Aqueous fungicide mixture formulation with enhanced activities

Abstract

The present invention provides a stable and efficient aqueous fungicide mixture formulation comprising a phthalimide fungicide and a strobilurin fungicide, and to methods for controlling or preventing fungal diseases in crop plants. This invention also provides an efficient aqueous fungicide mixture formulation for enhancing the activities of the phthalimide fungicide as well as the strobilurin fungicide by increasing solubilities in water of the active ingredients in the said formulation, resulting in enhancing contact mode of action of the phthalimide as well as increasing systemic activity of the strobilurin.

Description

[0001] AQUEOUS FUNGICIDE MIXTURE FORMULATION WITH ENHANCED ACTIVITIES

[0002] RELATED APPLICATIQN / S

[0003] This application claims benefits of Indian Provisional Application No. IN 202311003844 filed on January 19, 2023; the entire content of which is hereby incorporated by reference herein. Throughout this application, various publications are cited. Disclosures of the documents and publications referred to herein are hereby incorporated in their entireties by references into this application.

[0004] FIELD OF INVENTION

[0005] The present invention relates to a stable and efficient aqueous fungicide mixture formulation comprising a phthalimide fungicide selected from the group consisting of folpet, captan and any combination thereof and a strobilurin fungicide selected from the group comprising azoxystrobin, pyraclostrobin, picoxystrobin and any combination thereof, and to methods for controlling or preventing fungal diseases in crop plants. This invention provides an efficient aqueous fungicide mixture formulation comprising one phthalimide fungicide and a strobilurin fungicide, for enhancing the activities of the phthalimide fungicide as well as the strobilurin fungicide by increasing solubilities in water of the active ingredients in the formulation resulting in enhancing contact mode of action of the phthalimide as well as increasing systemic activity of the strobilurin.

[0006] BACKGROUND OF INVENTION

[0007] 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.

[0008] 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.

[0009] 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 aqueous formulation of a mixture of two or more hydrophobic actives with good solubilities in the formulation. In the absence of good solubilities of actives, the efficiency of formulation is said to be not well pronounced.

[0010] The subject matter of the present invention is aqueous fungicide mixture formulations comprising two or more hydrophobic actives, namely one phthalimide fungicide selected from the group consisting of folpet, captan and any combination thereof and a strobilurin fungicide such as azoxystrobin, pyraclostrobin, picoxystrobin and any combination thereof.

[0011] Phthalimide 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 that affect energy production.

[0012] The strobilurin fungicides are extremely useful in controlling a broad spectrum of common vegetable pathogens. All strobilurin fungicides inhibit fungal respiration by binding to the cytochrome b complex III at the Qo site in mitochondrial respiration. The fungicide works by inhibiting the fungi’s ability undergo normal respiration. The strobilurin chemistries have a very specific target site. Azoxystrobin, a strobilurin fungicide, has IUPAC name of methyl (E)-2-{2[6- (2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate. This carboxylic acid methyl ester has the molecular formula of C22H17N3O5 and the molecular mass of 403.4 gmol-1. Azoxystrobin retains the methyl P-methoxyacrylate group of the naturally-occurring strobilurins, which characterizes its structure:

[0013] The molecule of azoxystrobin also has a large hydrophobic moiety of three aromatic rings: a cyanophenyl ring, a pyrimidinyl ring, and a phenylacrylate ring. At 20 °C, the solubility of azoxystrobin in water is 6.7 mg L-1(pH 5.2 and 7.0) and 5.9 mg L-1(pH 9.2), which make this active reasonably hydrophobic.

[0014] The aqueous fungicide mixture formulations comprising Azoxystrobin and a phthalimide fungicide, such as, folpet is already known in the art. The CN 102150671 patent, assigned to Nutrichem International, discloses formulations comprising azoxystrobin and folpet with synergistic effect, which are useful for preventing and controlling fungi-induced plant diseases. Furthermore, CN 102669131 publication describes fungicidal suspension concentrate formulation containing azoxystrobin and folpet.

[0015] However, no prior art has ever addressed the problem of insufficient solubilization of hydrophobic actives, such as phthalimide and strobilurin in an aqueous fungicide mixture formulation, which is key to the efficiency of formulation regarding both efficacy as well as stability. The meticulous choice of suitable inert components or coformulants in the formulation may result in surprising outcome to the efficiency of the said formulation.

