FIELD OF THE INVENTION

The present invention relates to stable synergistic triple combination fungicidal composition comprising of a) strobilurin fungicide, b) systemic fungicide and c) polymeric dithiocarbamate fungicide complex with zinc salt.

The present invention relates to stable synergistic triple combination fungicidal composition comprising of a) strobilurin fungicide, b) systemic fungicide, c) polymeric dithiocarbamate fungicide complex with zinc salt and agrochemical auxiliaries.

The present invention also relates to stable synergistic fungicidal composition comprising combination of Picoxystrobin, Dimethomorph and Mancozeb.

The present invention specifically relates to stable synergistic fungicidal composition comprising combination of Picoxystrobin, Dimethomorph, Mancozeb and agrochemical auxiliaries.

The present invention specifically relates to stable synergistic fungicidal composition comprising combination of Picoxystrobin, Dimethomorph, Mancozeb, wetting agent, dispersing agent, rheology modifier and other agrochemical auxiliaries.

The present invention more specifically relates to stable synergistic fungicidal composition comprising combination of Picoxystrobin, Dimethomorph and Mancozeb at a weight in the ratio of 1 : 5 : 15 to 1 : 10 : 50, wetting agent, dispersing agent, rheology modifier and other agrochemical auxiliaries.

The present invention also relates to a process for the preparation of synergistic fungicidal composition by simple blending and milling.

BACKGROUND OF THE INVENTION

Fungicides are biocidal chemical compounds or biological organisms used to kill parasitic fungi or their spores. Fungi can cause serious damage in agriculture, resulting in critical losses of yield, quality, and profit. Fungicides are used both in agriculture and to fight fungal infections in animals. It is clear that, although pesticides remain indispensable in agriculture, a great potential still exists to improve their efficiency and thus reduce their input into the environmental and food chain. Depending on the field of application, and the mode of application, and depending on physical, chemical and biological parameters, the active substances are employed as active substance formulation in the form of a mixture with customary carriers, adjuvants and additives.

Picoxystrobin is a fungicide belonging to the strobilurin group of chemicals. It is a preventative and curative fungicide with systemic and translaminar movement, acting by inhibition of mitochondrial respiration by blocking electron transfer at the Qo centre of cytochrome Bel. It is used for control of a range of fungal diseases, including brown rust, tan spot, powdery mildew, and net blotch in cereals, pulses and oilseeds.

Picoxystrobin is a systemic and trans-laminar, Quinone outside Inhibitor (Qol) fungicide with preventive, curative and systemic acitivity for use on Canola, Cereal grains, dried Peas, Corn and Soybeans. It is applied by ground equipment, aerially or via chemigation methods for control of foliar and soil-borne plant diseases. It inhibits mitochrondial respiration by blocking electron transfer at the Qo center of cytochrome be 1. The formulated product is a suspension concentrate (SC).

Picoxystrobin is chemically, methyl (E)-3-methoxy-2-[2-(6-trifluoromethyl-2- pyridyloxymethyljphenyl] acrylate and has the following structure:

Dimethomorph is a systemic fungicide which protects plants from molds, as well as killing molds on plants and preventing their spread. It is a cinnamic acid derivative and a member of the morpholine chemical family. It is a mixture of two isomers but only the Z isomer has fungicidal activity. Dimethomorph is used as a wood preservative to control downy mildew on vines, and to control late blight on tomatoes and potatoes. The EPA has classified dimethomorph as toxicity class III - slightly toxic. Products containing dimethomorph bear the SIGNAL WORD: CAUTION. It is available as a wettable powder, a dispersible concentrate, and a suspension concentrate. Chemically Dimethomorph is 3-(4-chlorophenyl)-3-(3,4- dimethoxyphenyl)-l-morpholin-4-ylprop-2-en-l-one and has the following structure:

Dimethomorph is a fungicide effective against Oomycetes, especially Peronosporaceae and Phytophthora spp. (but not Pythium spp.) in Vines, Potatoes and Tomatoes. Used in combination with contact fungicides.

Mancozeb is a dithiocarbamate salt fungicides, non-systemic agricultural fungicide with multi- site, protective action on contact which mainly inhibit binding of bacteria in-vivo oxidation of pyruvate and pyruvate oxidation processes involved in lipoic dehydrogenase II mercapto group (SH). Widely used in the beet, cabbage, cabbage, celery, peppers, beans, tomatoes, eggplant, potatoes, melons, such as watermelons, cotton, peanuts, wheat, corn, rice, hops, tea, rubber, citrus, grapes, mango, banana, lychee, pear, persimmon, peach, rose, rose and tobacco.

