 days)
Appearance White suspension White suspension White suspension White suspension White suspension White suspension
Chlorantraniliprole content (%) w/w 4.10 4.06 4.03 2.05 2.02 2.06
Fenpropathrin content (%) w/w 10.04 10.09 10.02 8.09 8.05 8.08
pH (1%) 6.66 6.44 6.14 6.76 6.84 6.70
Dispersion stability 0h: Initial dispersion complete 0h: Initial dispersion complete 0h: Initial dispersion complete 0h: Initial dispersion complete 0h: Initial dispersion complete 0h: Initial dispersion complete
0.5h 0.5h 0.5h 0.5h 0.5h 0.5h
Cream: Nil Cream: Nil Cream: Nil Cream: Nil Cream: Nil Cream: Nil
Free oil: Nil Free oil: Nil Free oil: Nil Free oil: Nil Free oil: Nil Free oil: Nil
Sediment: Nil Sediment: Nil Sediment: Nil Sediment: Nil Sediment: Nil Sediment: Nil
24h: Re-dispersion complete 24h: Re-dispersion complete 24h: Re-dispersion complete 24h: Re-dispersion complete 24h: Re-dispersion complete 24h: Re-dispersion complete
24.5h 24.5h 24.5h 24.5h 24.5h 24.5h
Cream.: Nil Cream.: Nil Cream.: Nil Cream.: Nil Cream.: Nil Cream.: Nil
0.5h: Cream: Nil 0.5h: Cream: Nil 0.5h: Cream: Nil 0.5h: Cream: Nil 0.5h: Cream: Nil 0.5h: Cream: Nil
Free oil: Nil Free oil: Nil Free oil: Nil Free oil: Nil Free oil: Nil Free oil: Nil
Sediment: Nil Sediment: Nil Sediment: Nil Sediment: Nil Sediment: Nil Sediment: Nil
Wet sieve test (% retention on 75 micron) 0.01 0.02 0.01 0.01 0.01 0.01
Pourability (Residue) % 3.17 3.51 3.26 2.83 2.96 2.54
Persistent Foam (ml after one min.) 2 4 2 3 6 5
Particle size (Mic.) 2.17 2.10 2.09 2.19 2.22 2.10
Viscosity (cps) 283.1 289.1 274.4 264.1 295.1 274.4

Table 2 - continued
Parameter Example 3
Initial At 54±2 ?C
(14 days) At 0±2 ?C
(7 days)
Appearance White suspension White suspension White suspension
Chlorantraniliprole content (%) w/w 5.04 5.06 5.07
Fenpropathrin content (%) w/w 12.06 12.04 12.09
pH (1%) 6.76 6.64 6.14
Dispersion stability 0h: Initial dispersion complete 0h: Initial dispersion complete 0h: Initial dispersion complete
0.5h 0.5h 0.5h
Cream: Nil Cream: Nil Cream: Nil
Free oil: Nil Free oil: Nil Free oil: Nil
Sediment: Nil Sediment: Nil Sediment: Nil
24h: Re-dispersion complete 24h: Re-dispersion complete 24h: Re-dispersion complete
24.5h 24.5h 24.5h
Cream: Nil Cream.: Nil Cream.: Nil
0.5h: Cream: Nil 0.5h: Cream: Nil 0.5h: Cream: Nil
Free oil: Nil Free oil: Nil Free oil: Nil
Sediment: Nil Sediment: Nil Sediment: Nil
Wet sieve test (% retention on 75 micron) 0.02 0.02 0.01
Pourability (Residue) % 2.97 3.01 3.16
Persistent Foam (ml after one min.) 3 3 4
Particle size (Mic.) 2.47 2.66 2.59
Viscosity (cps) 263.3 279.1 264.9

Comparative Examples SC1 to SC3
[0076] Suspension concentrate (SC) formulations were prepared as comparative examples. The proportions of ingredients are set forth in Table 3 below.
Table 3
Ingredients
Function SC1
(% w/w) SC2
(% w/w) SC3
(% w/w)
Chlorantraniliprole Active ingredient 4.0 2.0 5.0
Fenpropathrin Active ingredient 10.0 8.0 12.5
Naphthalene sulfonic acid formaldehyde condensate sodium salt block copolymer Dispersing agent 2.0 2.0 2.0
Sodium Lignosulfonate Dispersing agent 4.0 4.0 4.0
Ethylene oxide propylene oxide block copolymer Dispersing agent 4.0 4.0 4.0
Sodium lauryl sulfate Suspending agent 2.0 2.0 2.0
Fatty alcohol ethoxylate Wetting agent 0.6 0.6 0.6
Xanthan gum Thickener 0.4 0.4 0.4
Glycerol Antifreeze 2.0 2.0 2.0
1.2-benzisothiazol-3(2H)-one Biocide 0.2 0.2 0.2
Polydimethylsiloxane Antifoam 0.5 0.5 0.5
Water Carrier QS to 100 QS to 100 QS to 100

Manufacturing Process
[0077] Water, biocide and thickener were combined and mixed in a mixing vessel to form a thickener solution. Chlorantraniliprole, fenpropathrin, dispersing agents, wetting agent, antifreeze agent, antifoam agent, suspending agent and a required amount of water were combined and mixed in a mixing vessel to form a SC premix, which was then wet milled in a horizontal bead mill until the average particle size was under 3 microns. The thickener solution was added to the milled SC premix and mixed until a homogeneous suspension was achieved.

