Stable pesticidal composition comprising dinotefuran and bifenthrin

Abstract

The present invention relates to synergistic and stable pesticidal compositions for controlling pests harmful to crop plants. More specifically, the compositions of the invention comprise at least one active compound selected from pyrethroid compounds, at least one neonicotinoid compound, an emulsifying system, a co-solvent and a solvent. In addition, the invention also provides a method for preparing the synergistic insecticidal composition.

Description

Technical Field

[0001] This invention relates to the field of agricultural pesticides, and more specifically, to a stable insecticidal composition and its preparation method. Background Technology

[0002] Controlling invertebrate pests is crucial for improving the planting efficiency of economically important crops. These pests not only damage growing and harvested crops but also cause significant reductions in crop yields. Pest management strategies for invertebrate pests include the use of single active ingredients or mixtures of two or more active compounds. However, there remains a significant need for more cost-effective and stable insecticidal compositions.

[0003] Furthermore, repeated and prolonged application of a single compound often leads to resistance to the active ingredient. Typically, such pests develop cross-resistance to other active ingredients with the same or similar mechanisms of action. Therefore, it is necessary to combine different categories and groups of active ingredients to achieve a broader range of disease control, while also providing both curative and preventative effects and maintaining stability.

[0004] There is an urgent need for a stable, synergistic, and environmentally friendly insecticidal composition. This composition should effectively control a wide range of pests, thereby preventing the emergence of resistant strains. Furthermore, it should possess broad-spectrum activity, minimize the amount of chemicals used in the field, and meet the requirements of sustainable agricultural practices. Another key factor for this composition is its stability under various environmental conditions, including maintaining effectiveness at low temperatures, where traditional active ingredients may degrade or become less effective. This stability ensures that the composition's efficacy is maintained from production to application, regardless of climate changes.

[0005] The present invention provides a composition that not only combats pest resistance strategies through multiple active strategies, but also maintains consistent performance over a wide temperature range.

[0006] The purpose of this invention The main objective of this invention is to provide an insecticidal composition with an improved activity spectrum.

[0007] Another object of the present invention is to provide an insecticidal composition for resistance management.

[0008] Another object of the present invention is to provide a stable synergistic insecticidal composition.

[0009] Another object of the present invention is to provide a stable synergistic insecticidal composition, especially under low temperature conditions.

[0010] Another object of the present invention is to provide a synergistic insecticidal composition with improved stability to extend shelf life.

[0011] Another object of the present invention is to provide a method for preparing a synergistic insecticidal composition.

[0012] Another object of the present invention is to provide a method for preventing and controlling pests and diseases in agriculture. Summary of the Invention

[0013] The present invention aims to provide an insecticidal composition comprising dinotefuran, bifenthrin, an emulsification system, and a cosolvent.

[0014] In another aspect of the invention, the emulsification system comprises a blend containing calcium alkylbenzene sulfonate, cashew phenol polyoxyethylene ether, NP ethoxylate, heavy aromatics & triethylene glycol monoethyl ether, castor oil ethoxylate, and n-butanol.

[0015] In another aspect of the invention, the emulsification system comprises a blend containing a calcium salt of an alkylbenzene sulfonate or ester, cashew phenol polyoxyethylene ether, NP ethoxylate, heavy aromatic hydrocarbons, and triethylene glycol monoethyl ether.

[0016] In another aspect of the invention, the insecticidal composition comprises: 1 to 40% by weight of fipronil; 1 to 40% by weight of bifenthrin; 1 to 30% by weight of the emulsification system; and 1 to 60% by weight of co-solvent.

[0017] In a preferred embodiment of the present invention, the co-solvent is N-methyl-2-pyrrolidone.

[0018] In another aspect of the invention, the insecticidal composition comprises: Fipronil; Bifenthrin; Emulsification system; Cosolvent; and Solvent.

[0019] In another aspect of the invention, the solvent is a mixed isomer of 1,2,4-trimethylbenzene and ethylmethylbenzene (C9 solvent).

[0020] In a further aspect of the invention, the composition further comprises a carrier, a binder, a disintegrant, a dispersant or dispersing agent, a wetting agent, a pH adjuster, a thickener, a biocide, a preservative, an antifreeze, a colorant, an antifoamer, a stabilizer, or any combination thereof.

[0021] In another aspect of the invention, a method for preparing an insecticidal composition is provided, the method comprising: a) Weigh the required amount of co-solvent; b) Add fipronil to the co-solvent while stirring to form a mixture; c) While continuously stirring, add the solvent and bifenthrin sequentially to the above mixture; and d) Add the emulsion system to the mixture of step c) under stirring to obtain the final insecticidal composition.

[0022] In one aspect of the invention, the mixture in step b) is stirred at a speed of 100 RPM for 40-60 minutes.

[0023] In another aspect of the invention, the composition comprises the addition of a carrier, binder, disintegrant, dispersant or dispersing agent, wetting agent, pH adjuster, thickener, biocide, preservative, antifreeze, colorant, defoamer, stabilizer, or any combination thereof. Detailed Implementation

[0024] In this article, the terms “formulation” and “composition” have the same meaning and can be used interchangeably.

[0025] Unless otherwise stated, all quantities expressed in “% w / w” or “%” refer to weight percentages relative to the total weight of the solution or composition.

[0026] In this article, the term "synergistic effect" refers to the effect of two or more active agents mixed together and applied in combination, which is greater than the sum of their individual effects.

[0027] As used in this article, the terms “active ingredient” (ai), “activator” or “active substance” refer to the component in the composition responsible for controlling insect pests.

[0028] The term "crop" should include a variety of desired crop plants or a single crop plant. The term "control" refers to suppressing the survival, growth, feeding, and / or reproduction of pests, or limiting the associated damage or loss to crop plants caused by pests. "Controlling" pests may or may not mean killing pests, although it may mean killing pests.

[0029] As used in this article, the terms “insecticide” or “pesticide” refer to any chemical substance used to eliminate or kill, suppress or otherwise adversely affect pests.

[0030] The term “stable” as used in this article refers to the chemical and / or physical stability of the active compound.

[0031] The term "low temperature" as used herein refers to a temperature below 10°C, preferably below 5°C, more preferably below 0°C, and most preferably -10°C.

