WO2019215593A1

WO2019215593A1 - Synergistic fungicidal composition and a process for preparation thereof

Info

Publication number: WO2019215593A1
Application number: PCT/IB2019/053711
Authority: WO
Inventors: Jayprakash Gopalkrishnan RAO; Seema Abhijit PATIL; Tanaji Shivaji BHAGAT
Original assignee: Indofil Industries Limited
Priority date: 2018-05-07
Filing date: 2019-05-07
Publication date: 2019-11-14

Abstract

The present invention relates to a synergistic fungicidal composition comprising a first triazole fungicide, a strobilurin fungicide, a second triazole fungicide and at least one agrochemically acceptable excipient. The present invention also relates to a process for preparation of a synergistic fungicidal composition.

Description

SYNERGISTIC FUNGICIDAL COMPOSITION AND A PROCESS FOR

PREPARATION THEREOF

FIELD

The present disclosure relates to a synergistic fungicidal composition and a process for preparation thereof.

BACKGROUND

The need for more food has to be met through higher yields of food per unit of land, water, energy, and time. Excessive use of mineral fertilizers and chemical pesticides has caused soil degradation, ground water pollution and the spread of the pests resistant to pesticides in several areas.

Enhancement of agricultural products requires the protection of the crops and its produce from pest damage. Various chemicals and their formulations have been developed and are in use currently for the effective management of fungi. Due to the excessive use of fungicides, the pests/fungi gain resistance and become hard to kill. Physically compatible pesticide mixtures exhibit better pest management. These mixtures show multifaceted advantages than when applied individually and provide a synergistic effect. Various fungicidal compositions have been developed to control various fungi/pests. However, economically efficient and ecologically safe fungicidal compositions having enhanced activity are still being sought.

Thus, there exists a need for fungicidal compositions that mitigate the hereinabove mentioned drawbacks.

OBJECTS

Some of the objects of the present disclosure, which at least one embodiment herein satisfies, are as follows:

It is an object of the present disclosure to ameliorate one or more problems of the prior art or to at least provide a useful alternative. Another object of the present disclosure is to provide a fungicidal composition having a synergistic effect.

Yet another object of the present disclosure is to provide a fungicidal composition having enhanced fungicidal activity and combats resistance shown by fungi.

Other objects and advantages of the present disclosure will be more apparent from the following description, which is not intended to limit the scope of the present disclosure.

SUMMARY

The present disclosure relates a synergistic fungicidal composition and a process for preparation thereof.

The synergistic fungicidal composition of the present disclosure comprises a combination of triazole fungicides and strobilurin fungicides that has enhanced fungicidal activity and is not prone to resistance towards fungi.

In an aspect of the present disclosure there is provided a synergistic fungicidal composition comprising at least one triazole fungicide, a strobilurin fungicide and at least one agrochemically acceptable excipient. These fungicides when used in combination exhibit fungicidal activity that exceeds the sum of the fungicidal activities of the individual components when used alone.

DETAILED DESCRIPTION

Embodiments, of the present disclosure, will now be described herein. Embodiments are provided so as to thoroughly and fully convey the scope of the present disclosure to the person skilled in the art. Numerous details are set forth, relating to specific components, and methods, to provide a complete understanding of embodiments of the present disclosure. It will be apparent to the person skilled in the art that the details provided in the embodiments should not be construed to limit the scope of the present disclosure. In some embodiments, well-known processes, well-known apparatus structures, and well-known techniques are not described in detail.

The terminology used, in the present disclosure, is only for the purpose of explaining a particular embodiment and such terminology shall not be considered to limit the scope of the present disclosure. As used in the present disclosure, the forms "a,” "an," and "the" may be intended to include the plural forms as well, unless the context clearly suggests otherwise. The terms "comprises," "comprising,"“including,” and“having,” are open ended transitional phrases and therefore specify the presence of stated features, integers, steps, operations, elements, modules, units and/or components, but do not forbid the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The particular order of steps disclosed in the method and process of the present disclosure is not to be construed as necessarily requiring their performance as described or illustrated. It is also to be understood that additional or alternative steps may be employed.

As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed elements.

Throughout this specification the word“comprise”, or variations such as“comprises” or “comprising”, will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.

The use of the expression“at least” or“at least one” suggests the use of one or more elements or ingredients or quantities, as the use may be in the embodiment of the invention to achieve one or more of the desired objects or results. While certain embodiments of the inventions have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. Variations or modifications to the formulation of this invention, within the scope of the invention, may occur to those skilled in the art upon reviewing the disclosure herein. Such variations or modifications are well within the spirit of this invention.

The terms first, second, third, etc., should not be construed to limit the scope of the present disclosure as the aforementioned terms may be only used to distinguish one element, component, region, layer or section from another component, region, layer or section. Terms such as first, second, third etc., when used herein do not imply a specific sequence or order unless clearly suggested by the present disclosure.

It is observed that triazole and strobilurin fungicides when applied individually show good fungicidal activity but the target fungi develop resistance to them owing to their single mode of action. Therefore there is a need to develop fungicidal compositions that exhibit good fungicidal activity as well as are not prone to resistance from the fungi.

