DESC:SYNERGISTIC COMPOSITION COMPRISING BENZIMIDAZOLE FUNGICIDE

FIELD OF THE INVENTION
The present invention relates to the control of pests that cause damage to crop plants. More particularly, the present invention relates to a composition comprising at least one active compound selected from benzimidazole fungicides, triazole fungicides, nitroguanidine insecticides, one or more surface active agents, and one or more agriculturally acceptable excipients and a process of preparation thereof.

BACKGROUND OF THE INVENTION
Pesticides are chemicals used in agriculture to protect plants from pests, weeds, and diseases. Pesticides include insecticides, fungicides, herbicides, and plant growth regulators. Fungal infection and insect infestation can occur concurrently in many economically essential and cash crops such as rice, peppers, grapes, and other agricultural crops. To control these conditions, compositions containing either a single active or a mix of actives are typically used. Control of plant diseases and pests is inevitable to obtain efficient agricultural output.

One of the major problems with the use of pesticides, is that the repeated and prolonged application of single compounds often leads to the development of resistance against the active compounds. Normally, such pests also develop cross-resistance against other actives having the same or similar mode of action. Hence, there is a need for combinations of actives belonging to different classes and groups to allow for a broader disease control spectrum that combines curative and preventive actives and has a lower dosage.

Synergistic agrochemical compositions are essential for protecting crops from pests and diseases and to enhance agricultural productivity. These compositions or formulations comprise more than one active ingredient to obtain a synergistic effect. However, the combination of different actives leads to challenges such as chemical stability and crystallization. The lack of stability and crystallization causes composition to lose efficacy, reduce shelf life and pose challenges in application, thereby limiting their practical applicability and usability.

In conventional practices, agricultural excipients such as stabilizers, or other additives are used to mitigate or minimize these issues, but they often fall short in providing long term stability, especially in a composition comprising two or more active ingredients, at times diminishing the desired synergistic effects.

CN104829340B relates to microcapsule graphene composite controlled release pesticide-fertilizer granules, comprising a microcapsule graphene composite material with pesticide active ingredients to provide a stable release and long-lasting effects.

Prior arts have addressed these challenges by modifying solvent systems, adjusting pH levels, or using encapsulation techniques such as microcapsules or similar. However, these are specific to certain kinds of formulations and fail to stabilize the ternary compositions having complex interactions.

Therefore, the present invention addresses the limitations of the prior art by providing a stable, efficient, and reliable agrochemical composition comprising three agrochemically active compounds with enhanced production feasibility and performance.

OBJECTIVES OF THE INVENTION
The primary objective of the invention is to provide a synergistic composition comprising at least three agrochemically active compounds and at least one surface active agent.

Another objective of the present invention is to provide a process for preparation of the synergistic composition.

Another objective of the present invention is to provide a synergistic composition comprising at least one active compound selected from benzimidazole fungicides, triazole fungicides, nitroguanidine insecticides, at least one surface active agent, and at least one agriculturally acceptable excipient.

Another objective of the present invention is to provide a synergistic composition with broad spectrum control of pests and diseases.

Another objective of the present invention is to provide a stable, efficient, and reliable synergistic composition with improved efficacy.

Another objective of the present invention is to provide a method for controlling pests and diseases in the agriculture field.

SUMMARY OF THE INVENTION
Accordingly, the present invention aims to provide a synergistic composition comprising at least one active compound selected from benzimidazole fungicides, triazole fungicides, nitroguanidine insecticides, at least one surface active agent and at least one agriculturally acceptable excipient.

In another aspect, the present invention provides a process for the preparation of a synergistic composition comprising at least one active compound selected each from benzimidazole fungicides, triazole fungicides, nitroguanidine insecticides, at least one surface active agent and at least one agriculturally acceptable excipient.

In another aspect of the present invention, the benzimidazole fungicide may be selected from benomyl, carbendazim, thiabendazole, albendazole, thiophanate, thiophanate-methyl, fuberidazole, chlorphenazole, debacarb, mecarbinzid, rabenzazole, furofanate or any combination thereof.

In another aspect of the present invention, the triazole fungicide may be selected from azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, etaconazole, fenbuconazole, flusilazole, fluquinconazole, flutriafol, hexaconazole, imibenconazole, penconazole, propiconazole, prothioconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimenol, triadimefon, tricyclazole, triticonazole or any combination thereof.

In another aspect of the present invention, the nitroguanidine insecticide may be selected from acetamiprid, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, thiacloprid or any combination thereof.

In another aspect of the present invention, the surface active agent is selected from poly(oxy-1,2-ethanediyl), a-sulfo-?-[2,4,6-tris(1-phenylethyl) phenoxy]-, ammonium salt, naphthalene and alkyl naphthalene sulphonic acids formaldehyde condensate, sodium salt, acrylic copolymer, 2-Propenoic acid, 2-methyl-, polymer with a-methyl-?-hydroxypoly(oxy-1,2-ethanediyl) and methyl 2-methyl-2-propenoate, graft or any combination thereof.

In another aspect, the synergistic composition of the present invention may be formulated as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW).

In another aspect of the present invention, the synergistic composition comprises one or more inactive excipients selected from the group comprising carrier(s), surfactant(s), binder(s), disintegrating agent(s), dispersants or dispersing agent(s), wetting agent(s), pH modifier(s), thickener(s), biocide(s), preservative(s), anti-freezing agent(s), defoamer(s), colorant(s), solvents, and/or stabilizer(s) or any combination thereof.

In another aspect, the present invention provides a process for the preparation of a synergistic composition comprising the steps of (a) charging a vessel with demineralized water (DM); (b) adding silicon defoamer and stirring the premix; (c) adding surface active agent, wetting agent, anti-freezing agent, and precipitated silica, and stirring the mixture; (d) adding the actives and colorant to the mixture and homogenizing; (e) milling the mixture by passing through a bead mill to obtain required particle size; (f) conveying the milled mixture to a second post feed vessel; (g) introducing a xanthan gum solution into the milled mixture and adding the remaining water; (h) mixing and homogenizing the mixture; (g) homogenizing the mixture further, in case, any lumps of xanthan gum are left; and (j) packing the mixture after passing through a normal sieve of 36 mesh if no lumps are observed.

In another aspect, the present invention provides a synergistic composition with improved stability and enhanced efficacy for broad spectrum control of pests and diseases.

BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1: illustrates a comparison of different treatments on soybean seeds, seeds treated with the composition of the present invention combination of thiophanate M, Flutriafol and Thiamethoxam; seeds treated with a composition comprising Thiophanate M 40 g/l (4%), Flutriafol 7.5 g/l (0.75%), and Clothianidin 320 g/l (32%); and untreated soybean seeds.

Figure 2: illustrates a comparison of different treatments on wheat seeds, seeds treated with the composition of the present invention combination of thiophanate M, Flutriafol and Thiamethoxam; seeds treated with a composition comprising Thiophanate M 40 g/l (4%), Flutriafol 7.5 g/l (0.75%), and Clothianidin 320 g/l (32%); and untreated soybean seeds.

Figure 3: shows the mycelium growth of Aspergillus niger at 10 DAI in treated vs. untreated samples.

Figure 4: shows the mycelium growth of Rhizoctonia solani at 15 DAI in treated vs. untreated samples.

Figure 5: shows the mycelium growth of Sclerotium rolfsii at 5 DAI in treated vs. untreated samples.

Figure 6: shows mycelium growth of Sclerotium rolfsii at 5 DAI in a sample treated with Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS vs. untreated sample.

Figure 7: shows mycelium growth of Rhizoctonia solani at 5 DAI in a sample treated with Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS vs. untreated sample.

Figure 8: shows mycelium growth of Sclerotium rolfsii at 5 DAI in a sample treated with Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS vs. untreated sample.

Figure 9: shows a plot treated with the present invention composition vs. an untreated plot affected by collar rot and white grub in ground nuts at 30 DAA.

Figure 10: shows a plot treated with the present invention composition vs. an untreated plot affected by collar rot and white grub in ground nuts at 45 DAA.

Figure 11: shows a plot treated with the present invention composition (Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS) vs. an untreated plot affected by collar rot and white grub in ground nuts at 30 DAA.

Figure 12: shows a plot treated with the present invention composition (Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS) vs. an untreated plot affected by collar rot and white grub in ground nuts at 45 DAA.

DETAILED DESCRIPTION OF THE INVENTION
The definitions provided herein below for the terminologies used in the present disclosure are for illustrative purposes only and in no manner limit the scope of the present invention disclosed in the present disclosure.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of the ordinary skills in the art to which the invention pertains. Other processes and materials similar, or equivalent, to those described herein may be used in the practice of the present invention.

It is to be noted that, as used in the specification, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, a reference to a composition containing “a compound” includes a mixture of two or more compounds. It should also be noted that the term “or” is generally employed in its sense, including “and/or,” unless the content clearly dictates otherwise.

The terms “formulation” and “composition” as used herein convey the same meaning and may be used interchangeably.

The terms “process” and “method” as used herein convey the same meaning and may be used interchangeably.
The expression of various quantities in terms of “% w/w” or “%” means the percentage by weight, relative to the weight of the total solution or composition, unless otherwise specified.

The term “synergistic”, as used herein, refers to the combined action of two or more active agents blended together and administered conjointly that is greater than the sum of their individual effects.

The term “active ingredient” (a.i.) or “active agent” or “actives” used herein refers to that component of the composition responsible for the control of insect pests.

The term “crop” shall include a multitude of desired crop plants or individual crop plants. The term “control” means to inhibit the ability of pests to survive, grow, feed, and/or reproduce, or to limit the pests’ related damage or loss to crop plants. To “control” pests may or may not mean killing the insects, although, it may mean killing the pests.

As used herein, the term “insecticide” or “pesticide”, refers to any chemical substance used to destroy/kill, inhibit, or otherwise adversely affect insect pests.

The term “Seed treatment” refers to the application of a fungicide, insecticide, multi-site fungicide, or both or a combination of both to seeds so as to disinfect them from seed borne or soil-borne pathogenic organisms and storage insects.

The term “plant propagation material” refers to the parts of the plant, such as seeds, which can be used for the propagation of the plant, and vegetative plant materials, such as cuttings and tubers (for example, potatoes). There may be mentioned, e.g., the seeds, roots, fruits, tubers, bulbs, rhizomes, and parts of plants. Germinated plants or young plants, which may be transplanted after germination or after emergence from the soil. “Fungicidal” refers to the ability of a substance to decrease or inhibit the growth of fungi. To “control” or “controlling” insects means to inhibit, through a toxic effect, the ability of insect pests to survive, grow, feed, and/or reproduce, or to limit insect-related damage or loss in crop plants, or to denote control and prevention of disease. Controlling effects include all deviations from natural development, for example: killing, retardation, and decrease of the fugal disease or insect pest. To “control” insects may or may not mean killing the insects, although it preferably means killing the insects.

The term “plant health” refers to the various sorts of improvements of plants that are not connected to the control of pests. For example, advantageous properties that may be mentioned are improved crop characteristics including emergence, crop yields, protein content, oil content, starch content, more developed root system (improved root growth), improved stress tolerance (e.g. against drought, heat, salt, UV, water, cold), reduced ethylene (reduced production and/or inhibition of reception), tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf color, pigment content, photosynthetic activity, less input needed (such as fertilizers or water), less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, enhanced plant vigour, increased plant stand and early and better germination; or any other advantages familiar to a person skilled in the art.

Accordingly, the present invention provides a novel synergistic composition comprising at least one compound selected from benzimidazole fungicides, triazole fungicides, nitroguanidine insecticides, at least one surface active agent and at least one agriculturally acceptable excipient.

As used herein, the active ingredient encompasses its agrochemically acceptable salt(s), derivative(s), or any other modified form.

In an exemplary embodiment, the present invention provides a process for preparing a synergistic composition comprising at least one active compound selected from benzimidazole fungicides, triazole fungicides, nitroguanidine insecticides, at least one surface active agent and at least one agriculturally acceptable excipient.

In another exemplary embodiment, the benzimidazole fungicide may be selected from benomyl, carbendazim, thiabendazole, albendazole, thiophanate, thiophanate-methyl, fuberidazole, chlorphenazole, debacarb, mecarbinzid, rabenzazole, furofanate or any combination thereof.

In a preferred embodiment, the benzimidazole is thiophanate or thiophanate-methyl.

In another exemplary embodiment, the triazole fungicide may be selected from azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, etaconazole, fenbuconazole, flusilazole, fluquinconazole, flutriafol, hexaconazole, imibenconazole, penconazole, propiconazole, prothioconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimenol, triadimefon, tricyclazole, triticonazole or any combination thereof.

In a preferred embodiment, the triazole fungicide is flutriafol.

In an embodiment of the present invention, the nitroguanidine insecticide may be selected from acetamiprid, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, thiacloprid or any combination thereof.

In a preferred embodiment, the nitroguanidine insecticide is selected from clothianidin or thiamethoxam.

In a preferred embodiment, the benzimidazole fungicide is thiophanate-methyl in the range of 1 to 50% by weight of the composition.

In another preferred embodiment, the triazole fungicide is flutriafol in the range of 0.5 to 60% by weight of the composition.

In another preferred embodiment, the present invention provides a synergistic composition comprising thiophanate-methyl, flutriafol, one nitroguanidine insecticide, at least one surface active agent and at least one agriculturally acceptable excipient.

In another exemplary embodiment, the nitroguanidine insecticide may be selected from acetamiprid, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, thiacloprid or any combination thereof.

In another preferred embodiment, the nitroguanidine insecticide is selected from thiamethoxam or clothianidin in the range of 1 to 60% by weight of the composition.

In another exemplary embodiment, the present invention provides a synergistic composition comprising a) thiophanate-methyl; b) flutriafol; c) at least one nitroguanidine insecticide selected from thiamethoxam and clothianidin; d) at least one surface active agent; and e) at least one agriculturally acceptable excipient.

In a preferred embodiment, the synergistic composition comprises of a) thiophanate-methyl; b) flutriafol; c) thiamethoxam, d) at least one surface active agent, and e) at least one agriculturally acceptable excipients.

In another preferred embodiment, the synergistic composition comprises of a) thiophanate-methyl; b) flutriafol; c) clothianidin, d) at least one surface active agent, and e) at least one agriculturally acceptable excipients.

In another preferred embodiment, the surface active agent is selected from poly (oxy-1,2-ethanediyl), a-sulfo-?-[2,4,6-tris(1-phenylethyl) phenoxy]-, ammonium salt, naphthalene and alkyl naphthalene sulphonic acids formaldehyde condensate, sodium salt, acrylic copolymer, 2-Propenoic acid, 2-methyl-, polymer with a-methyl-?-hydroxypoly (oxy-1,2-ethanediyl) and methyl 2-methyl-2-propenoate, graft or any combination thereof, in the range of 1 to 20% by weight of the composition.

