Description:SYNERGISTIC FUNGICIDAL COMPOSITION

FIELD OF THE INVENTION:
The present invention relates to a stable, synergistic fungicidal composition comprising Carbendazim chemically known as methyl benzimidazol-2yl carbamate, Metiram chemically known as zinc ammoniate ethyelenebis (dithiocarbamate)-poly(ethylenethiuram disulfide) and Soy protein or amino acid for control of fungal pests and enhancing crop vigour in agricultural crops. The present invention further relates to a process for preparing said fungicidal composition.

BACKGROUND OF THE INVENTION:
Fungal diseases of plants can cause severe pre- and post-harvest losses in agricultural crops. Fungi cause a great majority of infectious plant diseases and over 8,000 fungal species have been shown to cause disease.

Fungal infections cause pre-harvest damage to crop by killing them outright or weakening them thereby decreasing yields and rendering the plants susceptible to other infections. Post-harvest, fungal infection also results in significant loss of agricultural products during storage, processing and handling. Clearly, there is a significant need to control the fungal infection of plants and plant products and numerous chemical agents have been developed for this purpose, but till date no fully satisfactory agents, i.e. agents that completely control the fungus while at the same time being devoid of undesirable side effects, have been found.

Use of chemical fungicides is the primary method to prevent fungal diseases in plants. Excessive use of synthetic fungicides, however, may cause development of fungicide resistance in the pest population, resulting in the need for higher quantities of the pesticide for effective control. Fungicide residues have been found, for example, in groundwater, animal feed and food for human consumption because of pesticide use and can be harmful to animals and humans. Fungicides may also eliminate beneficial microorganisms which again may result in emergence of “new” diseases. Alternative ways to control plant pathogens are therefore needed so that reduced amounts of chemical fungicides are used while maintaining the same protection against pre- and post-harvest loss caused by fungi.

Potato (Solanum tuberosum L.) is one of the most important staple crops globally, contributing significantly to food security and rural livelihoods. However, its cultivation is frequently challenged by several biotic stresses, among which late blight, caused by the oomycete Phytophthora infestans, remains the most destructive disease. Late blight epidemics can lead to substantial yield losses, in some cases wiping out entire fields if left unmanaged.

Therefore, it is necessary to have a stable combination of fungicidal active ingredients with decreased phytotoxicity and increased fungicidal action. Also, it is necessary to have a composition which is easy to handle by the end user in terms of dosage calculation, and which does not cause any handling problems or toxicity to the end user.

Surprisingly, the inventors of the present invention have found that the active ingredient combination of Carbendazim chemically known as methyl benzimidazol-2ylcarbamate and Metiram chemically known as zinc ammoniate ethyelenebis (dithiocarbamate)-poly (ethylenethiuram disulfide) described herein can provide a much-needed solution to all the above-mentioned problems. The inventors have further developed a synergistic fungicidal composition comprising Carbendazim, Metiram and amino acids or Soy protein.

OBJECT(S) OF THE INVENTION:
It is an object of the present invention to provide a novel, synergistic, stable fungicidal composition comprising Carbendazim, chemically known as methyl benzimidazol-2yl carbamate, Metiram chemically known as zinc ammoniate ethyelenebis(dithiocarbamate)-poly (ethylenethiuram disulfide along with at least one agriculturally acceptable excipient.

It is another object of the present invention to provide a novel, synergistic, stable fungicidal composition comprising Carbendazim, chemically known as methyl benzimidazol-2yl carbamate, Metiram chemically known as zinc ammoniate ethyelenebis (dithiocarbamate)-poly (ethylenethiuram disulfide) and Soyprotein or amino acids for control of fungal pests in agricultural crops.

It is yet another object of the present invention to provide a synergistic fungicidal composition which is effective in controlling potato leaf blight disease.

It is yet another object of the present invention to provide a process for preparing said fungicidal composition in the form of wettable granules (WG) or microgranules (MG).

SUMMARY OF THE INVENTION:

In one aspect, the present invention provides a fungicidal composition comprising:
Carbendazim in an amount ranging from 5-30% w/w;
Metiram in an amount ranging from 30-65% w/w;
at least one agriculturally acceptable excipient.

In another aspect, the present invention provides a fungicidal composition comprising:
Carbendazim in an amount ranging from 5-30% w/w;
Metiram in an amount ranging from 30-65% w/w;
Soy protein or amino acids in an amount ranging from 0.1-2% w/w
at least one agriculturally acceptable excipient.

In another aspect, the present invention provides a process for preparing the fungicidal composition as a microgranule (MG), said process comprising:

Step 1: Taking required volume of demineralised water,
Step 2: Adding dispersing or wetting agent in required quantity,
Step 3: Adding desired amount of Carbendazim technical and Metiram technical to prepare a slurry,
Step 4: Adding suitable amount of antifoaming agent and carrier to the material as obtained in Step 3 and mixing the material well in a homogeniser,
Step 5: Passing the material or slurry obtained in step 4 through Dyno mill for particle size reduction to obtain particle size (D90) ≤ 10µ. Again mixing the Material so obtained in a homogenizer and then adding the balance quantity of dispersing agent and wetting agent followed by addition of antifoaming agent,
Step 6: Passing the material through spray dryer for micro granulation,
Step 7: Checking microgranules so obtained for quality parameters and proceeding for packaging or storage.

In another aspect, the present invention provides a process for preparing the fungicidal composition as a microgranule (MG), said process comprising:

Step 1: Taking required volume of demineralised water,
Step 2: Adding dispersing or wetting agent in required quantity,
Step 3: Adding desired amount of Carbendazim technical, metiram technical and Soy protein or amino acids to prepare a slurry,
Step 4: Adding suitable amount of antifoaming agent and carrier to the material as obtained in Step 3 and mixing the material well in a homogeniser,
Step 5: Passing the material or slurry obtained in step 4 through Dyno mill for particle size reduction to obtain particle size (D90) ≤ 10µ. Again mixing the material so obtained in a homogenizer and then adding the balance quantity of dispersing agent and wetting agent followed by addition of antifoaming agent.
Step 6: Passing the material through spray dryer for micro granulation.
Step 7: Checking microgranules so obtained for quality parameter and proceeding for packaging or storage.

