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Title:
A SYNERGISTIC FUNGICIDAL COMPOSITION
Document Type and Number:
WIPO Patent Application WO/2024/033949
Kind Code:
A1
Abstract:
The present invention relates to a stable synergistic fungicidal composition comprising a dithiocarbamate compound, a triazole fungicide compound, a saccharide-based suspension agent and at least one agrochemically acceptable excipient. The synergistic fungicidal composition provides increased resistance to fungal disease, improved shelf life, enhanced efficacy and better crop quality.

Inventors:
CHAUDHARI DEVENDRA BHAGWAN (IN)
SINGASANE BHUPESH KASHINATH (IN)
PATIL SEEMA ABHIJIT (IN)
ZAMBRE PRAKASH V (IN)
Application Number:
PCT/IN2023/050774
Publication Date:
February 15, 2024
Filing Date:
August 14, 2023
Export Citation:
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Assignee:
INDOFIL INDUSTRIES LTD (IN)
International Classes:
A01N47/10; A01N43/647; A01N59/00; A01P3/00
Domestic Patent References:
WO2020261030A12020-12-30
WO2021074831A12021-04-22
WO2018211383A12018-11-22
Foreign References:
CN105766957A2016-07-20
CN1751574A2006-03-29
IN201611015147A2017-12-29
Attorney, Agent or Firm:
KHAITAN & CO (IN)
Download PDF:
Claims:
CLAIMS:

1. A fungicidal composition comprising: a dithiocarbamate fungicide, a triazole fungicide, a saccharide -based suspension agent; and at least one agrochemically acceptable excipient.

2. The fungicidal composition as claimed in claim 1, wherein the dithiocarbamate fungicide is in the range of 20 wt.% to 80 wt.% based on the total weight of the composition.

3. The fungicidal composition as claimed in claim 1, wherein the dithiocarbamate fungicide is selected from the group comprising of amobam, asomate, azithiram, carbamorph, cufraneb, cuprobam, disulfiram, ferbam, metam, nabam, tecoram, thiram, urbacide, ziram, dazomet, etem, milneb, mancopper, mancozeb, maneb, metiram, polycarbamate, propineb and zineb.

4. The fungicidal composition as claimed in claim 1, wherein the triazole fungicide is in the range of 1 wt.% to 70 wt.% based on the total weight of the composition.

5. The fungicidal composition as claimed in claim 1, wherein the triazole fungicide is selected from azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole and pro thioconazole.

6. The fungicidal composition as claimed in claim 1, wherein the saccharide-based suspension agent is selected from monosaccharide, disaccharide, oligosaccharide and polysaccharide.

7. The fungicidal composition as claimed in claim 6, wherein the saccharide-based suspension agent is glucose, dextrose, fructose, ribose, arabinose, sucrose, trehalose, maltose, lactose, starch, cellulose, glycogen, chitin or mixture thereof.

8. The fungicidal composition as claimed in claim 1, wherein the agrochemically acceptable excipient is selected from solvent, solid carrier, dispersant, emulsifier, solubilizer, protective colloid, surfactant, adhesion agent, organic thickener, inorganic thickener, bactericide, antifreeze agent, antifoaming agent, stabilizer, biocide, plant growth promoter and the mixture thereof.

9. A fungicidal composition as claimed in claim 1, wherein the said composition comprises: a dithiocarbamate fungicide is in the range of 20 wt.% to 80 wt.% based on the total weight of the composition; a triazole fungicide is in the range of 1 wt.% to 70 wt.% based on the total weight of the composition; a saccharide-based suspension agent is in the range of 0.1 wt.% to 20 wt.% based on the total weight of the composition; and at least one agrochemically acceptable excipient.

10. The fungicidal composition as claimed in claim 1, wherein the fungicidal composition is formulated as a suspension concentrate, wettable powder, water dispersible granules, dust, soluble liquid concentrate, oil-in-water emulsion, water-in-oil emulsion, oil dispersion, suspoemulsion, oil dispersion, flowable suspension or water dispersible powder.