The present disclosure envisages a synergistic fungicidal composition and a process for preparation thereof.

It is a chance finding by the applicant that a synergistic fungicidal composition comprising a specific combination of two triazole fungicides and a strobilurin fungicide has synergistic fungicidal activity. A synergistic fungicidal product needs a right combination to prevent development of resistance by the fungi. The fungicidal composition of the present disclosure is successful in achieving enhanced fungicidal activity and also prevents development of resistance by the fungi. The fungicidal composition of the present disclosure shows fungicidal activity that exceeds the sum of the fungicidal activities of the individual components when used alone.

In accordance with a first aspect of the present disclosure, there is provided a synergistic fungicidal composition comprising at least one triazole fungicide, a strobilurin fungicide and at least one agrochemically acceptable excipient in pre-determined proportion with respect to each other.

In accordance with an embodiment of the present disclosure, the synergistic fungicidal composition comprises a first triazole fungicide, a strobilurin fungicide, a second triazole fungicide and at least one agrochemically acceptable excipient. In accordance with an embodiment of the present disclosure, the first triazole fungicide is present in an amount in the range of 1% to 75% by weight of the total mass of the composition.

In accordance with an embodiment of the present disclosure, the strobilurin fungicide is present in an amount in the range of 1% to 50% by weight of the total mass of the composition.

In accordance with an embodiment of the present disclosure, the second triazole fungicide is present in an amount in the range of 1% to 30% by weight of the total mass of the composition.

In accordance with an embodiment of the present disclosure, the agrochemically acceptable excipient is present in an amount in the range of 10% to 70% by weight of the total mass of the composition.

In accordance with an embodiment of the present disclosure, the first triazole fungicide and the second triazole fungicide are selected from the group consisting of azaconazole, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole- m, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, tricyclazole, triticonazole, triadimefon, triadimenol, oxpoconazole and uniconazole.

In accordance with an exemplary embodiment of the present disclosure, the first triazole fungicide is Tricyclazole.

Tricyclazole [CAS NO: 41814-78-2] is the common name for 5-methyl-l, 2, 4-triazolo [3, 4- b\ [1, 3] benzothiazole and possesses the following structure:

Tricyclazole is a commercial fungicide product used to control Magnaporthe grisea or Pyricularia oryzae, also known as rice blast fungus, in transplanted and direct-seeded rice at 100 g/ha. Products containing tricyclazole fungicide can be applied as a flat drench, transplant root soak, foliar and aerial application, or seed treatment. One or two applications by one or more of these methods give a season-long control of the disease. The amount of Tricyclazole can be in the range of 1 % to 75 % w/w of the total composition.

In accordance with an exemplary embodiment of the present disclosure, the second triazole fungicide is Hexaconazole.

Hexaconazole [CAS NO: 79983-71-4] is the common name for (RS)- 2-(2, 4-dichlorophenyl)- l-(l//-l, 2, 4-triazol-l-yl) hexan-2-ol and possesses the following structure:

Hexaconazole is a broad- spectrum systemic triazole fungicide used commercially for the control of many fungi particularly Ascomycetes and Basidiomycetes, e.g. Podosphaera leucotricha and Venturia inaequalis on apples, Guignardia bidwellii and Uncinula necator on vines, Hemileia vastatrix of coffee and Cercospora spp. It is also used for control of diseases in various fruits and vegetables. The amount of Hexaconazole can be in the range of 1 % to 30 % w/w of the total composition.

In accordance with an exemplary embodiment of the present disclosure, the first triazole fungicide is Tricyclazole and the second triazole fungicide is Hexaconazole.

In accordance with an embodiment of the present disclosure, the strobilurin fungicide is selected from the group consisting of azoxystrobin, kresoxim-methyl, picoxystrobin, fluoxastrobin, oryzastrobin, dimoxystrobin, pyraclostrobin and trifloxystrobin.

In accordance with an exemplary embodiment of the present disclosure, the strobilurin fungicide is Picoxystrobin or Azoxystrobin. In accordance with an exemplary embodiment of the present disclosure, the strobilurin fungicide is Picoxystrobin.

Picoxystrobin [CAS NO. 117428-22-5] is the common name for Methyl (E) -3-methoxy-2- [2- [6- (trifluoromethyl) -2-pyridyloxymethyl] phenyl} acrylate and possesses the following structure

Picoxystrobin is fungicide belonging to the strobilurin group of chemicals. It is a preventative and curative fungicide with systemic and translaminar movement, acting by inhibition of mitochondrial respiration by blocking electron transfer at the Qo centre of cytochrome Bel. Picoxystrobin demonstrates outstanding breadth of spectrum in cereals, being highly active against Septoria diseases of wheat, Helminthosporium diseases on wheat, barley and oats, Rhynchosporium diseases on barley and rye, Ramularia diseases on barley, Puccinia rust diseases and strobilurin-sensitive powdery mildews on wheat, barley, oats and rye. Its broad spectrum of activity means that the green leaf area of the crop is maintained during the important grain filling period. The amount of Picoxystrobin can be in the range of 1 % to 50 % w/w of the total composition.