[0016] The inert components or coformulants such as surfactants of a formulation must be chosen to bring crop protection active compounds, for example, hydrophobic fungicide actives, into such a formulation that the end user can apply them either as such or after dilution with water. The correct choice of suitable inert components or surfactants in the formulation often determines to a significant extent whether the active ingredient can display its full efficacy after application. When selecting suitable components to ensure the physicochemical stability and effectiveness of the formulation to the highest extent, it is necessary to be aware of the physico-chemical interactions of the inert components with the active ingredients within the formulation. There is a need to develop a highly physically stable formulation with suitable inert components or surfactant, which has high stability during the preparation, storage and application process of the formulation.

[0017] In light of the above, there is endeavor in the present invention for a novel stable aqueous fungicide mixture formulation with suitable inert components 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 solubilities and enhancing contact mode of action of the phthalimide as well as increasing systemic activity of the strobilurin, thereby enhancing efficiency. SUMMARY OF THE PRESENT SUBJECT MATTER

[0018] We have reasonably addressed the challenges as described above as a whole or in part by arriving at an efficient aqueous fungicide mixture formulation with suitable inert components therein, as defined below.

[0019] The present invention relates to an aqueous fungicide mixture formulation 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 strobilurin fungicide selected from the group comprising azoxystrobin, pyraclostrobin, picoxystrobin and any combination thereof; (c) an effective amount of a surfactant system comprising at least one anionic surfactant; and (d) an effective amount of a pH modifier.

[0020] The present invention also provides an aqueous fungicide mixture formulation 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 strobilurin fungicide selected from the group comprising azoxystrobin, pyraclostrobin, picoxystrobin and any combination thereof; (c) an effective amount of a surfactant system comprising at least one anionic surfactant; and (d) an effective amount of a pH modifier, wherein the phthalimide fungicide and the strobilurin fungicide is present in the ratio ranges from 10:1 to 1:10.

[0021] The present invention also provides an aqueous fungicide mixture formulation 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 strobilurin fungicide selected from the group comprising azoxystrobin, pyraclostrobin, picoxystrobin and any combination thereof; (c) an effective amount of a surfactant system comprising at least one anionic surfactant; and (d) an effective amount of a pH modifier, which further comprises agriculturally acceptable carriers, which are selected from a group comprising a stabilizer, a wetting agent, a defoamer, an anti-freezing agent, a biocide, a rheology modifier and any combination thereof.

[0022] The present invention also provides an aqueous fungicide mixture formulation comprising (a) an effective amount of folpet; (b) an effective amount of azoxystrobin; (c) an effective amount of a surfactant system comprising at least one anionic surfactant; and (d) an effective amount of a pH modifier.

[0023] The present invention further provides an aqueous fungicide mixture formulation comprising (a) an effective amount of folpet; (b) an effective amount of azoxystrobin; (c) an effective amount of a surfactant system comprising at least one anionic surfactant and any other surfactant selected from a group comprising non-ionic and polymeric surfactant; and (d) an effective amount of a pH modifier.

[0024] The present invention further provides an aqueous fungicide mixture formulation comprising (a) an effective amount of folpet; (b) an effective amount of azoxystrobin; (c) an effective amount of a surfactant system comprising at least one anionic surfactant and any other surfactant selected from a group comprising non-ionic and polymeric surfactant; and (d) an effective amount of a pH modifier, wherein the anionic surfactant is selected from a group of ethoxylated tristyryl phenol sulphate, napthalene formaldehyde condensate and alkyl naphthalene sulphonate, and the other surfactant is selected from a group of a poly carboxy late and butyl end capped polyalkoxylate.

[0025] The present invention further provides an aqueous fungicide mixture formulation comprising (a) an effective amount of folpet; (b) an effective amount of azoxystrobin; (c) an effective amount of a surfactant system comprising an anionic surfactant which is ethoxylated tristyryl phenol sulphate and the other surfactant which is butyl end capped polyalkoxylate; and (d) an effective amount of a pH modifier.

