The present invention is relates to a synergistic stable agrochemical formulation composition comprising synergistic effective amount of actives Azoxystrobin, Isoprothiolane and Validamycin, resulting enhanced bio-efficacy. The present invention further relates to a process for preparing such formulation having synergistic bio-effective composition and a method of effective use of such composition.

BACKGROUND OF THE INVENTION
Pesticides are substances that are meant to control pests or weeds. The Food and Agriculture Organization (FAO) has defined pesticide as: any substance or mixture of substances intended for preventing, destroying, or controlling any pest, including vectors of human or animal disease, unwanted species of plants or animals, causing harm during or otherwise interfering with the production, processing, storage, transport, or marketing of food, agricultural commodities, wood and wood products or animal feedstuffs, or substances that may be administered to animals for the control of insects, arachnids, or other pests in or on their bodies. The term includes substances intended for use as a plant growth regulator, defoliant, desiccant, or agent for thinning fruit or preventing the premature fall of fruit. Also used as substances applied to crops either before or after harvest to protect the commodity from deterioration during storage and transport.
In addition to above, Fungicides are biocidal chemical compounds or biological organisms used to kill parasitic fungi or their spores. A fungistatic inhibits their growth. Fungi can cause serious damage in agriculture, resulting in critical losses of yield, quality, and profit. Fungicides are used both in agriculture and to fight fungal infections in animals. Chemicals used to control oomycetes, which are not fungi, are also referred to as fungicides, as oomycetes use the same mechanisms as fungi to infect plants. As described in a review article, Almeida1 F. et al., The Still Underestimated Problem of Fungal Diseases Worldwide, Front. Microbiol., 12 February 2019, fungal disease can damage plants and crops, causing major losses in agricultural activities and food production (Savary et al., 2012). Animal pathogenic fungi are threatening bats, amphibians and reptiles with extinction (Casadevall, 2017). It is estimated that fungi are the highest threat for animal-host and plant-host species, representing the major cause (approximately 65%) of pathogen driven host loss (Fisher et al., 2012). In this complex scenario, it is now clear that the global warming and accompanying climate changes have resulted in increased incidence of many fungal diseases (Garcia-Solache and Casadevall, 2010). On the basis of all these factors, concerns on the occurrence of a pandemic of fungal origin in a near future have been raised (Casadevall, 2017). In this context, to stop forgetting and underestimating fungal diseases is mandatory.
Also, according to scientific article Jain A. et al., A review of plant leaf fungal diseases and its environment speciation, BIOENGINEERED, 2019, volume 10, No. 409-424, there is increasing difficulty in identifying new plant leaf diseases as a result of environmental change. In addition to often being highly destructive, plant diseases can be difficult to control and may develop resistance to commercial fungicides.
When two or more substances in combination demonstrate unexpectedly high biological activity, for example fungicidal activity, the resultant phenomenon may be referred to as synergism. The reason or mechanism for the synergy may not be always known, and may differ with different combinations, but the effect can always be observed experimentally. The term ‘synergism’ or ‘synergy’ hereinafter refers to a cooperative action encountered in a combination of two or more biologically active components in which the combined activity of the two or more components exceeds the sum of the activity of each component alone. The challenge involved in developing commercially acceptable products containing agriculturally active compounds in combination continues to increase due to the rapid emergence of more complex customer and regulatory requirements. These combinations must demonstrate chemical and physical stability under wide range of conditions along with improved control of fungal diseases in commercial important crops. There was a need to identify the factors influencing the emergence and the increasing incidences of these diseases. So, there was the need of composition having the widened spectrum of action preferably in use acting as one shot solution on the disease caused by fungi in various crop plants without causing resistance developed by pathogens.
Therefore, this innovation needs an inventive and extensive study for the development of fungicidal formulation composition having wider range of synergistic bio-efficacy.
Azoxystrobin is the common name for methyl (2E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy] phenyl}-3-methoxyacrylate, IUPAC name 2-[(6-{2-[(1E)-1-methoxy-3-oxobut-1-en-2-yl]phenoxy}pyrimidin-4-yl)oxy]benzonitrile. Azoxystrobin is known from European Patent EP 382375 B1 and has molecular formula C22H17N3O5 and belongs to strobilurin group of fungicides. Azoxystrobin can be described by following structural formula;

Azoxystrobin
Its fungicidal activity is described in The Pesticide Manual, Seventeenth Edition, 2015. Azoxystrobin controls a variety of pathogens at application rates between 100 and 375 grams/hectare (g/ha). It is a fungicide with protectant, curative, eradicant, translaminar and systemic properties. It inhibits spore germination and mycelial growth and also shows antisporulant activity. The standard formulation comprising composition of Azoxystrobin available in the art is 23% SC.
Moreover, Isoprothiolane is a systemic fungicide with curative and protective effects. Isoprothiolane is a chemical compound from the group of Dithiolanes and
introduced in 1974 by Nihon Noyaku as fungicide. Isoprothiolane has a conspicuous ketene- di thioacetal structure. It is chemically known as Diisopropyl 2- (1, 3-dithiolane-2-ylidene) malonate and having chemical structure formula represented as below,

Isoprothiolane
The standard formulation comprising composition of Isoprothiolane available in the art is 40% EC
Additionally, Validamycin IUPAC name: (1R,2R,3S,4S,6R)-2,3-dihydroxy-6-(hydroxymethyl)-4-{[(1S,4S,5S,6S)-4,5,6-trihydroxy-3-hydroxymethyl)cyclohex-2-en-1-yl]amino}cyclohexyl ß-D-glucopyranoside, Molecular formula: C20H35NO13, Molecular weight: 497.5) was reported to be an antibiotic by T. Iwasa et al. in J. Antibot., 1970, 23, 595 and was introduced in the year 1972. It is represented by following structure formula;

Validamycin
Validamycin is a non-systemic antibiotic with a fungistatic action. It causes abnormal branching of the tips of the pathogen, followed by cessation of further development. It inhibits trehalase, an enzyme which mediates the digestion of the carbohydrate trehalose and transport of glucose to the hyphal’s tips. The standard formulation comprising composition of Validamycin available in the art is 3% L.
The main concern of this invention was the development of synergistic bio-effective fungicidal agrochemical formulation, which is effective in wider range to control diseases caused by Magnaporthe oryzae, Peronosporaceae, species of fungi in the order Erysiphales such as Podosphaera xanthii (a.k.a. Sphaerotheca fuliginea), Phomopsis viticola, Phytophthora palmivora, Botrytis cinerea, Aspergillus niger, Alternaria alternata, Glomerella cingulata, Cladosporium cladosporioides, Fusarium sporotrichioides, Geotrichum candidum, Pyricularia oryzae, Xanthomonas oryzae, Helminthosporium sigmoideum, Fusarium nivale Myrothecium roridum, Pythium species, Rhizopus stolonifera , Penicillium chrysogenum, Penicillium expansum, Monilinia fructicola, Pestalotia longisetula on one hand with ensuring environmental safety and intrinsic property of stability on another hand.
As disclosed herein below, some documents are available as prior art which suggest the use of Azoxystrobin, Isoprothiolane and Validamycin, in various formulation for controlling the pest/ disease. For example Chinese Patent No. CN 102258022 B is relates to a bactericidal and insecticidal composition of Isoprothiolane to Flubendiamide in weight ratio of 50:1 to 1:50, which provides a synergism effect, used for controlling paddy diseases and pests. This document does not disclose synergistic formulation comprising bio-effective amount of Azoxystrobin, Isoprothiolane and Validamycin.
In addition to above, Indian Patent application no 3334/MUM/2014 discloses a synergistic WP and WDG fungicidal composition comprising azoxystrobin and tricyclazole.
Moreover, Indian Patent 309296 discloses a synergistic fungicidal composition comprising Difenoconazole, Validamycin, and additives, wherein Difenoconazole and Validamycin are present in ratios ranging from 0.33:1 to 3:1, preferably 1:1, suspension concentrate (SC).
Pending Chinese Patent Application No. 109964941 A, relates to the bactericidal composition comprises components in percentage by weight: 10 to 15% of Validamycin A, 18 to 26% of Azoxystrobin, 4 to 8% of a polymer dispersant, 2 to 6% of glycol, 0.1 to 0.5% of xanthan gum, 0.5 to 2% of aluminum-magnesium silicate, 6 to 8% of a bactericide, 2 to 5% of an antifoaming agent, and the balance being water. This document does not disclose synergistic formulation comprising bio-effective amount of Azoxystrobin, Isoprothiolane and Validamycin. Also, Isoprothiolane has a role as a phospholipid biosynthesis inhibitor and an antifungal agrochemical component in the instant invention composition, which provides the wider synergistic bio-efficacy.
None of the prior art is describing any method and formulation comprising synergistic combination of three actives Azoxystrobin, Isoprothiolane and Validamycin having wider range of pesticidal utility as one shot solution against plurality of fungal diseases comprises at least one disease found in Cotton, Rice (Paddy), Wheat, Corn, Maize, Tomato, Chilli, Onion, Bhindi (Okra), Groundnut, Cauliflower, Mango, Sugarcane, Grapes, Tea, Coffee, Soybean, Potato, Banana, Apple, Cucumber, Citrus, Cumin, Pomegranate, Watermelon and Turmeric.
Considering the importance of effective control of a broad spectrum of fungal diseases in economically important crops, the need for a stable, agrochemical use, eco-friendly and less expensive fungicidal composition was felt. However, identifying appropriate fungicide application rates and ratio of the combinations is essential to achieve efficacious disease control.
In order to provide the solution of long felt need of efficacious, stable and safe composition, the inventors of the present invention conducted extensive study and comes up with a stable synergistic fungicidal formulation having an effective composition prepared by without much complex manufacturing process which is economically efficient. Further, this formulation demonstrates no cross-resistance to the existing fungicidal agents, reduced toxicity and little negative or no impact on the environment. Therefore, the formulation with composition of instant invention have significant broad spectrum efficacy, safety, harmonious to environment i.e. safe to natural enemies, low toxicity and do not cause phytotoxicity to any parts of crop plants.