Of all strobilurins, Picoxystrobin is the most rapidly absorbed into plant tissue. In wheat and barley, 30-45% of the material applied to the foliar surface is absorbed into the cells of the leaf within 24 hours of application. This level of uptake confers excellent curative properties whilst maintaining material on the outside of the leaf to retain preventive benefits. The curative activity of picoxystrobin is the reason it is employed in early-season application in wheat and barley.

In accordance with an embodiment of the present disclosure, the synergistic fungicidal composition comprises Tricyclazole, Picoxystrobin, Hexaconazole and at least one agrochemically acceptable excipient in predetermined proportion with respect to each other.

In accordance with an embodiment of the present disclosure, the agrochemically acceptable excipient is selected from the group consisting of wetting agent, dispersing agent, disintegrating agent, binder, filler and/or diluent, polysaccharide polymeric material, defoamer, preservative and antifreeze agent.

In accordance with an embodiment of the present disclosure, the wetting agent can be selected from the group consisting of non-ionic surfactant, anionic surfactant and other wetting agents.

In accordance with an exemplary embodiment of the present disclosure, the non-ionic surfactant can be alcohol alkoxylates having moles of ethylene oxide in the range of 9 to 15.

In accordance with an exemplary embodiment of the present disclosure, the anionic surfactant can be selected from the group consisting of alkyl naphthalene sulfonate, dialkyl naphthalene sulfonates, alkyl naphthalene sulfonate condensate, sodium lauryl sulphate and sodium dodecyl benzene sulfonate.

In accordance with an exemplary embodiment of the present disclosure, the other wetting agents can be selected from the group consisting of alkyl ethylene oxide condensates, aryl ethylene oxide condensates, alkyl propylene oxide condensates, aryl propylene oxide condensates, alkylethoxylates, and arylethoxylates.

In a preferred embodiment of the present disclosure, the alkyl group and/or the aryl group in the wetting agent can be selected from the C₁-C₂₀ group.

In accordance with an embodiment of the present disclosure, the dispersing agent is selected from the group consisting of sodium lignosulfonate, calcium lignosulfonate, lignin sulphonate, naphthalenesulfonic acid-formaldehyde-polycondensate, sodium salt of alkyl naphthalene sulfonate, sulfonated aromatic polymer sodium salt, polycarboxylic acid homopolymer, sodium salt of polycarboxylic acid homopolymer, polcarboxylic acid copolymer, ethylene oxide/propylene oxide (EO/PO) block copolymers and sodium alt of polycarboxylic acid copolymer.

In accordance with an exemplary embodiment of the present disclosure, the alkyl group in the dispersing agent can be a C₁-C₂₀ alkyl group. In accordance with an exemplary embodiment of the present disclosure, the aromatic group in the sulfonated aromatic copolymer in the dispersing agent can be a CpC o aromatic group.

In accordance with an embodiment of the present disclosure, the disintegrating agent is selected from the group consisting of sodium chloride, sodium sulphate, ammonium sulphate, sodium carbonate, sodium bicarbonate, sodium tripolyphosphate (STPP).

In accordance with an embodiment of the present disclosure, the binder is selected from the group consisting of polyvinyl alcohol, polyvinyl-pyrrolidone or vinyl caprolactam either optionally substituted on the ring or in the vinyl group with lower alkyl ( to C₄ alkyl), or a mixture of these homopolymers, polyacrylamides.

In accordance with an embodiment of the present disclosure, 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, or salts.

In accordance with an embodiment of the present disclosure, the polysaccharide polymeric material is selected from the group consisting of xanthan gum, gum arabic, rhamsan gum, locust bean gum, carrageenan, welan gum, starch, carboxymethyl cellulose salt, sodium montmorillonite, polyethylene glycol, hexamethylpropylcellulose and bentonites; preferably, xanthan gum.

In accordance with an embodiment of the present disclosure, the defoamer can be selected from the group consisting of polydimethylsiloxane powder and polydimethylsiloxane liquid.

In accordance with an embodiment of the present disclosure, the preservative can be an isothiazolone mixture.

In accordance with an embodiment of the present disclosure, the antifreeze agent is selected from the group consisting of ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, polyethylene glycol. In accordance with an embodiment of the present disclosure, 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 accordance with an exemplary embodiment of the present disclosure, the synergistic fungicidal composition comprises:

a. a first triazole fungicide in an amount in the range of 1% to 75% by weight of the total mass of the composition;

b. a strobilurin fungicide in an amount in the range of 1% to 50% by weight of the total mass of the composition;

c. a second triazole fungicide in an amount in the range of 1% to 30% by weight of the total mass of the composition;

d. agrochemically acceptable excipient selected from the group consisting of wetting agent, dispersing agent, disintegrating agent, binder, filler and/or diluent, polysaccharide polymeric material, defoamer, preservative and antifreeze agent in an amount in the range of 10% to 70% by weight of the total mass of the composition.