Stability Study
[0078] The suspension concentrate (SC) formulations prepared in Comparative Examples SC1 to SC3 were subjected to storage stability study and the results are presented in Table 4 below.

Table 4
Parameter SC1 SC2
Initial At 54±2?C
(14 days) At 0±2?C
(7 days) Initial At 54±2?C
(14 days) At 0±2?C
(7 days)
Appearance Suspension Phase separation observed (forming a solid cake at the bottom of container) Sample became frozen and non-flowable Suspension Phase separation observed (forming a solid cake at the bottom of container) Sample became frozen and non-flowable
Chlorantraniliprole content % w/w 4.03 2.09
Fenpropathrin content (%) w/w 10.02 8.09
Suspensibility, % by mass Chlorantraniliprole: 98.34
Fenpropathrin: 98.44 Chlorantraniliprole: 97.54
Fenpropathrin: 98.44
Wet sieve test (% retention on 75 micron) 0.01 0.02
pH of 1% Aq. Suspension 6.94 6.75
Persistent Foam (ml After one min.) 40 41
Particle size 2.40 2.64
Viscosity (cps) 246 255

Table 4 - continued

Parameter SC3
Initial At 54±2?C
(14 days) At 0±2?C
(7 days)
Appearance Complies Phase separation observed (forming a solid cake at the bottom of container) Sample became frozen and non-flowable
Chlorantraniliprole content % w/w 5.06
Fenpropathrin content (%) w/w 12.08
Suspensibility, % by mass Chlorantraniliprole: 97.33
Fenpropathrin: 96.87
Wet sieve test (% retention on 75 micron) 0.02
pH of 1% Aq. Suspension 6.77
Persistent Foam (ml after one min.) 45
Particle size 2.52
Viscosity (cps) 266

[0079] The results presented in Table 2 show that the suspoemulsion (SE) formulations had good physical stability as no phase separation was observed after being stored at 54°C for 14 days and the formulations were intact under cold temperatures. However, with suspension concentrate (SC) formulations SC1 to SC3, phase separation occurred under the same storage conditions resulting in a cake build-up (see, Table 4). Also, the suspension concentrate (SC) formulations became frozen and non-flowable when stored at 0°C for 7 days (see, Table 4). This observation suggests that SE formulations of chlorantraniliprole and fenpropathrin are significantly more stable than the SC formulations.
FIELD STUDY:
[0080] The following are abbreviations that have been used in this specification.
· SE - Suspo Emulsion
· PTC - Pre-treatment count
· ROC - Reduction over control
· g.a.i. ha. - gram active ingredient per hectare
· ETL - Economic Threshold Level
· DAT - Days after treatment
· DAA - Days after application
· CTPR - Chlorantraniliprole

1. Location Shantiniketan, Birbhum District, West Bengal
2. Season Kharif – 2023
3. Year 2023- 24
4. Crop Brinjal
5. Variety/Hybrid VNR 51 C
6. Spacing 60 × 75 cm
7. Soil type Sandy loam Soil
8. Irrigated / rain fed Irrigated
Experimental details:
Design Randomized Complete Block Design (RCBD)
No. of treatments 7 (Bio-efficacy)
No. of replications 3
Plot size 50 sq.m.
Date of sowing
Date of transplanting 12/05/2023
18/06/2023
Number/ date of treatment imposition
Date of harvesting Two 1st application: 29-07-23,2nd Application: 13-08-23
03/10/2023
Type of sprayer/nozzle Knapsack sprayer / Hollow cone nozzle
Quantity of water used for dilution 500 lit/ha

Observations recorded
[0081] The experiment was carried out at Sriniketan - 731236, Birbhum, West Bengal, India during 2023 season in a randomized block design with eight treatments and three replications. Insecticide applications were taken up based on seasonal occurrence and Economic Threshold Level (ETL) of the Shoot & Fruit Borer (Leucinodes orbonalis Guenee) and Red spider mites (Tetranychus urticae) and white fly infesting brinjal Crop.
[0082] The number of total and infested shoot and fruit were counted on 10 randomly selected plants in the middle two rows of each field and the percentage of infested shoot and fruit was calculated using the following formula (A.K.Singh,2020).
Infested shoot or fruit (%) = (Po/Pr) X 100
where,
Pr = Total number of shoot or fruit per plot
Po = Number of infested shoot or fruit per plot
Finally, mean percentage of shoot and fruit infestation was calculated for each of the treatments from the three replicated plots. The percentage data for the damaged shoots and fruits were converted into its angular transformation. Data were subjected to analysis of variance (ANOVA).

