A SYNERGISTIC COMPOSITION COMPRISING A TRIAZOLINTHIONE FUNGICIDE AND PROCESS OF PREPARATION THEREOF FIELD OF THE INVENTION The present invention relates to a fungicidal composition comprising at least one Triazolinthione fungicide and at least one Triazole fungicide, a surface-active system, at least one spreading cum sticking agent and at least one agriculturally acceptable excipient. The invention also relates to a process for preparing the fungicidal composition, and use thereof. BACKGROUND OF THE INVENTION Fungi damage most of the crops and ornamental plants. Plant disease causes harm to ornamental, vegetable, field, grain, and fruit crops, resulting in major productivity losses and increased consumer costs. Plant diseases can be difficult to control and may develop resistance to commercial fungicides, in addition to being highly destructive. Fungicides are chemical substances that are used to kill parasitic fungi or their spores. Fungicides are used in agriculture as well as to combat fungal diseases in animals. The major problem with the prolonged use of pesticides or fungicides in the solo formulation is the development of resistance in the target organisms, which necessitates application of a higher concentration or high dose of the fungicide. Higher concentrations or doses of fungicide could be toxic to humans as well as have adverse effects on the environment. CN108371184 discloses a bactericidal compound containing prothioconazole and flufenoxystrobin. IN202237066507A discloses a composition comprising a conazole fungicide, a weak acid and water in the form of water dispersible granules and process of preparation of fungicidal composition. Often a composition comprising more than one active ingredients is formulated to address the challenges and issues associated with using solo active or their formulation thereof. However, it
is challenging to prepare a combination that is synergistic while maintaining stability and concentration of the actives. Additionally, combining more than one actives at high concentration often results in a composition that is viscous and non-flowable during the milling process. Furthermore, the temperature in the bead mill may increase to 50℃, causing the particle size to exceed the threshold of 10 microns, which leads to an unstable formulation. Therefore, the present invention addresses the above challenges by providing a more stable, broad spectrum, environmentally safe, efficient, and reliable agrochemical composition comprising one or more agrochemically active compounds with enhanced treatment efficacy and better performance. OBJECTIVES OF THE INVENTION The primary objective of the invention is to provide a synergistic fungicidal composition. Another objective of the present invention is to provide a synergistic fungicidal composition comprising at least two fungicides. Another objective of the present invention is to provide a simple and economical process for preparing the synergistic fungicidal composition. Yet another objective of the present invention is to provide a synergistic fungicidal composition comprising at least one triazolinthione fungicide, at least one triazole fungicide, a surface active system, at least one spreading cum sticking agent and at least one agriculturally acceptable excipient. Yet another objective of the present invention is to provide a synergistic fungicidal composition that increases crop yield. Yet another objective of the present invention is to provide a synergistic fungicidal composition that promotes plant health.
Another objective of the present invention is to provide a synergistic fungicidal composition with a broad spectrum control of pests and diseases. Some or all of these and other objectives of the invention may be achieved by way of the invention described hereinafter. SUMMARY OF THE INVENTION Accordingly, the present invention provides a synergistic fungicidal composition comprising at least one triazolinthione fungicide, at least one triazole fungicide, a surface active system, at least one spreading cum sticking agent and at least one agriculturally acceptable excipient. In one exemplary embodiment of the present invention, the fungicidal composition comprises: a) at least one triazolinthione fungicide in the range of 0.01-30%; b) at least one triazole fungicide in the range of 0.01-30%; c) a surface active system comprising, an inorganic matrix and a blend of anionic and non- ionic surfactants in the range of 0.1 to 20% by weight of the composition; d) at least one spreading cum sticking agent; and e) at least one agriculturally acceptable excipient. In an embodiment of the present invention, the synergistic composition comprising: a) prothioconazole; b) flutriafol; c) a surface active system having an inorganic matrix and a blend of anionic and non- ionic surfactants; d) at least one spreading cum sticking agent; and e) at least one agriculturally acceptable excipient. In yet another exemplary embodiment, the present invention provides a process for preparing a synergistic fungicidal composition. In an exemplary embodiment of the present invention, the prothioconazole is present in the range of 1 to 30% by weight of the composition.
In another exemplary embodiment, the flutriafol is present in the range of 1 to 30% by weight of the composition. In further embodiment of the present invention, the surface active system comprises an inorganic matrix in an amount of upto 20% by weight of the surface active system, and a blend of anionic and non-ionic surfactants present in an amount up to 80% by weight of the surface active system. In yet another exemplary embodiment of the present invention, the novel and synergistic fungicidal composition may be formulated as Suspension concentrate (SC), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Granules (GR), Water soluble granule (SG), Water dispersible granules (WDG), and Controlled- released granules (CRG). In another embodiment, the inorganic matrix is selected from the group comprising precipitated silica, amorphous silica, silicon dioxide, silicic acid, silicates, titanium dioxide, aluminum oxide, magnesium oxide, zinc oxide, talc, calcium phosphate, clays, diatomaceous earth, zeolites, bentonite, kaolin, hydrotalcite, and activated clays or any combination thereof. In yet another embodiment, the blend of anionic and non-ionic surfactants is selected from one or more styrenated phenol phosphate ester; blend of sodium aryl sulphonate, aryl sulphonate formaldehyde condensate and lignosulphonates; 2-Propenoic acid; 2-methyl-, polymer with α- methyl-ω-hydroxypoly(oxy-1,2-ethanediyl) and methyl 2-methyl-2-propenoate, graft; blend of Ethanol 2,2′,2′′-nitrilotris-, compound with α-[2,4,6-tris(1-phenylethyl)phenyl]-ω- hydroxypoly(oxy-1,2-ethanediyl) phosphate; alkyl phenol polyethanoxy ether; 2-2-oxydiethanol; and dihydrogen mono oxide or any combination thereof. In another embodiment, the spreading cum sticking agent is Polyalkyleneoxide modified Hepta Methyl Trisiloxane, in the range of 0.1 to 10% by weight of the composition. In yet another exemplary embodiment of the present invention, the agriculturally acceptable excipient is 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 yet another exemplary embodiment, the present invention provides a process for preparing a synergistic fungicidal composition comprising the steps of (a) charging a vessel with demineralized water (DM); (b) adding silicon defoamer and stirring the mixture; (c) adding surfactants, 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 mill to achieve a required particle size; (f) transferring the mixture of step (e) to a secondary post feed vessel; (g) adding spreading cum sticking agent, xanthan gum solution, biocide and the remaining amount of water to the mixture of step (f); (h) mixing and homogenizing the mixture of step (g); (i) sieving and packing the mixture of step (h). In yet another exemplary embodiment, the present invention provides a synergistic fungicidal composition with improved stability and enhanced efficacy for broad spectrum control of pests and diseases. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows mycelium growth of Alternaria brassicicola at 15 DAI in sample treated with Prothioconazole + Flutriafol (Medium dose) vs. untreated sample. Figure 2 shows mycelium growth of Collectotricum capsisi (chilli Anthracnose) at 15 DAI in sample treated with Prothioconazole + Flutriafol (High dose) vs. untreated sample. Figure 3 shows mycelium growth of Fusarium oxysporum at 15 DAI in sample treated with Prothioconazole + Flutriafol (Medium dose) vs. untreated sample. Figure 4 shows mycelium growth of Cercospora arachidicola (Ground nut Tikka Disease) at 15 DAI in sample treated with Prothioconazole + Flutriafol (Medium dose) vs. untreated sample.
Figure 5 shows mycelium growth of Pyricularia oryzae at 10 DAI in sample treated with Prothioconazole + Flutriafol (Medium dose) vs. untreated sample. DETAILED DESCRIPTION OF THE INVENTION The definitions provided herein below for the terminologies used in the present disclosure are for illustrative purpose only and in no manner limit, the scope of the present invention disclosed in the present disclosure. All technical and scientific phrases or terms used here have the same meanings as those that a person who is skilled in the field of study of the current subject matter would understand. Although other processes and materials similar to or equivalent, to those described herein may be used in the practice of the present invention, the preferred materials and process are described herein. 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. 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 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 “active ingredient” (a.i.) or “active agent” or “actives” used herein refers to that component of the composition responsible for control and killing of pests. The term “formulation” and “composition” as used herein convey the same meaning and may be used interchangeably. As used herein, the term “fungicide”, refers to any chemical substance used to destroy/kill, inhibit or otherwise adversely affect the pests. The term “process” and “method” as used herein convey the same meaning and may be used interchangeably.
The terms “spreading cum sticking agent” and “wetting agent” as used herein convey the same meaning and may be used interchangeably. In an exemplary embodiment, the active fungicidal compounds used in the present composition may be in the form of base or any salt form or ester form of the active which is known in art. 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 “fungicide” or “fungicidal” is similar to “pesticides” or “pesticidal” and is used interchangeably and both convey the same meaning. The term “disease control” as used herein denotes control and prevention of a disease. Controlling effects include all deviation from natural development, for example: killing, retardation, decrease of the fugal disease. The term „plants‟ refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits. The term “locus” of a plant as used herein is intended to embrace the place on which the plants are growing, where the plant propagation materials of the plants are sown or where the plant propagation materials of the plants will be placed into the soil. The term “crop” shall include a multitude of desired crop plants or individual crop plants. The term “Seed treatment” refers to the application of a fungicide, insecticide, multi-site fungicide, 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” is understood to denote generative parts of a plant, such as seeds, vegetative material such as cuttings or tubers, roots, fruits, tubers, bulbs, rhizomes and parts of plants, germinated plants and young plants which are to be transplanted after germination or after emergence from the soil.