11. A process for preparing a fungicidal composition, wherein the said process comprising the steps of: i. mixing predetermined quantities of excipients, , saccharide-based suspension agent and water in a homogenizer to obtain homogenized mixture of Surfactant premix; ii. adding required amount of triazole in a surfactant premix under stirring and milling the homogenized mixture in a wet mill to obtain a milled slurry; and iii. blending the milled slurry in a homogenizer with predetermined quantities of dithiocarbamate and excipient(s) to yield a product of desired composition.

12. A method for controlling fungi, the said method comprises applying to a pest, to a locus of the pest, an effective amount of the fungicidal composition as claimed in claim 1.

13. Use of the fungicidal composition as claimed in any of the preceding claims for controlling fungal diseases, wherein the said composition comprises: i) a dithiocarbamate fungicide is in the range of 20 wt.% to 80 wt.% based on the total weight of the composition; ii) a triazole fungicide is in the range of 1 wt.% to 70 wt.% based on the total weight of the composition; iii) a saccharide -based suspension agent is in the range of 0.1 wt.% to 20 wt.% based on the total weight of the composition; and iv) at least one fungicidally acceptable excipient.

Description:
TITLE OF THE INVENTION

A SYNERGISTIC FUNGICIDAL COMPOSITION

FIELD OF THE INVENTION

[001] The invention relates to a stable synergistic fungicidal composition for controlling fungal disease in plants, more particularly to a synergistic composition comprising at least two fungicidal agents; a saccharide-based suspension agent and at least one agrochemically acceptable excipient or other auxiliaries.

BACKGROUND OF THE INVENTION

[002] The control of plant diseases caused by fungal plant pathogens is extremely important in achieving high crop efficiency. The control of fungi is important since fungal growth on plants or on parts of plants inhibits production of foliage, fruit or seed, and the overall quality of a cultivated crop.

[003] Due to the vast economic ramifications of fungal propagation in agricultural and horticultural cultivations, a broad spectrum of fungicidal and fungistatic products have been developed for general and specific applications. Fungicides that effectively control plant fungi are constantly being sought by growers. Combinations of fungicides are often used to promote disease control and to delay the formation of resistance. It is desirable to use a mixture of active ingredients that have a therapeutic effect on plant pathogens and provide a combination of invasive and prophylactic controls to improve the range and effect of disease control.

[004] Moreover, it is always desirable to be able to reduce the content of chemicals released into the environment while effectively protecting crops from diseases caused by plant pathogens. Mixtures of fungicides can provide significantly better disease control than would be expected based on the activity of the individual components. [005] To formulate a product containing two or more active ingredients is a real challenge as it is difficult to predict problems such as compatibilities and stability of the formulated product. Incompatibility can lead to the mixture forming a precipitate, or lumps or do not disperse properly and settle out of suspension. This will also result in inefficient spraying of the pesticide, resulting in poor efficacy. It is therefore important for formulators to prepare stable formulations that allow for two actives to be combined in a single formulation, giving a favourable active profile, high stability and in some cases enhanced synergy, thus permitting reduced rate of application as compared with the individual application of the active compounds. There is therefore a need in the art for a formulation which is stable especially when two active compounds are combined providing a broader spectrum of control while reducing rate of application.

[006] The present invention aims to overcome these problems and provide specific advantage of not requiring additional stabilization for storage formulations.

SUMMARY OF THE INVENTION

[007] One aspect of the present invention relates to a stable synergistic fungicidal composition comprising at least two active ingredients - a dithiocarbamate compound, a triazole based fungicide compound, a saccharide-based suspension agent along with at least one agrochemically acceptable excipient or other auxiliaries.