[0032] Therefore, the present invention aims to provide a synergistic insecticidal composition comprising at least one active ingredient selected from pyrethroid compounds and neonicotinoid compounds.

[0033] In another embodiment, the present invention provides a method for preparing a synergistic composition comprising fipronil and at least one pyrethroid compound.

[0034] In this article, active ingredients encompass their agrochemically acceptable salts, derivatives, or any other modified forms.

[0035] In another exemplary embodiment, the composition comprises 1 to 60% by weight (%w / w) of a neonicotinoid compound and 1 to 50% by weight of a pyrethroid compound.

[0036] In one exemplary embodiment, the present invention provides a synergistic insecticidal composition comprising fipronil and bifenthrin.

[0037] In one exemplary embodiment, the synergistic insecticidal composition of the present invention is stable over a wide temperature range.

[0038] In another exemplary embodiment, the synergistic insecticidal composition of the present invention is effective and stable at low temperatures.

[0039] The inventors were surprised to find that the compositions within the above weight percentage range provided a synergistic effect.

[0040] In one embodiment, the synergistic insecticidal composition comprises 1-40% by weight of fipronil and 1-40% by weight of bifenthrin.

[0041] In one embodiment, the synergistic insecticidal composition includes: fipronil, bifenthrin, and an emulsifying system.

[0042] In one embodiment, the synergistic insecticidal composition includes fipronil, bifenthrin, an emulsifying system, and a co-solvent.

[0043] In another embodiment of the invention, the synergistic insecticidal composition comprises fipronil present in 1 to 40% by weight, bifenthrin present in 1 to 40% by weight, an emulsification system present in 1 to 40% by weight, a co-solvent present in 1 to 30% by weight, and a co-solvent present in 1 to 60% by weight.

[0044] Emulsifiers, emulsion systems, or ES (Extracellular Blends) comprise unique blends of multiple surfactants. These surfactants possess optimal hydrophilic-lipophilic balance (HLB) values, exhibiting both hydrophilic and lipophilic properties. This combination ensures superior stability of the composition and enhances its physicochemical properties. Furthermore, the interactions between these surfactants improve performance, maximizing the effectiveness of the agrochemical composition in agricultural applications. This enhances the stability of the emulsion and optimizes the application and action of agrochemicals on crops, thus providing a more reliable and effective agricultural solution.

[0045] The emulsion system comprises a blend of calcium salts containing alkylbenzene sulfonates or esters, cashew phenol polyoxyethylene ether NP ethoxylates, heavy aromatics & triethylene glycol monoethyl ethers, castor oil ethoxylates, and n-butanol.

[0046] In one embodiment, the emulsion system comprises a calcium salt containing alkylbenzene sulfonate or ester, cashew phenol polyoxyethylene ether, NP ethoxylate, and a blend of heavy aromatics and triethylene glycol monoethyl ether.

[0047] In another embodiment, the cosolvent is selected from N-methyl-2-pyrrolidone, N-butyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), or any combination thereof.

[0048] In a preferred embodiment, the cosolvent is N-methyl-2-pyrrolidone.

[0049] In another embodiment of the invention, the synergistic insecticidal composition comprises fipronil, bifenthrin, an emulsification system, a co-solvent, and a solvent.

[0050] In another embodiment, the solvent is a mixed isomer of 1,2,4-trimethylbenzene and ethylmethylbenzene (C9 solvent).

[0051] In an optional embodiment of the present invention, the synergistic insecticidal composition may comprise one or more of the following: carrier, binder, disintegrant, dispersant or dispersing agent, wetting agent, pH adjuster, thickener, biocide, preservative, antifreeze, colorant, defoamer, and stabilizer.

[0052] Furthermore, the present invention also provides a method for preparing a synergistic insecticidal composition, the method comprising: a) Weigh the required amount of co-solvent; b) Add fipronil to the co-solvent while stirring to form a mixture; c) Add the solvent and bifenthrin sequentially to the above mixture while continuously stirring; and d) The emulsion system is added to the mixture of step c) under stirring to obtain the final insecticidal composition.

[0053] In another exemplary embodiment, the synergistic composition of the present invention can be formulated as a capsule suspension (CS), a dispersible concentrate (DC), a dustable powder (DP), a powder for dry seed treatment (DS), an emulsifiable concentrate (EC), emulsifiable granules (EG), a water-in-oil emulsion (EO), an emulsifiable powder (EP), an emulsion for seed treatment (ES), an oil-in-water emulsion (EW), a flowable concentrate for seed treatment (FS), granules (GR), a microemulsion (ME), an oil dispersion (OD), an oil-miscible flowable concentrate (OF), and an oil-mixable solution (OL). Oil-dispersible powders (OP), suspension concentrates (SC), direct-application suspension concentrates (SD), suspension-emulsions (SE), water-soluble granules (SG), soluble concentrates (SL), spreading oils (SO), water-soluble powders (SP), water-soluble tablets (ST), ultra-low volume (ULV) suspensions, tablets (TB), ultra-low volume (ULV) liquids, water-dispersible granules (WG), wettable powders (WP), water-dispersible powders for pulp seed treatment (WS), water-dispersible tablets (WT), mixtures of CS and SC (ZC) or mixtures of CS and SE (ZE), and mixtures of CS and EW (ZW).

[0054] In another embodiment of the invention, the synergistic composition may include one or more inactive excipients selected from, but not limited to, carriers, surfactants, binders, disintegrants, dispersants or dispersing agents, wetting agents, pH adjusters, thickeners, biocides, emulsifiers, preservatives, antifreeze agents, antifoaming agents, defoamers, colorants, inert fillers, light absorbers, mixing aids, solvents, pH modifiers and buffers, corrosion inhibitors, fragrances, protective colloids and / or stabilizers, liquid and solid fertilizers, or combinations thereof.

[0055] In an exemplary embodiment, the insecticidal composition of the present invention is formulated in the form of an emulsion concentrate, which includes an active substance, an emulsion system, a solvent, and a cosolvent.

[0056] In another exemplary embodiment, the insecticidal composition of the present invention is formulated in the form of an emulsion concentrate, which includes one or more of the following: active substance, emulsion system, solvent, cosolvent, or carrier, binder, disintegrant, dispersant or dispersing agent, wetting agent, pH adjuster, thickener, biocide, preservative, antifreeze agent, colorant, defoamer and stabilizer.

