TERNARY FUNGICIDAL COMPOSITION AND A PROCESS FORPREPARATION THEREOF

FIELD OF THE INVENTION

[001] The invention relates to fungicidal compositions, more particularly to synergistic ternary fungicidal compositions.

BACKGROUND OF THE INVENTION

[002] Agriculture is a sector where external factors influence quantity and quality of produce. One such external factor that greatly influences the produce is the infestation of the crops by unwanted pests or insects or fungi. To combat this situation, globally the agriculture industry follows the golden triangle of using fertilizers, biocides and genetically engineered crops for preventing/controlling the menace of pests/insects/fungi and thereby achieving higher yields by reducing/eliminating yield losses. The current agriculture practice heavily depends on the use of biocides. The biocides are commonly applied to plants, as liquid or solid compositions. This practice has gained a high degree of commercial success because it has been shown that such control can increase crop yield. Over the past decade, the use of biocides has increased significantly.

[003] However, excessive use of this approach has pushed the crops to be more prone to these infections as the new crops lost their natural resistance and the pests/insects gaining resistance to the biocides. Due to this resistance there is a remarkable decrease in the crop yield. Pest/insect species evolve resistance to pesticides/insecticides via natural selection: the most resistant specimens survive and pass on their genetic traits to their offspring. Such a resistance is increasing globally and thus invariably reduces the crop yield.

[004] Therefore, effective use of biocides, require sound management, in view of the increasing insects/pests resistance, environmental hazards and worker exposure concerns. Thus, there is a need to increase the efficacy of the biocides by broadening their spectrum, for effectively controlling the growth of different pests or insects simultaneously. Single active ingredient compositions rarely meet such broad- spectrum requirements. Hence, compositions comprising two or more actives are required. Moreover, such compositions comprising two or more actives have several additional advantages such as elimination of tank mixing prior to use; reduction in inventory products; saving in time and money; and a reduction in the number of times the crop is sprayed with the insecticide/pesticide. Often this problem, of multiple spraying of a crop, goes unnoticed and results in inconsistent application of both the different actives, thereby obtaining variable results and yields.

[005] Combinations containing different actives have been practiced in the art, but problems with the physical stability of such combinations have caused issues with respect to the application and efficacy in many cases. Therefore, there exists a need for novel combination products involving biocides and having synergistic effect which can be extensively applicable in the field of agriculture for controlling wide spectra of fungi and which also exhibits good physical and chemical stability.

[006] In view of this, there is a need to develop novel combination products involving biocides and having synergistic effect which can be extensively applied in the field of agriculture for controlling wide spectra of fungi and which also exhibits good physical and chemical stability. SUMMARY OF THE INVENTION

[007] In one aspect, the present invention provides a synergistic fungicidal composition comprising: a. a dithiocarbamate fungicide in an amount in the range of 1% to 99% by weight of the total mass of the composition; b. at least two conazole fungicides in an amount in the range of 1% to 99% by weight of the total mass of the composition; and c. at least one agrochemically acceptable excipient in an amount in the range of 0.1% to 90% by weight of the total mass of the composition.

[008] In another aspect, the present invention provides a method for controlling fungi comprising the steps of applying the synergistic fungicidal composition to the fungi and/or their habitat.

[009] In still another aspect, the present invention provides for the use of the synergistic fungicidal composition for controlling fungi.

DETAILED DESCRIPTION OF THE INVENTION

[010] The present invention is directed towards a fungicidal composition and a process for preparation thereof. Further, use of this synergistic composition reduces the number of applications of various individual fertilizers components thus providing a cost-effective solution and overcomes the pesticidal/insecticidal resistance created for the individual component.

[Oi l] In one aspect of the present invention, the synergistic fungicidal composition comprises: a. a dithiocarbamate fungicide in an amount in the range of 1% to 99% by weight of the total mass of the composition; b. at least two conazole fungicides in an amount in the range of 1% to 99% by weight of the total mass of the composition; and c. at least one agrochemically acceptable excipient in an amount in the range of 0.1% to 90% by weight of the total mass of the composition.

