Formulation system for fungicide mixtures

Abstract

The present invention provides a fungicide mixture formulation system comprising an effective amount of a phthalimide fungicide selected from the group consisting of Folpet, Captan and any combination thereof; an effective amount of a second fungicide which is Prothioconazole; and an effective amount of a compatibility agent.

Description

[0001] FORMULATION SYSTEM FOR FUNGICIDE MIXTURES

[0002] RELATED APPLICATION / S

[0003] This application claims benefits of Indian Provisional Application No. IN 202411006814 filed on February 01, 2024; the entire content of which is hereby incorporated by reference herein. Throughout this application some publications are referenced. The disclosures of these documents in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which this invention pertains.

[0004] FIELD OF INVENTION

[0005] The present invention relates to a stable and efficient formulation system for fungicide mixture comprising a phthalimide fungicide selected from the group consisting of folpet, captan and any combination thereof, a second fungicide which is prothioconazole, and a suitable compatibility agent, and to methods for controlling or preventing fungal diseases in crop plants. This invention provides an efficient formulation system for fungicide mixture comprising a phthalimide fungicide and prothioconazole, for enhancing the activities of the phthalimide fungicide as well as prothioconazole by increasing stability in water of the respective fungicides in the formulation resulting in enhancing contact mode of action of the phthalimide as well as increasing systemic activity of prothioconazole.

[0006] BACKGROUND OF INVENTION

[0007] The vulnerability of crops to fungal infection makes fungi control one of the major management components of the total crop production system. Fungi are very destructive to crop plants and can significantly reduce crop yields and quality. Fungicides help minimize this damage by controlling various fungi. Many known fungicides are effective for specific crops and have a limited activity. In addition, a resistance is developed and there is a need to restore, increase and / or extend the activity.

[0008] Fungicides are the classes of compounds of natural or synthetic origin which act to protect plants against damage caused by various fungi. Despite the benefits derived from the use of fungicides in agriculture such as protection of crops and improved productivity, it is always desirable to reduce the amount of fungicides used in the fields owing to the potential health risks associated with an intensive use of agrochemicals. Another important issue associated with fungi attacks is the loss of nutrients which leads to a decrease in the overall yield of the crop. Formulations comprising one single active ingredient have shown a limited control over diseases.

[0009] Phthalimide compound is an imido derivative of phthalic acid. In organic chemistry, imide is a functional group consisting of two carbonyl groups bound to nitrogen. They are hydrophobic and neutral and can therefore cross biological membranes in vivo. Phthalimide fungicides such as captan and folpet are multi-site inhibitors and contact fungicides that affect energy production.

[0010] Prothioconazole is a broad-spectrum systemic fungicide developed by Bayer CropScience, disclosed in WO96 / 16048, for the control of diseases caused by basidiomycetes, ascomycetes, and deuteromycetes. Prothioconazole may be applied alone in a formulation or as a tank mix with other fungicides, insecticides, or herbicides.

[0011] Fungicide mixture formulations are typically used to broaden spectrum of control, to minimize the doses of chemicals used, to retard resistance development and to reduce the cost of the treatment through additive as well as synergistic effect. Although many mixture formulations of fungicidal agents have been studied, the challenge remains to prepare a stable and efficient formulation system of a mixture of two or more hydrophobic actives with good stability in the formulation. In the absence of good stability of the actives in the said formulation, the efficiency of formulation is said to be not well pronounced.

[0012] The subject matter of the present invention is a stable formulation system for fungicide mixture comprising two or more hydrophobic actives, namely one phthalimide fungicide selected from the group consisting of folpet, captan and any combination thereof and a second fungicide which is prothioconazole and any combination thereof.

[0013] There have been some endeavors in the relevant art to prepare effective formulations of a mixture of prothioconazole with other fungicide active compounds, however, no prior art has ever addressed the challenges specifically mixing a phthalimide fungicide with prothioconazole in a formulation system without significant degradation of any or both of the active compounds. The meticulous choice of suitable coformulants in the formulation may result in surprising outcome to the efficiency of the said formulation comprising a mixture of a phthalimide fungicide with prothioconazole.

[0014] In light of the above, there is endeavor in the present invention for a stable fungicide mixture formulation system with suitable coformulants therein, comprising a phthalimide fungicide selected from the group consisting of folpet, captan and any combination thereof and a strobilurin fungicide, for increasing the desirable activities by enhancing contact mode of action of the phthalimide as well as increasing systemic activity of the strobilurin, thereby enhancing efficiency.

[0015] SUMMARY OF THE PRESENT SUBJECT MATTER

[0016] The inventors of the present invention have reasonably addressed the challenges as described above as a whole or in part by arriving at an efficient stable fungicide mixture formulation system with suitable inert components therein, as defined below.