OBJECTIVE AND ADVANTAGES OF THE INVENTION
In order to provide the solution of long felt need of synergistic efficacious, stable and safe composition, the main objective of present invention was to identify appropriate synergistically effective ratio of the actives in composition which is essential to achieve bio-efficacious disease or pest control. After conducting extensive study the inventors comes up with an invention having scientific advancement with the commercial application along with economic significance. The inventors of instant invention by conducting the study has derived a synergistic agrochemical formulation comprising Azoxystrobin, Isoprothiolane and Validamycin as active ingredients with the followings furthermore objectives/advantages
1) Another objective of this invention was to make fungicidal formulation comprising of Azoxystrobin, Isoprothiolane, Validamycin and one or more inactive excipients, wherein the resultant formulation displays higher rainfastness and does not create phytotoxicity to any part of the plant after application.
2) Further objective of present invention is to develop composition providing significant synergistic fungicidal bio-efficacy with excellent pesticidal utility against plurality of pest and diseases found in crops and plants.
3) Another objective of this invention is to develop synergistic and stable composition which is safe upon use and simultaneously environmentally harmonious i.e. non-toxic to crop environment.
4) The development of synergistic and stable composition which results in significant crop yield and harmonious to natural enemies.
5) Present invention is advantageously in characteristics by having higher rainfastness and hydrolytic stability.

SUMMARY OF THE INVENTION
The present invention relates to an agrochemical synergistic formulation and its composition comprising Azoxystrobin, Isoprothiolane and Validamycin as active ingredients. The present invention also relates to process for preparing the said stable water dispersible granule formulation.
According to one of the basic aspect of present invention, particularly the weight ratio between Azoxystrobin, Isoprothiolane and Validamycin along with one or more inactive excipients is present in the ranges of 1: (1.5-4.0): (0.2-1.0). Hence, according to basic aspect appropriate synergistically effective ratio of the actives in composition applied in synergistic rates have achieved bio-efficacious disease or pest control.
According to basic aspect, the composition of present invention comprises Azoxystrobin in an amount in between 5% to 10.0% weight percent ratio with respect to said composition, Isoprothiolane in an amount in between 15.0% to 21.0 % weight percent ratio with respect to said composition and Validamycin as an antibiotic fungicide in an amount in between 2.0% to 6.0% weight percent ratio with respect to said composition. Accordingly, the present invention synergistically acts to results in significant grain yield after crop treatment without having harmful effects on natural enemies.
Yet another aspect of the present invention is that it is safe to crop environmental, have low toxicity and does not create phytotoxicity to any part of the plant.
Yet another aspect of the present invention is to prepare composition having excellent rainfastness property after application on plants or crops.
Yet another aspect of the present invention is that, it has hydrolytic stability i.e. the ability of composition ingredients to withstand chemical decomposition in the presence of water.
Yet another aspect of the present invention is to prepare composition in the form easy to use for farmers and can be prepared by without much complex manufacturing process.
According to one aspect of the present invention, it synergistically acts against Magnaporthe oryzae, Peronosporaceae, species of fungi in the order Erysiphales such as Podosphaera xanthii (a.k.a. Sphaerotheca fuliginea), Phomopsis viticola, Phytophthora palmivora, Botrytis cinerea, Aspergillus niger, Alternaria alternata, Glomerella cingulata, Cladosporium cladosporioides, Fusarium sporotrichioides, Geotrichum candidum, Pyricularia oryzae, Xanthomonas oryzae, Helminthosporium sigmoideum, Fusarium nivale Myrothecium roridum, Pythium species, Rhizopus stolonifera , Penicillium chrysogenum, Penicillium expansum, Monilinia fructicola, Pestalotia longisetula.
Other aspects of the invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learnt by the practice of the invention.

DETAILED DESCRIPTION OF THE INVENTION
The present invention is relates to a synergistic stable agrochemical formulation with composition having broad spectrum fungicidal property comprising a bio-effective amount of actives. The present invention is also related to a process for the preparation of said fungicidal composition.
The term “fungicide” or “fungicidal” or “fungal” is similar to “pesticide” or “pesticidal” & it is used interchangeably in this whole specification. Also, the term “fungicidal formulation” or “pesticidal formulation” or “agrochemical formulation” is used interchangeably in this whole specification. The phrase "fungicidally effective amount" or “effective amount” means the amount of a agrochemical actives or fungicide needed to achieve an observable effect on a fungicidal disease or pest and/or activity of a pest in a locus, this effect may come about when pest populations are repulsed from a locus, pests are incapacitated in or around a locus and/or pests are exterminated in or around a locus. Of course, a combination of these effects can occur. Generally, pest populations or activity or both are desirably reduced more than fifty percent, preferably more than 90 percent and most preferably more than 99 percent. The formulation of present invention synergistically acts to have excellent effect on fungicidal disease and pests thus it has excellent fungicidal or pesticidal utility in control of disease or pest. Synergism is the interaction or cooperation of two or more organizations, substances, or other agents to produce a combined effect greater than the sum of their separate effects. As described in the Herbicide Handbook of the Weed Science Society of America, Ninth Edition, 2007, p. 429, “synergism” [is] an interaction of two or more factors such that the effect when combined is greater than the predicted effect based on the response to each factor applied separately. Colby's formula is applied to determine synergistic effect, as provided in WEEDS 1967, 15, 22
The action expected for a given combination of three active components of instant invention can be calculated as follows:
E = X + Y + Z – { XY+XZ+YZ } + ( XYZ )
100 10000
Wherein;
X= is individual response of active (a) Azoxystrobin
Y = is individual response of active (b) Isoprothiolane, and
Z = is individual response of (c) Validamycin.
E (Expected Control %) = expected (or predicted) response of combination of (a)
+ (b) + (c) when applied
O (Observed Control %) = observed response of combination of (a) + (b) + (c)
when applied