[0026] The present invention also provides an aqueous fungicide mixture formulation 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 strobilurin fungicide selected from the group comprising azoxystrobin, pyraclostrobin, picoxystrobin and any combination thereof; (c) an effective amount of a surfactant system comprising at least one anionic surfactant; and (d) an effective amount of a pH modifier which is either trisodium citrate dihydrate or disodium hydrogen phosphate.

[0027] The present invention further provides an aqueous fungicide mixture formulation comprising (a) an effective amount of folpet; (b) an effective amount of azoxystrobin; (c) an effective amount of a surfactant system comprising an anionic surfactant which is ethoxylated tristyryl phenol sulphate and the other surfactant which is butyl end capped polyalkoxylate; and (d) an effective amount of a pH modifier which is either trisodium citrate dihydrate.

[0028] More specifically, the present invention also provides an aqueous fungicide mixture formulation comprising (a) an effective amount of folpet; (b) an effective amount of azoxystrobin; (c) an effective amount of a surfactant system comprising an anionic surfactant which is Soprophor 4D384 and the other surfactant which is Ethylan NS 500 LQ; and (d) an effective amount of a pH modifier which is Trisodium citrate dihydrate. The present invention also provides an aqueous fungicide mixture formulation 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 strobilurin fungicide selected from the group comprising azoxystrobin, pyraclostrobin, picoxystrobin and any combination thereof; (c) an effective amount of a surfactant system comprising at least one anionic surfactant; and (d) an effective amount of a pH modifier which is either trisodium citrate dihydrate or disodium hydrogen phosphate, wherein activities of the phthalimide fungicide and the strobilurin fungicide are increased by increasing solubilities in water resulting in enhancing contact mode of action of the phthalimide as well as increasing systemic activity of the strobilurin.

[0029] The present invention also provides a method of treating a plant or soil against fungal infection comprising applying the aqueous fungicide mixture formulation disclosed herein to the plant, propagation material of the plant, or soil so as to thereby treat the plant or soil against fungal infection.

[0030] The present invention also provides use of the aqueous fungicide mixture formulation disclosed herein for combatting phytopathogenic diseases on crop plants and also for treating a plant or soil against fungal infection.

[0031] The present invention further provides use of the aqueous fungicide mixture formulation disclosed herein for controlling fungal pathogens such as Septoria tritici, Puccinia striiformis, Puccinia recondite, Rhyncosporium secalis, Ramularia collo-cygni, Pymte and Puccinia hordei, on cereals such as Wheat, Rye, Triticale and Barley.

[0032] The present invention also provides a process for the preparation of the aqueous fungicide mixture formulation disclosed herein from individual component parts.

[0033] The present invention further provides a method of controlling fungal disease comprising applying to the locus of the aqueous fungicide mixture formulation disclosed herein. The present invention also provides a method for controlling an apple scab disease comprising applying the aqueous fungicide mixture formulation, disclosed herein, to the plant, propagation material of the plant, and / or a locus of the plant. The present invention further provides a use of the aqueous fungicide mixture formulation, disclosed herein, for controlling an apple scab disease.

[0034] The present invention provides a method for controlling vegetable crops disease comprising applying the aqueous fungicide mixture formulation, disclosed herein, to the plant, propagation material of the plant, and / or a locus of the plant. The present invention further provides a use of the aqueous fungicide mixture formulation, disclosed herein, for controlling vegetable crops disease. The present invention provides a method for controlling Early blight disease in potatoes, comprising applying the aqueous fungicide mixture formulation, disclosed herein, to the plant, propagation material of the plant, or a locus of the plant.

[0035] The present invention provides a method for controlling Early blight disease in tomato, comprising applying the aqueous fungicide mixture formulation, disclosed herein, to the plant, propagation material of the plant, and / or a locus of the plant.

[0036] The present invention also provides a method for controlling Sheath blight disease in rice, comprising applying the aqueous fungicide mixture formulation, disclosed herein, to the plant, propagation material of the plant, and / or a locus of the plant.

[0037] The present invention provides a method for controlling anthracnose disease in chilli, comprising applying the aqueous fungicide mixture formulation, disclosed herein, to the plant, propagation material of the plant, and / or a locus of the plant.

