WO2024142090A1 - A synergistic fungicidal composition for agricultural use - Google Patents

A synergistic fungicidal composition for agricultural use

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Publication number
WO2024142090A1
WO2024142090A1 PCT/IN2023/051202 IN2023051202W WO2024142090A1 WO 2024142090 A1 WO2024142090 A1 WO 2024142090A1 IN 2023051202 W IN2023051202 W IN 2023051202W WO 2024142090 A1 WO2024142090 A1 WO 2024142090A1
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amount
composition
alone
mixtures
sodium
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PCT/IN2023/051202
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French (fr)
Inventor
Sadashiv Kanyana Shetty
Raghuram Kanyana Shetty
Shriraj Sadashiv Shetty
Ajit Singh Gujral
Arthal Ramakrishnan
Raunak Raghuram SHETTY
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Mikusu India Private Limited
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Publication of WO2024142090A1 publication Critical patent/WO2024142090A1/en

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Abstract

The invention disclosed herein is a synergistic fungicidal composition comprising; (a) at least one strobilurin selected from Trifloxystrobin, Pyraclostrobin, Kresoxim methyl, Picoxystrobin or Azoxystrobin; (b) at least one triazole selected from Difenoconazole, Hexaconazole, Propiconazole, Tebuconazole, Cyproconazole, Prothioconazole, Tetraconazole, Triticonazole, Epoxiconazole or Flusilazole and (c) at least one fungicide selected from Dodine, Captan, Ziram, Propineb, Thiophanate Methyl, Metiram, Zineb, Chlorothalonil, Dimethomorph, Boscalid, Fluxapyroxad or Metrafenone-PM along with agrochemically acceptable excipients. The said synergistic fungicidal composition effectively controls the fungal infestation/diseases on variety of crops, fruits and vegetables, thereby improving crop health and increasing crop yield.

Description

Title : A SYNERGISTIC FUNGICIDAL COMPOSITION FOR AGRICULTURAL
USE
Technical field of the Invention:
The present invention relates to a synergistic fungicidal composition for Agricultural use. More particularly, the present invention relates to a synergistic fungicidal composition comprising; (a) at least one strobilurin selected from Trifloxystrobin, Pyraclostrobin, Kresoxim methyl, Picoxystrobin or Azoxystrobin; (b) at least one triazole selected from Difenoconazole, Hexaconazole, Propiconazole, Tebuconazole, Cyproconazole, Pro thioconazole, Tetraconazole, Triticonazole, Epoxiconazole or Flusilazole, and (c) at least one fungicide selected from Dodine, Captan, Ziram, Propineb, Thiophanate Methyl, Metiram, Zineb, Chlorothalonil, Dimethomorph, Boscalid, Fluxapyroxad or Metrafenone-PM; along with agrochemically acceptable excipients.
The present invention further relates to a method of effectively controlling fungal infestation/diseases by applying said synergistic fungicidal composition on variety of crops, fruits and vegetables, thereby improving crop health and increasing crop yield.
The present invention also relates to a process for preparation of said synergistic fungicidal composition.
Background and Prior art of the Invention:
Fungi are the major cause of crop loss worldwide. Most crops are subject to attack by several fungi. Fungi cause serious damage in agriculture, resulting in significant reduction in yield, productivity, quality and profit. Fungicides are compounds of natural or synthetic origin, which act to protect plants against damage caused by fungi. Fungicides prevent and cure diseases which have severe adverse effects on crop yield and quality. Current methods of agriculture rely heavily on the use of fungicides. Use of fungicides allows a grower to increase the yield and quality of the crop and consequently, increase the value of the crop. Although there are available numerous fungicides which aid in preventing diseases of plants, each of these has practical deficiencies, which restrict its use. In a single or solo administration of fungicide, the activity is very limited thereby disease control is narrow. The main concern with the repeated use of fungicide in solo formulations is the development of resistance by the pathogen for that particular fungicide and at the end one has to apply more concentrated formulation of the fungicide. The high amount of fungicide may result in the toxicity to human beings as well as have bad effects on the environment. To reduce the risk of development of resistant strains, mixtures of different active compounds are nowadays conventionally employed for controlling harmful fungus or pathogen. It is possible to ensure successful control over a relatively long period of time by combining active compounds having different mechanisms of action.
There is also a requirement of a stable fungicidal composition combining more than one active ingredient that has a synergistic effect and thereby reduce the need for multiple individual applications while providing better fungicidal activity. Further requirement also includes a combination products having synergistic effect which can be extensively applied in the field of agricultural for controlling wide spectra of fungi which also exhibits good physical and chemical stability.
The combinations of fungicides are often used to facilitate disease control, to broaden spectrum of control and to retard resistance development.
US9538761 discloses a pesticidal composition comprising sulphur, a fungicide selected from the group consisting of cymoxanil, fenhexamid, fenamidone, cyazofamid, chlorothalonil, kresoxim methyl, azoxystrobin, trifloxystrobin, pyraclostrobin, iprodione, validamycin, kasugamycin, cyprodinil, pencycuron, hexaconazole, prochloraz, epoxiconazole, prothioconaozole, trifloxystrobin, thiophanate methyl, spiroxamine, metrafenone or their salts thereof and at least one agrochemically acceptable excipient.
CN110710532 discloses an application of a sterilization composition containing trifloxystrobin and difenoconazole in reducing or preventing citrus plants from being infected by toxins formed by diaporthe fungi. A sterilization composition containing trifloxystrobin and difenoconazole is used for simultaneously treating or respectively treating leaves, fruits, branches and trunks of the citrus plants. CN102067881 discloses a novel formulation of a pesticide bactericide composition, and particularly relates to a difenoconazole and sulfur compounded suspending agent and a preparation method thereof.
IN202041037394 discloses a synergistic oil dispersion composition comprising Mancozeb, Pyraclostrobin, Propiconazole, rheology modifier, emulsifiers, dispersing agents and base oil. However, the use of said composition is only limited to paddy rice, dry-seeded rice crops and fungal diseases thereof.
Thus, there is still a need of new advantageous combinations to provide a variety of options to best satisfy particular plant disease control needs with higher uptake of active ingredient with enhanced efficacy, reduced toxicity and increased shelf life and stability. There is also a need for a synergistic combination which can provide broad spectrum control while having reduced rate of application and dose and yet provide enhanced disease control efficacy resulting in enhanced plant/crop yield.
Therefore, it is an object of the present invention is to provide a solution to aforesaid needs by preparing a synergistic composition with combination of fungicides which demonstrates high and faster disease control efficacy, reduced plant toxicity, reduced crop protection cost and reduced environmental load along with increased shelf life and stability of the composition.
The inventors of the present invention have come up with a unique synergistic fungicidal composition comprising combination of contact, translaminar and systemic fungicide; wherein the present synergistic composition act as protectant, curative and also eradicate fungal diseases. Since the present synergistic composition comprises broad spectrum fungicides, it also acts on variety of diseases. Further the mode of action of each component in the present synergistic fungicidal composition is different, hence there is no fear of resistance development or cross resistance under multiple spray schedules. Object of the Invention:
In accordance with the above, it is an object of the present invention is to provide a synergistic fungicidal composition for agricultural use comprising combination of; (a) at least one strobilurin selected from Trifloxystrobin, Pyraclostrobin, Kresoxim methyl, Picoxystrobin or Azoxystrobin; (b) at least one triazole selected from Difenoconazole, Hexaconazole, Propiconazole, Tebuconazole, Cyproconazole, Prothioconazole, Tetraconazole, Triticonazole, Epoxiconazole or Flusilazole and (c) at least one fungicide selected from Dodine, Captan, Ziram, Propineb, Thiophanate Methyl, Metiram, Zineb, Chlorothalonil, Dimethomorph, Boscalid, Fluxapyroxad or Metrafenone-PM along with agrochemically acceptable excipients.
Another object of the present invention is to provide a process for preparation of said synergistic fungicidal composition.
Yet another object of the present invention is to provide a method of effectively controlling fungal infestation/diseases by applying present synergistic fungicidal composition on variety of crops, fruits and vegetables.