[008] Another aspect of the present invention relates to a process preparation of a synergistic fungicidal composition comprising the steps of:

• mixing predetermined quantities of excipients, saccharide-based suspension agent and water in a homogenizer to obtain homogenized mixture of Surfactant premix;

• adding required amount of triazole in a surfactant premix under stirring and milling the homogenized mixture in a wet mill to obtain a milled slurry; and • blending the milled slurry in a homogenizer with predetermined quantities of dithiocarbamate, excipient(s) and rheology modifier to yield a product of desired composition.

[009] Another aspect of the present invention relates to a method for controlling phytopathogenic harmful fungi, which method comprises treating the fungi, their habitat or the plants to be protected against fungal attack, the soil, seed, areas, materials or spaces the soil or the plants to be protected against fungal attack with an effective amount of synergistic fungicidal composition.

DETAILED DESCRIPTION OF THE INVENTION

[010] Discussed below are some representative embodiments of the present invention. The invention in its broader aspects is not limited to the specific details and representative methods. An illustrative example is described in this section in connection with the embodiments and methods provided.

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

[012] The expression of various quantities in terms of “%” or “% w/w” means the percentage by weight of the total solution or composition unless otherwise specified.

[013] The present invention is directed towards a stable and synergistic fungicidal composition which does not degrade and remains active even during long periods of storage. Further, use of this stable composition comprising two or more active ingredients reduces the number of applications of various individual active components thus providing a cost-effective and labour- saving solution.

[014] One aspect of the present invention relates to a composition comprising: a dithiocarbamate fungicide, a triazole fungicide, a saccharide-based suspension agent; and at least one agrochemically acceptable excipient.

[015] In an embodiment of the invention, the fungicidal composition shows synergistic effect and improved stability.

[016] In one embodiment, the dithiocarbamate fungicide is selected from the group comprising of amobam, asomate, azithiram, carbamorph, cufraneb, cuprobam, disulfiram, ferbam, metam, nabam, tecoram, thiram, urbacide, ziram, dazomet, etem, milneb, mancopper, mancozeb, maneb, metiram, polycarbamate, propineb and zineb.

[017] The dithiocarbamate is a broad spectrum, non-systemic contact fungicide including their derivatives which have activity against phytopathogenic fungi, they are useful in control of many fungal disease in a wide range of field crops, fruits.

[018] Dithiocarbamate are known in the art as multi-site fungicides. These fungicides are used for bro ad- spectrum disease control in more than 70 crops. Mancozeb is especially important for controlling devastating and fast spreading diseases such as Phytophthora infestans, Venturia inaequalis etc. Dithiocarbamate fungicides, especially mancozeb, are particularly useful for disease control because of their broad spectrum of activity, high tolerance by crop plants, and general usefulness for controlling fungal plant diseases not controlled by active compounds that act on only a single target site in the fungus.

[019] In one embodiment, the dithiocarbamate fungicide is in the range of 20 wt.% to 80 wt.% based on the total weight of the composition. In one embodiment, the dithiocarbamate is present in an amount in between 20 wt.% to 70 wt.% based on the total weight of the composition.

[020] In one embodiment, the triazole fungicide is selected from azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole and pro thioconazole.

[021] In one embodiment, the triazole fungicide is in the range of 1 wt.% to 70 wt.% based on the total weight of the composition. In one embodiment, the triazole is present in an amount in between 1 wt.% to 60 wt.% based on the total weight of the composition. In one embodiment, the triazole is present in an amount in between 1 wt.% to 50 wt.% based on the total weight of the composition.

[022] Difenoconazole is one of the widely used broad-spectrum fungicide for the disease control in grapes, pome fruits, stone fruits, potatoes, sugar beet, oilseed rape, bananas, cereals, rice, soybean and vegetable crops. It has preventive and curative action. Difenoconazole is absorbed by the leaves with acropetal and strong translaminar translocation. It acts by inhibition of sterol demethylation during cell membrane erosterol biosynthesis thereby stopping development of fungus.