In another aspect, the present invention provides a process for preparing the fungicidal composition as a wettable granule (WG), said process comprising:

Step 1: Taking the required amount of Carbendazim Technical and Metribuzin Technical,
Step 2: Adding suitable amounts of dispersing agent and wetting agent,
Step 3: Adding suitable amounts of carrier (Silica & China Clay) and mixing uniformly,
Step 4: The material so obtained was subjected to a milling process through ACM (Air Classifying Mill) to obtain a particle size of less than 15µ (microns),
Step 5: Preparing a dough using the material obtained in step 4,
Step 6: Extruding the granules by basket extruder.

In another aspect, the present invention provides a process for preparing the fungicidal composition as a wettable granule (WG), said process comprising:

Step 1: Taking the required amount of Carbendazim technical, Metribuzin technical and Soyprotein or amino acids
Step 2: Adding suitable amounts of dispersing agent and wetting agent,
Step 3: Adding suitable amounts of carrier (Silica & China Clay) and mixing uniformly,
Step 4: The material so obtained was subjected to a milling process through ACM (Air Classifying Mill) to obtain a particle size of less than 15µ (microns),
Step 5: Preparing a dough using the material obtained in step 4,
Step 6: Extruding the granules by basket extruder.

In yet another aspect, the present invention provides a synergistic fungicidal composition that is highly effective in controlling potato blight disease.

TECHNICAL ADVANCEMENT OF THE INVENTION:
The fungicidal composition of the present invention comprises the active ingredient combination of Carbendazim chemically known as methyl benzimidazol-2ylcarbamate and Metiram, chemically known as zinc ammoniate ethyelenebis (dithiocarbamate)-poly (ethylenethiuram disulfide). In a preferred embodiment, the present invention may further comprise amino acids or Soy protein as the third component which enhances plant vigour that includes the overall health, vitality, and growth rate of a plant or crop.

Thus, the present synergistic fungicidal composition has several associated technical advantages including but not limited to:
Enhanced control of fungal disease or infestation, especially potato leaf blight disease
Synergistic bioefficacy.
Plant health and vitality benefits including growth rate and crop yield.
Lack of any phytotoxicity or negative effects on the treated crop

DETAILED DESCRIPTION OF THE INVENTION:
List of important abbreviations used in the detailed description
D.M. Demineralised Water
RTU Ready to Use
QS Quantum Satis
A.I/ a.i Active Ingredients
PDI Percent Disease Index
MG Microgranules
WG Wettable granules
DAA Days After Application
ASS Accelerated Stability testing
ACM Air Classifying Mill

Those skilled in the art will be aware that the invention described herein is subject to variations and modifications other than those specifically described. It is to be understood that the invention described herein includes all such variations and modifications. The invention also includes all such steps, features, compositions and compounds referred to or indicated in this specification, individually or collectively, and all combinations of any two or more of said steps or features.

Unless otherwise specified, all terms used in disclosing the invention, including technical and scientific terms, have the meaning as commonly understood by one of the ordinary skills in the art to which the invention belongs. For further guidance, term definitions may be included to better appreciate the teaching of the present invention.

As used herein, the term “plant” refers to any plant or part thereof including serial and subterranean parts of the plant. It is contemplated that the parts of the plant may be for example, flowers, fruits or vegetables, shoots, leaves, needles, stalks, stems, fruiting bodies, seeds also roots and that parts of the plants may or may not be attached to the remainder of the plant.

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 pests. The term ‘plants’ refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage and fruits.

It is to be understood that the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise.

It should be emphasized that the term “comprises/comprising” when used in this specification is taken to specify the presence of stated features, steps or components but does not preclude the presence or addition of one or more other features, steps, components or groups thereof.

The term "fungicidal" also called antimycotic, any toxic substance used to kill or inhibit the growth of fungi.

The term “fungicidally effective amount” refers to the quantity of a fungicide needed to inhibit the growth of fungi in a given environment. This amount is sufficient to achieve the desired level of control over the fungal population without causing significant harm to the host organism, be it a plant, animal, or an ecosystem.

The terms “weight percent”, “wt-%”, “percent by weight”, “%” by weight” and variations thereof, as used herein, refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100. It is understood that, as used here, “percent “, “%” and the like are intended to be synonymous with “weight percent”, “wt. %”, etc.

As used herein, the term “agriculturally acceptable excipient” refers to an ingredient, additive, component or supplement, liquid or solid, suitable for incorporation in agricultural compositions.

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

The term “technical” as used herein refers to technical grade chemicals that are often used in large-scale manufacturing processes, where the presence of some impurities is acceptable.

The term “Dyno mill” also referred to as a bead mill, is a type of high-energy wet grinding mill used to reduce particle size in liquid suspensions. It utilizes grinding media like beads (glass, ceramic, or steel) to grind and disperse particles in a liquid.

The term “Air classifying mills (ACMs)” refers to a machine used in pesticide formulation that enables ultra-fine grinding and particle size control, which are essential for effective dispersion and suspension of the active ingredients.

The term “Homogenizer” refers to a device that reduces particle size in a liquid mixture, making it uniform. This is often achieved by forcing the mixture through a narrow orifice under high pressure. Essentially, it's a machine that creates a more uniform and stable mixture.

Features that are described and/or illustrated with respect to one embodiment may be used in the same way or in a similar way in one or more other embodiments and/or in combination with or instead of the features of the other embodiments.

Carbendazim, chemically known as methyl benzimidazol-2ylcarbamate is a systemic fungicide with protective and curative action. It acts by inhibiting development of germ tubes, formation of appressoria and the growth of mycelia. The molecule was first introduced in 1974 by BASF AG, Hoechst AG (now Bayer Crop science) and E.I. du Pont de Nemours and Co.

Metiram, chemically known as zinc ammoniate ethylenebis(dithiocarbamate)-poly (ethylenethiuram disulfide) is a broad-spectrum, multi-site contact fungicide. It was introduced by BASF AG in Germany in 1958.