Mancozeb is chemically, manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt which is listed under FRAC code M:03 The "M" refers to Chemicals with Multi-Site Activity. "M" FRAC groups are defined as generally considered as a low risk group without any signs of resistance developing to the fungicides. The molecular formula is (C4H ₆ MnN2S4) _x (Zn) _y and the structural formula is:

Mancozeb is a polymeric complex of the monomer illustrated which contains 20% manganese and 2.5% zinc. US 3,379,610 A discloses / claims Mancozeb.

EP 0 278 595 Bl claims compositions of Picoxystrobin and the family patents claims Picoxystrobin.

The combinations with fungicidal active substances for widening the spectrum of action and/or for protecting the crop plants are also known. Though, the ability of these combination compounds to efficiently control diseases varies with a large number of the parameters including, but not limited, the type of the formulations of combination fungicide, the type of phytopathogenic fungi to be controlled, the type of the plant to be protected and ambient conditions, such as temperature, precipitations, humidity, length of the day, biological diversity of the micro environment, the like.

Picoxystrobin combinations with Cyproconazole, Cyprodinil, and Chlorothalonil have been reported and marketed in Europe. The formulations in combination of manganese ethylenebis (dithiocarbamate) (polymeric) complex with zinc salt (Mancozeb) with other fungicidal active substance, specially strobilurins, along with another systemic fungicide are not known so far.

Therefore, formulations of fungicidal active substances in combinations should generally have good chemical and physical stability, good application properties, user friendliness, having good biological activity and enhanced efficacy combined with high selectivity. Proper formulation and efficient delivery systems of combination fungicides are the key elements in the performance of different products.

There is a need in the art to provide environmentally safer and stable fungicidal compositions having more than two active ingredients with different physical and chemical properties with the primary goals includes: (1) providing an environmentally safe, easy and effective combination formulation of more than two fungicidal active with enhanced efficacy and less impact on photosynthetic activities on plant upon dilution in a carrier such as water or oil, and spray application to an area to be treated (2) maintaining the stability of the product during storage.

It was surprisingly and unexpectedly found by the present inventors that a selective combination of more than two fungicidal active ingredients comprising Picoxystrobin, Dimethomorph and Mancozeb exhibits a considerable synergistic effect, allowing a higher fungicidal activity obtained than that envisaged on the basis of the activities of individual ingredients.

OBJECTIVE OF INVENTION

The main objective of the present invention is to provide stable synergistic triple combination fungicidal composition comprising of a) strobilurin fungicide, b) systemic fungicide and c) polymeric dithiocarbamate fungicide complex with zinc salt.

Another objective of the present invention is to provide stable synergistic triple combination fungicidal composition comprising of a) strobilurin fungicide, b) systemic fungicide, c) polymeric dithiocarbamate fungicide complex with zinc salt and agrochemical auxiliaries.

Another objective of the present invention is to provide stable synergistic fungicidal composition comprising combination of Picoxystrobin, Dimethomorph and Mancozeb.

Another objective of the present invention is to provide stable synergistic fungicidal composition comprising combination of Picoxystrobin, Dimethomorph, Mancozeb and agrochemical auxiliaries.

Another objective of the present invention is to provide stable synergistic fungicidal composition comprising combination of Picoxystrobin, Dimethomorph, Mancozeb, wetting agent, dispersing agent, rheology modifier and other agrochemical auxiliaries.

Another objective of the present invention is to provide stable synergistic fungicidal composition comprising combination of Picoxystrobin, Dimethomorph and Mancozeb at a weight in the ratio of 1 : 5 : 15 to 1 : 10 : 50, wetting agent, dispersing agent, rheology modifier and other agrochemical auxiliaries.

Another objective of the present invention is to provide a process for the preparation of synergistic fungicidal composition by simple blending and milling. SUMMARY OF INVENTION

Accordingly, the present invention provides a stable synergistic triple combination fungicidal composition comprising of a) strobilurin fungicide, b) systemic fungicide and c) polymeric dithiocarbamate fungicide complex with zinc salt.

In one embodiment, the present invention provides a stable synergistic triple combination fungicidal composition comprising of a) strobilurin fungicide, b) systemic fungicide, c) polymeric dithiocarbamate fungicide complex with zinc salt and agrochemical auxiliaries.