[012] In an exemplary embodiment of the present invention, the synergistic fungicidal composition comprises a dithiocarbamate fungicide, a first conazole fungicide, a second conazole fungicide and at least one agrochemically acceptable excipient.

[013] In an embodiment, the at least two conazole fungicide is selected from the group comprising of climbazole, clotrimazole, imazalil, oxpoconazole, prochloraz, triflumizole, viniconazole, azaconazole, bitertanol, bromuconazole, cyproconazole, dif enoconazole, diniconazole, diniconazole M, epoxiconazole, etaconazole, fenbuconazole, fluoxytioconazole, fluquinconazole, flusilazole, flutriafol, furconazole, hexaconazole, imibenconazole, ipconazole, ipfentrifluconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazol, quinconazole simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole and uniconazole P. Preferably, the first conazole is difenoconazole and the second conazole is cyproconazole or prothioconazole.In another embodiment, the dithiocarbamate fungicide is selected from the group comprising of amobam, asomate, azithiram, carbamorph, cufraneb, cuprobam, disulfiram, ferbam, manam, metam, nabam, tecoram, thiram, urbacide, ziram, dazomet, etem, milneb, mancopper, mancozeb, maneb, metiram, polycarbamate, propineb and zineb. Preferably, the dithiocarbamate is mancozeb.

[014] In an exemplary embodiment of the present invention, the dithiocarbamate fungicide is present in an amount in the range of 1% to 85% by weight of the total mass of the composition. In one embodiment, the dithiocarbamate is present in an amount in between 1 wt.% to 65 wt.% based on the total weight of the composition. [015] In an exemplary embodiment of the present invention, the first conazole is present in an amount in the range of 1% to 85% by weight of the total mass of the composition. In one embodiment, the first conazole is present in an amount in between 1 wt.% to 65 wt.% based on the total weight of the composition.

[016] In an exemplary embodiment of the present invention, the second conazole is present in an amount in the range of 1% to 85% by weight of the total mass of the composition. In one embodiment, the second conazole is present in an amount in between 1 wt.% to 65 wt.% based on the total weight of the composition.

[017] In an exemplary embodiment of the present invention, the agrochemically acceptable excipient is present in an amount in the range of 0.1% to 90% by weight of the total mass of the composition. In one embodiment, the agrochemically acceptable excipient is present in an amount in between 0.1 wt.% to 80 wt.% based on the total weight of the composition.

[018] In an embodiment of the present invention, the synergistic fungicidal composition comprises Mancozeb, Dif enoconazole, Cyproconazole and at least one agrochemically acceptable excipient in predetermined ratio.

[019] In an embodiment of the present invention, the synergistic fungicidal composition comprises Mancozeb, Difenoconazole, Prothioconazole and at least one agrochemically acceptable excipient in predetermined ratio.

[020] In an exemplary embodiment of the present invention, the composition is a ternary fungicidal composition comprising Mancozeb in the range of 1 to 99 wt%, Difenoconazole in the range of 1 to 99 wt %, Cyproconazole Prothioconazole in the range of 1 to 99 wt % and agrochemically acceptable excipient in the range of 0.1 to 90 wt %.

[021] The agrochemically acceptable excipient in the composition of the present invention can be at least one selected from the group comprising of, but not limited to, dispersing agent, wetting agent, anti-caking agent, thickener, preservative, diluent, stabilizer, defoamer, anti- freezing agent, and anti-penetrating agent and/or mixtures thereof. The agrochemically acceptable excipients in a pre-determined ratio aids to improving the physical stability and also prevents the degradation of the fungicidal compounds leading to long term stability and spectrum activity.