Similarly, the observations were also recorded on per cent fruit damage at each picking with the following formulae:

For pest control, Red spider Mites and White fly; five plants were selected randomly in each plot and from each plant; top three leaves were selected for counting the Red spider Mite. Such observations were made at 3, 7, 10 & 14 days after application to determine the effectiveness of the insecticidal compositions. All the observations were recorded with the help of a hand lens (10X). Reduction of insect population in different treatments over control was used as an indicator of insecticidal efficacy which was calculated from the following formula
Population reduction (%) =
Treatment population – Control population
------------------------------------------------------- X 100
Control population

Table 5: Synergistic effect of SE composition comprising Chlorantraniliprole & Fenpropathrin for controlling Shoot borer (Leucinodes orbonalis) in Brinjal after first application
S.No Treatments Chlorantraniliprole Fenpropathrin GAI/ha Mean no. of Shoot Infestation Mean % control of Shoot damage Synergy (Colby method)
3 DAA 7 DAA 10 DAA 14 DAA 3 DAA 7 DAA 10 DAA 14 DAA 3 DAA 7 DAA 10 DAA 14 DAA
1 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 30 75 105 2.54 3.65 4.10 5.47 78.60 72.80 71.27 66.69
2 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 34 85 119 1.1 1.43 1.94 2.46 90.73 89.34 86.41 85.02
3 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 40 100 140 0.91 1.31 1.82 2.35 92.33 90.24 87.25 85.69 1.0 1.0 1.1 1.0
4 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 50 125 175 0.76 1.12 1.67 2.18 93.60 91.65 88.30 86.72
5 Clorantraniliprole 18.75% w/w 40 0 40 2.92 4.10 5.86 6.75 75.40 69.45 58.93 58.89
6 Fenpropathrin
30%w/w 0 100 100 2.94 4.37 5.95 6.88 75.23 67.44 58.30 58.10
7 Untreated control 11.87 13.42 14.27 16.42 - - - -
S.Em.± 0.13 0.11 0.1 0.11 - - - -
C.D. (p=0.05) 0.39 0.35 0.3 0.35 - - - -
GAI/ha: Gram active Ingredient/Hectare; DAA: Days after application; CD: Critical Difference

[0083] It is observed from Table 5 that the application of Treatment 3 (T3) Chlorantraniliprole 4% + Fenpropathrin 10% (14SE) w/w @ 140 GAI/ha as per the embodiment of present invention, was highly effective in controlling the brinjal shoot and fruit borer (Leucinodes orbonalis) at 3, 7, 10 & 14 days after first application and significantly superior than individual treatments i.e., treatment 5 (T5) Chlorantraniliprole 18.75% W/W @ 40 GAI/ha and treatment 6 (T6) Fenpropathrin 30% W/W @ 100 GAI/ha. It is seen that Treatments T3 exhibited higher mean percent reduction of shoot damage at 3, 7, 10 & 14 days after first application and also showed better reduction of shoot damage when compared to individual treatments Chlorantraniliprole 18.75% (T5) and Fenpropathrin 30% (T6). While comparing the similar strength of the individual treatments Chlorantraniliprole 18.75% (T5) and Fenpropathrin 30% (T6) corresponding to composition of Chlorantraniliprole 4% + Fenpropathrin 10% (14SE) @ 140 GAI/ha as treatment 3 (T3) expressed 92.33, 90.24, 87.25 and 85.69 mean percent reduction at 3, 7, 10 and 14 days after application, respectively which was statistically significant (when analysed through DMRT) over the individual treatments like T5 (Chlorantraniliprole 18.75%) which exhibited 75.40, 69.45, 58.93 and 58.89 mean percent reduction & T6 (Fenpropathrin 30%) exhibited 75.23, 67.44, 58.30 and 58.10 mean percent reduction of shoot damage. Accordingly, the results of T3 exhibits that the composition is synergistic in nature and the effectiveness is attributed to the composition as per the embodiments of the invention, where both actives are present in a single composition at a specific concentration. It can also be observed from these studies that the difference of mean no. of shoot infestation between the composition of the present invention versus individual treatments is more than the critical difference (CD), thus signifying that the composition is significantly effective. The effectiveness is further attributed to the form of the composition, i.e. Suspo Emulsion (SE) composition as shown in the present study.

Table 6: Synergistic effect of SE composition comprising Chlorantraniliprole & Fenpropathrin for controlling Shoot borer (Leucinodes orbonalis) in Brinjal after second application
S.No Treatments Chlorantraniliprole Fenpropathrin GAI/ha Mean no. of Shoot Infestation Mean % control of Shoot damage Synergy (Colby method)
3 DAA 7 DAA 10 DAA 14 DAA 3 DAA 7 DAA 10 DAA 14 DAA 3 DAA 7 DAA 10 DAA 14 DAA
1 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 30 75 105 1.98 2.67 3.95 4.98 88.66 86.50 81.84 79.98
2 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 34 85 119 0.43 0.82 1.46 1.95 97.54 95.85 93.29 92.16
3 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 40 100 140 0.32 0.70 1.37 1.86 98.17 96.46 93.70 92.52 1.0 1.0 1.0 1.0
4 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 50 125 175 0.2 0.61 1.28 1.75 98.85 96.92 94.11 92.97
5 Chlorantraniliprole 18.75% w/w 40 0 40 2.15 2.98 4.24 5.34 87.69 84.93 80.51 78.54
6 Fenpropathrin
30% w/w 0 100 100 2.24 3.14 4.65 5.81 87.17 84.13 78.62 76.65
7 Untreated control 17.46 19.78 21.75 24.88 - - - -
S.Em.± 0.09 0.08 0.07 0.08 - - - -
C.D. (p=0.05) 0.28 0.24 0.2 0.24 - - - -
GAI/ha: Gram active Ingredient/Hectare; DAA: Days after application; CD: Critical Difference