In an exemplary embodiment, the present invention provides a synergistic composition comprising a) thiophanate-methyl in the range of 1 to 40% by weight of the composition, b) flutriafol in the range of 0.5 to 40% by weight of the composition, c) at least one nitroguanidine insecticide selected from thiamethoxam or clothianidin in the range of 1 to 40% by weight of the composition, d) at least one surface active agent in the range of 1 to 20% by weight of the composition and e) at least one agriculturally acceptable excipient.

In another preferred embodiment, the present invention provides a synergistic composition comprising a) thiophanate-methyl in the range of 1 to 30% by weight of the composition, b) flutriafol in the range of 0.5 to 25% by weight of the composition, c) thiamethoxam in the range of 1 to 40% by weight of the composition, d) at least one surface active agent in the range of 1 to 10% by weight of the composition and e) at least one agriculturally acceptable excipient.

In another preferred embodiment, the present invention provides a synergistic composition comprising a) thiophanate-methyl in the range of 1 to 30% by weight of the composition, b) flutriafol in the range of 0.5 to 25% by weight of the composition, c) clothianidin in the range of 1 to 40% by weight of the composition, d) at least one surface active agent in the range of 1 to 10% by weight of the composition and e) at least one agriculturally acceptable excipient.

The synergistic composition of the present invention is useful for effectively controlling soil borne pests, improving germination, and also enhancing the vigour and yield of the plant. Further, the synergistic composition of the present invention is non-phytotoxic and has good stability.

The inventors have surprisingly found that the composition at the aforementioned weight percentage ranges provides synergistic effect.

In another exemplary embodiment, the synergistic composition of the present invention may be formulated as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW).

In a preferred embodiment, the synergistic composition of the present invention is formulated as a Flowable concentrate for seed treatment (FS), a Wettable powder (WP), and a Suspension concentrate (SC).

In another exemplary embodiment, the synergistic composition of the present invention may comprise one or more agriculturally acceptable excipient selected from the group comprising a carrier(s), surfactant(s), binder(s), disintegrating agent(s), dispersants or dispersing agent(s), wetting agents, pH modifier(s), thickener(s), biocide(s), Preservative(s), anti-freezing agent(s), antifoaming agent(s), colorant(s), defoamer(s), solvents, stabilizer(s) or any combination thereof.
A dispersant, also known as a dispersing agent, are a common ingredient in wettable powders, suspension concentrates, and water-dispersible granules. Surface active agents used as dispersants have the ability to strongly adsorb onto a particle surface and offer a charged or steric barrier to particle re-aggregation. Surface active agents that are often employed are anionic, non-ionic, or mixes of the two. Sodium lingo sulphonates are the most often used dispersants in wettable powder compositions.

In another exemplary embodiment of the present invention, the dispersing agents are present in the range of 1 to 20% by weight of the composition.

Anti-freezing agent(s) may be selected from the group comprising, but not limited to, glycols, mono-ethylene glycol, di-ethylene glycol, propylene glycol, polyethylene glycols, methoxy polyethylene glycols, polypropylene glycols, polybutylene glycols, glycerine, and ethylene glycol.

In another exemplary embodiment of the present invention, the anti-freezing agent is present in the range of 1 to 15% by weight of the composition.

Water-based formulations often cause foam during mixing operations in production. To reduce the tendency for foaming, anti-foaming agents are often added either during the production stage or before filling bottles. Generally, there are two anti-foaming agents: silicones and non-silicones. Silicones are usually aqueous emulsions of dimethyl polysiloxane, while the non-silicone anti-foam agents are water-insoluble oils, such as octanol and nonanol or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface.

In another exemplary embodiment of the present invention, the anti-foaming agent is present in the range of 0.01 to 5% by weight of the composition.

A wetting agent is a substance that, when added to a liquid, increases the spreading or penetration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble liquids or suspension concentrates, and during mixing of a product with water in a spray tank or other vessel to reduce the wetting time of wettable powders and to improve the penetration of water into water-dispersible granules. Wetting agent(s) may be selected from the group comprising, but not limited to, alcohols, C9-11-iso-, C10-rich, and ethoxylated.

In another exemplary embodiment of the present invention, the wetting agents are present in the range of 1 to 10% by weight of the composition.

Thickener(s) and/or viscosity modifiers may be selected from the group comprising, but not limited to, water-soluble polymer and inorganic fine powder, wherein water-soluble polymer such as xanthan gum, welan gum, guar gum, polyvinyl alcohol, carboxy methylcellulose, polyvinyl pyrrolidone, carboxyvinyl polymer, acrylic polymer, starch derivative or polysaccharide; or an inorganic fine powder selected from high purity silica, bentonite, or white carbon. These thickeners may be used alone or in combination.

In another exemplary embodiment of the present invention, the thickener is present in the range of 0.01 to 10% by weight of the composition.

Preservative(s) and/or biocide(s) may be selected from the group comprising, but not limited to, 20% aqueous dipropylene glycol solution of 1, 2-benzisothiazolin-3-one, formaldehyde potassium sorbate, 4-hydroxybenzoic acid esters, 2-methyl-4-isothiazolin-3-one, and 5-chloro-2-methyl-4-isothiazolin-3-one.

In another exemplary embodiment of the present invention, the biocide is present in the range of 0.01 to 5% by weight of the composition.

Solvent(s) may be selected from the group comprising of, but not limited to, water, demineralized water (DM); alcohols such as ethanol, propanol, n-octanol, isopropanol ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerine; 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 normal paraffin, isoparaffin, kerosene, mineral oil; aromatic hydrocarbons such as xylene, toluene, naphthalene, solvent naphtha, solvent C9, solvent C10, solvent C12, solvesso 100, solvesso 150, solvesso 200; chlorinated aliphatic or aromatic hydrocarbons such as chloro benzene, chloro ethylene, methylene chloride; esters such as ethyl acetate, diisopropyl phthalate, dimethyl adipate, methyl oleate, methyl tallowate; lactones such as gamma-butyrolactone; amides such as dimethyl formamide, N-methyl-2-pyrrolidone, N-octyl pyrolidone, N, N dimethyl decanamide; nitriles such as acetonitrile; organo sulfur compounds.
In another exemplary embodiment of the present invention, the solvent is present in the “Quantum Satis” i.e., Q.S quantity.

In another exemplary embodiment, the present invention provides a process for the preparation of synergistic compositions comprising the steps of (a) charging a vessel with demineralized water (DM); (b) adding silicon defoamer and stirring the mixture; (c) adding surface active agent, wetting agent, anti-freezing agent, and precipitated silica to the mixture of step (b) under continuous stirring; (d) adding and mixing actives to the mixture of step (c) and homogenizing; (e) milling the mixture of step (d) by passing through a bead mill; (f) transferring the mixture of step (e) to a secondary post feed vessel; (g) adding colorant, xanthan gum solution, biocide and rest water to the mixture of step (f); (h) mixing and homogenizing the mixture of step (g); (i) homogenizing the mixture of step (h) for another 5 to 10 minutes, in case, any lumps of xanthan gum are left; and (j) sieving and packing the mixture of step (g) if no lumps are observed.

In another preferred embodiment, the actives are selected from thiophanate-methyl, flutriafol, thiamethoxam and clothianidin.

In another preferred embodiment, the synergistic composition has a particle size in the range of 0.1 to 30 microns.

In another preferred embodiment, the present invention provides a process for the preparation of synergistic compositions comprising the following steps of (a) charging a vessel with demineralized water (DM); (b) adding silicon defoamer and stirring the mixture; (c) adding surface active agent, wetting agent, anti-freezing agent, and precipitated silica to the mixture of step (b) under continuous stirring for 20 minutes; (d) adding and mixing thiophanate-methyl, flutriafol, at least one nitroguanidine insecticide selected from thiamethoxam and clothianidin to the mixture of step (c) and homogenizing for 30 minutes; (e) milling the mixture of step (d) by passing through a bead mill; (f) transferring the mixture of step (e) to a secondary post feed vessel; (g) adding colorant, xanthan gum solution, biocide and rest water to the mixture of step (f); (h) mixing and homogenizing the mixture of step (g) for 30 minutes; (i) homogenizing the mixture of step (h) for another 5 to 10 minutes, in case, any lumps of xanthan gum are left; and (j) sieving and packing the mixture of step (g) after passing through a normal sieve of 36 mesh if no lumps are observed.

EXAMPLES
Below are the various examples for preparing different formulations according to the present invention. However, the below examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention.

The synergistic composition of the present invention comprising thiophanate methyl, flutriafol, at least one nitroguanidine insecticide selected from thiamethoxam and clothianidin, at least one surface active agent and at least one agriculturally acceptable excipient in the form of flowable concentrates for seed treatment (FS) is provided in table 1 to table 15, wettable powder (WP) is provided in table 16 to table 19, and suspension concentrate (SC) is provided in table 20 to table 25.

Example 1: Flowable concentrate for seed treatment (FS) composition

Example 1a:
Table 1: FS Composition (Thiophanate methyl 25% + Flutriafol 3.75% + Thiamethoxam 20% FS w/v)

S. No. Ingredients Function Quantity In % W/V
1. Thiophanate Methyl A. I A.I. 25 %
2. Flutriafol A. I A.I. 3.75 %
3. Thiamethoxam A.I A.I. 20 %
4. Poly (oxy-1, 2-ethanediyl), a-sulfo-?-[2, 4, 6-tris (1-phenylethyl) phenoxy]-, ammonium salt.
(CAS-No. 119432-41-6)
Surface Active agent
3.0 %
5. Naphthalene and alkyl naphthalene sulphonic acids formaldehyde condensate, sodium salt
(CAS number: 68425-94-5) 2.0%
6. Nonionic surfactants
alcohols, C12-15, ethoxylated
(CAS-No. 68131-39-5) Wetting agent 2.0 %
7. Propylene glycol
Anti-freezing agent 10%
8. Aqueous dispersion of pigment Colorant 12 %
9. Silicon Defoamer Antifoaming agent 0.5 %
10. Xanthan Gum powder
(CAS No. 11138-66-2) Viscosity modifier 0.10 %
11. 1,2-Benzisothiazolin-3- one @ 20 % as preservative
(CAS No. 2634-33-5) Biocide 0.25 %
12. Water Carrier QS
TOTAL 100

Process for preparation of the composition:
1. Charging a pre-feed vessel with deionized water, a silicone defoamer was added and stirred,
2. Ingredients such as Poly(oxy-1,2-ethanediyl), a-sulfo-?-[2,4,6-tris(1 phenylethyl) phenoxy]-, ammonium salt, naphthalene and alkyl naphthalene sulphonic acids formaldehyde condensate, sodium salt; nonionic surfactants; sodium dibutyl naphthalene sulphonate; precipitated silica; and propylene glycol, were added to the above mixture under continuous stirring for about 20 minutes,
3. Followed by adding active ingredients, thiophanate methyl, flutriafol, and thiamethoxam to the mixture and mixed thoroughly. The mixture was homogenized for about 30 minutes,
4. Thereafter, the mixture was milled by passing through a bead mill to obtain a particle size below 10 microns and transferred to a secondary post-feed vessel,
5. The colorant, xanthan gum solution, biocide and remaining water were added to the mixture and homogenized for about 30 minutes,
6. If any lumps of xanthan gum were present, the mixture was further homogenized for an additional 5 to 10 minutes to obtain a flowable concentrate (FS),
7. The material is packed after passing through a normal sieve of 36 mesh if no lumps are observed.

Table 2: Physiochemical Properties of the composition
S. No. Parameters Results
1. Physical state Viscous Liquid
2. Colour Red
3. Density (20ºC) 1.20 ± 0.1 g/ml @ 20°C
4. pH 1 % Aq. Solution 6.0 – 8.0
5. Wet Sieve Test % w/w 98.0 % min.
6. Persistent Foam Max. 60 ml after 1 min.
7. Viscosity (Brookfield) at 60 RPM spindle 3 300 - 600 cps
8. Particle Size D10 ? 5
D50 ? 7
D90 ? 10

Table 3: Storage Stability Data
Test Parameters 0 Day @ 25°C 28 Days @ 25°C 28 Days AHS @ 54°C.
Description Red viscous liquid Red viscous liquid Red viscous liquid
Thiophanate Methyl A. I 25.05 25.15 25.68
Flutriafol A. I 3.68 3.68 3.59
Thiamethoxam A. I 20.60 20.77 20.57
pH 1 % Aq. Solution 6.47 6.53 6.57
Density g/ml 1.16 1.158 1.159
Viscosity (Brookfield) at 60 RPM spindle 3 530 cps 552 cps 563 cps
Persistent Foam (0.5% aqua. Sol.) 20 ml 20 ml 20 ml
Wet Sieve (45 µ) Complies Complies Complies
Particle Size D10 2.91 4.12 4.51
D50 5.98 6.17 6.8
D90 9.54 9.79 9.86

The above tables 1-3 describes a composition comprising Thiophanate Methyl, Flutriafol, and Thiamethoxam, blended with a selected surfactant. The surfactant may be selected from but not limited to Poly (oxy-1, 2-ethanediyl), a-sulfo-?-[2,4,6-tris(1-phenylethyl) phenoxy]-, ammonium salt; nonionic surfactants; sodium dibutyl naphthalene sulfonate; precipitated silica; or propylene glycol.

Further, as evident from above tables the composition is a viscous liquid with a red color, density of 1.20 ± 0.1 g/ml at 20°C and a pH in the range of 6.0 to 8.0 in a 1% aqueous solution that ensures compatibility and stability in various applications. The composition meets a stringent wet sieve test criterion, achieving a minimum of 98.0% w/w, indicating high particulate consistency. The above composition maintains a maximum persistent foam volume of 60 ml after 1 minute, minimizing foam-related issues during use. Its viscosity, as measured with a Brookfield viscometer at 60 RPM, ranges from 300 to 600 cps, providing optimal flow characteristics for the composition’s application. Further, the particle size distribution of composition is optimized, i.e., D10 less than 5 µm, D50 less than 7 µm, and D90 less than 10 µm, thereby ensuring effective performance and application of the composition.

Additionally, the composition shows excellent stability under accelerated storage conditions and yields positive results across all parameters initially and after 28 days at 25°C, indicating reliable performance under standard conditions. It also maintains stability and effectiveness after 28 days at 54°C under accelerated heat storage (AHS) conditions, demonstrating its robustness and durability for long-term storage and use. This stability highlights the formulation’s suitability for various applications and environmental conditions.