Yet another object of the present invention is to provide a method of effectively improving crop health and increasing crop yield of variety of crops, fruits and vegetables using present synergistic fungicidal composition.
Yet another object of the present invention is to provide a synergistic fungicidal composition which is active against all life stages of major plant pathogens.
Yet another object of the present invention is to provide a synergistic fungicidal composition that controls disease severity on different variety of crops, fruits and vegetables.
Yet another object of the present invention is to provide a synergistic fungicidal composition which is totally safe with no phytotoxic effect on crops, fruits and vegetables. Yet another object of the present invention is to provide a synergistic fungicidal composition that is stable at higher temperature conditions without affecting content and suspensibility of actives.
Yet another object of the present invention is to provide a synergistic fungicidal composition with increased shelf life and storage stability.
Summary of the Invention:
In accordance with the above objective, in an aspect the present invention describes a synergistic fungicidal composition for agricultural use comprising combination of; (a) at least one strobilurin selected from Trifloxystrobin, Pyraclostrobin, Kresoxim methyl, Picoxystrobin or Azoxystrobin; (b) at least one triazole selected from Difenoconazole, Hexaconazole, Propiconazole, Tebuconazole, Cyproconazole, Prothioconazole, Tetraconazole, Triticonazole, Epoxiconazole or Flusilazole and (c) at least one fungicide selected from Dodine, Captan, Ziram, Propineb, Thiophanate Methyl, Metiram, Zineb, Chlorothalonil, Dimethomorph, Boscalid, Fluxapyroxad or Metrafenone-PM; along with agrochemically acceptable excipients.
In another aspect, the strobilurin selected from Trifloxystrobin, Pyraclostrobin, Kresoxim methyl, Picoxystrobin or Azoxystrobin is present in an amount of 0.1% to 25% by weight of the total composition.
In another aspect, the triazole selected from Difenoconazole, Hexaconazole, Propiconazole, Tebuconazole, Cyproconazole, Prothioconazole, Tetraconazole, Triticonazole, Epoxiconazole or Flusilazole is present in an amount of 0.50% to 30% by weight of the total composition.
In another aspect, the fungicide ingredient of the present composition selected from Dodine, Captan, Ziram (Zinc dimethyldithiocarbamate), Propineb, Thiophanate Methyl, Metiram, Zineb, Chlorothalonil, Dimethomorph, Boscalid, Fluxapyroxad or Metrafenone-PM is present in an amount of 5% to 62% by weight of the total composition.
In another aspect, the agrochemically acceptable excipients of the present composition are selected from dispersing/co-dispersing agents, wetting/co-wetting agents, anti-foaming agents/deformer, anti-freezing agents, coating agents, anti-bacterial agents/biocides, binder/co-binders, stabilizers, emulsifiers, curing agents, rheology modifiers, sticking agents, preservatives, solvent/co- solvents and fillers, and these excipients are present in an amount of 0.01% to 25% by weight of the total composition.
In yet another aspect, the synergistic fungicidal composition of the present invention is formulated in different dosage forms such as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Controlled (Slow or Fast) release granules (CR), Jambo balls or bags (bags in water soluble pouch), Solution for foliar spray (LS), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) Tablet (TB), Aerosol (AE), Ultra-low volume (ULV) suspension (SU), Ultra-low volume liquid (UL), Water dispersible granules (WG or WDG), Wettable powder (WP), Water dispersible powder (WDP), Water dispersible tablet (WT), Zeon concentrate (ZC) - mixed formulation of CS and SC, a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW).
In yet another aspect, the present invention discloses the process for preparation of different types of composition; wherein, these compositions are prepared by mixing appropriate quantity of active ingredients with agrochemically acceptable excipients under certain appropriate conditions.
In yet another aspect, the present invention describes a method of effectively controlling fungal infestation/diseases, improving crop health and increasing crop yield by applying synergistic fungicidal composition of the present invention on infected areas of different varieties of crops, fruits and vegetables. In yet another aspect, the present invention describes a synergistic fungicidal composition which is active against all life stages of major plant pathogens and it controls disease severity on different varieties of crops, fruits and vegetables without showing any phytotoxic effect.
In yet another aspect, the present invention describes a synergistic fungicidal composition that is stable at higher temperature conditions without affecting the suspensibility and content of actives, thereby increasing shelf life and storage stability of the composition.
Detailed Description of the Invention:
The present invention will now be described in detail in connection with certain embodiments, so that various aspects thereof may be fully understood and appreciated.
The phrase “Synergistic” used herein, refer as the interaction of two or more active agents combined together and apply conjointly to produce an effect which is greater than the sum of their individual effects.
The phrase “Fungicides” used herein refer as biocidal chemical compounds used to kill parasitic fungi or their spores and fight fungal infection.
The phrase, "Effective amount" used herein refer as an amount of the active ingredient that when applied is sufficient to achieve a good level of control.
The present invention discloses a unique synergistic fungicidal composition comprising combination of contact, translaminar and systemic fungicide.
Mode of action of fungicides:
Contact fungicides are also called as protectant fungicides. Contact fungicides do not enter the plant, but controls the growth of fungi when it comes in contact with fungicide during the application. They work on the leaf surface to prevent fungal spores from germinating or penetrating the plant. These fungicides require the most care in application as complete coverage is essential for effectiveness. Translaminar fungicides penetrate into the plant tissue and are moved within a plant organ such as a leaf, but do not travel to other parts of the plant. Translaminar fungicides redistribute the fungicide from the upper, sprayed leaf surface to the lower, unsprayed leaf surface.
Systemic fungicide is the one which is taken up by a plant and is then translocated within the plant system, it can there by protect the plant from infections and restrict/control the further growth of existing fungal infection.
The strobilurin fungicides works by inhibiting the fungi's ability undergo normal respiration. Strobilurins control a wide range of fungi classes such as ascomycetes, basidiomycetes and oomycetes. Strobilurins control certain diseases which caused by water molds, downy mildews, powdery mildews, leaf spotting and blighting fungi, fruit rotter and rusts. Also, they are used on a wide variety of crops, including cereals, field crops, fruits, tree nuts, vegetables and ornamentals.
Triazole fungicides are widely used to prevent fungal diseases in agriculture, thereby protecting vegetables, fruits and crops. Triazoles are used on many different types of plants including field crops, fruit trees, small fruit, vegetables, and turf. These fungicides are highly effective against many different fungal diseases, especially powdery mildews, rusts, and many leaf- spotting fungi.
The fungicide selected from Dodine, Captan, Ziram (Zinc dimethyldithiocarbamate), Propineb, Thiophanate Methyl, Metiram, Zineb, Chlorothalonil, Dimethomorph, Boscalid, Fluxapyroxad or Metrafenone-PM are having broad spectrum activity against various fungal disease, foliar disease and plant diseases such as black rot, early and late blight, powdery mildew, downy mildew and the like.
Thus the present invention combines these effective fungicides and provides a synergistic fungicidal composition that efficaciously controls the broad spectrum of fungal diseases. Accordingly, in one preferred embodiment, the present invention discloses a synergistic fungicidal composition for effective control of fungal infestation/diseases on variety of crops, fruits and vegetables comprising;
(a) at least one strobilurin selected from Trifloxystrobin, Pyraclostrobin, Kresoxim methyl, Picoxystrobin or Azoxy strobin in an amount of 0.1% to 25%;
(b) at least one triazole selected from Difenoconazole, Hexaconazole, Propiconazole, Tebuconazole, Cyproconazole, Prothioconazole, Tetraconazole, Triticonazole, Epoxiconazole or Flusilazole in an amount of 0.50% to 30%; and
(c) at least one fungicide selected from Dodine, Captan, Ziram (Zinc dimethyldithiocarbamate), Propineb, Thiophanate Methyl, Metiram, Zineb, Chlorothalonil, Dimethomorph, Boscalid, Fluxapyroxad or Metrafenone-PM in an amount of 5% to 62%; alongwith agrochemically acceptable excipients in an amount of 0.01% to 25% by weight of the total composition.