Ratio: Observed Control %
Expected Control %
For Synergy, O/E > 1, means synergy observed
The phrase “synergistically effective amount” or “bio-effective synergistic amount” or “bio-effective amount” of the formulation means a sufficient amount of the formulation to provide the desired fungicidal or pesticidal effect. In general, the formulation is employed in amounts that do not cause phytotoxic damage to any part of the plant and also it is safe to natural enemies. The amount of the formulation may vary depending on specific crops and other factors.
Particularly the weight ratio between Azoxystrobin, Isoprothiolane and Validamycin along with one or more inactive excipients is present in the ranges of 1: (1.5-4.2): (0.2-1.2). Hence, accordingly present appropriate synergistically effective weight ratios of the actives in composition have achieved bio-efficacious disease or pest control.
Azoxystrobin have mode of action as fungal respiration inhibitor. The azoxystrobin acts by preventing the respiration of fungi due to the disruption of electron transport chain, preventing ATP synthesis (this occurs as the azoxystrobin binds to the Qo site of Complex III within the mitochondrion).
Isoprothiolane belongs to dithiolane group. It is a systemic fungicide with curative and protective action. It gets absorbed by the plant and accumulated in the leaf tissues to avoid bacterial invasion, hinder bacterial metabolism and hence inhibits bacterial growth.
Validamycin is a non-systemic antibiotic with a fungistatic action. It causes abnormal branching of the tips of the pathogen, followed by cessation of further development. It inhibits trehalase, an enzyme which mediates the digestion of the carbohydrate trehalose and transport of glucose to the hyphal’s tips. Optionally, Kasugamycin can be used as an antibiotic fungicide.
In accordance to above mode of actions of actives inventors of instant invention after extensive study identified appropriate synergistically effective ratio of the actives in composition which is essential to achieve bio-efficacious disease or pest control. This has provided the solution of long felt need of synergistic efficacious, stable and safe composition.
According to preferred embodiments/ examples of instant invention, Azoxystrobin in synergistic fungicidal agrochemical formulation composition used in an amount in between 5% to 10.0% weight percent ratio with respect to said composition, preferably in an amount in between 5% to 8% by weight of the composition. Isoprothiolane is used in an amount in between 15.0% to 21.0 % weight percent ratio with respect to said composition, preferably in an amount in between 16.0% to 19.0% by weight of the composition and Validamycin as an antibiotic fungicide is used in an amount in between 2.0% to 6.0% weight percent ratio with respect to said composition. Preferably, antibiotic fungicide is present in an amount in between 2.5% to 4.0% by weight of the composition. The formulation of present invention acts synergistically superior and effective control on fungal infections in various crops along with beneficially having no cross-resistance to the existing fungicidal agents, reduced toxicity and little negative or no impact on the environment. This synergistic efficacy results in significant grain yield after crop treatment without having harmful effects on natural enemies. The instant synergistic fungicidal composition is being employed in a synergistically effective amount dose in ranging from 500 g/hectare to 1600 g/hectare, wherein that dose does not cause phytotoxic damage to any part of a plant and wherein said formulation is safe to a plurality of natural enemies. More preferably it is being employed in a synergistically effective amount dose in ranging from 1000 g/hectare to 1600 g/hectare. This synergistic efficacy results in significant grain yield after crop treatment without having harmful effects on natural enemies. The fungicidal utility of present invention in excellent control of pest and disease in various crops is given in Table 1.
Table 1
Crops Pest/Disease
Cotton Leaf spot and Grey mildew
Rice Blast & sheath blight, False smut and Grain discoloration
(Dirty Panicle)
Wheat Rust, Yellow rust, Powdery mildew
Corn Turcicum leaf blight
Maize Downy mildew, Turcicum leaf blight, Rust, Blight
Tomato Early and late blight, Septoria leaf spot
Chilli Powdery mildew, Downy mildew, Anthracnose, Fruit rot.
Onion Purple blotch, Stemphylium blight and Downy mildew
Bhindi (Okra) Post emergent damping off
Groundnut Tikka disease
Cauliflower Leaf spot, downy mildew
Mango Powdery mildew, Anthracnose.
Sugarcane Red rot, Smut and Rust
Grapes Downey Mildew& Powdery mildew, Leaf spot, Anthracnose
Tea Rust
Coffee Rust
Soybean Frog eye leaf spot, Alternaria leaf spot, Cercospora leaf spot, Seedling rot
Potato Late Blight, Early blight
Banana Sigatoka leaf spot
Apple Scab, Powdery mildew, Premature leaf fall & Alternaria leaf spot
Cucumber Leaf spot, Downy mildew, Powdery mildew
Citrus Gemmosis (Foot Rot)
Cumin Blight & Powdery mildew
Pomegranate Leaf & Fruit spot
Watermelon Leaf spot, downy mildew and powdery mildew
Turmeric Leaf blotch, leaf spot

The synergistic fungicidal composition is effective against Magnaporthe oryzae, Peronosporaceae, species of fungi in the order Erysiphales such as Podosphaera xanthii (a.k.a. Sphaerotheca fuliginea), Phomopsis viticola, Phytophthora palmivora, Botrytis cinerea, Aspergillus niger, Alternaria alternata, Glomerella cingulata, Cladosporium cladosporioides, Fusarium sporotrichioides, Geotrichum candidum, Pyricularia oryzae, Xanthomonas oryzae, Helminthosporium sigmoideum, Fusarium nivale Myrothecium roridum, Pythium species, Rhizopus stolonifera , Penicillium chrysogenum, Penicillium expansum, Monilinia fructicola, Pestalotia longisetula.
The synergistic fungicidal composition of present invention is having significant broad spectrum efficacy, environmental protection, low toxicity and no phytotoxicity.
The composition of the present invention is formulated in a manner which suits the specific application. Non-limiting examples of suitable formulations are; Wettable powder (WP), Soluble powder (SP), Soluble granule (SG), Water dispersible granule (WDG), Dispersible concentrate (DC), Powder for dry seed treatment (DS), Emulsion for seed treatment (ES), Water dispersible powder for slurry treatment (Ws), Flowable concentrate for seed treatment (FS), Tablet (TB) and Water dispersible tablets (WT) formulation.
According to preferred embodiments/ examples of instant invention the composition is formulated in Wettable powder (WP), Soluble powder (SP), Soluble granule (SG), Water dispersible granule (WDG), Dispersible concentrate (DC), most preferably according to the embodiment of instant invention, composition is formulated as Water dispersible granule (WDG or WG). The term water dispersible granular composition (WDG) is similar to wettable granular (WG) composition and it is used interchangeably in this whole specification.
The granules of present invention virtually can be in any desired shape, for example, spheres, cylinders, ellipses, rods, cones, discs, needles and irregular shapes. Ideally, the granules are approximately spherical and cylinders, which lends to desired flow characteristics of the granules in bulk form.
An adjuvant or agriculturally acceptable adjuvants used in the present invention are any material that is added to an agrochemical formulation or pesticidal formulation to enhance or modify the performance of the composition in particular form. An adjuvants used in the present invention are making the present invention a safer to ecological environmental, having low toxicity and having no phytotoxicity effects on any part of the plant.
The term “adjuvants or agriculturally acceptable adjuvants” is similar to “inactive excipients” and can be used interchangeably in this whole specification. In accordance with the present invention, the synergistic composition further comprises one or more agriculturally acceptable adjuvants or one or more inactive excipients.
In accordance with preferred embodiment of instant synergistic fungicidal composition, wherein one or more inactive excipients is selected from the group comprising of dispersing agent, wetting agent, defoamer, anti-caking agent, binder, filler, co-filler and combinations thereof.
A dispersant is a substance which adsorbs onto the surface of particles and helps to preserve the state of dispersion of the particles and prevents them from re- aggregating. Dispersants are added to agrochemical formulations to facilitate dispersion and suspension during manufacture, and to ensure the particles re-disperse into water in a spray tank. Surfactants that are used as dispersants have the ability to adsorb strongly onto a particle surface and provide a charged or steric barrier to re-aggregation of particles. The most commonly used surfactants are anionic, non-ionic, or mixtures of the two types. In accordance with preferred embodiment dispersing agent used in the instant invention is selected from the group comprising amine salt of phosphate tristyryl phenol ethoxylated, ethoxylated propoxylated polyarylphenol, polycarboxylate (trade name Geropon Ultrasperse), styrene acrylic polymer (trade name Atlox Metasperse 550 S), polyacrylate polymer sodium salt, lignin based sulphonate, 1,2-Benzisothiazolone and combinations thereof, and present in an amount in the range from 1% to 15% weight percent ratio with respect to said composition, preferably present in an amount in the range from 1% to 10% weight percent ratio with respect to said composition.
A wetting agent is a substance that when added to a liquid increases the spreading or penetration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble liquids or suspension concentrates; and during mixing of a product with water in a spray tank or other vessel to reduce the wetting time of wettable powders and to improve the penetration of water into water-dispersible granules. In accordance with preferred embodiment wetting agent is selected from the group comprising Ethoxylated polyaryl phenol phosphate ester, Naphthalene Sulphonic acid formaldehyde condensate, dioctyl sulphosuccinate, non-ionic ethoxylate, naphthalene alkyl aryl sulphonate, alkyl sulphate, Sodium alkyl sulphate (trade name Geropon L WET RP), aryl sulphate, alkylated naphthalene sulfonate sodium salt, sodium alkyl naphthalene sulfonate blend and combinations thereof, and present in an amount in the range from 1% to 10% weight percent ratio with respect to said composition. This adjuvant is helpful for translaminar actions of actives.
In order to reduce the tendency to foam, anti-foam agents are often added either during the production stage or before filling into bottles. Generally, there are two types of anti-foam agents, namely silicones and non-silicones. Silicones are usually aqueous emulsions of dimethyl polysiloxane while the non-silicone anti-foam agents are water-insoluble oils, such as octanol and nonanol, or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface. In accordance with preferred embodiment defoamer is selected from Silicone antifoam, Polydimethylsiloxane and combinations thereof, and present in an amount in the range from 0.1% to 5.0% weight percent ratio with respect to said composition.
In accordance with preferred embodiment suspending agent or anti-caking agent is selected from the group comprising silica (silicon dioxide), PPT silica, acrylic copolymer, Sulfosuccinates, Gerapon S.A., naphthalene sulphonate of formaldehyde condensate, Lignosulphonate, Calcium lignosulfonate, Sodium lignosulfonate, Ammonium lignosulfonate, and combinations thereof, and present in an amount in the range from 1% to 10% weight percent ratio with respect to said composition.
In accordance with preferred embodiment one or more filler and co-filler is selected from the group comprising bentonite clay, lactose monohydrate, china clay, silica, sodium bicarbonate, sodium citrate, starch, kaolin and diatomaceous earth, and combinations thereof. The fillers are used in quantum satis i.e. addition as much of this ingredient as is needed to achieve the desired result. Preferably fillers are used in the range from 1% to 60% weight percent ratio with respect to said composition.
One or more binder used in the present invention is selected from the group comprising of Lactose, Polyvinylpyrrolidone (PVK), Starch, Nimbid, Xanthan gum, Agar-agar and Arabic gum or a mixture thereof, , and present in an amount in the range from 0.1% to 5% weight percent ratio with respect to said composition. Preferably used in the range from 0.25% to 2.0% weight percent ratio with respect to said composition and most preferably in 1% weight percent ratio with respect to said composition.
Biocides / Microorganisms cause spoilage of formulated products. Therefore anti-microbial agents are used optionally in instant invention to eliminate or reduce their effect. Examples of such agents include, but are not limited to: propionic acid and its sodium salt; sorbic acid and its sodium or potassium salts; benzoic acid and its sodium salt; p-hydroxy benzoic acid sodium salt; methyl p-hydroxy benzoate; and biocide such as sodium benzoate, 1,2-benzisothiazoline-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, potassium sorbate, parahydroxy benzoates or mixtures thereof.
Instant invention water dispersible granular compositions have particle size of Min 98% passing through 75 micron sieve on wet sieving. Drying of said wet granules is done in such manner to obtain wettable granular composition having characteristics of loss on drying (LOD) not more than 3.0%.
The present invention composition has excellent rainfastness, translaminar property after application on plants or crops and hydrolytic stability i.e. ability of composition ingredients to withstand chemical decomposition in the presence of water.
Present invention is manufactured without much complex manufacturing process and is in the form easy to use for farmers. Instant composition is technical advance as compared to existing knowledge and also it is economically significant in having excellent wider efficacy by resulting in significant grain yield after crop treatment without having harmful effects on natural enemies.
An agrochemical fungicidal formulation of present invention is technical advance as compared to existing knowledge and also it is economically significant in having excellent wider efficacy by resulting in significant grain yield after crop treatment without having harmful effects on natural enemies. Additionally, the present invention can be prepared by without much complex manufacturing process and is in the form easy to use for farmers.
The following illustrations of examples are intended to illustrate a synergistic and stable fungicidal formulation having excellent fungicidal property, but in no way limit the scope of the present invention.
EXAMPLES
The illustrated examples of present invention are related to a synergistic fungicidal composition formulated as a stable fungicidal formulation, having excellent fungicidal property comprising synergistically effective amount of three actives prepared by without much complex manufacturing process which is economically efficient.