Example 1b:
Table 4: FS composition (Thiophanate methyl 25% + Flutriafol 3.75% + Clothianidin 20% FS w/v)

S. No. Ingredients Function Quantity In % W/V
1. Thiophanate Methyl A.I. 25 %
2. Flutriafol A. I A.I. 3.75 %
3. Clothianidin A.I A.I. 20 %
4. Poly(oxy-1,2-ethanediyl), a-sulfo-?-[2,4,6-tris(1-phenylethyl) phenoxy]-, ammonium salt.
(CAS-No. 119432-41-6) Surface Active agent
3.2 %
5. Naphthalene and alkyl naphthalene sulphonic acids formaldehyde condensate, sodium salt
(CAS number: 68425-94-5) 2.0%
6. Nonionic surfactants
alcohols, C12-15, ethoxylated
(CAS-No. 68131-39-5) Wetting agent 2.0 %
7. Propylene glycol
Anti-freezing agent 12%
8. Aqueous dispersion of pigment Colorant 15 %
9. Silicon Defoamer Antifoaming agent 0.5 %
10. Xanthan Gum powder
(CAS No. 11138-66-2) Viscosity modifier 0.10 %
11. 1,2-Benzisothiazolin-3- one @ 20 % as preservative
(CAS No. 2634-33-5) Biocide 0.25 %
12. Water Carrier QS
TOTAL 100

Process for preparation of the composition: Charging a pre-feed vessel with deionized water and a silicone defoamer and the mixture was stirred. Next, Poly (oxy-1, 2-ethanediyl), a-sulfo-?-[2,4,6-tris(1 phenylethyl) phenoxy]-, ammonium salt; nonionic surfactants; sodium dibutyl naphthalene sulphonate; precipitated silica; and propylene glycol were added to the mixture while continuously stirring for 20 minutes. The active ingredients - thiophanate methyl, flutriafol, and clothianidin - were added to the mixture and thoroughly mixed, followed by homogenizing for 30 minutes. The mixture was milled by passing through a bead mill to obtain a particle size below 10 microns. The milled mixture was then moved to a secondary post-feed vessel. The colorant, xanthan gum solution, biocide, and remaining water were added to the mixture, which was then mixed and homogenized for 30 minutes. If any lumps of xanthan gum were present, the mixture was further homogenized for 5 to 10 minutes to obtain a flowable concentrate (FS). If no lumps are observed, the material is packed after passing through a standard 36 mesh sieve.

Table 5: Physiochemical Properties of the Composition
S. No. Parameters Results
1. Physical state Viscous Liquid
2. Colour Red
3. Density (20ºC) 1.20 ± 0.1 g/ml @ 20°C
4. pH 1 % Aq. Solution 6.0 – 8.0
5. Wet Sieve Test % w/w 98.0 % min.
6. Persistent Foam Max. 60 ml after 1 min.
7. Viscosity (Brookfield) at 60 RPM spindle 3 300 - 600 cps
8. Particle Size D10 ? 5
D50 ? 7
D90 ? 10

Table 6: Storage Stability Data
Test Parameters 0 Day @ 25°C 28 Days @ 25°C 28 Days AHS @ 54°C.
Description Red viscous liquid Red viscous liquid Red viscous liquid
Thiophanate Methyl A. I 25.03 25.01 25.14
Flutriafol A. I 3.78 3.77 3.72
Clothianidin A. I 20.11 20.07 20.07
pH 1 % Aq. Solution 6.56 6.60 6.55
Density g/ml 1.16 1.157 1.156
Viscosity (Brookfield) at 60 RPM spindle 3 525 cps 520 cps 533 cps
Persistent Foam (0.5% aqua. Sol.) 20 ml 20 ml 15 ml
Wet Sieve (45 µ) Complies Complies Complies
Particle Size D10 2.85 4.04 4.31
D50 6.47 6.28 6.69
D90 9.63 9.67 9.75

The above tables 4-6 discloses a composition comprising Thiophanate Methyl, Flutriafol A.I, Clothianidin A.I, and at least one surfactant. The obtained composition as characterized in table 5 is a viscous liquid with red color, and density of 1.20 ±0.1 g/ml at 20°C and a pH of 6.0 to 8.0 in a 1% aqueous solution. Further, the composition meets a minimum wet sieve test requirement of 98.0% w/w and has a maximum persistent foam volume of 60 ml after 1 minute. The measured viscosity via Brookfield spindle 3 at 60 RPM, ranges from 300 to 600 cps. The particle size distribution of the composition is less than 5 µm for D10, less than 7 µm for D50 and less than 10 µm for D90. Furthermore, the composition exhibits excellent accelerated storage stability, showing positive results for all parameters at both 0 days and after 28 days at 25°C, as well as after 28 days at 54°C under accelerated heat storage conditions (AHS).

Example 1c:
Table 7: FS composition (Thiophanate methyl 28% + Flutriafol 8.75% + Thiamethoxam 12% FS w/v)
S. No. Ingredients Function Quantity In % W/V
1. Thiophanate Methyl A.I. 28 %
2. Flutriafol A. I A.I. 8.75 %
3. Thiamethoxam A.I A.I. 12 %
4. Poly (oxy-1,2-ethanediyl), a-sulfo-?-[2,4,6-tris(1-phenylethyl) phenoxy]-, ammonium salt.
(CAS-No. 119432-41-6)

Surface Active agent
3.7 %
5. Sodium dibutylnaphthalenesulphonate
(CAS number: 25417-20-3) 1.2%
6. Nonionic surfactants
alcohols, C12-15, ethoxylated
(CAS-No. 68131-39-5) Wetting agent 2.0 %
7. Propylene glycol
Anti-freezing agent 12%
8. Precipitated Silica Additive 0.5 %
9. Aqueous dispersion of pigment Colorant 15%
10. Silicon Defoamer Antifoaming agent 0.5 %
11. Xanthum Gum powder
(CAS No. 11138-66-2) Viscosity modifier 0.10 %
12. 1,2-Benzisothiazolin-3- one @ 20 % as preservative
(CAS No. 2634-33-5) Biocide 0.25 %
13. Water Carrier QS
TOTAL 100

Process for preparation of the composition:
After charging the pre-feed vessel with deionized water, a silicone defoamer was added, and the mixture was stirred. Then, Poly (oxy-1, 2-ethanediyl), a-sulfo-?-[2,4,6-tris(1 phenylethyl) phenoxy]-, ammonium salt; nonionic surfactants; sodium dibutyl naphthalene sulphonate; precipitated silica; and propylene glycol were added to the mixture while continuously stirring for 20 minutes. The active ingredients, namely thiophanate methyl, flutriafol, and thiamethoxam, were added to the mixture and thoroughly mixed, followed by homogenizing for 30 minutes. The resulting mixture was milled by passing it through a bead mill to achieve a particle size below 10 microns. The milled mixture was then transferred to a secondary post-feed vessel. Subsequently, the colorant, xanthan gum solution, biocide, and remaining water were added to the mixture. The mixture was mixed and homogenized for 30 minutes. If any lumps of xanthan gum were present, the mixture was further homogenized for an additional 5 to 10 minutes to obtain a flowable concentrate (FS). The material is packed after passing through a normal sieve of 36 mesh if no lumps are observed.

Table 8: Physiochemical Properties of the composition
S. No. Parameters Results
1. Physical state Viscous Liquid
2. Colour Red
3. Density (20ºC) 1.20 ± 0.1 g/ml @ 20°C
4. pH 1 % Aq. Solution 5.5 – 7.5
5. Flash Point NA
6. Wet Sieve Test % w/w 98.0 % min.
7. Persistent Foam Max. 60 ml after 1 min.
8. Viscosity (Brookfield) at 60 RPM spindle 3 300 - 600 cps
9. Particle Size D10 ? 5
D50 ? 7
D90 ? 10

Table 9: Storage Stability Data
S. No. Test Parameters 0 Day @ 25°C
1. Description Red viscous liquid
2. Thiophanate Methyl A. I 28.11
3. Flutriafol A. I 8.77
4. Thiamethoxam A. I 12.09
5. pH 1 % Aq. Solution 6.07
6. Density g/ml 1.22
7. Viscosity (Brookfield) at 60 RPM spindle 3 567 cps
8. Persistent Foam (0.5% aqua. Sol.) 10 ml
9. Wet Sieve (45µ) Complies
10. Particle Size D10 1.27
D50 3.68
D90 9.8
Example 1d:

As evident from tables 7 to 9, the composition comprising of Thiophanate Methyl, Flutriafol A.I, Thiamethoxam A.I, blended and a surfactant, wherein the surfactant may be selected from the Poly(oxy-1,2-ethanediyl), a-sulfo-?-[2,4,6-tris(1-phenylethyl) phenoxy]-, ammonium salt, nonionic surfactants, C12-15 ethoxylated alcohols, sodium dibutyl naphthalene sulphonate, propylene glycol, and precipitated silica or any combination thereof. Further, the composition has balanced physicochemical properties, i.e., viscous red with a density of 1.20 ± 0.1 g/ml at 20°C and a pH of 5.5 to 7.5 in a 1% aqueous solution. The composition meets the minimum sieve test requirement of 98.0% w/w, has a maximum persistent foam volume of 60 ml after 1 minute, and a viscosity of 300 to 600 cps as measured with a Brookfield spindle 3 at 60 RPM. The particle size of the composition is less than 5 µm for D10 and less than 7 µm for D50. The formulation demonstrates excellent accelerated storage stability with positive results for all parameters both at the initial stage and after 28 days at 25°C and after 28 days at 54°C under accelerated heat storage conditions (AHS).

Table 10: FS composition (Thiophanate methyl 9.5% + Flutriafol 10% + Clothianidin 25% FS w/v)
S. No. Ingredients Function Quantity In % W/V
1. Thiophanate Methyl A.I. 9.5 %
2. Flutriafol A. I A.I. 10%
3. Clothianidin A.I A.I. 25%
4. Acrylic copolymer in aqueous solution
(CAS-No. Proprietary blends) Surface Active Agents 3.2 %
5. Alkoxylated alcohol
(CAS-No. Proprietary blend) Wetting agent 4.0 %
6. Propylene glycol
Anti-freezing agent 12%
7. Precipitated Silica Additive 0.6 %
8. Aqueous dispersion of pigment Colorant 10%
9. Silicon Defoamer Antifoaming agent 0.7 %
10. Xanthum Gum powder
(CAS No. 11138-66-2) Viscosity modifier 0.10 %
11. 1,2-Benzisothiazolin-3- one @ 20 % as preservative
(CAS No. 2634-33-5) Biocide 0.25 %
12. Water Carrier QS
TOTAL 100

Process for preparation of the composition:
Charging a pre-feed vessel with deionized water and adding silicone defoamer, under continuous stirring. Next, acrylic copolymer in aqueous solution, alkoxylated alcohol, precipitated silica, and propylene glycol were added to the mixture while stirring for about 20 minutes. Then, the active ingredients - thiophanate methyl, flutriafol, and clothianidin - were added to the mixture and thoroughly mixed, followed by homogenizing for about 30 minutes. The resulting mixture was milled by passing through a bead mill to obtain a particle size below 10 microns. The milled mixture was then transferred to a secondary post-feed vessel. After that, the colorant, xanthan gum solution, biocide, and the remaining water were added to the mixture. The mixture was mixed and homogenized for 30 minutes. If any lumps of xanthan gum were present, the mixture was further homogenized for about 5 to 10 minutes to obtain a flowable concentrate (FS). The material is packed after passing through a normal sieve of 36 mesh if no lumps are observed.

Table 11: Physiochemical Properties of the Composition
S. No. Parameters Results
1. Physical state Viscous Liquid
2. Colour Red
3. Density (20ºC) 1.20 ± 0.1 g/ml @ 20°C
4. pH 1 % Aq. Solution 5.5 – 7.5
5. Flash Point NA
6. Wet Sieve Test % w/w 98.0 % min.
7. Persistent Foam Max. 60 ml after 1 min.
8. Viscosity (Brookfield) at 60 RPM spindle 3 300 - 600 cps
9. Particle Size D10 ? 5
D50 ? 7
D90 ? 10

Table 12: Storage Stability Data
S. No. Test Parameters 0 Day @ 25°C
1. Description Red viscous liquid
2. Thiophanate Methyl A. I 9.57
3. Flutriafol A. I 10.02
4. Clothianidin A. I 25.07
5. pH 1 % Aq. Solution 6.02
6. Density g/ml 1.40
7. Viscosity (Brookfield) at 60 RPM spindle 3 572 cps
8. Persistent Foam (0.5% aqua. Sol.) 15 ml
9. Wet Sieve (45 µ) Complies
10. Particle Size D10 1.02
D50 5.30
D90 9.83

The above tables 10-12 provide a composition comprising of Thiophanate Methyl, Flutriafol A.I., and Clothianidin A.I with a surfactant. Further, the surfactant may be selected from acrylic copolymer in aqueous solution, alkoxylated alcohol, propylene glycol, or precipitated silica. The composition was characterized as a viscous red liquid with a density of 1.20 ± 0.1 g/ml at 20°C. The pH of the formulation in a 1% aqueous solution is maintained between 5.5 and 7.5, ensuring a stable and effective range for its intended applications. Further, the said composition meets a minimum wet sieve test standard of 98.0% w/w, reflecting its high level of particulate consistency.

The composition has a maximum foam persistent volume of 60 ml measured after 1 minute, which is suitable for minimizing unwanted foam during use. As determined using a Brookfield spindle 3 at 60 RPM, the viscosity ranges from 300 to 600 cps, indicating the liquid’s desirable flow and application properties. Further, the composition's particle size distribution is less than 5 µm for D10, less than 7 µm for D50 and less than 10 µm for D90. The particle size ensures composition effectiveness and performance in various applications. Moreover, in terms of stability, the composition demonstrates excellent performance under accelerated storage conditions. The composition showed positive results for all evaluated parameters both at the initial stage and after 28 days of storage at 25°C. Additionally, it maintains stability and functionality after 28 days at 54°C under accelerated heat storage conditions (AHS), indicating its robustness and reliability over extended periods and varying conditions. This stability underscores the formulation’s suitability for long-term use and storage.