[023] In one embodiment, the saccharide-based suspension agent is selected from monosaccharide, disaccharide, oligosaccharide and polysaccharide. More specifically, the saccharide-based suspension agent is glucose, dextrose, fructose, ribose, arabinose, sucrose, trehalose, maltose, lactose, starch, cellulose, glycogen, chitin or mixture thereof.

[024] The saccharide-based suspension agents in the composition provides less drop in suspensibility of the fungicidal composition thereby providing enhanced stability to the composition and enhances a plant natural defence. Suspension agents provide stabilization effect and prevents the suspension drop on storage of the product.

[025] In one embodiment, the composition comprises: a dithiocarbamate fungicide is in the range of 20 wt.% to 80 wt.% based on the total weight of the composition, a triazole fungicide is in the range of 1 wt.% to 70 wt.% based on the total weight of the composition, a saccharide-based suspension agent is in the range of 0.1 wt.% to 20 wt.% based on the total weight of the composition; and at least one fungicidally acceptable excipient. [026] In one embodiment, the composition comprises: a dithiocarbamate fungicide is in the range of 20 wt.% to 80 wt.% based on the total weight of the composition, a triazole fungicide is in the range of 1 wt.% to 70 wt.% based on the total weight of the composition, combination of a saccharide-based suspension agent is in the range of 0.1 wt.% to 20 wt.% and dispersing agent in the range of 0.1 wt.% to 10 wt.% based on the total weight of the composition and at least one fungicidally acceptable excipient.

[027] In one embodiment, the composition comprises: a mancozeb is in the range of 20 wt.% to 80 wt.% based on the total weight of the composition, a triazole selected from dif enoconazole, cyproconazole, hexaconazole and prothioconazole is in the range of 1 wt.% to 70 wt.% based on the total weight of the composition, a saccharide -based suspension agent is in the range of 0.1 wt.% to 20 wt.% based on the total weight of the composition; and at least one fungicidally acceptable excipient.

[028] In an embodiment of the invention, the fungicidal composition of the present invention comprises Mancozeb and triazole in the ratio of 5-25: 0.5-7, preferably 13.3: 1, where the composition is a wettable powder formulation.

[029] In another embodiment of the invention, the fungicidal composition of the present invention comprises Mancozeb and triazole in the ratio of 10-50: 0.5-10, preferably 33:2, where the composition is a suspension concentrate formulation.

[030] In one embodiment, the fungicidal composition may further comprise one or more excipients. The employment of excipients used in the composition will depend upon the type of formulation and/or the manner in which the formulation is to be applied by the end user.

[031] In one embodiment, the agrochemically acceptable excipient includes but are not limited to customary formulation adjuvants or components, such as from solvent, solid carrier, dispersant, emulsifier, solubilizer, protective colloid, surfactant, adhesion agent, organic thickener, inorganic thickener, bactericide, antifreeze agent, antifoaming agent, stabilizer, biocide, plant growth promoter and the mixture thereof. [032] In one embodiment, the stabilizing agent is at least one selected from the group, consisting of Hexamethylene tetraamine, sodium bisulphite, phosphoric acid monoesters, phosphoric acid diesters, phosphoric acid mono- and di- ester mixture, sodium phosphates, butylated hydroxytoluene, castor oil ethoxylate, ethoxylated hydrogenated castor oil, vegetable oil and epoxidized soyabean oil or combinations thereof.

[033] In one embodiment, the antifoam includes to silicon emulsions, Octamethylcyclotetrasiloxane, alkyl tetra siloxanes, di alkyl tetra siloxanes, cyclic siloxanes, cycloaliphatic siloxanes or poly dimethylsiloxanes.

[034] In one embodiment, the emulsifiers includes Polyoxyethylene alkylamine, Polyoxyethylene linear alkyl ether, Ethoxylated Castor Oil, Epoxidized soyabean oil, Polyoxyethyene alkylamine quaternary, Polyoxyethyene tallow ethylmonium ethosulfate, Glycerol monostearate, Glycerol monooleate, ethoxylated monostearate / distearate / tri stearate ethoxylated monooleate / trioleate, Polyoxyethylene branched tridecyl Phosphate, Polyoxyethylene branched tridecyl phosphate neutralised, Polyoxyethylene alkyl ether phosphate, ethoxylated propoxylated sorbitan mono esters or tallow amine ethoxylate.