In another preferred embodiment, the present invention discloses a synergistic fungicidal composition for effective control of fungal infestation/diseases on variety of crops, fruits and vegetables comprising; a) Trifloxystrobin in an amount of 0.1% to 25%; b) Difenoconazole in an amount of 0.50% to 30%; and c) Dodine in an amount of 5% to 62%; alongwith agrochemically acceptable excipients in an amount of 0.01% to 25% by weight of the total composition.
The agrochemically acceptable excipients of the present synergistic fungicidal composition are selected from dispersing/co-dispersing agents, wetting/co-wetting agents, anti-foaming agents/deformer, anti-freezing agents, coating agents, anti-bacterial agents/biocides, binder/co-binders, stabilizers, emulsifiers, curing agents, rheology modifiers, sticking agents, preservatives, solvent/co-solvents, fillers and the like.
Examples of dispersing/co-dispersing agents include but not limited to sodium ligno sulphonates; sodium naphthalene sulphonate formaldehyde condensates; tristyryl phenol ethoxylate phosphate esters, polyarylphenyl ether phosphate, polyalkelene glycol ether, tristyrylphenol ethoxylate amine salt of phosphate, tristyryl phenol ethylated, acrylic co- polymer, acrylate copolymer, acrylic copolymer sodium salt, alkyl naphthalene sulfonate, naphthalene sulfonic acid, sodium alkyl naphthalene sulfonate blend, sodium polycarboxylate, sodium polyacrylate, ethoxylated oleyl cetyl alcohol, ethoxylated tristryl phenol sulphate, ethoxylated fatty alcohol, polymeric non-aqueous dispersing agent, polyoxyethylene isotridecanol, tristyrylphenol ethoxylate phosphate ester, sodium salt condensate with formaldehyde, aliphatic alcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graft copolymers, either alone or mixtures thereof.
Examples of wetting/co-wetting agents include but not limited to block copolymer, alkoxylated alcohol, ethoxylated propoxylated alcohol, polyalkoxylated butyl ether, sodium alkyl sulphate, sodium lauryl sulphate, sodium alkyl benzene sulfonate, dioctyl sulfosuccinate, polyoxyethylene sorbitol hexaoleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene polyoxypropylene sorbitan monolaurate, tristyrylphenol ethoxylate, alkoxyleted alcohol, block copolymer, sodium dioctyl sulpho succinate, alkyl phenol ethoxylates and aliphatic alcohol ethoxylates, either alone or mixtures thereof.
Examples of anti-foaming agent/deformer include but not limited to siloxane polyalkyleneoxide, polydimethylsiloxane, silicon based agents, either alone or mixtures thereof.
Examples of anti-freezing agent include but not limited to glycol, polyethylene glycols, monoethylene glycol, glycerin, diethylene glycol, propane- 1,2-diol, methoxy polyethylene glycols, polypropylene glycols, polybutylene glycols, glycerin and ethylene glycol, either alone or mixtures thereof.
Examples of coating agents include but not limited to Polyisocyanates, Polydiisocyanates, polymethylene polyphenylene isocyanate (PMPPI), hexamethylene diisocyanate (HMDI), Napthalene diisocyanate, Methylene bis-cyclohexylisocyanate, isophorone diisocyanate (IPDI) or 4,4' methylenebis (cyclohexyl isocyanate), polyphenylisocyanate, Polymethylene polyphenylisocyanate, Toluene diisocyanate, and/or trimers of HMDI or IPDI, Trimethyl hexamethylene, Xylene diisocyanate, Tetramethyl xylene diisocyanate, Hexahydrotoluylene diisocyanate (HTDI), methylene diphenyl diisocyanate (MDI) and blocked polyisocyanates either alone or mixtures thereof. Examples of anti-bacterial agent/biocide include but not limited to benzisothiazolin-3-one, formaldehyde, sodium benzoate, sodium o-phenyl phenate, 5-chloro-2-methyl-4-isothiazolin- 3-one, 2-methyl-4-isothiazolin-3-one, either alone or mixtures thereof.
Examples of binders/co-binder include but not limited to aluminium silicate, precipitated silica, fumed silica, diatomaceous earth, glucose polymers: amylose and amylopectin, a branched form, lactose anhydrous, silicic acid, sodium lignosulonate, modified phyllosilicate, either alone or mixtures thereof.
Examples of stabilizers include but not limited to polysaccharides, carboxymethyl cellulose, bentonite clay, aluminum magnesium silicate, either alone or mixtures thereof.
Examples of emulsifiers include but not limited to calcium dodecyl benzene sulfonate, tristyryl phenyl ethoxylate, calcium alkyl benzen sulfonate, either alone or mixtures thereof.
Examples of curing agents include but not limited to amine compound, aromatic amines, aliphatic amines, polyamides, cycloaliphatic amines, anhydrides and imidazoles, either alone or mixtures thereof.
Examples of rheology modifier include but not limited to polysaccharides, carboxymethyl cellulose, bentonite clay, aluminum magnesium silicate, either alone or mixtures thereof.
Examples of sticking agents include but not limited to polyvinylpyrrolidone, polyoxyethylene lauryl ether, either alone or mixtures thereof.
Examples of preservatives include but not limited to l,2-benzisothiazolin-3-one, benzoic acid, sodium benzoate, propionic acid, sorbic acid, and sodium diacetate, either alone or mixture thereof.
Example of solvent/co-solvent include but not limited to aromatic solvent, di-methyl formamide, N-methyl pyrrolidone, heavy aromatic naptha, either alone or mixtures thereof. Examples of filler include but not limited to DM water, silicon dioxide, china-clay, kaolin, talc, starch, urea formaldehyde resin, aluminium silicate, methylated oleic acid ester, methylated fatty acid ester, either alone or mixtures thereof.
In another embodiment, the synergistic fungicidal composition of the present invention is formulated in different dosage forms such as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Controlled (Slow or Fast) release granules (CR), Jambo balls or bags (bags in water soluble pouch), Solution for foliar spray (LS), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) Tablet (TB), Aerosol (AE), Ultra-low volume (ULV) suspension (SU), Ultra-low volume liquid (UL), Water dispersible granules (WG or WDG), Wettable powder (WP), Water dispersible powder (WDP), Water dispersible tablet (WT), Zeon concentrate (ZC) - mixed formulation of CS and SC, a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW).
In another preferred embodiment, the synergistic fungicidal composition of the present invention is formulated as Suspension concentrate (SC), Capsule suspension (CS), Water dispersible granule (WG or WDG), Wettable powder (WP), Zeon concentrate (ZC) - mixed formulation of CS and SC, Micro-emulsion (ME), Oil-dispersion (OD), Emulsifiable concentrate (EC) and the like.
In another embodiment, the active ingredients used in the present synergistic fungicidal composition viz., Trifloxystrobin, Dif enoconazole and Dodine is having 95%, 92% and 96% purity, respectively.
In another embodiment, the present invention discloses the process for preparation of different formulations/compositions types such as Suspension concentrate (SC), Capsule suspension (CS), Water dispersible granule (WG or WDG), Wettable powder (WP), Zeon concentrate (ZC) - mixed formulation of CS and SC, Micro-emulsion (ME), Oil-dispersion (OD), and Emulsifiable concentrate (EC); wherein these formulations/compositions prepared by mixing required quantity of active ingredients with agrochemically acceptable excipients under certain appropireate conditions. The process for preparation of each composition is provided in the example section.
The present invention discloses a synergistic fungicidal composition that is useful as plant disease control agents. The present invention therefore further comprises a method for effectively controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, or to the plant seed or seedling to be protected, an effective amount of a mixtures of the invention or a fungicidal composition containing said mixture.