Addition of soy protein or amino acids to the active ingredient combination serves as a biostimulant, enhancing plant vigor and stress tolerance. Soy protein basically serves as plant-derived bio-stimulant which is readily available commercially. Traditionally, it is made from soybean meal that has been dehulled and defatted. Soy protein extract contains various amino acids – Aspartic, Threonine, Serine, Glutamic acid, Proline, Glycine, Valine, Cystine, Isoleucine, Methionine, Tyrosine, Phenylalanine, Lysine, Histidine, Arginine, and the percentage of each amino acid may vary in the mixture.

Increasing frequency of adverse environmental conditions for crop growth, have driven development of active ingredient combination incorporating bio stimulants. These are substances that stimulate nutrient uptake, nutrient use efficiency, and tolerance to abiotic stresses and crop quality. Soy protein has a proven bio stimulating effect on the health of the crops.

It is stated that no biological material originating in India was used in the present invention. The source of amino acids or soy protein is mentioned below:

Source of amino acid/Soyprotein:
Soy Protein was procured from Sales Office 1900 Crown Colony 10 Drive, 3rd Floor, Quincy, Massachusetts, USA.

Soy protein functions as micronutrients and act synergistically along with the active ingredients in the composition in improving plant immune system. Soy protein improves the formulation, stability, and adhesion of the fungicide to plant surfaces and helps the fungicides spread more effectively and adhere to the plant, which can enhance its overall effectiveness. Further, the addition of Soy protein enhances protein synthesis in the meristematic tissues. The enhanced protein synthesis increases photosynthetic pigments in plants and that in turn results in accelerated photosynthetic reaction. Hence, the addition of Soy protein to the active ingredients additionally restores plant health.

The best results are however obtained when soy protein is incorporated in the composition in an optimum range and such optimum range needs to be determined through experimentation. Excess amount of Soy protein in the biological system will affect plant cells leading to adverse effects on the plant physiology, finally leading to phytotoxicity. Hence, determining optimum amounts of Soy protein to be incorporated in the composition is of significance to achieve desired results.

In a preferred embodiment, the fungicidal composition of the present invention is in the form of Ready to Use Formulation (RTU) composition. The ready to use formulation has various advantages over tank mixture of the active ingredients. These advantages include very less or no inhalation hazards, easy handling, lower chances of sedimentation, environmentally safer, good efficacy without phytotoxicity, lower transportation costs and is a scientific practice as against the usual farmer practice of tank mixing as the formulation is prepared after stability, compatibility studies.

In an embodiment, the present invention provides a novel, synergistic fungicidal composition comprising a) Carbendazim, chemically known as methyl benzimidazol-2ylcarbamate b) Metiram, chemically known as zinc ammoniate ethyelenebis (dithiocarbamate)-poly (ethylenethiuram disulfide) along with at least one agriculturally acceptable excipient.

In another embodiment, the present invention provides a novel, synergistic fungicidal composition comprising a) Carbendazim, chemically known as methyl benzimidazol-2ylcarbamate b) Metiram, chemically known as zinc ammoniate ethyelenebis (dithiocarbamate)-poly(ethylenethiuram disulfide) c) Soy protein or amino acids along with at least one agriculturally acceptable excipient.

In a preferred embodiment, the present invention provides a novel, synergistic fungicidal composition comprising a) Carbendazim, chemically known as methyl benzimidazol-2ylcarbamate in an amount ranging from 5-30% w/w b) Metiram, chemically known as zinc ammoniate ethyelenebis (dithiocarbamate)-poly(ethylenethiuram disulfide) in an amount ranging from 30-65% w/w along with at least one agriculturally acceptable excipient.

In another preferred embodiment, the present invention provides a novel, synergistic fungicidal composition comprising a) Carbendazim, chemically known as methyl benzimidazol-2ylcarbamate in an amount ranging from 5-30% w/w b) Metiram, chemically known as zinc ammoniate ethyelenebis(dithiocarbamate)-poly(ethylenethiuram disulfide) in an amount ranging from 30-65% w/w c) amino acids or soy protein in an amount ranging from 0.1-2% w/w of the fungicidal composition along with at least one agriculturally acceptable excipient.
In another preferred embodiment, the present invention provides a novel, synergistic fungicidal composition comprising a) Carbendazim, chemically known as methyl benzimidazol-2yl carbamate in an amount ranging from 5-30% w/w b) Metiram, chemically known as zinc ammoniate ethyelenebis (dithiocarbamate)-poly(ethylenethiuram disulfide) in an amount ranging from 30-65% w/w d) Dispersing agent in an amount ranging from 5-35% w/w e) Antifoaming agent in an amount ranging from 0.2-3% w/w f) Wetting agent in an amount ranging from 10-30% w/w g) Carrier in an amount ranging from 5-20% w/w of the fungicidal composition.

In another preferred embodiment, the present invention provides a novel, synergistic fungicidal composition comprising a) Carbendazim, chemically known as methyl benzimidazol-2ylcarbamatein an amount ranging from 5-30% w/w b) Metiram, chemically known as zinc ammoniate ethyelenebis(dithiocarbamate)-poly(ethylenethiuram disulfide) in an amount ranging from 30-65% w/w c) Soyprotein or amino acids in an amount ranging from 0.1-2% w/w d) Dispersing agent in an amount ranging from 5-35% w/w e) Antifoaming agent in an amount ranging from 0.2-3% w/w f) Wetting agent in an amount ranging from 10-30% w/w g) Carrier in an amount ranging from 5-20% w/w of the fungicidal composition.

In a preferred embodiment, the present invention provides a novel, synergistic fungicidal composition comprising a) Carbendazim is in an amount of 20% w/w, b) Metiram in an amount of 50% w/w and d) dispersing agent in an amount of 11.2% w/w e) Antifoaming agent in an amount of 0.3% w/w f) wetting agent in an amount of 18.5% w/w g) carrier in an amount of 5% w/w.

In a preferred embodiment, the present invention provides a novel, synergistic fungicidal composition comprising a) Carbendazim is in an amount of 20% w/w, b) Metiram in an amount of 50% w/w and c) amino acids or Soy protein in an amount of 0.2%w/w d) dispersing agent in an amount of 11% w/w e) Antifoaming agent in an amount of 0.3% w/w f) wetting agent in an amount of 18.5% w/w g) carrier in an amount of 5% w/w.