EXAMPLE-1:
Azoxystrobin 5% + Isoprothiolane 18% + Validamycin 3.5% water dispersible granule (WDG or WG) composition:
Ingredients Quantity% w/w
Azoxystrobin technical (98% purity) 5.3
Isoprothiolane technical (97% purity) 18.6
Validamycin technical (64% purity) 5.5
Alkyl sulphate (wetting agent) 3.00
Polycarboxylate (dispersing agent) 8.00
Styrene acrylic polymer (dispersing agent) 2.00
Polydimethylsiloxane emulsion (Defoamer) 0.50
Silica (anti-caking agent) 5.00
Polyvinylpyrrolidone (binder) 1.00
Sodium citrate (Co-filler) 2.00
Sodium Bicarbonate (Co-filler) 2.00
China Clay (filler) 47.10
Total 100.00

The stable synergistic Water Dispersible Granule formulation comprising above bio-efficacious synergistic instant invention composition can be prepared by following procedure:
Step -1: Preparation of Pre-blending mixture
Required quantities of technical were charged in a pre-mixer blender. Add required quantity of inactive excipients under stirring at RT. Stir the mixture for further 1 hour at 15oC to 45oC.
Step-2: Grinding by ACM (Air Classifier Mill)
Grinding of obtained mixture of Step 1 was done at 15oC to 45oC through ACM to obtain micronized mass.
Step-3: Preparation of Post-blending mixture
To this obtained mass of Step 2, add DM water under stirring at 25oC to 35oC to obtain dough, mixing was continued for further 30 minutes to get desired homogeneous mixture in dough form.
Step-4: Preparation of water dispersible granule by extrusion and drying
Obtained dough of Step 3, was extruded through extruder to obtain desired granules of mesh size minimum 98% passes through 75 Micron sieve on wet sieving. Drying was done until LOD is not more than 3.0% to obtain desired instant inventive wettable granular composition.

EXAMPLE-2 (STABILITY STUDY)
Stability study of Azoxystrobin 5% + Isoprothiolane 18% + Validamycin 3.5% water dispersible granule (WG or WDG) composition was done at RT (Room Temperature) and at 54 oC (For 14 Days), the results has been tabulated in Table 2
Table 2
S.No. Analysis Requirement Results
At RT At 54 oC
(For 14 Days)
1. Description Free flowing, off white to light grey colored granules, free from extraneous matter. Complies Complies
2. Azoxystrobin Content(% w/w) 5.00 ± 5% 5.2% 5.18%
3. Isoprothiolane Content(% w/w) 18.00 ± 5% 18.04% 18.02%
4. Validamycin Content(% w/w) 3.50± 0.5% 3.52% 3.50%
5. Suspensibility
(% w/w) Min. 50.00% 84.30% 60.00%
6. pH (1% Aq. Solution) 6-10 9.24 10.0
7. Loss on drying (LOD) Max. 3.0 % 1.45 1.10%
8. Persistent Foaming (1% solution in 342 ppm hard water) Max. 60 ml after 1 minute 25 ml 25 ml
9. Wet sieving, passing through 75 micron sieve Min. 98% 99.64% 99.70%
The study reveals that instant water dispersible granule formulation is stable.

EXAMPLE-3 (BIO-EFFICACY STUDY)
Azoxystrobin have mode of action as fungal respiration inhibitor. The azoxystrobin acts by preventing the respiration of fungi due to the disruption of electron transport chain, preventing ATP synthesis (this occurs as the azoxystrobin binds to the Qo site of Complex III within the mitochondrion). Isoprothiolane belongs to dithiolane group. It is a systemic fungicide with curative and protective action. It gets absorbed by the plant and accumulated in the leaf tissues to avoid bacterial invasion, hinder bacterial metabolism and hence inhibits bacterial growth. Validamycin is a non-systemic antibiotic with a fungistatic action. It causes abnormal branching of the tips of the pathogen, followed by cessation of further development. It inhibits trehalase, an enzyme which mediates the digestion of the carbohydrate trehalose and transport of glucose to the hyphal’s tips.
Accordingly, to mode of actions of actives inventors of instant invention after extensive study identified appropriate synergistically effective ratio of the actives in composition which is essential to achieve bio-efficaciously disease or pest control. This has provided the solution of long felt need of synergistic efficacious, stable and safe composition.
Bio efficacy study herein was done for synergistic fungicidal composition of Azoxystrobin 5% + Isoprothiolane 18% + Validamycin 3.5% water dispersible granule (WG or WDG) composition, in consideration for field experiment in view of bio efficacy and synergy. The results revealed that present agrochemical pesticidal composition have broader enhanced bio efficacy, it is synergistic, and have no effects on natural enemies’ i.e. environmentally harmonious, have no effect on phytotoxicity and increases productivity in plant/crop yield.