In yet another preferred embodiment, the present invention discloses a method of effectively controlling fungal infestation/diseases on infected varieties of crops, fruits and vegetables by applying synergistic fungicidal composition comprising;
(a) at least one strobilurin selected from Trifloxystrobin, Pyraclostrobin, Kresoxim methyl, Picoxystrobin or Azoxy strobin in an amount of 0.1% to 25%;
(b) at least one triazole selected from Difenoconazole, Hexaconazole, Propiconazole, Tebuconazole, Cyproconazole, Prothioconazole, Tetraconazole, Triticonazole, Epoxiconazole or Flusilazole in an amount of 0.50% to 30%; and
(c) at least one fungicide selected from Dodine, Captan, Ziram (Zinc dimethyldithiocarbamate), Propineb, Thiophanate Methyl, Metiram, Zineb, Chlorothalonil, Dimethomorph, Boscalid, Fluxapyroxad or Metrafenone-PM in an amount of 5% to 62%; alongwith agrochemically acceptable excipients in an amount of 0.01% to 25% by weight of the total composition.
Accordingly, in another preferred embodiment, the present invention discloses a method of effectively controlling fungal infestation/diseases on infected areas of variety of crops, fruits and vegetables by applying synergistic fungicidal composition comprising; a) Trifloxystrobin in an amount of 0.1% to 25%; b) Difenoconazole in an amount of 0.50% to 30%; and c) Dodine in an amount of 5% to 62%; alongwith agrochemically acceptable excipients in an amount of 0.01% to 25% by weight of the total composition.
In yet another embodiment, the present invention discloses a method of effectively improving crop health and increasing crop yield of variety of crops, fruits and vegetables by applying synergistic fungicidal composition of the present invention comprising;
(a) at least one strobilurin selected from Trifloxystrobin, Pyraclostrobin, Kresoxim methyl, Picoxystrobin or Azoxy strobin in an amount of 0.1% to 25%;
(b) at least one triazole selected from Dif enoconazole, Hexaconazole, Propiconazole, Tebuconazole, Cyproconazole, Prothioconazole, Tetraconazole, Triticonazole, Epoxiconazole or Flusilazole in an amount of 0.50% to 30%; and
(c) at least one fungicide selected from Dodine, Captan, Ziram (Zinc dimethyldithiocarbamate), Propineb, Thiophanate Methyl, Metiram, Zineb, Chlorothalonil, Dimethomorph, Boscalid, Fluxapyroxad or Metrafenone-PM in an amount of 5% to 62%; alongwith agrochemically acceptable excipients in an amount of 0.01% to 25% by weight of the total composition.
In yet another embodiment, the present invention discloses a method of effectively improving crop health and increasing crop yield of variety of crops, fruits and vegetables by applying synergistic fungicidal composition of the present invention comprising; (i) Trifloxystrobin in an amount of 0.1% to 25%; (ii) Difenoconazole in an amount of 0.50% to 30% and (iii) Dodine in an amount of 5% to 62% along with agrochemically acceptable excipients in an amount of 0.01% to 25% by weight of the total composition.
In yet another embodiment, the present invention discloses a method of controlling disease severity on different variety of crops, fruits and vegetables by applying synergistic fungicidal composition of the present invention comprising;
(a) at least one strobilurin selected from Trifloxystrobin, Pyraclostrobin, Kresoxim methyl, Picoxystrobin or Azoxy strobin in an amount of 0.1% to 25%;
(b) at least one triazole selected from Difenoconazole, Hexaconazole, Propiconazole, Tebuconazole, Cyproconazole, Prothioconazole, Tetraconazole, Triticonazole, Epoxiconazole or Flusilazole in an amount of 0.50% to 30%; and (c) at least one fungicide selected from Dodine, Captan, Ziram (Zinc dimethyldithiocarbamate), Propineb, Thiophanate Methyl, Metiram, Zineb or Chlorothalonil, Dimethomorph, Boscalid, Fluxapyroxad or Metrafenone-PM in an amount of 5% to 62%; alongwith agrochemically acceptable excipients in an amount of 0.01% to 25% by weight of the total composition.
In yet another embodiment, the present invention discloses a method of controlling disease severity on different variety of crops, fruits and vegetables by applying synergistic fungicidal composition of the present invention comprising; (i) Trifloxystrobin in an amount of 0.1% to 25%; (ii) Difenoconazole in an amount of 0.50% to 30% and (iii) Dodine in an amount of 5% to 62% along with agrochemically acceptable excipients in an amount of 0.01% to 25% by weight of the total composition.
In yet another embodiment, the present invention discloses a synergistic fungicidal composition comprising; (a) at least one strobilurin selected from Trifloxystrobin, Pyraclostrobin Kresoxim methyl, Picoxystrobin or Azoxystrobin; (b) at least one triazole selected from Difenoconazole, Hexaconazole, Propiconazole, Tebuconazole, Cyproconazole, Pro thioconazole, Tetraconazole, Triticonazole, Epoxiconazole or Flusilazole and (c) at least one fungicide selected from Dodine, Captan, Ziram, Propineb, Thiophanate Methyl, Metiram, Zineb, Chlorothalonil, Dimethomorph, Boscalid, Fluxapyroxad or Metrafenone-PM; along with agrochemically acceptable excipients; that is totally safe with no phytotoxic effect on crops, fruits and vegetables and is active against all life stages of major plant pathogens.
In yet another embodiment, the present invention discloses a synergistic fungicidal composition comprising; (a) at least one strobilurin selected from Trifloxystrobin, Pyraclostrobin Kresoxim methyl, Picoxystrobin or Azoxystrobin; (b) at least one triazole selected from Difenoconazole, Hexaconazole, Propiconazole, Tebuconazole, Cyproconazole, Pro thioconazole, Tetraconazole, Triticonazole, Epoxiconazole or Flusilazole and (c) at least one fungicide selected from Dodine, Captan, Ziram, Propineb, Thiophanate Methyl, Metiram, Zineb, Chlorothalonil, Dimethomorph, Boscalid, Fluxapyroxad or Metrafenone-PM; along with agrochemically acceptable excipients; that is stable at higher temperature conditions without affecting the suspensibility and active ingredient content, thereby increasing shelf life and storage stability of composition. The variety of crops on which the present composition is used include Field crops such as rice, wheat barley, millets, corn and the like; Oil seed crops such as peanut, soybean, brassica, cotton, sesame and the like; Fruits such as apple, banana, citrus-lime fruits, grape, watermelon, pomegranate and the like; Stone fruits such as cherries, peaches, plum, apricot, lychees, mango and the like; and Vegetables such as tomato, potato, brinjal, okra, cole crops, beans, chili, ginger, onion, garlic and the like.
The synergistic fungicidal composition of the present invention is effective against following diseases and pathogen that are appeared on different varieties of crops/plants:
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
In yet another embodiment, the present invention discloses a synergistic fungicidal composition that provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and Deuteromycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops. These pathogens include Oomycetes, including Phytophthora diseases such as Phytophthora infestans, Phytophthora megasperma, Phytophthora parasitica, Phytophthora cinnamoni, Phytophthora capsici; Pythium diseases such as Pythium aphani dermatum', and diseases in the Peronosporaceae family such as Plasmopara viticola, Peronospora sp. (including Peronospora tabacina and Peronospora parasitica), Pseudop eronospora sp. (including Pseudoperonospora cubensis) and Bremia lactucae.
Ascomycetes, including Altemaria diseases such as Alternaria Solani and Alternaria brasicae, Guignardia diseases such as Guignardia bidwel, Venturia diseases such as Venturia inaequalis, Septoria diseases such as Septoria nodorum and Septoria tritici; Powdery mildew diseases such as Erysiphe sp. (including Erysiphe graminis and Erysiphe polygoni), Uncinula necatur, Sphaerotheca filigena and Podosphaera leucotricha, Pseudocercosporella herpotrichoides, Botrytis diseases such as Botrytis cinerea, Monilinia fructicola, Sclerotinia diseases such as Sclerotinia sclerotiorum, Magnaporthe grisea, Phomopsis viti cola, Helminthosporium diseases such as Helminthosporium tritici repentis, Pyrenophora teres', anthracnose diseases such as Glomerella or Colletotrichum sp. (such as Colletotrichum graminicola); and Gaeumannomyces graminis.
Basidiomycetes, including rust diseases caused by Puccinia sp. (such as Puccinia recondita, Puccinia striformis, Puccinia hordei, Puccinia graminis, and Puccinia arachidis); Hemileia vastatrix; and Phakopsora pachyrhizi.