Example 1e:
Table 13: FS Composition (Thiophanate methyl 20% + Flutriafol 12.25% + Thiamethoxam 10% FS w/v)

S. No. Ingredients Function Quantity In % W/V
1. Thiophanate Methyl A.I. 20%
2. Flutriafol A. I A.I. 12.25 %
3. Thiamethoxam A.I A.I. 10%
4. Acrylic Copolymer solution
(CAS-No. 119724-54-8) Surface Active Agent 3.2 %
5. Alkoxylated alcohol
(CAS-No. Proprietary blend) Wetting agent 4.0 %
6. Propylene glycol
Anti-freezing agent 12%
7. Precipitated Silica Additive 0.5 %
8. Aqueous dispersion of pigment Colorant 10%
9. Silicon Defoamer Antifoaming agent 0.5 %
10. Xanthum Gum powder
(CAS No. 11138-66-2) Viscosity modifier 0.10 %
11. 1,2-Benzisothiazolin-3- one @ 20 % as preservative
(CAS No. 2634-33-5) Biocide 0.25 %
12. Water Carrier QS
TOTAL 100

Process for preparation of the Composition: Charging a pre-feed vessel with deionized water and a silicone defoamer, and the mixture was stirred. Then, acrylic copolymer in aqueous solution, alkoxylated alcohol, precipitated silica, and propylene glycol were added to the mixture while continuously stirring for 20 minutes. The active ingredients, namely thiophanate methyl, flutriafol, and thiamethoxam, were then added and thoroughly mixed into the mixture, followed by homogenization for 30 minutes. The resulting mixture was milled by passing it through a bead mill to achieve a particle size below 10 microns. The milled mixture was then transferred to a secondary post-feed vessel. Following that, the colorant, xanthan gum solution, biocide, and the remaining water were added to the mixture, which was then mixed and homogenized for 30 minutes. If any lumps of xanthan gum were present, the mixture was further homogenized for an additional 5 to 10 minutes in order to obtain a flowable concentrate (FS). The material is packed after passing through a 36-mesh sieve if no lumps are observed

Table 14: Physiochemical Properties of the Composition
S. No. Parameters Results
1. Physical state Viscous Liquid
2. Colour Red
3. Density (20ºC) 1.20 ± 0.1 g/ml @ 20°C
4. pH 1 % Aq. Solution 5.5 – 7.5
5. Flash Point NA
6. Wet Sieve Test % w/w 98.0 % min.
7. Persistent Foam Max. 60 ml after 1 min.
8. Viscosity (Brookfield) at 60 RPM spindle 3 300 - 600 cps
9. Particle Size D10 ? 5
D50 ? 7
D90 ? 10

Table 15: Storage Stability Data
S. No. Test Parameters 0 Day @ 25°C
1. Description Red viscous liquid
2. Thiophanate Methyl A. I 20.07
3. Flutriafol A. I 12.45
4. Thiamethoxam A. I 10.11
5. pH 1 % Aq. Solution 6.57
6. Density g/ml 1.27
7. Viscosity (Brookfield) at 60 RPM spindle 3 574 cps
8. Persistent Foam (0.5% aqua. Sol.) 15 ml
9. Wet Sieve (45 µ) Complies
10. Particle Size D10 1.23
D50 3.21
D90 9.87

The above tables 13 to 15 provide a composition comprising of Thiophanate Methyl, Flutriafol, Thiamethoxam A.I., and a surfactant selected from selected from acrylic copolymer solution (CAS-No. 119724-54-8), alkoxylated alcohol, propylene glycol, or precipitated silica. The composition is characterized as a viscous red liquid with a 1.20 ± 0.1 g/ml density at 20°C, a pH in the range of 5.5 to 7.5 in a 1% aqueous solution. The composition satisfies the minimum wet sieve test requirement of 98.0% w/w, indicating high-quality consistency in particulate size. It demonstrates controlled foam properties, with a maximum persistent foam volume of 60 ml measured after 1 minute. The viscosity, determined using a Brookfield spindle 3 at 60 RPM, falls within the 300 to 600 cps range, reflecting its optimal flow characteristics. The particle size distribution of the composition is less than 5 µm for D10, less than 7 µm for D50, and less than 10 µm for D90, ensuring effective application and performance. The compositon also exhibits excellent stability under accelerated storage conditions. It maintains consistent performance across all tested parameters both at the initial stage and after 28 days of storage at 25°C. Furthermore, it shows robust stability after 28 days at 54°C under accelerated heat storage conditions (AHS), indicating its reliability and durability over time.

Example 2: Wettable Powder (WP) Composition

Example 2a:
Table 16: WP Composition (Thiophanate methyl 25% + Flutriafol A.I 3.75% + Thiamethoxam A.I 20% WP w/w)
S. No. Ingredient Quantity In % W/W
1. Thiophanate Methyl 25 %
2. Flutriafol A. I 3.75 %
3. Thiamethoxam A.I 20 %
4. Surface Active agent
Sodium dibutyl naphthalene sulphonate 5%
5. Wetting agent
Sodium 2-[methyloleoylamino]ethane-1-sulphonate 3%
6. Sticking agent
Carboxymethyl cellulose 0.05%
7. China clay QS to 100% w/w
TOTAL 100% w/w

Process for preparation of the composition:
The manufacturing facility has been thoroughly cleaned and sanitized. The active ingredients - thiophanate methyl, flutriafol, and thiamethoxam - were accurately weighed and transferred to the pre-blender. The dispersing agent, wetting agent, sticking agent, and china clay were added to the mixture and mixed for 30 minutes in the pre-blender. The mixture was then milled using an ACM (Air Classifying Mill) to obtain a micronized powder with a particle size of less than 20 microns. The milled powder is collected in the post-blender and homogenized for 30 minutes. The powder is packed after quality control testing to ensure it meets the required specification.

Table 17: Physiochemical Properties of the Composition
S. No. Parameters Results
1. Physical state Powder
2. Odour Odourless
3. Suspensibility % w/w 60% min.
4. pH (1%) aqueous soln. 5.50-8.50
5. Wet Sieve Test % w/w 98% min.
6. Foaming (0.5% aqueous, soln.) 120 ml max.
7. Wettability 120 sec. max.

Example 2b:
Table 18: WP Composition (Thiophanate methyl 22% + Flutriafol A.I 8% + Clothianidin A.I 24% WP w/w)

S. No. INGREDIENT QUANTITY IN % W/W
1. Thiophanate Methyl 22%
2. Flutriafol A. I 8 %
3. Thiamethoxam A.I 24 %
4. Surface Active Agent
Sodium dibutylnaphthalenesulphonate 10%
5. Wetting agent
Sodium 2-[methyloleoylamino]ethane-1-sulphonate 4%
6. Sticking agent
Carboxymethyl cellulose 0.08%
7. China clay QS to 100% w/w
TOTAL 100% w/w

Process for preparation of the composition:
1. The manufacturing facility was cleaned and sanitized thoroughly.
2. The active ingredients i.e. thiophanate methyl, flutriafol, and clothianidin were accurately weighed and transferred to the pre-blender.
3. Further, the dispersing agent, wetting agent, sticking agent, and china clay were added to the mixture and mixed for 30 minutes in the pre-blender.
4. The mixture was milled using an ACM (Air Classifying Mill) to obtain a micronized powder with a particle size of less than 20 microns.
5. The milled powder is collected in the post-blender and homogenize for about 30 minutes.
6. The powder is packed after quality control testing if it meets the required specifications.

Table 19: Physiochemical Properties of the composition
S. No. Parameters Results
1. Physical state Powder
2. Odour Odourless
3. Suspensibility % w/w 60% min.
4. pH (1%) aqueous soln. 5.50-8.50
5. Wet Sieve Test % w/w 98% min.
6. Foaming (0.5% aqueous, soln.) 120 ml max.
7. Wettability 120 sec. max.

Example 3: Suspension Concentrate (SC) composition

Example 3a:

Table 20: SC Composition (Thiophanate methyl 22% + Flutriafol 5.75% + Thiamethoxam 22% SC w/v)
S. No. Ingredients Function Quantity In % W/V
1. Thiophanate Methyl A.I. 22 %
2. Flutriafol A. I A.I. 5.75 %
3. Thiamethoxam A.I A.I. 22 %
4. Poly (oxy-1, 2-ethanediyl), a-sulfo-?-[2,4,6-tris(1-phenylethyl) phenoxy]-, ammonium salt.
(CAS-No. 119432-41-6) Surface Active Agents 3.2 %
5. Nonionic surfactants CAS-No. 68131-39-5 Wetting agent 2.5 %
6. Naphthalene and alkyl naphthalene sulphonic acids formaldehyde condensate, sodium salt
(CAS number: 68425-94-5) Surface Active Agents 4.0%
7. Propylene glycol Anti-freezing agent 12%
8. Silicon Defoamer Antifoaming agent 0.7 %
9. Xanthan Gum powder
(CAS No. 11138-66-2) Viscosity modifier 0.10 %
10. 1,2-Benzisothiazolin-3- one @ 20 % as preservative
(CAS No. 2634-33-5) Biocide 0.25 %
11. Water Carrier QS
TOTAL 100

Process for preparation of the composition:
1. Charging a pre-feed vessel with deionized water, adding silicone defoamer and stirring the mixture.
2. Further, the dispersing agent, wetting agent, and propylene glycol were added to the mixture and stirred continuously for 20 minutes.
3. The active ingredients i.e., thiophanate methyl, flutriafol, and thiamethoxam, were added to the mixture and mixed thoroughly, followed by homogenizing for 30 minutes.
4. The mixture was milled by passing through a bead mill to obtain a particle size below 10 microns.
5. The milled mixture was transferred to a secondary post-feed vessel.
6. The colorant, xanthan gum solution, biocide and remaining water were added to the mixture.
7. The mixture was mixed and homogenized for 30 minutes.
8. If any lumps of xanthan gum were present, the mixture was further homogenized for 5 to 10 minutes to obtain a suspension concentrate (SC).
9. The material is packed after passing through a normal sieve of 36 mesh if no lumps are observed.

Table 21: Physiochemical Properties of the composition
S. No. Parameters Results
1. Density (20ºC) 1.20 ± 0.1 g/ml @ 20°C
2. pH 1 % Aq. Solution 6.0 – 8.0
3. Wet Sieve Test % w/w 98.0 % min.
4. Persistent Foam Max. 60 ml after 1 min.
5. Viscosity (Brookfield) at 60 RPM spindle 3 300 - 600 cps
6. Particle Size D10 ? 5
D50 ? 7
D90 ? 10

Table 22: Storage Stability Data
S. No. Test Parameters 0 Day @ 25°C 28 Days @ 25°C 28 Days AHS @ 54°C.
1. Description viscous liquid viscous liquid viscous liquid
2. Thiophanate Methyl A. I 22.06 22.16 22.08
3. Flutriafol A. I 5.72 5.75 5.70
4. Thiamethoxam A. I 22.00 22.07 22.04
5. pH 1 % Aq. Solution 6.37 6.43 6.77
6. Density g/ml 1.15 1.18 1.19
7. Viscosity (Brookfield) at 60 RPM spindle 3 546 cps 558 cps 562 cps
8. Persistent Foam (0.5% aqua. Sol.) 20 ml 20 ml 20 ml
9. Wet Sieve (45 µ) Complies Complies Complies
10. Particle Size D10 2.81 4.24 4.61
D50 6.59 6.75 6.88
D90 9.50 9.70 9.82

Example 3b:

Table 23: SC Composition (Thiophanate methyl 9.5% + Flutriafol 24% + Clothianidin 25% SC w/v)
S. No. Ingredients Function Quantity In % W/V
1. Thiophanate Methyl A.I. 9.5 %
2. Flutriafol A. I A.I. 24%
3. Clothianidin A.I A.I. 25%
4. Acrylic copolymer in aqueous solution
(2-Propenoic acid, 2-methyl-, polymer with a-methyl-?-hydroxypoly(oxy-1,2-ethanediyl) and methyl 2-methyl-2-propenoate, graft)

Surface Active agent 3.8 %
5. Alkoxylated alcohol
CAS-No. Proprietary blend Wetting agent 6.0 %
6. Propylene glycol
Anti-freezing agent 10%
7. Precipitated Silica Additive 0.6 %
8. Silicon Defoamer Antifoaming agent 0.7 %
9. Xanthum Gum powder
CAS No. 11138-66-2 Viscosity modifier 0.12 %
10. 1,2-Benzisothiazolin-3- one @ 20 % as preservative
CAS No. 2634-33-5 Biocide 0.28 %
11. Water Carrier QS
TOTAL 100

Process for preparation of the composition:
After charging the preferred vessel with deionized water, a silicone defoamer was added and stirred. Further, acrylic copolymer in aqueous solution, alkoxylated alcohol, precipitated silica, and propylene glycol were added to the mixture under continuous stirring for 20 minutes. The active ingredients, i.e., thiophanate methyl, flutriafol, and thiamethoxam, were added to the mixture and mixed thoroughly, followed by homogenizing for 30 minutes. The mixture was milled by passing through a bead mill to obtain a particle size below 10 microns. The milled mixture was transferred to a secondary post-feed vessel. The colorant, xanthan gum solution, biocide and remaining water were added to the mixture. The mixture was mixed and homogenized for 30 minutes. The mixture was further homogenized for 5 to 10 minutes if any lumps of xanthan gum were present to obtain suspension concentrate (SC). The material is packed after passing through a normal sieve of 36 mesh if no lumps are observed.