EXAMPLE 3.1 FIELD EXPERIMENT
Bio-efficacy study has been done on Rice (Paddy). The details of experiment are:-
i. Crop and Variety : Paddy & PB-1509
ii. Target diseases : Rice blast (Pyricularia oryzae)
Sheath blight (Rhizoctonia solani)
Bacterial leaf blight
(Xanthomonas oryzae)
iii. Plot size : 6 x 5m2 (30 sq. mt)
iv. Spacing : Row to Row 20 cm and Plant to
Plant 15 cm
v. Design : RBD (Randomized Block Design)
vi. No. of replications : 3 (Three)
vii. No. of treatments : 10 (Ten)
viii. No. of spraying/Application : Two
ix. Sprayer used : High volume spray/ Knapsack
sprayer
Treatment details:-
S. No. Treatments Dosage Dilution in water (L) per hectare
Water a.i. (g) per hectare
a.i. (g) per hectare
Formulation (g/ml) per hectare
T1 Azoxystrobin 5%+Isoprothiolane 18% + Validamycin 3.5% WDG 75+ 270 + 52.5 1500 500
T2 Azoxystrobin 8 %+Isoprothiolane 20 % + Validamycin 3.5% WDG 120 + 300 + 52.5 1500 500
T3 Azoxystrobin 10 %+Isoprothiolane 15 % + Validamycin 5% WDG 150 +225 + 75 1500 500
T4 Azoxystrobin 23 % SC +Isoprothiolane 40 % EC
(Tank Mix ) 125+ 300 500 + 750 500
T5 Azoxystrobin 23% SC + Validamycin 3.0 % L (Tank Mix) 125+ 60 500 + 2000 500
T6 Isoprothiolane 40 % EC + Validamycin 3.0 % L (Tank Mix ) 300 + 60 750 + 2000 500
T7 Azoxystrobin 23% SC
(Available in Market) 125 500 500
T8 Isoprothiolane 40 % EC
(Available in Market) 300 750 500
T9 Validamycin 3.0 % L
(Available in Market) 60 2000 500
T10 Control (Untreated ) - - -
* T1 to T10 are crop treatments
Observation methodology
Bio-Efficacy Analysis Methodology
All the recommended packages of agronomy practices such as tillage, puddling, spacing, fertilizer, irrigation, insect- pest and weed control for cultivation of the rice crop are used. The temperature varies from as low as 5°C to as high as 39°C respectively. The rice variety PB- 1509 was transplanted at 25 days old and with 20 cm x 15 cm hill spacing. The test combination fungicides were applied as foliar spray with the help of knap sack sprayer (high volume sprayer) 500 litres of water/ha was used and 1st spraying was done 40 days after transplanting crop having initial symptoms of the disease appeared on plants. And 2nd spray was done at 22 days after from 1st application. Observations on disease intensity were recorded after 3, 7 and 15 days of each application on 10 randomly selected plants from each treatment. The severity of rice diseases was assessed based on the relative lesion as mentioned in standard evaluation system (SES) for rice and subsequently its corresponding rating value on 0-9 scale as mention below.
Scale rating for blight disease:-
Rating Description
0 No infection
1 Vertical spread of the disease up to 20 % of plant height
3 Vertical spread of the disease up to 21 - 30 % of plant height
5 Vertical spread of the disease up to 31 – 45 of plant height
7 Vertical spread of the disease up to 46 - 65 % of plant height
9 Vertical spread of the disease up to 66 % of plant height

Scale rating for leaf blast disease:-
Rating Description
0 No lesions observed
1 Small brown specks of pinpoint size or larger brown specks without sporulating center
3 Small, roundish to slightly elongated necrotic sporulating spots, about 1-2 mm diameter
5 Narrow slightly elliptical lesions,1- 2 mm in breadth, more than 3 mm long with a brown margin
7 Broad spindle- shaped lesion with yellow, brown, and purple margin
9 Rapidly coalescing small, whitish, grayish or bluish lesions without distinct margins

Further these grades were converted to percent disease incidence (PDI) using the formula mentioned below.
Percent disease Index (PD Index) = Sum of individual disease ratings / Number of plants assessed * Maximum disease rating scale *100
Percent Disease Incidence (PD Incidence) = Total no. of infected plant / Total no. of plant assessed *100
Percent Disease Reduction (PDR) = Control treatment – Treated treatment / Control treatment *100
The data of diseases was analyzed on standard error (SE) & critical differences (CD) at 5 percent level of significance were worked out.
Bio-efficacious results against fungicidal disease after First application of Instant Invention composition Spray is tabulated in Table 3 and bio-efficacious results against fungicidal disease after Second application is tabulated in Table 4
Observation reveals that present invention composition is bi-efficaciously effective against diseases Rice blast (Pyricularia oryzae), Sheath blight (Rhizoctonia solani) and Bacterial leaf blight (Xanthomonas oryzae) in Rice (paddy) crop.

Table 3: Mean data of diseases management after first spray application on Rice (Paddy) Crop at 40 days after transplanting crop

Treatments Details Mean data of diseases management after first spray application on Rice (Paddy) Crop
Rice blast (Pyricularia oryzae) Sheath blight (Rhizoctonia solani) Bacterial leaf blight
(Xanthomonas oryzae)
PD
Index PD
Incidence PDR PD
Index PD
Incidence PDR PD
Index PD
Incidence PDR
T1 - Azoxystrobin5%+Isoprothiolane 18%+ Validamycin 3.5% WDG @ 1500 gm/ ha 10.85
1.41
(0.66) 85.07 12.50 1.51
(0.77) 82.86 11.33 1.0
(0.77) 87.83
T2 - Azoxystrobin8%+Isoprothiolane 20 %+ Validamycin 3.5% WDG @ 1500 gm/ ha 11.46
1.48
(0.9) 84.34 12.59 1.54
(0.77) 82.52 11.67 1.2
(0.77) 85.40
T3 Azoxystrobin10%+Isoprothiolane 15 %+ Validamycin 5% WDG @ 1500 gm/ ha 11.73
1.5
(0.17) 84.13 12.68 1.53
(1.05) 82.63 10.05 1.1
(0.00) 86.61
T4 - Azoxystrobin 23%SC+Isoprothiolane 40 % EC (Tank Mix ) @ 500 + 750 ml /ha 15.97
4.99
(0.45) 47.20 14.33 3.72
(1.39) 57.81 12.33 2.97
(1.05) 63.87
T5 - Azoxystrobin 23% SC+Validamycin3.0 %L
(Tank Mix) @ 500 + 2000 ml/ha 17.12
5.20
(0.46) 44.97 14.67 4.77
(0.90) 45.89 14.15 3.74
(0.42) 54.50
T6 - Isoprothiolane 40 % EC + Validamycin 3.0 % L
(Tank Mix ) @ 750 + 2000 ml/ha 17.34
6.12
(0.40) 35.24 15.50 4.49
(0.65) 49.05 14.25 3.74
(0.42) 54.50
T7 - Azoxystrobin 23% SC @ 500 ml/ha 17.87
6.33
(0.33) 33.02 15.07 5.99
(0.96) 32.04 15.50 4.49
(0.65) 45.38
T8 - Isoprothiolane 40 % EC @ 750 ml/ha 21.33
7.58
(0.85) 19.79 16.67 6.37
(0.46) 27.68 16.33 6.13
(0.28) 25.43
T9 - Validamycin 3.0 % L @ 2000 ml/ha 20.67
8.95
(0.65) 15.87 16.33 7.12
(0.41) 19.21 16.55 6.65
(0.25) 19.10
T10 - Control (Untreated ) 41.50
9.45
(0.30) 0.00 38.33 8.81
(0.19) 0.00 41.19 8.22
(0.21) 0.00
*C.D 1.87 1.80 1.77
*SE (m) +- 0.68 0.60 0.59
*SE= standard error; CD= critical difference. Figures in parenthesis are square root transformed values.

Table 4: Mean data of diseases management after second spray application on Rice (Paddy) Crop at 22 days after from 1st application.

Treatments Details Mean data of diseases management after second spray application on Rice (Paddy) Crop
Rice blast (Pyricularia oryzae) Sheath blight (Rhizoctonia solani) Bacterial leaf blight (Xanthomonas oryzae)
PD
Index PD
Incidence PDR PD
Index PD
Incidence PDR PD
Index PD
Incidence PDR
T1 - Azoxystrobin5%+Isoprothiolane 18%+ Validamycin 3.5% WDG @ 1500 gm/ ha 8.23 1.2
(0.77) 84.59 5.85 1.32
(0.59) 83.92 6.37 0.98
(0.59) 88.35
T2 - Azoxystrobin8%+Isoprothiolane 20 %+ Validamycin 3.5% WDG @ 1500 gm/ ha 9.97 1.24
(1.19) 84.10 5.14 1.00
(0.00) 87.82 7.50 1.01
(0.77) 87.99
T3 Azoxystrobin10%+Isoprothiolane 15 %+ Validamycin 5% WDG @ 1500 gm/ ha 8.59 1.31
(0.45) 83.18 6.25 1.41
(0.77) 82.82 4.50 1.00
(0.00) 88.11
T4 - Azoxystrobin 23%SC+Isoprothiolane 40 % EC (Tank Mix ) @ 500 + 750 ml /ha 14.37 3.74
(0.42) 51.99 14.71 3.74
(0.42) 54.45 14.76 3.74
(0.42) 55.53
T5 - Azoxystrobin 23% SC+Validamycin3.0 %L
(Tank Mix) @ 500 + 2000 ml/ha 15.63 3.74
(0.42) 51.99 14.44 3.37
(0.40) 58.95 13.09 2.97
(1.05) 64.68
T6 - Isoprothiolane 40 % EC + Validamycin 3.0 % L
(Tank Mix ) @ 750 + 2000 ml/ha 18.19 5.25
(0.33) 32.61 17.19 4.49
(0.65) 45.31 16.36 4.16
(0.84) 50.54
T7 - Azoxystrobin 23% SC @ 500 ml/ha 17.01 4.77
(0.90) 38.77 17.48 5.24
(0.33) 36.18 17.57 4.91
(0.33) 41.62
T8 - Isoprothiolane 40 % EC @ 750 ml/ha 19.04 5.85
(0.28) 24.90 20.88 5.85
(0.28) 28.75 22.51 5.57
(0.00) 33.77
T9 - Validamycin 3.0 % L @ 2000 ml/ha 19.75 6.13
(0.28) 21.31 21.15 6.37
(0.46) 22.41 16.07 4.16
(0.42) 50.54
T10 - Control (Untreated ) 45.78 7.79
(0.37) 0.00 43.87 8.21
(0.40) 0.00 47.46 8.41
(0.34) 0.00
*C.D 1.84 1.42 1.57
*SE (m) +- 0.61 0.48 0.52
*SE= standard error; CD= critical difference. Figures in parenthesis are square root transformed values.