Other pathogens including Rhizoctonia spp. (such as Rhizoctonia solani ', Fusarium diseases such as Fusarium roseum, Fusarium graminearum, Fusarium oxysporum, Verticilium dahliae, Sclerotium rolfsi, Rynchosporium secalis, Cercosporidium personatum, Cercospora arachidicola and Cercospora beticola, and other genera and species closely related to these pathogens.
In another optional embodiment the synergistic fungicidal composition of present invention can also be mixed with one or more insecticides, nematocides, bactericides, acaricides, growth regulators, chemo sterilants, semiochemi cals, repelents, atractants, pheromones, feeding stimulants or other biologicaly active compounds to form a multicomponent pesticide giving an even broader spectrum of agricultural protection. Examples of such agricultural protectants with which compositions of this invention can be formulated are: insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlorfenapyr, chlorpyrifos, chlorpyrifos-methyl, cyfluthrin, beta cyfluthrin, cyhalothrin, lambda-cyhalothrin, deltamethrin, diafenthiuron, diazinon, diflubenZuron, dimethoate, esfenvalerate, fenoxycarb, fenpropathrin, fenvalerate, fipronil. flucythrinate, tau-fluvalinate, fonophos, imidacloprid, indoxacarb, isofenphos, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, oxamyl, permethrin, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, rotenone, Sulprofos, tebufenozide, tefluthrin, terbufos, tetrachlorvinphos, thiodicarb, tralomethrin, trichlorfon and triflumuron; bactericides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatinoxide, fempropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; nematicides such as fenamiphos; and biological agents such as Bacilus thuringiensis, Bacilus thuringiensis deltaendotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi.
Also noteworthy is the use of a synergistic fungicidal composition of present invention to provide effective control over the diseases caused by abroad spectrum of fungal pathogens preventatively or curatively by applying an effective amount of present mixture or composition either pre-or post-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing, or can also be applied to the seed to protect the seed and seedling.
Examples:
The examples illustrating different embodiments of the present invention are provided herein. However, these are exemplary only and should not be regarded as limiting the elements of the present invention.
Example 1: Suspension Concentrate (SC) Compositions:
Figure imgf000024_0001
Figure imgf000025_0001
Example 2: Process for Preparation of Suspension Concentrate (SC):
Step 1: Homogenized the required quantity (as mentioned in the above table) of water, biocide, and defoamer followed by addition of gum powder with stirring till complete dissolution to obtain a gum solution (Gum Solution should be made 12-18 hour prior to use).
Step 2: Required quantity (as mentioned in the above table) of DM water, wetting agent, dispersing agent & suspending agents was added into the charged vessel followed by homogenization for 45-60 minutes using high shear homogenizer.
Step 3: Active ingredients and other remaining adjuvants excluding ‘antifreeze and thickeners’ were added into the homogenized slurry of step 2 to obtain a uniform slurry which is ready for grinding.
Step 4: Before grinding half quantity of required antifoam agent was added and then material was subjected to three cycles of grinding in Dyno mill. The remaining half quantity of the antifoam was added along with antifreeze after grinding process completes and before sampling process analysis.
Step 5: Finally gum solution as obtained in the step 1 was then added to obtain the Suspension Concentrate formulation. Example 3 to Example 6 - Suspension Concentrate (SC) Compositions:
Figure imgf000026_0001
Figure imgf000027_0001
Example 7 to Example 12 - Wettable Powder (WP) Compositions:
Figure imgf000027_0002
Figure imgf000028_0001
Example 13: Process for preparation of Wettable Powder (WP)
Step 1: Required quantity (as mentioned in the above table) of filler, wetting agent, dispersing agent, binder, anti-foaming agent and active agents were charged in premixing blender for homogenization for 30 minutes to obtain a pre -blended material.
Step 2: The pre-blended material was grinded through Jet mill/ air classifier mills followed by blending in post blender for a period of approx. 1.5 hr. to obtain a homogeneous material.
The homogenous material as obtained was unloaded and analyzed.
Example 14 to Example 19 - Water Dispersible Granule (WDG or WG) Compositions:
Figure imgf000028_0002
Figure imgf000029_0001
Figure imgf000030_0001
Example 20: Process for Preparation of WDG or WG
Step 1: Required quantity (as mentioned in the above table) of wetting agent, dispersing agent, antifoaming agent, binder and active ingredients was mixed in a premixing blender for homogenization for a period of 30 minutes to obtain a pre -blended material. Step 2: The pre-blended material as obtained in step 1 was blended through Jet mill/ air classifier mills followed by blending in post blender for a period of approx. 1.5 hour to obtain a homogeneous mixture.
Step 3: Required quantity of filler (QS) was then added to step 2 to make a dough. The dough was then passed through the extruder to obtain granules of required size. Step 4: Wet granules as obtained were passed through the fluidised bed drier followed by grading using vibrating screens to obtain the water dispersible granules.
Example 21 to Example 24 - Oil Dispersion (OD) Compositions:
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Example 25: Process for Preparation of Oil Dispersion (OD)
Step 1: Required quantity (as mentioned in the above table) of emulsifier was charged in a vessel and sticking agent was added and mixed well for 30 minutes using high shear homogenizer and pass through horizontal bead mill.
Step 2: Required quantity (as mentioned in the above table) of dispersing agent, wetting agent, sticking agent, anti-foaming agent, anti-freezing agents, binder and filler were added to step 1 and homogenized for 45-60 minutes using high shear homogeniser.
Step 3: Then all the active ingredients were added and again homogenised for further 30 minutes. This homogenised material was passed through horizontal bead mill to get required particle size. After completion of grinding cycles, the sample was analysed for particle size analysis.
Example 26: Micro-emulsion (ME) Composition:
Trifloxystrobin 7.5% + Dif enoconazole 10% + Dodine 12.5% ME
Figure imgf000033_0002
Example 27: Process for Preparation of Micro Emulsion (ME):
Step 1: Charge aromatic solvent and co-solvent into the vessel and then mix until completely soluble.
Step 2: Add active ingredients to solvent mixture of step 1 under stirring and at ambient temperature.
Step 3: Add emulsifier and stabilizers into mixture of step 2 and stir till get homogenized to obtain Micro Emulsion (ME). Example 28 to Example 29 - Emulsifiable Concentrate (EC) Compositions:
Figure imgf000034_0001
Example 30: Process for Preparation of Emulsifiable Concentrate (EC)
Step 1: Charge aromatic solvent and co-solvent into the vessel and then mix until completely soluble.
Step 2: Add active ingredients to solvent mixture of step 1 under stirring and at ambient temperature.
Step 3: Add emulsifier and stabilizers into mixture of step 2 and stir till get homogenized to obtained Emulsifiable Concentrate (EC).
Example 31: Capsule Suspension (CS) Composition:
Trifloxystrobin 5% + Difenoconazole 5.5% + Dodine 20% CS
Figure imgf000034_0002
Figure imgf000035_0001
Example 32: Process for Preparation of Capsule Suspension (CS) Preparation of Capsule suspension comprises organic phase, aqueous phase and emulsification and encapsulation phase.
Step I: Organic Phase
Figure imgf000035_0002
Preparation of organic phase: Close bottom valve and add required quantity of solvent in a clean and dry reactor (P-1). Start stirring and add active ingredient one by one. After addition of the active ingredients, add polyisocyanate and mix well. Apply the heating, if required.
Step II: Aqueous Phase
Figure imgf000035_0003
Preparation of aqueous phase: Add DM water in a clean vessel (P-2) fitted with stirrer. Add propane- 1,2-diol. Start the stirring and charge Poly dimethylsiloxane, acrylic co-polymer and Aluminium silicate with continuous mixing till homogeneous mass is obtain.