[0057] Exemplary emulsifier systems that can be used in the compositions of this invention include, but are not limited to: salts of alkyl sulfates or esters, such as diethanolamine lauryl sulfate; salts of aryl sulfonates or esters, such as calcium dodecylbenzenesulfonate; alkylphenol-epoxide addition products, such as nonylphenol ethoxylate; alcohol-epoxide addition products, such as tridecanol ethoxylate; soaps, such as sodium stearate; salts of alkyl naphthalene sulfonates or esters, such as sodium dibutylnaphthalene sulfonate; dialkyl esters of sulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitan esters, such as sorbitan oleate; quaternary ammonium salts, such as lauryltrimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; polyethylene glycol ether derivatives in organic solvents; block copolymers of ethylene oxide and propylene oxide; and monoalkyl and dialkyl phosphate salts. Mixtures of one or more of these emulsifiers may also be used. The emulsifier may be present in the composition at a content of about 0-80% by weight (% w / w).

[0058] The antioxidants that may be used in the compositions and formulations of the present invention include, but are not limited to, ascorbate palmitate and tetraisopalmitate, magnesium ascorbate phosphate, sodium ascorbate phosphate, ascorbate acetate, tocopherol and its derivatives (such as vitamin E acetate), mixtures of vitamin E, vitamin A and its derivatives (vitamin A palmitate and acetate), as well as coniferyl benzoate, retinoic acid and its derivatives, α-glucosylrutin, ferulic acid, citric acid, furfuryl glucosyl alcohol, carnosine, butylated hydroxytoluene, butylated hydroxyanisole, and trihydroxybutyrophenone. Mixtures of one or more of these antioxidants may also be used. The antioxidants are present at a content of about 0-10% w / w in the composition.

[0059] The thickeners disclosed for use in the compositions and formulations of this invention include, but are not limited to, xanthan gum, modified xanthan gum, agar, succinyl polysaccharide gum (Rheozan), alginate, alginate, hydrated magnesium aluminum silicate (e.g., attapulgite), calcium lactobionate, carrageenan, gellan gum, and guar gum. The thickener may be present in an amount of about 0-10% by weight of the composition.

[0060] Nonionic surfactants or dispersants that may be used in the compositions or formulations disclosed herein include, but are not limited to, polyoxyethylene-polyoxypropylene block copolymers, polyethylene glycol ethers of linear alcohols, reaction products of fatty acids with ethylene oxide and / or propylene oxide, as well as polyvinyl alcohol, polyvinylpyrrolidone, copolymers of polyvinyl alcohol and polyvinylpyrrolidone, and copolymers of (meth)acrylic acid and (meth)acrylates, and also alkyl ethoxylates and alkyl aryl ethoxylates, which may optionally be phosphorylated and optionally neutralized with a base, among which, for example, sorbitol ethoxylates and polyoxyalkyleneamine derivatives may be mentioned.

[0061] Anionic surfactants or dispersants suitable for realizing compositions or formulations according to this disclosure include, but are not limited to, alkali metal and alkaline earth metal salts of alkyl sulfonic acids or alkyl aryl sulfonic acids. More preferably, the anionic surfactant may be a sodium salt of a linear alkylbenzene sulfonate or ester.

[0062] In an exemplary embodiment, the surfactant / dispersant comprises anionic surfactant / dispersant.

[0063] Defoamers or defoamers suitable for achieving the compositions or formulations described in this disclosure include, but are not limited to, silicone oils, polymethylsiloxanes, dimethyl silicone oils, octanol, magnesium stearate, and combinations thereof. Mixtures of one or more of these defoamers may also be used.

[0064] Inert fillers suitable for achieving the compositions or formulations described in this disclosure include, but are not limited to, inorganic particles such as carbonates, silicates and oxides, organic substances such as urea-formaldehyde condensates, kaolin, rutile, silica, highly dispersed silica, silica gel, precipitated silica, colloidal silica, attapulgite kaolin, and natural and synthetic silicates, talc, etc., or any combination thereof.

[0065] Solvents that can be used to achieve the compositions and formulations disclosed herein include, but are not limited to, water, water-soluble solvents, alcohols, water-insoluble solvents, organic solvents, or combinations thereof. The solvent may be present in an amount of about 1-80% w / w of the composition.

[0066] Solvents or co-solvents may be selected from, but are not limited to: water, deionized water (DM); alcohols, such as ethanol, propanol, n-octanol, isopropanol, ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerol; polyol ethers, such as ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, dipropylene glycol dimethyl ether; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethers, such as dipropyl ether, dioxane, tetrahydrofuran; aliphatic hydrocarbons, such as n-alkanes, isoalkanes, kerosene, mineral oil; aromatic hydrocarbons, such as xylene, toluene, naphthalene, naphtha, C9 solvent, C10 solvent, C12 solvent, aromatic oil (solvesso) 100, aromatic oil 150, aromatic oil 200; chlorinated aliphatic hydrocarbons or aromatic hydrocarbons, such as chlorobenzene, vinyl chloride, dichloromethane, 1,2,4-trimethylbenzene and ethylmethylbenzene (C9) Solvents); esters, such as ethyl acetate, diisopropyl phthalate, dimethyl adipate, methyl oleate, methyl tallowate; lactones, such as γ-butyrolactone; amides, such as dimethylformamide, N-methyl-2-pyrrolidone (NMP), N-octylpyrrolidone, N,N-dimethyldecylamide; nitriles, such as acetonitrile; cyclohexane, dimethylformamide, isophorone, and N-methylpyrrolidone; organosulfur compounds.

[0067] Dispersants, also known as dispersing agents, are substances that adsorb onto the surface of particles, maintaining their dispersed state and preventing reaggregation. Adding dispersants to agrochemical formulations helps disperse and suspend particles during production and ensures their redispersibility in water within the spray can. They are common components in wettable powders, suspensions, and water-dispersible granules. Surfactants used as dispersants strongly adsorb onto the particle surface and prevent particle reaggregation through charge or steric hindrance. Commonly used surfactants are anionic, nonionic, or mixtures of both. Sodium lignosulfonate is the most commonly used dispersant in wettable powder compositions.

[0068] The dispersant may be selected from, but is not limited to, acrylic copolymer solutions, C9-11 isomeric alcohols, C10 enriched alcohols, and ethoxylated alcohols.