[035] In one embodiment, the dispersing agent includes, but is not limited to, Anionic graft polymer, Kraft lignin Polymer, Napthalene sulphonate formaldehyde condensate, Amine alkyl benzenesulfonate, Sodium Ligno Sulphonate, Blend of Naphthalene sulphonate sodium salts, Blend of Lignin sulphonates sodium salts, Ethoxylated Lignin sulphonates, Linear alkyl benzene sulphonate, tri stearyl phenol ethoxylates, Polycarboxylates, Acrylic copolymer solution, Modified styrene acrylic polymer, Ammonium distyrylphenyl ether sulphate or salts of polystyrene sulphonic acids.

[036] In one embodiment, the wetting agent includes Poly alkylene oxide block copolymer, Salts of Di-octyl sulfosuccinate, Alcohol alkoxylate diester, Sodium N-methyl oleoyl taurate, Sodium cocoyl sarcosinate, sodium lauryl sulphate, Sodium dioctyl sulfosuccinate, alkyl polyglucoside, Naphthalenesulfonic acids, branched and linear Butyl derivatives sodium salts or Sodium Lauryl sulphate.

[037] In one embodiment, the antifreeze agents include Propylene glycol, 1 methoxyl 2 propoanol, Butyl cellosolve or ethylene glycol.

[038] The preservatives include, but is not limited to, l-2-benziisothiazolin-3-one, 5-Chloro-2- methyl-4-isothiazolin-3-one or 2-methyl-4-isothiazolin-3-one.

[039] The rheology modifiers include Polyester block co-polymer, Poly saccharides, Polyamide, Clay, xanthum gum or Silicates.

[040] The film-forming agent is at least one selected from the group consisting of hydrophilic polymers, hydrobhobic polymers, Poly(vinylpyrrolidone) or vinypyrrolidone-vinylacetate.

[041] The disintegrating agent is selected from the group consisting of sodium chloride, sodium sulphate, ammonium sulphate, sodium carbonate, sodium bicarbonate, sodium tripolyphosphate (STPP), Crosslinked carboxyl methyl cellulose, crosslinked PVA, crosslinked starch, crosslinked alginic acid and Ca silicate, etc. The solvents, include aromatic hydrocarbon solvent such as SOLVESSO®, paraffinic hydrocarbon solvent such as EXXSOL®, cyclic hydrocarbon solvent such as cyclohexanone, N-methylpyyrolidone, mixed xylene, cyclohexane, Dimethyl sulphoxide, Diemthyl formamide, toluene, ethyl methyl ketone, Tetrahydrofuran, Other solvent / co solvent includes such as N butyl Pyrolliodone, Dimethylamide of C8/C10 fatty acid, Dimethylamide of CIO fatty acid, Dimethyl Amide, Dipropylene Glycol, Caprylic/Capric Triglyceride, Canola Oil Methyl Ester, Methyloleate/Linoleate Methyl Ester, N,N-Dimethyl 9-Dodecenamide, Methyl Caprylate/Caprate, N, N-Dimethyloctanamide (N, N-Dimethylcaprylamide) and N, N-Dimethyl- Decanamide [(N, N-Dimethylcapramide)], alkanes or alkanol, etc.