Synergism Analysis of instant invention composition after application or crop treatment
Synergism is the interaction or cooperation of two or more organizations, substances, or other agents to produce a combined effect greater than the sum of their separate effects. As described in the Herbicide Handbook of the Weed Science Society of America, Ninth Edition, 2007, p. 429, “synergism” [is] an interaction of two or more factors such that the effect when combined is greater than the predicted effect based on the response to each factor applied separately. Colby's formula is applied to determine synergistic effect, as provided in WEEDS 1967, 15, 22
The action expected for a given combination of three active components of instant invention can be calculated as follows:
E = X + Y + Z – { XY+XZ+YZ } + (XYZ)
100 10000
Wherein;
X= is individual response of active (a) Azoxystrobin
Y = is individual response of active (b) Isoprothiolane, and
Z = is individual response of (c) Validamycin.
E (Expected Control %) = expected (or predicted) response of combination of ((a)
+ (b) + (c) when applied
O (Observed Control %) = observed response of combination of (a) + (b) + (c)
when applied

Ratio: Observed Control % (% O value)
Expected Control % (% E value)
For Synergy, O/E > 1, means synergy observed
Synergistic data analysis observation reveals that instant fungicidal composition is bio-effectively synergistic against Rice blast (Pyricularia oryzae), Sheath blight (Rhizoctonia solani) and Bacterial leaf blight (Xanthomonas oryzae) when applied as First spray 40 days after transplanting crop having initial symptoms of the disease appeared on plants and Second spray application at 22 days after from 1st application. Bio-effectively synergistic observations respectively against Rice blast (Pyricularia oryzae), Sheath blight (Rhizoctonia solani) and Bacterial leaf blight (Xanthomonas oryzae) were recorded in tables 5, table 6 & table 7.
Table 5: Bio-efficacious Synergistic result of Azoxystrobin + Isoprothiolane + Validamycin composition effect against Rice blast (Pyricularia oryzae)
Treatments details Synergistic Data against Paddy Diseases Rice blast (Pyricularia oryzae)
% Diseases reduction observed % Diseases reduction Expected Colby Ratio O/E
Synergy if, O/E > 1
% O value
(Mean value) % E value
(Mean value) O/E Ratio Synergy
T1 - Azoxystrobin5%+Isoprothiolane 18%+ Validamycin 3.5% WDG @ 1500 gm/ ha 84.83 56.87 1.49 Yes
T2 - Azoxystrobin8%+Isoprothiolane 20 %+ Validamycin 3.5% WDG @ 1500 gm/ ha 84.22 56.87 1.48 Yes
T3 -Azoxystrobin10%+Isoprothiolane 15 %+ Validamycin 5% WDG @ 1500 gm/ ha 83.65 56.87 1.47 Yes
T4 - Azoxystrobin 23%SC+Isoprothiolane 40 % EC (Tank Mix ) @ 500 + 750 ml /ha 49.59 56.87 0.87 NO
T5 - Azoxystrobin 23% SC+Validamycin3.0 %L
(Tank Mix) @ 500 + 2000 ml/ha 48.48 56.87 0.85 NO
T6 - Isoprothiolane 40 % EC + Validamycin 3.0 % L ( Tank Mix ) @ 750 + 2000 ml/ha 33.93 56.87 0.59 NO
T7 - Azoxystrobin 23% SC @ 500 ml/ha 35.89 56.87 0.63 NO
T8 - Isoprothiolane 40 % EC @ 750 ml/ha 22.35 56.87 0.39 NO
T9 - Validamycin 3.0 % L @ 2000 ml/ha 18.59 56.87 0.33 NO
T10 - Control (Untreated ) 0.00 0.00 0.00 0.00

Table 6: Bio-efficacious Synergistic result of Azoxystrobin + Isoprothiolane + Validamycin composition effect against Sheath blight (Rhizoctonia solani)
Treatments details Synergistic Data against Paddy Diseases Sheath blight (Rhizoctonia solani)
% Diseases reduction observed % Diseases reduction Expected Colby Ratio O/E
Synergy if, O/E > 1
% O value
(Mean value) % E value
(Mean value) O/E Ratio Synergy
T1 - Azoxystrobin5%+Isoprothiolane 18%+ Validamycin 3.5% WDG @ 1500 gm/ ha 83.39 62.51 1.33 Yes
T2 - Azoxystrobin8%+Isoprothiolane 20 %+ Validamycin 3.5% WDG @ 1500 gm/ ha
85.17 62.51 1.36 Yes
T3 -Azoxystrobin10%+Isoprothiolane 15 %+ Validamycin 5% WDG @ 1500 gm/ ha 82.90 62.51 1.32 Yes
T4 - Azoxystrobin 23%SC+Isoprothiolane 40 % EC (Tank Mix ) @ 500 + 750 ml /ha 56.13 62.51 0.89 NO
T5 - Azoxystrobin 23% SC+Validamycin3.0 %L
(Tank Mix) @ 500 + 2000 ml/ha 52.42 62.51 0.83 NO
T6 - Isoprothiolane 40 % EC + Validamycin 3.0 % L ( Tank Mix ) @ 750 + 2000 ml/ha 47.18 62.51 0.75 NO
T7 - Azoxystrobin 23% SC @ 500 ml/ha 34.11 62.51 0.54 NO
T8 - Isoprothiolane 40 % EC @ 750 ml/ha 28.22 62.51 0.45 NO
T9 - Validamycin 3.0 % L @ 2000 ml/ha 20.81 62.51 0.33 NO
T10 - Control (Untreated ) 0.00 0.00 0.00 0.00

Table 7: Bio-efficacious Synergistic result of Azoxystrobin + Isoprothiolane + Validamycin composition effect against Bacterial leaf blight (Xanthomonas oryzae)
Treatments details Synergistic Data against Paddy Diseases Bacterial leaf blight (Xanthomonas oryzae)
% Diseases reduction observed % Diseases reduction Expected Colby Ratio O/E
Synergy if, O/E > 1
% O value
(Mean value) % E value
(Mean value) O/E Ratio Synergy
T1 - Azoxystrobin5%+Isoprothiolane 18%+ Validamycin 3.5% WDG @ 1500 gm/ ha 88.09 80.73 1.09 Yes
T2 - Azoxystrobin8%+Isoprothiolane 20 %+ Validamycin 3.5% WDG @ 1500 gm/ ha
86.70 80.73 1.07 Yes
T3 -Azoxystrobin10%+Isoprothiolane 15 %+ Validamycin 5% WDG @ 1500 gm/ ha 87.36 80.73 1.08 Yes
T4 - Azoxystrobin 23%SC+Isoprothiolane 40 % EC (Tank Mix ) @ 500 + 750 ml /ha 59.70 80.73 0.74 NO
T5 - Azoxystrobin 23% SC+Validamycin3.0 %L
(Tank Mix) @ 500 + 2000 ml/ha 59.59 80.73 0.73 NO
T6 - Isoprothiolane 40 % EC + Validamycin 3.0 % L ( Tank Mix ) @ 750 + 2000 ml/ha 52.52 80.73 0.65 NO
T7 - Azoxystrobin 23% SC @ 500 ml/ha 43.50 80.73 0.54 NO
T8 - Isoprothiolane 40 % EC @ 750 ml/ha 29.60 80.73 0.36 NO
T9 - Validamycin 3.0 % L @ 2000 ml/ha 34.82 80.73 0.43 NO
T10 - Control (Untreated ) 0.00 0.00 0.00 0.00
EXAMPLE 3.2: STUDY FOR EFFECTS ON NATURAL ENEMIES
The results of study of impact of present composition on the occurrence of natural enemies population (NEP) Ladybird beetle, Spiders, Green lacewing insect, and Minute pirate bug population after final 2nd spray was done and found that their population was not affected in the treated plots. Hence, the instant agrochemical pesticidal composition is safe to natural enemies. The result tabulated in Table 8.
Table 8
Treatment details Ladybird beetle (Coccinella spp.) Spiders Green Lacewing (Chrysoperla spp) Minute Pirate Bug (Orius Spp.)
0 Day Mean of NEP after Spray 0 Day Mean of NEP after Spray 0 Day Mean of NEP after Spray 0 Day Mean of NEP after Spray
T1 - Azoxystrobin5%+Isoprothiolane 18%+ Validamycin 3.5% WDG @ 1500 gm/ ha 0.00 1.17 1.80 2.80 0.00 0.10 0.00 0.17
T2 - Azoxystrobin8%+Isoprothiolane 20 %+ Validamycin 3.5% WDG @ 1500 gm/ ha 0.00 0.92 1.30 2.95 0.01 0.20 0.00 0.00
T3 Azoxystrobin10%+Isoprothiolane 15 %+ Validamycin 5% WDG @ 1500 gm/ ha 0.33 0.83 2.10 3.05 0.00 0.33 0.00 0.00
T4 - Azoxystrobin 23%SC+Isoprothiolane 40 % EC (Tank Mix ) @ 500 + 750 ml /ha 1.00 0.00 1.90 1.65 0.00 0.00 0.00 0.00
T5 - Azoxystrobin 23% SC + Validamycin3.0 %L
(Tank Mix) @ 500 + 2000 ml/ha 0.4 0.23 0.3 0.22 0.09 0.00 0.00 0.00
T6 - Isoprothiolane 40 % EC + Validamycin 3.0 % L
(Tank Mix ) @ 750 + 2000 ml/ha 0.00 0.42 2.00 2.15 0.06 0.20 0.00 0.00
T7 - Azoxystrobin 23% SC @ 500 ml/ha 0.00 0.58 2.70 1.50 0.00 0.00 0.00 0.00
T8 - Isoprothiolane 40 % EC @ 750 ml/ha 0.00 0.50 2.40 1.45 0.03 0.00 0.00 0.00
T9 - Validamycin 3.0 % L @ 2000 ml/ha 0.00 1.17 1.35 1.75 0.00 0.03 0.00 0.17
T10 - Control (Untreated ) 0.00 1.95 1.40 3.45 0.00 0.06 0.00 0.00