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. In accordance with an exemplary embodiment, the present invention provides a synergistic fungicidal composition comprising at least one Triazolinthione fungicide and at least one Triazole fungicide. 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 synergistic fungicidal composition comprising at least one Triazolinthione fungicide, at least one Triazole fungicide, a surface active system, at least one spreading cum sticking agent and at least one agriculturally acceptable excipient. In an exemplary embodiment, the fungicidal composition comprises Prothioconazole, at least one Triazole fungicide, a surface active system, at least one spreading cum sticking agent and at least one agriculturally acceptable excipient. In another exemplary embodiment, the fungicidal composition comprises at least one Triazolinthione fungicide, Flutriafol, a surface active system, at least one spreading cum sticking agent and at least one agriculturally acceptable excipient.
In another exemplary embodiment, the synergistic fungicidal composition comprises of Prothioconazole selected from the class of Triazolinthione fungicides and Flutriafol selected from the class of Triazole fungicides. In a preferred embodiment, the present invention provides a synergistic fungicidal composition comprising Prothioconazole, Flutriafol, a surface active system, at least one spreading cum sticking agent and at least one agriculturally acceptable excipient. In another exemplary embodiment of the present invention, prothioconazole is present in the range of 0.01- 30% by weight of the composition. In another exemplary embodiment of the present invention, flutriafol is present in the range of 0.01- 30% by weight of the composition. The composition of the present invention comprises a surface-active system. The surface active system comprises inorganic matrix and a blend of anionic and non-ionic surfactants. The surface active system comprises 5 to 20% by weight of inorganic matrix and about 95 to 80% by weight of blend of anionic and non-ionic surfactants. Further, it ensures that the composition remains effective over time, with well-balanced particle size, fine suspension, viscosity, and suspensibility of the active ingredients. The surface-active system optimizes the dispersion, leading to improved performance and consistent behavior of the composition throughout its shelf life. In another embodiment of the present invention, the surface active system comprises an inorganic matrix and a blend of anionic and non-ionic surfactants in the range of 0.1 to 20% by weight of the composition. In a preferred embodiment, the surface active system comprises upto 20% of inorganic matrix and upto 80% a blend of anionic and non-ionic surfactants. In a preferred embodiment, the surface active system comprises upto 15% of inorganic matrix and upto 85% a blend of anionic and non-ionic surfactants.
In an embodiment of the present invention, the inorganic matrix is selected from the group comprising of precipitated silica, amorphous silica, silicon dioxide, silicic acid, silicates, titanium dioxide, aluminum oxide, magnesium oxide, zinc oxide, talc, calcium phosphate, clays, diatomaceous earth, zeolites, bentonite, kaolin, hydrotalcite, and activated clays or any combination thereof. In another preferred embodiment of the present invention, the inorganic matrix is precipitated silica in the range of 0.1 to 10% by weight of the composition. In another exemplary embodiment of the present invention, the anionic and non-ionic surfactants are selected from one or more styrenated phenol phosphate ester; blend of sodium aryl sulphonate, aryl sulphonate formaldehyde condensate and lignosulphonates; 2-Propenoic acid; 2- methyl-, polymer with α-methyl-ω-hydroxypoly(oxy-1,2-ethanediyl) and methyl 2-methyl-2- propenoate, graft; blend of Ethanol 2,2′,2′′-nitrilotris-, compound with α-[2,4,6-tris(1- phenylethyl)phenyl]-ω-hydroxypoly(oxy-1,2-ethanediyl) phosphate; alkyl phenol polyethanoxy ether; 2-2-oxydiethanol; and dihydrogen mono oxide in the range of 0.1 to 20% by weight of the composition. In another preferred embodiment of the present invention, the anionic and non-ionic surfactants comprise of styrenated phenol phosphate ester and a blend of sodium aryl sulphonate, aryl sulphonate formaldehyde condensate and lignosulphonates in the range of 0.5 to 10% by weight of the composition. In another exemplary embodiment, the present invention provides a synergistic fungicidal composition comprising Prothioconazole in the range of 0.01 to 30% by weight of the composition, Flutriafol in the range of 0.01 to 30% by weight of the composition, a surface active system comprising an inorganic matrix and a blend of anionic and non-ionic surfactants in the range of 0.1 to 20% by weight of the composition, at least one spreading cum sticking agent in the range of 0.1 to 10% by weight of the composition and at least one agriculturally acceptable excipient.
In another preferred embodiment, the present invention provides a synergistic fungicidal composition comprising Prothioconazole in the range of 1 to 30% by weight of the composition, Flutriafol in the range of 1 to 30% by weight of the composition, a surface active system comprising an inorganic matrix and a blend of anionic and non-ionic surfactants in the range of 0.1 to 20% by weight of the composition, at least one spreading cum sticking agent in the range of 0.1 to 5% by weight of the composition and at least one agriculturally acceptable excipient. A spreading cum sticking agent enhances the spreading characteristics of a spray solution, resulting in superior coverage on the leaf surface and prolonged residual control. This extended residual control is attributed to the agent's ability to improve the uniformity of the spray solution's application across the leaf surface, which in turn facilitates deeper penetration into the leaf. The improved spreading properties ensure that the active ingredients are more effectively distributed and retained, thereby enhancing the overall efficacy and duration of the treatment. In another preferred embodiment of the present invention, the spreading cum sticking agent is Polyalkyleneoxide modified Hepta Methyl Trisiloxane in the range of 0.1 to 5% by weight of the composition. The synergistic fungicidal composition of the present invention is effective in controlling soil borne pests, improving spreading properties, and also enhancing the stability and efficacy of the composition. The inventors have surprisingly found that the composition at the aforementioned weight percentage ranges provides a synergistic effect. In another exemplary embodiment, the synergistic fungicidal composition of the present invention is formulated as Capsule suspension (CS), Dispersible concentrate (DC), 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), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble
granule (SG), Water soluble powder (SP), Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), a mixed formulation of CS and SC (ZC). In another preferred embodiment, the synergistic fungicidal composition of the present invention is formulated as an Aqueous Dispersion (AD), Wettable Powder (WP), Water Dispersible Granule (WG), Dispersion Concentrate (DC) and emulsion concentrate (EC). In another exemplary embodiment of the present invention, the synergistic fungicidal composition may comprise one or more agriculturally acceptable excipients selected from the group comprising of carrier(s), surfactant(s), binder(s), disintegrating agent(s), dispersants or dispersing agent(s), wetting agents, thickener(s), biocide(s), Preservative(s), anti-freezing agent(s), defoamer(s), solvents, and/or stabilizer(s) or any combination thereof. A dispersant, also known as a dispersing agent, is a substance that adsorbs onto the surface of particles, preserving their dispersion and preventing them from re-aggregating. Dispersants are added to an agrochemical composition to aid in particle dispersion and suspension during manufacturing and to ensure particle re-disperse in water in a spray tank. They are a common ingredient in wettable powders, suspension concentrates, and water dispersible granules. Surfactants used as dispersants have the ability to adsorb strongly onto a particle surface and provide a charged or stearic barrier to re-aggregation of particles. The most commonly used surfactants are either anionic, non-ionic, or combination thereof. Dispersing agents may be selected from the group consisting of, but not limited to acrylic graft copolymer, Alcohols, C9-11-iso-, C10-rich, ethoxylated. Non-ionic surfactants such as alkyl aryl ethylene oxide condensates and EO-PO block copolymers may be combined with anionic surfactants. In recent years, new types of very high molecular weight polymeric surfactants have been developed as dispersants. These have very long hydrophobic backbones and a large number of ethylene oxide chains forming the „teeth‟ of a „comb‟ surfactant. These high molecular weight polymers may give long-term stability to suspension concentrates because the hydrophobic backbones have many anchoring points onto
the particle surfaces. Examples of dispersants used herein including but are not limited to sodium lingo sulphonates; poly aryl phenyl ether phosphate, tristyryl phenol ethylated /Acrylic graft Copolymer/ ethoxylated tristryl phenol sulphate, naphthalene sulfonic acid, sodium salt condensate with formaldehyde, ethoxylated oleyl cetyl alcohol, polyalkelene glycol ether, ethoxylated fatty alcohol; EO-PO block copolymers; and graft copolymers or mixtures thereof. The blend of anionic and non-ionic surfactants is selected from the group consisting of, one or more styrenated phenol phosphate ester; blend of sodium aryl sulphonate, aryl sulphonate formaldehyde condensate and lignosulphonates; 2-Propenoic acid; 2-methyl-, polymer with α- methyl-ω-hydroxypoly(oxy-1,2-ethanediyl) and methyl 2-methyl-2-propenoate, graft; blend of Ethanol 2,2′,2′′-nitrilotris-, compound with α-[2,4,6-tris(1-phenylethyl)phenyl]-ω- hydroxypoly(oxy-1,2-ethanediyl) phosphate; alkyl phenol polyethanoxy ether; 2-2-oxydiethanol; and dihydrogen mono oxide, styrenated phenol phosphate ester, naphthalene and alkyl naphthalene sulphonic acids formaldehyde condensate, sodium salt, sodium dibutyl naphthalene sulphonate, linear alcohol derivative powder, sodium lignosulfonate, sodium poly naphthalene formaldehyde sulfonate, olefin sulfonate, or any combination thereof In one exemplary embodiment of the present invention, surfactants/dispersing agents are present in the range of 0.01-10% by weight of the total composition. The anti-freezing agents may be selected from the group consisting of polyethylene glycols, mono ethylene glycol, methoxy polyethylene glycols, glycol, propylene glycol, polypropylene glycols, poly butylene glycols, glycerin, ethylene glycol, di ethylene glycol or mixture thereof. In one exemplary embodiment of the present invention and method, the anti-freezing agent is present in the range of 0-20% by weight of the total composition. Water-based formulations often produce foam during production mixing procedures. Anti-foam chemicals are frequently added during the manufacturing stage or before filling into bottles to reduce the tendency to foam. Anti-foam agents are classified into two types, silicones and non- silicones. Silicones are usually aqueous emulsions of dimethyl polysiloxane. Non-silicone anti-
foam agents are water-insoluble oils such as octanol and nonyl, or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface. Defoamer/antifoaming agents are used in agrochemical formulations to prevent foaming during the mixing and spraying. They are typically added to the composition, as foam prevents efficient container filling. Antifoaming agents may be selected from the group comprising silicon emulsion based anti-foam agents, siloxane polyalkyleneoxide, trisiloxane ethoxylates, and mixtures thereof. In another exemplary embodiment of the present invention, defoamers may be present in the range of 0.01-2.0% by weight of the total composition. A wetting agent is a substance that, when added to a liquid, increases its spreading or penetrating ability by lowering the interfacial tension between the liquid and the surface it is spreading on. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacturing 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 improve water penetration into water-dispersible granules. Wetting agents used in suspension concentrate, wettable powder, and water dispersible granule formulations include, but not limited to, sodium lauryl sulphate; sodium dioctylsulphosuccinate, alkyl phenol ethoxylates, and aliphatic alcohol ethoxylates or mixtures thereof. In one exemplary embodiment of the present invention, wetting agents or/and dispersing agents may present in the range of 0.01 - 6.0% by weight of the total composition. Anti-microbial agents are used to eliminate or diminish the effect of micro-organisms. Examples of such agent include but are not limited to, propionic acid and its sodium salt, Sorbic acid and its Sodium or Potassium salts, Benzoic acid and its Sodium salt, p-hydroxy Benzoic acid sodium salt, methyl p -hydroxy benzoate, and biocides such as sodium benzoate, 1, 2-benzisothiazoline- 3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, potassium sorbate, parahydroxybenzoates or mixtures thereof.