d. agrochemically acceptable excipient comprising:

(i) a wetting agent in an amount in the range of 1% to 10% by weight of the total mass of the composition;

(ii) at least one dispersing agent in an amount in the range of 1 % to 30% by weight of the total mass of the composition;

(iii) a disintegrating agent in an amount in the range of 1% to 15% by weight of the total mass of the composition;

(iv) a film forming agent in an amount in the range of 1% to 5% by weight of the total mass of the composition; (v) a filler in an amount in the range of 1% to 40% by weight of the total mass of the composition; and

(vi) a defoamer in an amount in the range of 0.2% to 3% by weight of the total mass of the composition.

a. Tricyclazole in an amount in the range of 1% to 75% by weight of the total mass of the composition;

b. Picoxystrobin in an amount in the range of 1% to 50% by weight of the total mass of the composition;

c. Hexaconazole in an amount in the range of 1 % to 30% by weight of the total mass of the composition;

d. at least one agrochemically acceptable excipient in an amount in the range of 10% to 70% by weight of the total mass of the composition.

In accordance with an embodiment of the present disclosure, the synergistic fungicidal composition can be in at least one dosage form selected from the group consisting of wettable powder, water dispersible granules, suspension concentrate, granules, dusts, soluble liquid concentrate, oil-in-water emulsion, water-in-oil emulsion, oil dispersion, ZC formulation, emulsifiable concentrate, suspoemulsion and capsule suspension.

The synergistic fungicidal composition of the present invention may be sold as a pre-mix composition or a kit of parts such that individual actives may be mixed before spraying.

In accordance with an embodiment of the present disclosure, the constituents of the synergistic fungicidal composition may be tank mixed and sprayed at the locus of the infection or alternatively, be mixed with surfactants and then sprayed.

In accordance with an embodiment of the present disclosure, the synergistic fungicidal composition of the present disclosure may be used for foliar application, ground applications or applications to plant propagation materials such as seeds. In accordance with a second aspect of the present disclosure, there is provided a process for preparation of a synergistic fungicidal composition.

In accordance with an embodiment of the present disclosure, the process for preparation of a synergistic fungicidal composition comprises the following steps:

a. pulverizing, separately, predetermined quantities of a first triazole fungicide, a strobilurin fungicide and a second triazole fungicide to obtain a substantially homogenized powder of each;

b. blending predetermined quantities of each of the substantially homogenized powders, a wetting agent, a dispersing agent, a disintegrating agent, a filler and a defoamer to obtain a substantially homogenized mixture;

c. adding a predetermined quantity of water to a predetermined quantity of the substantially homogenized mixture and kneading to obtain a dough;

d. extruding the dough to obtain wet extruded granules;

e. drying the wet extruded granules under controlled drying conditions and at a temperature within a predetermined range to obtain dried extruded granules; and

f. sieving the dried extruded granules to obtain granules having granule size within a predetermined range.

a. blending predetermined quantities of a first triazole fungicide, a strobilurin fungicide, a second triazole fungicide, a wetting agent, a dispersing agent, a disintegrating agent, a filler and a defoamer to obtain a first substantially homogenized mixture;

b. pounding the first substantially homogenized mixture to obtain a second substantially homogenized mixture having a predetermined particle size;

c. adding a predetermined quantity of water to a predetermined quantity of the second substantially homogenized mixture and kneading to obtain a dough;

d. extruding the dough to obtain wet extruded granules;

f. sieving the dried extruded granules to obtain granules having granule size within a predetermined range. In accordance with an embodiment of the present disclosure, the process for preparation of a synergistic fungicidal composition comprises the following steps:

a. pounding or grinding predetermined quantities of at least one triazole fungicide along with a strobilurin fungicide to obtain a powder;

b. blending the powder with water, dispersing agents, wetting agents, binders, defoamers, disintegrating agents and carriers to obtain a slurry having a predetermined proportion of total solids;

c. spray drying the slurry to obtain dried granules; and

d. sieving the dried granules to obtain granules having granule size of a predetermined range.

In accordance with an exemplary embodiment of the present disclosure, the particle size of the substantially homogenized powder is in the rage of 2 pm to 9 pm.

In accordance with an exemplary embodiment of the present disclosure, the wet extruded granules are dried at a temperature in the range of 35 °C to 65 °C.

In accordance with an exemplary embodiment of the present disclosure, the dried extruded granules are sieved to obtained granules having granule size in the range of 0.5 mm to 2.5 mm.

In accordance with an exemplary embodiment of the present disclosure, the slurry has total solids in the range of 50% to 65% by weight.

In accordance with an exemplary embodiment of the present disclosure, the dried granules are sieved to obtain granules having granule size in the range of 100 pm to 850 pm.

In accordance with a third aspect of the present disclosure, there is provided a method of controlling and eliminating fungal diseases from plants, said method comprising applying to a plant susceptible to attack by fungi, an effective amount of the synergistic fungicidal composition of the present disclosure.