[022] In an embodiment of the present invention the dispersing agent can be selected from the group comprising of EO/PO block copolymers, acrylic graft copolymers, polyoxyethylene octyl phenol ether sulfates, graft co-polymer base dispersing agent, phenol polyoxyethylene aryl sulfonate succinate, polycarboxylates, lignin sulfonates, alkaline earth metal and ammonium salts of aromatic sulfonic acids, alkyl naphthalene sulfonate, bis (alkyl) naphthalene sulfonate formaldehyde condensates, naphthalene sulfonic acid formaldehyde condensates, such as lignin sulfonic acid polyoxyethylene alkyl phenol formaldehyde condensate ethyl sulfates, alkylbenzene calcium sulfonate, alkylbenzene sulfonate, naphthalene sulfonate formaldehyde condensates sodium salts, polyoxyethylene alkylphenol ethyl, ethyl polyoxyethylene fatty amine, polyoxyethylene fatty acid esters and polyoxyethylene esters of ethylene-ethyl.

[023] In an exemplary embodiment of the present invention, the dispersing agent is present in an amount in the range of 0.1% to 50% by weight of the total mass of the composition. In one embodiment, the dispersing agent is present in an amount in between 0.1 wt.% to 20 wt.% based on the total weight of the composition

[024] In an embodiment of the present invention the wetting agent can be selected from the group comprising of fatty alcohol sulfates salts of aliphatic monoesters of sulphuric acid including sodium lauryl sulphate, sulfoakylamides and salts thereof, N - methyl - N - oleyl taurate Na salt, akylarylsulfonates, akylbenzene sulfonates, akylnaphthalene sulfonates and salts thereof and salts of ligninsulfonic acid, aryl sulfonates (such as sodium dodecylbenzene sulfonate, sodium alkylnaphthalene sulfonate), calcium alkylbenzene sulfonate, castor oil ethoxylates, alkyl sulfates, alkyl polyoxyethylene alcohol ether sulfate, polyoxyethylene alkyl phenol ether sulfate, polyoxyethylene alkyl phenol ether formaldehyde condensate sulfates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates succinic, single polyoxyethylene alkylphenyl ether sodium succinate, ethylene oxide adducts of fatty alcohol sulfonates and alkylphenol formalin condensates of ethylene oxide adduct sulfonates.

[025] In an exemplary embodiment of the present invention, the wetting agent is present in an amount in the range of 0.1% to 50% by weight of the total mass of the composition. In one embodiment, the wetting agent is present in an amount in between 0.1 wt.% to 20 wt.% based on the total weight of the composition.

[026] In an embodiment of the present invention the anti-caking agent can be selected from the group comprising of silica or clay or talc or silicates.

[027] In an exemplary embodiment of the present invention, the anti-caking agent is present in an amount in the range of 0.1% to 50% by weight of the total mass of the composition. In one embodiment, the anti-caking agent is present in an amount in between 0.1 wt.% to 20 wt.% based on the total weight of the composition.

[028] In an embodiment of the present invention the anti-penetrating agent can be selected from the group comprising of methyl oleate, oleic acid methyl ester, or methyl soyate.

[029] In an exemplary embodiment of the present invention, the anti-penetrating agent is present in an amount in the range of 0.1% to 50% by weight of the total mass of the composition. In one embodiment, the anti-penetrating agent is present in an amount in between 0.1 wt.% to 20 wt.% based on the total weight of the composition.

[030] In an embodiment of the present invention the thickener can be selected from the group comprising of xanthan gum, carboxy methyl cellulose, Hydroxy propyl methyl cellulose.

[031] In an exemplary embodiment of the present invention, the thickener is present in an amount in the range of 0.1% to 50% by weight of the total mass of the composition. In one embodiment, the thickener is present in an amount in between 0.1 wt.% to 20 wt.% based on the total weight of the composition.

[032] In an embodiment of the present invention, the stabilizer can be selected from the group comprising of phosphoric acid monoesters, phosphoric acid diesters, phosphoric acid mono- and di-ester mixture, sodium phosphates, Hexamethylene tetramine, sodium metabisulfite, butylated hydroxytoluene, castor oil ethoxylate, ethoxylated hydrogenated castor oil, vegetable oil and epoxidized soyabean oil or combinations thereof.

[033] In an exemplary embodiment of the present invention, the stabilizer is present in an amount in the range of 0.1% to 50% by weight of the total mass of the composition. In one embodiment, the stabilizer is present in an amount in between 0.1 wt.% to 20 wt.% based on the total weight of the composition.