[0017] The present invention relates to fungicide mixture formulation system comprising (a) an effective amount of a phthalimide fungicide selected from the group consisting of Folpet, Captan and any combination thereof; (b) an effective amount of a second fungicide which is Prothioconazole; and (c) an effective amount of a compatibility agent, wherein the formulation system optionally comprises a polyol additive selected from a group comprising glucose, galactose, fructose, ribose, lactose, maltose, ethylene glycol, glycerol, sorbitol, inositol, mannitol, lactitol, xylitol and erythritol.

[0018] The present invention also relates to fungicide mixture formulation system as described herein comprising (a) an effective amount of a phthalimide fungicide selected from the group consisting of Folpet, Captan and any combination thereof; (b) an effective amount of a second fungicide which is Prothioconazole; and (c) an effective amount of a compatibility agent which is a derivative of either a metal or a non-metal element.

[0019] The present invention further relates to a fungicide mixture formulation system as described herein comprising (a) an effective amount of a phthalimide fungicide selected from the group consisting of Folpet, Captan and any combination thereof; (b) an effective amount of a second fungicide which is Prothioconazole; and (c) an effective amount of a compatibility agent which is selected from a group comprising Aluminium Chloride, Aluminium Sulphate, Aluminium Nitrate, Stannous Chloride, Stannous Sulphate, Stannic Chloride, Lead nitrate, Boric acid and any combination thereof.

[0020] The present invention also specifically provides a fungicide mixture formulation system as described herein comprising the phthalimide fungicide in the mixture is either Folpet or Captan.

[0021] The present invention provides a fungicide mixture formulation system as described herein comprising the amounts of phthalimide fungicide and Prothioconazole is in a ratio from 40: 1 to 1 : 1.

[0022] The present invention provides a fungicide mixture formulation system as described herein comprising the amounts of the compatibility agent and the phthalimide fungicide is from 1 :50 to 10: 1. The invention also provides a fungicide mixture formulation system as described herein comprising the amounts of the compatibility agent and the phthalimide fungicide is from 1 : 10 to 1 : 1.

[0023] The present invention provides a fungicide mixture formulation system as described herein, where the formulation system further comprises agriculturally acceptable carriers, which are selected from a group comprising a stabilizer, a dispersing agent, a wetting agent, a defoamer, an anti-freezing agent, a biocide, a rheology modifier and any combination thereof.

[0024] The present invention provides a fungicide mixture formulation system as described herein, wherein the formulation is either a concentrated ready-mix formulation or a tank mix formulation.

[0025] The present invention provides a fungicide mixture formulation system as described herein, where the formulation system maintains an amount of Prothioconazole which is at least 90% w / w of the total amount of Prothioconazole that is used for the preparation of the formulation system.

[0026] The present invention provides a fungicide mixture formulation system as described herein, where all the formulation systems further comprises an additional fungicide.

[0027] The present invention provides a fungicide mixture formulation system as described herein, where all the formulation systems further comprise the additional fungicide is selected from the group consisting of strobilurin fungicides, benzamide fungicide, morpholines, Qil fungicide, SDHI and any combinations thereof.

[0028] The present invention specifically provides a fungicide mixture formulation system as described herein, where all the formulation systems further comprise the additional fungicide which is a strobilurin fungicide. The present invention also specifically provides a fungicide mixture formulation system as described herein, where all the formulation systems further comprise the additional fungicide which comprises picoxystrobin and / or azoxystrobin and / or fluxapyroxad.

[0029] The present invention provides a use of a compatibility agent or any combination thereof as described herein, for formulating or preparing a fungicide mixture formulation system comprises the phthalimide fungicide and prothioconazole, wherein the formulation system maintains an amount of Prothioconazole which is at least 90% of the total amount of Prothioconazole that is used for the preparation of the formulation system.

[0030] The present invention provides a use of a compatibility agent or any combination thereof as described herein, for formulating or preparing a fungicide mixture formulation system comprises Folpet and Prothioconazole, wherein the formulation system maintains an amount of Prothioconazole which is at least 90% of the total amount of Prothioconazole that is used for the preparation of the formulation system.

[0031] The present invention provides a use of a compatibility agent or any combination thereof as described herein, for formulating or preparing a fungicide mixture formulation system comprises Captan and Prothioconazole, wherein the formulation system maintains an amount of Prothioconazole which is at least 90% of the total amount of Prothioconazole that is used for the preparation of the formulation system.

[0032] The present invention provides a use of a compatibility agent or any combination thereof as described herein, where the use of compatibility agent is for reducing the rate and / or extent of reduction or for preventing the reduction of the amount of an Prothioconazole in presence of phthalimide fungicide, so that the rate and / or extent of reduction in the amount of the Prothioconazole amount is lower than the rate and / or extent of reduction of the amount of the Prothioconazole in the same formulation system without compatibility agent.

[0033] The present invention provides a method of treating a plant or soil against fungal infection comprising applying the fungicide mixture formulation system as described herein, to a plant, a locus thereof, to propagation material of the plant, or soil so as to thereby treat the plant or soil against fungal infection.