[042] The Co-solvent includes Bicyclic Tetraether, alkanes, alkenes, Dibasic ester solvents, Alkylene carbonates including Esters, hydrocarbons amides, aldehyde, ketones, ether, esters, Carbonate based, Aromatic Ester solvent, Benzyl Acetate, Dimethyl propylene mono methyl ether, Formylmorpholine, 2-ethylhexyl ester of natural L-Lactic acid.( Ethtyl Hexyl lactate), alcohol, Ethyl acetate, Polyethylene glycol, Chloroform or chlorinated hydrocarbons. [043] The filler and/or diluent is selected from the group consisting of starches and their derivatives, sugars and sugar alcohols, silicates, calcium phosphates, calcium sulfate, dextrates, kaolin clay, bentonite clay, attapulgite, diatomaceous earth, magnesium carbonate, polymethacrylates, talc and salts.

[044] Water is used as a diluent to dilute the active ingredient to a desired concentration. The water used is purified water and selected from the group consisting of deionized water and distilled water.In an embodiment, the composition may be in the form of suspension concentrate, wettable powder, water dispersible granules, dust, soluble liquid concentrate, oil-in-water emulsion, water- in-oil emulsion, oil dispersion, suspoemulsion, oil dispersion, flowable suspension or water dispersible powder.

[045] In accordance with an exemplary embodiment of the present invention, the stable synergistic fungicidal composition comprises a dithiocarbamate fungicide is in the range of 20 wt.% to 80 wt.% based on the total weight of the composition, a triazole fungicide is in the range of 1 wt.% to 70 wt.% based on the total weight of the composition, a saccharide-based suspension agent is in the range of 0.1 wt.% to 20 wt.% and at least one dispersing agent in the range of 0.1 wt.% to 10 wt.% based on the total weight of the composition and atleast one agrochemically acceptable excipient.

[046] In accordance with an exemplary embodiment of the present invention, the stable synergistic fungicidal composition comprises a dithiocarbamate fungicide is in the range of 20 wt.% to 80 wt.% based on the total weight of the composition, a triazole fungicide is in the range of 1 wt.% to 70 wt.% based on the total weight of the composition, a saccharide-based suspension agent is in the range of 0.1 wt.% to 20 wt.% based on the total weight of the composition and at least one agrochemically acceptable excipient selected from the group comprising of dispersing agents, antifreeze agent, antifoaming/defoamers, wetting agents, disintegrating agents, thickener, diluents, binders, preservative, filler, carrier or rheology modifier in an amount in the range of 5% to 70% by weight of the total weight of the composition. [047] In accordance with an exemplary embodiment of the present disclosure, the synergistic fungicidal composition a dithiocarbamate fungicide is in the range of 20 wt.% to 80 wt.% based on the total weight of the composition, a triazole fungicide is in the range of 1 wt.% to 70 wt.% based on the total weight of the composition, a saccharide-based suspension agent is in the range of 0.1 wt.% to 20 wt.% based on the total weight of the composition and agrochemically acceptable excipient comprising at least one dispersing agent in an amount in the range of 1% to 20% by weight of the total weight of the composition, at least one wetting agent in an amount in the range of 1% to 15% by weight of the total weight of the composition at least one diluent in an amount in the range of 10% to 70% by weight of the total weight of the composition, at least one defoamer in an amount in the range of 0.01% to 5% by weight of the total weight of the composition, an antifreeze agent in an amount in the range of 1% to 15% by weight of the total weight of the composition, at least one preservative in an amount in the range of 0.001% to 3% by weight of the total weight of the composition, a rheology modifier in an amount in the range of 0.1% to 50 % by weight of the total weight of the composition and at least one carrier in an amount in the range of 0.01% to 10% by weight of the total weight of the composition.

[048] One aspect of the present invention relates to a process for preparing a stable fungicidal composition.

[049] In one embodiment of the invention, the process for preparing a Wettable Powder formulation comprises the steps of milling difenoconazole technical to the desired particle size and blending with auxiliaries, saccharide-based suspension agent and Mancozeb to obtain the final product in wettable powder.