[0084] It is observed from Table 6 that the application of Treatment 3 (T3) Chlorantraniliprole 4% + Fenpropathrin 10% (14SE) w/w @ 140 GAI/ha as per the embodiment of present invention, was highly effective in controlling the brinjal shoot and fruit borer (Leucinodes orbonalis) at 3, 7, 10 & 14 days after second application and significantly superior than individual treatments i.e., treatment 5 (T5) Chlorantraniliprole 18.75% W/W @ 40 GAI/ha and treatment 6 (T6) Fenpropathrin 30% W/W @ 100 GAI/ha. It is seen that Treatments T3 exhibited higher mean percent reduction of shoot damage at 3, 7, 10 & 14 days after second application and also showed better reduction of shoot damage when compared to individual treatments Chlorantraniliprole 18.75% (T5) and Fenpropathrin 30% (T6). While comparing the similar strength of the individual treatments Chlorantraniliprole 18.75% (T5) and Fenpropathrin 30% (T6) corresponding to composition of Chlorantraniliprole 4% + Fenpropathrin 10% (14SE) @ 140 GAI/ha as treatment 3 (T3) expressed 98.17, 96.46, 93.70 and 92.52 mean percent reduction at 3, 7, 10 and 14 days after application, respectively which was statistically significant (when analysed through DMRT) over the individual treatments like T5 (Chlorantraniliprole 18.75%) which exhibited 87.69, 94.93, 80.51 and 78.54 mean percent reduction & T6 (Fenpropathrin 30%) exhibited 87.17, 84.13, 78.62 and 76.65 mean percent reduction of shoot damage. Accordingly, the results of T3 exhibits that the composition is synergistic in nature and the effectiveness is attributed to the composition as per the embodiments of the invention, where both actives are present in a single composition at a specific concentration. It can also be observed from these studies that the difference of mean no. of shoot infestation between the composition of the present invention versus individual treatments is more than the critical difference (CD), thus signifying that the composition is significantly effective. The effectiveness is further attributed to the form of the composition, i.e. Suspo Emulsion (SE) composition as shown in the present study.

Table 7: Synergistic effect of SE composition comprising Chlorantraniliprole & Fenpropathrin for controlling Red Spider mites (Tetranychus urticae) in Brinjal after First application
Sl.No Treatments Chlorantraniliprole Fenpropathrin GAI/ha Mean no. of Red spider mites/3 leaves/plant Mean % control of Red Spider Mites Synergy (Colby method)
3 DAA 7 DAA 10 DAA 14 DAA 3 DAA 7 DAA 10 DAA 14 DAA 3 DAA 7 DAA 10 DAA 14 DAA
1 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 30 75 105 2.65 3.15 4.02 5.32 72.54 70.23 67.48 65.09
2 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 34 85 119 1.08 1.52 1.98 2.31 88.81 85.63 83.98 84.84
3 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 40 100 140 0.93 1.40 1.82 2.15 90.36 86.77 85.28 85.89 1.0 1.0 1.0 1.0
4 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 50 125 175 0.82 1.31 1.71 2.08 91.50 87.62 86.17 86.35
5 Chlorantraniliprole
18.75% w/w 40 0 40 2.86 3.46 4.59 5.92 70.36 67.30 62.86 61.15
6 Fenpropathrin
30% w/w 0 100 100 2.9 3.52 4.68 5.98 69.95 66.73 62.14 60.76
7 Untreated control 9.65 10.58 12.36 15.24 - - - -
S.Em.± 0.23 0.15 0.21 0.28 - - - -
C.D. (p=0.05) 0.71 0.45 0.63 0.87 - - - -
GAI/ha: Gram active Ingredient/Hectare; DAA: Days after application; CD: Critical Difference