[0069] Antifreeze agents can be selected from, but are not limited to, glycols, monoethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, methoxy polyethylene glycol, polypropylene glycol, polybutylene glycol, glycerol, and ethylene glycol. Water-based formulations often produce foam during mixing operations in production. To reduce the tendency to foam, antifoaming agents are usually added during the production stage or before bottling. There are generally two types of antifoaming agents: silicone-based and non-silicone-based. Silicone-based antifoaming agents are typically aqueous emulsions of dimethylpolysiloxane, while non-silicone-based antifoaming agents are water-insoluble oils, such as octanol and nonanol, or silica. In both cases, the function of the antifoaming agent is to displace the surfactant from the air-water interface.

[0070] Antifoaming agents may be selected from, but are not limited to: silicone emulsion defoamers, siloxane polyalkylene oxides, polydimethylsiloxane, trisiloxane ethoxylates and their blends.

[0071] The wetting agent may be selected from, but is not limited to, C9-11 isomer alcohols, C10 enriched alcohols, and ethoxylated alcohols.

[0072] Thickeners may be selected from, but are not limited to, water-soluble polymers and inorganic fine powders, including water-soluble polymers such as xanthan gum, vetiver gum, guar gum, polyvinyl alcohol, carboxymethyl cellulose, polyvinylpyrrolidone, carboxyethylene polymers, acrylic polymers, starch derivatives, or polysaccharides; or inorganic fine powders selected from high-purity silica, bentonite, or precipitated silica. These thickeners may be used alone or in combination.

[0073] Preservatives may be selected from, but are not limited to: a 20% dipropylene glycol aqueous solution of 1,2-benzisothiazolin-3-one, potassium formaldehyde sorbate, 4-hydroxybenzoate, 2-methyl-4-isothiazolin-3-one, and 5-chloro-2-methyl-4-isothiazolin-3-one.

[0074] In another preferred embodiment, the present invention provides a method for preparing a synergistic composition, comprising the following steps: (a) adding a required amount of NMP to a container and stirring at 100 rpm; (b) adding a required amount of active ingredient and stirring until completely dissolved; (c) adding an emulsifier during stirring; and (d) taking a sample for quality inspection.

[0075] According to one embodiment, the synergistic composition comprises fipronil, bifenthrin, an emulsification system, and a cosolvent for one or more inactive excipients, wherein the active ingredient is present at the concentration described below:

[0076] Example The following are examples of different compositions according to the present invention. However, the following examples are for illustrative purposes only and do not constitute a limitation of the invention, as many variations can be made within its spirit and scope.

[0077] Example 1 Table 1: Emulsified Concentrate (EC) Compositions of 22% Fipronil and 5.5% Bifenthrin

[0078] The composition is prepared as follows: Weigh the required amount of N-methyl-2-pyrrolidone (NMP) into a beaker, and then add the required amount of fipronil. Stir the mixture at 100 RPM for approximately 40 minutes until completely dissolved. Subsequently, while continuing to stir, add the required amounts of solvent C-9 and bifenthrin to the mixture until completely dissolved. Then, add the emulsifier and continue stirring for another 20 minutes to obtain an emulsion concentrate (EC). Finally, after analysis, package the resulting composition.

[0079] Table 2: Physicochemical properties of the composition

[0080] Table 3: Storage stability observation

[0081] Example 2: Table 4: Emulsified Concentrate (EC) Compositions of 20% Fipronil and 20% Bifenthrin

[0082] Preparation method of the composition: Weigh the required amount of NMP into a beaker, then add the required amount of fipronil and stir the mixture at 100 RPM for 40 minutes until completely dissolved. Next, add specific amounts of DMSO and bifenthrin to the mixture while continuously stirring until completely dissolved. Then, add the required amount of emulsification system and stir continuously for another 20 minutes to obtain the emulsion concentrate (EC).

[0083] Table 5: Physicochemical properties of the composition

[0084] Table 6: Storage stability observation

[0085] Example 3: Table 7: Emulsion Concentrate (EC) Compositions of 10% Fipronil and 15% Bifenthrin

[0086] Preparation method of the composition: Weigh the required amount of NMP into a beaker, add the required amount of fipronil, and stir the mixture at 100 RPM for 40 minutes to ensure complete dissolution. Then, add specific amounts of solvent C-9 and bifenthrin to the mixture, stirring continuously until the mixture is completely dissolved. Afterward, add the necessary emulsifier and continue stirring for another 20 minutes to obtain the emulsion concentrate (EC). Package the material after analysis.

[0087] Table 8: Physicochemical properties of the composition

[0088] Table 9: Storage Stability Observation

[0089] Example 4:

[0090] Table 10: Emulsified Concentrate (EC) Compositions of 28% Fipronil and 3.5% Bifenthrin

[0091] Preparation method of the composition: Weigh the required amounts of NMP and fipronil, transfer them to a beaker, and stir at 100 RPM for 40 minutes until completely dissolved. Then, add the required amounts of solvent C9 and bifenthrin to the blend, stirring continuously until the blend is completely dissolved. Afterward, add the necessary emulsifier and stir for another 20 minutes to obtain the emulsion concentrate (EC).

[0092] Table 11: Physicochemical properties of the composition

[0093] Table 12: Storage stability observation

[0094] Example 5: Table 13: Emulsified Concentrate (EC) Compositions of 8.5% Fipronil and 25% Bifenthrin

[0095] Preparation method of the composition: Weigh the required amount of NMP into a beaker, then add the required amount of fipronil. Stir the blend at 100 RPM for 40 minutes to ensure complete dissolution. Then, add DMSO and bifenthrin to the blend while stirring continuously until the blend is completely dissolved. After that, add the emulsion system and stir continuously for another 20 minutes to obtain the emulsion concentrate (EC).

[0096] Table 14: Physicochemical properties of the composition

[0097] Table 15: Storage Stability Observation

[0098] Example 6: Table 16: Emulsified Concentrate (EC) Compositions of 17.5% Fipronil and 24.5% Bifenthrin

[0099] Preparation method of the composition:

[0100] Weigh the required amount of NMP, add fipronil to a beaker, and stir the mixture at 100 RPM for 40 minutes to ensure complete dissolution. Then, add the specified amounts of solvent C-9 and bifenthrin while continuously stirring until completely dissolved. Afterward, add the necessary emulsifier and stir for another 20 minutes to obtain the emulsion concentrate (EC).