In one exemplary embodiment of the present invention, biocides or anti-microbial agents may be present in the range of 0.01 – 1 % by weight of the total composition. Thickeners, gelling agents, and viscosity modifiers are commonly used in the formulation of suspension concentrates, emulsions, and suspoemulsions to alter the rheology or flow properties of the liquid and to avoid separation and settling of the dispersed particles or droplets. Thickening, gelling, and anti-settling agents are classified as either water-insoluble particles or water-soluble polymers. Clay and silicas may be used for preparing suspension concentrate compositions. These materials include, but are limited to, montmorillonite (e.g., bentonite); magnesium aluminum silicate; and attapulgite. For many years, water-soluble polysaccharides have been used as thickening, and gelling agents. Natural extracts of seeds and seaweed, as well as synthetic derivatives of cellulose or mixtures thereof, are the most often utilized polysaccharides. Guar gum, locust bean gum, carrageenam, xanthan gum, alginates, methyl cellulose, sodium carboxymethyl cellulose (SCMC), hydroxyethyl cellulose (HEC) or combination thereof are examples of these materials. Other anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol, polyethylene oxide or any combination thereof. In one exemplary embodiment of the present invention, thickeners or viscosity modifiers may be present in the range of 0.1 – 1% by weight of the total composition. Solvent(s) or carrier 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 C
9, solvent C
10, solvent C
12, 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 one exemplary embodiment of the present invention, the carriers may be present in the “Quantum Satis” i.e., Q.S quantity. In another exemplary embodiment, the present invention provides a process for preparing a synergistic fungicidal composition comprising the steps of (a) charging a vessel with demineralized water (DM); (b) adding silicon defoamer and stirring the mixture; (c) adding surfactants, 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 mill to achieve a required particle size; (f) transferring the mixture of step (e) to a secondary post feed vessel; (g) adding spreading cum sticking agent, xanthan gum solution, biocide and the remaining amount of water to the mixture of step (f); (h) mixing and homogenizing the mixture of step (g); (i) sieving and packing the mixture of step (h). In another preferred embodiment, the actives are prothioconazole and flutriafol in the range of 1 to 30% by weight of the composition. In another preferred embodiment, the synergistic fungicidal composition has particle size in the range of 0.1 to 30 microns. In another preferred embodiment, the present invention provides a process for preparing a synergistic fungicidal composition comprising the following steps of (a) charging a vessel with demineralized water (DM); (b) adding silicon defoamer and stirring the mixture for 30 minutes; (c) adding surfactants, anti-freezing agent, and precipitated silica to the mixture of step (b) under continuous stirring for 45 minutes; (d) adding and mixing prothioconazole and flutriafol to the mixture of step (c) and homogenizing for another 45 minutes; (e) milling the mixture of step (d) by passing through a bead mill to achieve a required particle size; (f) transferring the mixture of step (e) to a secondary post feed vessel; (g) adding spreading cum sticking agent, xanthan gum solution, biocide and the remaining amount of water to the mixture of step (f); (h) mixing and
homogenizing the mixture of step (g) for 1 hour, in case, any lumps of xanthan gum are left, homogenizing the mixture further for another 5 to 10 minutes; and (i) sieving and packing the mixture of step (h) after passing through a normal sieve of 36 mesh if no lumps are observed. EXAMPLES Below are the various examples for preparing different composition 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. Example 1: Aqueous Dispersion (AD) Composition Example 1a: Table 1: Aqueous Dispersion (AD) composition of 12.5% Prothioconazole and 11.5% Flutriafol S. No. Ingredients Function Quantity In % W/V 1. Prothioconazole A.I 12.5 2. Flutriafol A.I 11.5 3. Styrenated Phenol phosphate ester 4. blend of Sodium Aryl Sulphonate, Aryl Sulphonate Surface Active Formaldehyde Condensate and lignosulphonates
System 6.0 5. Precipitated Silica 6. Propylene glycol Anti-freezing 6.0 (CAS No.57-55-6) agent 7. Silicon Defoamer Defoaming agent 0.5 8. Polyalkyleneoxide modified Hepta Methyl Spreading cum 0.5 Trisiloxane sticking agent 9. Xanthan Gum powder Viscosity modifier 0.24 (CAS No.11138-66-2) 10. 1,2-Benzisothiazolin-3- one @ 20 % as Preservative 0.25 preservative (CAS No.2634-33-5) 11. Water Carrier QS T
OTAL 100 Process for preparation of the composition:
Charging a pre-feed vessel with deionized water, a silicone defoamer was added and stirred for 30 minutes. Then, a mixture of styrenated phenol phosphate ester, anionic and non-ionic surfactants, propylene glycol, and precipitated silica was added to the mixture while continuously stirring for 45 minutes. After that, the active ingredients Prothioconazole and Flutriafol were added and thoroughly mixed, followed by homogenizing for 45 minutes. The mixture was then milled by passing through a bead mill to achieve a particle size below 10 microns. The milled mixture was transferred to a secondary post-feed vessel. Following this, Poly alkylene oxide-modified Hepta Methyl Trisiloxane, a xanthan gum solution, 1, 2- Benzisothiazolin-3-one, and the remaining water were added to the mixture. The mixture was then mixed and homogenized for 1 hour. If any lumps of xanthan gum were present, the mixture was further homogenized for an additional 5 to 10 minutes to obtain an aqueous dispersion (AD). 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 Off white to light beige 3. Relative density (20ºC) 1.07 ± 0.1 g/ml @ 20°C 4. Suspensibility % w/w 80.0 in. 5. Degree of Dispersion % w/w Above 90 % 6. pH 1 % Aq. Solution 5.5 – 7.5 7. Flash point NA 8. Wet Sieve Test % w/w 98.0 % min. 9. Persistent Foam Max.60 ml after 1 min. 10. Viscosity (Brookfield) at 60 RPM spindle 3 300 - 600 cps D10 ≤ 3 11. Particle Size D50 ≤ 7 D90 ≤ 10 Table 3: Storage Stability Data
Test Parameters 0 Day @ 25°C 28 Days @ 25°C 28 Days AHS @ 5
4°C Description
Off-white Off-white s
uspension suspension Off-white suspension Prothioconazole A. I 12.57 12.57 12.54 Flutriafol A. I 11.59 11.58 11.55 Prothioconazole
Suspensibility 97.13 97.19 93.82
Flutriafol Suspensibility 96.37 96.43 91.18 pH 1 % Aq. Solution 6.77 6.67 6.64 Density g/ml 1.07 1.065 1.07 Viscosity (Brookfield) at 60
RPM spindle 3 390 cps 390 cps 382 cps Persistent Foam (0.5% aqua.