In an embodiment of the present invention, said at least one agriculturally acceptable excipient. is selected from the group comprising of dispersing agent, wetting agent, antifoaming agent and a carrier or combinations thereof.

In a preferred embodiment of the present invention, said dispersing agent is selected from the group comprising polymeric anionic dispersant, polyarylphenyl ether phosphate, tristyryl phenol ethoxylate, Polymethyl methacrylate-polyethylene glycol graft copolymer, acrylate copolymer, acrylic copolymer, acrylic graft copolymer, non-ionic proprietary surfactant, Methyl naphthalene sulfonic acid, polymer with formaldehyde, sodium salt, ethoxylated tristryl phenol Sulphate, alkyl naphthalene formaldehyde condensate, naphthalene sulfonic acid, sodium salt condensate with formaldehyde, ethoxylated oleyl cetyl alcohol, polyalkelene glycol ether, ethoxylated fatty alcohol, Sodium polymethyl methacrylate, sodium polyacrylate, sodium lignosulphonate, calcium lignosulphonate, alkylphenol polyoxyethylene ether, sodium salt of naphthalene sulfonate condensate, polycarboxylate, fatty alcohol polyoxyethylene ether, alcohol polyglycol ether or mixtures thereof and present in the range of 5-35% w/w of the total composition.

In a preferred embodiment of the present invention, said wetting agent is selected from the group comprising tristyrylphenol ethoxylate non-ionic emulsifier, mixture of non-ionic surfactants, alkoxylated alcohol, block copolymer, alcohol polyglycol ether, alkyl olefin sulphates, dioctyl sulpho succinate, alkyl naphthalene sulphate,Di-isopropyl Napthalene sulphonate, Polyalkoxy ethers, alkyl phenol ethoxylates, tri-styrenated phenol ethoxylate, EO/PO block co-polymers, butyl polyalkylene oxide block copolymer, sodium lauryl sulphate, sodium ligno sulphates or mixtures thereof and present in the range of 10-30% w/w of the total composition.

In a preferred embodiment of the present invention, said anti-foaming agent, is selected from silicon emulsion based anti-foam agents, Siloxane polyalkyleneoxide, Polydimethylsiloxane, trisiloxane ethoxylates, silicone oil, silicone compound, C10~C20 saturated fat acid compounds or C8~C10 aliphatic alcohols compound, vegetable oil based antifoam, tallow based fatty acids, polyalkyleneoxide polydimethylsiloxane emulsion and mixtures thereof and present in the range of 0.2-3% w/w of the total composition.

In a preferred embodiment of the present invention, the carrier is selected from the group comprising silicon dioxide, china clay, kaolin, starch, bentonite, precipitated silica, fumed silica, talcum powder, lactose, ammonium sulpha or mixture thereof and present in the range of 5-20% w/w of the total composition.

Many formulations may be developed with the disclosed composition. The present composition may work well as different formulations selected from the group comprising water-soluble concentrates (SL), emulsifiable concentrates (EC), emulsions (EW), micro-emulsions (ME), Suspension concentrates (SC), oil-based suspension concentrates (OD), flowable suspensions (FS), water-dispersible granules (WG), water-soluble granules (SG), wettable powders (WP), water soluble powders (SP), granules (GR), encapsulated granules (CG), fine granules (FG), macro granules (GG), dry flowable (DF), aqueous Suspo-emulsions (SE), capsule suspensions (CS) and microgranules (MG).

In a preferred embodiment, the present composition is in the form of wettable granules (WG) or microgranules (MG).

Wettable granules are easier to handle, and store compared to some other solid formulations like dusts. They are less prone to generating dust during handling, which can be an issue with dust formulations. These granules readily disperse in water, forming a stable suspension. This ensures a consistent distribution of the active ingredient when mixed with water for application.

When properly mixed with water, wettable granules provide uniform coverage over the treated area. This uniformity enhances the efficacy of the agrochemical by ensuring consistent application.

Wettable granules have additives that enhance their adherence to plant surfaces. This promotes better retention and absorption of the active ingredients, improving efficacy. As they are designed for dispersion in water, wettable granules typically have lower environmental impact compared to certain formulations that might contain more volatile ingredients or solvents.

Wettable granules often have good stability, with longer shelf lives compared to some liquid formulations. This stability helps maintain the effectiveness of the active ingredients over time.

They are relatively easy to mix with water, requiring minimal agitation for dispersion. This ease of mixing contributes to their convenience during application.

Microgranules (MG) are small, solid particles, typically between 0.075 to 4 mm in diameter. They contain a pesticide active ingredient, along with other additives like carriers, adjuvants, and wetting agents. The pesticide is either adsorbed onto the carrier material or encapsulated within a microcapsule. Microgranules can be produced through various methods, including spray drying, granulation, and encapsulation. Microgranules as a formulation, offer many advantages such as:

Reduced drift:
The smaller particle size compared to granules means less wind drift, leading to more localized application.
Improved safety:
Microgranules are less likely to cause inhalation problems than dusts.
Controlled release:
Microcapsules can be designed to release the pesticide over time, providing longer-lasting protection.
Targeted application:
They can be designed for specific applications, such as soil treatment or seed coating.
Convenience:
Microgranules can be easily applied using specialized equipment like micro granulators. These are well suited for application as soil pesticides, seed treatments, etc.

In another embodiment, the present invention further provides a process of preparing a fungicidal composition as a wettable granule said process comprising following steps:

Step 1: Taking the required amount of Carbendazim Technical and Metribuzin Technical
Step 2: Adding suitable amounts of dispersing agent and wetting agent
Step 3: Adding suitable amounts of carrier (Silica & China Clay) and mixing uniformly.
Step 4: The material so obtained was subjected to a milling process through ACM (Air Classifying Mill) to obtain a particle size of less than 15µ (microns).
Step 5: Preparing a dough using the material obtained in step 4
Step 6: Extruding the granules by basket extruder.