[0034] DETAILED DESCRIPTION OF THE PRESENT SUBJECT MATTER

[0035] Definitions

[0036] Prior to setting forth the present subject matter in detail, it may be helpful to provide definitions of certain terms to be used herein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this subject matter pertains.

[0037] Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying tables, wherein like reference numerals refer to like elements throughout. In this regard, the present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described below to explain aspects of the present disclosure.

[0038] As used herein, the term "pesticide" broadly refers to an agent that can be used to control and / or kill a pest. The term is understood to include but is not limited to fungicides, insecticides, nematicides, herbicides, acaricides, parasiticides or other control agents. For chemical classes and applications, as well as specific compounds of each class, see "The Pesticide Manual Thirteenth Edition" (British Crop Protection Council, Hampshire, UK, 2003), as well as "The e-Pesticide Manual, Version 3" (British Crop Protection Council, Hampshire, UK, 2003-04), the contents of each of which are incorporated herein by reference in their entirety.

[0039] As used herein, the term “mixture” means but is not limited to an assemblage of agrochemicals for application either by simultaneous, contemporaneous and / or succession application. A combination in any time of application of the individual components e.g. succession and / or in any physical form, e.g. blend, solution, suspension, dispersion, emulsion, alloy, or the like. Mixture also may refer to combining and applying the active components as one composition and / or formulating each of the active component in the mixture or combination as separated compositions and application at the same time or in separated applications at the same time or different times.

[0040] As used herein, the term “system” means but is not limited to an assemblage of active ingredients and / or acceptable coformulants for application either by simultaneous, contemporaneous and / or succession application. It also means a combination in any time of application of the individual components e.g. succession and / or in any physical form, e.g. blend, solution, suspension, dispersion, emulsion, alloy, or the like. “System” also may refer to combining and applying the active components and acceptable coformulants as one composition and / or formulating each of the active component in the mixture or combination as separated compositions and application at the same time or in separated applications at the same time or different times.

[0041] The admixture or individual components may be in any physical form, e.g. blend, solution, suspension, dispersion, emulsion, alloy, or the like.

[0042] As used herein, the term “fungicidally effective amount” refers to an amount of the active component that is commercially recommended for use to control fungi. The commercially recommended amount for each active component, often specified as application rates of the commercial formulation, may be found on the label accompanying the commercial formulation. The commercially recommended application rates of the commercial formulation may vary depending on factors such as the plant species and the fungus to be controlled.

[0043] As used herein, the term “treating a plant or soil against fungal infection” includes, but is not limited to, protecting the plant or soil against fungal attack, preventing fungal infection of the plant or soil, controlling fungal disease infecting the plant or soil, and reducing fungal infection of the plant or soil. As used herein, the term “more effective” includes, but is not limited to, increasing efficacy of fungal disease control, prolonging protection and reducing the amount of time needed to achieve a given level of fungal control, prolonging the duration of protection against fungal attack after application and extending the protection period against fungal attack and / or reducing the amount of time needed to achieve a level of fungal control compared to the fungicide formulation without suitable inert components therein. In particular, “more effective” includes increasing efficacy of fungal disease control in an untreated area.

[0044] As used herein, the term “effective” when used in connection with any mixture or formulation may be but is not limited to increase in controlling fungal disease, increase in preventing fungal disease, decrease time for effective controlling fungal disease, decrease the amount of the fungicide(s) which is required for effective controlling fungal disease, extend the controlling effect of the individual fungicide in the mixture in terms of type of crop and disease, prolong the time of controlling effect of the mixture compared to the individual fungicide in the mixture in terms of type of crop and disease, prolong the time of controlling effect of the individual fungicide in the mixture in terms of type of crop and disease. In particular, the term “effective” may refer to, increasing efficacy of fungal disease control in untreated plant area, reducing the amount of time needed to achieve a given level of fungal control, extending the protection period against fungal attack and / or reducing the amount of time needed to achieve a level of fungal control.

[0045] As used herein, the term "effective amount" refers to an amount of the agrochemical composition or of the mixture which is sufficient for controlling harmful fungi on crop plants and does not cause any significant damage to the treated crop plants.

[0046] As used herein, the term "agriculturally acceptable carrier" means carriers which are known and accepted in the art for the formation of compositions for agricultural or horticultural use.

[0047] As used herein, the term "inert components" or “coformulants” is defined as any substance that itself is not an active ingredient but is added to the composition or formulation such as additives, thickening agent, sticking agents, surfactants, anti-oxidation agent, antifoaming agents and thickeners.

[0048] As used herein, the term “ready -mix formulation” is described as a formulation system wherein two or more active ingredients are mixed in a process of preparation of a single formulation. As used herein, the term “tank mix formulation” is described as a formulation system wherein two or more formulations comprising different active ingredients, respectively in the said formulations, are mixed with each other by pouring or adding one said formulation to another.