[034] In an embodiment of the present invention the defoamer can be selected from the group comprising of polydimethylsiloxane powder and polydimethylsiloxane liquid, Silicon base antifoam.

[035] In an exemplary embodiment of the present invention, the defoamer is present in an amount in the range of 0.1% to 50% by weight of the total mass of the composition. In one embodiment, the defoamer is present in an amount in between 0.1 wt.% to 20 wt.% based on the total weight of the composition.

[036] In an embodiment of the present invention the preservative can be isothiazolinone, isothiazolinone mixture, benzisothiazolinone or combination thereof.

[037] In an exemplary embodiment of the present invention, the preservative is present in an amount in the range of 0.1% to 50% by weight of the total mass of the composition. In one embodiment, the preservative is present in an amount in between 0.1 wt.% to 20 wt.% based on the total weight of the composition. [038] In an embodiment of the present invention the anti-freeze agent can be selected from the group comprising of ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, polyethylene glycol.

[039] In an exemplary embodiment of the present invention, the anti-freezing agent is present in an amount in the range of 0.1% to 50% by weight of the total mass of the composition. In one embodiment, the anti-freezing is present in an amount in between 0.1 wt.% to 20 wt.% based on the total weight of the composition.

[040] In an embodiment of the present invention the 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 comprising of deionized water and distilled water.

[041] In an exemplary embodiment of the present invention, the synergistic fungicidal composition comprises: a dithiocarbamate fungicide in an amount in the range of 1% to 99% by weight of the total mass of the composition; a first conazole fungicide in an amount in the range of 1% to 99% by weight of the total mass of the composition; a second conazole fungicide in an amount in the range of 1% to 99% by weight of the total mass of the composition; and at least one agrochemically acceptable excipient in an amount in the range of 0.1% to 90% by weight of the total mass of the composition.

[042] In an exemplary embodiment of the present invention, the synergistic fungicidal composition comprises: a dithiocarbamate fungicide in an amount in the range of 1% to 85% by weight of the total mass of the composition; a first conazole fungicide in an amount in the range of 1% to 85% by weight of the total mass of the composition; a second conazole fungicide in an amount in the range of 1% to 85% by weight of the total mass of the composition; and at least one agrochemically acceptable excipient selected from the group comprising of dispersing agent, wetting agent, anticaking agent, thickener, preservative, diluent, stabilizer, defoamer, anti-freezing agent, and antipenetrating agent and/or mixtures thereof in an amount in the range of 0.1% to 90% by weight of the total mass of the composition.

[043] In an exemplary embodiment of the present invention, the synergistic fungicidal composition comprises: a dithiocarbamate fungicide in an amount in the range of 1% to 85% by weight of the total mass of the composition; a first conazole fungicide in an amount in the range of 1% to 85% by weight of the total mass of the composition; a second conazole fungicide in an amount in the range of 1% to 85% by weight of the total mass of the composition; at least one agrochemically acceptable excipient selected from the group comprising of dispersing agent in an amount in the range of 0.1% to 50% by weight of the total mass of the composition, wetting agent in an amount in the range of 0.1% to 50% by weight of the total mass of the composition, anti-caking agent in an amount in the range of 0.1% to 50% by weight of the total mass of the composition, thickener in an amount in the range of 0.1% to 50% by weight of the total mass of the composition, preservative in an amount in the range of 0.1% to 50% by weight of the total mass of the composition, diluent in an amount in the range of 0.1% to 70% by weight of the total mass of the composition, stabilizer in an amount in the range of 0.1% to 50% by weight of the total mass of the composition, defoamer in an amount in the range of 0.1% to 50% by weight of the total mass of the composition, anti-freezing agent in an amount in the range of 0.1% to 50% by weight of the total mass of the composition, and anti-penetrating agent in an amount in the range of 0.1% to 50% by weight of the total mass of the composition and/or mixtures thereof. [044] In accordance with an exemplary embodiment of the present disclosure, the fungicidal composition is formulated as a suspension concentrate (SC) formulation, Water Dispersible Granules (WG), Wettable Powder (WP), ZC a mixed formulation of capsule suspension (CS) and suspension concentrate (SC), Suspoemulsion (SE), Oil Dispersion(OD), Flowable suspension (FS), water dispersible powder for slurry treatment (WS) or powder for dry seed treatment (DS).