Table 24: Physiochemical Properties of the composition
S. No. Parameters Results
1. Physical state Viscous Liquid
2. Relative density (20ºC) 1.20 ± 0.1 g/ml @ 20°C
3. pH 1 % Aq. Solution 5.5 – 7.5
4. Flash point NA
5. Wet Sieve Test % w/w 98.0 % min.
6. Persistent Foam Max. 60 ml after 1 min.
7. Viscosity (Brookfield) at 60 RPM spindle 3 300 – 600 cps
8. Particle Size D10 ? 5
D50 ? 7
D90 ? 10

Table 25: Storage Stability Data
S. No. Test Parameters 0Day @ 25°C
1. Description viscous liquid
2. Thiophanate Methyl A. I 9.27
3. Flutriafol A. I 24.08
4. Clothianidin A. I 25.12
5. pH 1 % Aq. Solution 6.21
6. Density g/ml 1.37
7. Viscosity (Brookfield) at 60 RPM spindle 3 564cps
8. Persistent Foam (0.5% aqua. Sol.) 15ml
9. Wet Sieve (45 µ) Complies
10. Particle Size D10 1.27
D50 5.32
D90 9.78

Example 4:
Table 26: Present invention composition with and without surface active agents
Composition with Surface Active Agent Composition without Surface Active Agent
Ingredients Quantity In % W/V Ingredients Quantity In % W/V
Thiophanate Methyl A.I. 25 % Thiophanate Methyl A.I. 25 %
Flutriafol A.I. 3.75 % Flutriafol A. I 3.75 %
Thiamethoxam A.I 20 % Thiamethoxam A.I 20 %
Poly(oxy-1,2-ethanediyl), a-sulfo-?-[2,4,6-tris(1-phenylethyl) phenoxy]-, ammonium salt.
(CAS-No. 119432-41-6)
(Surface Active Agent) 3.0 % Blend of Ethanol 2, 2, 2- nitrilotris-, compd. With alpha-(2,4,6-tris(1-phenylethyl)phenyl)- omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate, Alkyl phenol polyethanoxy ether, 2-2-oxydiethanol & Dihydrogen mono oxide (CAS-No. 105362-40-1, 9016-45-9, 111-46-6 & 7732-18-5) 4.0 %
Nonionic surfactants
alcohols, C12-15, ethoxylated
(CAS-No. 68131-39-5) 2.0 % Sodium Lignosulfonate
(CAS-No. 8061-51-6) 0.53 %
Naphthalene and alkyl naphthalene sulphonic acids formaldehyde condensate, sodium salt
(Surface Active Agent)
(CAS number: 68425-94-5) 2.0%

-

-
Propylene glycol
10% Propylene glycol 8.0 %
Aqueous dispersion of pigment 12 % Red Dye 2.5 %
Silicon Defoamer 0.5 % Silicon Defoamer 0.5 %
Xanthan Gum powder
(CAS No. 11138-66-2) 0.10 % Xanthan Gum powder
(CAS No. 11138-66-2) 0.12 %
1,2-Benzisothiazolin-3- one @ 20 % as preservative
(CAS No. 2634-33-5) 0.25 % 1,2-Benzisothiazolin-3- one @ 20 % as preservative
(CAS No. 2634-33-5) 0.25 %
Water QS Water QS
TOTAL 100 TOTAL 100

Table 27: Physiochemical properties of the composition with and without surface active agents.
Physiochemical Properties with Surface Active Agents Physiochemical Properties without Surface Active Agents
Parameters Results Parameters Results
Physical state Viscous Liquid Physical state Gel type liquid
Colour Red Colour Light red
pH 1 % Aq. Solution 6.0 – 8.0 pH 1 % Aq. Solution 7.8
Wet Sieve Test % w/w 98.0% min. Wet Sieve Test % w/w Complies
Persistent Foam Max. 60 ml after 1 min. Persistent Foam Nil
Viscosity (Brookfield) at 60 RPM spindle 3 300 - 600 cps Viscosity (Brookfield) at 60 RPM spindle 3 900 cps

Observation: The composition without surface active agents possessed multiple challenges such as gel-like consistency, variation in color, unfavorable results in the wet sieve, foaming test, and high viscosity. The increase in viscosity negatively impacted the stability as well as the performance of the composition. However, the composition with surface active agents showed better stability, enhanced suspensibility, reduced foaming, and optimal viscosity thereby improving the overall performance of the composition.

Storage stability observation without surface active agents: The composition without surface active agents formed hard sediments at the bottom after storing for 14 days at 54°C. This physical change negatively impacted the composition due to increased particle size and reduced flowability.

Example 5: Evaluation of synergistic composition of present invention for bio-efficacy against different crops & diseases

Methodology
Methodology for Laboratory Study-Food Poison Techniques:
• The different compositions were taken in the trial for treatment; the recommended doses of various compositions were added in 1000 ml of sterilized potato dextrose agar in a conical flask and mixed well. Food for the pathogens was poisoned this way, and then poisoned media was poured into sterilized plastic petri plates.
• Disc measuring 9 mm diameter of the actively growing mycelium pathogen of 10 days culture was placed in the centre of the petri dish with poisoned media. Plates without chemical (only potato dextrose agar media) served as untreated control plates. Plates were incubated at 24-25 °C for the growth of pathogens. All the treatment sets were replicated 5 times. The average growth of the pathogen was measured from all the treatment sets at 5, 10 and 15 DAI (Days after inoculation).

Methodology for Field Evaluation:
A trial was conducted on Groundnut in Reddipalem, Bapatla, Andhra Pradesh. The application of the compositions were done as per the seed treatment schedule. A total of 8 treatments with three replications each were taken. In each treatment, five plants were selected and tagged, and the same plants were observed with respect to various parameters such as shoot length, root length, vigour index and per cent disease incidence.

Procedure for Seed treatment:
The required quantity of seeds were put into the transparent polybag. The required amount of treatment compositions was measured as per the recommended doses and mixed with 10 ml of water to form the uniform coating of chemical on seed surface. Treated seeds were dried for 15-20 minutes under shade before sowing.

Formulae Used for the Observation Parameters
Food Poison Techniques:

Radial growth of mycelium was measured after five, ten, and fifteen days of incubation (DAI). The results were compared with control plates. The mean of all the replication was taken for calculations.

The percent inhibition of the fungus in treatments was calculated using following formula:
L = [(C – T)/C] x 100

Where, L is the percent inhibition; C is the colony radius in the control plate, and T is the radial growth of the pathogen in the poisoned plates (Chemically treated media plates).

Field Evaluation:
Bio-efficacy observation on the appearance of collar rot diseases in ground nut treated & untreated. Per cent disease incidence (PDI) on 0 day (as Pre count), 15th, 30th, and 45th day after sowing and count the number of dead plants per m2 for per cent disease incidence (PDI) and count the number of dead plants per m2 for per cent white grub damage at 15, 30 & 45 days after application (DAA).

The scored data was converted into per cent disease Incidence (PDI) using the formula given below:
Percent Disease Incidence (PDI) = No. of infected plants × 100
Total no. of plants

Percent disease reduction over control (PDC) was calculated by using the formula given below:

Percent disease reduction over control = PDI of control – PDI of treatment × 100
PDI of treatment
Germination percentage (Observation from counted seed sown per m2 to germinated seeds per m2) 15 days after sowing (DAS) using the formula given below:

Germination percentage = No. of total germinated seeds × 100
Total No. of seeds tested/sown

Growth parameters: Observation was taken by randomly selecting & tagging five plants/plot and recorded the data from same plants for every observation.

Vigour index formula: Shoot length & Root length of selected plants were recorded at 15 DAS & 30 DAS from each plot.

The vigour index (VI) of the plants was estimated by using the below-mentioned formulae:
Seedling Vigour index = (Root length + Shoot length) x Germination percentage where RL is root length (cm), SL is shoot length (cm) and GP is germination percentage.
Example 6: Laboratory Experiment Details
TRIAL 1: Bio-efficacy of synergistic composition of Thiophanate methyl, Flutriafol, and Thiamethoxam or Clothianidin against Aspergillus niger

Season Kharif 2023
Location Research Laboratory, Ambala
Age of Culture 10 days old
Temperature Range during Trial 25°C ± 2°C
Single plate size 90 mm
Date of inoculation 08-08-2023
Number of applications 1
Target Pest Aspergillus niger
Time of observation 5 DAI, 10 DAI (Days after inoculation)
Method of application Food poison Technique

Table 28: Effect of different treatments on Percent disease inhibition (PDI) against Aspergillus niger collar rot disease pathogen.
S. No Treatment Details Dose (g or ml/litre of PDA Percent disease inhibition (PDI)
5 DAI 10 DAI
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20%) FS 1ml 100.00 100.00
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29gm + 0.15ml 90.42 87.43
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15ml + 0.67ml 87.36 83.04
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29gm + 0.67ml 68.39 75.66
T5 Thiophanate methyl 70% WP 0.29gm 66.67 72.55
T6 Flutriafol 25% SC 0.15ml 78.54 81.43
T7 Thiamethoxam 30% FS 0.67ml 40.61 14.07
T8 Control NA 0.00 0.00
DAI: (Days after inoculation)
Table 29: Synergistic effect of combination of Thiophanate methyl, Flutriafol, and Thiamethoxam or Clothianidin against Aspergillus niger plant parasitic fungus at 10 DAI.
S. No. Treatment details Dose (g or ml/ litre of PDA Percent disease inhibition (PDI)
Observed Expected Ratio Synergy
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20 %) FS 1 ml 100.00 78.99 1.27 Yes
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 89.43 94.90 0.92 No
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 83.04 84.04 0.99 No
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 75.66 76.41 0.99 No
T5 Thiophanate methyl 70% WP 0.29 gm 72.55 - - -
T6 Flutriafol 25% SC 0.15 ml 81.43 - - -
T7 Thiamethoxam 30% FS 0.67 ml 14.07 - - -
T8 Control NA 0.00 - - -

Per cent Disease Inhibition: Table 29 shows that the present invention composition comprising thiophanate methyl (20%) + Flutriafol (3.75%) + Thiamethoxam (20%) FS provided the highest percentage of disease inhibition, thereby showing synergy as compared to other treatments.

Example 7:

TRIAL 2: Bio-efficacy of synergistic composition of Thiophanate methyl, Flutriafol, and Thiamethoxam or Clothianidin against Rhizoctonia solani

Season Kharif 2023
Location Research Laboratory, Ambala
Age of Culture 10 days old
Temperature Range during Trial 25°C ± 2°C
Single plate size 90 mm
Date of inoculation 01-08-2023
Number of applications 1
Target Pest Rhizoctonia solani
Time of observation 5 DAI, 10 DAI, 15 DAI (Days after inoculation)
Method of application Food poison Technique

Table 30: Effect of different treatments on Percent disease inhibition (PDI) against Rhizoctonia solani fungus.
S. No Treatment Details Dose (g or ml/ litre of PDA Percent disease inhibition (PDI)
5 DAI 10 DAI 15DAI
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20%) FS 1 ml/kg 83.00 71.58 70.18
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 79.45 66.60 66.67
T3 Flutriafol 25%SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 64.43 61.62 64.73
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 29.64 38.80 52.12
T5 Thiophanate methyl 70% WP 0.29 gm 26.48 34.23 49.70
T6 Flutriafol 25% SC 0.15 ml 64.82 60.17 62.06
T7 Thiamethoxam 30% FS 0.67 ml 20.55 36.31 36.24
T8 Control NA 0.00 0.00 0.00

Table 31: Synergistic effect of combination of Thiophanate methyl, Flutriafol, and Thiamethoxam or Clothianidin against Rhizoctonia solani fungus at 10 DAI.
S. No. Treatment details Dose (g or ml/ litre of PDA Percent disease inhibition (PDI)
Observed Expected Ratio Synergy
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20 %) FS 1 ml 71.58 68.36 1.05 Yes
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 66.60 73.80 0.90 No
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 61.62 74.63 0.83 No
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 38.80 58.11 0.67 No
T5 Thiophanate methyl 70% WP 0.29 gm 34.23 - - -
T6 Flutriafol 25% SC 0.15 ml 60.17 - - -
T7 Thiamethoxam 30% FS 0.67 ml 36.31 - - -
T8 Control NA 0.00 - - -
Percent Disease Inhibition: It is evident from the above, that the present invention’s composition comprising Thiophanate methyl (20%) + Flutriafol (3.75%) + Thiamethoxam (20%) FS provided highest per cent disease inhibition thereby showing synergy as compared to other treatments.
Example 8:
TRIAL 3: Bio-efficacy of synergistic composition of Thiophanate methyl, Flutriafol, and Thiamethoxam or Clothianidin against Sclerotium rolfsii

Season Kharif 2023
Location Research laboratory Ambala
Age of Culture 10 days old
Temperature Range during Trial 25°C ± 2°C
Single plate size 90 mm
Date of inoculation 07-08-2023
Number of applications 1
Target Pest Sclerotium rolfsii
Time of observation 3 DAI, 5 DAI (Days after inoculation)
Method of application Food poison Technique

Table 32: Effect of different treatments on Percent Disease Inhibition (PDI) against Sclerotium rolfsii fungus.
S. No. Treatment Details Dose (g or ml/ litre of PDA Percent disease inhibition (PDI)
3 DAI 5 DAI
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20%) FS 1 ml/kg seeds 75.39 74.56
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 69.94 63.44
T3 Flutriafol 25%SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 65.11 57.78
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 27.88 18.56
T5 Thiophanate methyl 70% WP 0.29 gm 24.92 17.22
T6 Flutriafol 25% SC 0.15 ml 59.66 58.00
T7 Thiamethoxam 30% FS 0.67 ml 1.71 2.22
T8 Control NA 0.00 0.00

Table 33: Synergistic effect of the combination of Thiophanate methyl, Flutriafol, and Thiamethoxam or Clothianidin against Sclerotium rolfsii plant parasitic fungus at 5 DAI.
S. No. Treatment details Dose (g or ml/ litre of PDA Percent disease inhibition (PDI)
Observed Expected Ratio Synergy
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20 %) FS 1ml 74.56 65.56 1.14 Yes
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 63.44 65.23 0.97 No
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 57.78 58.93 0.98 No
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 18.56 19.06 0.97 No
T5 Thiophanate methyl 70% WP 0.29 gm 17.22 - - -
T6 Flutriafol 25% SC 0.15 ml 58.00 - - -
T7 Thiamethoxam 30% FS 0.67 ml 2.22 - - -
T8 Control NA 0.00 - - -

Per cent Disease Inhibition: It is evident from the above tables that the present invention composition comprising Thiophanate methyl (20%) + Flutriafol (3.75%) + Thiamethoxam (20%) FS provided highest per cent disease inhibition thereby showing synergy as compared to other treatments.

Example 9:
TRIAL 4: Bio-efficacy of synergistic composition of Thiophanate methyl (4%), Flutriafol (0.75%), and Clothianidin (32%) FS against Aspergillus niger fungus.

Season Kharif 2023
Location Ambala Laboratory
Age of Culture 10 days old
Temperature Range during Trial 25°C ± 2°C
Single plate size 90mm
Date of inoculation 08-08-2023
Number of applications 1
Target Pest Aspergillus niger
Time of observation 5 DAI, 10 DAI (Days after inoculation)
Method of application Food poison Technique

Table 34: Effect of different treatments on Percent disease inhibition (PDI) against Aspergillus niger fungus.

S. No. Treatment Details Dose (g or ml/litre of PDA Percent disease inhibition (PDI)
5 DAI 10 DAI
T1 Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS 5 ml 100.00 100.00
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 90.42 86.39
T3 Flutriafol 25%SC + Clothianidin 50%WDG 0.15 ml + 3.2 gm 76.44 81.08
T4 Thiophanate methyl 70% WP + Clothianidin 50%WDG 0.29 gm + 3.2 g m 68.77 73.24
T5 Thiophanate methyl 70% WP 0.29 gm 66.67 72.55
T6 Flutriafol 25% SC 0.15 ml 78.54 81.43
T7 Clothianidin 50%WDG 3.2 gm 39.85 9.00
T8 Control NA 0.00 0.00

Table 35: Synergistic effect of combination of Thiophanate methyl (4%), Flutriafol (0.75%), and Clothianidin (32%) FS against Aspergillus niger plant parasitic fungus at 10 DAI.

S. No. Treatment details Dose (g or ml/litre of PDA Percent disease inhibition (PDI)
Observed Expected Ratio Synergy
T1 Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS 5 ml 100.00 84.73 1.18 Yes
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 89.39 94.90 0.91 No
T3 Flutriafol 25% SC + Clothianidin 50% WDG 0.15 ml + 3.2 gm 81.08 83.10 0.98 No
T4 Thiophanate methyl 70% WP + Clothianidin 50% WDG 0.29 gm + 3.2 gm 73.24 75.02 0.98 No
T5 Thiophanate methyl 70% WP 0.29 gm 72.55 - - -
T6 Flutriafol 25% SC 0.15 ml 81.43 - - -
T7 Clothianidin 50% WDG 3.2 gm 9.00 - - -
T8 Control NA 0.00 - - -

Per cent Disease Inhibition: It is evident from the above that the present invention composition comprising Thiophanate methyl (4%) + Flutriafol (0.75%) + Clothianidin (32%) FS provided highest per cent disease inhibition, thereby showing synergy as compared to other treatments.