[0085] It is observed from Table 7 that the application of Treatment 3 (T3) Chlorantraniliprole 4% + Fenpropathrin 10% (14SE) w/w @ 140 GAI/ha as per the embodiment of present invention, was highly effective in controlling the brinjal Red Spider mites (Tetranychus urticae) at 3, 7, 10 & 14 days after first application and significantly superior than individual treatments i.e., treatment 5 (T5) Chlorantraniliprole 18.75% W/W @ 40 GAI/ha and treatment 6 (T6) Fenpropathrin 30% W/W @ 100 GAI/ha. It is seen that Treatments T3 exhibited higher mean percent control of red spider mite population at 3, 7, 10 & 14 days after first application and also showed higher mean percent control of red spider population per three leaves per plant when compared to individual treatments Chlorantraniliprole 18.75% (T5) and Fenpropathrin 30% (T6). While comparing the similar strength of the individual treatments Chlorantraniliprole 18.75% (T5) and Fenpropathrin 30% (T6) corresponding to composition of Chlorantraniliprole 4% + Fenpropathrin 10% (14SE) @ 140 GAI/ha as treatment 3 (T3) expressed 90.36, 86.77, 85.28 and 85.89 mean percent reduction at 3, 7, 10 and 14 days after application, respectively which was statistically significant (when analysed through DMRT) over the individual treatments like T5 (Chlorantraniliprole 18.75%) which exhibited 70.36, 67.30, 62.86 and 61.15 mean percent reduction & T6 (Fenpropathrin 30%) exhibited 69.95, 66.73, 62.14 and 60.76 mean percent reduction of mites population. Accordingly, the results of T3 exhibits that the composition is synergistic in nature and the effectiveness is attributed to the composition as per the embodiments of the invention, where both actives are present in a single composition at a specific concentration. It can also be observed from these studies that the difference of mean no. of Red spider mites/3 leaves/plant between the composition of the present invention versus individual treatments is more than the critical difference (CD), thus signifying that the composition is significantly effective. The effectiveness is further attributed to the form of the composition, i.e. Suspo Emulsion (SE) composition as shown in the present study.

Table 8: Synergistic effect of SE composition comprising Chlorantraniliprole & Fenpropathrin for controlling Red Spider mites (Tetranychus urticae) in Brinjal after second application
S.No Treatments Chlorantraniliprole Fenpropathrin GAI/ha Mean no. of Red spider mites/3 leaves/plant Mean % control of Red Spider Mites Synergy: (Colby method)
3 DAA 7 DAA 10 DAA 14 DAA 3 DAA 7 DAA 10 DAA 14 DAA 3 DAA 7 DAA 10 DAA 14 DAA
1 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 30 75 105 2.81 3.56 3.98 4.85 82.81 80.06 79.54 78.61
2 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 34 85 119 0.86 1.25 1.52 1.83 94.74 93 92.19 91.93
3 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 40 100 140 0.71 1.05 1.43 1.71 95.66 94.12 92.65 92.46 1.0 1.0 1.0 1.0
4 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 50 125 175 0.6 0.92 1.32 1.6 96.33 94.85 93.21 92.94
5 Chlorantraniliprole
18.75% w/w 40 0 40 2.84 3.67 4.15 4.97 82.63 79.44 78.66 78.08
6 Fenpropathrin
30% w/w 0 100 100 2.86 3.68 4.18 5 82.51 79.38 78.51 77.94
7 Untreated control 16.35 17.85 19.45 22.67 - - - -
S.Em.± 0.1 0.12 0.08 0.09 - - - -
C.D. (p=0.05) 0.3 0.36 0.25 0.28 - - - -
GAI/ha: Gram active Ingredient/Hectare; DAA: Days after application; CD: Critical Difference

[0086] It is observed from Table 8 that the application of Treatment 3 (T3) Chlorantraniliprole 4% + Fenpropathrin 10% (14SE) w/w @ 140 GAI/ha as per the embodiment of present invention, was highly effective in controlling the brinjal Red Spider mites (Tetranychus urticae) at 3, 7, 10 & 14 days after second application and significantly superior than individual treatments i.e., treatment 5 (T5) Chlorantraniliprole 18.75% W/W @ 40 GAI/ha and treatment 6 (T6) Fenpropathrin 30% W/W @ 100 GAI/ha. It is seen that Treatments T3 exhibited higher mean percent control of red spider mite population at 3, 7, 10 & 14 days after second application and also showed higher mean percent control of red spider population per three leaves per plant when compared to individual treatments Chlorantraniliprole 18.75% (T5) and Fenpropathrin 30% (T6). While comparing the similar strength of the individual treatments Chlorantraniliprole 18.75% (T5) and Fenpropathrin 30% (T6) corresponding to composition of Chlorantraniliprole 4% + Fenpropathrin 10% (14SE) @ 140 GAI/ha as treatment 3 (T3) expressed 95.66, 94.12, 92.65 and 92.46 mean percent reduction at 3, 7, 10 and 14 days after application, respectively which was statistically significant (when analysed through DMRT) over the individual treatments like T5 (Chlorantraniliprole 18.75%) which exhibited 82.63, 79.44, 78.66 and 78.08 mean percent reduction & T6 (Fenpropathrin 30%) exhibited 82.51, 79.38, 78.51 and 77.94 mean percent reduction of mites population. Accordingly, the results of T3 exhibits that the composition is synergistic in nature and the effectiveness is attributed to the composition as per the embodiments of the invention, where both actives are present in a single composition at a specific concentration. It can also be observed from these studies that the difference of mean no. of Red spider mites/3 leaves/plant between the composition of the present invention versus individual treatments is more than the critical difference (CD), thus signifying that the composition is significantly effective. The effectiveness is further attributed to the form of the composition, i.e. Suspo Emulsion (SE) composition as shown in the present study.