In one embodiment, the present invention provides a stable synergistic triple combination fungicidal composition comprising of a) strobilurin fungicide, b) systemic fungicide, c) polymeric dithiocarbamate fungicide complex with zinc salt, wherein said strobilurin fungicide is Picoxystrobin, said systemic fungicide is Dimethomorph and said polymeric dithiocarbamate fungicide complex with zinc salt is Mancozeb.

In another embodiment, the present invention provides a stable synergistic fungicidal composition comprising combination of Picoxystrobin, Dimethomorph and Mancozeb.

In another embodiment, the present invention provides a stable synergistic fungicidal composition comprising combination of Picoxystrobin, Dimethomorph, Mancozeb and agrochemical auxiliaries.

In another embodiment, the present invention provides a stable synergistic fungicidal composition comprising combination of Picoxystrobin, Dimethomorph, Mancozeb, wetting agent, dispersing agent, rheology modifier and other agrochemical auxiliaries.

In another embodiment, the present invention provides a stable synergistic fungicidal composition comprising combination of Picoxystrobin, Dimethomorph, Mancozeb, wetting agent, dispersing agent, rheology modifier and other agrochemical auxiliaries, wherein said other agrochemical auxiliaries are fillers and adjuvants. In another embodiment, the present invention provides a stable synergistic fungicidal composition comprising combination of Picoxystrobin, Dimethomorph and Mancozeb at a weight in the ratio of 1 : 5 : 15 to 1 : 10 : 50, wetting agent, dispersing agent, rheology modifier and other agrochemical auxiliaries.

In another embodiment, the present invention provides a synergistic fungicidal composition comprising: a. a strobilurin fungicide in the range of 1% to 10% (w/w) of the total weight of the composition, b. a systemic fungicide in the range of 1% to 30% (w/w) of the total weight of the composition, c. a polymeric dithiocarbamate fungicide complex with zinc salt in the range of 1% to 70% (w/w) of the total weight of the composition, and d. agrochemical auxiliaries in the range of 0.1% to 70% (w/w) of the total weight of the composition.

In another embodiment, the present invention provides a synergistic fungicidal composition comprising: a. Picoxystrobin in the range of 1% to 10% (w/w), b. Dimethomorph in the range of 1% to 30% (w/w), c. Mancozeb in the range of 1% to 70% (w/w), d. wetting agent in the range of 1% to 15% (w/w), e. dispersing agent in the range of 1% to 15% (w/w), and f. other agrochemical auxiliaries in the range of 0.1% to 50% (w/w).

In another embodiment, the present invention provides a synergistic fungicidal composition comprising: a. Picoxystrobin in the range of 1% to 10% (w/w), b. Dimethomorph in the range of 1% to 30% (w/w), c. Mancozeb in the range of 1% to 70% (w/w), d. sodium diisopropyl naphthalene sulfonate in the range of 1% to 15% (w/w), e. sodium lignosulphonate in the range of 1% to 15% (w/w), and f. other agrochemical auxiliaries in the range of 0.1% to 50% (w/w). In another embodiment, the present invention provides a synergistic fungicidal wettable powder composition comprising: a. Picoxystrobin in the range of 1% to 10% (w/w), b. Dimethomorph in the range of 1% to 30% (w/w), c. Mancozeb in the range of 1% to 70% (w/w), d. wetting agent in the range of 1% to 15% (w/w), e. dispersing agent in the range of 1% to 15% (w/w), f. rheology modifier in the range of 1% to 10% (w/w), g. filler in the range of 1% to 30% (w/w), and h. adjuvant in the range of 1% to 10% (w/w).

In another embodiment, the present invention provides a synergistic fungicidal wettable powder composition comprising: a. Picoxystrobin in the range of 1% to 10% (w/w), b. Dimethomorph in the range of 1% to 30% (w/w), c. Mancozeb in the range of 1% to 70% (w/w), d. sodium diisopropyl naphthalene sulfonate in the range of 1% to 15% (w/w), e. sodium lignosulphonate in the range of 1% to 15% (w/w), f. precipitated silicon dioxide in the range of 1% to 10% (w/w), g. hydrous aluminosilicate in the range of 1% to 30% (w/w) and h. blend of amino acids in the range of 1% to 10% (w/w).

In another embodiment, the present invention provides a process for the preparation of synergistic fungicidal composition by simple blending and milling.

In another embodiment, the present invention provides a process for the preparation of fungicidal wettable powder composition comprising steps of: a. weighing and mixing active agents and auxiliaries, b. milling the sample through air jet milling instrument, and c. collecting the material and packing.