[045] Typically, the present composition is in the form of a ready-to use stable liquid composition (Suspension concentrate) which demonstrates synergistic effects with good physical and chemical stability.

[046] In an exemplary embodiment of the present invention, the moisture content in the fungicidal composition of the present invention can be in the range of 20 to 70 and the particle size e in the range of 1 to 5 micron.

[047] In another aspect of the present invention, disclosed is a process for preparing the ternary fungicidal composition. The process comprises mixing of at least two fungicidal compounds with a dispersing agent, a wetting agent, a second dispersing agent, a defoaming agent and water to obtain a premix in form of a slurry. This slurry is concentrated to obtain a concentrate suspension of a pre-determined particle size. This concentrate suspension is then mixed with another fungicidal compound, defoamer, anticaking agent, oil a preservative, a thickener and water and blended to obtain the ternary fungicidal composition.

[048] In another embodiment of the present invention, the ternary fungicidal composition is prepared by mixing, half of the pre-determined quantity of defoaming agent with pre-determined quantity of water, followed by pre- determined amounts of anionic emulsifier, emulsifier nonionic surfactant, Polymeric surfactant, a mixture of conazoles to obtain a premix in form of a slurry. The premix slurry is then passed through a bead mill to obtain a concentrate suspension of a pre-determined particle size in a predetermined range 1 to 5 micron. The concentrate suspension is mixed with a dithiocarbamate fungicide, balance quantity of silicon base defoamer, oil, anticaking agent, viscosity modifying agent, preservative and balance quantity of water to obtain the ternary fungicidal composition.

[049] In accordance with an exemplary embodiment of the present disclosure, the fungicidal composition is formulated as a suspension formulation containing Mancozeb, Difenoconazole and Cyproconazole mixture.

[050] In another embodiment of the present invention, the ternary fungicidal composition is prepared by mixing, half of the pre-determined quantity of defoaming agent with pre-determined quantity of water, followed by pre- determined amounts of dispersant 1, wetting agent, dispersant 2, antifreezing agent, stabilizers and mixture of conazoles to obtain a premix in form of a slurry. The premix slurry is then passed through a bead mill to obtain a concentrate suspension of a pre-determined particle size in a predetermined range 1 to 5 micron. The concentrate suspension is mixed with a dithiocarbamate fungicide, balance quantity of silicon base defoamer, viscosity modifying agent, preservative, stabliser and balance quantity of water to obtain the ternary fungicidal composition.

[051] In accordance with an exemplary embodiment of the present disclosure, the fungicidal composition is formulated as a suspension formulation containing Mancozeb, Difenoconazole and Pro thioconazole mixture.

[052] In yet another embodiment, the present invention relates to a method for controlling fungi comprising the steps of applying the synergistic fungicidal composition to the fungi and/or their habitat.

[053] Another embodiment of the present invention relates to the use of the synergistic fungicidal composition for controlling fungi. [054] Advantageously, the present invention provides a synergistic ternary fungicidal composition that provides the advantages of increased resistance to pest and disease, improved shelf life, better crop quality and yield as well as improved growth and enhanced efficacy.

EXAMPLES

[055] The following example is illustrative of the invention but not limitative of the scope thereof:

Example 1: Example 2

Bio-efficacy for Inventive examples 1 and 2

The synergistic fungicidal compositions of the present invention, prepared in accordance with Examples 1 and 2, were tested at given concentrations with two way possible tank mix combinations i.e., Mancozeb 75%WP + Difenoconazole 25% EC (Tank mix), Mancozeb 75%WP + Cyproconazole 25% (Tank Mix) & Difenoconazole 25% EC + Cyproconazole 25% EC (Tank Mix) along with solo individual fungicides i.e. Mancozeb 75%WP, Difenoconazole 25% EC & Cyproconazole 25% EC and Untreated Control against Grey mildew (Ramularia areola) of Cotton. 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 1 ^st spray and subsequent observations were recorded after each spray. For recording the observations ten hills from each plot were graded on (0-9) disease scoring scale for Grey mildew (Ramularia areola) of Cotton.