Step III: Preparation of Emulsification and Encapsulation Phase a) Material from aqueous phase vessel (P-2) and organic phase vessel (P-1) is collected into a 100 liter Vessel (P-3) by means of flow meter and control valve, followed by mixing with stirrer at 55 °C to form a pre-mix slurry. b) Passed pre-mix slurry of step (a) through IKA homogenize @ of 5500 rpm feeding rate and collect into a clean vessel (P-4) fitted with stirrer and maintain temperature 60°C under starring. c) Meanwhile start addition of previously prepared amine compound solution in vessel (P-5) with a fix rate in homogenized mass (note that amine solution addition should be complete after complete homogenize the mixture through IKA). d) Stir solution of step (c) for 2 hrs. at 55°C temperature and cool to room temperature. e) Add previously hydrated xanthan gum to step (d) and mix well to get a homogenous CS composition.
Example 33: Zeon concentrate (ZC) Composition:
[A mixed composition of Capsule Suspension (CS) and Suspension Concentrate (SC)]
Figure imgf000036_0001
Figure imgf000037_0001
Example 34: Process for Preparation of Zeon concentrate (ZC)
Phase I: Process for Preparation of Capsule Suspension (CS)
Preparation of Capsule suspension comprises organic phase, aqueous phase and emulsification and encapsulation phase.
Step I: Organic Phase
Figure imgf000037_0002
Preparation of organic phase: Close bottom valve and add required quantity of solvent in a clean and dry reactor (P-1). Start stirring and add active ingredient one by one. After addition of the active ingredients, add polyisocyanate and mix well. Apply the heating, if required.
Step II: Aqueous Phase
Figure imgf000037_0003
Preparation of aqueous phase: Add DM water in a clean vessel (P-2) fitted with stirrer. Add propane- 1,2-diol. Start the stirring and charge Poly dimethylsiloxane, acrylic co-polymer and Aluminium silicate with continuous mixing till homogeneous mass is obtain. Step III: Preparation of Emulsification and Encapsulation Phase f) Material from aqueous phase vessel (P-2) and organic phase vessel (P-1) is collected into a 100 liter Vessel (P-3) by means of flow meter and control valve, followed by mixing with stirrer at 55 °C to form a pre-mix slurry. g) Passed pre-mix slurry of step (a) through IKA homogenize @ of 5500 rpm feeding rate and collect into a clean vessel (P-4) fitted with stirrer and maintain temperature 60°C under starring. h) Meanwhile start addition of previously prepared amine compound solution in vessel (P-5) with a fix rate in homogenized mass (note that amine solution addition should be complete after complete homogenize the mixture through IKA). i) Stir solution of step (c) for 2 hrs. at 55°C temperature and cool to room temperature. j) Add previously hydrated xanthan gum to step (d) and mix well to get a homogenous CS composition.
Phase II: Suspension Concentrate (SC)
Figure imgf000038_0001
Preparation of Suspension Concentrate Phase: a) Add DM water in a clean vessel fitted with stirrer; b) stirring and adding Polydimethylsiloxane, Alkoxylated alcohol, acrylic co-polymer and Aluminium silicate followed by mixing continuously till homogeneous mass is formed; c) milling homogenous mass of step (b) through bead mill to achieve required particle size; d) after achieving required particle size transfer the mass of step (c) into mixing vessel; e) adding Polysaccharide to step (d) and making it homogeneous to get SC part.
Phase III: Final mixing: Capsule Suspension (CS) Phase + Suspension Concentrate (SC)
Phase: Mixing both phases i.e. capsulated phase and suspension phase together properly to get a final ZC composition.
Bio-efficacy Studies:
Test Compositions Preparations:
1. Test compositions were first mixed with purified water or solvents depending on the polarity of the test sample.
2. The resulting test compositions were then used in the following trials.
3. Test compositions were sprayed to the point of run-off on the test plants at the equivalent rates as mentioned in the Table 1 as g/ha of the active ingredient.
4. The tests were replicated three times and the results reported as the mean average of the three replicates.
Table 1:
Figure imgf000039_0001
Table 2: Efficacy of composition is tested against following diseases:
Figure imgf000039_0002
Figure imgf000040_0003
The Results of Bio-efficacy tests of present synergistic fungicidal composition are given in below Experiments 1 to 8 and Tables 3, 4 and 5. A rating of ‘ 100’ indicates 100% disease control and a rating of ‘0’ indicates no disease control (relative to control). Columns labeled ‘Observed % disease control’ (ODC) indicates average of three replications. Columns labeled ‘Expected disease control’ (EDC) indicate the expected value for each treatment mixture using the COLBY Equation. Treatments showing substantially greater control than expected are labeled with *.
COLBY Equation:
The presence of a synergistic effect between two active ingredients is established with the aid of the Colby equation (se S. R. Colby, "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations', Weeds, 1967, 15, 20-22):
Figure imgf000040_0001
The presence of a synergistic effect between three active ingredients is established with the aid of the Colby equation (se S. R. Colby, "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations', Weeds, 1967, 15, 20-22):
Figure imgf000040_0002
Using the method of Colby, the presence of a synergistic interaction between three active ingredients is established by first calculating the predicted activity, p, of the mixture based on activities of the three components applied alone. If 'p' is lower than the experimentally established efficacy, Synergism has occurred. In the equation above, A is the fungicidal activity in percentage control of one component applied alone at rate x. The B term is the fungicidal activity in percentage control of the second component applied at rate y and similarly C is the corresponding value for the third component applied at rate z. The equation estimates p, the fungicidal activity of the mixture of A at rate X with B at rate y and C at rate z if their effects are strictly additive and no interaction has occurred. Example 35 - Trial 1:
Figure imgf000041_0001
Experiment 1: Chilli seedlings were inoculated with a spore dust of Leveillula taurica, (causal organism of chilli powdery mildew) and incubated in a growth chamber at 20°C for 48 hrs prior to application. The test compositions were then sprayed to the point of run-off on the inoculated chilli seedlings. The following day the seedlings were moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.
Experiment 2: The test compositions were sprayed to the point of run-off on Chilli seedlings. The following day the seedlings were inoculated with a spore dust of Leveillula taurica, (causal organism of chilli powdery mildew) and incubated in a growth chamber at 20°C for 7 days, after which disease ratings were taken.
Experiment 3: The test compositions were sprayed to the point of run-off on Chilli seedlings. Five days later, the seedlings were inoculated with a spore dust of Leveillula taurica, (causal organism of chilli powdery mildew) and incubated in a growth chamber at 20°C for 7days, after which disease ratings were taken.
Table 3:
Figure imgf000041_0003
Figure imgf000041_0002
Figure imgf000042_0001
Figure imgf000043_0001
Example 36 - Trial 2:
Figure imgf000044_0001
Experiment 4: Chilli seedlings were inoculated with a spore Suspension of Collectotrichum capsici (causal organism of Fruit Rot/ Antracnose) and incubated in a saturated atmosphere at 20°C for 48 hrs. The test compositions were then sprayed to the point of run-off on the chilli seedlings. The following day the seedlings were moved to a growth chamber at 20°C for 7 days, after which disease ratings were recorded.
Experiment 5: The test compositions were sprayed to the point of run-off on Chilli seedlings. The following day the seedlings were inoculated with a spore Suspension of Collectotrichum capsici (causal organism of Fruit Rot/ Antracnose) and incubated in a saturated atmosphere at 20°C for 48 hrs, and then moved to a growth chamber at 20°C for 8 days, after which disease ratings were recorded.
Experiment 6: The test compositions were sprayed to the point of run-off on Chilli seedlings. Five days later, the seedlings were inoculated with a spore Suspension of Collectrotrichum capsici (causal organism of Fruit rot/Anhtracnose) and incubated in a saturated atmosphere at 20°C for 48 hrs, and then moved to a growth chamber at 20°C for 8 days, after which disease ratings were recorded.
Table 4:
Figure imgf000044_0002
Figure imgf000045_0001
Figure imgf000046_0001
Example 37 - Trial 3:
Figure imgf000046_0002
Experiment 7: Tomato seedlings were inoculated with a spore Suspension of Alternaria solani (causal organism of tomato early blight) 72 hrs. prior to application and incubated in a saturated atmosphere at 20°C for 24 hrs, then moved to a growth chamber at 20°C for 48 hrs. The test compositions were then sprayed to the point of run-off on the wheat seedlings. The following day the seedlings were moved to a growth chamber at 20°C for 4 days, after which disease ratings were recorded.