[0038] The present invention also relates to a use of the aqueous fungicide mixture formulation, disclosed herein, for protecting and prolonging the lifespan of medium to high resistance risk fungicides. The present invention also relates to a method of protecting and prolonging the lifespan of medium to high resistance risk fungicides comprising applying to the plant, propagation material of the plant, and / or a locus of the plant the aqueous fungicide mixture formulation, disclosed herein.

[0039] DETAILED DESCRIPTION OF THE PRESENT SUBJECT MATTER

[0040] Definitions

[0041] 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.

[0042] Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings, 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.

[0043] 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.

[0044] 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.

[0045] The admixture or individual components may be in any physical form, e.g. blend, solution, suspension, dispersion, emulsion, alloy, or the like.

[0046] 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.

[0047] 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.

[0048] 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. 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.

[0049] 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.

[0050] 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.

[0051] 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, anti-foaming agents and thickeners.

[0052] 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).

[0053] 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.

[0054] 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. 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] Fungicide mixture formulations

[0065] There is always a perennial challenge to formulate an aqueous fungicide mixture composition comprising two or more hydrophobic actives, such as, a phthalimide fungicide with an additional fungicide such as a strobilurin fungicide with suitable inert components or coformulants to arrive at an efficient formulation through hydrophobic actives solubilization, thereby enhancing efficiency.

[0066] In general, systemic activity and contact activity of agrochemical actives can be enhanced if the actives can be maintained in solubilised state during application. However, due to limitation of solubility in water the agrochemical formulations are prepared as emulsifiable concentrate (EC) in non-aqueous solvents, water-based dispersion of particles as suspension concentrate (SC), soluble liquid (SE), suspoemulsions (SE), and capsule suspensions (CS).

[0067] In the art, water insoluble active ingredients having good hydrolytic stability are formulated as dispersion of actives suspended in water, which is suspension concentrate (SC). However, having the agrochemical active in solubilized state in SC formulation leads to nucleation and growth of solubilized active as suspended particle with enormous increase in particle size and viscosity resulting in storage stability challenges such as sedimentation, phase separation. While addressing those challenges, the inventors recognized that azoxystrobin, for example, which is known for systemic mode of action, if maintained in a solubilized state helps in systemic translocation of active across the plant substrate such as leaf and root as well as fungal pest and enhances its activity. Also, the solubilized form of contact mode active, such as folpet, can help in its activity by various forms of nucleation driven particle growth by solubilisation during drying after application. Therefore, inventors have tried to develop an aqueous formulation of a mixture composition of two actives (for example, azoxystrobin and folpet) with increasing solubility of the each active, which can help in enhanced systemic and contact mode of action of both actives after application.

[0068] In this endeavor, the inventors have attempted several options to make an efficient formulation comprising two or more hydrophobic actives, for example, a phthalimide fungicide such as folpet, and a strobilurin fungicide, such as azoxystrobin. Several combinations of inert components or surfactants were tried.

[0069] After several experimentations, it is surprisingly found that a surfactant system comprising at least one anionic surfactant, with the aid of a pH modifier leads to a stable aqueous fungicide mixture formulation, which results in increased solubility of the each active, which can help in enhanced systemic and contact mode of action of both actives after application.

[0070] In an embodiment, the present invention provides an aqueous fungicide mixture formulation 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 strobilurin fungicide selected from the group comprising azoxystrobin, pyraclostrobin, picoxystrobin and any combination thereof; (c) an effective amount of a surfactant system comprising at least one anionic surfactant; and (d) an effective amount of a pH modifier.

[0071] In an embodiment, the present invention provides an aqueous fungicide mixture formulation 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 strobilurin fungicide selected from the group comprising azoxystrobin, pyraclostrobin, picoxystrobin and any combination thereof; (c) an effective amount of a surfactant system comprising at least one anionic surfactant; and (d) an effective amount of a pH modifier, wherein the phthalimide fungicide and the strobilurin fungicide is present in the ratio ranges from 10:1 to 1:10.