Sol.) 80 ml 50 ml 20 ml Wet Sieve (45 µ) Complies Complies Complies D10 1.86 1.84 1.90 Particle Size D50 4.35 4.58 5.17 D90 9.76 9.67 9.95 Example 1b: Table 4: Aqueous Dispersion (AD) composition of 7.5% Prothioconazole and 14.5% Flutriafol S. No. Ingredients Function Quantity In % W/V 1. Prothioconazole A.I 7.5 2. Flutriafol A.I 14.5 3. Acrylic Copolymer Solution (2-Propenoic acid, 2- 4.5 methyl-, polymer with .alpha.-methyl-.omega.- hydroxypoly(oxy-1,2-ethanediyl) and methyl 2- Surface Active methyl-2-propenoate, graft) System (CAS No.119724-54-8) blend of Sodium Aryl Sulphonate, Aryl 3.0 Sulphonate Formaldehyde Condensate and lignosulphonates 4. Precipitated Silica 1 5. Propylene glycol Anti-freezing agent 8.0 (CAS No.57-55-6) 6. Silicon Defoamer Defoaming agent 0.4 7. Polyalkyleneoxide modified Spreading cum 0.5 HeptaMethylTrisiloxane sticking agent 8. Xanthan Gum powder Viscosity modifier 0.24 (CAS No.11138-66-2) 9. 1,2-Benzisothiazolin-3- one @ 20 % as Preservative 0.25 preservative (CAS No.2634-33-5) 10. Water Carrier QS TOTAL 100 Process for preparation of the Composition:
Charging a prefeed vessel with deionized water, a silicone defoamer was added and stirred for 30 minutes. Then, an acrylic copolymer solution, a blend of anionic and non-ionic surfactants, propylene glycol, and precipitated silica were added to the mixture while continuously stirring for 45 minutes. Next, the active ingredients Prothioconazole and Flutriafol were thoroughly mixed into the solution, followed by homogenizing for 45 minutes. The resulting mixture was milled by passing it through a bead mill to obtain a particle size below 10 microns. The milled mixture was then transferred to a secondary post-feed vessel. Polyalkyleneoxide-modified HeptaMethylTrisiloxane, a xanthan gum solution, 1, 2-Benzisothiazolin-3-one, and the remaining water were added to the mixture, which was then mixed and homogenized for 1 hour. If any lumps of xanthan gum were present, the mixture was further homogenized for an additional 5 to 10 minutes to obtain an aqueous dispersion (AD). The material was packed after passing through a 36 mesh sieve if no lumps were observed. Table 5: Storage Stability Data Test Parameters 0 Day @ 25°C Description Off-white suspension Prothioconazole A. I
7.70 Flutriafol A. I 14.67 Prothioconazole Suspensibility
97.28 Flutriafol Suspensibility
96.24 pH 1 % Aq. Solution 6.75 Density g/ml 1.054 Viscosity (Brookfield) at 60 RPM spindle 3 472 cps Persistent Foam (0.5% aqua. Sol.) 21 mL Wet Sieve (45 µ) Complies D10 1.67 Particle Size (D10, D50, D90) D50 3.24 D90 6.84 Example 1c: Table 6: Aqueous Dispersion (AD) composition of 14.5% Prothioconazole and 10.5% Flutriafol S. No. Ingredients Function Quantity In % W/V 1. Prothioconazole A.I 14.5 2. Flutriafol A.I 10.5
3. Blend of Ethanol 2, 2, 2- nitrilotris-, compd. With 4.0 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 Surface (CAS No.105362-40-1, 9016-45-9, 111-46-6, 7732-18- Active 5) System 4. Naphthalene and alkyl naphthalene sulphonic acids 2.0 formaldehyde condensate, sodium salt. (CAS No.: 68425-94-5) 5. Precipitated Silica 0.8 6. Propylene glycol Anti freezing 7.0 (CAS No.57-55-6) agent 7. Silicon Defoamer Defoaming 0.5 agent 9. Polyalkyleneoxide modified Hepta Methyl Trisiloxane Spreading 0.6 cum sticking agent 10. Xanthan Gum powder Viscosity 0.24 (CAS No.11138-66-2) modifier 11. 1,2-Benzisothiazolin-3- one @ 20 % as preservative Preservative 0.25 (CAS No.2634-33-5) Water Carrier QS T
OTAL 100 Process for preparation of the Composition: Charging a pre-feed vessel with deionized water, a silicone defoamer was added and the mixture was stirred for 30 minutes. Subsequently, the following ingredients were added to the mixture while continuously stirring for 45 minutes: Ethanol, 2,2,2-nitrilotris-; compound with alpha- (2,4,6-tris(1-phenylethyl)phenyl)-omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate; alkyl phenol polyethanoxy ether; 2,2'-oxydiethanol; dihydrogen monoxide; naphthalene and alkyl naphthalene sulfonic acids formaldehyde condensate, sodium salt; propylene glycol; and precipitated silica. The active ingredients, Prothioconazole and Flutriafol, were then added and thoroughly mixed, followed by homogenization for 45 minutes. The resulting mixture was milled to achieve a particle size below 10 microns using a bead mill and transferred to a secondary post- feed vessel. Polyalkyleneoxide-modified Hepta Methyl Trisiloxane, a xanthan gum solution, and 1, 2-Benzisothiazolin-3-one, along with the remaining water, were added to the mixture, which was then mixed and homogenized for 1 hour. If any lumps of xanthan gum were present, the mixture was further homogenized for an additional 5 to 10 minutes to obtain an aqueous
dispersion (AD). The material is packed after passing through a normal sieve of 36 mesh if no lumps are observed. Table 7: Storage Stability Data Test Parameters 0 Day @ 25°C Description Off-white suspension Prothioconazole A. I 14.78 Flutriafol A. I 10.57 Prothioconazole Suspensibility 96.90 Flutriafol Suspensibility 95.69 pH 1 % Aq. Solution 6.35 Density g/ml 1.07 Viscosity (Brookfield) at 60 RPM spindle 3 454 cps Persistent Foam (0.5% aqua. Sol.) 30mL Wet Sieve (45 µ) Complies D10 1.67 Particle Size D50 3.35 D90 8.30 Example 2: Wettable Powder (WP) composition Table 8: Wettable Powder (WP) composition of 30.0% Prothioconazole and 15.0% Flutriafol S. No. INGREDIENTS FUNCTIONS QUANTITY IN % W/W 1. Prothioconazole A.I. 30.0 2. Flutriafol A.I. 15.0 3. Sodium dibutyl naphthalene sulphonate 8.0 4. Linear Alcohol Derivative Powder Surface Active 2.0 5. Sodium Lignosulfonate System 2.0 6. Precipitated Silica
2.0 7. China clay Carrier QS to 100% w/w TOTAL 100 Process for preparation of the composition: The active ingredients i.e. Prothioconazole and Flutriafol were accurately weighed and transferred to the pre-blender. Then, the dispersing agent, wetting agent, co-dispersant, and china clay were added to the mixture and mixed for 30 minutes in the pre-blender. After that, the
mixture was milled using an ACM (Air Classifying Mill) to obtain a micronized powder with a particle size of less than 20 microns. The milled powder was transferred to the post-blender and homogenized for an additional 30 minutes. Finally, the powder was packed after quality control testing to ensure it met the required specifications. Table 9: Physiochemical Properties of the composition S. No. Parameters Specification Results 1
. Physical state Powder
Powder 2. Color Off-white Off-white 3
. Odor Odorless Odorless 4. A.I. % w/w Prothioconazole 30.0 30.07 Flutriafol 15.0 15.05 5. Suspensibility % w/w Prothioconazole 60% min. 85.67% Flutriafol 60% min. 80.42% 6
. pH (1%) aqueous soln. 5.50-8.50 6.75 7. Wet Sieve Test % w/w 98% min. Complies 8. Foaming (0.5% aquas, soln.) 60 ml max.
20ml 9. Wettability 120 sec. max.