Experiment 8: The test compositions were sprayed to the point of run-off on tomato seedlings. The following day the seedlings were inoculated with a spore suspension of Alternaria solani (causal organism of tomato early blight) and incubated in a saturated atmosphere at 20°C for 24 hrs, and then moved to a growth chamber at 20°C for 7 days, after which disease ratings were made.
Table 5:
Figure imgf000047_0001
Figure imgf000048_0001
Observation: It can be observed from Table 3, 4 and 5 that the compositions of the present invention comprising Trifloxistrobin + Difenoconazole + Dodine showed synergistic effect and increased disease control as compared to binary and solo treatments. The present synergistic compositions also showed better disease control as compared to conventionally used compositions.
Example 38 - Trial 4:
Figure imgf000048_0002
Details of Experiment:
Figure imgf000048_0003
Table 6: Details of the treatments done
Figure imgf000048_0004
Figure imgf000049_0001
Table 6(a):
1st Spray: At the emergence of the pest at ETL level (Economic Threshold Level)
2nd Spray: 15 days after the First Spray
Table 6(b): Observations:
Figure imgf000049_0002
Table 6(c): Disease severity was recorded by using the following scale prescribed by Mayee
& Datar, 1986
Figure imgf000049_0003
Table 7:
Figure imgf000050_0001
Observation: It is observed from the above Table 7 that the disease severity percentages exhibited by marketed solo, binary and untreated control samples is in the range of 23% to 41%; whereas, the present compositions exhibits the disease severity in the range of 15 to
19%. Thus the present compositions effectively controls the spread of disease over crop/plant. Example 39 - Phytotoxicity Study:
The data on phytotoxic effects such as injury on leaf chlorosis, leaf tip burning, leaf necrosis, epinasty, hyponasty, scorching, vein clearing and wilting at 7 days after each spraying revealed that, all the tested dose of Trifloxystrobin + Difenconozole + Dodine at lower and higher level and of different type of pre-mixed formulations didn't show phytotoxicity on chilli crop (Table 8). These findings were in conformity with that the present fungicidal composition as tank mixture and pre-mix did not show any phytotoxicity symptoms on chilly crop.
Table 8: Phytotoxicity observation on Chilli crop
Figure imgf000051_0001
Figure imgf000052_0001
It is observed from above Table 8 that, most of the treatments at different rate of applications as solo or in combination as binary or ternary were safe to crop except exhibiting the fungicidal effects. Example 40: Yield Data
Figure imgf000053_0001
Table 9:
Figure imgf000053_0002
Figure imgf000054_0001
Figure imgf000055_0001
From above Table 9 it can be seen that the compositions of the present invention i.e. T13-33 exhibits increased yield of Chilli as compared to other solo treatments Ti to T12. The present compositions also exhibits increase yield of Chilli as compared to marketed samples T34 and T35.
Example 41: Stability Study Data
Study of physical parameters of a present compositions were conducted. The compositions were prepared and kept at ambient temperature and at 54°C for 14 days (accelerated heat stability test). Data recorded is provided in below tables.
Table 10: Stability of Oil Dispersion (OD)
Figure imgf000055_0002
Figure imgf000056_0001
AHS- Accelerated Heat Stability
Table 11: Stability of Water Dispersible Granule (WDG)
Figure imgf000056_0002
Figure imgf000057_0001
AHS- Accelerated Heat Stability
Table 12: Stability of Suspension Concentrate (SC)
Figure imgf000057_0002
Figure imgf000058_0001
AHS- Accelerated Heat Stability
Table 13: Stability of Wettable Powder (WP)
Figure imgf000058_0002
Figure imgf000059_0001
AHS- Accelerated Heat Stability
Observation: It is observe from the above Tables 10 to 13 that the active ingredient content and suspensibility of the present compositions was observed to be constant after 14 days @ 54°C, leading to stable compositions that provides increasing shelf life and storage stability to the compositions.

Claims

We Claim,
1. A synergistic fungicidal composition for effective control of fungal infestation/diseases on variety of crops, fruits and vegetables comprising; a) at least one strobilurin selected from Trifloxystrobin, Pyraclostrobin, Kresoxim methyl, Picoxystrobin or Azoxy strobin in an amount of 0.1% to 25%; b) at least one triazole selected from Difenoconazole, Hexaconazole, Propiconazole, Tebuconazole, Cyproconazole, Prothioconazole, Tetraconazole, Triticonazole, Epoxiconazole or Flusilazole in an amount of 0.50% to 30%; and c) at least one fungicide selected from Dodine, Captan, Ziram (Zinc dimethyldithiocarbamate), Propineb, Thiophanate Methyl, Metiram, Zineb, Chlorothalonil, Dimethomorph, Boscalid, Fluxapyroxad or Metrafenone-PM in an amount of 5% to 62%; along with agrochemically acceptable excipients in an amount of 0.01% to 25% by weight of the total composition.
2. The synergistic insecticidal composition for effective control of fungal infestation/diseases on variety of crops, fruits and vegetables as claimed in claim 1; wherein said composition comprising; a) Trifloxystrobin in an amount of 0.1% to 25%; b) Difenoconazole in an amount of 0.50% to 30%; c) Dodine in an amount of 5% to 62%; along with agrochemically acceptable excipients in an amount of 0.01% to 25% by weight of the total composition.
3. The synergistic insecticidal composition as claimed in claims 1 and 2; wherein said agrochemically acceptable adjuvants/excipients are selected from dispersing/co- dispersing agents, wetting/co-wetting agents, anti-foaming agents/deformer, antifreezing agents, coating agents, anti-bacterial agents/biocides, binder/co-binders, stabilizers, emulsifiers, curing agents, rheology modifiers, sticking agents, preservatives, solvent/co-solvents and fillers.
4. The synergistic insecticidal composition as claimed in claim 3; wherein said dispersing/co-dispersing agent is selected from sodium ligno sulphonates; sodium naphthalene sulphonate formaldehyde condensates; tristyryl phenol ethoxylate phosphate esters, poly arylphenyl ether phosphate, polyalkelene glycol ether, tristyrylphenol ethoxylate amine salt of phosphate, tristyryl phenol ethylated, acrylic co-polymer, acrylate copolymer, acrylic copolymer sodium salt, alkyl naphthalene sulfonate, naphthalene sulfonic acid, sodium alkyl naphthalene sulfonate blend, sodium polycarboxylate, sodium polyacrylate, ethoxylated oleyl cetyl alcohol, ethoxylated tristryl phenol sulphate, ethoxylated fatty alcohol, polymeric non-aqueous dispersing agent, polyoxyethylene isotridecanol, tristyrylphenol ethoxylate phosphate ester, sodium salt condensate with formaldehyde, aliphatic alcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graft copolymers, either alone or mixtures thereof.
5. The synergistic insecticidal composition as claimed in claim 3; wherein said wetting/co-wetting agent is selected from block copolymer, alkoxylated alcohol, ethoxylated propoxylated alcohol, polyalkoxylated butyl ether, sodium alkyl sulphate, sodium lauryl sulphate, sodium alkyl benzene sulfonate, dioctyl sulfosuccinate, polyoxyethylene sorbitol hexaoleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene polyoxypropylene sorbitan monolaurate, tristyrylphenol ethoxylate, alkoxyleted alcohol, block copolymer, sodium dioctyl sulpho succinate, alkyl phenol ethoxylates and aliphatic alcohol ethoxylates, either alone or mixtures thereof.
6. The synergistic insecticidal composition as claimed in claim 3; wherein said antifoaming agent/deformer is selected from siloxane polyalkyleneoxide, polydimethylsiloxane, silicon based agents, either alone or mixtures thereof.
7. The synergistic insecticidal composition as claimed in claim 3; wherein said antifreezing agent is selected from glycol, polyethylene glycols, monoethylene glycol, glycerin, diethylene glycol, propane- 1,2-diol, methoxy polyethylene glycols, polypropylene glycols, polybutylene glycols, glycerin and ethylene glycol, either alone or mixtures thereof.