In another embodiment, the present invention further provides a process of preparing a fungicidal composition as a wettable granule said process comprising following steps:

Step 1: Taking the required amount of Carbendazim Technical, Metribuzin Technical and Soy protein or amino acids
Step 2: Adding suitable amounts of dispersing agent and wetting agent
Step 3: Adding suitable amounts of carrier (Silica & China Clay) and mixing uniformly.
Step 4: The material so obtained was subjected to a milling process through ACM (Air Classifying Mill) to obtain a particle size of less than 15µ (microns).
Step 5: Preparing a dough using the material obtained in step 4
Step 6: Extruding the granules by basket extruder.

In another embodiment, the present invention further provides a process of preparing a fungicidal composition in the form of micro granules, said process comprising following steps:

Step 1: Taking required volume of demineralised water
Step 2: Adding dispersing and wetting agent in required quantity
Step 3: Adding desired amount of Carbendazim technical and metiram technical to prepare a slurry
Step 4: Adding suitable amount of antifoaming agent and carrier to the material as obtained in Step 3 and mixing the material well in a homogeniser
Step 5: Passing the material or slurry obtained in step 4 through Dyno mill for particle size reduction to obtain particle size (D90) ≤ 10µ. Again mixing the Material so obtained in a homogenizer and then adding the balance quantity of dispersing agent and wetting agent followed by addition of antifoaming agent.
Step 6: Passing the material through spray dryer for micro granulation.
Step 7: checking microgranules so obtained for quality parameter and proceeding for packaging or storage.

In another aspect, the present invention provides a process for preparing the fungicidal composition as a microgranule (MG), said process comprising:

Step 1: Taking required volume of demineralised water
Step 2: Adding dispersing or wetting agent in required quantity
Step 3: Adding desired amount of Carbendazim technical, metiram technical and Soy protein or amino acids to prepare a slurry
Step 4: Adding suitable amount of antifoaming agent and carrier to the material as obtained in Step 3 and mixing the material well in a homogeniser
Step 5: Passing the material or slurry obtained in step 4 through Dyno mill for particle size reduction to obtain particle size (D90) ≤ 10µ. Again mixing the material so obtained in a homogenizer and then adding the balance quantity of dispersing agent and wetting agent followed by addition of antifoaming agent.
Step 6: Passing the material through spray dryer for micro granulation.
Step 7: Checking microgranules so obtained for quality parameter and proceeding for packaging or storage.

The present invention also provides a method for controlling pests in various agriculture crops, comprises applying fungicidally effective amount of a fungicidal composition to the target crop or portion thereof.

In a preferred embodiment, the present invention provides a method of treating potato late blight disease, said method comprising applying a fungicidally effective amount of the fungicidal composition to potato plant.

In an embodiment of the present invention, said fungicidal composition is effective against a range of fungal diseases including but not limited to late blight disease in potato, leaf blight disease in tomato, early blight disease in potato.

In a preferred embodiment of the present invention, the fungicidal composition is particularly effective against potato late blight disease.

In an embodiment, the fungicidal composition of the present invention may be effectively used and applied in crops including but not limited to Potato, Tomato, Cucurbits, Chilli and Soybean.

Surprisingly, inventors of the present invention have found that the presently claimed fungicidal composition when applied at significantly lesser dosages than the recommended dosages (regulatorily approved) dosage of the individual active ingredients or solo active ingredient formulations, exhibit superior efficacy in terms of percent control of target pest expressed in terms of PDI.

In other words, the present inventors have surprisingly found that these fungicides when combined in desired weight percentage, which is reduced as compared to their individual active recommended or regulatorily approved dosages, the fungicidal effect of the composition is unexpectedly enhanced.

Further, it has been found that the active compound combination of the presently claimed composition exhibits a synergistic effect and not merely an additive effect. Thus, clearly, the customary dosages of the individual actives are substantially reduced, leading to lesser amount of soil residues and environmental pollution when the composition of the present invention is used.

In an embodiment, the fungicidal composition of the present fungicidal invention may be applied to a plant/crop by spraying, irrigating, dusting, broadcasting, pouring, mist blowing, soil mixing, foaming, spreading on, drenching, dipping or drip irrigation. In a preferred embodiment, the fungicidal composition is applied through broadcasting.

The foregoing description of the embodiments has been provided for purposes of illustration and not intended to limit the scope of the present invention. Individual components of a particular embodiment are generally not limited to that embodiment but are interchangeable. Such variations are not to be regarded as a departure from the present invention, and all such modifications are considered to be within the scope of the present invention.

The present invention is further described in light of the following experiments which are set forth for illustration purposes only and not to be construed for limiting the scope of the invention. The following experiments can be scaled up to industrial/commercial scale and the results obtained can be extrapolated to industrial scale.

EXAMPLES
The examples below 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 (a): Preparation of fungicidal composition as wettable granule (WG)
Table no. 1 below provides a fungicidal composition as described in the present invention, formulated as wettable granule (WG) or a microgranule (MG). For purpose of convenience, the code “CF-2050 WG” has been used to denote a preferred embodiment of the present invention.

Table 1: Chemical Composition of CF-2050 WG
Ingredients Tentative percentage w/w
Carbendazim (Basis of 100%) 20
Metiram (Basis of 100%) 50
Amino acids/Soyprotein 0.2
Dispersing agent (Sodium lignosulphonate) 9.0
Anti foaming agent (Polydimethylsiloxane) 0.3
Wetting agent (Sodium Lauryl sulphate) 15.5
Carrier (China clay) 5
Total 100

Example 1 (b)
Stability testing of the presently disclosed composition CF 2050WG was carried out. Accelerated stability testing (ASS) uses exaggerated storage conditions (like higher temperatures and humidity) to simulate a product's long-term degradation over a shorter period, allowing for faster prediction of shelf life. In essence, accelerated stability testing is a tool for efficiently evaluating the stability of a product under various conditions and predicting its shelf life.