50 sec Example 3: Wettable Granule (WG) composition Table 10: Wettable Granule (WG) composition of 15.2% Prothioconazole and 12.0% Flutriafol S. No. Ingredients Functions Quantity In % W/W 1. Prothioconazole Active 15.2 2. Flutriafol Active 12.0 3. Sodium Poly Naphthalene Formaldehyde 6 Sulfonate (CAS 9084-06-4) Surface Active 4. Olefin sulfonate System 4 (CAS 68439-57-6) 5. Precipitated silica 2 6. China clay Carrier QS to 100% w/w TOTAL 100% w/w Process for preparation of the composition:
The active ingredients i.e. prothioconazole and flutriafol, were transferred to the pre-blender and mixed for 20 minutes. The mixture was then subjected to air jet milling to reduce the particle size to below 20 microns. After milling, the mixture was transferred to a post-mixing vessel and mixed for another 20 minutes. Water was added and mixed for 10 minutes to prepare a dough suitable for granulation. The cylindrical granulation was carried out with the prepared dough, and the wet granules were transferred to a dryer and dried at a temperature of 50-60℃. Table 11: Physiochemical Properties of the Composition
S. No. Parameters Specification Results 1. Physical state Solid Solid 2. Colour White to cream color White to cream color 3
. Odour Odorless Odorless A.I. % w/w 4. Prothioconazole 15.20 15.26 Flutriafol 12.00 12.04 5. pH 1 % Aq. Solution 5.0-8.5 7.52 Suspensibility % w/w 6. Prothioconazole 60% min. 82.85% Flutriafol 60% min. 85.61% 7
. Dispersion Dispersible Dispersible Example 4: Dispersion Concentrate (DC) composition Table 12: Dispersion Concentrate (DC) composition of 5.5% Prothioconazole and 10.5% Flutriafol S. No. Ingredients Function Quantity In % W/W 1. Prothioconazole A.I. 5.5 2. Flutriafol A.I. 10.5 3. Sodium Lignosulfonate 0.2 5. Formulated Product of Anionic/Nonionic Surface active 15.0 surfactant System 6 Precipitated Silica 0.1 Polyvinylpyrrolidone Stabilizer 1.0 7. Water Carrier 2.0 8. N-Methyl-2-pyrrolidone Solvent Q.S. Process for preparation of the composition: Required amount of N-Methyl-2-pyrolidone (NMP) was measured and transferred to a beaker, then stirred at 100 RPM. The active
ingredients, prothioconazole and flutriafol, along with the stabilizer polyvinylpyrrolidone, were added to the beaker while stirring continuously. Solution of sodium lignosulfonate in water was added to the mixture and stirred continuously for 20 minutes to ensure complete dissolution. Finally, a blend of anionic and non-ionic surfactants with precipitated silica was added to the mixture and mixed for another 20 minutes to obtain a dispersion concentrate. Table 13: Physiochemical Properties of the composition S. No. Parameters Specification Results 1. Physical state Liquid Liquid 2. Color Yellow to Brown Yellow 3. Odor Aromatic Aromatic 4. Dispersion Stability Stable Stable 5. pH (1% aqua sol.) 4.0 – 6.0 4.19 6. Density at 20
0C g/ml 1.08 g/ml ± 0.1 1.072 7. Solubility with water Dispersible Dispersible Example 6: Composition with high concentration of Actives Example 6a: Table 14: Aqueous Dispersion (AD) composition of 35.0% Prothioconazole and 15.0% Flutriafol S. No. Ingredients Function Quantity In % W/V 1. Prothioconazole A.I 35.0 2. Flutriafol A.I 15.0 3. Styrenated Phenol phosphate ester 3.5 4. blend of Sodium Aryl Sulphonate, Aryl Surface Active 2.0 Sulphonate Formaldehyde Condensate and System lignosulphonates 5. Precipitated Silica 0.5 6. Propylene glycol Anti-freezing agent 6.0 (CAS No.57-55-6) 7. Silicon Defoamer Defoaming agent 0.5 8. Polyalkyleneoxide modified Spreading cum 0.5 HeptaMethylTrisiloxane sticking agent 9. Xanthan Gum powder Viscosity modifier 0.24 (CAS No.11138-66-2) 10. 1,2-Benzisothiazolin-3- one @ 20 % as Preservative 0.25 preservative
(CAS No.2634-33-5) 11. Water Carrier QS TOTAL 100 Process for preparation of the composition: Charging a prefeed vessel with deionized water, a silicone defoamer and mixture was stirred for 30 minutes. Then, a blend of anionic and non-ionic surfactants, styrenated phenol phosphate ester, propylene glycol, and precipitated silica were added to the mixture while continuously stirring for 45 minutes. Next, the active ingredients, Prothioconazole and Flutriafol, were thoroughly mixed into the mixture, followed by homogenization for 45 minutes. The resulting mixture was milled by passing it through a bead mill to achieve a particle size below 10 microns, and then transferred to a secondary post-feed vessel. Polyalkyleneoxide-modified Hepta Methyl Trisiloxane, a solution of xanthan gum, 1,2-Benzisothiazolin-3-one, and the remaining water were added to the mixture, which was then mixed and homogenized for 20 minutes. If any lumps of xanthan gum were present, the mixture was further homogenized for an additional 5 to 10 minutes to obtain an aqueous dispersion (AD). The material is packed after passing through a 36 mesh sieve if no lumps are observed. Table 15: Physiochemical Properties of the composition S. N
o. Parameters Results 1. Physical state Viscous Liquid 2. Colour Off white to light beige 3. Relative density (20ºC) N.M. 4. Suspensibility % w/w N.M. 5. Degree of Dispersion % w/w N.M. 6. pH 1 % Aq. Solution N.M. 7. Wet Sieve Test % w/w N.M. 8. Persistent Foam N.M. 9. Viscosity (Brookfield) at 60 RPM spindle 3
Too viscous cannot measured D10 ≤ 14 10. Particle Size D50 ≤ 37 D90 ≤ 64 Observation: During milling, the material became thick and un-flowable at the high concentration of active ingredients. The bead mill‟s temperature rose to 50°C, causing the
particle size to exceed the desired limit of 10 microns. As a result, the composition did not achieve the intended outcome and failed. Example 6b: Table 16: Aqueous Dispersion (AD) composition of 16.0% Prothioconazole and 35.0% Flutriafol
S. No. Ingredients Function Quantity In % W/V 1. Prothioconazole A.I 16.0 2. Flutriafol A.I 35.0 3. Acrylic copolymer solution Dispersing agent 4.2 4. blend of Sodium Aryl Sulphonate, Aryl 3.0 Sulphonate Formaldehyde Condensate and Surface Active System lignosulphonates 5. Precipitated Silica 0.7 6. Propylene glycol Anti-freezing agent 6.0 (CAS No.57-55-6) 7. Silicon Defoamer Defoaming agent 0.5 8. Polyalkyleneoxide modified Spreading cum 0.5 HeptaMethylTrisiloxane sticking agent 9. Xanthan Gum powder Viscosity modifier 0.24 (CAS No.11138-66-2) 10. 1,2-Benzisothiazolin-3- one @ 20 % as Preservative 0.25 preservative (CAS No.2634-33-5) 11. Water Carrier QS TOTAL 100 Process for preparation of the composition: After charging the prefeed vessel with deionized water, a silicone defoamer was added and stirred for 30 minutes. Next, an acrylic copolymer solution, a blend of anionic and non-ionic surfactants, propylene glycol, and precipitated silica were added to the mixture while continuously stirring for 45 minutes. Then, the active ingredients, Prothioconazole and Flutriafol, were added and thoroughly mixed, followed by homogenization for 45 minutes. The resulting mixture was milled by passing through a bead mill to achieve a particle size below 10 microns. The milled mixture was then transferred to a secondary post-feed vessel. Polyalkyleneoxide- modified HeptaMethylTrisiloxane, a xanthan gum solution, 1, 2-Benzisothiazolin-3-one, and the
remaining water were added to the mixture. The mixture was mixed and homogenized for 20 minutes. If any lumps of xanthan gum were present, the mixture was further homogenized for 5 to 10 minutes to obtain an aqueous dispersion (AD). The material is packed after passing through a 36-mesh sieve if no lumps are observed. Table 17: Physiochemical Properties of the Composition S. N
o. Parameters Results 1. Physical state Viscous Liquid 2. Colour Off-white to light beige 3. Relative density (20ºC) N.M. 4. Suspensibility % w/w N.M. 5. Degree of Dispersion % w/w N.M. 6. pH 1 % Aq. Solution N.M. 7. Wet Sieve Test % w/w N.M. 8. Persistent Foam N.M. 9. Viscosity (Brookfield) at 60 RPM spindle 3
Too viscous cannot measured D10 ≤ 15 10. Particle Size D50 ≤ 39 D90 ≤ 67 Observation: During milling, the material became thick and un-flowable at the high concentration of active ingredients. The temperature of the bead mill rose to 50°C, causing the particle size to exceed the desired limit of 10 microns. As a result, the composition did not achieve the intended outcome and failed. It is evident from Tables 14 to 17 above that even when the amount of one of the actives is increased beyond the claimed ranges, the composition cannot be prepared. Example 7: Table 18: Present invention composition with and without surface active system Composition with Surface Active System Composition without Surface Active System Quantity Ingredients In %
Ingredients Quantity In W/V
% W/V Prothioconazole 12.5 Prothioconazole 12.5
Flutriafol 11.5 Flutriafol 11.5 Styrenated Phenol
Styrenated Phenol phosphat phosphate ester
3.5 e e
ster 6.5 blend of Sodium Aryl Sulphonate, Aryl Sulphonate Surface Formaldehyde Active 2 Propylene glycol 6 Condensate and System lignosulphonates Precipitated Silica 0.5 Silicon Defoamer 0.5 Propylene glycol 6
Polyalkyleneoxide modified H
epta Methyl Trisiloxane 0.5 Silicon Defoamer 0.5 Xanthan Gum powder 0.24 Polyalkyleneoxide modified Hepta 1,2-Benzisothiazolin-3- one