[0101] Table 17: Physicochemical properties of the composition

[0102] Table 18: Storage Stability Observations

[0103] Example 7: Composition with other solvents Table 19: Emulsified Concentrate (EC) Compositions of 20% Fipronil and 20% Bifenthrin with Other Solvents

[0104] The composition is prepared as follows: The required amount of n-butanol was measured and transferred to a beaker, then stirred at 100 rpm. During two hours of continuous stirring, the active ingredients fipronil and bifenthrin, along with the preservative BHT and emulsifier, were added to the beaker. It was observed that fipronil was not completely dissolved. Therefore, the experiment was terminated.

[0105] Table 20: Physicochemical properties of the composition

[0106] The active ingredient, fipronil, was observed to be insoluble in n-butanol. Furthermore, the composition exhibited negative properties in several key parameters, including physical state, color, and odor, all of which failed to meet acceptable standards. Therefore, compositions lacking the co-solvent, solvent, and emulsification system of this invention failed to achieve the expected results and are therefore unqualified.

[0107] Example 8: Experiment 1: Bioactivity evaluation of the insecticidal combination of fipronil and bifenthrin against rice stem borer (Scirpophaga incertulas)

[0108] Table 21: Processing details of active ingredients.

[0109]

[0110] *ES - Emulsifying System, CE - Conventional Emulsifier

[0111] method This experiment was conducted under field conditions in Panchhu, Nellore, Andhra Pradesh, focusing on the rice hybrid variety “MTU 1010”. A randomized block design (RBD) with three replicates was used. Each plot covered an area of ​​25 square meters to allow for accurate measurements. Following the treatment protocol, test samples were applied using a backpack sprayer at the time of pest infestation, using 500 liters of water per hectare.

[0112] observe Before spraying, the estimated number of pests was observed. Pest numbers were counted by randomly selecting five plants from each replicate and recording the number of pests in each replicate. Observations were made and recorded on days 5, 10, and 15 after spraying.

[0113] Table 22: Control effects of different treatments on rice stem borer.

[0114]

[0115]

[0116] *ES - Emulsification system, CE - Conventional emulsifier, DAA - Days after application

[0117] Table 23: Synergistic effects of different treatments on rice stem borer at 10 DAA.

[0118]

[0119] *ES - Emulsification system, CE - Conventional emulsifier, DAA - Days after application

[0120] The data clearly show that treatments 3 and 2 significantly reduced the incidence of heart-death symptoms caused by the rice stem borer (Scirpophaga incertulas), decreasing by 93.40% and 90.71%, respectively. Compared with the control group, these treatments showed a significant decrease in the Scirpophaga incertulas population. Furthermore, treatment 3 (fipronil 220 + bifenthrin 55 g / L EC (ES) at 750 ml) was the most effective in reducing the Scirpophaga incertulas population.

[0121] Table 24: Yield Study of Rice Stem Borer

[0122] Observation results: Treatment with the emulsifiable concentrate composition of the present invention increased crop yield, indicating that the composition of the present invention has synergistic effects and bioavailability.

[0123] Example 9: Experiment 2: Evaluation of the biological control efficacy of the insecticidal combination of fipronil and bifenthrin against rice stem borer.

[0124]

[0125] Table 25: Processing details of the active ingredient composition.

[0126]

[0127] method:

[0128] The experimental design employed a randomized block design (RBD) with three replicates. Each plot was 25 square meters in area to ensure accurate measurements. According to the treatment protocol, test samples were applied using a backpack sprayer at the time of pest appearance, with a water volume of 500 liters per hectare.

[0129] observe: The estimated number of pests was observed before spraying. Five plants from each treatment were randomly selected, and the number of rice stem borers on each plant was recorded. Observations were made on the 3rd, 7th, and 15th days after spraying.

[0130] Table 26: Effects of different treatments on rice stem borers.

[0131]

[0132] *ES - Emulsification system, CE - Conventional emulsifier, DAA - Days after application

[0133] Table 27: Synergistic effects of different treatments on rice stem borer after 7 DAA.

[0134]

[0135] *ES - Emulsification system, CE - Conventional emulsifier, DAA - Days after application

[0136] result Before treatment, there were 1 to 2 leafrollers on each leaf. The plot treated with dinotefuran 220 + bifenthrin 55g / l EC (ES) at a dose of 750 ml showed the largest average reduction in leafroller population, reaching 94.59%, followed by the plot treated with dinotefuran 220 + bifenthrin 55g / l EC (ES) at a dose of 500 ml, which reduced the number of leafrollers by 89.19%.

[0137] Table 28: Yield Study of Rice Stem Borer

[0138] Observation results: Treatment with the emulsified concentrate composition of the present invention increased crop yield, indicating that the composition of the present invention has synergistic effects and bioavailability.

[0139] Example 10: Table 29: Effects of different treatments on the natural enemy populations of rice

[0140] *ES - Emulsification system, CE - Conventional emulsifier, DAA - Days after application result The compositions of this invention are safe for natural enemies in the rice ecosystem. There was no difference in the population size of natural enemies between any treatment and the untreated control.

[0141] Example 11: Evaluation of the phytotoxicity of the composition of the present invention to rice.

[0142] Visual observations were conducted at 7, 14, and 21 days after product application (DAA). The parameters observed were leaf tip / surface damage, dwarfing, necrosis, chlorosis, vein clarity, apical growth, basal growth, and wilting, based on a 0-10 scale as shown in the table below. A total of 20 plants were observed from each plot.

[0143] Table 30: Phytotoxicity Symptom Scores and Ratings for Leaf Tip / Surface Damage

[0144] Table 31: Phytotoxic effects of different treatments on rice after 7 DAA at recommended doses.

[0145]

[0146] *DAA - Days after application, L - Leaf tip / surface damage, S - Dwarfing, N - Necrosis, C - Chlorosis, V - Pulse appearance, E - Upper growth spurt, H - Lower growth spurt, W - Wilting

[0147] Table 32: Phytotoxic effects of different treatments on rice after 14 DAA at recommended doses

[0148] *DAA - Days after application, L - Leaf tip / surface damage, S - Dwarfing, N - Necrosis, C - Chlorosis, V - Pulse appearance, E - Upper growth spurt, H - Lower growth spurt, W - Wilting

[0149] Table 33: Phytotoxic effects of different treatments on rice after 21 DAA at recommended doses.