The observation and parameters are enlisted in the table 2 below:

Table 2: Observations of Accelerated stability testing of 2050 WG

Example 2: Bioefficacy evaluation of CF 2050WG
Attributes Observation
S. No Parameters Specification Initial ASS@54°C±2°C for 14 Days

1.
Description The material shall be in the form of stable light brown to dark brown colour free flowing granules.
Complies
Complies
2. Carbendazim active Content % by mass 20.0 (±5%) 20.10 20.04
3. Metiram active Content % by mass 50.0 (+5%, -3%) 50.08 50.05
4. pH (1% Aqueous Dispersion) 5.0-8.0 6.88 6.95
5. Suspensibility, % by mass Min. 75.0 86.2 84.8
6. Persistent Foam after 1 Minute in ml Max. 60 40 42
7. Wet Sieve Test through 75µ, % by mass Min. 99.0 99.5 99.6
8. Wettability in Seconds Max. 120 60 62

The presently disclosed fungicidal composition was tested for its bio efficacy against Late blight disease in Potato during the Kharif season 2024-2025 at Karnal, Haryana. The plants were aligned in the plot size of 50 sqm. The trial was laid out in a random block design consisting of a total of 8 treatments in three replications. The trial was conducted at a temperature of 25oC under 74% relative humidity and wind speed of approximately 3.7 m/s.

Measured quantity of the chemical was added to the required volume of water @ 375 lit. /ha for spraying. The spray tank was filled with ½ the quantity of clean required volume of water and then the measured chemical (according to the dose) was added followed by the rest half quantity of water. The solution was stirred well before application. Knapsack sprayer fitted with boom along with flood jet nozzle was used to apply the fungicidal composition. Table 3 below provides the treatment details:

Table 3: Treatment details
Treatments Dose a.i./ha (gm) Dose Formulation (gm/ml/ha)
Treatment no.
Untreated - -
T1 Carbendazim 50% WP 250 500
T2 Metiram 70% WG 1750 2500
T3 CF-1540 WG 150 + 400 1000
T4 CF-1540 WG 187.5 + 500 1250
T5 CF-1540 WG 225 + 600 1500
T6 CF-2050 WG 200 + 500 1000
T7 CF-2050 WG 250 + 625 1250
T8 CF-2560 WG 250 + 600 1000

Note:
CF-1540 WG 15% Carbendazim + 40% Metiram+ 0.2% amino acids or Soyprotein
CF-2050 WG 20% Carbendazim + 50% Metiram + 0.2% amino acids or Soy protein
CF-2560 WG 25% Carbendazim + 60% Metiram + 0.2% amino acids or Soy protein

EVALUATION OF BIO-EFFICACY AGAINST DISEASE MANAGEMENT

Evaluation of percent disease control in Potato leaf blight disease
Randomly selected 75 leaves/replication and 3 replication/plot were observed and were visually rated as per the rating below. The percent disease index (PDI) was calculated as per given formula:

Grade Spots on Leaves
0 No visible symptoms
1 < 1% leaf area affected
3 1-10% leaf area affected
5 11-25% leaf area affected
7 26-50% leaf area affected
9 >50 leaf area affected

Sum of numerical rating

PDI = ---------------------------------------------------------------------------- x 100
Total no. of plants/Leaves observed X Maximum grade

Table 4: Synergistic effect of composition against Late blight disease in Potato crop in two-way combination (Carbendazim 20% + Metiram 50%)
S. No. Treatment Dose a.i./ha (gm) Dose Formulation (gm/ml/ha) %disease control (Observed) %disease control expected (Colby’s formula)
1 Untreated - - 0.00
2 Carbendazim 50% WP 250 500 55.88
3 Metiram 70% WG 1750 2500 47.06
4 CF-1540 WG 150 + 400 1000 63.53 76.64
5 CF-1540 WG 187.5 + 500 1250 64.12 76.64
6 CF-1540 WG 225 + 600 1500 68.82 76.64
7 CF-2050 WG 200 + 500 1000 77.29 76.64
8 CF-2050 WG 250 + 625 1250 85.29 76.64
9 CF-2560 WG 250 + 600 1000 82.94

Table 5: Synergistic effect of composition against Late blight disease in Potato crop in three way Combination Carbendazim 20% + Metiram 50% + Amino acid 0.2 % WG
S. No. Treatment Dose a.i./ha (gm) Dose Formulation (gm/ml/ha) % disease control (Observed) % disease control expected (Colby’s formula)
1 Untreated - - 0.00
2 Carbendazim 50% WP 250 500 58.82 82.33
3 Metiram 70% WG 1750 2500 52.94 82.33
4 Amino acid 0.2 % EC 0.25 125ml 8.82 82.33
5 CF-2050 WG 200 + 500 1000 82.35 82.33
6 CF-2050 WG 250 + 625 1250 85.29 82.33
8 CF-2052 WG 200 + 500+20 1000 85.29 82.33
9 CF-2052 WG 250 + 625+25 1250 89.41 82.33

Statistical Analysis:
Analysis of Variance (ANOVA):
ANOVA was performed to compare the mean pest population, crop health parameters, and yield data across treatments. Significant differences among treatments were identified using the least significant difference (LSD) test at a 5% significance level (Gomez & Gomez, 1984).

Colby’s Method for Synergism/Antagonism:
To determine interaction effects, the observed percent disease control of Combination Carbendazim 20% + Metiram 50% + Amino acid 0.2 % WG against Potato Late blight on Potato crop in two-three-way combinations were compared with expected percent disease control using Colby's formula (Colby, 1967).

The synergistic action expected for a given combination of two-way active components can be calculated as follows:
E=A+B-AB/100
The synergistic action expected for a given combination of three-way active components can be calculated as follows:
E=(A+B+C)-((AB+BC+CA))/100+ABC/10000
where 𝐸 is the expected mortality, and A, B and C are the observed mortalities of individual components.
Synergistic effects were indicated if the observed mortality was greater than the expected mortality, while antagonistic effects were noted if the observed mortality was lower.

Validation and Interpretation:
Results from ANOVA provided insights into treatment effectiveness, while Colby’s method elucidated the interactions among insecticide components. The combined results guided the evaluation of the novel formulation's performance in pest suppression and yield enhancement.

Example 3: Evaluation of Phytotoxicity

Phytotoxicity observations:
Phytotoxicity symptoms of Combination Carbendazim 20% + Metiram 50% + Amino acid 0.2 % WG against Potato Late blight on Potato crop, including leaf injury on tips and surfaces, were systematically scored and rated using a standardized scale ranging from 0 to 10, where 0 indicated no visible symptoms and 10 represented severe damage.