[0049] As used herein the term "plant" or "crop" includes reference to agricultural crops including field crops (soybean, maize, wheat, rice, etc.), vegetable crops (potatoes, cabbages, etc.), fruits (peach, etc.), semi-perennial crops (sugarcane) and perennial crops (coffee and guava).

[0050] As used herein the term "plant" or “crop” includes reference to whole plants, plant organs (e.g. leaves, stems, twigs, roots, trunks, limbs, shoots, fruits etc.), plant cells, seedling or plant seeds. This term also encompasses plant crops such as fruits.

[0051] The term “plant” may also include the propagation material thereof, which may include all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers, which can be used for the multiplication of the plant. It may also include spores, corms, bulbs, rhizomes, sprouts, basal shoots, stolons, and buds and other parts of plants, including seedlings and young plants, which are to be transplanted after germination, rooting or after emergence from soil or any other kind of substrate, be it artificial or natural.

[0052] As used herein the term "propagation material" is to be understood to denote all the generative parts of the plant such as seeds and spores, vegetative structures such as bulbs, corms, tubers, rhizomes, roots stems, basal shoots, stolons and buds.

[0053] As used herein, the term "locus" includes not only areas where fungal infection / disease may already be shown, but also areas where fungal infection / disease have yet to show and also area under cultivation. Locus include but is not limited to soil and other plant growth medium.

[0054] As used herein, the term "locus" includes a habitat, breeding ground, plant, propagation material, soil, area, material or environment in which a fungal disease is growing or may grow.

[0055] As used herein, the terms “control” or “controlling” or "treating" refers but is not limited to preventing fungal disease, protecting plants from fungal disease, delaying the onset of fungal disease, and combating or killing fungal disease. They also may include the curative and / or eradication action of compounds and compositions on underway fungal diseases. Controlling fungal disease infecting the plant, propagation material of the plant or locus of the plant, controlling a plant or soil disease caused by phytopathologic fungi (pathogen), controlling fungal attack on the plant or, propagation material of the plant or locus of the plant refers to curative application and / or protectant / preventive application and / or persistence application.

[0056] The term "applying" or "application", as used herein, refers but is not limited to applying the compounds and compositions of the invention to the plant, to a site of infestation by fungi, to a potential site of infestation by the fungi, which may require protection from infestation, or the environment around the habitat or potential habitat of the fungi. It also refers to the activity of compounds and compositions on plants and fungal tissues with which they come into contact. The application may be by methods described in the present invention such as by spraying, dipping, etc.

[0057] Throughout the application, descriptions of various embodiments the term “comprising” is used; however, it will be understood by one of skill in the art, that in some specific instances, an embodiment can alternatively be described using the language “consisting essentially of’ or “consisting of.” The term “a” or “an” as used herein includes the singular and the plural, unless specifically stated otherwise. Therefore, the terms “a,” “an” or “at least one” can be used interchangeably in this application.

[0058] As used herein, for example, the expression “formulation system maintains an amount of Prothioconazole which is at least 90% w / w of the total amount of Prothioconazole that is used for the preparation of the formulation system” means that the amount of free Prothioconazole in the end formulation system which is detected by HPLC, is at least 90% of total Prothioconazole used to prepare the formulation system, which in turn, means maximum 10% degradation of Prothioconazole in the end formulation system.

[0059] Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0060] In this regard, use of the term “about” herein specifically includes ±10% from the indicated values in the range. In addition, the endpoints of all ranges directed to the same component or property herein are inclusive of the endpoints, are independently combinable, and include all intermediate points and ranges.

[0061] As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items. Expressions such as "at least one of," when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.

[0062] For purposes of better understanding the present teachings and in no way limiting the scope of the teachings, each numerical parameter should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. In this regard, used of the term "about" herein specifically includes ±10% from the indicated values in the range. In addition, the endpoints of all ranges directed to the same component or property herein are inclusive of the endpoints, are independently combinable, and include all intermediate points and ranges.

[0063] Fungicide mixture formulations

[0064] There is always a considerable challenge to formulate a fungicide mixture formulation comprising Prothioconazole as one of the active ingredients and an additional fungicide, such as, a phthalimide fungicide with suitable inert components, without substantial degradation of Prothioconazole in the same fungicide mixture formulation.

[0065] The inventors observed that Prothioconazole undergoes huge degradation when formulated as mixture along with a phthalimide fungicide, such as Folpet. Degradation of Prothioconazole in the formulation is observed even up to 95% and above within a day at ambient condition in the formulation containing both actives. While addressing those challenges, the inventors recognized that the identification of suitable coformulants as compatibility agents are key in the fungicide mixture formulation prepared as ready mix and Tank mix that can protect degradation of Prothioconazole in the same formulation.

[0066] In this endeavor, the inventors have attempted several options to make an efficient formulation system comprising Prothioconazole as one of the active ingredients, and an additional fungicide, such as, a phthalimide fungicide with a suitable inert compatibility agent. Several combinations of inert components or surfactants were tried.