EXAMPLE 3.3: STUDY FOR PHYTOTOXICITY EFFECT ON RICE (PADDY) CROP
Treatment details:
S. No. Crop Treatments Dosage Dilution in water (L) per hectare
Water
a.i. (g) per hectare
Formulation (g/ml) per hectare
T1 Azoxystrobin 5%+Isoprothiolane 18% + Validamycin 3.5% WDG 397.50 1500 500
T2 Azoxystrobin 8 %+Isoprothiolane 20 % + Validamycin 3.5% WDG 795.00 3000 500
T3 Azoxystrobin 10 %+Isoprothiolane 15 % + Validamycin 5% WDG 1590.00 6000 500
T4 Control (Untreated ) - - 500

Methodology: Crop phytotoxicity effects rating scale:-
Effects Rating Damage in Percent Remarks
None 0 0% No crop injury
Slight 1 1-10% Some crop discoloration, stunting, necrosis, or leaf malformations.
2 11 - 20% Clear crop response symptoms just noticeable without the aid of a side-by-side untreated.
Moderate 3 21 - 30% Very visible crop injury, but crop would be expected to recover.
4 31 - 40% Significant injury but symptoms may still disappear by harvest.
Severe 5 41- 50 % Injury more persistent, recovery doubtful.
6 51 - 60% Near severe injury no recovery possible
7 61- 75 % Severe effect. Permanent injury and some crop death.
Complete 8 76 - 99% Very severe effect. Heavy crop injury with no recovery. Crop nearly destroyed.
9 100% Complete crop death

The data of phytotoxicity effects was observed on 1st, 3rd, 7th, 10th and 15th days after Azoxystrobin 5%+Isoprothiolane 18% + Validamycin 3.5% WDG spray application @ 397.50 g. a.i./ha (1500 g/ha), @ 795.50 g. a.i./ha (3000 g/ha) and @ 1590.00 g. a.i./ha (6000 g/ha) of fungicides and recorded in Table 9. In the phytotoxicity effects data was observed on different parameters chlorosis, necrosis, epinasty, hyponasty. All Treatments were found good and healthy crop and no phytotoxicity effects observed on rice crop after application of present agrochemical pesticidal composition.
Table 9
T.No. Phytotoxicity symptoms –Days after application
Chlorosis Necrosis Epinasty Hyponasty
T1 0 0 0
0
T2 0 0 0
0

T3 0 0 0
0

T4 0 0 0
0

EXAMPLE 3.4: CROP YIELD OBTAINED IN BIO-EFFICACY STUDY
This has been found that a treatment with instant synergistic fungicidal agrochemical formulation resulting in more crop yield, which implies that instant invention, is synergistic and bio-effective. The crop yield on Rice (Paddy) has been recorded in Table 10.
Table 10: Rice Crop Yield Data
Treatment Details
Yield
(q/ha)
T1-Azoxystrobin5%+Isoprothiolane 18%+ Validamycin 3.5% WDG @ 1500 gm/ ha 82.19
T2- Azoxystrobin8%+Isoprothiolane 20 %+ Validamycin 3.5% WDG @ 1500 gm/ ha 80.76
T3 Azoxystrobin10%+Isoprothiolane 15 %+ Validamycin 5% WDG @ 1500 gm/ ha 80.15
T4 - Azoxystrobin 23%SC+Isoprothiolane 40 % EC (Tank Mix ) @ 500 + 750 ml /ha 62.55
T5 - Azoxystrobin 23% SC+Validamycin3.0 %L (Tank Mix) @ 500 + 2000 ml/ha 63.72
T6 - Isoprothiolane 40 % EC + Validamycin 3.0 % L ( Tank Mix ) @ 750 + 2000 ml/ha 60.89
T7 - Azoxystrobin 23% SC @ 500 ml/ha 60.33
T8 - Isoprothiolane 40 % EC @ 750 ml/ha 62.27
T9 - Validamycin 3.0 % L @ 2000 ml/ha 48.12
T10 - Control (Untreated ) 45.23

EXAMPLE 4: Residue/ persistence study of Azoxystrobin5%+Isoprothiolane 18%+ Validamycin 3.5% WDG in Rice (Paddy) crop and soil.
Residue study of Azoxystrobin5%+Isoprothiolane 18%+ Validamycin 3.5% WDG on Rice grain , husk, straw & soil was tested in comparison to control and found that no residue/ persistence of Azoxystrobin, Isoprothiolane and Validamycin was deducted at harvest in soil & rice crop segments such as Rice grain , husk, straw.
S.No. Treatments Residue/persistence of Azoxystrobin 5%+Isoprothiolane18%+Validamycin3.5% WDG in rice crop & soil at harvest
1 Azoxystrobin5%+Isoprothiolane 18%+ Validamycin 3.5% WDG Below deduction Limit (BDL)
2 Control Below deduction Limit (BDL)
The extensive study results is attributed to the fact that each component of present invention comprising actives Azoxystrobin, Isoprothiolane, Validamycin in particular amount is complementary to each other. Thus formulation with one or more inactive excipients selected from the group comprising of dispersing agent, wetting agent, defoamer, anti-caking agent, binder, filler and co-filler formulated to bio efficacious synergistic formulation which is safe to natural enemies and it not toxicity. It is harmonious to plant/crop environment and does not have phytotoxicity on any parts of plant. Hence, instant composition is advantageous to fulfil the needs of farmer in having excellent wider synergistic bio-efficacy by resulting in significant grain yield after crop treatment.
While this invention has been described in detail with reference to certain preferred embodiments, it should be appreciated that the present invention is not limited to those precise embodiments rather, in view of the present disclosure, which describes the current best mode for practicing the invention, many modifications and variations, would present themselves to those skilled in the art without departing from the scope and spirit of this invention. This invention is susceptible to considerable variation in its practice within the spirit and scope of the appended claims.

We Claim:

1. A synergistically effective fungicidal agrochemical formulation having composition comprising of:
a) Azoxystrobin in an amount in between 5% to 10.0% weight percent ratio with respect to said composition;
b) Isoprothiolane in an amount in between 15.0% to 21.0 % weight percent ratio with respect to said composition;
c) Validamycin as an antibiotic fungicide in an amount in between 2.0% to 6.0% weight percent ratio with respect to said composition; and
d) one or more inactive excipients selected from the group comprising of dispersing agent, wetting agent, defoamer, anti-caking agent, binder, filler and co-filler.

2. The formulation as claimed in claim 1, comprising Azoxystrobin, Isoprothiolane, Validamycin and one or more inactive excipients, wherein the weight ratio of Azoxystrobin: Isoprothiolane: Validamycin is present between in the ranges of 1: (1.5-4.2): (0.2-1.2).