In another embodiment, the present invention provides a process for the preparation of fungicidal wettable powder composition comprising steps of: a. weighing and mixing Picoxystrobin, Dimethomorph, Mancozeb, sodium diisopropyl naphthalene sulfonate, sodium lignosulphonate, precipitated silicon dioxide, hydrous aluminosilicate and blend of aminoacids, b. milling the sample through air jet milling instrument, and c. collecting the material and packing.

DETAILED DESCRIPTION OF THE INVENTION

The term "comprising", which is synonymous with "including", "containing", or "characterized by" here is defined as being inclusive or open-ended, and does not exclude additional, unrecited elements or method steps, unless the context clearly requires otherwise.

The term "agrochemically effective amount" is that quantity of active agent, applied in any amount which will provide the required control of diseases caused by phytopathogenic fungi on commercial crops. The particular amount is dependent upon many factors including, for example, type of formulations, the crop, disease sought to be controlled and environmental conditions. The selection of the proper quantity of active agent to be applied, however, is within the expertise of one skilled in the art.

The active compound combinations according to the invention have very good fungicidal properties and can be employed for controlling phytopathogenic fungi, such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes, etc, which causes the disease in field and green house crops like cereals, pulses, oilseeds, vegetables, fruits, spices and ornamental crops. The composition of the present invention could be applied to plants, seeds, fruits, soil as preventive and curative state.

The wetting agent is a compound that facilitates rapid wetting of the powder when added to the water. The wetting agent employed in the formulation composition is selected from the group consisting of non-ionic surfactants, anionic surfactant and a mixture of anionic and non-ionic surfactant and polymeric surfactant. The wetting agent as used herein is selected from and not limited to a blend of anionic and nonionic surfactants (Atlox 5406B), polyoxyethylene alkyl ether (Atlox- 4894), polymethyl methacrylate-polyethylene glycol graft copolymer (Atlox 4913), alkyl naphthalene sulfonates (such as Morwet IP, Morwet EFW, Morwet 3028) sodium diisopropyl naphthalene sulfonate (Supragil WP), polycondensation product of naphthalene sulfonic acid, which is alkyl naphthalene sulphonate sodium salt, polyalkyl naphthalene sulphonate; Aqarius BP14332 Yellow IH, salts of alkylphenol condensates, salts of sulphonated lignins, salts of poly acid resin copolymers, salts of polyphenol formaldehyde resins, salts of polyarylether sulphates such as tristyrylphenolethoxylate sulphate salts, alkoxylated alkylphenols and alcohols as well as block copolymers of ethyleneoxide and propylene oxide. Preferred wetting agent used in the composition of the present invention is sodium diisopropyl naphthalene sulfonate (Supragil WP).

The wetting agent is present in the composition in a range of about 1% to 15%, more preferably 2% to 10% of the total weight of the composition.

The wetting agent may also be used as a dispersing agent.

The compositions of the present invention contain additional dispersing agents selected from and not limited to sodium lignosulphonates; sodium naphthalene sulphonate formaldehyde condensates; tristyrylphenol ethoxylate phosphate esters; aliphatic alcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graft copolymers, polycarboxylates, alkyl naphthalene sulfonates (such as Morwet IP, Morwet EFW, Morwet 3028,), phenol sulphonic acid condensates, alkyl sulfonates, alkenyl sylfonates, mixture of alkyl sulfonates and alkenyl sylfonates (Lissapol D), alkyl suflosuccinates (Geropon), L-Wet, methyl oleyltaurates and poly vinyl alcohols. Preferred dispersing agents are polycarboxylates, alkyl naphthalene sulfonates, phenol sulphonic acid condensates, lignosulphonates, methyl oleyltaurates and poly vinyl alcohols, STEPSPERSE DF-600 is a blend of nonionic surfactant and sodium lignosulfonate, BREAK-THRU® DA 646 is a non-ionic dispersant based on a specialty polyether, BREAK-THRU® DA 647, a modified polyether, is a non-ionic dispersant, BREAK-THRU® DA 655 is a polyether phosphate, BREAK-THRU® DA 675 is a non-ionic, aqueous based organically modified polymer, Atlox Metasperse™ 550S Modified styrene acrylic polymer (Jeemol BX). Dispersing agents disclosed in US 6,677,399; US 6,767,865; EP 1 16 470; US 9,526,241 can be used in the present invention. Once the granule has been diluted in water, ready for spraying (with the aid of the wetting agent), a dispersant is required to maintain the particles in suspension and prevent them from agglomerating. The dispersing agent is a compound which ensures that the particles remain suspended in water. The dispersing agent can be ionic or non-ionic or a mixture of such surface active agents or graft co-polymer dispersant.