[0067] After several experimentations, it is surprisingly found that in a formulation system of mixture containing Folpet and Prothioconazole, the compatibility agents like Aluminium chloride, Aluminium sulphate, Stannous chloride, Stannic chloride, Stannous sulphate, were identified, which prevent degradation of Prothioconazole and Folpet when prepared as either suspension concentrate or Tank mix formulations. For example, the Tank mix was prepared by mixing (a) Folpet WG and Prothioconazole EC or (b) Folpet SC and Prothioconazole SC having defined active content. The stability of suspension concentrate, for instance, was observed until 2 weeks at room temperature. The stability of tank mix was also observed up to 20 hr after tank mix preparation at different intervals of 30 min, 2 hr and 6 hr and more.

[0068] In an embodiment, the present invention provides a fungicide mixture formulation system comprising (a) an effective amount of a phthalimide fungicide selected from the group consisting of Folpet, Captan and any combination thereof; (b) an effective amount of a second fungicide which is Prothioconazole; and (c) an effective amount of a compatibility agent, wherein the formulation system optionally comprises a polyol additive selected from a group comprising glucose, galactose, fructose, ribose, lactose, maltose, ethylene glycol, glycerol, sorbitol, inositol, mannitol, lactitol, xylitol and erythritol.

[0069] In an embodiment, the present invention provides a fungicide mixture formulation system as described herein comprising (a) an effective amount of a phthalimide fungicide selected from the group consisting of Folpet, Captan and any combination thereof; (b) an effective amount of a second fungicide which is Prothioconazole; and (c) an effective amount of a compatibility agent which is a derivative of either a metal or a non-metal element.

[0070] In an embodiment, the present invention further provides a fungicide mixture formulation system as described herein comprising (a) an effective amount of a phthalimide fungicide selected from the group consisting of Folpet, Captan and any combination thereof; (b) an effective amount of a second fungicide which is Prothioconazole; and (c) an effective amount of a compatibility agent which is selected from a group comprising Aluminium Chloride, Aluminium Sulphate, Aluminium Nitrate, Stannous Chloride, Stannous Sulphate, Stannic Chloride, Lead nitrate, Boric acid and any combination thereof.

[0071] In an embodiment, the present invention provides a fungicide mixture formulation system as described herein comprising the phthalimide fungicide in the mixture is either Folpet or Captan.

[0072] In an embodiment, the present invention provides a fungicide mixture formulation system as described herein comprising the amounts of phthalimide fungicide and Prothioconazole is in a ratio from 40: 1 to 1 : 1.

[0073] In an embodiment, the present invention provides a fungicide mixture formulation system as described herein comprising the amounts of the compatibility agent and the phthalimide fungicide is from 1 :50 to 10: 1. In a specific embodiment, the invention also provides a fungicide mixture formulation system as described herein comprising the amounts of the compatibility agent and the phthalimide fungicide is from 1 : 10 to 1 : 1.

[0074] In an embodiment, the present invention provides a fungicide mixture formulation system as described herein, where the formulation system further comprises agriculturally acceptable carriers, which are selected from a group comprising a stabilizer, a dispersing agent, a wetting agent, a defoamer, an anti-freezing agent, a biocide, a rheology modifier and any combination thereof.

[0075] In an embodiment, the present invention provides a fungicide mixture formulation system as described herein, wherein the formulation is either a concentrated ready-mix formulation or a tank mix formulation.

[0076] In an embodiment, the present invention provides a fungicide mixture formulation system as described herein, where the formulation system maintains an amount of Prothioconazole which is at least 90% of the total amount of Prothioconazole that is used for the preparation of the formulation system.

[0077] In some embodiments, the formulation comprises an amount of the Prothioconazole that is 95-99% of the Prothioconazole which was used for formulating or preparing the said formulation.

[0078] In some embodiment, the compatibility agent is a compound that increases the fungicidal efficacy of a formulation comprising phthalimide fungicide and Prothioconazole compared to the same formulation without the compatibility agent.

[0079] In some embodiments, the formulation comprises an amount of compatibility agent such that the composition is more effective for controlling fungi compared to a formulation prepared using the same phthalimide fungicide in the same amount and Prothioconazole in the same amount but without the compatibility agent.

[0080] In some embodiments, the amount of the compatibility agent is effective for reducing the rate and / or extent of reduction or for preventing the reduction of the amount of prothioconazole in the formulation. In some embodiments, the amount prothiconazole in the formulation is measured by HPLC. HPLC measurements may be taken using any one of the methods described throughout this application.