Methyl Trisiloxane 0.5 @ 20 % as preservative 0.25 Xanthan Gum powder 0.24 (CAS No.2634-33-5) 1,2-Benzisothiazolin-3- one @ 20
% as preservative 0.25 Water QS Water QS
TOTAL 100 TOTAL 100 Table 19: Physiochemical properties of the composition with and without surface active system Physiochemical properties with Surface Phsiochemical Properties without Surface Active System Active System Parameters Results Parameters Results
Physical state Viscous Liquid Physical state Partial gelly type L
iquid Colour Off white to light b
eige Colour Off white Relative density (20ºC) 1.07 ± 0.1 g/ml @ 2
0°C Relative density (20ºC) NA Suspensibility % w/w 80.0 min. Suspensibility % w/w 67 Wet Sieve Test % w/w 98.0 % min. Wet Sieve Test % w/w Not Complies
Persistent Foam Max. 60 ml after 1 m
in. Persistent Foam 50ml
Viscosity (Brookfield) at 3
00 Viscosity (Brookfield) at 6
0 RPM spindle 3 - 600 cps 60 RPM spindle 3 above 800 As evident from the above table, the composition without a surface active system possessed multiple challenges, such as gel-like consistency, variation in colour, poor suspensibility, unfavourable results in the wet sieve, persistent foaming, and high viscosity. The increase in viscosity negatively impacted the spray-ability and spreadability of the composition, thereby affecting its stability and performance. However, the present invention composition with a surface active system has better stability, enhanced suspensibility, reduced foaming, and optimal viscosity, ensuring improved spray-ability and spreadability. These improvements significantly enhanced the overall performance of the composition. Example 8: Method for Evaluating Spreading Properties A 1% solution was prepared by diluting 1 ml of the composition in 100 ml of water. A drop of this solution was placed onto the surface of multiple leaf. After 30 seconds, the spreading diameter of the solution was measured in millimeters using different graph paper for accuracy. Table 20: Spreading properties of Aqueous Dispersion composition of 12.5% Prothioconazole and 11.5% Flutriafol Room Temperature Study Treatments 1 month 3 months 6 months Spreading effectiveness (Diameter in mm) Prothioconazole 12.5% + Flutriafol 25 23 21 11.5% Aqueous Dispersion Prothioconazole 25% SC 9 7 5 Flutriafol 25% SC 17 15 12 The aqueous dispersion composition comprising Prothioconazole at 12.5% and Flutriafol at 11.5% exhibits superior spreading properties. This composition significantly enhances bio- efficacy in field conditions by ensuring even distribution over the target area. As a result, it provides prompt and effective control of target insect pests. Additionally, the formulation's
excellent rainfast properties are particularly advantageous during adverse weather conditions, such as rainy days, thereby maintaining its efficacy and performance under varying environmental conditions. Example 9: 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 used in the trial for treatment. The recommended doses of different compositions were added to 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 chemicals (only potato dextrose agar media) were untreated control plates. Plates were incubated at 24-25 °C for the growth of pathogens. All the treatment sets were replicated five times. The average growth of the pathogen was measured from all the treatment sets at 5, 10 and 15 DAI (Days after inoculation). 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 control plate and T is the radial growth of the pathogen in the poisoned plates (Chemically treated media plates). Example 10: TRIAL 1: Bio-efficacy of synergistic composition of Prothioconazole and Flutriafol against Alternaria brassicicola. 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 04-08-2023 Number of applications
1 Target Disease Alternaria brassicicola Time of observation 5 DAI, 10 DAI & 15DAI (Days after inoculation) Method of application Food poison Technique Table 21: Effect of different treatments on Percent Disease Inhibition (PDI) against Alternaria brassicicola plant parasitic fungus. Gram Percent disease inhibition S. No. Treatment Details
ai/ha Dose (g or (PDI) Gram ai ml/litre of PDA 5 DAI 10 DAI 15 DAI Prothioconazole + 62.5+57.5 T1 Flutriafol AD (Low 1 ml 100.00 100.00 100.00 Dose) Prothioconazole + T2 Flutriafol AD (Medium 93.75+ 8
1.5 ml 100.00 100.00 100.00 Dose)
6.25 Prothioconazole + 125+ 115 T3 Flutriafol AD (Higher 2 ml 100.00 100.00 100.00 Dose) T
4 Prothioconazole 25% E
C 62.5 0.5 ml 45.14 47.59 65.86 T5 Flutriafol 25% SC
57.5 0.46 ml 94.29 92.66 90.66 T6 Control NA 0.00 0.00 0.00 *DAI: (Days after inoculation) Note: Laboratory dose was taken as per field equivalent dose
Table 22: Synergistic effect of combination of Prothioconazole and Flutriafol (all doses) against Alternaria brassicicola plant parasitic fungus at 10 DAI. Dose (g Percent disease inhibition (PDI) S. T
reatmen Gram or
No. t Details ai/ha ml/litre Observed Expected Ratio Synergy of PDA Prothioconazole + T1 Flutriafol AD (Low 62.5+57.5 1 ml 100.00 96.15 1.04 Yes Dose) Prothioconazole + T2 Flutriafol AD 93.75+ 8
6 1.5ml 100.00 96.15 1.04 Yes (Medium Dose)
.25 Prothioconazole + T3 Flutriafol AD (Higher 125+ 115 2 ml 100.00 96.15 1.04 Yes Dose) T
4 Prothioconazole 25% E
C 62.5 0.5 ml 47.59 - - - T5 Flutriafol 25% SC 57.5 0.46 ml 92.66 - - - T6 Control NA 0.00 - - - Percent Disease Inhibition: The present invention composition comprising Prothioconazole and Flutriafol provided the highest percentage of disease inhibition at all doses, thereby showing synergy as compared to other treatments. Example 11: Laboratory Experiment Details TRIAL 2: Bio-efficacy of synergistic composition of Prothioconazole and Flutriafol (all doses) against Collectotricum capsici (Chilli Anthracnose). 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
31-07-2023 Number of applications 1 Target Disease Collectotricum capsici (Chilli Antracnose)
Time of observation 5 DAI, 10 DAI & 15DAI (Days after inoculation)
Method of application Food poison Technique Table 23: Effect of different treatments on Percent disease inhibition (PDI) against Colletotrichum capsici (chilli Anthracnose) plant parasitic fungus. Dose ( Percent disease inhibition
S. No. Treatment Details Gram g or (PDI) ai/ha ml/litre of PDA 5 DAI 10 DAI 15 DAI T
1 Prothioconazole + 62.5+57.5 Flutriafol AD (Low Dose) 1 ml 100.00 100.00 100.00 Prothioconazole + 93.75+ T2 Flutriafol AD (Medium 86.25 1.5 ml 100.00 100.00 100.00 Dose) Prothioconazole + 125+ 115 T3 Flutriafol AD (Higher 2 ml 100.00 100.00 100.00 Dose) T4 Prothioconazole 25% EC
62.5 0.5 ml 54.63 72.87 77.78 T5 Flutriafol 25% SC
57.5 0.46 ml 79.63 89.53 85.02 T6 Control NA 0.00 0.00 0.00 *DAI: (Days after inoculation) Note: Laboratory dose was taken as per field equivalent dose Table 24: Synergistic effect of combination of Prothioconazole and Flutriafol (all doses) against Collectotricum capsici (chilli Anthracnose) plant parasitic fungus at 10 DAI. Dose (g Percent disease inhibition (PDI) S. T
re Gram or N
o. atment details ai/ha ml/litre Observed Expected Ratio Synergy of PDA Prothioconazole + T1 Flutriafol AD (Low 62.5+57.5 1 ml 100.00 97.16 1.03 Yes Dose) Prothioconazole + T2 Flutriafol AD 93.75+ 8
6.2 1.5 ml 100.00 97.16 1.03 Yes (Medium Dose)
5 Prothioconazole + T3 Flutriafol AD 125+ 115 2 ml 100.00 97.16 1.03 Yes (Higher Dose) T
4 Prothioconazole 62.5 0.5 ml 72.8 - - - 2
5% EC 7 T
5 Flutriafol 25% SC 57.5 0.46 ml 89.53 - - - T
6 Control NA 0.00 - - -
Percent Disease Inhibition: The present invention composition comprising Prothioconazole and Flutriafol provided the highest per cent disease inhibition at all doses, thereby showing synergy as compared to other treatments. Example 12: TRIAL 3: Bio-efficacy of the synergistic composition of Prothioconazole and Flutriafol (all doses) against Fusarium oxysporum. Season Kharif 2023 Location Research Laboratory, Ambala A
ge of Culture 10 days old Temperature Range during Trial 25°C ± 2°C Single plate size 90 mm Date of inoculation 02-08-2023 Number of applications 1 Target Disease Fusarium oxysporum Time of observation 5 DAI, 10 DAI & 15DAI (Days after inoculation) Method of application Food poison Technique Table 25: Effect of different treatments on Percent disease inhibition (PDI) against Fusarium oxysporum plant parasitic fungus. Do Percent disease inhibition
S. No. Treatment Details Gram se (g or (PDI) ai/ha ml/litre of PDA 5 DAI 10 DAI 15 DAI T
1 Prothioconazole + Flutriafol A
D (Low Dose) 62.5+57.5 1 ml 100.00 100.00 100.00 T
2 Prothioconazole + Flutriafol 93.75+ AD (Medium Dose)
86.25 1.5 ml 100.00 100.00 100.00 T
3 Prothioconazole + Flutriafol A
D (Higher Dose) 125+ 115 2 ml 100.00 100.00 100.00 T4 Prothioconazole 25% EC 62.5 0.5 ml 94.58 77.11 79.57 T5 Flutriafol 25% SC 57.5 0.46 ml 91.87 69.96 73.05 T6 Control NA 0.00 0.00 0.00 *DAI: (Days after inoculation) Note: Laboratory dose was taken as per field equivalent dose Table 26: Synergistic effect of combination of Prothioconazole and Flutriafol (all doses) against Fusarium oxysporum plant parasitic fungus at 10 DAI.