The dispersing agent is present in the composition in a range of about 1% to 15%, more preferably 2% to 10% of the total weight of the composition.

Rheology modifiers are sometimes referred to as thickeners or viscosity modifiers. A good rheology modifier structures the formulation but when a force is applied it becomes flowable and easily poured. Without proper stabilisation, products can suffer formulation breakdown mechanisms such as flocculation and coalescence. The significant role of polymeric surfactant or dispersants and emulsifiers in producing highly stable formulations is that it will keep particles apart from each other preventing these formulation breakdown processes.

However, another variant that needs to be considered for formulation stabilization is the viscosity or thickness of the formulation. Increasing the viscosity of a formulation improves stability, by acting as a barrier to sedimentation and creaming which can be altered by adding a rheology modifier. To obtain the desired level of stability to particle sedimentation in composition, choosing the rheology modifier and the polymer or oligomer capable of hydrogen bonding that provides the desired thickening effect is necessary.

There are a variety of materials, both natural and man-made, that have been used as rheology modifiers to stabilize oil dispersion formulations against sedimentation such as, for example, clays and organoclays, hydrophilic and hydrophobic silicas, hydrogenated castor oils and their derivatives, polyamides, oxidized waxes, associative thickeners, which form structures by themselves due to their limited solubility in solvents, and steric dispersants (e.g., comb polymers such as polyvinylpyrrolidinones or polyacrylates).

Preferred rheology modifiers include, natural polymers selected from the group guar gum, locust bean gum, xanthan gum, carrageenan, alginates, methyl cellulose, carboxymethyl sodium carboxymethylcellulose, hydroxyethylcellulose, modified starches; other polysaccharides and modified polysaccharides, polyethylene alcohol, glycerol alkyl resinsand cellulose derivatives, natural oils, mineral oils such as kyros oil, vegetable oil derivatives such as SURFOM® ESP 8105, the organoclays such as Bentone, Bentone SD and Benathix Plus and the fumed silicas such as Aerosil R974, Aerosil 200 and Aerosil 972, Aerosil R816 (silanehexadecyltrimethoxy hydrolysis product with silica), Precipitated Silicon dioxide, and equivalent products thereof.

The rheology modifier is present in the composition in a range of about 1% to 10%, more preferably 1% to 5% of the total weight of the composition.

The inert fillers/carriers as used in the present invention are includes but are not limited to water, natural minerals such as calcite, talc, hydrous aluminosilicate (china clay series), and montmorillonite or attapulgite clays including various forms of bentonite, Kaolin; lactose, starches, calcium carbonate, calcium sulphate, calcium phosphate, sodium tripoly phosphate (STPP), woodflours, activated carbon, sugars, diatomaceous earth, cereal flours, fine-grain inorganic solids, and the like. Clays and inorganic solids which may be used include calcium bentonite, perlite, mica, vermiculite, silica, silicate salts, quartz powder, montmorillonite and mixtures thereof. Sugars which may be useful include dextrin and maltodextrin. Cereal flours include wheat flour, oat flour and barley flour and a mixture thereof. Preferred inert fillers are lactose anhydrous and china clay. Highly disperse silica or highly disperse absorptive polymers may also be used to improve physical properties.

The fillers/carriers is present in the composition in a range of about 1% to 30%, more preferably 5% to 25% of the total weight of the composition.

The adjuvants as used in the present invention are blend of amino acids.

The adjuvants are present in the composition in a range of about 1% to 10%, more preferably 1% to 5% of the total weight of the composition. In one embodiment it is possible to prepare the mixture of step i) by first coarse wet-milling and then fine wet-milling the active ingredient, so that the final average particle size is below 20 microns, preferably below 10 microns, in the presence of oil, milling can be carried out in a colloid mill, ball mill, sand mill, and preferably in grinding ball mills.

The three active ingredients may be present in the composition or applied in any amounts relative to each other, to provide the enhanced or synergistic effect of the mixture. Three active ingredients may be present in the synergistic fungicidal composition in any suitable amount, and is generally present in an amount of from 1% to 90% by weight of the composition, preferably from 1% to 70% by weight of the composition. However, variables of the ratios of each of the active ingredients can be used and the selection of the particular amount is dependent upon many factors including, for example, type of formulations, the crop, disease sought to be controlled and environmental conditions. The selection of the proper quantity of active agent to be applied, however, is within the expertise of one skilled in the art.