[0081] In some embodiments, the amount of the compatibility agent is effective for maintaining the amount of Prothioconazole in the composition at an amount that is 80-99% of the amount of the Prothioconazole used for formulating or preparing the formulation. In some embodiments, the amount of the compatibility agent is effective for maintaining the amount of Prothioconazole in the formulation at an amount that is 85-99% of the amount of the Prothioconazole used for formulating or preparing the formulation. In some embodiments, the amount of the compatibility agent is effective for maintaining the amount of Prothioconazole in the formulation at an amount that is 90-99% of the amount of the Prothioconazole used for formulating or preparing the formulation. In some embodiments, the amount of the compatibility agent is effective for maintaining the amount of Prothioconazole in the formulation at an amount that is 95-99% of the amount of the Prothioconazole used for formulating or preparing the formulation. The amount of Prothioconazole in the formulation may be detected by HPLC at same RT as the Prothioconazole used to formulate / prepare the formulation.

[0082] In some embodiments, the formulation comprises an amount of the Prothioconazole that is at least 95% of the amount of Prothioconazole used for formulating or preparing the formulation. In some embodiments, the formulation comprises an amount of the Prothioconazole that is at least 96% of the amount of Prothioconazole used for formulating or preparing the formulation. In some embodiments, the formulation comprises at least 97% of the amount of the Prothioconazole which was used for formulating or preparing the formulation.

[0083] In some embodiments, the formulation comprises 95-99% of the amount of the Prothioconazole which was used for formulating or preparing the formulation. The amount of free Prothioconazole in the formulation may be detected by HPLC at same RT as the Prothioconazole used to formulate the formulation.

[0084] In some embodiments, the reduction in the Prothiocnazole concentration is equal or less than 10% after storage for 2 weeks at ambient temperature.

[0085] In some embodiments, the reduction in the Prothiocnazole concentration is equal or less than 5% after storage for 2 weeks at ambient temperature.

[0086] In some embodiments, the reduction in the amount of the Prothioconazole in presence of phthalimide fungicide when the phthalimide fungicide and prothioconazole are mixed in the presence of compatibility agent is lower than when the phthalimide fungicide and prothioconazole are mixed in the absence of compatibility agent.

[0087] In some embodiments, the invention provides a formulation comprising any one of the combinations described herein and at least one agriculturally acceptable carrier.

[0088] In some embodiments, the formulation comprises water-immiscible carrier.

[0089] In some embodiments, the agriculturally acceptable carrier is water.

[0090] In some embodiments, the phthalimide fungicide is suspended in the water. In some embodiments, the Prothioconazole is suspended in the water.

[0091] In some embodiments, the Prothioconazole is dissolved in the water-immiscible carrier.

[0092] A formulation according to the invention preferably is in the form of a suspension concentrate (SC), suspoemulsion (SE), emulsion (EW), a water dispersible granule (WG), a wettable powder (WP), a dispersion concentrate (DC), a dry powder seed treatment (DS), a water slurriable powder (WS), or a flowable seed treatment (FS). A preferred formulation is a suspoemulsion (SE) and suspension concentrate (SC).

[0093] In an embodiment, the present invention provides a fungicide mixture formulation system as described herein, where all the formulation systems further comprise an additional fungicide.

[0094] In an embodiment, the present invention provides a fungicide mixture formulation system as described herein, where all the formulation systems further comprise the additional fungicide is selected from the group consisting of strobilurin fungicides, benzamide fungicide, morpholines, Qil fungicide, SDHI and any combinations thereof.

[0095] In an embodiment, the present invention provides a fungicide mixture formulation system as described herein, where all the formulation systems further comprise the additional fungicide which is a strobilurin fungicide. The present invention also in an embodiment, specifically provides a fungicide mixture formulation system as described herein, where all the formulation systems further comprise the additional fungicide which comprises picoxystrobin and / or azoxystrobin and / or fluxapyroxad.

[0096] In an embodiment, the present invention further provides a use of a compatibility agent or any combination thereof as described herein, for formulating or preparing a fungicide mixture formulation system comprises the phthalimide fungicide and prothioconazole, wherein the formulation system maintains an amount of Prothioconazole which is at least 90% w / w of the total amount of Prothioconazole that is used for the preparation of the formulation system.

[0097] In an embodiment, present invention provides a use of a compatibility agent or any combination thereof as described herein, for formulating or preparing a fungicide mixture formulation system comprises Folpet and Prothioconazole, wherein the formulation system maintains an amount of Prothioconazole which is at least 90% of the total amount of Prothioconazole that is used for the preparation of the formulation system.

[0098] In an embodiment, present invention provides a use of a compatibility agent or any combination thereof as described herein, for formulating or preparing a fungicide mixture formulation system comprises Captan and Prothioconazole, wherein the formulation system maintains an amount of Prothioconazole which is at least 90% of the total amount of Prothioconazole that is used for the preparation of the formulation system.

[0099] In an embodiment, present invention provides a use of a compatibility agent or any combination thereof as described herein, where the use of compatibility agent is for reducing the rate and / or extent of reduction or for preventing the reduction of the amount of an Prothioconazole in presence of phthalimide fungicide, so that the rate and / or extent of reduction in the amount of the Prothioconazole amount is lower than the rate and / or extent of reduction of the amount of the Prothioconazole in the same formulation system without compatibility agent.