Example 10:

TRIAL 5: Bio-efficacy of synergistic composition of Thiophanate methyl (4%), Flutriafol (0.75%), and Clothianidin (32%) FS against Rhizoctonia solani fungus.
Season Kharif 2023
Location Research Laboratory Ambala
Age of Culture 10 days old
Temperature Range during Trial 25°C ± 2°C
Single plate size 90 mm
Date of inoculation 01-08-2023
Number of applications 1
Target Pest Rhizoctonia solani
Time of observation 5 DAI, 10 DAI, 15DAI (Days after inoculation)
Method of application Food poison Technique

Table 36: Effect of different treatments on Percent disease inhibition (PDI) against Rhizoctonia solani fungus.
S. No. Treatment Details Dose (g or ml/litre of PDA Percent disease inhibition (PDI)
5 DAI 10 DAI 15DAI
T1 Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS 5 ml 83.79 70.54 70.91
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 79.45 66.60 66.67
T3 Flutriafol 25%SC + Clothianidin 50%WDG 0.15 ml + 3.2 gm 65.22 63.28 65.33
T4 Thiophanate methyl 70% WP + Clothianidin 50%WDG 0.29 gm + 3.2 gm 25.30 37.97 54.55
T5 Thiophanate methyl 70% WP 0.29 gm 26.48 34.23 49.70
T6 Flutriafol 25% SC 0.15 ml 64.82 60.17 62.06
T7 Clothianidin 50%WDG 3.2 gm 14.23 32.37 33.70
T8 Control NA 0.00 0.00 0.00

Table 37: Synergistic effect of combination of Thiophanate methyl (4%), Flutriafol (0.75%), and Clothianidin (32%) FS against Rhizoctonia solani fungus at 10DAI.
S. No. Treatment details Dose (g or ml/litre of PDA Percent disease inhibition (PDI)
Observed Expected Ratio Synergy
T1 Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS 5 ml 70.54 69.37 1.02 Yes
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 66.60 75.05 0.89 No
T3 Flutriafol 25%SC + Clothianidin 50% WDG 0.15 ml + 3.2 gm 63.28 74.34 0.85 No
T4 Thiophanate methyl 70% WP + Clothianidin 50% WDG 0.29 gm + 3.2 gm 37.97 55.52 0.68 No
T5 Thiophanate methyl 70% WP 0.29 gm 34.23 - - -
T6 Flutriafol 25% SC 0.15 ml 60.17 - - -
T7 Clothianidin 50% WDG 3.2 gm 32.37 - - -
T8 Control NA 0.00 - - -

Per cent Disease Inhibition: The above tables 36-37, evidence that the present invention composition comprising Thiophanate methyl (4%) + Flutriafol (0.75%) + Clothianidin (32%) FS provided highest percent disease inhibition thereby showing synergy as compared to other treatments.

Example 11:

TRIAL 6: Bio-efficacy of synergistic composition of Thiophanate methyl (4%), Flutriafol (0.75%), and Clothianidin (32%) FS against Sclerotium rolfsii fungus.

Season Kharif 2023
Location Ambala Laboratory
Age of Culture 10 days old
Temperature Range during Trial 25°C ± 2°C
Single plate size 90mm
Date of inoculation 07-08-2023
Number of applications 1
Target Pest Sclerotium rolfsii
Time of observation 3 DAI, 5 DAI (Days after inoculation)
Method of application Food poison Technique

Table 38: Effect of different treatments on Percent disease inhibition (PDI) against Sclerotium rolfsii fungus.
S. No. Treatment Details Dose (g or ml/litre of PDA Percent disease inhibition (PDI)
3 DAI 5 DAI
T1 Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS 5 ml 75.39 73.00
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 69.94 63.44
T3 Flutriafol 25% SC + Clothianidin 50% WDG 0.15 ml + 3.2 gm 65.42 58.69
T4 Thiophanate methyl 70% WP + Clothianidin 50% WDG 0.29 gm + 3.2 gm 31.31 17.89
T5 Thiophanate methyl 70% WP 0.29 gm 24.92 17.22
T6 Flutriafol 25% SC 0.15 ml 59.66 58.00
T7 Clothianidin 50% WDG 3.2 gm 1.25 2.67
T8 Control NA 0.00 0.00

Table 39: Synergistic effect of combination of Thiophanate methyl (4%), Flutriafol (0.75%), and Clothianidin (32%) FS against Sclerotium rolfsii fungus at 10 DAI.

S. No.
Treatment details Dose (g or ml/litre of PDA Percent disease inhibition (PDI)
Observed Expected Ratio Synergy
T1 Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS 5 ml 73.00 65.63 1.11 Yes
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm +0.15 ml 63.44 65.23 0.97 No
T3 Flutriafol 25% SC + Clothianidin 50% WDG 0.15 ml + 3.2 gm 58.69 59.12 0.99 No
T4 Thiophanate methyl 70% WP + Clothianidin 50% WDG 0.29 gm + 3.2 gm 17.89 19.43 0.92 No
T5 Thiophanate methyl 70% WP 0.29 gm 17.22 - - -
T6 Flutriafol 25% SC 0.15 ml 58.00 - - -
T7 Clothianidin 50% WDG 3.2 gm 2.67 - - -
T8 Control NA 0.00 - - -

Per cent Disease Inhibition: It is evident from the above table 38-39, that the present invention’s composition comprising Thiophanate methyl (4%) + Flutriafol (0.75%) + Clothianidin (32%) FS provided highest per cent disease inhibition thereby showing synergy as compared to other treatments.

Example 12:
TRIAL 7: Bio-efficacy of synergistic composition of Thiophanate methyl, Flutriafol, and Thiamethoxam against collar rot (Aspergillus niger) & white grub (Holotrichia serrata).
Season Kharif 2023
Location Reddipalem, Bapatla, Andhra Pradesh
Crop Ground nut
Age of Crop 0 days
Temperature Range during Trial 25°-32°C
Variety Tag 24
Single plot size 5*5 m2
Date of Sowing 23-06-2023
Number of applications 1
Time & Method of Treatment At time of sowing, Seed treatment
Date of application/Treatment 23-06-2023
Target Pest Collar rot (Aspergillus niger) & white grub (Holotrichia serrata).

Table 40: Treatment Details
S. No. Treatments Active Ingredient (AI) (10kg seeds) Dose (g or ml/kg of seeds)
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20%) FS 2.0 + 0.375 + 2.0 ml/10kg seeds 1 ml/kg seeds
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 2.0 + 0.375 ml/10kg seeds 0.29 gm + 0.15 ml
T3 Flutriafol 25%SC + Thiamethoxam 30% FS 0.375 + 2.0 ml/10kg seeds 0.15 ml + 0.67 ml
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 2.0 + 2.0 ml/10kg seeds 0.29 gm + 0.67 ml
T5 Thiophanate methyl 70% WP 2.0 ml/10kg seeds 0.29 gm
T6 Flutriafol 25% SC 0.375 ml/10kg seeds 0.15 ml
T7 Thiamethoxam 30% FS 2.0 ml/10kg seeds 0.67 ml
T8 Control NA NA

Table 41: Effect of different treatments on Per cent germination in ground nut crop.
S. No. Treatments Dose (g or ml/kg of seeds) Per cent (%) Germination
15DAA
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20%) FS 1 ml/kg seeds 88.00
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + .15 ml 85.00
T3 Flutriafol 25%SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 84.00
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 86.00
T5 Thiophanate methyl 70% WP 0.29 gm 86.00
T6 Flutriafol 25% SC 0.15 ml 80.00
T7 Thiamethoxam 30% FS 0.67 ml 83.00
T8 Control NA 78.00

Percent Germination: It is evident from the above tables 40-41, that the present invention composition comprising Thiophanate methyl (20%) + Flutriafol (3.75%) + Thiamethoxam (20%) FS provided highest per cent germination as compared to other treatments.

Table 42: Effect of different treatments on mean Shoot length & Root length in ground nut crop.
S. No. Treatment Dose Per kg seeds Shoot length in (cm) Root length in (cm)
15DAA 30DAA 15DAA 30DAA
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20%) FS 1 ml 15.53 31.93 10.13 19.53
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 15.33 31.33 9.87 19.07
T3 Flutriafol 25%SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 14.80 30.53 9.87 18.13
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 15.73 31.20 10.27 19.47
T5 Thiophanate methyl 70% WP 0.29 gm 15.60 30.87 10.07 19.40
T6 Flutriafol 25% SC 0.15 ml 14.67 29.67 7.80 17.20
T7 Thiamethoxam 30% FS 0.67 ml 17.00 30.80 9.93 19.00
T8 Control NA 15.87 29.73 9.67 18.73

Shoot length & Root length: Table 42, shows that the present invention’s composition comprising Thiophanate methyl (20%) + Flutriafol (3.75%) + Thiamethoxam (20%) FS provided highest shoot length and root length at 30 DAA as compared to other treatments.

Table 43: Effect of different treatments on mean vigour index in ground nut crop.
S. No. Treatments Dose (g or ml/kg of seeds) Seedling Vigour index
15DAA 30DAA
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20%) FS 1 ml 2258.60 4530.40
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm +0.15 ml 2143.20 4281.60
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 2072.20 4088.80
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm +0.67 ml 2237.00 4356.60
T5 Thiophanate methyl 70% WP 0.29 gm 2206.40 4323.40
T6 Flutriafol 25% SC 0.15 ml 1797.80 3749.60
T7 Thiamethoxam 30% FS 0.67 ml 2236.60 4131.20
T8 Control NA 1991.20 3781.20

Seedling Vigour index: Table 43 shows that the present invention’s composition comprising Thiophanate methyl (20%) + Flutriafol (3.75%) + Thiamethoxam (20%) FS provided the highest vigour index at 30 DAA as compared to other treatments.
Seedling vigour is an important trait of seed quality that enables rapid development of healthy plants during germination. This can reduce the probability of plants succumbing to pests and increase the probability of establishing a healthy crop. Seedling vigour can also affect crop growth and yield indirectly by influencing percentage emergence and time from sowing to emergence. These factors can alter plant population density, spatial arrangement, and crop duration.

Higher the seed vigour index indicates more no of healthier seed growth and seedling health on emergence. Lower the index indicates poor seedling health.

Table 44: Effect of different treatments on Percent Disease Incidence (PDI) of ground nut collar rot (Aspergillus niger) disease.

S. No. Treatments Dose (g or ml/kg of seeds) Per cent (%) Disease incidence (PDI)
Pre-count 15DAA 30DAA 45 DAA
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20%) FS 1 ml 0.00 0.00 4.77 8.30
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 0.00 1.28 7.09 10.46
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 0.00 1.19 8.34 10.68
T4 Thiophanate methyl 70% WP Thiamethoxam 30% FS 0.29 gm + 0.67 ml 0.00 2.26 9.08 15.90
T5 Thiophanate methyl 70% WP 0.29 gm 0.00 2.30 13.64 21.61
T6 Flutriafol 25% SC 0.15 ml 0.00 1.33 8.85 13.84
T7 Thiamethoxam 30% FS 0.67 ml 0.00 9.61 34.92 54.19
T8 Control NA 0.00 14.12 45.02 62.98

Percent incidence of collar rot: Above table 44 shows that the present invention composition comprising Thiophanate methyl (20%) + Flutriafol (3.75%) + Thiamethoxam (20%) FS provided the lowest incidence of collar rot at 30 DAA and 45 DAA as compared to other treatments.

Table 45: Effect of different treatments on percent reduction over control against ground nut collar rot (Aspergillus niger) disease.
S. No. Treatments Dose (g or ml/kg of seeds) Per cent (%) Disease control (PDC)
15 DAA 30 DAA 45 DAA
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20%) FS 1 ml/kg seeds 100.00 88.57 85.71
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 90.91 82.86 81.63
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 90.91 80.00 81.63
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 81.82 77.14 71.43
T5 Thiophanate methyl 70% WP 0.29 gm 81.82 74.29 61.22
T6 Flutriafol 25% SC 0.15 ml 90.91 80.00 77.55
T7 Thiamethoxam 30% FS 0.67 ml 27.27 17.14 8.16
T8 Control NA 0.00 0.00 0.00

Percent Disease Control: Table 45, shows that the present invention composition comprising Thiophanate methyl (20%) + Flutriafol (3.75%) + Thiamethoxam (20%) FS provided highest percent disease control against ground nut collar rot at 15 DAA as compared to other treatments.

Table 46: Synergistic effect of combination of Thiophanate methyl, Flutriafol, and Thiamethoxam against groundnut collar rot (Aspergillus niger) disease at 30 DAA.

S. No. Treatment details Dose (ml or gm/kg seeds) Per cent (%) Reduction over control
Observed Expected Ratio Synergy
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20 %) FS 1 ml 88.57 75.36 1.18 Yes
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 82.86 94.86 0.87 No
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 80.00 83.43 0.96 No
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 77.14 78.69 0.98 No
T5 Thiophanate methyl 70% WP 0.29 gm 74.29 - - -
T6 Flutriafol 25% SC 0.15 ml 80.00 - - -
T7 Thiamethoxam 30% FS 0.67 ml 17.14 - - -
T8 Control NA 0.00 - - -

Percent reduction over control: Table 46 shows that the present invention’s composition comprising Thiophanate methyl (20%) + Flutriafol (3.75%) + Thiamethoxam (20%) FS provided the highest percent disease reduction over control thereby showing synergy as compared to other treatments.

Table 47: Effect of different treatments on per cent infestation of ground nut white grub (Holotrichia serrata).

S. No. Treatments Dose (g or ml/kg of seeds) Per cent infestation of white grub
Pre-count 15 DAA 30 DAA 45 DAA
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20%) FS 1 ml/kg seeds 0.00 0.00 3.53 14.05
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 0.00 0.00 30.94 50.40
T3 Flutriafol 25%SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 0.00 0.00 4.76 16.64
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 0.00 0.00 5.67 17.01
T5 Thiophanate methyl 70% WP 0.29 gm 0.00 0.00 34.14 52.34
T6 Flutriafol 25% SC 0.15 ml 0.00 0.00 33.78 48.72
T7 Thiamethoxam 30% FS 0.67 ml 0.00 0.00 6.04 19.22
T8 Control NA 0.00 1.28 41.11 65.65

Percent infestation of white grub: Table 47 shows that the present invention composition comprising Thiophanate methyl (20%) + Flutriafol (3.75%) + Thiamethoxam (20%) FS provided the lowest infestation of white grub at 30 DAA and 45 DAA as compared to other treatments.