Dose (g Percent Disease inhibition (PDI) S. Gra o
. Treatme m or N
nt details ai/ha ml/litre Observed Expected Ratio Synergy of PDA Prothioconazole + T1 Flutriafol AD (Low 62.5+57.5 1 ml 100.00 93.12 1.07 Yes Dose) Prothioconazole + T2 Flutriafol AD 93.75+ ium Dose)
86. 1.5ml 100.00 93.12 1.07 Yes (Med
25 Prothioconazole + T3 Flutriafol AD 125+ 115 2 ml 100.00 93.12 1.07 Yes (Higher Dose) T
4 Prothioconazole 2
5% EC 62.5 0.5 ml 77.11 - - - T5 Flutriafol 25% SC 57.5 0.46 ml 69.96 - - - T6 Control NA 0.00 - - - Percent Disease Inhibition (PDI): The present invention composition comprising Prothioconazole and Flutriafol provided highest per cent disease inhibition at all doses thereby showing synergy as compared to other treatments. Example 13: TRIAL 4: Bio-efficacy of synergistic composition of Prothioconazole and Flutriafol (all doses) against Cercospora arachidicola (Ground nut Tikka Disease). Season Kharif 2023 L
ocation 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 03-08-2023 Number of applications 1 Target Disease Cercospora arachidicola (Ground nut Tikka Disease) T
ime of observation 5 DAI, 10 DAI & 15DAI (Days after inoculation) Method of application Food poison Technique Table 27: Effect of different treatments on Percent disease inhibition (PDI) against Cercospora arachidicola (Ground nut Tikka Disease) parasitic fungus. Dose (g or Percent disease inhibition
S. No. Treatment details Gram ai/ha ml/litre of (PDI) PDA 5 DAI 10 DAI 15 DAI
T1 Prothioconazole + Flutriafol A
D (Low Dose) 62.5+57.5 1 ml 80.25 82.02 74.29 T
2 Prothioconazole + Flutriafol 93.75+ AD (Medium Dose)
86.25 1.5ml 84.94 84.40 79.25 T
3 Prothioconazole + Flutriafol A
D (Higher Dose) 125+ 115 2ml 100.00 85.14 81.24 T4 Prothioconazole 25% EC 62.5 0.5 ml 58.27 58.10 62.36 T5 Flutriafol 25% SC 57.5 0.46 ml 48.15 55.13 58.76 T6 Control NA 0.00 0.00 0.00 *DAI: (Days after inoculation) Note: Laboratory dose was taken as per field equivalent dose Table 28: Synergistic effect of combination of Prothioconazole and Flutriafol (all doses) against Cercospora arachidicola (Ground nut Tikka Disease) plant parasitic fungus at 10 DAI. Dose (g Percent disease inhibition (PDI) S. No. Treatment details
Gram or a
i/ha ml/litre Observed Expected Ratio Synergy of PDA Prothioconazole + T1 Flutriafol AD (Low 62.5+57.5 1 ml 82.02 81.20 1.01 Yes Dose) Prothioconazole + T2 Flutriafol AD 93.75+ 8
6 1.5ml 84.40 81.20 1.04 Yes (Medium Dose)
.25 Prothioconazole + T3 Flutriafol AD 125+ 115 2ml 85.14 81.20 1.05 Yes (Higher Dose) T
4 Prothioconazole 2
5% EC 62.5 0.5 ml 58.10 - - - T5 Flutriafol 25% SC 57.5 0.46 ml 55.13 - - - T6 Control NA 0.00 - - - Percent Disease Inhibition: The present invention composition comprising Prothioconazole and Flutriafol provided the highest per cent disease inhibition at all doses, thereby showing synergy as compared to other treatments. Example 14: TRIAL 5: Bio-efficacy of synergistic composition of Prothioconazole and Flutriafol (all doses) against Pyricularia oryzae (Paddy Blast Diseases).
Season Kharif 2023 Location Research Laboratory, Ambala A
ge of Culture 10 days old Temperature Range during Trial 25°C ± 2°C Single plate size 90 mm Date of inoculation 14-08-2023 Number of applications 1 Target Disease Pyricularia oryzae (Paddy Blast Disease) Time of observation 5 DAI, 10 DAI & 15DAI (Days after inoculation) Method of application Food poison Technique Table 29: Effect of different treatments on Percent disease inhibition (PDI) against Pyricularia oryzae (Paddy Blast) plant parasitic fungus. Dose (g Percent disease inhibition
S. No. Treatment details Gram or ml/litr (PDI) ai/ha e of PDA 5 DAI 10 DAI 15 DAI T
1 Prothioconazole + Flutriafol A
D (Low Dose) 62.5+57.5 1 ml 100.00 100.00 95.07 T
2 Prothioconazole + Flutriafol 93.75+ AD (Medium Dose)
86.25 1.5 ml 100.00 100.00 100.00 T
3 Prothioconazole + Flutriafol A
D (Higher Dose) 125+ 115 2 ml 100.00 100.00 100.00 T4 Prothioconazole 25% EC 62.5 0.5 ml 79.09 78.51 82.39 T5 Flutriafol 25% SC 57.5 0.46 ml 81.36 78.87 81.77 T6 Control NA NA 0.00 0.00 0.00 *DAI: (Days after inoculation) Note: Laboratory dose was taken as per field equivalent dose Table 30: Synergistic effect of combination of Prothioconazole and Flutriafol (all doses) against Pyricularia oryzae (Paddy Blast) plant parasitic fungus at 10 DAI. Dose (g Percent disease inhibition (PDI) S. T
reatmen Gram or N
o. t details ai/ha ml/litre Observed Expected Ratio Synergy of PDA T
1 Prothioconazole + Flutriafol AD 62.5+57.5 1 ml 100.00 95.46 1.05 Yes
(Low Dose) Prothioconazole + T2 Flutriafol AD 93.75+ 8
1.5 ml 100.00 95.46 1.05 Yes (Medium Dose)
6.25 Prothioconazole + T3 Flutriafol AD 125+ 115 2 ml 100.00 95.46 1.05 Yes (Higher Dose) T
4 Prothioconazole 2
5% EC 62.5 0.5 ml 78.51 - - - T5 Flutriafol 25% SC 57.5 0.46 ml 78.87 - - - T6 Control NA 0.00 - - - Percent Disease Inhibition: The present invention composition comprising Prothioconazole and Flutriafol provided highest per cent disease inhibition at all doses thereby showing synergy as compared to other treatments. Field Trial Studies: Methodology for Field Evaluation: The application was done according to the treatment schedule and given as a foliar spray. A total of six treatments with three replications each were taken up. In each treatment, five plants were selected, and the same plant was observed with respect to various parameters, such as per cent disease index and per cent disease control. Formulae Used for the Observation Parameters. Field Evaluation/observations: The study was undertaken at a farmer field at Peddadevulapalla, Miryalguda Telangana, during Rabi 2023-24. The experiment was conducted on a paddy blast caused by Pyricularia oryzae to determine the effective molecule for management. One spray was applied at the initiation of the disease. Taken observations on percent disease severity at 0, 5, 10, 15 & 20 days after each application from 5 tagged plants from each plot based on below respective disease rating scales. To record blast incidence, the per cent incidence/leaf was counted to calculate the per cent disease incidence (PDI). The formula for calculating the PDI is below. Some of numerical ratings PDI = ---------------------------------------------------------------------------- X 100
Total number of plants observed X maximum rating scale Disease rating Scale: Paddy Blast: Scale for scoring of rice leaf blast disease (IRRI, 2013; Singh et al., 2013b) S
cale Disease severity 0 Lesions are not present 1 Small brown specks of pinpoint size or larger brown specks without sporulating centre Small roundish to slightly elongated, necrotic grey spots, about 1-2 mm in diameter, 2 with a distinct brown margin. Lesions are mostly found on the lower leaves Lesions type is same as in scale 2, but a significant number of lesions on upper leaf 3 area 4 Typical susceptible blast lesions, 3 mm or longer infecting less than 4 % of leaf area 5 Typical susceptible blast lesions infecting 4-10% of the leaf area 6 Typical susceptible blast lesions infecting 11 – 25% of the leaf area 7 Typical susceptible blast lesions infecting 26 - 50% of the leaf area Typical susceptible blast lesions infecting 51- 75% of the leaf area and many leaves are 8 dead 9 More than 75% leaf area affected Percent disease reduction over control (PDC) was calculated by using formula given below:
Bio-efficacy studies of Prothioconazole + Flutriafol against Paddy Blast disease (Pyricularia oryzae) Experiment Details: Season Kharif 2023
Location Peddadevulapalla, Miryalguda, Telangana
Crop Paddy Age of Crop 45 days Temperature Range during Trial 17-30°C Variety BPT 5204 Single plot size
5*5 m2 Date of Transplanting 01-11-2023
Number of applications 1 Time & Method of Treatment First application at the onset of disease and second at 15 days interval depend on disease severity Date of application/Treatment 15-12-2023 Target Pest Paddy Blast Pyricularia oryzae Table 31: Treatment Details: S
.no Treatment Details Gram ai/ha Dose (g or ml/ha T
1 Prothioconazole + Flutriafol 62.5+57.5 500ml (Low Dose) T
2 Prothioconazole + Flutriafol (
Medium Dose) 93.75+ 86.25 750ml T
3 Prothioconazole + Flutriafol 125+ 115 1000ml (Higher Dose) T4 Prothioconazole 25% EC 62.5 250ml T5 Flutriafol 25% SC
57.5 230ml T6 Control - - Table 32: Effect of composition on Percent disease inhibition (PDI) of Prothioconazole + Flutriafol against Paddy Blast (Pyricularia oryzae) Effectiveness of Prothioconazole + Flutriafol against Pady Blast
S.no Treatment Details Gram (Pyricularia oryzae). ai/ha Percent disease index (PDI) 5 DAA 10 DAA 15 DAA 20DAA T
1 Prothioconazole + Flutriafol 62.5+57.5 (Low Dose) 2.22 5.19 7.41 14.81 T
2 Prothioconazole + Flutriafol 93.75+ (Medium Dose)
86.25 2.22 4.44 5.19 7.41 T
3 Prothioconazole + Flutriafol 125+ 115 (Higher Dose) 1.48 3.70 4.44 5.93 T4 Prothioconazole 25% EC 62.5 2.96 8.89 16.30 24.44 T5 Flutriafol 25% SC 57.5 2.96 11.85 24.44 35.56 T
6 Control 7.41 27.41 54.07 71.11 DAA (days after application)
% Percent disease index (PDI): The lowest incidence of Paddy Blast (Pyricularia oryzae) was seen in Prothioconazole + Flutriafol @ 1000ml, 750ml & 500ml respectively. The highest disease occurrence was recorded in case of control. Table 33: Effect of composition on per cent reduction over control of Prothioconazole + Flutriafol against Pady Blast (Pyricularia oryzae) Effectiveness of PIPL PF240/22 against Pady Blast (Pyricularia oryzae). S
.no Treatment D
etails Gram ai/ha Per cent (%) Disease control (PDC) 5 1
0 15 20DAA D
AA DAA DAA Prothioconazole 62.5+57.5 T1 + Flutriafol 70.00 81.08 86.30 79.17 (Low Dose) Prothioconazole T2 + Flutriafol 93.75+ 86.25 70.00 83.78 90.41 89.58 (Medium Dose) Prothioconazole 125+ 115 T3 + Flutriafol 80.00 86.49 91.78 91.67 (Higher Dose) T
4 Prothioconazole 2
5% EC 62.5 60.00 67.57 69.86 65.63 T
5 Flutriafol 25% 57.5 SC 60.00 56.76 54.79 50.00 T6 Control - 0.00 0.00 0.00 0.00 DAA (days after application) % Percent Disease Control (PDC): The highest per cent disease control of Paddy Blast (Pyricularia oryzae) was seen in Prothioconazole + Flutriafol @ 1000ml, 750ml & 500ml respectively. The highest disease occurrence was recorded in case of control. Table 34: Synergistic effect of Prothioconazole + Flutriafol against Pady Blast (Pyricularia oryzae) @10DAA S. G Percent disease Control (PDC) .