[0072] In an embodiment, the present invention provides an aqueous fungicide mixture formulation 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 strobilurin fungicide selected from the group comprising azoxystrobin, pyraclostrobin, picoxystrobin and any combination thereof; (c) an effective amount of a surfactant system comprising at least one anionic surfactant; and (d) an effective amount of a pH modifier, which further comprises agriculturally acceptable carriers, which are selected from a group comprising a stabilizer, a wetting agent, a defoamer, an anti-freezing agent, a biocide, a rheology modifier and any combination thereof.

[0073] In an embodiment, the present invention provides an aqueous fungicide mixture formulation comprising (a) an effective amount of folpet; (b) an effective amount of azoxystrobin; (c) an effective amount of a surfactant system comprising at least one anionic surfactant; and (d) an effective amount of a pH modifier.

[0074] In an embodiment, the present invention provides an aqueous fungicide mixture formulation comprising (a) an effective amount of folpet; (b) an effective amount of azoxystrobin; (c) an effective amount of a surfactant system comprising at least one anionic surfactant and any other surfactant selected from a group comprising non-ionic and polymeric surfactant; and (d) an effective amount of a pH modifier.

[0075] In an embodiment, the present invention provides an aqueous fungicide mixture formulation comprising (a) an effective amount of folpet; (b) an effective amount of azoxystrobin; (c) an effective amount of a surfactant system comprising at least one anionic surfactant and any other surfactant selected from a group comprising non-ionic and polymeric surfactant; and (d) an effective amount of a pH modifier, wherein the anionic surfactant is selected from a group of ethoxylated tristyryl phenol sulphate, napthalene formaldehyde condensate and alkyl naphthalene sulphonate, and the other surfactant is selected from a group of a poly carboxy late and butyl end capped polyalkoxylate.

[0076] In an embodiment, the present invention provides an aqueous fungicide mixture formulation comprising (a) an effective amount of folpet; (b) an effective amount of azoxystrobin; (c) an effective amount of a surfactant system comprising an anionic surfactant which is ethoxylated tristyryl phenol sulphate and the other surfactant which is butyl end capped polyalkoxylate; and (d) an effective amount of a pH modifier.

[0077] In an embodiment, the present invention provides an aqueous fungicide mixture formulation 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 strobilurin fungicide selected from the group comprising azoxystrobin, pyraclostrobin, picoxystrobin and any combination thereof; (c) an effective amount of a surfactant system comprising at least one anionic surfactant; and (d) an effective amount of a pH modifier which is either trisodium citrate dihydrate or disodium hydrogen phosphate.

[0078] In an embodiment, the present invention provides an aqueous fungicide mixture formulation comprising (a) an effective amount of folpet; (b) an effective amount of azoxystrobin; (c) an effective amount of a surfactant system comprising an anionic surfactant which is ethoxylated tristyryl phenol sulphate and the other surfactant which is butyl end capped polyalkoxylate; and (d) an effective amount of a pH modifier which is either trisodium citrate dihydrate.

[0079] In a specific embodiment, the present invention provides an aqueous fungicide mixture formulation comprising (a) an effective amount of folpet; (b) an effective amount of azoxystrobin; (c) an effective amount of a surfactant system comprising an anionic surfactant which is Soprophor 4D384 and the other surfactant which is Ethylan NS 500 LQ; and (d) an effective amount of a pH modifier which is Trisodium citrate dihydrate.

[0080] In an embodiment, the present invention provides an aqueous fungicide mixture formulation 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 strobilurin fungicide selected from the group comprising azoxystrobin, pyraclostrobin, picoxystrobin and any combination thereof; (c) an effective amount of a surfactant system comprising at least one anionic surfactant; and (d) an effective amount of a pH modifier which is either trisodium citrate dihydrate or disodium hydrogen phosphate, wherein activities of the phthalimide fungicide and the strobilurin fungicide are increased by increasing solubilities in water resulting in enhancing contact mode of action of the phthalimide as well as increasing systemic activity of the strobilurin.

[0081] In an embodiment, the present invention provides a method of treating a plant or soil against fungal infection comprising applying the aqueous fungicide mixture formulation disclosed herein to the plant, propagation material of the plant, or soil so as to thereby treat the plant or soil against fungal infection.

[0082] In an embodiment, the present invention provides use of the aqueous fungicide mixture formulation disclosed herein for combatting phytopathogenic diseases on crop plants and also for treating a plant or soil against fungal infection.