Formulation includes water soluble concentrate (SL), an emulstifiable concentrate (EC), an emulsion (EW), a microemulsion (ME), a suspension concentrates (SC), an oil-based dispersions (OD), a flowable suspension (FS), water soluble powder (WS), water-dispersible granule (WDG), water-soluble granule (SG), a water-dispersible powder (WP), a water soluble powder (SP), a granule (GR), an encapsulated granule (CG), a fine granule (FG), a macrogranule (GG), an aqueous suspoemulsion (SE), capsule suspension (CS) and a microgranule (MG).

Preferably, the synergistic fungicidal composition can be formulated as water soluble powder (WS), wettable powder (WP) or water-dispersible granule (WG). Most preferably, the synergistic fungicidal composition can be formulated as wettable powder (WP).

The compositions of the present invention can be diluted with water or water solutions of agronomic compounds before use to produce a sprayable composition which is used in treating plants or increasing plant growth. Dilution in water usually results in suspensions, emulsions, suspoemulsions or solutions of the agrochemical active ingredient at a concentration of at least 0.001 g/1.

The formulated composition may for example be applied in spray form, e.g., employing appropriate dilutions. The rates of application (use) of the composition of the present invention may vary, for example, according to type of use, soil type, season, climate, soil ecology, type of plants, but is such that the combination of the present invention in an effective amount to provide the desired action. The application rate of the composition for a given set of conditions can readily be determined by trials. The composition of the present invention may contain or be mixed with other pesticides, such as fungicides, insecticides and nematicides, growth factor and fertilizers, to enhance the activity of the association of the invention or to widen its spectrum of activity.

A particular mode of administering the composition of the present invention is the administration to the aboveground parts of plants, in particular to the leaves thereof (leaf-application). The number of applications and the administered doses are chosen in accordance with the biological and climatic conditions of life of the causative agent. The antifungal compositions though, can also be applied to the soil and get into the plants through the root system (systemic activity), in case the locus of the plants is sprayed with a liquid composition or if the components are added to the soil in a solid formulation e.g. in the form of granulate (soil application).

The active compound combinations according to the invention have potent fungicidal activity and can be employed for controlling phytopathogenic fungi, in crop protection and in the protection of materials.

The fungicidal compositions according to the present invention possess advantageous curative, preventive and antisporulant fungicidal activity to protect plants, fruit and seeds. The present composition can be used to protect plants or parts of plants, e.g. fruit, blossoms, flowers, foliage, stems, roots, cuttings, tubers of plants or culture plants infected, harmed or destroyed by micro-organisms, whereby later- growing parts of plants are protected against such micro-organisms. Application may be made by ground or aerial spray equipment. As examples of the wide variety of culture plants in which the combinations of present invention can be used, there may be named for example cereals, e.g. wheat, barley, rye, oats, rice, sorghum and the like; beets, e.g. sugar beet and fodder beet; pome and stone fruit and berries, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries; leguminous plants, e.g. beans, lentils, peas, soy beans; oleaginous plants, e.g. rape, mustard, poppy, olive, sunflower, coconut, castor-oil plant, cocoa, ground-nuts; cucurbitaceae, e.g. pumpkins, gherkins, melons, cucumbers, squashes; fibrous plants, e.g. cotton, flax, hemp, jute; citrus fruit, e.g. orange, lemon, grapefruit, mandarin; vegetables, e.g. spinach, lettuce, asparagus, brassicaceae such as cabbages and turnips, carrots, onions, tomatoes, potatoes, hot and sweet peppers; laurel-like plants, e.g. avocado, cinnamon, camphor tree; or plants such as maize, tobacco, nuts, coffee, sugar-cane, tea, vines, hops, bananas, rubber plants, as well as ornamental plants, e.g. flowers, shrubs, deciduous trees and evergreen trees such as conifers. This enumeration of culture plants is given with the purpose of illustrating the invention and not to delimiting it thereto.

A particular mode of administering an antifungal composition of the present invention is the administration to the aboveground parts of plants, in particular to the leaves thereof (leaf-application). The number of applications and the administered doses are chosen in accordance with the biological and climatic conditions of life of the causative agent. The antifungal compositions though, can also be applied to the soil and get into the plants through the root system (systemic activity), in case the locus of the plants is sprayed with a liquid composition or if the components are added to the soil in a solid formulation e.g. in the form of granulate (soil application).

The fungicidal compositions of the present invention can also be used for protecting seed against fungi. To that effect the present fungicidal compositions can be coated on seed, in which case the seed grains are drenched consecutively with a liquid composition of the active ingredients or if they are coated with a previously combined composition. The compositions can also be sprayed or atomized onto the seed.