[0100] In an embodiment, present invention provides a method of treating a plant or soil against fungal infection comprising applying the fungicide mixture formulation system as described herein, to a plant, a locus thereof, to propagation material of the plant, or soil so as to thereby treat the plant or soil against fungal infection.

[0101] The following examples illustrate the practice of the present invention in some of its embodiments but should not be construed as limiting the scope of the invention. Other embodiments will be apparent to one skilled in the art from consideration of the specification and examples. It is intended that the specification, including the examples, is considered exemplary only without limiting the scope and spirit of the invention.

[0102] PREPARATORY EXAMPLES:

[0103] Formulations:

[0104] Some exemplary embodiments of the formulation system of the present invention are illustrated in the below Tables:

[0105] Table 01 : Screening the effects of Compatibility agent(s) for Prothioconazole + Folpet SC.

[0106] Table 02: Stabilization of Prothioconazole +Folpet SC by different Compatibility agents:

[0107] It is very clearly seen from the above tables that some of the compatibility agents have a considerable stabilizing effect on the ready mixture formulation of phthalimide fungicide and Prothioconazole.

[0108] Following screenings were also conducted to analyze the stabilizing effect of the compatibility agents on the tank mix fungicidal formulations in terms of degradation of Prothioconazole. Table 03: Stabilization of Prothioconazole degradation in the tank mix prepared by combining Folpet WG and Prothioconazole EC.

[0109]

[0110] Representative procedure for preparing ready mix Folpet+Prothioconazole SC:

[0111] 1. Demineralized water, Propylene Glycol, Atlox 4894, Atlox 4913, SAG 1572, Proxel GX1, Vangel B, trisodium citrate, and compatibility agent (as required) are added and mixing is continued for 15 min under high shear.

[0112] 2. Prothioconazole technical (as required) is added followed by Folpet technical (as required) to the above mixture and continued mixing for 30 min under high shear. 3. The above slurry is passed through bead mill to achieve particle size reduction, D90 less than 5 micron.

[0113] 4. Previously prepared Agrhopol 2% gel solution is added to the milled suspension and continued stirring for up to 2-3 hr to obtain the final suspension concentrate, Folpet+ Prothioconazole SC.

[0114] Procedure for preparing Tank Mix of Folpet and Prothioconazole:

[0115] 1. Compatibility agent (as required) is added to water and mixed for lOmin to form clear solution.

[0116] 2. Folpet SC or Folpet WG is added as required to above solution and mixed for 15 min.

[0117] 3. Prothioconazole EC or Prothioconazole SC is added, as required, to the above mixture and stirred for 15 min to obtain the tank mix of Folpet and Prothioconazole.

[0118] Tank mix composition prepared with Prothioconazole 25 % EC and Folpet 80% WG (Ref: FP TM 032)

[0119] Tank mix formulation prepared with Prothioconazole 30% SC and Folpet 40% SC (Ref:

[0120] FP TM 02)

[0121] The processes of preparation of Folpet SC, Folpet WG, Prothioconazole EC, Prothioconazole SC required for Tank mix are described below:

[0122] Folpet SC:

[0123] 1. Demineralized water, Propylene Glycol, Atlox 4894, Atlox 4913, SAG 1572, Proxel GX1, Vangel B and compatibility agent (as required) are added and continued mixing for 15min under high shear.

[0124] 2. Folpet technical (as required) is added to the above solution and continued mixing for 30 min under high shear.

[0125] 3. The above slurry is passed through bead mill to achieve particle size reduction, D90 less than 5 micron.

[0126] 4. Previously prepared Agrhopol 2% gel solution is added to the milled suspension and continued stirring for up to 2-3 hr to obtain the suspension concentrate.

[0127] Folpet WG:

[0128] 1. Talc, Tamol DN, Vanisperse CB, Geropon T / 36, Rhodopon LZS 94RPB, Geronol AF80 and Folpet technical (as required) are added into the pre-blender and mixed for 15min.

[0129] 2. The above premix powder is micronized to achieve particle size with D90 less than 8 micron.

[0130] 3. The dough is prepared by adding required quantity of Silwet L-77 and demineralized water to the above micronized premix.

[0131] 4. Extrude and dry the wet water dispersible granules in fluid bed dryer. Sieve the dried water dispersible granules to remove fines and obtain the final water dispersible granules Folpet WG.

[0132] Prothioconazole EC:

[0133] 1. Coformulant Armid DM10, Rhodacal 60BER, Soprophor 796P are mixed well for 15 min with continuous stirring.

[0134] 2. Prothioconazole technical (as required) is added to the above solution and continued mixing for 30 min with stirring to get clear emulsifiable solution.

[0135] Prothioconazole SC:

[0136] 1. Demineralized water, Propylene Glycol, Atlox 4894, Atlox 4913, SAG 1572, Proxel GX1, Vangel B and compatibility agent (as required) are added and continued mixing for 15min under high shear.