[0150]

[0151] *DAA - Days after application, L - Leaf tip / surface damage, S - Dwarfing, N - Necrosis, C - Chlorosis, V - Pulse appearance, E - Upper growth spurt, H - Lower growth spurt, W - Wilting

[0152] Table 34: Phytotoxic effects of different treatments on rice after 7 DAA at double dose (2X).

[0153]

[0154] *DAA - Days after application, L - Leaf tip / surface damage, S - Dwarfing, N - Necrosis, C - Chlorosis, V - Pulse appearance, E - Upper growth spurt, H - Lower growth spurt, W - Wilting

[0155] Table 35: Phytotoxic effects of different treatments on rice after 14 DAA at double dose (2X).

[0156]

[0157] *DAA - Days after application, L - Leaf tip / surface damage, S - Dwarfing, N - Necrosis, C - Chlorosis, V - Pulse appearance, E - Upper growth spurt, H - Lower growth spurt, W - Wilting

[0158] Table 36: Phytotoxic effects of different treatments on rice after 21 DAA at double dose (2X).

[0159]

[0160] *DAA - Days after application, L - Leaf tip / surface damage, S - Dwarfing, N - Necrosis, C - Chlorosis, V - Pulse appearance, E - Upper growth spurt, H - Lower growth spurt, W - Wilting

[0161] Tables 31 to 33 above show that no phytotoxic symptoms such as leaf tip damage, leaf surface damage, wilting, vein blemishes, necrosis, apical dominance, or basal dominance were observed in rice crops at any dosage of dinotefuran 220 + bifenthrin 55 g / l EC(ES). Furthermore, Tables 34, 35, and 36 show that no phytotoxicity was observed even when using double the dosage of dinotefuran 220 + bifenthrin 55 g / l EC(ES). Therefore, the composition of the present invention can be considered completely safe for rice crops.

[0162] Example 12: Experiment 3: Evaluation of the bioefficacy of the insecticidal combination of fipronil and bifenthrin against cotton leafhopper (Cotton Jassids).

[0163]

[0164] Table 37: Processing details of active ingredients.

[0165]

[0166] *ES - Emulsification System, CE - Conventional Emulsifier

[0167] method The experiment was conducted under field conditions in Kharagone, Madhya Pradesh, using the cotton hybrid variety “Asha 1”. A randomized block design (RBD) with three replicates was employed. Each plot was 25 square meters. To ensure accurate measurements, five plants were labeled for each treatment, and pest numbers were recorded before application. According to the treatment protocol, the test samples were applied using a backpack sprayer equipped with a hollow cone nozzle when pests appeared, using 500 liters of water per hectare.

[0168] observe Before spraying, the estimated number of pests was observed. Five plants from each treatment were randomly selected, and the number of leafhoppers on each leaf was recorded. Observations were made on the 3rd, 7th, and 15th days after spraying.

[0169] Table 38: Control effects of different treatments on cotton leafhoppers.

[0170]

[0171] *ES - Emulsification system, CE - Conventional emulsifier, DAA - Days after application

[0172] Table 39: Synergistic effects of different treatments on cotton leafhoppers at 7 DAA

[0173] *ES - Emulsification system, CE - Conventional emulsifier, DAA - Days after application

[0174] result Recorded data indicated that the leafhopper population was uniformly distributed in the experimental area prior to application. Observations one day before spraying showed that the number of leafhoppers per plant ranged from 3.07 to 3.40, with no significant differences between treatments. However, seven days after application (DAA), all treatments showed a significant reduction in leafhopper populations compared to the control. Among all treatments, dinotefuran 220 + bifenthrin 55 g / l EC (ES) was the most effective in reducing leafhopper populations at doses of 750 ml and 500 ml.

[0175] Table 40: Production Study of Cotton Leafhopper

[0176] Observation: Treatment with the emulsified concentrate composition of the present invention increased crop yield, indicating that the composition of the present invention has synergistic effects and bioavailability.

[0177] Example 13: Experiment 4: Evaluation of the biological control efficacy of the insecticidal combination of fipronil and bifenthrin against cotton aphids.

[0178] Table 41: Processing details of active ingredient combinations

[0179] *ES - Emulsification system, CE - Conventional emulsifier

[0180] method The experiment was conducted under field conditions in Aurangabad, Maharashtra, using the cotton hybrid variety “RCH659”. A randomized block design (RBD) with three replicates was employed. Each plot was 25 square meters. For accurate measurements, five plants were labeled for each treatment, and pest numbers were recorded before application. According to the treatment protocol, the test samples were applied using a backpack sprayer equipped with a hollow cone nozzle when pests appeared, at a water volume of 500 liters per hectare.

[0181] observe Before spraying, the estimated number of pests was observed. Five plants from each treatment were randomly selected, and the number of aphids on each leaf was recorded. Observations were made on days 3, 7, and 15 after spraying.

[0182] Table 42: Control effects of different treatments on cotton aphids

[0183] *ES - Emulsification system, CE - Conventional emulsifier, DAA - Days after application

[0184] Table 43: Synergistic effects of different treatments on cotton aphids after 7 DAA.

[0185]

[0186] *ES - Emulsification system, CE - Conventional emulsifier, DAA - Days after application

[0187] result Recorded data indicated that the aphid population was uniformly distributed in the experimental area prior to application. Observations one day before spraying showed that the number of aphids per plant ranged from 8.53 to 10.53, with no significant differences between treatments. However, three days after application (DAA), all treatments showed a significant reduction in aphid populations compared to the control. Among all treatments, dinotefuran 220 + bifenthrin 55 g / l EC (ES) was most effective in reducing aphid populations at doses of 750 ml and 500 ml. These results demonstrate that, among all treatments, the 750 ml dose of dinotefuran 220 + bifenthrin 55 g / l EC (ES) showed the highest percentage reduction (%ROC) relative to the control, proving it to be the most effective in reducing aphid populations.

[0188] Table 44: Cotton Aphid Yield Study

[0189] Observation: Treatment with the emulsified concentrate composition of the present invention increased crop yield, indicating that the composition of the present invention has synergistic effects and bioavailability.