When using the active compound combinations according to the invention, the application rate can be varied within a relatively wide range, depending on the kind of application. For the treatment of parts of plants, the active-compound combination application rates are generally between 0.1 and 10000 g/ha, preferably between 100 and 2500 g/ha. For seed dressing, the active compound combination application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 20 g per kilogram of seed. For the treatment of the soil, the active-compound combination application rates are generally between 0.1 and 10000 g ha preferably between 1 and 5000 g/ha.

The following examples describes the nature of the invention which are given only for the purpose of illustrating the present invention in more detail and are not limitative and relate to solutions, which have been particularly effective on bench scale.

EXAMPLES

Example 1: Pesticide composition with Picoxystrobin 2.5% + Dimethomorph 16.5% + Mancozeb 50 % (WP):

Manufacturing process:

All the raw materials were weighed dispensed and the mixture was mixed in a ribbon blender for 15 minutes. The mixture was passed through air jet milling instrument, Inlet pressure - 4kg/cm2 and Grinding pressure - 6kg/ cm2 for milling the sample. The milled material was collected and packed. The particle size distribution(PSD) of the milled material should be <10 p.

Field trials of Dimethomorph +Mancozeb +Picoxystrobin Combination

Trial - 1 : Field Bio-efficacy trials on Grapes downy mildew

The downy mildew of grapes is caused by the fungal pathogen Plasmopara viticola. This is potentially devasting disease can infect grape foliage at any stage of crop development. Although all green parts of the grapevine are susceptible, the first symptoms of downy mildew of grapes, caused by Plasmopara viticola, are usually seen on the leaves as soon as 5 to 7 days after infection. Foliar symptoms appear as yellow circular spots with an oily appearance (oil spots) young oil spots on young leaves are surrounded by a brownish-yellow halo. This halo fades as the oil spot matures. The spots are yellow in white grape varieties and red in some red grape varieties. Under favourable weather conditions, large numbers of oil spots may develop and coalesce to cover most of the leaf surface. After suitably warm, humid nights, a white downy fungal growth (sporangia) will appear on the underside of the leaves and other infected plant parts. The disease gets its name "downy mildew" from the presence of this downy growth. The mature berries, although they may be symptomatic and harbor the pathogen, may not support sporulation even when provided with ideal conditions. Infected parts of young fruit bunches turn brown, wither, and die rapidly. If infections occur on the young bunch stalk, the entire inflorescence may die. Developing young berries will either die or, if between 3 and 5 mm in diameter, become discoloured.

The field trial was conducted to evaluate the efficacy of innovative mixtures of Dimethomorph + Mancozeb + Picoxystrobin WP against Plasmopara viticola fungus in grapes. Trial was conducted with randomized block design with net plot size of 5m x 6m. Grape crop was raised with all standard agronomic practices. Spraying was done with manual operated backpack knapsack sprayer with 500 L of water spray volume per hectare at 45 days after transplanting. The visual observations were recorded for % disease control from ten leaf per plot. The observations were recorded at before spraying, 5 DAA (Days after application) and 10 DAA (Days after application).

Table 1: Control of Downy mildew in grapes

WP - Wettable powder, SC - Suspension concentrate, and DAA - Days after application.

The trial results shown excellent efficacy of Dimethomorph 16.5% +Mancozeb 50 % +Picoxystrobin 2.5% WP combinations against downy mildew disease of grape. The solo application of three active ingredients tested here, were not able to provide satisfactory control of Downy mildew disease. The combination of Dimethomorph 16.5% + Mancozeb 50 % + Picoxystrobin 2.5% WP found very promising against grapes downy mildew in terms of efficacy as well as residual control.

Trial - 2: Field Bio-efficacy trials in Potato Early blight

The Early blight of Potato is caused by the fungal pathogen Alternaria solani. This is potentially devasting disease can infect Potato foliage at any stage of crop development. Symptoms of early blight occur on fruit, stem and foliage of tomatoes and stem, foliage, and tubers of potatoes. Initial symptoms on leaves appear as small 1-2 mm black or brown lesions and under conducive environmental conditions the lesions will enlarge and are often surrounded by a yellow halo. Lesions greater than 10 mm in diameter often have dark pigmented concentric rings. This so-called “bullseye” type lesion is highly characteristic of early blight. As lesions expand and new lesions develop entire leaves may turn chlorotic and dehisce, leading to significant defoliation. Lesions occurring on stems are often sunken and lens-shaped with a light centre and have the typical concentric rings. On young tomato seedlings lesions may completely girdle the stem, a phase of the disease known as “collar rot,” which may lead to reduced plant vigor or death. Warm, humid (24-29°C/ 75-84°F) environmental conditions are conducive to infection. In the presence of free moisture and at an optimum of 28-30°C (82-86°F), conidia will germinate in approximately 40 min. Desiccated germ tubes are able to renew growth when re-wetted, and, hence, infection can occur under conditions of alternating wet and dry periods.