Table 9: Synergistic effect of SE composition comprising Chlorantraniliprole & Fenpropathrin for controlling Whitefly (Bemisia tabaci) in Brinjal after first application
S.No Treatments Chlorantraniliprole Fenpropathrin GAI/ha Mean no. of White fly/3 leaves/plant Mean % control of Whitefly Synergy (Colby method)
3 DAA 7 DAA 10 DAA 14 DAA 3 DAA 7 DAA 10 DAA 14 DAA 3 DAA 7 DAA 10 DAA 14 DAA
1 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 30 75 105 2.64 3.12 4.05 5.11 74.24 73.15 67.47 62.76
2 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 34 85 119 0.82 1.42 2.13 2.67 92.00 87.78 82.89 80.54
3 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 40 100 140 0.68 1.30 2.04 2.55 93.37 88.81 83.61 81.41 1.0 1.0 1.0 1.0
4 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 50 125 175 0.55 1.12 1.95 2.42 94.63 90.36 84.34 82.36
5 Chlorantraniliprole
18.75% w/w 40 0 40 2.77 3.64 4.53 5.72 72.98 68.67 63.61 58.31
6 Fenpropathrin
30% w/w 0 100 100 2.75 3.71 4.62 5.80 73.17 68.07 62.89 57.73
7 Untreated control 10.25 11.62 12.45 13.72 - - - -
S.Em.± 0.1 0.11 0.06 0.1 - - - -
C.D. (p=0.05) 0.3 0.34 0.2 0.3 - - - -
GAI/ha: Gram active Ingredient/Hectare; DAA: Days after application; CD: Critical Difference

[0087] It is observed from Table 9 that the application of Treatment 3 (T3) Chlorantraniliprole 4% + Fenpropathrin 10% (14SE) w/w @ 140 GAI/ha as per the embodiment of present invention, was highly effective in controlling the brinjal Whitefly (Bemisia tabaci) at 3, 7, 10 & 14 days after first application and significantly superior than individual treatments i.e., treatment 5 (T5) Chlorantraniliprole 18.75% W/W @ 40 GAI/ha and treatment 6 (T6) Fenpropathrin 30% W/W @ 100 GAI/ha. It is seen that Treatments T3 exhibited higher mean percent control of whitefly population at 3, 7, 10 & 14 days after first application and also showed higher mean percent control of whitefly population per three leaves per plant when compared to individual treatments Chlorantraniliprole 18.75% (T5) and Fenpropathrin 30% (T6). While comparing the similar strength of the individual treatments Chlorantraniliprole 18.75% (T5) and Fenpropathrin 30% (T6) corresponding to composition of Chlorantraniliprole 4% + Fenpropathrin 10% (14SE) @ 140 GAI/ha as treatment 3 (T3) expressed 93.37, 88.81, 83.61 and 81.41 mean percent reduction at 3, 7, 10 and 14 days after application, respectively which was statistically significant (when analysed through DMRT) over the individual treatments like T5 (Chlorantraniliprole 18.75%) which exhibited 72.98, 68.67, 63.61 and 58.31 mean percent reduction & T6 (Fenpropathrin 30%) exhibited 73.17, 68.07, 62.89 and 57.73 mean percent reduction of whitefly population. Accordingly, the results of T3 exhibits that the composition is synergistic in nature and the effectiveness is attributed to the composition as per the embodiments of the invention, where both actives are present in a single composition at a specific concentration. It can also be observed from these studies that the difference of mean no. of White fly/3 leaves/plant between the composition of the present invention versus individual treatments is more than the critical difference (CD), thus signifying that the composition is significantly effective. The effectiveness is further attributed to the form of the composition, i.e. Suspo Emulsion (SE) composition as shown in the present study.

Table 10: Synergistic effect of SE composition comprising Chlorantraniliprole & Fenpropathrin for controlling Whitefly (Bemisia tabaci) in Brinjal after second application
S.No Treatments Chlorantraniliprole Fenpropathrin GAI/ha Mean no. of White fly/3 leaves/plant Mean % control of Whitefly Synergy (Colby method)
3 DAA 7 DAA 10 DAA 14 DAA 3 DAA 7 DAA 10 DAA 14 DAA 3 DAA 7 DAA 10 DAA 14 DAA
1 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 30 75 105 2.43 3.64 4.61 5.76 83.78 76.41 71.92 68.26
2 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 34 85 119 0.62 0.95 1.54 2.00 95.86 93.84 90.62 88.98
3 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 40 100 140 0.5 0.82 1.41 1.90 96.66 94.69 91.41 89.53 1.0 1.0 1.0 1.0
4 Chlorantraniliprole 4% + Fenpropathrin 10% SE w/w 50 125 175 0.38 0.71 1.30 1.72 97.46 95.40 92.08 90.52
5 Clorantraniliprole
18.75% w/w 40 0 40 2.65 3.89 4.91 5.95 82.31 74.79 70.10 67.22
6 Fenpropathrin
30% w/w 0 100 100 2.63 3.92 4.95 5.92 82.44 74.59 69.85 67.38
7 Untreated control 14.98 15.43 16.42 18.15 - - - -
S.Em.± 0.23 0.15 0.21 0.28 - - -
C.D. (p=0.05) 0.71 0.45 0.63 0.87 - - -
GAI/ha: Gram active Ingredient/Hectare; DAA: Days after application; CD: Critical Difference