The synergistic fungicidal composition of the present disclosure can be applied before or after infection of the plants or the propagation materials thereof by fungi. The synergistic fungicidal composition of the present disclosure may be applied to the soil before emergence of the plants, either pre -planting or post-planting or as a foliar spray at different stages of crop development, with either one or two applications early or late post emergence.

The fungicidal composition of the present disclosure has enhanced fungicidal activity and combats resistance shown by the fungi.

EXAMPLES

Example Tl: Tricvclazole 18% + Picoxystrobin 10% + Hexaconazole 4.5% WG:

52g Hexaconazole technical, l06g Picoxystrobin technical, l95g Tricyclazole technical, 20g sodium lauryl sulphate, 80g naphthalenesulfonic acid-formaldehyde-polycondensate, 70g kraft lignin sulphonate, lOOg ammonium sulphate, 20g film forming agent, 342g filler and l5g defoamer are blended in the ribbon blender for 2 hours to obtain substantially homogenized mixture A. Mixture A was ground in the Jet Mill to obtain Mixture B, a Wettable Powder, having particle size in the range of 2 to 9pm.

The wettable powder was charged into a dough maker by adding l70g of water and blended to obtain dough. The dough was extruded using a basket extruder to obtain granules having granule size in the range of 0.8 mm to 1.5 mm, which was further dried in fluid bed dryer at 45 °C to obtain a product of the final composition.

Example T2: Tricvclazole 20.5% + Picoxystrobin 12.5% + Hexaconazole 4% WG:

47g Hexaconazole technical, l33g Picoxystrobin technical, 22lg Tricyclazole technical, 20g sodium lauryl sulphate, 80g naphthalenesulfonic acid-formaldehyde-polycondensate, 70g kraft lignin sulphonate, lOOg ammonium sulphate, 20g film forming agent, 294g filler and l5g defoamer are blended in the ribbon blender for 2 hours to obtain substantially homogenized mixture A. Mixture A was ground in the Jet Mill to obtain a Wettable Powder, having particle size in the range of 2 to 9pm.

The wettable powder was charged into a dough maker by adding l72g of water and blended to obtain dough. The dough was extruded using a basket extruder to obtain granules having granule size in the range of 0.8 mm to 1.5 mm, which was further dried in fluid bed dryer at 45 °C to obtain a product of the final composition.

Example T3: Tricvclazole 22% + Picoxystrobin 14.5% + Hexaconazole 3.5% WG:

4l.5g Hexaconazole technical, l54g Picoxystrobin technical, 239g Tricyclazole technical, 20g sodium lauryl sulphate, 80g naphthalenesulfonic acid-formaldehyde- polycondensate, 70g kraft lignin sulphonate, lOOg ammonium sulphate, 20g film forming agent, 260.5g filler and l5g defoamer are blended in the ribbon blender for 2 hours to obtain substantially homogenized mixture A. Mixture A was ground in the Jet Mill to obtain a Wettable Powder, having particle size in the range of 2 to 9pm microns.

The wettable powder was charged into a dough maker by adding l75g of water and blended to obtain dough. The dough was extruded using a basket extruder to obtain granules having granule size in the range of 0.8 mm to 1.5 mm, which was further dried in fluid bed dryer at 45 °C to obtain a product of the final composition.

Example T4: Tricvclazole 35% + Picoxystrobin 15% + Hexaconazole 6.5% WG:

75g Hexaconazole technical, l60g Picoxystrobin technical, 377g Tricyclazole technical, 20g sodium lauryl sulphate, 80g naphthalenesulfonic acid-formaldehyde-polycondensate, 70g kraft lignin sulphonate, lOOg ammonium sulphate, 20g film forming agent, 83g filler and l5g defoamer are blended in the ribbon blender for 2 hours to obtain substantially homogenized mixture A. Mixture A was ground in the Jet Mill to obtain a Wettable Powder, having particle size in the range of 2 to 9 pm.

The wettable powder was charged into a dough maker by adding l80g of water and blended to obtain dough. The dough was extruded using a basket extruder to obtain granules having granule size in the range of 0.8 mm to 1.5 mm, which was further dried in fluid bed dryer at 45 °C to obtain a product of the final composition.

Example 5: Tricvclazole 20.5% + Picoxystrobin 12.5% + Hexaconazole 4% SC:

47g Hexaconazole, l33g Picoxystrobin and 22 lg Tricyclazole were admixed to form a mixture of actives. To this, 31 lg of water along with tristrylphenol ethoxylate 20g, sodium lingo sulphonate lOg, propylene glycol 75g as an anti-freezing agent, Defoamer 5g were added in Repulp tank fitted with homogenizer manufactured by Remi Motors Ltd. The homogenizer was operated at 3000 rpm for 35 minutes to obtain slurry. The obtained slurry was then passed through bead mill using 0.8mm beads with a bead loading of 80-85% until a particle size of below 3 pm was achieved. Particle size was analyzed by Malvern particle size analyzer. The finely milled slurry was pumped to mix blend tank where Defoamer 5g, preservative 3g and Thickener solution l70g were added. The mixture in the mix blend tank 5 was operated at 3000 rpm for 100 minutes to obtain homogeneous slurry.