[0137] 2. Prothioconazole technical (as required) is added to the above solution and continued mixing for 30 min under high shear.

[0138] 3. The above slurry is passed through bead mill to achieve particle size reduction, D90 less than 5 micron.

[0139] 4. Previously prepared Agrhopol 2% gel solution is added to the milled suspension and continue stirring for up to 2-3 hr to obtain the suspension concentrate.

Claims

WHAT IS CLAIMED IS:

1. A fungicide mixture formulation system comprising(a) an effective amount of a phthalimide fungicide selected from the group consisting of Folpet, Captan and any combination thereof;(b) an effective amount of a second fungicide which is Prothioconazole; and(c) an effective amount of a compatibility agent wherein the formulation system optionally comprises a polyol additive selected from a group comprising glucose, galactose, fructose, ribose, lactose, maltose, ethylene glycol, glycerol, sorbitol, inositol, mannitol, lactitol, xylitol and erythritol.

2. The fungicide mixture formulation system of claim 1, wherein the compatibility agent is a derivative of either a metal or a non-metal element.

3. The fungicide mixture formulation system of claim 2, wherein the compatibility agent is selected from a group comprising Aluminium Chloride, Aluminium Sulphate, Aluminium Nitrate, Stannous Chloride, Stannous Sulphate, Stannic Chloride, Lead nitrate, Boric acid and any combination thereof.

4. The fungicide mixture formulation system of claim 1, wherein the phthalimide fungicide is selected from group consisting of Folpet and Captan.

5. The fungicide mixture formulation system of any of claim 1 to 4, wherein the ratio of amounts of the phthalimide fungicide and Prothioconazole is from 40: 1 to 1 : 1.

6. The fungicide mixture formulation system of any of claim 1 to 4, wherein the ratio of amounts of the compatibility agent and the phthalimide fungicide is from 1 :50 to 10: 1.

7. The fungicide mixture formulation system of claim 6, wherein the ratio of amounts of the compatibility agent and the phthalimide fungicide is from 1 : 10 to 1 : 1.

8. The fungicide mixture formulation system of any of claim 1-7 further comprising agriculturally acceptable carriers, which are selected from a group comprising a stabilizer, a dispersing agent, a wetting agent, a defoamer, an anti-freezing agent, a biocide, a rheology modifier and any combination thereof.

9. The fungicide mixture formulation system of any of claim 1-8 wherein the formulation is a concentrated ready-mix formulation.

10. The fungicide mixture formulation system of any of claim 1-8 wherein the formulation is a tank mix formulation.

11. The fungicide mixture formulation system of any of claim 1-10, wherein the formulation system maintains an amount of Prothioconazole which is at least 90% of the total amount of Prothioconazole that is used for the preparation of the formulation system.

12. The fungicide mixture formulation system of any one of claims 1-11, wherein the formulation system further comprises an additional fungicide.

13. The fungicide mixture formulation system of claim 12, wherein the additional fungicide is selected from the group consisting of strobilurin fungicides, benzamide fungicide, morpholines, Qil fungicide, SDHI and any combinations thereof.

14. The fungicide mixture formulation system of claim 13, wherein the additional fungicide comprises a strobilurin fungicide.

15. The fungicide mixture formulation system of claim 13, wherein the additional fungicide comprises picoxystrobin and / or azoxystrobin and / or fluxapyroxad.

16. Use of a compatibility agent or any combination thereof according to claim 1-3, for formulating or preparing a fungicide mixture formulation system comprises the phthalimide fungicide and Prothioconazole, wherein the formulation system maintains an amount of Prothioconazole which is at least 90% of the total amount of Prothioconazole that is used for the preparation of the formulation system.

17. The use of the compatibility agent of claim 16, wherein the use is for formulating or preparing a fungicide mixture formulation system comprises Folpet and Prothioconazole, wherein the formulation system maintains an amount of Prothioconazole which is at least 90% of the total amount of Prothioconazole that is used for the preparation of the formulation system.

18. The use of the compatibility agent of claim 16, wherein the use is for formulating or preparing a fungicide mixture formulation system comprises Captan and Prothioconazole, wherein the formulation system maintains an amount of Prothioconazole which is at least 90% of the total amount of Prothioconazole that is used for the preparation of the formulation system.

19. The use of the compatibility agent of any of claim 16-18, wherein the use of compatibility agent is for reducing the rate and / or extent of reduction or for preventing the reduction of the amount of an Prothioconazole in presence of phthalimide fungicide, so that the rate and / or extent of reduction in the amount of the Prothioconazole amount is lower than the rate and / or extent of reduction of the amount of the Prothioconazole in the same formulation system without compatibility agent.

20. A method of treating a plant or soil against fungal infection comprising applying the fungicide mixture formulation system of any of claim 1-15, to a plant, a locus thereof, to propagation material of the plant, or soil so as to thereby treat the plant or soil against fungal infection.