[0088] It is observed from Table 10 that the application of Treatment 3 (T3) Chlorantraniliprole 4% + Fenpropathrin 10% (14SE) w/w @ 140 GAI/ha as per the embodiment of present invention, was highly effective in controlling the brinjal Whitefly (Bemisia tabaci) at 3, 7, 10 & 14 days after second application and significantly superior than individual treatments i.e., treatment 5 (T5) Chlorantraniliprole 18.75% W/W @ 40 GAI/ha and treatment 6 (T6) Fenpropathrin 30% W/W @ 100 GAI/ha. It is seen that Treatments T3 exhibited higher mean percent control of whitefly population at 3, 7, 10 & 14 days after second application and also showed higher mean percent control of whitefly population per three leaves per plant when compared to individual treatments Chlorantraniliprole 18.75% (T5) and Fenpropathrin 30% (T6). While comparing the similar strength of the individual treatments Chlorantraniliprole 18.75% (T5) and Fenpropathrin 30% (T6) corresponding to composition of Chlorantraniliprole 4% + Fenpropathrin 10% (14SE) @ 140 GAI/ha as treatment 3 (T3) expressed 96.66, 94.69, 91.41 and 89.53 mean percent reduction at 3, 7, 10 and 14 days after application, respectively which was statistically significant (when analysed through DMRT) over the individual treatments like T5 (Chlorantraniliprole 18.75%) which exhibited 82.31, 74.79, 70.10 and 67.22 mean percent reduction & T6 (Fenpropathrin 30%) exhibited 82.44, 74.59, 69.85 and 67.38 mean percent reduction of whitefly population. Accordingly, the results of T3 exhibits that the composition is synergistic in nature and the effectiveness is attributed to the composition as per the embodiments of the invention, where both actives are present in a single composition at a specific concentration. It can also be observed from these studies that the difference of mean no. of White fly/3 leaves/plant between the composition of the present invention versus individual treatments is more than the critical difference (CD), thus signifying that the composition is significantly effective. The effectiveness is further attributed to the form of the composition, i.e. Suspo Emulsion (SE) composition as shown in the present study.
[0089] The synergistic insecticidal composition Chlorantraniliprole 4% + Fenpropathrin 10% (14SE) w/w @ 140 GAI/ha of the present invention gave good control of shoot & fruit borer, red spider mites and white fly on brinjal. Further, the use of the synergistic insecticidal composition resulted in no phytotoxic symptoms on Brinjal crop.
[0090] Overall, the present invention offers a composition comprising two insecticides that, at specific w/w ratios and varying doses, demonstrate an unexpected and remarkable synergistic ability to control crop-damaging insects. Notably, while highly effective against harmful insects, this composition does not adversely impact the agronomic characteristics of crops. Furthermore, it is non-phytotoxic to crop plants at recommended doses, making it an appealing and effective alternative to the use of individual insecticides.