[0190] Example 14: Experiment 5: Evaluation of the biological control efficacy of the insecticidal combination of fipronil and bifenthrin against cotton bollworm.

[0191] Table 45: Processing details of the active ingredient composition

[0192] *ES - Emulsification System, CE - Conventional Emulsifier

[0193] method The experiment was conducted under field conditions in Ambala, Punjab, using the cotton hybrid variety “F2228”. A randomized block design (RBD) with three replicates was employed. Each plot was 25 square meters. For accurate measurements, five plants were labeled for each treatment, and pest numbers were recorded before application. According to the treatment protocol, the test samples were applied using a backpack sprayer equipped with a hollow cone nozzle when pests appeared, at a water volume of 500 liters per hectare.

[0194] observe Before spraying, the estimated number of pests was observed. Five plants from each treatment were randomly selected, and the number of bollworms on each leaf was recorded. Observations were made on days 3, 7, and 10 after spraying.

[0195] Table 46: Control effects of different treatments on cotton bollworm

[0196] *ES - Emulsification system, CE - Conventional emulsifier, DAA - Days after application

[0197] Table 47: Synergistic effects of different treatments on bollworms after 7 DAA

[0198] *ES - Emulsification system, CE - Conventional emulsifier, DAA - Days after application

[0199] result Recorded data indicated that the bollworm population was evenly distributed in the experimental area prior to treatment. Observations one day before spraying showed that the number of bollworms per plant ranged from 1 to 2, with no significant differences between treatments. However, 7 days after application (DAA), all treatments showed a significant reduction in aphid populations compared to the control. Among all treatments, dinotefuran 220 + bifenthrin 55 g / l EC (ES) was the most effective in reducing bollworm populations at doses of 750 ml and 500 ml.

[0200] Table 48: Cotton Bollworm Yield Study

[0201] Observation: Treatment with the emulsified concentrate composition of the present invention increased crop yield, indicating that the composition of the present invention has synergistic effects and bioavailability.

[0202] Example 15: Table 49: Effects of different treatments on cotton natural enemy populations

[0203] *ES - Emulsification system, CE - Conventional emulsifier, DAA - Days after application

[0204] result The compositions of this invention are safe for natural enemies in the cotton ecosystem. There was no difference in natural enemy population numbers between any treated and untreated controls.

[0205] Example 16: Evaluation of the phytotoxicity of the composition of the present invention to cotton.

[0206] Visual observations were conducted 7, 14, and 21 days after product application (DAA). The observed parameters were leaf tip / surface damage, dwarfing, necrosis, chlorosis, vein clarity, apical growth, basal growth, and wilting, scored from 0 to 10 (see table below). A total of 20 plants were observed in each plot.

[0207] Table 50: Phytotoxicity Symptom Scores and Ratings for Leaf Tip / Surface Damage

[0208] Table 51: Phytotoxic effects of different treatments on cotton after 7 DAA at recommended doses

[0209] *DAA - Days after application, L - Leaf tip / surface damage, S - Dwarfing, N - Necrosis, C - Chlorosis, V - Pulse appearance, E - Upper growth spurt, H - Lower growth spurt, W - Wilting

[0210] Table 52: Phytotoxic effects on cotton after different treatments following 14 DAA at recommended doses

[0211] *DAA - Days after application, L - Leaf tip / surface damage, S - Dwarfing, N - Necrosis, C - Chlorosis, V - Pulse appearance, E - Upper growth spurt, H - Lower growth spurt, W - Wilting

[0212] Table 53: Phytotoxic effects of different treatments on cotton after 21 DAA at recommended doses

[0213] *DAA - Days after application, L - Leaf tip / surface damage, S - Dwarfing, N - Necrosis, C - Chlorosis, V - Pulse appearance, E - Upper growth spurt, H - Lower growth spurt, W - Wilting

[0214] Table 54: Phytotoxic effects of different treatments on cotton after 7 DAA at double dose (2X).

[0215]

[0216] *DAA - Days after application, L - Leaf tip / surface damage, S - Dwarfing, N - Necrosis, C - Chlorosis, V - Pulse appearance, E - Upper growth spurt, H - Lower growth spurt, W - Wilting

[0217] Table 55: Phytotoxic effects of different treatments on cotton after 14 DAA at double dose (2X).

[0218]

[0219] *DAA - Days after application, L - Leaf tip / surface damage, S - Dwarfing, N - Necrosis, C - Chlorosis, V - Pulse appearance, E - Upper growth spurt, H - Lower growth spurt, W - Wilting

[0220] Table 56: Phytotoxic effects of different treatments on cotton after 21 DAA at double dose (2X).

[0221]

[0222] *DAA - Days after application, L - Leaf tip / surface damage, S - Dwarfing, N - Necrosis, C - Chlorosis, V - Pulse appearance, E - Upper growth spurt, H - Lower growth spurt, W - Wilting

[0223] Tables 51 to 53 above show that no phytotoxic symptoms such as leaf tip damage, leaf surface damage, wilting, vein blemishes, necrosis, apical dominance, or basal dominance were observed in cotton crops when using dinotefuran 220 + bifenthrin 55 g / l EC(ES) at all dosages. Furthermore, Tables 54, 55, and 56 show that no phytotoxicity was observed even when using double the dosage of dinotefuran 220 + bifenthrin 55 g / l EC(ES). Therefore, the composition of the present invention can be considered completely safe for cotton crops.

[0224] Example 17: Stability assessment of different compositions Table 57: Compositions of the present invention at low temperatures

[0225] Table 57 shows that the compositions of the present invention remain stable across a wide temperature range. No signs of crystallization or phase separation were observed, and excellent water miscibility confirms their emulsifying properties. Furthermore, samples stored below 10°C remained liquid throughout the testing period, demonstrating their stability.

[0226] Table 58: Stability at 0℃ and -10℃, and solubility in water

[0227] Table 58 confirms that all compositions of the present invention exhibit excellent stability at low temperatures. The compositions remain in a stable liquid state, indicating successful emulsification that effectively delivers the active ingredients while avoiding the risk of degradation due to temperature fluctuations. These properties make these formulations particularly suitable for agricultural applications, where low-temperature stability is crucial.