Example 6: Tricvclazole 35% + Picoxystrobin 15% + Hexaconazole 6.5% WP:

75g Hexaconazole technical was pulverized at a feed rate of 10 to 30 g/min. to obtain pulverized Hexaconazole technical having particle size in the range of 1 to 8pm.l60g 10 Picoxystrobin technical was pulverized in a jet mill at a feed rate of 10 to 30 g/min to obtain pulverized picoxystrobin having particle size in the range of 1 to lOpm. 377g Tricyclazole technical was pulverized in a jet mill at a feed rate of 10 to 20 g/min to obtain pulverized tricyclazole having particle size in the range of 1 to 7pm. Pulverized Hexaconazole, Picoxystrobin and tricyclazole were admixed along with 20g sodium lauryl sulphate, 50g 15 naphthalenesulfonic acid-formaldehyde -polycondensate, 30g Kraft lignin sulphonate, 50g precipitated silica, 237g filler and lg defoamer in a ribbon blender and blended for 2 hours at 20 rpm to obtain homogeneous wet table powder formulation.

EXPERIMENTS

20

1. STORAGE STABILITY

The synergistic fungicidal compositions as formulated in Examples 1 to 4 were characterized to determine their storage stability.

25 The water dispersible granules were characterized for active content parameter to see drop. The parameters were determined before and after aging at 54±2°C for 14 days. The results obtained are provided herein below in the form of Table 1.

Table 1 illustrates the storage stability of the synergistic fungicidal composition

*BA: Before aging, AA: After aging

As illustrated in Table 1, the synergistic fungicidal compositions are stable on storage and there is no significant degradation of the active ingredients after 14 days.

2. CHARACTERIZATION OF SUSPENSION CONCENTRATE

The suspension concentrate was characterized for parameters such as active content and suspensibility of the synergistic fungicidal composition as formulated in Example 5. The parameters were determined before and after aging at 54±2°C for 14 days. The results obtained are provided herein below in the form of Table 2. Table 2: Characterization of suspension concentrate

As illustrated in Table 2, the suspension concentrate does not show significant change in active content and suspensibility after a period of 14 days. 3. CHARACTERIZATION OF WETTABLE POWDER

The wettable powder was characterized for parameters such as active content, suspensibility and wetting out time of the synergistic fungicidal composition as formulated in Example 6. The parameters were determined before and after aging at 54±2°C for 14 days. The results obtained are provided herein below in the form of Table 3.

Table 3: Characterization of Wettable Powder

As illustrated in Table 3, the wettable powder does not show a significant change in active content, suspensibility and wetting out time after a period of 14 days.

4. EVALUATION OF FUNGICIDE COMBINATIONS FOR BIO-EFFICACY AGAINST SHEATH BLIGHT. BROWN SPOT AND BLAST DISEASES OF PADDY

The synergistic fungicidal compositions of the present disclosure, prepared in accordance with Examples 1 to 4, were tested at given concentrations with two way possible tank mix combinations i.e., Tricyclazole 75% WP + Picoxystrobin (Tank Mix), Hexaconazole 5%SC + Picoxystrobin 22.72% SC (Tank Mix) & Tricyclazole 75% WP +Hexaconazole 5% SC (Tank mix) along with solo individual fungicides i.e., Picoxystrobin 22.72% SC, Tricyclazole 75% WP & Hexaconazole 5% SC and Untreated Control against Sheath Blight, Blast and Brown spot of Paddy. The fungicides were applied as foliar spray with Knapsack Sprayer fitted with solid cone nozzle. Application was initiated with initiation of disease in the field. The sprayings were done at 15 days interval.

The appearance of the visible symptom of the diseases was recorded before I^st spray and subsequent observations were recorded after 5, 10 & 15 days of each spray. For recording the observations ten hills from each plot were graded on (0-9) disease scoring scale for Sheath Blight, Brown spot and Blast.

Disease Ratings:

Scale (Grade) Percent disease Intensity reaction

0 No disease = Immune

1 1 - 5 % infection Mild 3 6 - 10 % infection Moderate

5 11 - 25 % infection = Alarming

7 26 - 50 % infection = Severe

9 >50 % infection = highly severe

Percent disease index (PDI) was calculated using the following formula:

Sum of all numerical ratings

5 PDI = - X 100

Total plants observed X Maximum rating scale

The PDI values were transformed by angular transformation and analyzed statistically. The disease control DC (%) was calculated by the following formula.

Disease % in control - Disease % in treatment

DC (%) X 100

Disease % in control

15 Table 4: Bio-efficacv of different Fungicides treatments against Sheath blight of Paddy

The results presented in Table 4 show that at the time of initiation of trial there was no Sheath blight disease in any treatment which indicates the uniformity of trial plot across all the treatments. At 15 days after application, the highest Sheath blight was recorded in control 5 (6.67%). All the fungicide treatments significantly reduced the disease severity than untreated control, but the significant lowest Sheath blight disease was observed in T1 to T4 (0.00%).