Treatme ram N
o nt details ai/ha Observed Expected Ratio Synergy T
1 Prothioconazole + Flutriafol 62.5+57.5 86.30 86.38 1.00 Yes (Low Dose) T
2 Prothioconazole + Flutriafol 93.75+ (Medium Dose)
86.25 90.41 86.38 1.05 Yes
T3 Prothioconazole + Flutriafol 125+ 115 91.78 86.38 1.06 Yes (Higher Dose) T
4 Prothioconazole 25% EC 62.5 69.86 T
5 Flutriafol 25% SC 57.5 54.79 T
6 Control 0.00 Evaluation of Phytotoxicity: ^Visual observations were recorded at 7, 14 and 21 days after the application (DAA) of the compositions. 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.^ 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 35: Phytotoxic effect of various treatments on ground nut crop 7 DAA^at recommended dose 7 DAA^ S. No.^ Treatment details^ Dose (g or ml/ha L^ S^ N^ C^ V^ E^ H^ W^ Prothioconazole + Flutriafol T1
PIPL (2L3o0w12 D @os1em)l/kg seeds 500m U
lntreated
0 plot a
0ffect
0ed b
0y col
0lar ro
0t & w
0hite
0 grub Plate 02: PIPL23012 vs untreated plot affected by collar rot & white grub in ground nut @45DAA
Prothioconazole + Flutriafol T2
(Medium Dose) 750ml 0 0 0 0 0 0 0 0 Prothioconazole + Flutriafol T3
(Higher Dose) 1000ml 0 0 0 0 0 0 0 0 T4 Prothioconazole 25% EC 250 ml 0 0 0 0 0 0 0 0 T5 Flutriafol 25% SC 230 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 36: Phytotoxic effect of various treatments on ground nut crop 14 DAA^at recommended dose 14 DAA^ S. No.^ Treatment details^ Dose (g or ml/ha L^ S^ N^ C^ V^ E^ H^ W^ Prothioconazole + Flutriafol T1
(Low Dose) 500ml 0 0 0 0 0 0 0 0 Prothioconazole + Flutriafol T2
(Medium Dose) 750ml 0 0 0 0 0 0 0 0 Prothioconazole + Flutriafol T3
(Higher Dose) 1000ml 0 0 0 0 0 0 0 0 T4 Prothioconazole 25% EC 250 ml 0 0 0 0 0 0 0 0 T5 Flutriafol 25% SC 230 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 37: Phytotoxic effect of various treatments on ground nut crop 14 DAA^at recommended dose
21 DAA^ S. No.^ Treatment details^ Dose (g or ml/ha L^ S^ N^ C^ V^ E^ H^ W^ Prothioconazole + Flutriafol T1
(Low Dose) 500ml 0 0 0 0 0 0 0 0 Prothioconazole + Flutriafol T2
(Medium Dose) 750ml 0 0 0 0 0 0 0 0 Prothioconazole + Flutriafol T3
(Higher Dose) 1000ml 0 0 0 0 0 0 0 0 T4 Prothioconazole 25% EC 250 ml 0 0 0 0 0 0 0 0 T5 Flutriafol 25% SC 230 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 38: Phytotoxic effect of various treatments on ground nut crop 7 DAA^at 2X dose 7 DAA^ S. No.^ Treatment details^ Dose (g or ml/ha L^ S^ N^ C^ V^ E^ H^ W^ Prothioconazole + Flutriafol T1
(Low Dose) 1000ml 0 0 0 0 0 0 0 0 Prothioconazole + Flutriafol T2
(Medium Dose) 1500ml 0 0 0 0 0 0 0 0 Prothioconazole + Flutriafol T3
(Higher Dose) 2000ml 0 0 0 0 0 0 0 0 T4 Prothioconazole 25% EC 500 ml 0 0 0 0 0 0 0 0 T5 Flutriafol 25% SC 460 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 39: Phytotoxic effect of various treatments on ground nut crop 14 DAA^at 2X dose 14 DAA^ S. No.^ Treatment details^ Dose (g or ml/ha L^ S^ N^ C^ V^ E^ H^ W^ Prothioconazole + Flutriafol T1
(Low Dose) 1000ml 0 0 0 0 0 0 0 0 Prothioconazole + Flutriafol T2
(Medium Dose) 1500ml 0 0 0 0 0 0 0 0 Prothioconazole + Flutriafol T3
(Higher Dose) 2000ml 0 0 0 0 0 0 0 0 T4 Prothioconazole 25% EC 500 ml 0 0 0 0 0 0 0 0 T5 Flutriafol 25% SC 460 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 40: Phytotoxic effect of various treatments on ground nut crop 21 DAA^at 2X dose D
ose (g or ml/h 21 DAA^
S. No.^ Treatment details^ a L^ S^ N^ C^ V^ E^ H^ W^ Prothioconazole + Flutriafol T1
(Low Dose) 1000ml 0 0 0 0 0 0 0 0 Prothioconazole + Flutriafol T2
(Medium Dose) 1500ml 0 0 0 0 0 0 0 0 Prothioconazole + Flutriafol T3
(Higher Dose) 2000ml 0 0 0 0 0 0 0 0 T4 Prothioconazole 25% EC 500 ml 0 0 0 0 0 0 0 0 T5 Flutriafol 25% SC 460 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 35 to 40 above indicate that application of Prothioconazole + Flutriafol in all doses showed no phytotoxicity symptoms like leaf injury on tip/surface, stunting, necrosis, chlorosis, vein clearing, epinasty, hyponasty and wilting. Further, as evident from above tables 38 to 40 the application of Prothioconazole + Flutriafol at even double dose shows no phytotoxicity. Thus, applying the present invention composition may be considered completely safe for crops. Example 15: Other Exemplary composition of the present invention Table 41 S. No. Ingredients Function Quantity In % W/V 1. Prothioconazole A.I 12.5 2. Flutriafol A.I 11.5 3. Styrenated Phenol phosphate ester 4.5 4. blend of Sodium Aryl Sulphonate, Aryl Surface Active 3.0 Sulphonate Formaldehyde Condensate and System lignosulphonates 5. Precipitated Silica 0.8 6. Propylene glycol Anti-freezing agent 4.0 (CAS No.57-55-6) 7. Silicon Defoamer Defoaming agent 0.7 8. Polyalkyleneoxide modified Hepta Methyl Spreading cum 0.6 Trisiloxane sticking agent 9. Xanthan Gum powder Viscosity modifier 0.22 (CAS No.11138-66-2) 10. 1,2-Benzisothiazolin-3- one @ 20 % as Preservative 0.23 preservative (CAS No.2634-33-5) 11. Water Carrier QS TOTAL 100 Table 42 S. No. Ingredients Function Quantity In % W/V 1. Prothioconazole A.I 12.5 2. Flutriafol A.I 11.5
3. Styrenated Phenol phosphate ester 2.5 4. blend of Sodium Aryl Sulphonate, Aryl Surface Active 4.0 Sulphonate Formaldehyde Condensate and System lignosulphonates 5. Precipitated Silica 1.0 6. Propylene glycol Anti-freezing agent 5.0 (CAS No.57-55-6) 7. Silicon Defoamer Defoaming agent 0.6 8. Polyalkyleneoxide modified Hepta Methyl Spreading cum 0.5 Trisiloxane sticking agent 9. Xanthan Gum powder Viscosity modifier 0.24 (CAS No.11138-66-2) 10. 1,2-Benzisothiazolin-3- one @ 20 % as Preservative 0.24 preservative (CAS No.2634-33-5) 11. Water Carrier QS TOTAL 100 Table 43 S. No. Ingredients Function Quantity In % W/V 1. Prothioconazole A.I 12.5 2. Flutriafol A.I 11.5 3. Styrenated Phenol phosphate ester 3.0 4. blend of Sodium Aryl Sulphonate, Aryl Surface Active 4.00 Sulphonate Formaldehyde Condensate and System lignosulphonates 5. Precipitated Silica 0.9 6. Propylene glycol Anti-freezing agent 5.0 (CAS No.57-55-6) 7. Silicon Defoamer Defoaming agent 0.5 8. Polyalkyleneoxide modified Hepta Methyl Spreading cum 0.7 Trisiloxane sticking agent 9. Xanthan Gum powder Viscosity modifier 0.24 (CAS No.11138-66-2) 10. 1,2-Benzisothiazolin-3- one @ 20 % as Preservative 0.25 preservative (CAS No.2634-33-5) 11. Water Carrier QS TOTAL 100
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.