Table 48: Effect of different treatments on percent reduction over control against ground nut white grub (Holotrichia serrata) disease.

S. No. Treatments Dose (g or ml/kg of seeds) Per cent (%) ROC of white grub
15 DAA 30 DAA 45 DAA
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20%) FS 1 ml/kg seeds 100.00 90.63 76.47
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 100.00 18.75 15.69
T3 Flutriafol 25%SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 100.00 87.50 72.55
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 100.00 84.38 70.59
T5 Thiophanate methyl 70% WP 0.29 gm 100.00 6.25 9.80
T6 Flutriafol 25% SC 0.15 ml 100.00 15.63 23.53
T7 Thiamethoxam 30% FS 0.67 ml 100.00 84.38 68.63
T8 Control NA 0.00 0.00 0.00

Percent Disease Control: Table 48 shows that the present invention composition’s comprising Thiophanate methyl (20%) + Flutriafol (3.75%) + Thiamethoxam (20%) FS provided highest percent reduction over control against ground nut white grub at 15 DAA and 30 DAA as compared to other treatments.
Example 13: Evaluation of Phytotoxicity of synergistic composition comprising Thiophanate methyl, Flutriafol, and Thiamethoxam.

Visual observations were recorded at 7, 14 and 21 days after the application (DAA) of tested product. The parameters observed were leaf injury on tip/surface, stunting, necrosis, chlorosis, vein clearing, epinasty, hyponasty and wilting based on 0-10 scale given in below table. A total of 20 plants per plot were observed.

Table 49: Phytotoxicity symptoms scoring and rating for leaf injury on tip/surface
?Leaf injury on tips /surface? Rating
0%? 0?
1-10%? 1?
11-20%? 2?
21-30%? 3?
31-40%? 4?
41-50%? 5?
51-60%? 6?
61-70%? 7?
71-80%? 8?
81-90%? 9?
91-100%? 10?

Table 50: Phytotoxic effect of various treatments on ground nut crop after 7 DAA?at recommended dose
S. No.? Treatment details? Dose kg/ha? 7 DAA?
L? S? N? C? V? E? H? W?
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20 %) FS 1 ml/kg seeds 0 0 0 0 0 0 0 0
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 0 0 0 0 0 0 0 0
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 0 0 0 0 0 0 0 0
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 0 0 0 0 0 0 0 0
T5 Thiophanate methyl 70% WP 0.29 gm 0 0 0 0 0 0 0 0
T6 Flutriafol 25% SC 0.15 ml 0 0 0 0 0 0 0 0
T7 Thiamethoxam 30% FS 0.67 ml 0 0 0 0 0 0 0 0
*DAA – Days after application, L-Leaf injury on tips/surface, S-stunting, N-Necrosis, C-Chlorosis, V- Vein clearing, E-Epinasty, H-Hyponasty, W-wilting?

Table 51: Phytotoxic effect of various treatments on ground nut crop after 14 DAA?at recommended dose
S. No.? Treatment details? Dose Kg/ha? 14 DAA?
L? S? N? C? V? E? H? W?
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20 %) FS 1 ml/kg seeds 0 0 0 0 0 0 0 0
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 0 0 0 0 0 0 0 0
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 0 0 0 0 0 0 0 0
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 0 0 0 0 0 0 0 0
T5 Thiophanate methyl 70% WP 0.29 gm 0 0 0 0 0 0 0 0
T6 Flutriafol 25% SC 0.15 ml 0 0 0 0 0 0 0 0
T7 Thiamethoxam 30% FS 0.67 ml 0 0 0 0 0 0 0 0
*DAA – Days after application, L-Leaf injury on tips/surface, S-stunting, N-Necrosis, C-Chlorosis, V- Vein clearing, E-Epinasty, H-Hyponasty, W-wilting?

Table 52: Phytotoxic effect of various treatments on ground nut crop after 21 DAA?at recommended dose
S. No.? Treatment details? Dose Kg/ha? 21 DAA?
L? S? N? C? V? E? H? W?
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20 %) FS 1 ml/kg seeds 0 0 0 0 0 0 0 0
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 0 0 0 0 0 0 0 0
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 0 0 0 0 0 0 0 0
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 0 0 0 0 0 0 0 0
T5 Thiophanate methyl 70% WP 0.29 gm 0 0 0 0 0 0 0 0
T6 Flutriafol 25% SC 0.15 ml 0 0 0 0 0 0 0 0
T7 Thiamethoxam 30% FS 0.67 ml 0 0 0 0 0 0 0 0
*DAA – Days after application, L-Leaf injury on tips/surface, S-stunting, N-Necrosis, C-Chlorosis, V- Vein clearing, E-Epinasty, H-Hyponasty, W-wilting?

Table 53: Phytotoxic effect of various treatments on ground nut crop after 7 DAA?at double dose (2X)
S. No.? Treatment details? Dose Kg/ha? 7 DAA?
L? S? N? C? V? E? H? W?
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20 %) FS 1 ml/kg seeds 0 0 0 0 0 0 0 0
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 0 0 0 0 0 0 0 0
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 0 0 0 0 0 0 0 0
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 0 0 0 0 0 0 0 0
T5 Thiophanate methyl 70% WP 0.29 gm 0 0 0 0 0 0 0 0
T6 Flutriafol 25% SC 0.15 ml 0 0 0 0 0 0 0 0
T7 Thiamethoxam 30% FS 0.67 ml 0 0 0 0 0 0 0 0
*DAA – Days after application, L-Leaf injury on tips/surface, S-stunting, N-Necrosis, C-Chlorosis, V- Vein clearing, E-Epinasty, H-Hyponasty, W-wilting

Table 54: Phytotoxic effect of various treatments on ground nut crop after 14 DAA?at double dose (2X)
S. No.? Treatment details? Dose Kg/ha? 14 DAA?
L? S? N? C? V? E? H? W?
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20 %) FS 1 ml/kg seeds 0 0 0 0 0 0 0 0
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 0 0 0 0 0 0 0 0
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 0 0 0 0 0 0 0 0
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 0 0 0 0 0 0 0 0
T5 Thiophanate methyl 70% WP 0.29 gm 0 0 0 0 0 0 0 0
T6 Flutriafol 25% SC 0.15 ml 0 0 0 0 0 0 0 0
T7 Thiamethoxam 30% FS 0.67 ml 0 0 0 0 0 0 0 0
*DAA – Days after application, L-Leaf injury on tips/surface, S-stunting, N-Necrosis, C-Chlorosis, V- Vein clearing, E-Epinasty, H-Hyponasty, W-wilting?

Table 55: Phytotoxic effect of various treatments on ground nut crop after 21 DAA?at double dose (2X)
S. No.? Treatment details? Dose Kg/ha? 21 DAA?
L? S? N? C? V? E? H? W?
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20 %) FS 1 ml/kg seeds 0 0 0 0 0 0 0 0
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 0 0 0 0 0 0 0 0
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 0 0 0 0 0 0 0 0
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 0 0 0 0 0 0 0 0
T5 Thiophanate methyl 70% WP 0.29 gm 0 0 0 0 0 0 0 0
T6 Flutriafol 25% SC 0.15 ml 0 0 0 0 0 0 0 0
T7 Thiamethoxam 30% FS 0.67 ml 0 0 0 0 0 0 0 0
*DAA – Days after application, L-Leaf injury on tips/surface, S-stunting, N-Necrosis, C-Chlorosis, V- Vein clearing, E-Epinasty, H-Hyponasty, W-wilting?

Tables 50 to 55 above evidence that the application of Thiophanate methyl + Flutriafol + Thiamethoxam in all doses showed no phytotoxicity symptoms like leaf injury on tips, leaf injury on the surface, wilting, vein clearing, necrosis, epinasty and hyponasty in ground nut crop. Further, as evident from tables 53, 54 and 55, the application of Thiophanate methyl + Flutriafol + Clothianidin at even double dose shows no phytotoxicity. Thus, applying the present invention composition may be considered completely safe for crops.

Example 14:
TRIAL 8: Bio-efficacy of synergistic composition of Thiophanate methyl, Flutriafol, and Clothianidin against collar rot (Aspergillus niger) & white grub (Holotrichia serrata).

Season Kharif 2023
Location Reddipalem, Bapatla, Andhra Pradesh
Crop Ground nut
Ag of Crop Seed treatment
Temperature Range during Trial 25°-32°C
Variety Tag 24
Single plot size 5*5 m2
Date of Transplanting/Sowing 23-06-2023
Number of applications 1
Date of application 23-06-2023
Target Pest White grub & collar rot
Method of application Seed treatment

Table 56: Treatment Details
S. No. Treatments Active Ingredient (AI) (10kg seeds) Dose (g or ml/kg of seeds)
T1 Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS 2.0 + 0.375 + 16 ml 5 ml/kg seeds
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 2.0 + 0.375 ml 0.29 gm + 0.15 ml
T3 Flutriafol 25%SC + Clothianidin 50%WDG 0.375 + 16 gm 0.15 ml + 3.2 gm
T4 Thiophanate methyl 70% WP + Clothianidin 50%WDG 2.0 + 16 gm 0.29 gm + 3.2 gm
T5 Thiophanate methyl 70% WP 2.0 ml 0.29 gm
T6 Flutriafol 25% SC 0.375 ml 0.15 ml
T7 Clothianidin 50%WDG 16 gm 3.2 gm
T8 Control NA NA

Table 57: Effect of different treatments on Per cent germination in ground nut crop.
S. No. Treatments Dose
(g or ml/kg of seeds) Per cent (%) Germination
15 DAA
T1 Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS 5 ml 87.00
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 85.00
T3 Flutriafol 25%SC + Clothianidin 50% WDG 0.15 ml + 3.2 gm 83.00
T4 Thiophanate methyl 70% WP + Clothianidin 50% WDG 0.29 gm + 3.2 gm 86.00
T5 Thiophanate methyl 70% WP 0.29 gm 86.00
T6 Flutriafol 25% SC 0.15 ml 80.00
T7 Clothianidin 50% WDG 3.2 gm 81.00
T8 Control NA 78.00

Percent Germination: Table 57 shows that the present invention composition comprising Thiophanate methyl (4%) + Flutriafol (0.75%) + Clothianidin (32%) FS provided the highest percent germination as compared to other treatments.

Table 58: Effect of different treatments on mean Shoot length & Root length in ground nut crop.
S. No. Treatment Dose per kg seeds Shoot length in (cm) Root length in (cm)
15DAA 30DAA 15DAA 30DAA
T1 Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS 5 ml 15.67 31.60 10.07 19.47
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 15.33 31.33 9.87 19.07
T3 Flutriafol 25%SC + Clothianidin 50% WDG 0.15 ml + 3.2 gm 14.73 30.27 9.80 19.00
T4 Thiophanate methyl 70% WP + Clothianidin 50% WDG 0.29 gm + 3.2 gm 15.00 30.67 10.20 19.53
T5 Thiophanate methyl 70% WP 0.29 gm 15.60 30.87 10.07 19.40
T6 Flutriafol 25% SC 0.15 ml 14.67 29.67 7.80 17.20
T7 Clothianidin 50% WDG 3.2 gm 16.27 31.40 9.93 19.07
T8 Control NA 15.87 29.73 9.67 18.73

Shoot length & Root length: The above table 58 evidence that the present invention composition comprising Thiophanate methyl (4%) + Flutriafol (0.75%) + Clothianidin (32%) FS provided the highest shoot length and root length at 30 DAA as compared to other treatments.

Table 59: Effect of different treatments on mean vigour index in ground nut crop.
S. No. Treatments Dose
(g or ml/kg of seeds) Seedling Vigour index
15DAA 30DAA
T1 Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS 5 ml 2239.00 4442.20
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 2143.20 4281.60
T3 Flutriafol 25%SC + Clothianidin 50% WDG 0.15 ml + 3.2 gm 2036.00 4089.00
T4 Thiophanate methyl 70% WP + Clothianidin 50% WDG 0.29 gm + 3.2 gm 2192.60 4368.60
T5 Thiophanate methyl 70% WP 0.29 gm 2206.40 4323.40
T6 Flutriafol 25% SC 0.15 ml 1797.80 3749.60
T7 Clothianidin 50% WDG 3.2 gm 2121.80 4087.00
T8 Control NA 1991.20 3781.20

Seedling Vigour index: The above table 59, evidence that the present invention composition comprising Thiophanate methyl (4%) + Flutriafol (0.75%) + Clothianidin (32%) FS provided the highest vigour index at 30 DAA as compared to other treatments.

Table 60: Effect of different treatments on Percent disease incidence (PDI) of ground nut collar rot (Aspergillus niger) disease.

S. No. Treatments Dose (g or ml/kg of seeds) Per cent (%) Disease incidence (PDI)
Pre-count 15DAA 30DAA 45 DAA
T1 Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS 5 ml/kg seeds 0.00 0.00 5.87 9.29
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 0.00 1.28 7.09 10.46
T3 Flutriafol 25%SC + Clothianidin 50% WDG 0.15 ml + 3.2 gm 0.00 1.19 8.42 13.27
T4 Thiophanate methyl 70% WP + Clothianidin 50% WDG 0.29 gm + 3.2 gm 0.00 2.30 11.50 17.29
T5 Thiophanate methyl 70% WP 0.29 gm 0.00 2.30 13.64 21.61
T6 Flutriafol 25% SC 0.15 ml 0.00 1.33 8.85 13.84
T7 Clothianidin 50% WDG 3.2 gm 0.00 9.84 37.02 55.65
T8 Control NA 0.00 14.12 45.02 62.98

Percent incidence of collar rot: The above table 60, shows that the present invention composition comprising Thiophanate methyl (4%) + Flutriafol (0.75%) + Clothianidin (32%) FS provided the lowest incidence of collar rot at 30 DAA and 45 DAA as compared to other treatments.

Table 61: Effect of different treatments on percent reduction over control against ground nut collar rot (Aspergillus niger) disease.

S. No. Treatments Dose (g or ml/kg of seeds) Per cent (%) Disease control (PDC)
15 DAA 30 DAA 45 DAA
T1 Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS 5 ml/kg seeds 100.00 85.71 83.67
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 90.91 82.86 81.63
T3 Flutriafol 25%SC + Clothianidin 50% WDG 0.15 ml + 3.2 gm 90.91 80.00 77.55
T4 Thiophanate methyl 70% WP + Clothianidin 50% WDG 0.29 gm + 3.2 gm 81.82 77.14 69.39
T5 Thiophanate methyl 70% WP 0.29 gm 81.82 74.29 61.22
T6 Flutriafol 25% SC 0.15 ml 90.91 80.00 77.55
T7 Clothianidin 50% WDG 3.2 gm 27.27 14.29 8.16
T8 Control NA 0.00 0.00 0.00

Percent Disease Control: The above table 61, shows that the present invention composition comprising Thiophanate methyl (4%) + Flutriafol (0.75%) + Clothianidin (32%) FS provided the highest percent disease control against ground nut collar rot at 15 DAA as compared to other treatments.