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

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

Table I illustrates the Bio-efficacy of Mancozeb 41 % + Difenoconazole 2.14% + Cyproconazole

1.7% SC against Grey mildew (Ramularia areola) of Cotton.

Example 1 Mancozeb 41 % + Difenoconazole 2.14% + Cyproconazole 1.7% SC (Tl) @ 2000 ml/ha recorded the best control of Grey mildew (Ramularia areola) of Cotton with 7.07 percent disease incidence (PDI), i.e., 84% control over untreated control, after 15 days after third application, which was superior over Mancozeb 35 % + Difenoconazole 5% + Cyproconazole 3% SC (T2) @ 2000 ml/ha with PDI of 9.27. But both the treatments were superior over rest of the treatments.

However, Difenoconazole 25% EC + Cyproconazole 25% EC (Tank Mix) (T5) @ 600 +450 ml/ha recorded 13.13 PDI was on par with Cyproconazole 25% EC (T8) @ 450 ml/ha with 14.00 PDI and were superior over other treatments, Mancozeb 75%WP + Cyproconazole 25% (Tank mix) (T4) @ 1500 gm/ha + 450 ml/ha with 15.13 PDI; Mancozeb 75%WP + Difenoconazole 25% EC (Tank mix) (T3) @ 1500 gm/ha + 600 ml/ha with 17.20 PDI; Difenoconazole 25% EC (T7) @ 600 ml/ha with 18.13 PDI; Mancozeb 75%WP (T6) @ 1500 gm/ha recorded PDI of 24.93, whereas untreated control recorded the disease of 42.93 PDI of

Grey mildew of Cotton. Table 2 illustates the Bio-efficacy of Mancozeb 40 % + Difenoconazole 2.1% +

Prothioconazole 2.6% SC against Grey mildew (Ramularia areola) of Cotton

Example 2 Mancozeb 40 % + Difenoconazole 2.1% + Prothioconazole 2.6% SC (Tl) @ 2000 ml/ha recorded the best control of Grey mildew (Ramularia areola) of Cotton with 4.93 percent disease incidence (PDI) i.e., 91 percent control over untreated control, after 15 days after third application and was superior over Mancozeb 35 % + Difenoconazole 5% + Prothioconazole 4% SC (T2) @ 2000 ml/ha with 9.13 PDI. But both were superior over rest of the treatments.

However, Mancozeb 75%WP + Prothioconazole 25% EC (Tank mix) (T4) @ 1500 gm/ha + 450 ml/ha. recorded with 12.20 PDI which is superior over other treatments, followed by Difenoconazole 25% EC + Prothioconazole 25% EC (Tank Mix) (T5) @ 600 + 450 ml/ha with 15.27 PDI; Prothioconazole 25% EC @ 450 ml/ha with 17.13 PDI; Mancozeb 75%WP + Difenoconazole 25% EC (T3) @ 1500 gm/ha + 600 ml/ha. recorded 18.13 PDI, Difenoconazole 25% EC @ 600 ml/ha recorded PDI of 21.87; Mancozeb 75%WP @ 1500 gm/ha recorded PDI of 30.07, whereas untreated control recorded the disease of 54.4 PDI of Grey mildew of Cotton.

Thus, it is clearly shown that the inventive ternary fungicidal composition exhibits high resistance to diseases even after 15 days of application as compared to known compositions. Overall, the three-way combination of test product shows synergistic effect for controlling the diseases. Also it is shown that the inventive three way fungicidal composition can be used effectively and safely for the management of diseases over the use of individual fungicides as is evident from the Tables 1 and 2. [056] The foregoing description of the invention has been set merely to illustrate the invention and is not intended to be limiting. Since the modifications of the disclosed embodiments incorporating the spirit and substance of the invention may occur to the person skilled in the art, the invention should be construed to include everything within the scope of the disclosure.