[050] In one embodiment of the present invention, a process for preparation of a suspension concentrate formulation comprising the steps of: i. mixing predetermined quantities of excipients, saccharide-based suspension agent and water in a homogenizer to obtain homogenized mixture of Surfactant premix; ii. adding required amount of triazole in a surfactant premix under stirring and milling the homogenized mixture in a wet mill to obtain a milled slurry; and iii. blending the milled slurry in a homogenizer with predetermined quantities of dithiocarbamate and excipient(s) to yield a product of desired composition.

[051] In another embodiment of the invention, the process for preparing a Suspension concentrate formulation comprises the steps of : i) Mixing predetermined quantities of Wetting/Dispersing agent, defoamer, Anti freezing agent and water in a homogenizer to obtain homogenized mixture of Surfactant premix. ii) Adding required amount of Difenoconazole technical in a surfactant premix under stirring and milling the homogenized mixture in a wet mill to obtain milled slurry having particle size (d50) in the range of 1 to 8pm. iii)Blending the milled slurry in a homogenizer with predetermined quantities of Mancozeb, thickener, defoamer, stabilizers, additional quantities of dispersing agent and saccharide- based suspension agent to yield the product of desired composition in water-based form.

[052] In another aspect, the invention relates to a process for preparation of a synergistic fungicidal composition comprising the steps of:

Pre-blending: Mixing the formulation components surfactants and Difenoconazole to a blender and mix until uniform. ing: Process the blended formulation through an air jet mill to achieve the desired particle size, preferably d (50) < 10 pm.

Post-blending: Mix the milled formulation and blended with Mancozeb homogenously to ensure even distribution of components in the powder.

[053] The stable aqueous Suspension Concentrate of fungicidal composition prepared in accordance with an embodiment of the invention utilizes surfactant at lower concentration while resulting in imparting synergistic stability effect to the composition as established with the accelerated storage study. [054] Advantageously, the present invention provides a composition that serves the dual purpose of addressing the issue of stability of formulations comprising combination of two or more active ingredients as well as provides enhanced synergistic fungicidal effect while also meeting the fungicidal requirement as compared with the individual application. The composition provides the advantages of synergistic fungicidal activity and enhanced stability. The composition while enhancing the greening of crops to which it is administered also improves the quality, appearance and yield of crops, reduces fungal disease incidence in the crops to which it is applied and at the same time improves quality of fruit in various crops like grapes, tomato, melon, strawberry, cucurbit, apple, pear & peach.

[055] One embodiment relates to a method for controlling phytopathogenic harmful fungi, which method comprises treating the fungi, their habitat or the plants to be protected against fungal attack, the soil, seed, areas, materials or spaces the soil or the plants to be protected against fungal attack with an effective amount of synergistic composition.

EXAMPLES

[056] The present invention is more particularly described in the following examples that are intended as illustration only, since numerous modifications and variations within the scope of the present invention will be apparent to those skilled in the art. Unless otherwise noted, all parts, percentages and ratios reported in the following examples are on a weight basis, and all reagents used in the examples were obtained or are available from the chemical suppliers.

[057] The following examples illustrate the basic methodology and versatility of the present invention.

[058] In this experiment, different compositions were developed using Mancozeb [Component

A] and different triazoles (Component B) as active fungicidal agents; and, using saccharide suspending agent (Component C) and excepients. [059] The composition included the following active ingredients and excipients -

Example 1 - Composition Formulation Mancozeb 64% + Difenoconazole 4.8% WP

Pre-blending: making blend 6g of dispersing agent Kraft lignin polymer and 2g of dextrose suspending agent and mixing with 4g of wetting agent Sodium dioctylsulfosuccinate and 5.6g of silica to obtain premix. 5.3 g of Difenoconazole is added to the premix into a blender and mix until uniform.

Milling: Process the blended formulation through an air jet mill to achieve the desired particle size, preferably d (50) < 10 pm.

Post-blending: Mix the milled formulation and blended with 77.1 g Mancozeb to obtain homogenous wettable powder formulation.