[0228] Example 18 Table 59: Comparative Examples of Low-Temperature Stability between Emulsified and Non-Emulsified Systems

[0229] Stability tests were conducted on compositions containing and without ES, specifically by evaluating their appearance changes over 7 days at different temperatures. Examples 1 and 2 (the compositions of the present invention) contain ES, and these compositions exhibited significant stability at all test temperatures (25°C, 10°C, 5°C, 0°C, and -10°C). These compositions (Examples 1 and 2) are clear, transparent liquids, characterized by a yellow color, indicating good robustness under the specified conditions.

[0230] In contrast, Example 7 (the composition without ES) showed significant turbidity and phase separation at different temperatures (25°C, 10°C, 5°C, 0°C and -10°C), thus confirming that the composition was unstable and lacked compatibility.

[0231] Therefore, the ES-containing compositions of the present invention remain stable at different temperatures, have the desired appearance, and have an extended shelf life.

[0232] Further evaluation was conducted on the stability of the above composition at 0°C and -10°C, as well as its solubility in water.

[0233] Table 60: Stability at 0℃ and -10℃ and solubility in water

[0234] observe:

[0235] The low-temperature stability of the composition was evaluated after being kept at 0°C and -10°C for 7 days, and its water solubility was also tested.

[0236] The compositions of the present invention (Examples 1 and 2), formulated with ES, exhibit excellent stability, and the emulsions retain desirable properties, showing no signs of instability and demonstrating their resilience at low temperatures.

[0237] However, Example 7 (the composition without ES) presented several issues, such as compatibility problems, stability concerns, and signs of crystallization within the emulsion. These issues demonstrate that the absence of ES in the preparation of the composition leads to a significant decrease in performance, highlighting the crucial role of ES in improving emulsion stability and overall quality.

[0238] As can be seen from the foregoing, numerous modifications and variations can be made without departing from the true spirit and scope of the novel concept of this invention. It should be understood that no limitations are intended or should be inferred from the specific embodiments described. It should also be understood that all such modifications and improvements have been omitted herein for brevity and readability, but they are all within the scope of the following claims. Claims (as amended under Article 19 of the Treaty) 1. An insecticidal composition comprising: Fipronil, which exists in a content of 1 to 40% by weight; Bifenthrin, which exists in an amount of 1 to 40% by weight; The emulsified system exists in a concentration of 1 to 30% by weight; A co-solvent, present in an amount of 1 to 60% by weight; and Solvent, The co-solvent is N-methyl-2-pyrrolidone; and The solvent is a mixed isomer of 1,2,4-trimethylbenzene and ethylmethylbenzene (C9 solvent). 2. The insecticidal composition according to claim 1, wherein the emulsification system is a blend of calcium salt of alkylbenzene sulfonate or ester, cashew phenol polyoxyethylene ether, NP ethoxylate, heavy aromatics & triethylene glycol monoethyl ether, castor oil ethoxylate and n-butanol. 3. The insecticidal composition according to claim 1, wherein the emulsion system is a blend of calcium salt of alkylbenzene sulfonate or ester, cashew phenol polyoxyethylene ether, NP ethoxylate, heavy aromatics & triethylene glycol monoethyl ether. 4. The insecticidal composition according to any one of claims 1 to 3, further comprising a carrier, binder, disintegrant, dispersant or dispersing agent, wetting agent, pH adjuster, thickener, biocide, preservative, antifreeze agent, colorant, defoamer, stabilizer, or any combination thereof. 5. A method for preparing an insecticidal composition, the method comprising: a) Weigh out the required amount of co-solvent; b) Add fipronil to the co-solvent while stirring to form a mixture; c) While continuously stirring, add the solvent and bifenthrin sequentially to the above mixture; and d) Add the emulsion system to the mixture from step c) with stirring to obtain the final insecticidal composition. 6. The method according to claim 5, wherein the mixture in step b) is stirred at 100 RPM for 40-60 minutes. 7. The method according to claim 5, further comprising adding a carrier, binder, disintegrant, dispersant or dispersing agent, wetting agent, pH adjuster, thickener, biocide, preservative, antifreeze, colorant, defoamer, stabilizer or any combination thereof.

Claims

1. An insecticidal composition comprising: Fipronil; Bifenthrin; Emulsification systems; and Cosolvent.

2. The insecticidal composition according to claim 1, wherein the emulsification system is a blend of calcium salt of alkylbenzene sulfonate or ester, cashew phenol polyoxyethylene ether, NP ethoxylate, heavy aromatics & triethylene glycol monoethyl ether, castor oil ethoxylate and n-butanol.

3. The insecticidal composition according to claim 1, wherein the emulsion system is a blend of calcium salt of alkylbenzene sulfonate or ester, cashew phenol polyoxyethylene ether, NP ethoxylate, heavy aromatics & triethylene glycol monoethyl ether.

4. The insecticidal composition according to claim 1, wherein... Fipronil exists in a concentration of 1 to 40% by weight; Bifenthrin exists in amounts ranging from 1 to 40% by weight; The emulsified system is present in a concentration of 1 to 30% by weight; and The cosolvent is present in an amount of 1 to 60% by weight.

5. The insecticidal composition according to claim 1, wherein the co-solvent is N-methyl-2-pyrrolidone.

6. An insecticidal composition comprising: Fipronil; Bifenthrin; Emulsification system; Cosolvent; and Solvent.

7. The insecticidal composition according to claim 6, comprising a solvent, said solvent being a mixed isomer of 1,2,4-trimethylbenzene and ethylmethylbenzene (C9 solvent).

8. The insecticidal composition according to any one of claims 1 to 7, further comprising a carrier, binder, disintegrant, dispersant or dispersing agent, wetting agent, pH adjuster, thickener, biocide, preservative, antifreeze, colorant, defoamer, stabilizer or any combination thereof.

9. A method for preparing an insecticidal composition, the method comprising: a) Weigh out the required amount of co-solvent; b) Add fipronil to the co-solvent while stirring to form a mixture; c) Add the solvent and bifenthrin to the mixture in sequence while stirring continuously; as well as d) Add the emulsion system to the mixture from step c) with stirring to obtain the final insecticidal composition.

10. The method according to claim 9, wherein the mixture in step b) is stirred at 100 RPM for 40-60 minutes.

11. The method according to claim 9, further comprising adding a carrier, binder, disintegrant, dispersant or dispersing agent, wetting agent, pH adjuster, thickener, biocide, preservative, antifreeze, colorant, defoamer, stabilizer or any combination thereof.

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