Table 62: Synergistic effect of combination of Thiophanate methyl (4%) + Flutriafol (0.75%) Clothianidin (32%) against groundnut collar rot (Aspergillus niger) disease at 30 DAA.

S. No. Treatment details Dose (ml or gm/kg seeds) % Reduction over control
Observed Expected Ratio Synergy
T1 Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS 5 ml/kg seeds 85.71 78.61 1.09 YES
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 82.86 94.86 0.87 NO
T3 Flutriafol 25%SC + Clothianidin 50% WDG 0.15 ml + 3.2 gm 80.00 82.86 0.97 NO
T4 Thiophanate methyl 70% WP + Clothianidin 50% WDG 0.29 gm + 3.2 gm 77.14 77.96 0.99 NO
T5 Thiophanate methyl 70% WP 0.29 gm 74.29 - - -
T6 Flutriafol 25% SC 0.15 ml 80.00 - - -
T7 Clothianidin 50% WDG 3.2 gm 14.29 - - -
T8 Control NA 0.00 - - -

Percent reduction over control: The above table 62, shows that the present invention composition comprising Thiophanate methyl (4%) + Flutriafol (0.75%) + Clothianidin (32%) FS provided the highest percent disease reduction over control thereby showing synergy as compared to other treatments.

Table 63: Effect of different treatments on per cent infestation of ground nut white grub (Holotrichia serrata).

S. No. Treatments Dose (g or ml/kg of seeds) Per cent (%) infestation of white grub
Pre-count 15 DAA 30 DAA 45 DAA
T1 Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS 5 ml 0.00 0.00 2.30 10.48
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 0.00 0.00 30.94 50.40
T3 Flutriafol 25%SC + Clothianidin 50% WDG 0.15 ml + 3.2gm 0.00 0.00 3.62 13.23
T4 Thiophanate methyl 70% WP + Clothianidin 50% WDG 0.29 gm + 3.2 gm 0.00 0.00 4.60 14.99
T5 Thiophanate methyl 70% WP 0.29 gm 0.00 0.00 34.14 52.34
T6 Flutriafol 25% SC 0.15 ml 0.00 0.00 33.78 48.72
T7 Clothianidin 50% WDG 3.2 gm 0.00 0.00 4.94 16.02
T8 Control NA 0.00 1.28 41.11 65.65
Per cent infestation of white grub: Table 63 shows that the present invention composition comprising Thiophanate methyl (4%) + Flutriafol (0.75%) + Clothianidin (32%) FS provided lowest infestation of white grub at 30 DAA and 45 DAA as compared to other treatments.

Table 64: Effect of different treatments on percent reduction over control against ground nut white grub (Holotrichia serrata) disease.
S. No. Treatments Dose (g or ml/kg of seeds) Per cent (%) ROC of white grub
15 DAA 30 DAA 45 DAA
T1 Thiophanate M 40 g/l (4%) + Flutriafol 7.5 g/l (0.75%) + clothianidin 320 g/l (32%) FS 5 ml/kg seeds 100.00 93.75 82.35
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 100.00 18.75 15.69
T3 Flutriafol 25%SC + Clothianidin 50% WDG 0.15 ml + 3.2 gm 100.00 90.63 78.43
T4 Thiophanate methyl 70% WP + Clothianidin 50% WDG 0.29 gm + 3.2 gm 100.00 87.50 74.51
T5 Thiophanate methyl 70% WP 0.29 gm 100.00 6.25 9.80
T6 Flutriafol 25% SC 0.15 ml 100.00 15.63 23.53
T7 Clothianidin 50% WDG 3.2 gm 100.00 87.50 74.51
T8 Control NA 0.00 0.00 0.00

Percent Disease Control: Table 64 shows that the present invention composition comprising Thiophanate methyl (4%) + Flutriafol (0.75%) + Clothianidin (32%) FS provided the highest percent reduction over control against ground nut white grub at 15 DAA and 30 DAA as compared to other treatments.

Example 15: Evaluation of Phytotoxicity of synergistic composition comprising Thiophanate methyl, Flutriafol, and Clothianidin.

Visual observations were recorded at 7, 14 and 21 days after the application (DAA) of tested product. The parameters observed were leaf injury on tip/surface, stunting, necrosis, chlorosis, vein clearing, epinasty, hyponasty and wilting based on 0-10 scale given in below table. A total of 20 plants per plot were observed.

Table 65: Phytotoxicity symptoms scoring and rating for leaf injury on tip/surface

Leaf injury on tips /surface? Rating?
0%? 0?
1-10%? 1?
11-20%? 2?
21-30%? 3?
31-40%? 4?
41-50%? 5?
51-60%? 6?
61-70%? 7?
71-80%? 8?
81-90%? 9?
91-100%? 10?

Table 66: Phytotoxic effect of various treatments on ground nut crop after 7 DAA?at recommended dose.

S. No.? Treatment details? Dose kg/ha? 7 DAA?
L? S? N? C? V? E? H? W?
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20 %) FS 1 ml/kg seeds 0 0 0 0 0 0 0 0
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 0 0 0 0 0 0 0 0
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 0 0 0 0 0 0 0 0
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 0 0 0 0 0 0 0 0
T5 Thiophanate methyl 70% WP 0.29 gm 0 0 0 0 0 0 0 0
T6 Flutriafol 25% SC 0.15 ml 0 0 0 0 0 0 0 0
T7 Thiamethoxam 30% FS 0.67 ml 0 0 0 0 0 0 0 0
*DAA – Days after application, L-Leaf injury on tips/surface, S-stunting, N-Necrosis, C-Chlorosis, V- Vein clearing, E-Epinasty, H-Hyponasty, W-wilting?

Table 67: Phytotoxic effect of various treatments on ground nut crop after 14 DAA?at recommended dose
S. No.? Treatment details? Dose Kg/ha? 14 DAA?
L? S? N? C? V? E? H? W?
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20 %) FS 1 ml/kg seeds 0 0 0 0 0 0 0 0
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 0 0 0 0 0 0 0 0
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 0 0 0 0 0 0 0 0
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 0 0 0 0 0 0 0 0
T5 Thiophanate methyl 70% WP 0.29 gm 0 0 0 0 0 0 0 0
T6 Flutriafol 25% SC 0.15 ml 0 0 0 0 0 0 0 0
T7 Thiamethoxam 30% FS 0.67 ml 0 0 0 0 0 0 0 0
*DAA – Days after application, L-Leaf injury on tips/surface, S-stunting, N-Necrosis, C-Chlorosis, V- Vein clearing, E-Epinasty, H-Hyponasty, W-wilting?

Table 68: Phytotoxic effect of various treatments on ground nut crop after 21 DAA?at recommended dose
S. No.? Treatment details? Dose Kg/ha? 21 DAA?
L? S? N? C? V? E? H? W?
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20 %) FS 1 ml/kg seeds 0 0 0 0 0 0 0 0
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 0 0 0 0 0 0 0 0
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 0 0 0 0 0 0 0 0
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 0 0 0 0 0 0 0 0
T5 Thiophanate methyl 70% WP 0.29 gm 0 0 0 0 0 0 0 0
T6 Flutriafol 25% SC 0.15 ml 0 0 0 0 0 0 0 0
T7 Thiamethoxam 30% FS 0.67 ml 0 0 0 0 0 0 0 0
*DAA – Days after application, L-Leaf injury on tips/surface, S-stunting, N-Necrosis, C-Chlorosis, V- Vein clearing, E-Epinasty, H-Hyponasty, W-wilting
?
Table 69: Phytotoxic effect of various treatments on ground nut crop after 7 DAA?at double dose (2X)
S. No.? Treatment details? Dose Kg/ha? 7 DAA?
L? S? N? C? V? E? H? W?
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20 %) FS 1 ml/kg seeds 0 0 0 0 0 0 0 0
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 0 0 0 0 0 0 0 0
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 0 0 0 0 0 0 0 0
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 0 0 0 0 0 0 0 0
T5 Thiophanate methyl 70% WP 0.29 gm 0 0 0 0 0 0 0 0
T6 Flutriafol 25% SC 0.15 ml 0 0 0 0 0 0 0 0
T7 Thiamethoxam 30% FS 0.67 ml 0 0 0 0 0 0 0 0
* DAA – Days after application, L-Leaf injury on tips/surface, S-stunting, N-Necrosis, C-Chlorosis, V- Vein clearing, E-Epinasty, H-Hyponasty, W-wilting?

Table 70: Phytotoxic effect of various treatments on ground nut crop after 14 DAA?at double dose (2X)
S. No.? Treatment details? Dose Kg/ha? 14 DAA?
L? S? N? C? V? E? H? W?
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20 %) FS 1 ml/kg seeds 0 0 0 0 0 0 0 0
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 0 0 0 0 0 0 0 0
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 0 0 0 0 0 0 0 0
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 0 0 0 0 0 0 0 0
T5 Thiophanate methyl 70% WP 0.29 gm 0 0 0 0 0 0 0 0
T6 Flutriafol 25% SC 0.15 ml 0 0 0 0 0 0 0 0
T7 Thiamethoxam 30% FS 0.67 ml 0 0 0 0 0 0 0 0
* DAA – Days after application, L-Leaf injury on tips/surface, S-stunting, N-Necrosis, C-Chlorosis, V- Vein clearing, E-Epinasty, H-Hyponasty, W-wilting?

Table 71: Phytotoxic effect of various treatments on ground nut crop after 21 DAA?at double dose (2X)
S. No.? Treatment details? Dose Kg/ha? 21 DAA?
L? S? N? C? V? E? H? W?
T1 Thiophanate M 200 g/l (20%) + Flutriafol 37.5 g/l (3.75%) + Thiamethoxam 200 g/l (20 %) FS 1 ml/kg seeds 0 0 0 0 0 0 0 0
T2 Thiophanate methyl 70% WP + Flutriafol 25% SC 0.29 gm + 0.15 ml 0 0 0 0 0 0 0 0
T3 Flutriafol 25% SC + Thiamethoxam 30% FS 0.15 ml + 0.67 ml 0 0 0 0 0 0 0 0
T4 Thiophanate methyl 70% WP + Thiamethoxam 30% FS 0.29 gm + 0.67 ml 0 0 0 0 0 0 0 0
T5 Thiophanate methyl 70% WP 0.29 gm 0 0 0 0 0 0 0 0
T6 Flutriafol 25% SC 0.15 ml 0 0 0 0 0 0 0 0
T7 Thiamethoxam 30% FS 0.67ml 0 0 0 0 0 0 0 0
* DAA – Days after application, L-Leaf injury on tips/surface, S-stunting, N-Necrosis, C-Chlorosis, V- Vein clearing, E-Epinasty, H-Hyponasty, W-wilting?

Tables 66 to 71 above indicate that application of Thiophanate methyl + Flutriafol + Clothianidin in all doses showed no phytotoxicity symptoms like leaf injury on tips, leaf injury on the surface, wilting, vein clearing, necrosis, epinasty and hyponasty in ground nut crop. Further, as evident from tables 69, 70 and 71, the application of Thiophanate methyl + Flutriafol + Clothianidin at even double dose shows no phytotoxicity. Thus, applying the present invention composition may be considered completely safe for crops.

From the foregoing it will be observed that numerous modifications and variations can be effectuated without departing from the true spirit and scope of the novel concepts of the present invention. It is to be understood that no limitations with respect to the specific embodiments illustrated is intended or should be inferred. It should be understood that all such modifications and improvements have been deleted herein for the sake of conciseness and readability but are properly within the scope of the following claims.
,CLAIMS:We Claim:
1. A synergistic composition comprising:
a) thiophanate-methyl;
b) flutriafol;
c) at least one nitroguanidine insecticide selected from thiamethoxam and clothianidin;
d) at least one surface active agent; and
e) at least one agriculturally acceptable excipient.

2. The synergistic composition as claimed in claim 1, wherein said thiophanate-methyl is present in the range of 1 to 50% by weight of the composition.

3. The synergistic composition as claimed in claim 1, wherein said flutriafol is present in the range of 0.5 to 60% by weight of the composition.

4. The synergistic composition as claimed in claim 1, wherein said nitroguanidine insecticide is present in the range of 1 to 60% by weight of the composition.

5. The synergistic composition as claimed in claim 1, wherein said surface active agent is selected from poly(oxy-1,2-ethanediyl), a-sulfo-?-[2,4,6-tris(1-phenylethyl) phenoxy]-, ammonium salt, naphthalene and alkyl naphthalene sulphonic acids formaldehyde condensate, sodium salt, acrylic copolymer, 2-Propenoic acid, 2-methyl-, polymer with a-methyl-?-hydroxypoly(oxy-1,2-ethanediyl) and methyl 2-methyl-2-propenoate, graft in the range of 1 to 10% by weight of the composition.

6. The synergistic composition as claimed in claim 1, wherein said agriculturally acceptable excipient is selected from the group comprising carrier(s), binder(s), disintegrating agent(s), dispersants or dispersing agent(s), wetting agents, pH modifier(s), thickener(s), biocide(s), preservative(s), anti-freezing agent(s), colorant(s), defoamer(s), solvents, and/or stabilizer(s) or any combination thereof.

7. The synergistic composition as claimed in claim 1, wherein said composition is in the form of a Flowable concentrate for seed treatment (FS), Wettable powder (WP), and Suspension concentrate (SC).
8. A process for the preparation of synergistic composition comprising the steps of:
a) charging a vessel with demineralized water (DM);
b) adding silicon defoamer and stirring the mixture;
c) adding surface active agent, wetting agent, anti-freezing agent, and precipitated silica to the mixture of step (b) under continuous stirring;
d) adding and mixing actives to the mixture of step (c) and homogenizing;
e) milling the mixture of step (d) by passing through a bead mill;
f) transferring the mixture of step (e) to a secondary post feed vessel;
g) adding colorant, xanthan gum solution, biocide and rest water to the mixture of step (f);
h) mixing and homogenizing the mixture of step (g);
i) homogenizing the mixture of step (h) for another 5 to 10 minutes, in case, any lumps of xanthan gum are left; and
j) sieving and packing the mixture of step (g) if no lumps are observed.

9. The process as claimed in claim 8, wherein said actives are selected from thiophanate-methyl, flutriafol, thiamethoxam and clothianidin.

10. The process as claimed in claim 8, wherein said composition has particle size in the range of 0.1 to 30 microns.