8. The synergistic insecticidal composition as claimed in claim 3; wherein said coating agent is selected from Polyisocyanates, Poly diisocyanates, polymethylene polyphenylene isocyanate (PMPPI), hexamethylene diisocyanate (HMDI), Napthalene diisocyanate, Methylene bis-cyclohexylisocyanate, isophorone diisocyanate (IPDI) or 4,4' methylenebis (cyclohexyl isocyanate), polyphenylisocyanate, Polymethylene polyphenylisocyanate, Toluene diisocyanate, and/or trimers of HMDI or IPDI, Trimethyl hexamethylene, Xylene diisocyanate, Tetramethyl xylene diisocyanate, Hexahydrotoluylene diisocyanate (HTDI), methylene diphenyl diisocyanate (MDI) and blocked polyisocyanates either alone or mixtures thereof.
9. The synergistic insecticidal composition as claimed in claim 3; wherein said antibacterial agent/biocide is selected from benzisothiazolin-3-one, formaldehyde, sodium benzoate, sodium o-phenyl phenate, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl- 4-isothiazolin-3-one, either alone or mixtures thereof.
10. The synergistic insecticidal composition as claimed in claim 3; wherein said binder / co-binder is selected from aluminium silicate, precipitated silica, fumed silica, diatomaceous earth, glucose polymers: amylose and amylopectin, a branched form, lactose anhydrous, silicic acid, sodium lignosulonate, modified phyllosilicate, either alone or mixtures thereof.
11. The synergistic insecticidal composition as claimed in claim 3; wherein said stabilizer is selected from polysaccharides, carboxymethyl cellulose, bentonite clay, aluminum magnesium silicate, either alone or mixtures thereof.
12. The synergistic insecticidal composition as claimed in claim 3; wherein said emulsifier is selected from calcium dodecyl benzene sulfonate, tristyryl phenyl ethoxylate, calcium alkyl benzen sulfonate, either alone or mixtures thereof.
13. The synergistic insecticidal composition as claimed in claim 3; wherein said curing agent is selected from amine compound, aromatic amines, aliphatic amines, polyamides, cycloaliphatic amines, anhydrides and imidazoles, either alone or mixtures thereof.
14. The synergistic insecticidal composition as claimed in claim 3; wherein said rheology modifier is selected from polysaccharides, carboxymethyl cellulose, bentonite clay, aluminum magnesium silicate, either alone or mixtures thereof.
15. The synergistic insecticidal composition as claimed in claim 3; wherein said sticking agent is selected from polyvinylpyrrolidone, polyoxyethylene lauryl ether, either alone or mixtures thereof.
16. The synergistic insecticidal composition as claimed in claim 3; wherein said preservative is selected from l,2-benzisothiazolin-3-one, benzoic acid, sodium benzoate, propionic acid, sorbic acid, and sodium diacetate, either alone or mixture thereof.
17. The synergistic insecticidal composition as claimed in claim 3; wherein said solvent / co- solvent is selected from aromatic solvent, di-methyl formamide, N-methyl pyrrolidone, heavy aromatic naptha, either alone or mixtures thereof.
18. The synergistic insecticidal composition as claimed in claim 3; wherein said filler is selected from DM water, silicon dioxide, china-clay, kaolin, talc, starch, urea formaldehyde resin, aluminium silicate, methylated oleic acid ester, methylated fatty acid ester, either alone or mixtures thereof.
19. The synergistic insecticidal composition as claimed in claim 1 and 2; wherein said composition is formulated in different dosage forms such as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in- water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Controlled (Slow or Fast) release granules (CR), Jambo balls or bags (bags in water soluble pouch), Solution for foliar spray (LS), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) Tablet (TB), Aerosol (AE), Ultra-low volume (ULV) suspension (SU), Ultra-low volume liquid (UL), Water dispersible granules (WG or WDG), Wettable powder (WP), Water dispersible powder (WDP), Water dispersible tablet (WT), Zeon concentrate (ZC) - mixed formulation of CS and SC, a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW).
20. The synergistic insecticidal composition as claimed in claims 1, 2 and 19; wherein said composition is preferably, formulated in the form of Suspension concentrate (SC), Capsule suspension (CS), Water dispersible granule (WG or WDG), Wettable powder (WP), mixed formulation of CS and SC (ZC), Micro -emulsion (ME), Oil-dispersion (OD), and Emulsifiable concentrate (EC).
21. A method of effectively controlling fungal infestation/diseases on infected varieties of crops, fruits and vegetables by applying synergistic fungicidal composition comprising; (a) at least one strobilurin selected from Trifloxystrobin, Pyraclostrobin, Kresoxim methyl, Picoxystrobin or Azoxy strobin in an amount of 0.1% to 25%; (b) at least one triazole selected from Difenoconazole, Hexaconazole, Propiconazole, Tebuconazole, Cyproconazole, Prothioconazole, Tetraconazole, Triticonazole, Epoxiconazole or Flusilazole in an amount of 0.50% to 30%; and (c) at least one fungicide selected from Dodine, Captan, Ziram (Zinc dimethyldithiocarbamate), Propineb, Thiophanate Methyl, Metiram, Zineb or Chlorothalonil, Dimethomorph, Boscalid, Fluxapyroxad or Metrafenone-PM in an amount of 5% to 62%; alongwith agrochemically acceptable excipients in an amount of 0.01% to 25% by weight of the total composition.
22. A method of improving crop health and increasing crop yield of variety of crops, fruits and vegetables by applying synergistic fungicidal composition comprising; (a) at least one strobilurin selected from Trifloxystrobin, Pyraclostrobin, Kresoxim methyl, Picoxystrobin or Azoxystrobin in an amount of 0.1% to 25%; (b) at least one triazole selected from Difenoconazole, Hexaconazole, Propiconazole, Tebuconazole, Cyproconazole, Prothioconazole, Tetraconazole, Triticonazole, Epoxiconazole or Flusilazole in an amount of 0.50% to 30%; and (c) at least one fungicide selected from Dodine, Captan, Ziram (Zinc dimethyldithiocarbamate), Propineb, Thiophanate Methyl, Metiram, Zineb, Chlorothalonil, Dimethomorph, Boscalid, Fluxapyroxad or Metrafenone-PM in an amount of 5% to 62%; alongwith agrochemically acceptable excipients in an amount of 0.01% to 25% by weight of the total composition.
23. A method of controlling disease severity on different variety of crops, fruits and vegetables by applying synergistic fungicidal composition comprising; (a) at least one strobilurin selected from Trifloxystrobin, Pyraclostrobin, Kresoxim methyl, Picoxystrobin or Azoxystrobin in an amount of 0.1% to 25%; (b) at least one triazole selected from Difenoconazole, Hexaconazole, Propiconazole, Tebuconazole, Cyproconazole, Prothioconazole, Tetraconazole, Triticonazole, Epoxiconazole or Flusilazole in an amount of 0.50% to 30%; and (c) at least one fungicide selected from Dodine, Captan, Ziram (Zinc dimethyldithiocarbamate), Propineb, Thiophanate Methyl, Metiram, Zineb or Chlorothalonil, Dimethomorph, Boscalid, Fluxapyroxad or Metrafenone-PM in an amount of 5% to 62%; alongwith agrochemically acceptable excipients in an amount of 0.01% to 25% by weight of the total composition.
24. The method of effective controlling fungal infestation, disease severity, improving crop health and increasing crop yield of crops, fruits and vegetables as claimed in claims 1, 2, 21 to 23; wherein said variety of crops, fruits and vegetables are selected from Field crops such as rice, wheat barley, millets, com; Oil seed crops such as peanut, soybean, brassica, cotton, sesame; Fruits such as apple, banana, citrus-lime fruits, grape, watermelon, pomegranate; Stone fruits such as cherries, peaches, plum, apricot, lychees, mango; and Vegetables such as tomato, potato, brinjal, okra, cole crops, beans, chili, ginger, onion and garlic.
PCT/IN2023/051202 2022-12-31 2023-12-20 A synergistic fungicidal composition for agricultural use WO2024142090A1 (en)

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IN202221077637 2022-12-31

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