3. The formulation as claimed in claim 1, wherein dispersing agent is selected from the group comprising of amine salt of phosphate tristyryl phenol ethoxylated, ethoxylated propoxylated polyarylphenol, polycarboxylate, styrene acrylic polymer, polyacrylate polymer sodium salt, lignin based sulphonate, 1, 2-Benzisothiazolone and combinations thereof, and present in an amount in the range from 1% to 15% weight percent ratio with respect to said composition.

4. The formulation as claimed in claim 1, wherein wetting agent is selected from the group comprising of Ethoxylated polyaryl phenol phosphate ester, Naphthalene Sulphonic acid formaldehyde condensate, dioctyl sulphosuccinate, non-ionic ethoxylate, naphthalene alkyl aryl sulphonate, alkyl sulphate, sodium alky sulphate, aryl sulphate, alkylated naphthalene sulfonate sodium salt, sodium alkyl naphthalene sulfonate blend and combinations thereof, and present in an amount in the range from 1% to 10% weight percent ratio with respect to said composition.

5. The formulation as claimed in claim 1, wherein defoamer is selected from Silicone antifoam, Polydimethylsiloxane and combinations thereof, and present in an amount in the range from 0.1% to 5.0% weight percent ratio with respect to said composition.

6. The formulation as claimed in claim 1, wherein anti-caking agent is selected from the group comprising of silica (silicon dioxide), PPT silica, acrylic copolymer, Sulfosuccinates, naphthalene sulphonate of formaldehyde condensate, Lignosulphonate, Calcium lignosulfonate, Sodium lignosulfonate, Ammonium lignosulfonate, and combinations thereof, and present in an amount in the range from 1% to 10% weight percent ratio with respect to said composition.

7. The formulation as claimed in claim 1, wherein binder is selected from the group comprising of Lactose, Polyvinylpyrrolidone (PVK), Starch, Nimbid, Xanthan gum, Agar-agar and Arabic gum or a mixture thereof, and present in an amount in the range from 0.1% to 5% weight percent ratio with respect to said composition.

8. The formulation as claimed in claim 1, wherein filler and co-filler is selected from the group comprising of bentonite clay, lactose monohydrate, china clay, silica, sodium bicarbonate, sodium citrate, starch, kaolin and diatomaceous earth, and combinations thereof.

9. The formulation as claimed in claims 1 to 8, wherein said formulation is water dispersible granule formulation.
10. The formulation as claimed in claim 9, wherein said water dispersible granule is of shape selected from the group comprising of spheres, cylinders, extruded, ellipses, rods, cones, discs, needles and irregular shapes, wherein said cylinders, extruded water dispersible granule have particle size of Min 98% passing through 75 micron sieve on wet sieving.

11. The formulation as claimed in claims 1 to 10, wherein said formulation is employed in a synergistically effective amount dose in ranging from 1000g per hectare to 1600g per hectare.

12. The formulation as claimed in claims 1 to 11, wherein said formulation is effective against Leaf spot, Grey mildew, Blast & sheath blight, Smut, Grain discoloration (Dirty Panicle), Rust, Yellow rust, Powdery mildew, Turcicum leaf blight, Downy mildew, Early and late blight, Septoria leaf spot, Anthracnose, Fruit rot, Purple blotch, Stemphylium blight, Post emergent damping off, Tikka disease, Red rot, Frog eye leaf spot, Alternaria leaf spot, Cercospora leaf spot, Seedling rot, Sigatoka leaf spot, Scab, Premature leaf fall, Gemmosis (Foot Rot) and Leaf blotch.

(Digitally Signed)
Dated 25th day of May 2020 Durgesh Kumar Chaudhary
IN/PA-3592
Authorised Registered Indian Patent Agent
To
The Controller of Patents,
The Patent Office, at New Delhi

A SYNERGISTIC FUNGICIDAL AGROCHEMICAL FORMULATION

ABSTRACT OF THE INVENTION
A stable synergistic fungicidal agrochemical formulation with widened spectrum of action on plurality of pest & disease comprising bio-effective synergistic amount of actives Azoxystrobin in an amount ranging from 5.0 % to 10.0 % weight percent ratio, Isoprothiolane in an amount ranging from 15.0 % to 21.0 % weight percent ratio and Validamycin in an amount ranging from 2.0 % to 6.0 % weight percent ratio with respect to the said fungicidal formulation composition. The present invention is also related to a process for the preparation of said stable synergistic pesticidal formulation and in further use having significant broad agrochemical utility in many crops, without causing phytotoxic damage to any part of the plant, non-toxic and environmentally harmonious i.e. safe to natural enemies.

,CLAIMS:CLAIMS
We Claim:
1. A synergistically effective fungicidal agrochemical formulation having composition comprising of:
a) Azoxystrobin in an amount in between 5% to 10.0% weight percent ratio with respect to said composition;
b) Isoprothiolane in an amount in between 15.0% to 21.0 % weight percent ratio with respect to said composition;
c) Validamycin as an antibiotic fungicide in an amount in between 2.0% to 6.0% weight percent ratio with respect to said composition; and
d) one or more inactive excipients selected from the group comprising of dispersing agent, wetting agent, defoamer, anti-caking agent, binder, filler and co-filler.

2. The formulation as claimed in claim 1, comprising Azoxystrobin, Isoprothiolane, Validamycin and one or more inactive excipients, wherein the weight ratio of Azoxystrobin: Isoprothiolane: Validamycin is present between in the ranges of 1: (1.5-4.2): (0.2-1.2).

3. The formulation as claimed in claim 1, wherein dispersing agent is selected from the group comprising of amine salt of phosphate tristyryl phenol ethoxylated, ethoxylated propoxylated polyarylphenol, polycarboxylate, styrene acrylic polymer, polyacrylate polymer sodium salt, lignin based sulphonate, 1, 2-Benzisothiazolone and combinations thereof, and present in an amount in the range from 1% to 15% weight percent ratio with respect to said composition.

4. The formulation as claimed in claim 1, wherein wetting agent is selected from the group comprising of Ethoxylated polyaryl phenol phosphate ester, Naphthalene Sulphonic acid formaldehyde condensate, dioctyl sulphosuccinate, non-ionic ethoxylate, naphthalene alkyl aryl sulphonate, alkyl sulphate, sodium alky sulphate, aryl sulphate, alkylated naphthalene sulfonate sodium salt, sodium alkyl naphthalene sulfonate blend and combinations thereof, and present in an amount in the range from 1% to 10% weight percent ratio with respect to said composition.

5. The formulation as claimed in claim 1, wherein defoamer is selected from Silicone antifoam, Polydimethylsiloxane and combinations thereof, and present in an amount in the range from 0.1% to 5.0% weight percent ratio with respect to said composition.

6. The formulation as claimed in claim 1, wherein anti-caking agent is selected from the group comprising of silica (silicon dioxide), PPT silica, acrylic copolymer, Sulfosuccinates, naphthalene sulphonate of formaldehyde condensate, Lignosulphonate, Calcium lignosulfonate, Sodium lignosulfonate, Ammonium lignosulfonate, and combinations thereof, and present in an amount in the range from 1% to 10% weight percent ratio with respect to said composition.

7. The formulation as claimed in claim 1, wherein binder is selected from the group comprising of Lactose, Polyvinylpyrrolidone (PVK), Starch, Nimbid, Xanthan gum, Agar-agar and Arabic gum or a mixture thereof, and present in an amount in the range from 0.1% to 5% weight percent ratio with respect to said composition.

8. The formulation as claimed in claim 1, wherein filler and co-filler is selected from the group comprising of bentonite clay, lactose monohydrate, china clay, silica, sodium bicarbonate, sodium citrate, starch, kaolin and diatomaceous earth, and combinations thereof.

9. The formulation as claimed in claims 1 to 8, wherein said formulation is water dispersible granule formulation.
10. The formulation as claimed in claim 9, wherein said water dispersible granule is of shape selected from the group comprising of spheres, cylinders, extruded, ellipses, rods, cones, discs, needles and irregular shapes, wherein said cylinders, extruded water dispersible granule have particle size of Min 98% passing through 75 micron sieve on wet sieving.

11. The formulation as claimed in claims 1 to 10, wherein said formulation is employed in a synergistically effective amount dose in ranging from 1000g per hectare to 1600g per hectare.

12. The formulation as claimed in claims 1 to 11, wherein said formulation is effective against Leaf spot, Grey mildew, Blast & sheath blight, Smut, Grain discoloration (Dirty Panicle), Rust, Yellow rust, Powdery mildew, Turcicum leaf blight, Downy mildew, Early and late blight, Septoria leaf spot, Anthracnose, Fruit rot, Purple blotch, Stemphylium blight, Post emergent damping off, Tikka disease, Red rot, Frog eye leaf spot, Alternaria leaf spot, Cercospora leaf spot, Seedling rot, Sigatoka leaf spot, Scab, Premature leaf fall, Gemmosis (Foot Rot) and Leaf blotch.