[0083] In an embodiment, the present invention provides use of the aqueous fungicide mixture formulation disclosed herein for controlling fungal pathogens such as Septoria tritici, Puccinia striiformis, Puccinia recondite, Rhyncosporium secalis, Ramularia collo-cygni, Pyrnte and Puccinia hordei, on cereals such as Wheat, Rye, Triticale and Barley. In an embodiment, the present invention provides a process for the preparation of the aqueous fungicide mixture formulation disclosed herein from individual component parts.

[0084] In an embodiment, the present invention provides a method of controlling fungal disease comprising applying to the locus of the aqueous fungicide mixture formulation disclosed herein. The present invention also provides a method for controlling an apple scab disease comprising applying the aqueous fungicide mixture formulation, disclosed herein, to the plant, propagation material of the plant, and / or a locus of the plant. The present invention further provides a use of the aqueous fungicide mixture formulation, disclosed herein, for controlling an apple scab disease.

[0085] In an embodiment, the present invention provides a method for controlling vegetable crops disease comprising applying the aqueous fungicide mixture formulation, disclosed herein, to the plant, propagation material of the plant, and / or a locus of the plant. The present invention further provides a use of the aqueous fungicide mixture formulation, disclosed herein, for controlling vegetable crops disease.

[0086] In an embodiment, the present invention provides a method for controlling early blight disease in potatoes, comprising applying the aqueous fungicide mixture formulation, disclosed herein, to the plant, propagation material of the plant, or a locus of the plant.

[0087] In an embodiment, the present invention provides a method for controlling Early blight disease in tomato, comprising applying the aqueous fungicide mixture formulation, disclosed herein, to the plant, propagation material of the plant, and / or a locus of the plant.

[0088] In an embodiment, the present invention provides a method for controlling Sheath blight disease in rice, comprising applying the aqueous fungicide mixture formulation, disclosed herein, to the plant, propagation material of the plant, and / or a locus of the plant.

[0089] In an embodiment, the present invention provides a method for controlling anthracnose disease in chilli, comprising applying the aqueous fungicide mixture formulation, disclosed herein, to the plant, propagation material of the plant, and / or a locus of the plant.

[0090] In an embodiment, the present invention provides a use of the aqueous fungicide mixture formulation, disclosed herein, for protecting and prolonging the lifespan of medium to high resistance risk fungicides. The present invention also relates to a method of protecting and prolonging the lifespan of medium to high resistance risk fungicides comprising applying to the plant, propagation material of the plant, and / or a locus of the plant the aqueous fungicide mixture formulation, disclosed herein. PREPARATORY EXAMPLES:

[0091] Formulation:

[0092] One exemplary embodiment of the formulation of the present invention is illustrated in the below Table 1: Table 1

[0093] Following experimentations have been performed to test the solubility of the active ingredients in presence or absence of various surfactants:

[0094] Table 2. Solubility of azoxystrobin and folpet in the absence of surfactants Table 3. Solubility of azoxystrobin and folpet with different amount of surfactant Soprophor 4D384 and Ethylan NS500.

[0095] Table: 4. Different compositions containing azoxystrobin and folpet with different surfactants Table 5. Solubility of azoxystrobin and folpet in aqueous phase of different compositions as in Table 4 (#R1 to #R4).

[0096] Conclusion: From the above experimental formulation recipes it is clearly seen that when an anionic surfactant is absent (as in batch #R2) in the recipe the solubility of active ingredients in the aqueous phase is reduced drastically. At least one anionic surfactant in the recipe is essential for an aqueous formulation to have greater and effective solubility of the active ingredients such as azoxystrobin and folpet.

Claims

WHAT IS CLAIMED IS:

1. An aqueous fungicide mixture formulation 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 strobilurin fungicide selected from the group comprising azoxystrobin, pyraclostrobin, picoxystrobin and any combination thereof;(c) an effective amount of a surfactant system comprising at least one anionic surfactant; and(d) an effective amount of a pH modifier.

2. The aqueous fungicide mixture formulation of claim 1, wherein the phthalimide fungicide and the strobilurin fungicide is present in the ratio ranges from 10:1 to 1:10.