The field trial was conducted to evaluate the efficacy of innovative mixtures of Dimethomorph + Mancozeb + Picoxystrobin WP against Altemaria solani fungus in Potato. Trial was conducted with randomized block design with net plot size of 5m x 6m. Potato crop was raised with all standard agronomic practices. Spraying was done with manual operated backpack knapsack sprayer with 500 L of water spray volume per hectare at 45 days after transplanting. The visual observations were recorded for % disease control from ten leaf per plot. The observations were recorded at before spraying, 7 DAA (Days after application) and 14 DAA (Days after application).

Table 2: Early blight disease control in Potato:

WP - Wettable powder, SC - Suspension concentrate, and DAA - Days after application. The trial results shown excellent efficacy of Dimethomorph 16.5% +Mancozeb 50 % +Picoxystrobin 2.5% WP combinations against Early blight disease of Potato. The solo application of three active ingredients tested here, were not able to provide satisfactory control of Early blight disease. The combination of Dimethomorph 16.5% + Mancozeb 50 % + Picoxystrobin 2.5% WP found very promising against Potato Early blight in terms of efficacy as well as residual control.

Trial - 3: Field Bio-efficacy trials Potato Late blight

The late blight of Potato is caused by the fungal pathogen Phytophthora infestans. This is potentially devasting disease can infect Potato foliage at any stage of crop development. Late blight of potato is identified by blackish/brown lesions on leaves and stems that may be small at first and appear water- soaked or have chlorotic borders but expand rapidly and the entire leaf becomes become necrotic. In humid conditions, P. infestans produces sporangia and sporangiophores on the surface of infected tissue and the resulting white sporulation can be seen at the margins of lesions on abaxial (lower) surfaces of leaves. As many lesions accumulate, the entire plant can be destroyed in a matter of days after the first lesions are observed if the appropriate fungicide applications are not used. Potato tubers can become infected in the field when sporangia are washed from lesions on the foliage and enter the soil. Infections generally begin in tuber cracks, eyes, or lenticels. Infected tuber tissues are copper brown, reddish or purplish in colour. Sporulation may occur on the surface of infected tubers in storage or on discarded cull piles. Infected tubers are often invaded by soft rot bacteria which rapidly convert adjoining healthy potatoes into a smelly, rotten mass that must be discarded. Temperature and moisture are the most important environmental factors affecting late blight development. Sporangia are formed on the lower leaf surfaces and infected stems when relative humidity is < 90%. Sporulation can occur from 3-26°C (37-79°F), but the optimum range is 18-22°C (64-72°F). Sporangia germinate directly via a germ tube at 21-26°C (70-79°F). Below 18°C (65°F), sporangia produce 6 to 8 zoospores which require water for swimming. Each zoospore is capable of initiating an infection, which explains why disease is more severe in cool, wet conditions. Cool nights, warm days, and extended wet conditions from rain and fog can result in late blight epidemics in which entire potato fields are destroyed in less than two weeks.

The field trial was conducted to evaluate the efficacy of innovative mixtures of Dimethomorph + Mancozeb + Picoxystrobin WP against Phytophthora infestans fungus in Potato. Trial was conducted with randomized block design with net plot size of 5m x 6m. Potato crop was raised with all standard agronomic practices. Spraying was done with manual operated backpack knapsack sprayer with 500 L of water spray volume per hectare at 45 days after transplanting. The visual observations were recorded for % disease control from ten leaf per plot. The observations were recorded at before spraying, 7 DAA (Days after application) and 14 DAA (Days after application).

Table 3: Late blight disease control in Potato

WP - Wettable powder, SC - Suspension concentrate, and DAA - Days after application.

The trial results show excellent efficacy of Dimethomorph 16.5% +Mancozeb 50 % +Picoxystrobin 2.5% WP combinations against late blight disease of Potato. The solo application of three active ingredients tested here, were not able to provide satisfactory control of Late blight disease. The combination of Dimethomorph 16.5% + Mancozeb 50 % + Picoxystrobin 2.5% WP found very promising against Potato Late blight in terms of efficacy as well as residual control.