INDUSTRIAL APPLICABILITY AND ECONOMICAL SIGNIFICANCE
[0091] The synergistic and stable insecticidal composition, wherein Chlorantraniliprole and Fenpropathrin are mixed in a distinctive strength in the formulated product, can be considered as a novel invention. This formulation product of two insecticides (in the distinctive strength as mentioned above) provides better performance (bioefficacy) than its individual components due to the following aspects: a) This formulation is effective against insect pests with better spectrum of efficacy over its individual components. b) The formulation is found stable for two years, which could be an advantage for its effective commercialization c) Both the individual molecules i.e. Chlorantraniliprole and Fenpropathrin belong to different chemical groups and have different mode of actions, which make them ideal combination partners for using in Integrated Pest Management practices as well as resistance management strategies. d) There has not been any composition commercialized in India based on the combination of Chlorantraniliprole and Fenpropathrin. e) This formulation has exhibited its bioefficacy on Rice, Soybean and Brinjal crops. These crops harbor a variety of insect pests and due to this, farmers come across with a lot of economic losses. Therefore, this composition can be considered worthy to farmers earning better profits from their farm outputs.
,CLAIMS:1. A suspoemulsion formulation comprising:
(i) a continuous water phase, comprising:
chlorantraniliprole;
a dispersing agent; and
water having chlorantraniliprole suspended therein;
(ii) an oil phase emulsified in the continuous water phase, the oil phase comprising:
fenpropathrin; and
a solvent having fenpropathrin dissolved therein.
2. The formulation as claimed in claim 1, wherein the continuous water phase further comprises a wetting agent.
3. The formulation as claimed in claim 1, wherein the oil phase is an oil-in-water emulsion (EW) phase, comprising:
fenpropathrin;
a solvent having fenpropathrin dissolved therein;
an emulsifier; and
water.
4. The formulation as claimed in claim 1, further comprising at least one excipient selected from an anti-foaming agent, an antifreeze agent, a biocide, a thickener, a suspending agent, an antioxidant, and a colorant.
5. The formulation as claimed in claim 1, wherein the chlorantraniliprole is present in an amount of from 0.1% to 50% by weight of the suspoemulsion formulation.
6. The formulation as claimed in claim 1, wherein the fenpropathrin is present in an amount of from 1% to 70% by weight of the suspoemulsion formulation.
7. The formulation as claimed in claim 1, wherein the dispersing agent is present in an amount of from 0.1% to 30% by weight of the suspoemulsion formulation.
8. The formulation as claimed in claim 2, wherein the wetting agent is present in an amount of from 0.1% to 25% by weight of the suspoemulsion formulation.
9. The formulation as claimed in claim 1, wherein the solvent is present in an amount of from 2% to 40% by weight of the suspoemulsion formulation.
10. The formulation as claimed in claim 3, wherein the emulsifier is present in an amount of from 0.1% to 20% by weight of the suspoemulsion formulation.
11. The formulation as claimed in claim 1, wherein the water is present in an amount of from about 5 to about 95% by weight of the suspoemulsion formulation.
12. The formulation as claimed in claim 1, wherein the formulation comprises particles in the size range of from 0.1 micron to 25 microns.
13. The formulation as claimed in claim 1, wherein the dispersing agent is selected from methyl methacrylate graft copolymer with polyethylene glycol, alkoxylated polyarylphenol phosphate esters or salts or acid forms thereof, lignosulphonates, phenyl naphthalene sulphonates, ethoxylated alkyl phenols, ethoxylated fatty acids, alkoxylated linear alcohols, polyaromatic sulfonates, sodium alkyl aryl sulfonates, maleic anhydride copolymers, phosphate esters, condensation products of aryl/alkyl sulphonic acids and formaldehyde, addition products of ethylene oxide and fatty acid esters, sulfonates of condensed naphthalene, lignin derivatives, naphthalene formaldehyde condensates, polycarboxylates, sodium alkyl benzene sulfonates, salts of sulfonated naphthalene, ammonium salts of sulfonated naphthalene, salts of polyacrylic acids, salts of phenol sulfonic acids, and mixtures thereof.
14. The formulation as claimed in claim 2, wherein the wetting agent is selected from alkyl phenol ethoxylate, fatty oil ethoxylate, fatty alcohol ethoxylate, phenyl naphthalene sulphonates, alkyl naphthalene sulfonates, sodium alkyl naphthalene sulfonate, sodium salt of sulfonated alkyl carboxylate, polyoxyalkylated ethyl phenols, polyoxyethoxylated fatty alcohols, polyoxyethoxylated fatty amines, lignin derivatives, alkane sulfonates, alkylbenzene sulfonates, salts of polycarboxylic acids, salts of esters of sulfosuccinic acid, alkylnaphthalenesulfonates, alkylbenzenesulfonates, alkylpolyglycol ether sulfonates, alkyl ether phosphates, alkyl ether sulfates and alkyl sulfosuccinic monoesters, and mixtures thereof.
15. The formulation as claimed in claim 1, wherein the solvent is a water-insoluble solvent selected from aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, ketones, esters, ethers, mineral oils, vegetable oils, and mixtures thereof.
16. The formulation as claimed in claim 3, wherein the emulsifier is selected from ionic and non-ionic emulsifiers; or wherein the emulsifier is selected from fatty acid esters, fatty alcohol esters, vegetable oil ethoxylates, ethers, alkyl sulphonates, aryl sulphonates and mixtures thereof.
17. The formulation as claimed in claim 4,
wherein the anti-foaming agent is a silicone anti-foaming agent; or
wherein the antifreeze agent is selected from ethylene glycol, propylene glycol, glycerine, urea, and mixtures thereof; or
wherein the biocide is selected from 1,2-benzisothiazolin-3-one, 5-chloro-2-methyl-2H-isothiazol-3-one, 1,2-benzisothiazol-3(2H)-one, 2-methyl-2H-isothiazol-3-one, formaldehyde, and mixtures thereof; or
wherein the thickener is selected from xanthan gum, polyvinyl alcohol, cellulose and its derivatives, hydrated clay minerals, magnesium aluminium silicates, and mixtures thereof; or
wherein the suspending agent is selected from magnesium aluminium silicate, modified hydrophobic silica, colloidal silica, precipitated silica, hydrophobic silica powder, and mixtures thereof.
18. A process for preparing a suspoemulsion comprising, mixing an oil-in-water emulsion phase with a continuous water phase,
wherein the oil-in-water emulsion phase is prepared by mixing fenpropathrin, a water-insoluble solvent that solubilizes fenpropathrin, an emulsifier and water; and
wherein the continuous water phase is prepared by mixing chlorantraniliprole, a dispersing agent, a wetting agent, water and optionally one or more further agrochemically acceptable excipients, wherein the suspoemulsion comprises particles in the size range of from 0.1 micron to 25 microns.