3. The aqueous fungicide mixture formulation of any of claim 1-2 further comprising agriculturally acceptable carriers, which are selected from a group comprising a stabilizer, a wetting agent, a defoamer, an anti-freezing agent, a biocide, a rheology modifier and any combination thereof.

4. The aqueous fungicide mixture formulation of any of claim 1-3, wherein the phthalimide fungicide is folpet, and the strobilurin fungicide is azoxystrobin.

5. The aqueous fungicide mixture formulation of any of claim 1-3, wherein the surfactant system comprising at least one anionic surfactant and any other surfactant selected from a group comprising non-ionic and polymeric surfactant.

6. The aqueous fungicide mixture formulation of claim 5, wherein the anionic surfactant is selected from a group of ethoxylated tristyryl phenol sulphate, napthalene formaldehyde condensate and alkyl naphthalene sulphonate.

7. The aqueous fungicide mixture formulation of claim 5, wherein the other surfactant is selected from a group of a polycarboxylate and butyl end capped polyalkoxylate.

8. The aqueous fungicide mixture formulation of claim 5, wherein the anionic surfactant is ethoxylated tristyryl phenol sulphate, and the other surfactant is butyl end capped polyalkoxylate.

9. The aqueous fungicide mixture formulation of claim 8, wherein the anionic surfactant is Soprophor 4D384, and the other surfactant is Ethylan NS 500 LQ.

10. The aqueous fungicide mixture formulation of any of claim 1-3, wherein the pH modifier is either Trisodium citrate dihydrate or disodium hydrogen phosphate.

11. The aqueous fungicide mixture formulation of claim 10, wherein the pH modifier is Trisodium citrate dihydrate.

12. The aqueous fungicide mixture formulation of any of claim 1-11, wherein activities of the phthalimide fungicide and the strobilurin fungicide are increased by increasing solubilities in water resulting in enhancing contact mode of action of the phthalimide as well as increasing systemic activity of the strobilurin.

13. A method of treating a plant or soil against fungal infection comprising applying the aqueous fungicide mixture formulation of any of claim 1-12, propagation material of the plant, or soil so as to thereby treat the plant or soil against fungal infection.

14. A method for controlling an apple scab disease comprising applying the aqueous fungicide mixture formulation of any of claim 1-12, to the plant, propagation material of the plant, and / or a locus of the plant.

15. Use of the aqueous fungicide mixture formulation of any of claim 1-12 for combatting phytopathogenic diseases on crop plants and also for treating a plant or soil against fungal infection.

16. The use of the aqueous fungicide mixture formulation of claim 15, for controlling fungal pathogens on cereals.

17. The use of the aqueous fungicide mixture formulation of claim 16, wherein fungal pathogens are selected from the species Septoria tritici, Puccinia striiformis, Puccinia recondite,Rhyncosporium secalis, Ramularia collo-cygni, Pyrnte and Puccinia hordei, and wherein the cereals are selected from Wheat, Rye, Triticale and Barley.

18. The use of the aqueous fungicide mixture formulation of claim 16, for controlling an apple scab disease.

19. The use of the aqueous fungicide mixture formulation of claim 16, for controlling vegetable crops disease.

20. A method for controlling Early blight disease in potatoes, comprising applying the aqueous fungicide mixture formulation of any of claim 1-12, to the plant, propagation material of the plant, or a locus of the plant.

21. A method for controlling Early blight disease in tomato, comprising applying the aqueous fungicide mixture formulation of any of claim 1-12, to the plant, propagation material of the plant, and / or a locus of the plant.

22. A method for controlling Sheath blight disease in rice, comprising applying the aqueous fungicide mixture formulation of any of claim 1-12, to the plant, propagation material of the plant, and / or a locus of the plant.

23. A method for controlling anthracnose disease in chilli, comprising applying the aqueous fungicide mixture formulation of any of claim 1-12, to the plant, propagation material of the plant, and / or a locus of the plant.

24. A method of protecting and prolonging the lifespan of medium to high resistance risk fungicides comprising applying to the plant, propagation material of the plant, and / or a locus of the plant the aqueous fungicide mixture formulation of any of claim 1-12.

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