At 15 days after second application, the highest disease was recorded in control (10.67%). The significant lowest Sheath blight disease was observed in T4 (0.67%) which was at par 10 with two way combinations & significantly superior over rest of the treatments. At 15 days after third application also similar trend observed as of after second application.

Where, the significant lowest Sheath blight disease was observed in T4 (1.34%) which was significantly superior over rest of all treatments.

5 The highest percent disease control (PDC) was recorded in treatment T4 (89.95%), followed by T2 (59.98%), T3 & T10 (55.02%). The lowest disease control was recorded in treatment T5 (14.99%), followed by T7 (35.00%) and T9 (40.02%).

Table 5: Bio-efficacv of different Fungicides treatments against Brown spot of Paddy

The results presented in Table 5 show that at the time of initiation of trial the Brown spot was not initiated. At 15 days after first application, the highest disease was recorded in control (2.67%). The significant lowest disease was observed in rest of the treatments (T2 to T10) 5 and they are significantly superior over untreated control.

At 15 days after second application, there was no disease progress observed in treatments T4. The highest disease was recorded in control (3.34%). The significant lowest disease was observed in and T9 (0.67%) and T3, T7, T8, T10 (1.34%), which were on par with rest of the 10 treatments.

At 15 days after third application, the significant lowest disease was observed in treatment T4 (0.67%), which was significantly superior over rest of all treatments.

15 The highest percent disease control (PDC) was recorded in treatment T4 (90.87%) followed by T3, T7, T9 (63.62%), T10 (72.75%), T2, T6 (45.50%). The lowest disease control was recorded in treatment T1 (18.25%).

Table 6: Bio-efficacv of different Fungicides treatments against Blast of Paddy

The results presented in Table 6 show that at the time of initiation of trial the leaf blast was not observed when initiated. At 15 days after first application, the highest disease was recorded in control (2.67%). The significant lowest disease was observed in T1-T4 (0.00%)

5 and T8-T9 (0.00%), which was at par with all the treatments and superior over untreated control.

At 15 days after second application, there was no disease progress observed in treatments T2 to T5. The highest disease was recorded in control (4.67%). The significant lowest disease

10 was observed in T2-T5 (0.00%) and T8-T9 (0.00%), which were at par with T6 (1.34%), T7 (0.67%), and T10 (0.1.34%).

At 15 days after third application also similar trend observed. The significant lowest disease was observed in treatment T4 (0.67%), which was at par with T5, T3, T7, T8 & T9 (0.67%)

15 followed by T7 (1.34%). The highest disease was observed in untreated control (7.34%).

These treatments (T4) were significantly superior over rest of all treatments.

The Neck blast of paddy was recorded after complete panicle emergence and recorded percent disease incidence as T4 (0.67%) which was significantly superior over rest of the

20 treatments and untreated control recorded (17.34%) disease incidence.

The highest percent disease control (PDC) was recorded in treatment T4 (96.13%) followed by T2 (80.73%), T8 (76.93%). The lowest disease control was recorded in treatment T6 (11.53%) followed by T7 (26.93%).

25

5. TO STUDY THE EFFECT OF THE TEST FUNGICIDES ON THE YIELD OF PADDY

Individual plot wise yield was recorded and calculated treatment wise yield and converted

30 into yield per hectare (q/ha) at harvest and statistically analyzed the data. Table 7: Effect of different Fungicides treatments on Yield of Paddy

As illustrated in Table 7, all the treatments significantly increase the yield than Untreated 5 Control (28.8 q/ha). The highest yield was observed in treatment T4 (39.87 q/ha), which was significantly superior over all treatment with T3 (36.60 q/ha), T2 (35.80 q/ha) followed by T10 (34.10 q/ha) and T9 (33.90 q/ha). All test fungicide treatments (Tl to T4) were significantly superior over solo fungicide treatments (T5 to T7) and two way tank mix combination treatments (T8 to T10).

10 6. TO STUDY THE PHYTOTOXICITY EFFECT OF TEST FUNGICIDES ON

PADDY

Observations were taken on damage caused to plants, if any, by the application of different treatments taking into the account phytotoxic symptoms viz. leaf injury on tips and leaf 5 surface, wilting, vein clearing, necrosis, epinasty and hyponasty on ten plants per plot. The observations were recorded before spray and 1, 3, 5, 7, 10 & 15* day after applications. For Phytotoxicity study on leaf injury on tips and leaf surface the Scale (0-10) used is given below.