Table 1: Stability Study of Example 1

Example 2: Mancozeb 38% + Difenoconazole 2.4% SC Table 2: Stability Study of Example 2

The Example- 1 and Example 2 were taken further to evaluate physicochemical parameters. It was found that the compositions of Example 1 and Example 2 remained physico chemically stable when tested at ambient conditions i.e. room temperature and high temperature. Example 2 remained flowable suspension. Amount of active content also been evaluated at ambient and AHS stages. It was found that active content remained almost constant without any significant deterioration or loss. Example 2A: Mancozeb 67% + Cyproconazole 3% WG

Comparative Examples

A comparative study was conducted to understand the effect of saccharide suspension agent and dispersing agent in the agrochemical composition. Composition prepared in Example-3 where Saccharide suspension agent was not added. Composition prepared in Example-4 where kraft lignin polymer dispersing agent was not added. Composition prepared in Example-5 and Example

6 as per known in the art.

[060] Table 3: Comparative study

Study : All the compositions were evaluated in ambient as well as in Accelerated Heat Stability (AHS) conditions. Results of the study are presented in Table 4. Table 4 - Stability analysis of composition

It was observed that composition of Example 1 was found to be stable in ambient conditions. This composition remained stable and free from extraneous matter. However, Example 3, Example 4, Example 5 and Example 6 failed in AHS conducted for 14 days at 54°C. Settling was observed and became solidified thus failed to comply the standard specifications when tested in AHS. It was concluded that the suspensibility of the formulation was observed to be constant in composition prepared as per present invention while the comparative formulations which does not contain saccharide based suspending agent, suffered a remarkable drop in suspensibility. Further it has been noted that the comparative formulation led to the formation of large amount of foam.

Experiment 2 - Bio-efficacy of Example 1 Difenoconazole 4.8% + Mancozeb 64 % WP against

Powdery Mildew (Erysiphe Polygoni) of Black gram [061] A field trial was conducted to study the effect of the inventive compositions (Example 1) on efficacy against Tikka early leaf spot (Cercospora arachidicola) on Ground Nut. A comparative formulation as per Example 3 was also tested to compare the observations.

[062] Treatment methodology - Treatment was carried out by spraying the trial compositions as well as their separate constituents either individually or in combination at the specified dosages.

Disease progression was evaluated 8 days after application with up to 3 different applications carried out.

[063] The results were evaluated against untreated plants to determine the efficacy in reduction of the disease. They are presented in Table 5 below.

Table 5 - Bio-efficacy of Dif enoconazole 4.8% + Mancozeb 64 % WP against Powdery Mildew Erysiphe Polygoni) of Black gram

CONCLUSION:

[064] Foliar Application of T2 Difenoconazole 4.8 % + Mancozeb 64% WP (Example 1) @ 1250 gm/ha found to be more effective in controlling Powdery mildew (Erysiphe Polygoni) of Black gram with 5.0 percent disease incidence (PDI) i.e., 91 percent control over untreated control, at 8 days after third application and it was on par with T1 Difenoconazole 4.8 % + Mancozeb 64% WP with 6.0 PDI.

[065] However, T3 Difenoconazole 25% + Mancozeb 75%WP EC (Tank mix) @ 192 gm/ha +853.33 ml/ha. also recorded lowest PDI of 10.33 which is the next best treatment, followed by Difenoconazole 25% EC @ 600 gm/ha with 12.0 PDI; Mancozeb 75%WP @ 1500 gm/ha with 43.3 PDI whereas untreated control recorded the disease of 56.67 PDI of Powdery mildew of Black gram.

[066] Advantageously, the compositions according to the present invention are effective for providing the required fungicidal activity, much more efficiently when compared with the individual application. The composition provides the advantages of increased resistance to fungal disease, improved shelf life, better crop quality and enhanced efficacy.

[067] The foregoing description of the invention has been set merely to illustrate the invention and is not intended to be limiting. While the present invention has been described with respect to certain embodiments, it will be apparent to those skilled in the art that various changes and modification may be made without departing from the scope of the invention as defined in the following claims.