During the evaluation at 1, 3, 5, 7, and 10 days after application, no phytotoxicity symptoms such as necrosis, vein clearing, epinasty, hyponasty, or wilting were observed on the treated plants. The absence of leaf injury and other adverse effects confirmed the safety of the tested insecticide combination, indicating its suitability for use without compromising the health and vigor of the crop as indicated in table no. 4.

Table 6: Phytotoxicity effect of composition Carbendazim 20% + Metiram 50% + Amino acid 0.2 % WG against Potato Late blight on Potato crop
Treatment Dose a.i./ha (gm) Dose Formulation (gm/ml/ha) 1
DAA 3
DAA 5
DAA 7
DAA 10
DAA
Untreated - 0 0 0 0 0
Carbendazim 50% WP 250 500 0 0 0 0 0
Metiram 70% WG 1750 2500 0 0 0 0 0
CF-1540 WG 150 + 400 1000 0 0 0 0 0
CF-1540 WG 187.5 + 500 1250 0 0 0 0 0
CF-1540 WG 225 + 600 1500 0 0 0 0 0
CF-2050 WG 200 + 500 1000 0 0 0 0 0
CF-2050 WG 250 + 625 1250 0 0 0 0 0
CF-2560 WG 250 + 600 1000 0 0 0 0 0

The average values for different mixtures of insecticides on cotton were assessed against Potato Late blight, focusing on key parameters such as the number of squares per plant, number of flowers per plant, number of balls per plant, and total yield (qt/acre). Results also indicated a progressive improvement in plant productivity and yield with increasing doses, demonstrating the efficacy of the mixtures in controlling Potato Late blight and promoting overall crop health and productivity.

Conclusion
The efficacy of the combinations- Carbendazim 20% + Metiram 50% and Carbendazim 20% + Metiram 50% + Amino acid 0.2% WG was evaluated for managing Potato Late Blight disease. The study employed ANOVA and Colby’s method to assess disease control and potential synergistic effects. Two-way and three-way combinations were tested to determine their effectiveness in reducing disease severity and enhancing crop yields.

ANOVA results revealed significant differences in disease suppression and yield improvements across all tested doses. Among these, dosage of consistently provided superior control of Potato Late Blight infestations, achieving the most substantial reductions in disease mortality and the highest yield enhancements.

The results indicate that the active ingredient dosage of carbendazim 200- 250 a.i. (g)/ha combined with active ingredient dosage of metiram in the range of 500-625 a.i. (g)/ha corresponding to formulation dosage of 1000-1250 ai (g)/ha outperformed the solo active formulation and other tested dosages with statistically significant improvements in disease management.

To further evaluate the interactions among the components of the formulation, Colby’s method was employed. The analysis demonstrated strong synergistic effects, as the observed disease control exceeded the expected additive results. This synergy was most evident at the dosage of 250 + 625+ 0.25 a.i./ha (gm) where the combined formulation exhibited amplified efficacy against Potato Late Blight disease.

The pronounced synergy observed at this dose indicates the superior performance of the combination compared to the individual components used alone or in simpler mixtures. Interestingly, intermediate doses also showcased notable effectiveness, suggesting that the combination can manage disease infestations effectively even at reduced concentrations. This result offers practical value for growers seeking cost-effective and environmentally friendly solutions without compromising on plant health and vigour. Such dual benefits provide significant economic and agricultural advantages for potato growers, aligning with modern sustainability goals.

The results underscore the robustness of both the two-way and three-way combination as a comprehensive disease management strategy for agricultural crops especially potato crop. Additionally, the synergy observed between Carbendazim, Metiram, and Soyprotein or amino acid contributes to the overall success of this approach.

The synergistic interactions ensure the formulation outperforms simple additive combinations, making it especially valuable for managing resistant or persistent diseases. Furthermore, the ability of the combination to deliver strong results even at lower doses underscores its potential as a sustainable solution, minimizing input costs and environmental impact.

In conclusion, the combination of Carbendazim 20% + Metiram 50% and Carbendazim 20% + Metiram 50% + Amino acid 0.2% WG are highly effective in controlling Potato Late Blight disease. The optimal formulation dosage of 1000-1250 g/ha (corresponding to carbendazim dosage range of 200- 250 ai(g)/ha combined with metiram dosage range of 500-625 + 625 + 0.25 a.i.(g)/ha and 0.25 g/ha of Soyprotein or amino acids delivered the best results, offering growers a reliable, economical, and sustainable approach to fungal disease management. By improving disease control without any phytotoxicity, this combination represents a valuable innovation in potato disease management strategies.
, Claims:We Claim:
1. A synergistic fungicidal composition, wherein said fungicidal composition comprises:
a. Carbendazim in an amount ranging from 5-30% w/w;
b. Metiram in an amount ranging from 30-65% w/w;
c. at least one agriculturally acceptable excipient.

2. A synergistic fungicidal composition, wherein said fungicidal composition comprises:
a. Carbendazim in an amount ranging from 5-30% w/w;
b. Metiram in an amount ranging from 30-65% w/w;
c. Amino acids or soy protein in an amount ranging from 0.1-2% w/w;
d. at least one agriculturally acceptable excipient.

3. The synergistic fungicidal composition as claimed in claim 1 or 2, wherein said at least one agriculturally acceptable excipient is selected from the group comprising a dispersing agent, wetting agent, anti-foaming agent, a carrier and combinations thereof.

4. The synergistic fungicidal composition as claimed in claim 1 or 2, wherein said dispersing agent is selected from the group comprising polymeric anionic dispersant, polyarylphenyl ether phosphate, tristyryl phenol ethoxylate, Polymethyl methacrylate-polyethylene glycol graft copolymer, acrylate copolymer, acrylic copolymer, acrylic graft copolymer, non-ionic proprietary surfactant, Methyl naphthalene sulfonic acid, polymer with formaldehyde, sodium salt, ethoxylated tristryl phenol Sulphate, alkyl naphthalene formaldehyde condensate, naphthalene sulfonic acid, sodium salt condensate with formaldehyde, ethoxylated oleyl cetyl alcohol, polyalkelene glycol ether, ethoxylated fatty alcohol, Sodium polymethyl methacrylate, sodium polyacrylate, sodium lignosulphonate, calcium lignosulphonate, alkylphenol polyoxyethylene ether, sodium salt of naphthalene sulfonate condensate, polycarboxylate, fatty alcohol polyoxyethylene ether, alcohol polyglycol ether or mixtures thereof.