10 Phytotoxicity Rating Scale (PRS)

Crop response/ Crop injury Rating

(MX) 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 8: Phyto-toxicity effect of different Fungicide treatments on Paddy

For phototoxic symptoms- Leaf injury on tips and Leaf surface, Wilting, Vein Clearing,

Necrosis, Epinasty and Hyponasty

As illustrated in Table 8, the three fungicide ready combinations were sprayed at doses X (1000 g/ha) and 2X (2000 g/ha) to check the phytotoxic effects like leaf injury on tips/surface, vein clearing, wilting, necrosis, hyponasty and epinasty on the Paddy crop. The observations on these phytotoxicity parameters were observed on before spray and at 1, 3, 5, 7, 10 and 15 days after application. But there was no any phytotoxicity observed on Paddy crop after spraying in any treatment. Even there was no any adverse effect noticed on Paddy crop in the field applied with fungicides combinations at highest dose of @2000 g/ha.

Overall, the three way combination test fungicides shows synergistic effect for controlling the diseases. Also for prolong the effectiveness of fungicides liable to encounter resistance problems and to limit crop losses, the test fungicides can be used effectively and safely for the management of diseases than solo Tricyclazole 75% WP, Picoxystrobin 22.72% SC and Hexaconazole 5% SC and their two way possible tank mix combinations. TECHNICAL ADVANCEMENTS

The present disclosure described herein above has several technical advantages including, but not limited to, the realization of a synergistic fungicidal composition which has enhanced fungicidal activity and combats resistance shown by fungi. The present disclosure further provides an easy and simple process for the preparation of the synergistic fungicidal composition.

The numerical values given for various physical parameters, dimensions, and quantities are only approximate values and it is envisaged that the values higher than the numerical value assigned to the physical parameters, dimensions and quantities fall within the scope of the invention unless there is a statement in the specification to the contrary.

While considerable emphasis has been placed herein on the specific features of the preferred embodiment, it will be appreciated that many additional features can be added and that many changes can be made in the preferred embodiment without departing from the principles of the disclosure. These and other changes in the preferred embodiment of the disclosure will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation.

Claims

CLAIMS:

1. A synergistic fungicidal composition comprising:

c. a second triazole fungicide in an amount in the range of 1% to 30% by weight of the total mass of the composition; and

2. The synergistic fungicidal composition as claimed in claim 1, wherein the first triazole fungicide and the second triazole fungicide are selected from the group consisting of azaconazole, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-m, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, tricyclazole, triticonazole, triadimefon, triadimenol, oxpoconazole and uniconazole.

3. The synergistic fungicidal composition as claimed in claim 2, wherein the first triazole fungicide is Tricyclazole.

4. The synergistic fungicidal composition as claimed in claim 2, wherein the second triazole fungicide is Hexaconazole.

5. The synergistic fungicidal composition as claimed in claim 1, wherein the strobilurin fungicide is selected from the group consisting of azoxystrobin, kresoxim-methyl, picoxystrobin, fluoxastrobin, oryzastrobin, dimoxystrobin, pyraclostrobin and trifloxystrobin.

6. The synergistic fungicidal composition as claimed in claim 5, wherein the strobilurin fungicide is Picoxystrobin or Azoxystrobin.

7. The synergistic fungicidal composition as claimed in claim 1, wherein the agrochemically acceptable excipients are selected from the group consisting of wetting agent, dispersing agent, disintegrating agent, binder, filler and/or diluent, polysaccharide polymeric material, defoamer, preservative and antifreeze agent.

8. The synergistic fungicidal composition as claimed in claim 1, wherein said composition comprises:

9. The synergistic fungicidal composition as claimed in claim 1, wherein said composition comprises:

d. agrochemically acceptable excipient comprising:

(ii) at least one dispersing agent in an amount in the range of 1% to 30% by weight of the total mass of the composition;

(iii) a disintegrating agent in an amount in the range of 1% to 15% by weight of the total mass of the composition; (iv) a film forming agent in an amount in the range of 1% to 5% by weight of the total mass of the composition;

(v) a filler in an amount in the range of 1% to 40% by weight of the total mass of the composition; and

10. The synergistic fungicidal composition as claimed in claim 1, wherein said composition comprises:

11. The synergistic fungicidal composition as claimed in claim 1 , wherein said composition is formulated as at least one dosage form selected from the group consisting of wettable powder, water dispersible granules, suspension concentrate, granules, dusts, soluble liquid concentrate, oil-in-water emulsion, water-in-oil emulsion, oil dispersion, ZC formulation, emulsifiable concentrate, suspoemulsion and capsule suspension.

12. The synergistic fungicidal composition as claimed in claim 1, wherein said composition is a tank-mix

13. A process for preparation of a synergistic fungicidal composition, said process comprising:

a. blending predetermined quantities of a first triazole fungicide, a strobilurin fungicide, a second triazole fungicide, a wetting agent, a dispersing agent, a disintegrating agent, a filler and a defoamer to obtain a first substantially homogenized mixture; b. pounding the first substantially homogenized mixture to obtain a second substantially homogenized mixture having a predetermined particle size;

d. extruding the dough to obtain wet extruded granules;

14. A process for the preparation of a synergistic fungicidal composition; said process comprising:

c. spray drying the slurry to obtain dried granules; and

15. A method of controlling and eliminating fungal disease from plants, said method comprising applying to a plant susceptible to attack by fungi, an effective amount of the synergistic fungicidal composition as claimed in claims 1 to 12.