5. The synergistic fungicidal composition as claimed in claim 1 or 2, wherein said wetting agent is selected from the group comprising tristyrylphenol ethoxylate non-ionic emulsifier, mixture of non-ionic surfactants, alkoxylated alcohol, block copolymer, alcohol polyglycol ether, alkyl olefin sulphates, dioctyl sulpho succinate, alkyl naphthalene sulphate,Di-isopropyl Napthalene sulphonate, Polyalkoxy ethers, alkyl phenol ethoxylates, tri-styrenated phenol ethoxylate, EO/PO block co-polymers, butyl polyalkylene oxide block copolymer, sodium lauryl sulphate, sodium ligno sulphates or mixtures thereof.

6. The synergistic fungicidal composition as claimed in claim 1 or 2, wherein said antifoaming agent is selected from the group comprising silicon emulsion based anti-foam agents, Siloxane polyalkyleneoxide, Polydimethylsiloxane, trisiloxane ethoxylates, silicone oil, silicone compound, C10~C20 saturated fat acid compounds or C8~C10 aliphatic alcohols compound, vegetable oil based antifoam, tallow based fatty acids, polyalkyleneoxide polydimethylsiloxane emulsion and mixtures thereof.

7. The synergistic fungicidal composition as claimed in claim 1 or 2, wherein said carrier is selected from the group comprising silicon dioxide, china clay, kaolin, starch, bentonite, precipitated silica, fumed silica, talcum powder, lactose, ammonium sulpha or mixture thereof.

8. The fungicidal composition as claimed in claim 2, wherein said dispersing agent is present in an amount ranging from 5-35% w/w, said wetting agent is present in an amount ranging from 10-30% w/w, said anti- foaming agent is present in an amount ranging from 0.2-3% w/w and said carrier is present in an amount ranging from 5-20% w/w.

9. The fungicidal composition as claimed in preceding claims, wherein said fungicidal composition is formulated in a form selected from the group consisting water-soluble concentrates (SL), emulsifiable concentrates (EC), emulsions (EW), micro-emulsions (ME), Suspension concentrates (SC), oil-based suspension concentrates (OD), flowable suspensions (FS), water-dispersible granules (WG), water-soluble granules (SG), wettable powders (WP), water soluble powders (SP), granules (GR), encapsulated granules (CG), fine granules (FG), macro granules (GG), dry flowable (DF), aqueous Suspo-emulsions (SE), capsule suspensions (CS) and microgranules (MG).

10. The fungicidal composition as claimed in claim 4, wherein said fungicidal composition is in the form of a wettable granule or a microgranule formulation.
11. The fungicidal composition as claimed in claim 1, wherein said fungicidal composition comprises Carbendazim in an amount of 20% w/w, Metiram in an amount of 50% w/w, dispersing agent in an amount of 9%w/w, wetting agent in an amount of 15.5%w/w, antifoaming agent in an amount of 0.3%w/w and carrier in an amount of 5%w/w.

12. The fungicidal composition as claimed in claim 1, wherein said fungicidal composition comprises Carbendazim in an amount of 20% w/w, Metiram in an amount of 50% w/w, Soyprotein or amino acids in an amount of 0.2% w/w, dispersing agent in an amount of 9% w/w, wetting agent is present in an amount of 15.5% w/w, antifoaming agent is present in an amount of 0.3%w/w and carrier is present in an amount of 5% w/w.

13. A process for preparing the fungicidal composition claimed in claim 1 in the form of a microgranule, said process comprising:

i. taking suitable volume of demineralised water;
ii. adding dispersing agent in an amount ranging from 5-35% w/w and wetting agent in an amount ranging from 10-30% w/w;
iii. adding carbendazim technical in an amount ranging from 5-30% w/w, metiram technical in an amount ranging from 30-65% w/w and soyprotein or amino acid in an amount ranging from 0.1-2% w/w to prepare a slurry;
iv. adding antifoaming agent in an amount ranging from 0.2-3% w/w to the material which was then mixed well in a homogenizer;
v. passing the material or slurry obtained in step (iv) through dyno mill for particle size reduction to obtain particle size (d90) ≤ 10µ. this was followed by again mixing the material in a homogenizer and adding the balance quantity of dispersing agent, wetting agent and antifoaming agent;
vi. passing the material through spray dryer for micro granulation;
vii. checking the microgranules obtained for quality parameters and proceeding with packaging or storage.

14. A process for preparing the fungicidal composition claimed in claim 1 in the form of a wettable granule (WG), said process comprising:
Step 1: Taking the actives -Carbendazim Technical in an amount ranging from 5-30% w/w, Metribuzin Technical in an amount ranging from 30-65%w/w and soy protein or amino acid in an amount ranging from 0.1-2% w/w.
Step 2: Adding dispersing agent in an amount ranging from 5-35% w/w and wetting agent in an amount ranging from 10-30% w/w.
Step 3: Adding carrier (Silica & China Clay) in an amount ranging from 5-20% w/w and mixing uniformly.
Step 4: Carrying out milling process of the material through ACM (Air Classifying Mill) to obtain a particle size of less than 15µ (microns).
Step 5: Preparing a dough using the material obtained in step 4
Step 6: Extruding the granules by basket extruder.

15. A method for controlling fungal infestation in agriculture crops, said method comprising applying fungicidally effective amount of a fungicidal composition as claimed in claims 1-12 to the target crop or at the locus where the said target crop is growing.

16. The method as claimed in claim 15, wherein said fungicidally effective amount of the fungicidal composition comprises:
a. Carbendazim in an amount ranging from of 5-30% w/w;
b. Metiram in an amount ranging from 30-65% w/w;
c. Soyprotein or amino acids in an amount ranging from 0.1-2% w/w;
e. at least one agriculturally acceptable excipient.